Methanol reforming hydrogen production reactor based on thermal / electric synergy

Abstract

This disclosure provides a methanol reforming hydrogen production reactor based on thermo-electric synergy, which adopts a stacked assembly structure in the form of an electrolyzer. The anode bipolar plate has a gas flow channel inside, at least a portion of which has a porous metal structure. A first catalytic layer is loaded on the surface of this porous metal structure for catalyzing the thermochemical reforming reaction of methanol and water vapor. A second catalytic layer is loaded on the anode gas diffusion electrode for catalyzing the electrochemical oxidation reaction of hydrogen. A third catalytic layer is loaded on the cathode gas diffusion electrode for catalyzing the electrochemical reduction reaction of protons. This reactor fully utilizes the space and specific surface area of ​​the flow channel by extending the thermochemical reforming reaction zone from the surface of the membrane electrode to the interior of the gas flow channel of the anode bipolar plate, significantly improving the catalyst loading and reaction efficiency. Simultaneously, the electrochemical process continuously consumes hydrogen on the anode side, reducing its partial pressure and driving the thermochemical reforming reaction towards hydrogen production, resulting in a methanol conversion rate higher than that of a pure thermochemical or pure electrolysis process. This achieves the synergistic utilization of low-grade electrical and thermal energy.

Description

Technical Field

[0001] This disclosure relates to the field of methanol-to-hydrogen technology, and in particular to a methanol reforming-to-hydrogen reactor based on thermal / electric synergy. Background Technology

[0002] Energy is a crucial material foundation for human civilization and socio-economic development. With increasing global energy demand and escalating environmental pollution and climate change, developing clean and efficient energy utilization technologies has become key to addressing the global energy crisis. Hydrogen, as a high-energy-density, zero-carbon-emission secondary energy source, is considered an important component of the future energy system. However, difficulties in hydrogen storage and transportation hinder its large-scale application, making in-situ hydrogen production technology a research hotspot. Methanol, as an ideal liquid hydrogen carrier, possesses advantages such as wide availability, convenient storage and transportation, and suitable reaction temperatures, making methanol reforming hydrogen production technology a focus of widespread attention.

[0003] Methanol reforming for hydrogen production is primarily achieved through a methanol-steam reforming reaction. Traditional methanol reforming methods for hydrogen production are divided into two categories: thermochemical reforming and electrolytic hydrogen production. Thermochemical reforming is carried out at 200–300°C under the action of a catalyst, but due to thermodynamic equilibrium limitations, the single-pass conversion rate is limited, and the products contain impurities such as CO, requiring additional pressure swing adsorption or membrane separation equipment to purify the hydrogen, resulting in a large system size and complex structure. While electrolytic hydrogen production can directly obtain high-purity hydrogen, it requires a high electrolysis voltage, resulting in high energy consumption and stringent requirements for power quality.

[0004] Thermochemical / electrochemical co-production of hydrogen is a crucial approach to addressing this issue. It introduces an electrochemical process into thermochemical reforming, using a membrane electrode assembly to transfer hydrogen generated at the anode to the cathode in a timely manner, reducing the hydrogen partial pressure at the anode and thus disrupting the thermodynamic equilibrium of the reforming reaction. This improves methanol conversion, while high-purity hydrogen is directly obtained at the cathode. This technological approach combines the advantages of thermochemistry and electrochemistry, enabling efficient hydrogen production at lower temperatures and voltages. However, existing thermochemical reforming reactions in thermochemical / electrochemical co-production reactors are limited to the membrane electrode surface, resulting in limited reaction space and catalyst loading. The gas flow channels of the anode bipolar plates have a single function, failing to fully utilize their internal space and specific surface area. The coupling between the thermochemical and electrochemical processes is not tight enough, leaving room for improvement in the overall reactor performance. Therefore, expanding the reaction space of thermochemical / electrochemical co-production reactors, increasing catalyst loading and reaction efficiency, while simplifying the system structure and achieving multifunctional integration of the reactor's internal space are pressing technical challenges that need to be addressed in this field. Summary of the Invention

[0005] To address the aforementioned technical problems, this disclosure provides a methanol reforming hydrogen production reactor based on thermo-electric synergy, which at least solves the technical difficulties in existing thermo-electric synergy reactors, such as the reaction space being limited to the surface of the membrane electrode, the catalyst loading being limited, the anode bipolar plate having a single function, and the thermochemical and electrochemical processes not being tightly coupled.

[0006] This disclosure provides a methanol reforming hydrogen production reactor based on thermo-electric synergy. The reactor employs an electrolytic cell structure and, from the anode side to the cathode side, sequentially includes an anode bipolar plate, an anode gas diffusion electrode, a high-temperature proton exchange membrane, a cathode gas diffusion electrode, and a cathode bipolar plate. The anode bipolar plate has a gas flow channel internally, at least a portion of the gas flow channel's wall surface being a porous metal structure, and the surface of the porous metal structure is loaded with a first catalytic layer. The first catalytic layer is used to catalyze the thermochemical reforming reaction of methanol and water vapor. The anode gas diffusion electrode includes a first porous conductive substrate and a second catalytic layer supported thereon, the second catalytic layer being used to catalyze the electrochemical oxidation reaction of hydrogen. The high-temperature proton exchange membrane is used for selectively conducting protons. The cathode gas diffusion electrode includes a second porous conductive substrate and a third catalytic layer supported thereon, the third catalytic layer being used to catalyze the electrochemical reduction reaction of protons.

[0007] According to embodiments of this disclosure, the anode bipolar plate is characterized by comprising a metal substrate and porous metal channels disposed within the metal substrate, wherein the inner surface of the porous metal channels is loaded with the first catalyst layer. The porous metal channels are made of foamed metal materials, selected from foamed nickel, foamed copper, foamed iron-nickel alloys, etc., with a porosity of 70%~95% and a pore size of 0.1 mm~2.0 mm; or selected from fiber-sintered porous materials such as copper fiber sintered felt, titanium fiber sintered felt, or other porous materials with good thermal conductivity. This porous metal channel possesses multiple functions, including gas transport, heat transfer, charge conduction, and thermochemical reforming reactions.

[0008] Furthermore, the first catalyst layer is a methanol reforming catalyst, selected from Cu-based, Ni-based, Pt-based, and Pd-based catalysts, which have methanol oxidation functions, and is loaded onto the inner surface of the porous metal channel through impregnation, spraying, or electroless plating. The second catalyst layer is selected from Pt / C, PtRu / C, Pd / C, and other catalysts with electrochemical oxidation functions; the third catalyst layer is selected from Pt / C, Pd / C, and other catalysts with electrochemical reduction functions.

[0009] According to embodiments of this disclosure, the high-temperature proton exchange membrane is a phosphoric acid-doped polybenzimidazole membrane with an operating temperature range of 100°C to 250°C, exhibiting excellent proton conductivity and thermal stability within this temperature range.

[0010] According to an embodiment of this disclosure, the cathode bipolar plate is provided with a gas flow channel for exporting high-purity hydrogen generated at the cathode.

[0011] According to an embodiment of this disclosure, the reactor operates as follows: Methanol vapor is introduced into the gas channel of the anode bipolar plate. During its flow within the porous metal channel, it comes into contact with the first catalyst layer loaded on the pore surface and undergoes a thermochemical reforming reaction driven by thermal energy, generating a hydrogen-rich mixed gas. After applying voltage, the hydrogen in the hydrogen-rich mixed gas diffuses to the second catalyst layer of the anode gas diffusion electrode, where it undergoes an electrochemical oxidation reaction and dissociates into protons and electrons. The protons migrate through a high-temperature proton exchange membrane to the third catalyst layer of the cathode gas diffusion electrode, where they combine with electrons to undergo an electrochemical reduction reaction, generating high-purity hydrogen.

[0012] Furthermore, the electrochemical oxidation reaction continuously consumes hydrogen on the anode side, reducing the hydrogen partial pressure on the surface of the first catalyst layer. According to Le Chatelier's principle, this drives the thermochemical reforming reaction to move in the direction of hydrogen generation, thereby achieving a higher methanol conversion rate at the same temperature. Simultaneously, due to the intervention of the thermochemical reforming reaction, hydrogen is generated on the anode side before voltage is applied, allowing the electrochemical oxidation reaction to proceed at extremely low voltages below 0.1 V, thus realizing the utilization of low-grade electrical energy.

[0013] According to embodiments of this disclosure, the temperature range of the thermal energy is 150°C to 250°C, and it can be provided by an external heat source, including but not limited to solar energy, combustion heat, industrial waste heat, electric heating, etc.; the applied voltage includes but is not limited to power supply forms such as photovoltaic, fuel cell, power grid, wind power, etc.

[0014] Compared with the prior art, the present invention has at least the following beneficial effects:

[0015] By extending the thermochemical reforming reaction zone from the surface of the membrane electrode to the interior of the gas flow channel of the anode bipolar plate, the space and specific surface area of ​​the flow channel are fully utilized, significantly improving the catalyst loading and reaction efficiency. The combination of the high specific surface area and high thermal conductivity of the porous material flow channel achieves integrated reaction-heat transfer-mass transfer.

[0016] Furthermore, due to the intervention of the thermochemical reforming reaction, hydrogen gas is generated on the anode side before voltage is applied, allowing the electrochemical oxidation reaction to proceed at low voltage. This enables the utilization of low-grade electrical energy and expands the energy adaptability of the reactor. Simultaneously, the electrochemical process continuously consumes hydrogen gas on the anode side, reducing its partial pressure and driving the thermochemical reforming reaction towards hydrogen production, resulting in a methanol conversion rate higher than that of a pure thermochemical process or a pure electrolysis process.

[0017] Furthermore, the reactor structure disclosed herein differs from a simple modification of a traditional electrolyzer. Instead, it is an innovative design based on the characteristics of thermo / electric synergistic reaction. It transforms the originally single-function gas flow channel into a multifunctional unit that also has thermochemical reaction capabilities, thereby achieving intensive utilization of the reactor's internal space and providing an efficient solution for scenarios such as distributed hydrogen production and low-grade energy utilization. Attached Figure Description

[0018] The above and other objects, features and advantages of this disclosure will become clearer from the following description of embodiments with reference to the accompanying drawings, in which:

[0019] Figure 1 This schematic diagram illustrates the structural block diagram of a methanol reforming hydrogen production reactor based on thermal / electric synergy provided in an embodiment of the present disclosure;

[0020] Figure 2 A schematic diagram of the structure of the anode bipolar plate provided in an embodiment of this disclosure is shown.

[0021] Figure 3 The diagram illustrates the effect of hydrogen separation provided in the embodiments of this disclosure.

[0022] Figure 4 The diagram illustrates the hydrogen production rate effect provided by the embodiments of this disclosure.

[0023] [Attached image labels]

[0024] 1-Anode bipolar plate; 2-Anode gas diffusion electrode; 3-High-temperature proton exchange membrane; 4-Cathode gas diffusion electrode; 5-Cathode bipolar plate; 6-Porous metal flow channel; 7-Metal substrate; 8-Flow channel inlet. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments and accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this disclosure. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without inventive effort are within the scope of protection of this disclosure.

[0026] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0027] In this disclosure, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this disclosure according to the specific circumstances.

[0028] Throughout the accompanying drawings, identical elements are represented by the same or similar reference numerals. Conventional structures or constructions have been omitted where they may cause confusion in understanding this disclosure. Furthermore, the shapes, dimensions, and positional relationships of the components in the drawings do not reflect actual size, scale, or actual positional relationships. Additionally, any reference numerals placed between parentheses in the claims should not be construed as limiting the claims.

[0029] Similarly, to simplify this disclosure and aid in understanding one or more of the various aspects of the disclosure, in the above description of exemplary embodiments of the present disclosure, various features of the present disclosure are sometimes grouped together in a single embodiment, figure, or description thereof. The use of terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refers to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the present disclosure. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0030] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include one or more of that feature.

[0031] In realizing the concept of this disclosure, it was discovered that in existing thermo-electric co-reactors, the thermochemical reforming reaction is confined to the surface of the membrane electrode, resulting in limited reaction space and restricted catalyst loading. Furthermore, the gas channel of the anode bipolar plate only serves a transport function, lacking full utilization of its internal space and specific surface area. Therefore, this disclosure designs the gas channel of the anode bipolar plate as a porous metal structure and loads it with a reforming catalyst, extending the thermochemical reforming reaction zone from the membrane electrode surface to the entire interior of the channel. This significantly improves catalyst loading and reaction efficiency, achieving multifunctional integration of the reactor's internal space.

[0032] Figure 1The schematic diagram illustrates the structural block diagram of a methanol reforming hydrogen production reactor based on thermal / electric synergy provided in an embodiment of the present disclosure.

[0033] like Figure 1 As shown, the methanol reforming hydrogen production reactor based on thermal / electric synergy includes, from the anode side to the cathode side: an anode bipolar plate 1, an anode gas diffusion electrode 2, a high-temperature proton exchange membrane 3, a cathode gas diffusion electrode 4, and a cathode bipolar plate 5. The bipolar plates and membrane electrodes are sealed with gaskets and pressed together by end plates and fastening bolts to form a whole.

[0034] The anode bipolar plate 1 has a gas flow channel inside, at least a portion of the wall of the gas flow channel is a porous metal structure, and the surface of the porous metal structure is loaded with a first catalyst layer, which is used to catalyze the thermochemical reforming reaction of methanol and water vapor. The anode bipolar plate 1 simultaneously performs multiple functions such as gas distribution, heat transfer, charge conduction, and thermochemical reforming reaction.

[0035] The anode gas diffusion electrode 2 is disposed on the side of the anode bipolar plate 1 near the high-temperature proton exchange membrane 3, and includes a first porous conductive substrate and a second catalytic layer supported thereon. Under low voltage, the second catalytic layer is used to catalyze the electrochemical oxidation reaction of hydrogen.

[0036] A high-temperature proton exchange membrane 3 is disposed between the anode gas diffusion electrode 2 and the cathode gas diffusion electrode 4 to selectively conduct protons while isolating the anode-side gas and the cathode-side gas.

[0037] The cathode gas diffusion electrode 4 is disposed on the other side of the high-temperature proton exchange membrane 3, and includes a second porous conductive substrate and a third catalytic layer supported thereon. The third catalytic layer is used to catalyze the electrochemical reduction reaction of protons.

[0038] The cathode bipolar plate 5 is located on the side of the cathode gas diffusion electrode 4 away from the high-temperature proton exchange membrane 3, and a gas flow channel is provided inside it to export the high-purity hydrogen generated by the cathode.

[0039] Figure 2 A schematic diagram of the structure of the anode bipolar plate provided in an embodiment of the present disclosure is shown.

[0040] like Figure 2 As shown, the anode bipolar plate includes a metal substrate 7 and porous metal channels 6 disposed inside the metal substrate 7. The metal substrate 7 is made of highly conductive graphite or stainless steel, with a thickness of 3-5 mm, and has good mechanical strength and thermal and electrical conductivity. The porous metal channels 6 are embedded inside the metal substrate 7, forming gas flow channels, and a first catalyst layer is loaded on the inner surface of its pores.

[0041] In this embodiment, the porous metal flow channel 6 is made of nickel foam material with a porosity of 85%, an average pore size of 0.5 mm, and a thickness of 2 mm. Nickel foam has a three-dimensional interconnected pore structure and a specific surface area as high as 2000~5000 m². 2 / m 3 It has a thermal conductivity of approximately 15 W / (m·K), combining low flow resistance with high thermal conductivity. The porous metal flow channel 6 is preferably connected to the metal substrate 7 via a high-temperature welding process, forming a robust metallurgical interface to ensure efficient heat and electrical conduction.

[0042] The porous metal flow channel 6 has a first catalyst layer loaded on its inner pore surface. This first catalyst layer is a Cu / ZnO / Al₂O₃ methanol reforming catalyst, loaded via an impregnation method, with a loading amount of 10-20 wt%. The specific preparation method involves impregnating a nickel foam matrix in a mixed solution of copper nitrate, zinc nitrate, and aluminum nitrate, followed by drying, calcination, and reduction treatment to ensure the catalyst is uniformly distributed on the inner pore surface. The catalyst layer thickness is approximately 5-10 μm, ensuring catalytic activity without increasing gas flow resistance.

[0043] The anode bipolar plate 1 is also provided with a flow channel inlet 8 and a flow channel outlet. The flow channel inlet 8 is connected to the methanol steam supply pipeline, and the flow channel outlet is connected to the anode tail gas discharge pipeline. Methanol steam enters the porous metal flow channel 6 from the flow channel inlet 8, flows in a tortuous manner within the porous structure, and comes into full contact with the first catalyst layer loaded on the pore surface, undergoing a thermochemical reforming reaction.

[0044] The anode gas diffusion electrode 2 includes a first porous conductive substrate and a second catalyst layer coated thereon. The first porous conductive substrate is made of hydrophobically treated carbon paper with a microporous layer coated on its surface to improve gas diffusion performance and water drainage. The second catalyst layer uses a Pt / C catalyst, which is uniformly coated onto the substrate surface by a spraying process, and the catalyst layer thickness is approximately 15 μm. This catalyst exhibits high activity for the hydroxide reaction.

[0045] The high-temperature proton exchange membrane 3 is a phosphate-doped polybenzimidazole (PBI) membrane with a thickness of 50 μm and a phosphate doping level of 5-6 molecules of H3PO4 per PBI repeating unit. This membrane exhibits a proton conductivity of 0.05-0.08 S / cm in the temperature range of 160-200℃, and also demonstrates excellent thermal stability and mechanical strength. The anhydrous operation of the PBI membrane eliminates the need for a complex water management system, making it suitable for intermediate-temperature hydrogen production scenarios.

[0046] The cathode gas diffusion electrode 4 includes a second porous conductive substrate and a third catalyst layer coated thereon. The material and structure of the second porous conductive substrate are the same as those of the anode gas diffusion electrode 2. The third catalyst layer uses a Pt / C catalyst with a thickness of approximately 10 μm and exhibits high proton reduction activity.

[0047] The structure of the cathode bipolar plate 5 is identical to the inner structure of the anode bipolar plate 1. It is made of the same material and features a corresponding serpentine gas flow channel for discharging the high-purity hydrogen generated at the cathode. The cathode bipolar plate 5 does not have a porous metal structure; its outer side is isolated from the environment by an insulation layer to reduce heat loss.

[0048] According to embodiments of this disclosure, the specific operational process of the methanol reforming hydrogen production reactor based on thermal / electric synergy at low voltage is as follows:

[0049] First, the system is preheated. An external heat source heats the reactor to its operating temperature range. In this embodiment, the reaction temperature is set at 190°C.

[0050] Methanol feedstock and deionized water are mixed in a mixer at a molar ratio of 1:1.3 and then pumped to the evaporation chamber via a metering pump. The evaporation chamber uses an external heat source to heat the mixture until it is completely vaporized, forming methanol water vapor.

[0051] Methanol water vapor enters the porous metal channel 6 of the anode bipolar plate 1 through the inlet 8. Within the porous metal channel 6, the methanol water vapor contacts the first catalyst layer supported on the pore surface, undergoing a thermochemical reforming reaction driven by thermal energy. This reaction is strongly endothermic, and the required heat is provided by an external heat source through conduction via the metal substrate 7 and the porous metal channel 6. The high specific surface area of ​​the porous metal channel 6 ensures sufficient contact between the catalyst and the reactant gas, while its high thermal conductivity guarantees rapid replenishment of the heat of reaction.

[0052] The hydrogen-rich mixture generated by the thermochemical reforming reaction flows out from the porous metal channel 6 and enters the region of the anode gas diffusion electrode 2. Simultaneously, an external power source applies a stable voltage to the reactor. Driven by this voltage, the hydrogen in the hydrogen-rich mixture undergoes an electrochemical oxidation reaction H2 → 2H+ in the second catalytic layer of the anode gas diffusion electrode 2. + + 2e - The reaction continuously consumes hydrogen on the anode side, causing the hydrogen level to drop.

[0053] The generated protons migrate through the high-temperature proton exchange membrane 3 to the cathode side, where they combine with electrons transported from the anode to the cathode via the external circuit in the third catalytic layer of the cathode gas diffusion electrode 4, resulting in an electrochemical reduction reaction: 2H+ + + 2e - → H2

[0054] The hydrogen generated at the cathode is collected through the gas flow channel of the cathode bipolar plate 5 and discharged from the hydrogen outlet. After condensation to remove trace amounts of water vapor, it can be directly used in fuel cells or other applications.

[0055] The main components of the anode tail gas are CO2, a small amount of H2 and unreacted methanol. The tail gas is discharged from the outlet of the flow channel and can be further recycled.

[0056] According to embodiments of this disclosure, the above-described methanol reforming hydrogen production reactor based on thermal / electric synergy operates similarly at high voltage to at low voltage. When the applied voltage is higher than that of methanol or water, in addition to the electrochemical oxidation of hydrogen, methanol and water vapor undergo electrolysis in the second catalyst layer to produce protons and electrons.

[0057] In this embodiment, the electrochemical and thermochemical processes form a significant synergistic effect: the electrochemical oxidation reaction continuously consumes hydrogen on the anode side, reducing its partial pressure, and according to Le Chatelier's principle, drives the thermochemical reforming reaction to move in the direction of hydrogen generation; due to the intervention of the thermochemical reforming reaction, hydrogen has been generated on the anode side before the voltage is applied, so that the electrochemical oxidation reaction can be carried out at a low voltage, far lower than the voltage required for direct methanol electrolysis. This realizes the utilization of low-grade electrical energy and expands the energy adaptability of the reactor.

[0058] This disclosed reactor has no special restrictions on the form of heat source and can be adapted to various heat sources: ① Electric heating: The reactor is directly heated through a heating jacket or heating rod, with precise temperature control, suitable for laboratory and small-scale devices. ② Combustion heating: High-temperature flue gas is generated by burning fuel (natural gas, methanol, tail gas, etc.) in the combustion chamber, and then heated through a heat exchanger, suitable for self-heating operation. ③ Waste heat utilization: Industrial waste heat (such as flue gas waste heat, process waste heat) is used to heat the reactor, improving energy utilization efficiency. ④ Solar energy: Thermal oil is heated through a concentrator, and then the reactor is heated through a heat exchanger, suitable for solar hydrogen production scenarios. ⑤ Multi-source coupling: Multiple heat sources can be connected simultaneously, and the heat can be optimized and scheduled through a control subsystem.

[0059] The reactor can be configured with a control subsystem to achieve automated operation. The control subsystem includes temperature sensors, pressure sensors, flow controllers, and voltage regulation modules located inside the reactor.

[0060] Set the target temperature T_set and the allowable fluctuation range ΔT. When the measured temperature T < T_set - ΔT, increase the power of the external heat source; appropriately reduce the methanol feed rate; and slightly increase the applied voltage (to enhance electrochemical heat generation). When the measured temperature T > T_set + ΔT, decrease the power of the external heat source; appropriately increase the methanol feed rate (to utilize the latent heat of vaporization for cooling); and slightly decrease the applied voltage. When the measured temperature is within the target range, maintain the current operating parameters. Through the above adjustments, the reactor temperature is controlled to remain stable within the target range, ensuring long-term stable operation.

[0061] Figure 3A schematic diagram illustrating the hydrogen separation effect provided in the embodiments of this disclosure is shown. To verify the effect of the electrochemical hydrogen pump on reducing the partial pressure of hydrogen at the anode and its driving effect on thermochemical equilibrium in the reaction pathway of this disclosure, a comparative experiment was conducted as follows: A conventional high-temperature electrolyzer was used, with Pt / C catalysts used in both the anode and cathode catalyst layers; a N2 mixture containing 5% H2 was introduced at a flow rate of 15 mL / min on the anode side, and pure N2 was introduced at a flow rate of 30 mL / min on the cathode side; the reactor temperature was maintained at 170°C, and the transmembrane transport characteristics of hydrogen were investigated by applying different voltages. The experimental results are as follows. Figure 3 As shown, when the applied voltage is 0.05 V, the electrolyzer exhibits a significant hydrogen separation effect, with hydrogen evolution detected on the cathode side, and the hydrogen evolution rate increasing with increasing voltage. This phenomenon indicates that under extremely low voltage conditions, the electrochemical oxidation process can effectively consume hydrogen on the anode side, significantly reducing its local partial pressure, thereby driving hydrogen transmembrane transport to the cathode side. This conclusion provides key experimental support for the technical path of the embodiments of this disclosure: that is, by continuously reducing the anode hydrogen partial pressure through an electrochemical process, the thermodynamic equilibrium of the methanol reforming reaction can be effectively broken, driving the reaction to move in the direction of hydrogen production, and realizing thermal / electric synergistic enhanced hydrogen production.

[0062] Figure 4 The diagram illustrates the hydrogen production rate provided in the embodiments of this disclosure. To verify the effect of the electrochemical hydrogen pump effect on reducing the partial pressure of hydrogen at the anode and its driving effect on thermochemical equilibrium in the reaction pathway of this disclosure, a comparative experiment was conducted as follows: A conventional high-temperature electrolyzer was used, with Pt / C catalysts used in both the anode and cathode catalyst layers. A 2M methanol-water solution was introduced into the anode side, and the hydrogen production rate was tested under different temperature and voltage conditions. The experimental results show that at 180℃ and 0.2V, the hydrogen production rate per unit mass of catalyst reaches 63.24 mol·h⁻¹·g⁻¹, which is higher than the hydrogen production rate at 250℃ and without voltage. When the voltage is further increased to exceed the electrolysis voltage of methanol and water, the hydrogen production rate increases significantly.

[0063] The above results verify the feasibility and reliability of the reaction path described in the embodiments of this disclosure.

[0064] This disclosed reactor can be applied to the following scenarios: ① Distributed hydrogen production, providing on-site hydrogen production solutions for hydrogen refueling stations and fuel cell power plants, avoiding the risks of hydrogen storage and transportation. ② Utilization of industrial by-product gas, using industrial waste heat to drive the reaction and convert low-grade heat energy into high-grade hydrogen energy. ③ Renewable energy coupling, coupling with fluctuating energy sources such as solar and wind power to achieve synergistic utilization of electrical and thermal energy. ④ On-board hydrogen production, using engine waste heat to drive the reaction and provide hydrogen for on-board fuel cells, solving the problem of on-board hydrogen storage. ⑤ Chemical synthesis, the anode exhaust gas is rich in CO2 and H2, which can be directly used in chemical processes such as methanol synthesis and methanation.

[0065] In summary, the embodiments of this disclosure, by designing the gas flow channel of the anode bipolar plate as a porous metal structure and loading it with a reforming catalyst, extend the thermochemical reforming reaction zone from the surface of the membrane electrode to the entire interior of the flow channel, making full use of the space and specific surface area of ​​the flow channel, and significantly improving the catalyst loading and reaction efficiency. The combination of the high specific surface area and high thermal conductivity of the porous metal flow channel achieves integrated reaction-heat transfer-mass transfer.

[0066] Furthermore, due to the intervention of the thermochemical reforming reaction, hydrogen gas is generated on the anode side before voltage is applied, allowing the electrochemical oxidation reaction to proceed at low voltage. This enables the utilization of low-grade electrical energy and expands the energy adaptability of the reactor. Simultaneously, the electrochemical process continuously consumes hydrogen gas on the anode side, reducing its partial pressure and driving the thermochemical reforming reaction towards hydrogen production, resulting in a methanol conversion rate higher than that of a pure thermochemical process or a pure electrolysis process.

[0067] Furthermore, the reactor structure disclosed herein differs from a simple modification of a traditional electrolyzer. Instead, it is an innovative design based on the characteristics of thermo / electric synergistic reaction. It transforms the originally single-function gas flow channel into a multifunctional unit that also has thermochemical reaction capabilities, thereby achieving intensive utilization of the reactor's internal space and providing an efficient solution for scenarios such as distributed hydrogen production and low-grade energy utilization.

[0068] The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of this disclosure. It should be understood that the above descriptions are merely specific embodiments of this disclosure and are not intended to limit this disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the protection scope of this disclosure.

Claims

1. A methanol reforming hydrogen production reactor based on thermal / electric synergy, characterized in that, The reactor adopts a stacked assembly structure in the form of an electrolytic cell, which includes, from the anode side to the cathode side, the following components: The anode bipolar plate (1) has a gas flow channel inside, at least part of the wall of the gas flow channel is a porous metal structure, and the surface of the porous metal structure is loaded with a first catalyst layer, which is used to catalyze the thermochemical reforming reaction of methanol water vapor. Anode gas diffusion electrode (2) is used to generate electrochemical oxidation reaction; High-temperature proton exchange membrane (3) is used for selective proton transfer; The cathode gas diffusion electrode (4) is used to generate an electrochemical reduction reaction; The cathode bipolar plate (5) is used to transfer heat, electricity and gas.

2. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 1, characterized in that, The anode bipolar plate includes a porous metal flow channel (6) and a metal substrate (7). The porous metal flow channel (6) is used to transport gas, transfer heat and electricity; The porous metal channel (6) is coated with a first catalytic layer, which is used to carry out thermochemical reforming reactions.

3. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 2, characterized in that, The porous metal is selected from porous materials such as foamed metal and sintered metal fibers.

4. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 1, characterized in that, The anode gas diffusion electrode (2) includes a first porous conductive substrate and a second catalytic layer coated thereon, the second catalytic layer being used to carry out an electrochemical oxidation reaction.

5. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 1, characterized in that, The cathode gas diffusion electrode (4) includes a second porous conductive substrate and a third catalytic layer coated thereon, the third catalytic layer being used for electrochemical reduction reaction.

6. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 1, characterized in that, Methanol vapor is introduced into the gas channel of the anode bipolar plate (1), and under the drive of thermal energy, a thermochemical reforming reaction occurs in the first catalyst layer to generate a hydrogen-containing mixed gas. The hydrogen in the hydrogen-containing mixture undergoes an electrochemical oxidation reaction in the second catalytic layer of the anode gas diffusion electrode (2) under the drive of electrical energy, dissociating into protons and electrons; The protons migrate through the high-temperature proton exchange membrane (3) to the third catalytic layer of the cathode gas diffusion electrode (4), where they combine with electrons to undergo an electrochemical reduction reaction, generating high-purity hydrogen gas.

7. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 6, characterized in that, The electrochemical oxidation reaction continuously consumes hydrogen in the hydrogen-containing mixture, reducing the hydrogen partial pressure on the surface of the first catalyst layer and driving the thermochemical reforming reaction to move in the direction of generating hydrogen.

8. The methanol reforming hydrogen production reactor based on thermal / electric synergy according to claim 6, characterized in that, When a voltage higher than that applied to the methanol or water electrolysis is applied, the second catalyst layer undergoes an additional electrochemical oxidation reaction of methanol or water, producing protons and electrons.

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