A low-power-consumption pem hydrogen production device with intermittent electrolysis coupled with multi-type cyclic electric pair electric oxidation

Abstract

The utility model relates to a kind of low power consumption PEM hydrogen production device of intermittent electrolysis coupled multi-type cycle electric pair electric oxidation, and the utility model aims to solve the problem of high cost and the problem of slow kinetics transfer and high thermodynamic higher potential of traditional electrolytic hydrogen production system using noble metal as anode in traditional water electrolysis process.A kind of low power consumption PEM hydrogen production device of intermittent electrolysis coupled multi-type cycle electric pair electric oxidation, including multi-type low power consumption cycle electric pair system solution storage tank, ion exchanger, flow sensor, transformer, rectifier, programmable pulse power supply, PEM electrolytic cell, anode carbon-based catalyst, proton exchange membrane, cathode, high pressure storage tank.The utility model synergizes hydrogen production reaction and transfer process, realizes synergistic energy-saving hydrogen production from thermodynamic and kinetic level, realizes the green cycle of system, and is expected to provide more efficient and energy-saving technical development route for distributed production of renewable energy green hydrogen.

Description

Technical Field

[0001] This utility model relates to an apparatus for producing hydrogen by electrolysis of water. Background Technology

[0002] The technological layout of a low-power hydrogen production chain for efficient renewable energy utilization encompasses the entire hydrogen energy industry chain, including upstream hydrogen production, midstream storage and transportation, and downstream hydrogen consumption. Furthermore, hydrogen energy plays a crucial role in high-carbon emission sectors such as transportation, industry, and construction, achieving large-scale decarbonization and carbon reduction. The transportation sector is the second largest source of global carbon emissions, accounting for approximately 25% of the total. Hydrogen fuel cell vehicles have inherent advantages in heavy-duty, long-range, and high-intensity transportation systems. In the industrial sector, hydrogen, with its high reducing agent and high calorific value, is used as a raw material or to provide high-grade heat energy in the production processes of steel, metallurgy, petrochemicals, and cement, representing a significant means of deep decarbonization in industry. In the construction sector, using hydrogen to replace natural gas for heating is an important development direction for achieving a low-carbon transformation of energy consumption in the building sector.

[0003] In traditional water electrolysis, noble metal Ir-based catalysts are typically used as the anode material, and Pt electrodes are used as the cathode. Water is decomposed by applying a constant potential. However, due to the slow kinetics of the four-electron transfer in the anodic OER reaction, a high thermodynamic potential (>1.23 V vs. RHE) is required to drive the OER. Utility Model Content

[0004] The purpose of this invention is to solve the problems of high cost in traditional water electrolysis processes using precious metals as anodes and slow kinetic transfer and high thermodynamic potential in traditional electrolytic hydrogen production systems, and to provide a low-power PEM hydrogen production device that couples intermittent electrolysis with multiple types of cyclic electro-oxidation.

[0005] This invention combines the intermittent nature of renewable energy power generation, such as wind and solar power, with a pulsed power supply strategy through pulsed dynamic electrolysis and multi-type redox cycle electro-oxidation to produce hydrogen at low power consumption. Simultaneously, the water electrolysis device can be directly connected to the power grid, utilizing surplus renewable energy for large-scale hydrogen production. This addresses the temporal and spatial volatility issues faced by renewable energy sources, enabling the large-scale absorption of intermittent surplus renewable energy. The produced green hydrogen aligns with future net-zero carbon emission targets.

[0006] A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation includes a multi-type low-power cyclic electro-coupled system solution storage tank 3, an ion exchanger 4, a second circulation pump 5, a flow sensor 6, a transformer 7, a rectifier 8, a programmable pulse power supply 9, a PEM electrolyzer 10, an anode carbon-based catalyst 11, a proton exchange membrane 12, a cathode 13, a reduction stirred reactor storage tank 14, a third circulation pump 15, a heater 16, an acid remover 17, a first dryer 19, a second dryer 20, a gas storage tank 21, a compressor 22, a pressure sensor 23, and a high-pressure storage tank 25.

[0007] The PEM electrolyzer 10 is equipped with a proton exchange membrane 12, which divides the PEM electrolyzer 10 into an anode region and a cathode region. The anode carbon-based catalyst 11 is disposed in the anode region, and the cathode 13 is disposed in the cathode region. The anode carbon-based catalyst 11 is connected to the positive terminal of the programmable pulse power supply 9, and the cathode 13 is connected to the negative terminal of the programmable pulse power supply 9. The transformer 7 is electrically connected to the programmable pulse power supply 9 through a rectifier 8.

[0008] Water supply pipe 26, feed pipe 27 and exhaust pipe 28 are respectively connected to the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3; the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3 is connected to the anode area of ​​PEM electrolysis cell 10 through ion exchanger 4, second circulation pump 5 and flow sensor 6; the anode area of ​​PEM electrolysis cell 10 is also connected to the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3 through reduction stirring reactor storage tank 14, third circulation pump 15 and heater 16;

[0009] Hydrogen generated during electrolysis is output from the cathode area of ​​PEM electrolysis cell 10. The cathode area of ​​PEM electrolysis cell 10 is connected to one end of the first dryer 19 and the second dryer 20 through the deacidifier 17. The other end of the first dryer 19 and the second dryer 20 is connected to the gas storage tank 21. The gas storage tank 21 is connected to the high-pressure storage tank 25 through the compressor 22 and the pressure sensor 23.

[0010] The principle of this utility model:

[0011] Water is the raw material for hydrogen production through water electrolysis. During the electrolysis process, electrical energy is converted into chemical energy. Oxygen is produced at the anode through oxidation, and hydrogen is produced at the cathode through reduction. Under standard conditions (25 °C, 101.32 kPa), the thermodynamic voltage for water decomposition is 1.23 V, but the voltage required for the reaction to occur is usually greater than the theoretical value. The basic principle is shown in equation (1-1):

[0012] ;

[0013] Hydrogen production via water electrolysis involves two electrode reactions: the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. HER is a two-electron reaction, and its reaction mechanism is shown in equations (1-2) and (1-3). In the HER reaction, H… + First, it adsorbs onto the active sites on the electrode surface, then... Formed through single-electron transfer The H atoms adsorbed on the active site eventually form H2.

[0014] ;

[0015] OER is a four-electron reaction with a more complex reaction mechanism, as shown in equations (1-4)-(1-7). OER comprises four elementary reactions, in which OH- ions in the solution are adsorbed in the first two elementary reactions. - Generated and In the third elementary reaction With OH - Reaction generation ,at last With OH - H2O and O2 are generated.

[0016] ;

[0017] In constant-current water electrolysis, reactants are continuously consumed at the electrode interface, and products cannot diffuse into the electrolyte in time, disrupting the electrochemical equilibrium and making high-current hydrogen production difficult. However, in pulsed water electrolysis, the mass transfer process between reactants / products and the electrode interface is continuous during the "power-on" and "power-off" phases. The reactant concentration at the electrode interface is constantly updated, and products have sufficient diffusion conditions, thereby reducing the mass transfer impedance of the electrode and achieving efficient and energy-saving hydrogen production.

[0018] For example, unlike traditional OER, SO3 2- The oxidation potential is even lower, approximately 0.6 V vs. RHE, as shown in equations (1-8)-(1-10). This is achieved with SO3, which has lower energy consumption. 2- Replacing the energy-intensive OER reaction with an oxidation reaction can achieve lower energy consumption for hydrogen production.

[0019] .

[0020] Advantages of this utility model:

[0021] I. This invention addresses the key technological bottlenecks of traditional proton exchange membrane electrolysis (PEMWE) hydrogen production, such as high energy consumption and slow anodic reaction. It introduces a low-power PEM hydrogen production device that couples intermittent electrolysis with multiple types of cyclic electro-oxidation, achieving a new generation of low-energy, high-efficiency green hydrogen production. The device utilizes a programmable pulse power supply 9 to adjust pulse power supply parameters and output various pulse waveforms, including: ① a stepped rising / falling pulse power supply method; ② a linear rising / falling pulse power supply method; and ③ an exponential rising / falling pulse power supply method. It features flexible control capabilities such as wide frequency (0.01-10 Hz), wide duty cycle (5%-95%), and adjustable amplitude (0-3 V). Through scalable dynamic operating condition power supply modes, the device can simulate the fluctuating power characteristics of renewable energy sources such as photovoltaics and wind power, enabling dynamic energy input to regulate reaction kinetics. This invention not only offers high flexibility in power supply modes but also achieves controllable online data acquisition of parameters related to electrode structure, solution composition, and operating conditions, providing a feasible technical path and pilot-scale system reference for efficient, low-cost green hydrogen production driven by distributed renewable energy.

[0022] II. Both half-reactions in water electrolysis occur at the electrode / solution interface. As the reaction time increases, a diffusion layer forms at the electrode interface, slowing down the ion renewal rate within the diffusion layer and thus reducing the rate of the catalytic reaction, hindering the normal progress of the reaction. During pulsed power supply, the diffusion layer forms and grows, but disappears after the power is cut off. Adjusting the pulse parameters can eliminate the diffusion layer and double layer at the electrode / solution interface, enhancing mass transfer of bulk ions / molecules to the electrode / solution interface. In the water electrolysis system, there are two half-reactions. The anodic oxidation of water to produce oxygen consumes a large proportion of energy and is the main research direction for reducing power consumption. Specifically, the theoretical electrode potential of the anodic oxidation reaction of water is 1.23 V vs. RHE, while the electrode potential of multi-type cyclic electro-coupled oxidation is lower than 1 V vs. RHE, which can significantly reduce the overall electrolyzer voltage. It is worth noting that the pulsed dynamic electrolysis coupled low-power hydrogen production method can effectively increase the electrolysis current, promote the transport of cathode bubbles on the electrode surface and the mass transfer rate of the low-power circulating couple from the electrolytic liquid phase to the electrolysis surface, thereby improving the hydrogen production efficiency of the electrolysis hydrogen production system; at the same time, the pulsed potential can also enhance the mass transfer process of the circulating couple at the electrode interface, thereby increasing the total amount of electron transfer at the anode interface, improving hydrogen production efficiency and reducing energy consumption.

[0023] Third, the preparation process of this utility model is simple, and the inexpensive commercial material graphite felt (GF) is used as the anode electrode. Since the GF electrode only serves as a carrier for the conduction of redox cycle electro-oxidation in the electrolyte, compared with the expensive and scarce precious metal anode catalyst, the GF electrode can greatly reduce the cost of pulse dynamic electrolysis coupling multiple types of low power consumption redox cycle electro-oxidation to assist hydrogen production, and is more suitable for large-scale production and application.

[0024] IV. In this utility model, the reactants oxidized by the circulating couple generated by electrolysis enter the reduction stirred reactor storage tank 14, and then enter the multi-type low power consumption circulating couple system solution storage tank 3 through the reduction stirred reactor storage tank 14, forming a self-circulating system.

[0025] V. This utility model also has the following technical innovations: First, it achieves the synergistic regulation of electro-oxidation by multiple types of circulating couples and pulsed dynamic power supply for the first time, significantly improving reaction kinetics and charge utilization; second, it effectively reduces the hydrogen production starting voltage to below 1.23V, greatly reducing the unit hydrogen production energy consumption; third, it constructs a programmable, multi-parameter controllable modular experimental platform, which has the ability to flexibly adjust and collect data on multiple factors such as power supply mode, electrode structure and solution composition; during the operation of the device, the circulating pump delivers the pre-configured multi-type circulating couple electrolyzer solution to the anode area of ​​the PEM electrolyzer, and the low-power-consumption circulating couple in the solution undergoes electro-oxidation reaction on the surface of the catalytic electrode, effectively replacing the slow OER, significantly reducing the anode overpotential and increasing the proton generation rate; the entire system operates at room temperature (25℃), and the low-power-consumption PEM hydrogen production device with intermittent electrolysis coupled with multi-type circulating couple electro-oxidation synergistically enhances the hydrogen production reaction and transfer process, achieving synergistic energy-saving hydrogen production from the thermodynamic and kinetic levels, realizing the green cycle of the system, and is expected to provide a more efficient and energy-saving technical development route for the distributed production of green hydrogen from renewable energy. Attached Figure Description

[0026] Figure 1This is a schematic diagram of a low-power PEM hydrogen production device based on intermittent electrolysis coupled with multiple types of cyclic electro-coupled oxidation, as described in this utility model. In the diagram, 1 is the first circulating pump, 2 is the first condenser, 3 is the multi-type low-power cyclic electro-coupled system solution storage tank, 4 is the ion exchanger, 5 is the second circulating pump, 6 is the flow sensor, 7 is the transformer, 8 is the rectifier, 9 is the programmable pulse power supply, 10 is the PEM electrolyzer, 11 is the anode carbon-based catalyst, 12 is the proton exchange membrane, 13 is the cathode, 14 is the reduction stirred reactor storage tank, 15 is the third circulating pump, 16 is the heater, 17 is the acid remover, 18 is the second condenser, 19 is the first dryer, 20 is the second dryer, 21 is the gas storage tank, 22 is the compressor, 23 is the pressure sensor, 24 is the third condenser, 25 is the high-pressure storage tank, 26 is the water supply pipe, 27 is the feed pipe, and 28 is the exhaust gas pipe. Detailed Implementation

[0027] Specific Implementation Method 1: This implementation method is a low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation, including a multi-type low-power cyclic electro-coupled system solution storage tank 3, an ion exchanger 4, a second circulation pump 5, a flow sensor 6, a transformer 7, a rectifier 8, a programmable pulse power supply 9, a PEM electrolyzer 10, an anode carbon-based catalyst 11, a proton exchange membrane 12, a cathode 13, a reduction stirring reactor storage tank 14, a third circulation pump 15, a heater 16, an acid remover 17, a first dryer 19, a second dryer 20, a gas storage tank 21, a compressor 22, a pressure sensor 23, and a high-pressure storage tank 25;

[0028] The PEM electrolyzer 10 is equipped with a proton exchange membrane 12, which divides the PEM electrolyzer 10 into an anode region and a cathode region. The anode carbon-based catalyst 11 is disposed in the anode region, and the cathode 13 is disposed in the cathode region. The anode carbon-based catalyst 11 is connected to the positive terminal of the programmable pulse power supply 9, and the cathode 13 is connected to the negative terminal of the programmable pulse power supply 9. The transformer 7 is electrically connected to the programmable pulse power supply 9 through a rectifier 8.

[0029] Water supply pipe 26, feed pipe 27 and exhaust pipe 28 are respectively connected to the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3; the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3 is connected to the anode area of ​​PEM electrolysis cell 10 through ion exchanger 4, second circulation pump 5 and flow sensor 6; the anode area of ​​PEM electrolysis cell 10 is also connected to the multi-type low-power consumption circulating electrolytic couple system solution storage tank 3 through reduction stirring reactor storage tank 14, third circulation pump 15 and heater 16;

[0030] Hydrogen generated during electrolysis is output from the cathode area of ​​PEM electrolysis cell 10. The cathode area of ​​PEM electrolysis cell 10 is connected to one end of the first dryer 19 and the second dryer 20 through the deacidifier 17. The other end of the first dryer 19 and the second dryer 20 is connected to the gas storage tank 21. The gas storage tank 21 is connected to the high-pressure storage tank 25 through the compressor 22 and the pressure sensor 23.

[0031] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that a first condenser 2 is provided outside the exhaust pipe 28. The other steps are the same as in Specific Implementation Method One.

[0032] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that a first circulation pump 1 is installed between the water supply pipe 26 and the multi-type low-power consumption circulating electrode system solution storage tank 3. Other steps are the same as in Specific Implementation Method One or Two.

[0033] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that a second condenser 18 is provided outside the pipeline connecting the PEM electrolytic cell 10 to the first dryer 19 and the second dryer 20. The other steps are the same as in Specific Implementation Methods One to Three.

[0034] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that a third condenser 24 is provided outside the pipeline connecting the pressure sensor 23 and the high-pressure storage tank 25. The other steps are the same as in Specific Implementation Methods One to Four.

[0035] Specific Implementation Method Six: The difference between this implementation method and Specific Implementation Methods One through Five is that the solution in the multi-type low-power consumption circulating electric couple system solution storage tank 3 contains Fe. 2+ Ions and SO3 2- Ions. The other steps are the same as in specific embodiments one through five.

[0036] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that both the gas storage tank 21 and the high-pressure storage tank 25 are equipped with pressure regulating valves. The other steps are the same as in Specific Implementation Methods One to Six.

[0037] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the PEM electrolytic cell 10 is made of titanium or stainless steel with a titanium coating. The other steps are the same as in Specific Implementation Methods One to Seven.

[0038] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the anode carbon-based catalyst 11 is graphite felt, carbon cloth, carbon paper, carbon black, porous activated carbon, or carbon nanotubes. The other steps are the same as in Specific Implementation Methods One to Eight.

Claims

1. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation, characterized in that... The PEM hydrogen production device includes a multi-type low-power-consumption circulating electrostatic couple system solution storage tank (3), an ion exchanger (4), a second circulating pump (5), a flow sensor (6), a transformer (7), a rectifier (8), a programmable pulse power supply (9), a PEM electrolyzer (10), an anode carbon-based catalyst (11), a proton exchange membrane (12), a cathode (13), a reduction stirring reactor storage tank (14), a third circulating pump (15), a heater (16), an acid remover (17), a first dryer (19), a second dryer (20), a gas storage tank (21), a compressor (22), a pressure sensor (23), and a high-pressure storage tank (25). The PEM electrolyzer (10) is equipped with a proton exchange membrane (12), which divides the PEM electrolyzer (10) into an anode region and a cathode region. The anode carbon-based catalyst (11) is located in the anode region, and the cathode (13) is located in the cathode region. The anode carbon-based catalyst (11) is connected to the positive terminal of the programmable pulse power supply (9), and the cathode (13) is connected to the negative terminal of the programmable pulse power supply (9). The transformer (7) is electrically connected to the programmable pulse power supply (9) through a rectifier (8). Water supply pipe (26), feed pipe (27) and exhaust pipe (28) are respectively connected to the multi-type low-power consumption circulating electro-couple system solution storage tank (3); the multi-type low-power consumption circulating electro-couple system solution storage tank (3) is connected to the anode area of ​​PEM electrolyzer (10) through ion exchanger (4), second circulation pump (5) and flow sensor (6); the anode area of ​​PEM electrolyzer (10) is also connected to the multi-type low-power consumption circulating electro-couple system solution storage tank (3) through reduction stirring reactor storage tank (14), third circulation pump (15) and heater (16); Hydrogen generated during electrolysis is output from the cathode area of ​​the PEM electrolytic cell (10). The cathode area of ​​the PEM electrolytic cell (10) is connected to one end of the first dryer (19) and the second dryer (20) through the deacidifier (17). The other end of the first dryer (19) and the second dryer (20) is connected to the gas storage tank (21). The gas storage tank (21) is connected to the high-pressure storage tank (25) through the compressor (22) and the pressure sensor (23).

2. The low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... The exhaust pipe (28) is equipped with a first condenser (2).

3. The low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... A first circulation pump (1) is provided between the water supply pipe (26) and the multi-type low-power consumption circulating electric couple system solution storage tank (3).

4. The low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... A second condenser (18) is provided outside the pipeline connecting the PEM electrolytic cell (10) to the first dryer (19) and the second dryer (20).

5. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... A third condenser (24) is provided outside the pipeline connecting the pressure sensor (23) to the high-pressure storage tank (25).

6. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... The solution in the multi-type low-power-consumption circulating electrode system solution storage tank (3) contains Fe. 2+ Ions and SO3 2- ion.

7. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled oxidation as described in claim 1, characterized in that... Both the gas storage tank (21) and the high-pressure storage tank (25) are equipped with pressure regulating valves.

8. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... The PEM electrolytic cell (10) is made of titanium or stainless steel with a titanium coating.

9. A low-power PEM hydrogen production device with intermittent electrolysis coupled with multiple types of cyclic electro-coupled electro-oxidation as described in claim 1, characterized in that... The anode carbon-based catalyst (11) is graphite felt, carbon cloth, carbon paper, carbon black, porous activated carbon or carbon nanotubes.

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