CN223548114U - A kilowatt-level electrolytic water hydrogen production coupled oxidation reaction device - Google Patents
A kilowatt-level electrolytic water hydrogen production coupled oxidation reaction deviceInfo
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- CN223548114U CN223548114U CN202423024441.3U CN202423024441U CN223548114U CN 223548114 U CN223548114 U CN 223548114U CN 202423024441 U CN202423024441 U CN 202423024441U CN 223548114 U CN223548114 U CN 223548114U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The utility model discloses a kilowatt-level electrolytic water hydrogen production coupling oxidation reaction device which comprises a power supply system, a reactor system, a raw material supply system, a cooling system and a gas detection system, wherein the power supply system is electrically connected with the reactor system, the reactor system comprises an integrated condensation reactor and a static mixer which are connected with each other, the raw material supply system comprises a raw material tank, the raw material tank is communicated with the static mixer, the cooling system comprises a mixer cold trap and a reactor cold trap, the mixer cold trap is communicated with the static mixer, the reactor cold trap is communicated with the integrated condensation reactor, the gas detection system comprises a gas-liquid separation tank, a water washing tank, a gas dryer and a hydrogen purity analyzer which are sequentially connected, and a gas inlet of the gas-liquid separation tank is communicated with a gas outlet of the integrated condensation reactor. The utility model realizes the safe and stable operation of the kilowatt-level reaction system, realizes the kilowatt-level stable operation of various biomass platform molecules and simultaneously realizes the safe co-production of hydrogen.
Description
Technical Field
The utility model belongs to the field of electrolytic water hydrogen production coupling oxidation, and particularly relates to a kilowatt-level electrolytic water hydrogen production coupling oxidation reaction device.
Background
The hydrogen has the advantages of wide source, high heat value, cleanness, regeneration and the like, and the direct production of the hydrogen from water by using the electrochemical technology driven by renewable energy sources (such as solar energy and wind energy) is recognized as an environment-friendly way. However, the current technology for producing hydrogen by electrolyzing water still faces the great challenges that the anode end is an oxygen separation process, the reaction kinetics of the oxygen separation process is slow, so that the hydrogen production energy consumption is high, and the oxygen separation process generates low-value oxygen which is generally directly emptied. The oxidation of the active oxygen catalytic organic matters generated in the oxidation process is an effective solution for realizing the hydrogen production coupling oxidation of the electrolyzed water, and the oxidation process of most organic matters is more favorable in dynamics, so that the hydrogen production energy consumption can be reduced, and meanwhile, products with high added values can be produced, and the economic benefit is improved.
In recent years, the hydrogen production by water electrolysis and the oxidation of organic matters are attracted to a plurality of researches, the types of the organic matters are rich, and particularly biomass platform molecules, such as 5-hydroxymethylfurfural, glycerol, glucose and the like, are ideal raw materials for preparing the oxygen-containing compounds. Research based on organic matter oxidation is mainly focused on the aspects of synthesis of catalysts and disclosure of reaction mechanisms, and particularly important progress is made in synthesis of high-activity catalysts, such as alloying, noble metal single-atom/nanoparticle loading, defects, high-entropy alloys, nanotopography regulation and the like. However, the current research is mainly focused on low substrate concentration and small-scale conversion, and the research on large-scale reaction is lacking, so that industrial production is difficult to realize. One of the keys to achieve a scaled reaction is to develop a reactor that matches the reaction scale. In order to better research the amplification rule of the coupling oxidation of the hydrogen production by the electrolysis of water, the coupling oxidation of the hydrogen production by the electrolysis of water under high concentration and high current is realized based on the oxidation of 5-hydroxymethylfurfural through series research and development and improvement (Nat.Commun.2023, 14,5621,ZL 202320352381.4,ZL 202321352376.X,ZL 202323420373.8) of a reactor.
Industrial production requires pilot studies (above kilowatt level) to explore the feasibility and practical operability of the process, and thus requires construction of a reaction apparatus matching with it. Based on the exploration of the reaction process and the amplification rule, a complete kilowatt-level electrolytic water hydrogen production coupling oxidation reaction device is developed and designed for preparing various bulk/fine chemicals by oxidizing various organic matters, and the industrial process of the electrolytic water hydrogen production coupling oxidation process is facilitated to be promoted.
Disclosure of utility model
The utility model provides a reaction device for preparing hydrogen by electrolysis of water in kilowatt level, which is provided for realizing pilot scale hydrogen preparation coupling oxidation by electrolysis of water.
The utility model is realized by the following technical scheme:
The reaction device comprises a power supply system, a reactor system, a raw material supply system, a cooling system and a gas detection system, wherein the power supply system comprises at least one direct current power supply, the direct current power supply is electrically connected with the reactor system through a cable, the reactor system comprises at least one integrated condensation reactor and at least one static mixer, the outlet of the static mixer is communicated with the feed inlet of the integrated condensation reactor, the raw material supply system comprises a plurality of raw material tanks, each raw material tank is communicated with the inlet of the static mixer through a raw material conveying pipeline, the cooling system comprises a mixer cold trap and a reactor cold trap, the outlet of the mixer cold trap is communicated with the cooling liquid inlet of the static mixer, the outlet of the reactor cold trap is communicated with the cooling liquid inlet of the integrated condensation reactor, the gas detection system comprises a gas-liquid separation tank, a water washing tank, a gas dryer and a hydrogen purity analyzer which are sequentially connected, and the gas inlet of the gas-liquid separation tank is communicated with the gas outlet of each integrated condensation reactor through a cathode gas circuit.
In the above technical solution, when a plurality of dc power sources are provided, each dc power source is controlled individually.
In the above technical solution, when a plurality of integrated condensation reactors are provided, a plurality of integrated condensation reactors are connected in series, in parallel or in a combination of series and parallel.
In the technical scheme, the number of the raw material tanks is the same as the number of the raw material types required by the electrolytic water hydrogen production coupling oxidation reaction.
In the above technical scheme, the raw material conveying pipeline comprises a raw material conveying main line and a plurality of raw material conveying branch lines which are communicated with the raw material conveying main line, wherein the raw material conveying main line is communicated with an outlet at the lower end of the raw material tank, the other end of the raw material conveying branch line is communicated with an inlet of the static mixer, a raw material conveying pump is arranged on the raw material conveying branch line, and a pressure valve is arranged at an outlet of the raw material conveying pump.
In the above technical solution, the raw material supply system further includes electronic balances having the same number as the raw material tanks, and the raw material tanks are placed on the electronic balances.
In the technical scheme, the outside of the cooling liquid conveying pipeline between the mixer cold trap and the static mixer and the cooling liquid conveying pipeline between the reactor cold trap and the integrated condensation reactor are coated with the heat insulation layers.
In the above technical scheme, the cooling system further comprises a mixer water separator arranged at the outlet of the mixer cold trap and a reactor water separator arranged at the outlet of the reactor cold trap, the number of branches of the mixer water separator is the same as that of the static mixers, the number of the reactor water separators is not more than that of the integrated condensation reactors, and each branch of the mixer water separator and each branch of the reactor water separator are provided with a flow control valve.
In the above technical scheme, the gas detection system further comprises a hydrogen mass flowmeter, and the hydrogen mass flowmeter is arranged on a pipeline between the gas dryer and the hydrogen purity analyzer.
In the above technical scheme, the gas detection system further comprises a combustible gas alarm, wherein the combustible gas alarm is arranged at the top of the integrated condensation reactor and is close to the gas discharge port.
The beneficial effects of the utility model are as follows:
The utility model provides a reaction device for producing hydrogen by water electrolysis of kilowatt level and coupling oxidation, which realizes continuous, stable and controllable synthesis of various bulk/fine chemicals under the power of kilowatt level, and simultaneously, high-purity hydrogen is co-produced by a cathode, thereby promoting the industrialization process of the water electrolysis hydrogen production and coupling oxidation.
Drawings
Fig. 1 is a schematic structural view of the present utility model.
Figure 2 is a comparison of the performance of the utility model at different currents for use in the oxidation process of 5-hydroxymethylfurfural.
Wherein:
1. The device comprises a direct current power supply, an integrated condensing reactor, a static mixer, a raw material tank, a raw material conveying pump, an electronic balance, a pressure valve, a mixer cold trap, a reactor cold trap, a gas-liquid separation tank, a water washing tank, a gas dryer, a hydrogen purity analyzer, a hydrogen mass flowmeter, a fuel gas alarm and a fuel gas alarm, wherein the direct current power supply, the integrated condensing reactor, the static mixer, the raw material tank, the raw material conveying pump, the electronic balance, the pressure valve, the mixer cold trap, the reactor cold trap, the gas-liquid separation tank, the water washing tank, the gas dryer, the hydrogen purity analyzer, the hydrogen mass flowmeter and the fuel gas alarm are respectively arranged in sequence.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the technical solution of the present utility model better understood by those skilled in the art, the technical solution of the present utility model will be further described below by means of specific embodiments in combination with the accompanying drawings of the specification.
Example 1
As shown in FIG. 1, the reaction device for producing hydrogen by kilowatt-level electrolyzed water and coupling oxidation comprises a power supply system, a reactor system, a raw material supply system, a cooling system and a gas detection system;
the power supply system comprises at least one direct current power supply 1, and the direct current power supply is electrically connected with the reactor system through a cable;
the power range of the direct current power supply 1 is more than or equal to 400A, the maximum current used by the cable is larger than the range of the direct current power supply to ensure the power utilization safety of the device, and when a plurality of direct current power supplies 1 are arranged, each direct current power supply 1 is independently controlled;
In this embodiment, the power supply system includes four dc power sources;
the reactor system comprises at least one integrated condensation reactor 2 and at least one static mixer 3, wherein the outlet of the static mixer 3 is communicated with the feed inlet of the integrated condensation reactor 2;
When a plurality of integrated condensation reactors 2 are arranged, the plurality of integrated condensation reactors 2 are connected in series, in parallel or in a combination of series and parallel;
The integrated condensing reactor 2 has the same structure as the reactor mechanism 2 of the modular device-202321352376. X for preparing 2, 5-furandicarboxylic acid and hydrogen by electrocatalytic reaction, and the difference is that the inside of the anode reaction cavity of the integrated condenser is provided with a serpentine launder.
The number of static mixers 3 is not greater than the number of integrated condensation reactors 2;
In this embodiment, the reactor system comprises eight integrated condensation reactors 2 and four static mixers 3, wherein the eight integrated condensation reactors 2 are connected together in series (a circuit, an electrolyte flow path and a cooling liquid flow path are all connected in series) between every two integrated condensation reactors 2 to form a group of reactor units, and four groups of reactor units are independent from each other, and each group of reactor units is controlled by a direct current power supply and corresponds to one static mixer;
The anolyte outlets of the four groups of reactor units are converged into one path, each path is provided with a ball valve, and when the group of reactor units are not used, the valves are closed; the cathode gas outlets of the eight integrated condensation reactors 2 are mutually independent, the outlets on the upper side are collected into one path, the outlets on the lower side are collected into one path, each outlet is provided with a ball valve, and when the integrated condensation reactor 2 is in an unused state, the valve is closed;
The raw material supply system comprises a plurality of raw material tanks 4, each of which is communicated with the inlet of the static mixer 3 through a raw material conveying pipeline;
the number of the raw material tanks 4 is the same as the number of the raw material types required by the electrolytic water hydrogen production coupling oxidation reaction;
The raw material conveying pipeline comprises a raw material conveying main line and a plurality of raw material conveying branch lines which are all communicated with the raw material conveying main line, the raw material conveying main line is communicated with an outlet at the lower end of the raw material tank 4, the other end of the raw material conveying branch line is communicated with an inlet of the static mixer 3, a raw material conveying pump 5 is arranged on the raw material conveying branch line, and a pressure valve 7 is arranged at the outlet of the raw material conveying pump 5;
The raw material supply system further comprises electronic balances 6, the number of which is the same as that of the raw material tanks 4, the raw material tanks 4 are arranged on the electronic balances 6, and the accuracy of the raw material conveying pump 5 can be primarily judged through mass change signals of the electronic balances 6;
The raw material tank 4 is made of acid-alkali-resistant and corrosion-resistant materials;
the flow range of the raw material conveying pump 5 is determined according to the types of reactants and the magnitude of current;
The pressure valve 7 is used for monitoring the liquid pressure in the raw material conveying branch line so as to judge whether the raw material conveying pump normally operates and the pipeline state;
the cooling system comprises a mixer cold trap 8 and a reactor cold trap 9, wherein an outlet of the mixer cold trap 8 is communicated with a cooling liquid inlet of the static mixer 3 through a cooling liquid conveying pipeline, and a cooling liquid outlet of the static mixer 3 is communicated with an inlet of the mixer cold trap 8 through a cooling liquid conveying pipeline;
the outside of the cooling liquid conveying pipeline is coated with an insulating layer;
The cooling system also comprises a mixer water separator arranged at the outlet of the mixer cold trap 8 and a reactor water separator arranged at the outlet of the reactor cold trap 9, wherein the number of branches of the mixer water separator is the same as that of the static mixers 3, the number of the reactor water separators is not more than that of the integrated condensation reactors 2, and each branch of the mixer water separator and the reactor water separator is provided with a flow control valve so as to balance the flow of each path of cooling liquid to keep consistent;
in this embodiment, the number of branches of the mixer water separator and the reactor water separator is four, namely one-quarter;
The gas detection system comprises a gas-liquid separation tank 10, a water washing tank 11, a gas dryer 12 and a hydrogen purity analyzer 13 which are connected in sequence;
The air inlet of the gas-liquid separation tank 10 is communicated with the air outlet of each integrated condensation reactor 2 through a cathode air path, and the air outlet of the gas-liquid separation tank 10 is communicated with the air inlet of the washing tank 11 through a pipeline;
the gas inlets of the gas-liquid separation tank 10 and the water washing tank 11 are arranged at the position below the liquid level, and the gas outlets are arranged at the position above the liquid level;
The bottom of the gas-liquid separation tank 10 is provided with a float liquid outlet, and when the liquid amount reaches a set value, a float can automatically jack up the liquid in the discharge tank;
The air outlet of the water washing tank 11 is communicated with the inlet of the gas dryer 12, and the bottom of the water washing tank 11 is provided with a liquid outlet;
The outlet of the gas dryer 12 is communicated with a hydrogen purity analyzer 13;
The gas detection system further comprises a hydrogen mass flowmeter 14, wherein the hydrogen mass flowmeter 14 is arranged on a pipeline between the gas dryer 12 and the hydrogen purity analyzer 13;
The gas detection system further comprises a combustible gas alarm 15, wherein the combustible gas alarm 15 is arranged at the top of the integrated condensation reactor 2 and is close to a gas discharge hole.
The reaction device for producing hydrogen by the kilowatt-level electrolyzed water and coupling oxidation further comprises a shell which is covered outside a power supply system, a reactor system, a raw material supply system, a cooling system and a gas detection system, wherein an exhaust fan is arranged at the top of the shell, and at least one side wall of the shell is provided with a detection window;
The reaction device for producing hydrogen by the kilowatt-level electrolyzed water and coupling oxidation further comprises an emergency braking system, wherein the emergency braking system comprises a relay and an air switch, the relay and the air switch are arranged on a connecting circuit between a power supply system and a reactor system, and the relay and the air switch are arranged at the top end of the exterior of the reaction device and are used for cutting off the total power supply of the reaction device in emergency.
The utility model realizes the monitoring of the flow accuracy and stability of the liquid delivery pump by arranging the electronic balance and the pressure valve, realizes the monitoring of the purity of the prepared hydrogen by arranging the gas detection system, monitors the operation safety condition of the reactor in real time by arranging the combustible gas alarm, has certain flexibility, can be assembled with different types and different sizes of reactors to match different substrates and different scale reactions, and provides possibility for the industrial production of the coupling oxidation of the hydrogen production by the electrolysis of water.
The application method of the utility model comprises the following steps:
In the using process, the reactor is connected in the device, the reactor comprises a power line, an electrolyte pipeline and a gas pipeline, alkaline electrolyte and aqueous solution containing substrates are respectively stored in two raw material storage tanks, valves on a liquid outlet of the anolyte, a gas outlet and a cooling liquid pipeline are opened according to the number of the reactors, the temperature of a cold trap is set according to reaction conditions and refrigeration is carried out, an exhaust fan on a shell of the device is opened, and finally the gas circuit of the whole reaction device is checked to ensure good air tightness. When the reaction device operates, firstly, a raw material conveying pump is started to pump electrolyte into the reactor, a cold trap circulation switch is started to pump cooling liquid into a cooling cavity of the reactor and a cooling cavity of a static mixer, smooth circulation of the electrolyte and the cooling liquid is confirmed, no leakage is caused, then, a power supply of a direct current power supply is started to perform electrolytic reaction, whether operating voltage is normal or not is observed, whether bubbles in a gas-liquid separation tank and a water washing tank bulge or not is observed, when the fact that the local hydrogen concentration is detected to be too high, an alarm is given out, the power supply is cut off, and stable operation of kilowatt-level reaction is ensured through a multistage safety detection means.
In the reaction process, operators need to sample and test the anolyte liquid outlet at irregular intervals to ensure stable performance.
Application example 1
In the process of preparing 2, 5-furandicarboxylic acid by coupling hydrogen production with 5-hydroxymethylfurfural through electrolysis of water, the embodiment 1 is applied, in the application example, the concentration of the 5-hydroxymethylfurfural aqueous solution is 4.2mol/L, the alkaline electrolyte is 5.7mol/L of potassium hydroxide, the 5-hydroxymethylfurfural and the potassium hydroxide solution are introduced into a static mixer according to the flow rate of 1:2, and the concentration of the 5-hydroxymethylfurfural in the reactor is 1.4mol/L.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is cobalt nickel molybdate (NiCoMoO 4), the catalyst loading is 2.0+ -0.05 mg cm -2, the cathode catalyst is commercial ruthenium oxide (RuO 2), and the catalyst loading is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Germany Fuma company for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃. Four sets of reactors were operated in sequence.
As shown in FIG. 2, a set of reactors (total catalyst area 400cm 2, total current 400A) was operated at a current density of 1A cm -2, a flow rate of aqueous 5-hydroxymethylfurfural of 9.87mL min -1, and a flow rate of KOH of 19.74mL min -1. The average tank pressure of the two reactors is 2.74V, the running power of the single reactor is 1096W, and kilowatt level running is realized. Under this operating condition, the conversion of 5-hydroxymethylfurfural was 92.6%, the selectivity of 2, 5-furandicarboxylic acid was 94.6% and the faraday efficiency was 88.7%.
Two, three and four sets of reactors (total current 800A, 1200A and 1600A, respectively) were operated at a current density of 1A cm -2, corresponding to a flow rate of aqueous 5-hydroxymethylfurfural solution of 9.87mL min -1 and a flow rate of KOH of 19.74mL min -1 in each set of reactors. In the operation process, the tank pressure of the reactors is kept to be 2.7V, the total operation power reaches 4.3kW when the four groups of reactors are operated simultaneously, and the reaction performance is kept consistent with that of a single group of reactors without attenuation. The good expansibility of the reaction device is demonstrated, and the number of the reactor groups is increased or decreased according to actual requirements.
Application example 2
In the process of preparing furoic acid by coupling hydrogen production by water electrolysis and furaldehyde oxidation, in the application example, the concentration of the furaldehyde aqueous solution is 0.6mol/L, the alkaline electrolyte is 4.2mol/L of potassium hydroxide, the furaldehyde and the potassium hydroxide solution are introduced into a static mixer at a flow rate of 2:1, and the concentration of the furaldehyde in the reactor is 0.4mol/L.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is cobalt nickel molybdate (NiCoMoO 4), the catalyst loading is 2.0+ -0.05 mg cm -2, the cathode catalyst is commercial ruthenium oxide (RuO 2), and the catalyst loading is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Germany Fuma company for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃.
A set of reactors (total catalyst area 400cm 2, total current 400A) was run at a current density of 1A cm -2, a flow rate of the aqueous furfural solution of 207.28mL min -1 and a flow rate of KOH of 103.64mL min -1. The average tank pressure of the two reactors is 2.8V, the running power of the single reactor is 1120W, and kilowatt level running is realized. Under the running condition, the conversion rate of the furfural is 71.3 percent, the selectivity of the furoic acid is 99.5 percent, and the Faraday efficiency is 70.0 percent.
Application example 3
In the process of preparing adipic acid by coupling hydrogen production with cyclohexanediol through electrolysis of water, the application example is that the concentration of cyclohexanediol aqueous solution is 1mol/L, alkaline electrolyte is 4mol/L potassium hydroxide, cyclohexanediol and potassium hydroxide solution are introduced into a static mixer at a flow rate of 1:1, and the concentration of cyclohexanediol in the reactor is 0.5mol/L.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is cobalt nickel molybdate (NiCoMoO 4), the catalyst loading is 2.0+ -0.05 mg cm -2, the cathode catalyst is commercial ruthenium oxide (RuO 2), and the catalyst loading is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Germany Fuma company for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃.
A set of reactors (total catalyst area 400cm 2, total current 400A) was operated at a current density of 1A cm -2, with a cyclohexanediol aqueous solution flow rate of 41.44mL min -1 and KOH flow rate of 41.44mL min -1. The average tank pressure of the two reactors is 2.78V, the operation power of the single group of reactors is 1112W, and kilowatt level operation is realized. Under this operating condition, the conversion of cyclohexanediol was 83.0%, the selectivity to adipic acid was 89.8% and the faraday efficiency was 75.7%.
Application example 4
In the process of preparing formic acid by coupling hydrogen production with glycerin oxidation by using electrolyzed water, in the application example, glycerin and potassium hydroxide raw materials are prepared together, the composition of electrolyte is glycerin with the concentration of 1mol/L and potassium hydroxide with the concentration of 4mol/L, and alkaline electrolyte containing glycerin is introduced into an integrated condensation reactor through a raw material conveying pump.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is cobalt nickel molybdate (NiCoMoO 4), the catalyst loading is 2.0+ -0.05 mg cm -2, the cathode catalyst is commercial ruthenium oxide (RuO 2), and the catalyst loading is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Germany Fuma company for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃.
A set of reactors (total catalyst area 400cm 2, total current 400A) was operated at a current density of 1A cm -2 and the flow rate of the glycerol-containing electrolyte was 31.09mLmin -1. The average tank pressure of the two reactors is 2.75V, the running power of the single reactor is 1100W, and kilowatt level running is realized. Under this operating condition, the conversion of glycerol was 90.0%, the selectivity for formic acid was 89.5% and the faraday efficiency was 82.3%.
Application example 5
In the process of preparing lactic acid by coupling hydrogen production with glycerin oxidation by using electrolyzed water, in the application example, glycerin and potassium hydroxide raw materials are prepared together, the composition of electrolyte is glycerin with the concentration of 1mol/L and potassium hydroxide with the concentration of 3mol/L, and alkaline electrolyte containing glycerin is introduced into an integrated condensation reactor through a raw material conveying pump.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is AuPtPd (AuPtPd/Ni (OH) 2 @NF) loaded by nickel hydroxide, the cathode catalyst is commercial ruthenium oxide (RuO 2), the loading amount of the catalyst is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Fuma, germany, for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃.
A set of reactors (total catalyst area 400cm 2, total current 400A) was operated at a current density of 1A cm -2 and the flow rate of the electrolyte containing glycerol was 124.37mLmin -1. The average tank pressure of the two reactors is 2.8V, the running power of the single reactor is 1120W, and kilowatt level running is realized. Under this operating condition, the conversion of glycerol was 89.5%, the selectivity for lactic acid was 88.5% and the faraday efficiency was 83.4%.
Application example 6
In the process of preparing succinic acid by coupling hydrogen production by water electrolysis and oxidation of 1, 4-butanediol, in the application example, 1, 4-butanediol and potassium hydroxide raw materials are prepared together, 1mol/L of 1, 4-butanediol and 3mol/L of potassium hydroxide are used as electrolyte, and alkaline electrolyte containing 1, 4-butanediol is introduced into an integrated condensation reactor through a raw material conveying pump.
In this application example, the areas of the single anode and the single cathode are 100cm 2 (i.e., the areas of the anode and the cathode electrode in each reactor are 200cm 2, the catalyst area of each group of reactors is 400 cm), the anode catalyst is cobalt nickel molybdate (NiCoMoO 4), the catalyst loading is 2.0+ -0.05 mg cm -2, the cathode catalyst is commercial ruthenium oxide (RuO 2), and the catalyst loading is 1+ -0.05 mg cm -2, and the membrane electrode is prepared by using an anion exchange membrane (model: FAA-3-50) of Germany Fuma company for assembling the reactors. The mixer cold trap temperature was set at 8 ℃, and the reactor cold trap temperature was set at 3 ℃.
A set of reactors (total catalyst area 400cm 2, total current 400A) was operated at a current density of 1A cm -2, and the electrolyte flow rate containing 1, 4-butanediol was 31.09mL min -1. The average tank pressure of the two reactors is 2.73V, the running power of the single reactor is 1092W, and kilowatt level running is realized. Under this operating condition, the conversion of 1, 4-butanediol was 92.3%, the selectivity for succinic acid was 93.1%, and the faraday efficiency was 88.5%.
In the description of the present utility model, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present utility model and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present utility model. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present utility model, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present utility model, unless explicitly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected, mechanically connected, electrically connected, directly connected, indirectly connected via an intervening medium, or in communication between two elements. The specific meaning of the above terms in the present utility model can be understood by those of ordinary skill in the art in a specific case.
The applicant declares that the above is only a specific embodiment of the present utility model, but the scope of the present utility model is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present utility model disclosed by the present utility model fall within the scope of the present utility model and the disclosure.
Claims (10)
1. The reaction device for producing hydrogen by kilowatt-level electrolyzed water and coupling oxidation is characterized by comprising a power supply system, a reactor system, a raw material supply system, a cooling system and a gas detection system;
The power supply system comprises at least one direct current power supply (1), and the direct current power supply is electrically connected with the reactor system through a cable;
The reactor system comprises at least one integrated condensation reactor (2) and at least one static mixer (3), wherein the outlet of the static mixer (3) is communicated with the feed inlet of the integrated condensation reactor (2);
The raw material supply system comprises a plurality of raw material tanks (4), wherein each raw material tank is communicated with an inlet of a static mixer (3) through a raw material conveying pipeline;
The cooling system comprises a mixer cold trap (8) and a reactor cold trap (9), wherein an outlet of the mixer cold trap (8) is communicated with a cooling liquid inlet of the static mixer (3), and an outlet of the reactor cold trap (9) is communicated with a cooling liquid inlet of the integrated condensation reactor (2);
The gas detection system comprises a gas-liquid separation tank (10), a water washing tank (11), a gas dryer (12) and a hydrogen purity analyzer (13) which are sequentially connected, wherein a gas inlet of the gas-liquid separation tank (10) is communicated with a gas discharge port of each integrated condensation reactor (2) through a cathode gas circuit.
2. The reaction device for producing hydrogen and coupling oxidation by water electrolysis and water electrolysis of kilowatt level according to claim 1, wherein when a plurality of direct current power supplies (1) are arranged, each direct current power supply (1) is independently controlled.
3. The reaction device for producing hydrogen and coupling oxidation by water electrolysis and water electrolysis of kilowatt level according to claim 1, wherein when a plurality of integrated condensation reactors (2) are arranged, the integrated condensation reactors (2) are connected in series, in parallel or in a combination of series and parallel.
4. The reaction device for producing hydrogen and coupling oxidation by using kilowatt-level electrolyzed water according to claim 1, wherein the number of the raw material tanks (4) is the same as the number of the raw material types required by the electrolytic water hydrogen and coupling oxidation reaction.
5. The reaction device for producing hydrogen and coupling oxidation by kilowatt-level electrolyzed water according to claim 1, wherein the raw material conveying pipeline comprises a raw material conveying main line and a plurality of raw material conveying branch lines which are all communicated with the raw material conveying main line, the raw material conveying main line is communicated with an outlet at the lower end of a raw material tank (4), the other end of the raw material conveying branch line is communicated with an inlet of a static mixer (3), a raw material conveying pump (5) is arranged on the raw material conveying branch line, and a pressure valve (7) is arranged at an outlet of the raw material conveying pump (5).
6. The reaction device for producing hydrogen and coupling oxidation by water electrolysis and water electrolysis of kilowatt level according to claim 1, wherein the raw material supply system further comprises electronic balances (6) with the same number as the raw material tanks (4), and the raw material tanks (4) are arranged on the electronic balances (6).
7. The reaction device for producing hydrogen and coupling oxidation by kilowatt-level electrolyzed water according to claim 1, wherein the heat preservation layers are coated on the outer parts of a cooling liquid conveying pipeline between the mixer cold trap (8) and the static mixer (3) and a cooling liquid conveying pipeline between the reactor cold trap (9) and the integrated condensing reactor (2).
8. The reaction device for producing hydrogen and coupling oxidation by kilowatt-level electrolyzed water according to claim 1, wherein the cooling system further comprises a mixer water separator arranged at the outlet of the mixer cold trap (8) and a reactor water separator arranged at the outlet of the reactor cold trap (9), the number of branches of the mixer water separator is the same as that of the static mixers (3), the number of the reactor water separators is not more than that of the integrated condensation reactors (2), and each branch of the mixer water separator and the reactor water separator is provided with a flow control valve.
9. The reaction device for producing hydrogen and coupling oxidation by water electrolysis and water electrolysis of kilowatt level according to claim 1, wherein the gas detection system further comprises a hydrogen mass flowmeter (14), and the hydrogen mass flowmeter (14) is arranged on a pipeline between the gas dryer (12) and the hydrogen purity analyzer (13).
10. The reaction device for producing hydrogen and coupling oxidation by water electrolysis and water electrolysis of kilowatt level according to claim 1, wherein the gas detection system further comprises a combustible gas alarm (15), and the combustible gas alarm (15) is arranged at the top of the integrated condensation reactor (2) and is close to a gas discharge port.
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