Kilowatt-scale reaction device for water-electrolysis-based hydrogen production coupled with oxidation

Abstract

A kilowatt-scale reaction device for water-electrolysis-based hydrogen production coupled with oxidation, comprising a power supply system, a reactor system, a raw material supply system, a cooling system, and a gas detection system. The reactor system comprises integrated condensation reactors (2) connected to each other and a static mixer (3). The raw material supply system comprises raw material tanks (4). The raw material tanks (4) are communicated with the static mixer (3). The cooling system comprises a mixer cold trap (8) and a reactor cold trap (9). The mixer cold trap (8) is communicated with the static mixer (3). The reactor cold trap (9) is communicated with the integrated condensation reactors (2). A reaction system operates safely and stably, enabling co-production of high-purity hydrogen at a cathode while achieving electrocatalytic oxidation of various biomass molecules, thereby expanding the reaction scale.

Description

A kilowatt-level electrolytic water hydrogen production coupled oxidation reaction device Technical Field

[0001] This utility model belongs to the field of hydrogen production through electrolysis coupled with oxidation, and specifically relates to a kilowatt-level reaction device for hydrogen production through electrolysis coupled with oxidation. Background Technology

[0002] Hydrogen has advantages such as wide availability, high calorific value, cleanliness, and renewability. Electrochemical technology driven by renewable energy sources (such as solar and wind power) to directly produce hydrogen from water is widely recognized as a green and environmentally friendly approach. However, current water electrolysis hydrogen production technology still faces significant challenges: the anode is the oxygen evolution process, which has slow reaction kinetics, resulting in high energy consumption for hydrogen production. Furthermore, the low-value oxygen produced during oxygen evolution is generally directly released into the air. Utilizing the reactive oxygen species generated during the oxidation process to catalyze the oxidation of organic matter, coupled with oxidation in water electrolysis hydrogen production, is an effective solution. The oxidation process of most organic matter is kinetically more favorable, reducing energy consumption for hydrogen production while simultaneously producing high-value-added products, thus improving economic efficiency.

[0003] In recent years, the coupling of water electrolysis for hydrogen production with organic oxidation has attracted considerable research attention. Organic compounds are diverse, especially biomass platform molecules such as 5-hydroxymethylfurfural, glycerol, and glucose, which are ideal raw materials for the preparation of oxygen-containing compounds. Research on organic oxidation has primarily focused on catalyst synthesis and elucidating reaction mechanisms, with significant progress made in the synthesis of highly active catalysts, such as alloying, noble metal single-atom / nanoparticle loading, defects, high-entropy alloys, and nanomorphology control. However, current research mainly concentrates on low substrate concentrations and small-scale conversions, lacking studies on large-scale reactions, making industrial production difficult. One key to achieving large-scale reactions is the development of reactors that match the reaction scale. To better study the scale-up characteristics of hydrogen production coupled with oxidation through water electrolysis, based on the oxidation of 5-hydroxymethylfurfural, and through a series of studies and reactor development and improvement (Nat. Commun. 2023, 14, 5621, ZL 2023 2 0352381.4, ZL 2023 2 1352376.X, ZL 2023 2 3420373.8), high-efficiency hydrogen production coupled with oxidation through water electrolysis under high concentration and high current was achieved.

[0004] Industrial production requires pilot-scale studies (at the kilowatt level and above) to explore the feasibility and practical operability of the process, thus necessitating the construction of a matching reaction device. Based on the exploration of the reaction process and scale-up rules, a complete kilowatt-level electrolysis water-to-hydrogen coupled oxidation reaction device was developed and designed for the oxidation of various organic compounds to prepare various bulk / fine chemicals, which is conducive to promoting the industrialization of the electrolysis water-to-hydrogen coupled oxidation process.

[0005] Utility Model Content

[0006] This invention is proposed to realize pilot-scale electrolysis of water to produce hydrogen coupled with oxidation, and its purpose is to provide a kilowatt-level electrolysis of water to produce hydrogen coupled with oxidation reaction device.

[0007] This utility model is achieved through the following technical solution:

[0008] A kilowatt-level electrolytic water production hydrogen production coupled with oxidation reactor includes a power supply system, a reactor system, a raw material supply system, a cooling system, and a gas detection system. The power supply system includes at least one DC power supply, which is electrically connected to the reactor system via a cable. The reactor system includes at least one integrated condenser reactor and at least one static mixer; the outlet of the static mixer is connected to the inlet of the integrated condenser reactor. The raw material supply system includes multiple raw material tanks, each connected to the inlet of the static mixer via a raw material delivery pipeline. The cooling system includes a mixer cold trap and a reactor cold trap; the outlet of the mixer cold trap is connected to the coolant inlet of the static mixer, and the outlet of the reactor cold trap is connected to the coolant inlet of the integrated condenser reactor. The gas detection system includes a gas-liquid separator, a water washing tank, a gas dryer, and a hydrogen purity analyzer connected in sequence; the inlet of the gas-liquid separator is connected to the gas outlet of each integrated condenser reactor via a cathode gas path.

[0009] In the above technical solution, when multiple DC power supplies are set, each DC power supply is controlled independently.

[0010] In the above technical solution, when multiple integrated condensing reactors are set, the multiple integrated condensing reactors are connected in series, in parallel, or in a series-parallel combination.

[0011] In the above technical solution, the number of raw material tanks is the same as the number of types of raw materials required for the electrolysis of water to produce hydrogen coupled with oxidation reaction.

[0012] In the above technical solution, the raw material conveying pipeline includes a main raw material conveying line and multiple branch raw material conveying lines that are all connected to the main raw material conveying line. The main raw material conveying line is connected to the lower outlet of the raw material tank, and the other end of the branch raw material conveying line is connected to the inlet of the static mixer. A raw material conveying pump is installed on the branch raw material conveying line, and a pressure valve is installed at the outlet of the raw material conveying pump.

[0013] In the above technical solution, the raw material supply system also includes an electronic balance with the same number of raw material tanks, and the raw material tanks are placed on the electronic balance.

[0014] In the above technical solution, the coolant delivery pipe between the mixer cold trap and the static mixer, as well as the coolant delivery pipe between the reactor cold trap and the integrated condenser reactor, are all covered with an insulation layer.

[0015] In the above technical solution, the cooling system further includes a mixer water distributor located at the outlet of the mixer cold trap and a reactor water distributor located at the outlet of the reactor cold trap. The number of branches of the mixer water distributor is the same as the number of static mixers, and the number of reactor water distributors is no more than the number of integrated condensing reactors. A flow control valve is provided on each branch of the mixer water distributor and the reactor water distributor.

[0016] In the above technical solution, the gas detection system further includes a hydrogen mass flow meter, which is installed on the pipeline between the gas dryer and the hydrogen purity analyzer.

[0017] In the above technical solution, the gas detection system also includes a combustible gas alarm, which is installed on the top of the integrated condensation reactor and near the gas outlet.

[0018] The beneficial effects of this utility model are:

[0019] This invention provides a kilowatt-level electrolysis water hydrogen production coupled with oxidation reaction device, which enables the continuous, stable, and controllable synthesis of various bulk / fine chemicals at kilowatt-level power, while simultaneously producing high-purity hydrogen at the cathode, thus promoting the industrialization of electrolysis water hydrogen production coupled with oxidation. Attached Figure Description

[0020] Figure 1 is a structural schematic diagram of this utility model.

[0021] Figure 2 shows a performance comparison of this invention under different currents during the oxidation of 5-hydroxymethylfurfural.

[0022] in:

[0023] 1. DC power supply; 2. Integrated condenser reactor; 3. Static mixer; 4. Raw material tank; 5. Raw material transfer pump; 6. Electronic balance; 7. Pressure valve; 8. Mixer cold trap; 9. Reactor cold trap; 10. Gas-liquid separator; 11. Water washing tank; 12. Gas dryer; 13. Hydrogen purity analyzer; 14. Hydrogen mass flow meter; 15. Combustible gas alarm.

[0024] For those skilled in the art, other related figures can be obtained from the above figures without any creative effort. Detailed Implementation

[0025] To enable those skilled in the art to better understand the technical solution of this utility model, the technical solution of this utility model will be further described below with reference to the accompanying drawings and specific embodiments.

[0026] Example 1

[0027] As shown in Figure 1, a kilowatt-level electrolytic water hydrogen production coupled oxidation reaction device includes a power supply system, a reactor system, a raw material supply system, a cooling system, and a gas detection system.

[0028] The power supply system includes at least one DC power supply 1, which is electrically connected to the reactor system via a cable.

[0029] The power range of the DC power supply 1 is ≥400A; the maximum operating current of the cable is greater than the DC power supply range to ensure the electrical safety of the device; when multiple DC power supplies 1 are set, each DC power supply 1 is controlled independently.

[0030] In this embodiment, the power supply system includes four DC power supplies;

[0031] The reactor system includes at least one integrated condenser reactor 2 and at least one static mixer 3; the outlet of the static mixer 3 is connected to the feed inlet of the integrated condenser reactor 2.

[0032] When multiple integrated condensing reactors 2 are set up, the multiple integrated condensing reactors 2 are connected in series, in parallel, or in a series-parallel combination.

[0033] The integrated condenser reactor 2 has the same structure as the reactor mechanism 2 in the patent "A modular device for electrocatalytic preparation of 2,5-furandicarboxylic acid and hydrogen-202321352376.X", the only difference being that: the integrated condenser of this utility model is provided with a serpentine flow channel inside the anode reaction chamber.

[0034] The number of static mixers 3 is no greater than the number of integrated condenser reactors 2;

[0035] In this embodiment, the reactor system includes eight integrated condensing reactors 2 and four static mixers 3; the eight integrated condensing reactors 2 are connected in series between every two integrated condensing reactors 2 (the circuit, electrolyte flow path and coolant flow path are all connected in series) and are referred to as a group of reactor units, with a total of four independent groups of reactor units. Each group of reactor units is controlled by a DC power supply and corresponds to a static mixer.

[0036] The anode electrolyte outlets of the four reactor units are combined into one, and each is equipped with a ball valve. The valve is closed when the reactor unit is not in use. The cathode gas outlets of the eight integrated condensing reactors 2 are independent of each other. The outlets located on the upper side are combined into one, and the outlets located on the lower side are combined into one. Each outlet is equipped with a ball valve. The valve is closed when the integrated condensing reactor 2 is not in use.

[0037] The raw material supply system includes multiple raw material tanks 4, each of which is connected to the inlet of the static mixer 3 via a raw material conveying pipeline;

[0038] The number of raw material tanks 4 is the same as the number of types of raw materials required for the electrolysis of water to produce hydrogen coupled with oxidation reaction;

[0039] The raw material conveying pipeline includes a main raw material conveying line and multiple branch raw material conveying lines that are connected to the main raw material conveying line. The main raw material conveying line is connected to the lower outlet of the raw material tank 4, and the other end of the branch raw material conveying line is connected to the inlet of the static mixer 3. A raw material conveying pump 5 is installed on the branch raw material conveying line, and a pressure valve 7 is installed at the outlet of the raw material conveying pump 5.

[0040] The raw material supply system also includes an electronic balance 6 in the same number as the raw material tank 4. The raw material tank 4 is placed on the electronic balance 6. The accuracy of the raw material conveying pump 5 can be preliminarily judged by the mass change signal of the electronic balance 6.

[0041] The raw material tank 4 is made of acid and alkali resistant and corrosion resistant material;

[0042] The flow rate range of the raw material delivery pump 5 is determined according to the type of reactant and the magnitude of the current.

[0043] The pressure valve 7 is used to monitor the liquid pressure in the raw material conveying branch line to determine whether the raw material conveying pump is operating normally and the pipeline status.

[0044] The cooling system includes a mixer cold trap 8 and a reactor cold trap 9. The outlet of the mixer cold trap 8 is connected to the coolant inlet of the static mixer 3 through a coolant delivery pipe, and the coolant outlet of the static mixer 3 is connected to the inlet of the mixer cold trap 8 through a coolant delivery pipe. The outlet of the reactor cold trap 9 is connected to the coolant inlet of the integrated condensing reactor 2 through a coolant delivery pipe, and the coolant outlet of the integrated condensing reactor 2 is connected to the inlet of the reactor cold trap 9 through a coolant delivery pipe.

[0045] The coolant delivery pipeline is externally covered with an insulation layer;

[0046] The cooling system also includes a mixer water distributor located at the outlet of the mixer cold trap 8 and a reactor water distributor located at the outlet of the reactor cold trap 9. The number of branches of the mixer water distributor is the same as the number of static mixers 3, and the number of reactor water distributors is no more than the number of integrated condensing reactors 2. Each branch of the mixer water distributor and the reactor water distributor is equipped with a flow control valve to balance the flow rate of each coolant and keep it consistent. The cooling temperature of the mixer cold trap 8 and the reactor cold trap 9 is determined according to the actual reaction operation.

[0047] In this embodiment, both the mixer distributor and the reactor distributor have four branches, i.e., one branch divides into four.

[0048] The gas detection system includes a gas-liquid separator 10, a water washing tank 11, a gas dryer 12, and a hydrogen purity analyzer 13 connected in sequence.

[0049] The gas inlet of the gas-liquid separator 10 is connected to the gas outlet of each integrated condenser reactor 2 through a cathode gas path, and the gas outlet of the gas-liquid separator 10 is connected to the gas inlet of the water washing tank 11 through a pipeline.

[0050] The air inlets of both the gas-liquid separator 10 and the water washing tank 11 are located below the liquid surface, and the air outlets are located above the liquid surface.

[0051] The bottom of the gas-liquid separator 10 is provided with a float discharge port. When the liquid volume reaches the set value, the float will automatically rise and discharge the liquid in the tank. The float discharge port is connected to a storage tank through a pipeline. The storage tank is used to store the liquid discharged from the gas-liquid separator.

[0052] The air outlet of the water washing tank 11 is connected to the inlet of the gas dryer 12, and the liquid outlet is provided at the bottom of the water washing tank 11.

[0053] The outlet of the gas dryer 12 is connected to the hydrogen purity analyzer 13.

[0054] The gas detection system also includes a hydrogen mass flow meter 14, which is installed on the pipeline between the gas dryer 12 and the hydrogen purity analyzer 13.

[0055] The gas detection system also includes a combustible gas alarm 15, which is located on the top of the integrated condensation reactor 2 and near the gas outlet.

[0056] The kilowatt-level electrolytic water hydrogen production coupled oxidation reaction device also includes an outer shell covering the power supply system, reactor system, raw material supply system, cooling system and gas detection system; an exhaust fan is provided on the top of the outer shell, and a detection window is provided on at least one side wall of the outer shell;

[0057] The kilowatt-level electrolytic water hydrogen production coupled oxidation reaction device also includes an emergency braking system, which includes a relay and an air switch. The relay and air switch are installed on the connection circuit between the power supply system and the reactor system. The relay and air switch are installed at the top of the outside of the reaction device and are used to cut off the main power supply of the reaction device in an emergency.

[0058] This invention achieves accurate and stable monitoring of the flow rate of the liquid transfer pump by setting up an electronic balance and a pressure valve; it also sets up a gas detection system to monitor the purity of the produced hydrogen; and it sets up a combustible gas alarm to monitor the safe operation of the reactor in real time. The reaction device has a certain degree of flexibility and can be equipped with different types and sizes of reactors to match different substrates and different scales of reactions, which makes it possible to industrialize the production of hydrogen through electrolysis coupled with oxidation.

[0059] How to use this utility model:

[0060] During operation, first connect the reactor to the device, including the power cord, electrolyte line, and gas line; the alkaline electrolyte and the aqueous solution containing the substrate are stored in two separate raw material tanks; open the valves on the anode electrolyte outlet, gas outlet, and coolant line according to the number of reactors; set the temperature of the cold trap according to the reaction conditions and perform cooling; turn on the exhaust fan on the device casing; finally, check the gas path of the entire reaction device to ensure good airtightness. When the reaction device is running, first turn on the raw material delivery pump to pump the electrolyte into the reactor, and turn on the cold trap circulation switch to pump the coolant into the cooling chamber of the reactor and the cooling chamber of the static mixer, confirming that the electrolyte and coolant flow smoothly and without leakage; then turn on the DC power supply to perform the electrolysis reaction, observe whether the operating voltage is normal, and observe whether bubbles are bubbling out in the gas-liquid separator and water washing tank; when a local hydrogen concentration is detected to be too high, an alarm is triggered and the power is cut off; multi-level safety detection measures ensure the stable operation of the kilowatt-level reaction.

[0061] During the reaction process, operators need to take samples from the anolyte outlet periodically for testing to ensure stable performance.

[0062] Application Example 1

[0063] Example 1 was applied to the process of preparing 2,5-furandicarboxylic acid by coupling the electrolysis of water to produce hydrogen with the oxidation of 5-hydroxymethylfurfural. In this application example, the concentration of the 5-hydroxymethylfurfural aqueous solution was 4.2 mol / L, the alkaline electrolyte was 5.7 mol / L potassium hydroxide, and the 5-hydroxymethylfurfural and potassium hydroxide solutions were introduced into a static mixer at a flow rate of 1:2. The concentration of 5-hydroxymethylfurfural in the reactor was 1.4 mol / L.

[0064] In this application example, the area of ​​each anode and cathode is 100 cm².2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm², and the anode catalyst is nickel cobalt molybdate (NiCoMoO₄) with a catalyst loading of 2.0 ± 0.05 mg / cm². -2 The cathode catalyst was commercial ruthenium oxide (RuO2), and the catalyst loading was 1 ± 0.05 mg / cm³. -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C. Four reactors were run sequentially.

[0065] As shown in Figure 2, at a current density of 1 A cm⁻¹ -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), the flow rate of the 5-hydroxymethylfurfural aqueous solution was 9.87 mL / min. -1 The flow rate of KOH was 19.74 mL / min. -1 The average tank pressure of the two reactors was 2.74V, and the operating power of a single reactor was 1096W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of 5-hydroxymethylfurfural was 92.6%, the selectivity for 2,5-furandicarboxylic acid was 94.6%, and the Faraday efficiency was 88.7%.

[0066] At a current density of 1A cm -2 Two, three, and four reactors were operated under the same conditions (total currents of 800A, 1200A, and 1600A, respectively), corresponding to a flow rate of 9.87 mL / min for the 5-hydroxymethylfurfural aqueous solution in each reactor. -1 The flow rate of KOH was 19.74 mL / min. -1 During operation, the reactor tank pressure remained at approximately 2.7V. With all four reactors operating simultaneously, the total operating power reached 4.3kW, and the reaction performance remained consistent with that of a single reactor, showing no decline. This demonstrates the good scalability of the reactor unit, allowing for the addition or reduction of reactor groups according to actual needs.

[0067] Application Example 2

[0068] Example 1 was applied to the process of producing hydrogen through water electrolysis coupled with furfural oxidation to prepare furoic acid. In this application example, the concentration of the furfural aqueous solution was 0.6 mol / L, the alkaline electrolyte was 4.2 mol / L potassium hydroxide, and the furfural and potassium hydroxide solutions were introduced into the static mixer at a flow rate of 2:1. The concentration of furfural in the reactor was 0.4 mol / L.

[0069] In this application example, the area of ​​each anode and cathode is 100 cm². 2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm², and the anode catalyst is nickel cobalt molybdate (NiCoMoO₄) with a catalyst loading of 2.0 ± 0.05 mg / cm². -2 The cathode catalyst was commercial ruthenium oxide (RuO2), and the catalyst loading was 1 ± 0.05 mg / cm³. -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C.

[0070] At a current density of 1A cm -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), the flow rate of furfural aqueous solution was 207.28 mL / min. -1 The flow rate of KOH was 103.64 mL / min. -1 The average tank pressure of the two reactors was 2.8V, and the operating power of a single reactor was 1120W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of furfural was 71.3%, the selectivity of furoic acid was 99.5%, and the Faraday efficiency was 70.0%.

[0071] Application Example 3

[0072] Example 1 was applied to the process of preparing adipic acid by coupling hydrogen production through water electrolysis with cyclohexanediol oxidation. In this application example, the concentration of the cyclohexanediol aqueous solution was 1 mol / L, the alkaline electrolyte was 4 mol / L potassium hydroxide, and the cyclohexanediol and potassium hydroxide solution were introduced into the static mixer at a flow rate of 1:1. The concentration of cyclohexanediol in the reactor was 0.5 mol / L.

[0073] In this application example, the area of ​​each anode and cathode is 100 cm². 2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm², and the anode catalyst is nickel cobalt molybdate (NiCoMoO₄) with a catalyst loading of 2.0 ± 0.05 mg / cm². -2 The cathode catalyst was commercial ruthenium oxide (RuO2), and the catalyst loading was 1 ± 0.05 mg / cm³. -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C.

[0074] At a current density of 1A cm -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), the flow rate of the cyclohexanediol aqueous solution was 41.44 mL / min. -1 The flow rate of KOH was 41.44 mL / min. -1 The average tank pressure of the two reactors was 2.78V, and the operating power of a single reactor was 1112W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of cyclohexanediol was 83.0%, the selectivity of adipic acid was 89.8%, and the Faraday efficiency was 75.7%.

[0075] Application Example 4

[0076] Example 1 was applied to the process of preparing formic acid by electrolysis of water to produce hydrogen coupled with the oxidation of glycerol. In this application example, glycerol and potassium hydroxide raw materials were prepared together. The electrolyte consisted of 1 mol / L glycerol and 4 mol / L potassium hydroxide. The alkaline electrolyte containing glycerol was fed into an integrated condenser reactor through a raw material delivery pump.

[0077] In this application example, the area of ​​each anode and cathode is 100 cm². 2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm², and the anode catalyst is nickel cobalt molybdate (NiCoMoO₄) with a catalyst loading of 2.0 ± 0.05 mg / cm². -2 The cathode catalyst was commercial ruthenium oxide (RuO2), and the catalyst loading was 1 ± 0.05 mg / cm³. -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C.

[0078] At a current density of 1A cm -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), electrolyte flow rate containing glycerol 31.09 mL / min. -1 The average tank pressure of the two reactors was 2.75V, and the operating power of a single reactor was 1100W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of glycerol was 90.0%, the selectivity of formic acid was 89.5%, and the Faraday efficiency was 82.3%.

[0079] Application Example 5

[0080] Example 1 was applied to the process of preparing lactic acid by electrolysis of water to produce hydrogen coupled with glycerol oxidation. In this application example, glycerol and potassium hydroxide raw materials were prepared together. The electrolyte consisted of 1 mol / L glycerol and 3 mol / L potassium hydroxide. The alkaline electrolyte containing glycerol was fed into an integrated condenser reactor through a raw material delivery pump.

[0081] In this application example, the area of ​​each anode and cathode is 100 cm². 2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm². The anode catalyst is AuPtPd supported on nickel hydroxide (AuPtPd / Ni(OH)₂@NF), and the cathode catalyst is commercial ruthenium oxide (RuO₂) with a catalyst loading of 1 ± 0.05 mg / cm². -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C.

[0082] At a current density of 1A cm -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), electrolyte flow rate containing glycerol 124.37 mL / min. -1 The average tank pressure of the two reactors was 2.8V, and the operating power of a single reactor was 1120W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of glycerol was 89.5%, the selectivity of lactic acid was 88.5%, and the Faraday efficiency was 83.4%.

[0083] Application Example 6

[0084] Example 1 was applied to the process of producing hydrogen through water electrolysis coupled with the oxidation of 1,4-butanediol to prepare succinic acid. In this application example, 1,4-butanediol and potassium hydroxide raw materials were prepared together. The electrolyte consisted of 1 mol / L of 1,4-butanediol and 3 mol / L of potassium hydroxide. The alkaline electrolyte containing 1,4-butanediol was introduced into an integrated condenser reactor through a raw material delivery pump.

[0085] In this application example, the area of ​​each anode and cathode is 100 cm². 2 (That is, the area of ​​the anode and cathode electrodes in each reactor is 200 cm²) 2 Each reactor group has a catalyst area of ​​400 cm², and the anode catalyst is nickel cobalt molybdate (NiCoMoO₄) with a catalyst loading of 2.0 ± 0.05 mg / cm². -2The cathode catalyst was commercial ruthenium oxide (RuO2), and the catalyst loading was 1 ± 0.05 mg / cm³. -2 Membrane electrodes (MEAs) were fabricated using anion exchange membranes (model: FAA-3-50) from FMA GmbH, Germany, for reactor assembly. The mixer cold trap temperature was set to 8°C, and the reactor cold trap temperature was set to 3°C.

[0086] At a current density of 1A cm -2 Operating a set of reactors under the following conditions (total catalyst area 400 cm²) 2 (Total current 400A), electrolyte flow rate containing 1,4-butanediol 31.09 mL / min. -1 The average tank pressure of the two reactors was 2.73V, and the operating power of a single reactor was 1092W, achieving kilowatt-level operation. Under these operating conditions, the conversion rate of 1,4-butanediol was 92.3%, the selectivity of succinic acid was 93.1%, and the Faraday efficiency was 88.5%.

[0087] In the description of this utility model, it should be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicating orientation or positional relationships based on the orientation or positional relationships shown in the accompanying drawings, are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this utility model, unless otherwise stated, "a plurality of" means two or more.

[0088] In the description of this utility model, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0089] The applicant declares that the above description is only a specific embodiment of the present utility model, but the protection scope of the present utility model is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present utility model fall within the protection and disclosure scope of the present utility model.

Claims

1. A kilowatt-level electrolytic water production hydrogen production coupled with oxidation reaction device, characterized in that: This includes a power supply system, a reactor system, a raw material supply system, a cooling system, and a gas detection system; The power supply system includes at least one DC power source (1), which is electrically connected to the reactor system via a cable; The reactor system includes at least one integrated condenser reactor (2) and at least one static mixer (3); the outlet of the static mixer (3) is connected to the feed inlet of the integrated condenser reactor (2); The raw material supply system includes multiple raw material tanks (4), each of which is connected to the inlet of the static mixer (3) via a raw material conveying pipeline; The cooling system includes a mixer cold trap (8) and a reactor cold trap (9). The outlet of the mixer cold trap (8) is connected to the coolant inlet of the static mixer (3), and the outlet of the reactor cold trap (9) is connected to the coolant inlet of the integrated condenser reactor (2). The gas detection system includes a gas-liquid separator (10), a water washing tank (11), a gas dryer (12), and a hydrogen purity analyzer (13) connected in sequence; the gas inlet of the gas-liquid separator (10) is connected to the gas outlet of each integrated condenser reactor (2) through a cathode gas path.

2. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: When multiple DC power supplies (1) are set, each DC power supply (1) is controlled independently.

3. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: When multiple integrated condensing reactors (2) are set up, the multiple integrated condensing reactors (2) are connected in series, in parallel or in a series-parallel combination.

4. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The number of raw material tanks (4) is the same as the number of types of raw materials required for the hydrogen production coupled oxidation reaction by water electrolysis.

5. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The raw material conveying pipeline includes a main raw material conveying line and multiple branch raw material conveying lines that are connected to the main raw material conveying line. The main raw material conveying line is connected to the lower outlet of the raw material tank (4). The other end of the branch raw material conveying line is connected to the inlet of the static mixer (3). A raw material conveying pump (5) is installed on the branch raw material conveying line. A pressure valve (7) is installed at the outlet of the raw material conveying pump (5).

6. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The raw material supply system also includes an electronic balance (6) of the same number as the raw material tanks (4), with the raw material tanks (4) placed on the electronic balances (6).

7. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The coolant delivery pipes between the mixer cold trap (8) and the static mixer (3) and between the reactor cold trap (9) and the integrated condenser reactor (2) are all covered with an insulation layer.

8. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The cooling system also includes a mixer water distributor located at the outlet of the mixer cold trap (8) and a reactor water distributor located at the outlet of the reactor cold trap (9). The number of branches of the mixer water distributor is the same as the number of static mixers (3), and the number of reactor water distributors is no more than the number of integrated condensing reactors (2). A flow control valve is provided on each branch of the mixer water distributor and the reactor water distributor.

9. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The gas detection system also includes a hydrogen mass flow meter (14), which is installed on the pipeline between the gas dryer (12) and the hydrogen purity analyzer (13).

10. The kilowatt-level electrolytic water production hydrogen production coupled oxidation reaction device according to claim 1, characterized in that: The gas detection system also includes a combustible gas alarm (15), which is located on the top of the integrated condensation reactor (2) and near the gas outlet.

Images