Integrated device for electrocatalytic methane to methanol

Abstract

The utility model discloses an integrated device of electrocatalysis methane preparation methanol relates to electrochemical energy conversion technical field. In order to overcome the active site of catalyst cannot effectively contact methane molecule, severely limited the reaction rate, caused the current density to be generally low, the residence time of the methanol generated in the cavity is too long, extremely easy to occur the continuous depth oxidation on the catalyst surface, and the existing experimental device is usually formed by the " splicing " of multiple independent units, and the complex external pipeline connection is passed through among each unit. The utility model discloses methane supply and collection unit, argon supply and collection unit, electrolyte supply and circulation unit, electrocatalysis reaction unit, product collection and separation unit. The utility model's compact structure and space efficiency are high, and the operation safety and reliability are significantly improved, and the physical means of effectively inhibiting the side reaction, the special reactor structure of intensifying mass transfer, realize the on -line continuous concentration and high -purity recovery of product, and the device function integrity is strong.

Description

Technical Field

[0001] This utility model relates to the field of electrochemical energy conversion technology, and in particular to an integrated device for electrocatalytic methane to methanol production. Background Technology

[0002] Electrocatalytic methane oxidation technology utilizes clean electrical energy as a driving force to directly convert methane into methanol at room temperature and pressure. The reaction process is green and controllable, avoiding the high energy consumption and safety hazards of traditional high-temperature and high-pressure processes, and is considered one of the disruptive technological pathways for achieving high-value utilization of methane. In recent years, research in this field has mainly focused on the design and development of high-performance electrocatalysts, and significant progress has been made. However, the disconnect between the "equipment" and the "technology" severely restricts the technology's transition from the laboratory to practical application. Currently, most laboratory research in this field relies on traditional H-type electrolytic cells or their simple variants. When these conventional reaction devices are applied to the electrocatalytic production of methanol from methane, they suffer from the following inherent and systemic technical defects:

[0003] Reactant mass transfer bottlenecks and three-phase interface construction challenges: Methane has extremely low solubility in aqueous electrolytes, an inherent physicochemical limitation in this field. In H-type electrolyzers, methane is typically introduced into the liquid electrolyte in the cathode chamber via bubbling. The gas-liquid-solid three-phase reaction interface is limited to a finite number of bubbles attached to the catalyst surface, resulting in extremely low reactant transfer efficiency. This prevents most catalyst active sites from effectively contacting methane molecules, severely limiting the reaction rate and causing generally low current densities that cannot meet the requirements of industrial applications.

[0004] Product selectivity is difficult to control: Methanol, as the target product, has a lower CH bond energy than methane and is more easily oxidized under reaction conditions. In traditional batch or semi-batch reactors, the generated methanol cannot be quickly removed from the reaction zone, resulting in excessive residence time within the chamber. This makes it highly susceptible to continuous deep oxidation on the catalyst surface, generating formic acid, formate, and ultimately, complete oxidation to carbon dioxide. This is one of the key reasons why the Faraday efficiency and product selectivity of this reaction have always been difficult to improve.

[0005] Low system integration and poor operational stability: Existing experimental setups are typically "pieced together" from multiple independent units such as reactors, material conveying, and product collection, connected by complex external piping. This non-integrated design not only results in a large system size and cumbersome operation but also introduces multiple potential gas leak points (especially posing safety hazards when high-pressure methane gas is involved). Furthermore, the flow and mixing of gases and liquids are difficult to control precisely, affecting the reproducibility of experimental data and the reliability of the process.

[0006] In summary, existing technologies lack a dedicated reaction device capable of synergistically addressing the three core challenges of "mass transfer limitation," "product over-oxidation," and "system integration." There is an urgent need in those skilled in the art to design a novel, integrated device that not only provides an ideal physicochemical environment for efficient electrocatalytic reactions but also possesses functions such as enhanced mass transfer and rapid product removal, thereby fully realizing the potential of high-performance catalysts and propelling electrocatalytic methane-to-methanol technology from the laboratory to practical application. Utility Model Content

[0007] The purpose of this invention is to overcome the problem that the active sites of the catalyst cannot effectively contact methane molecules, which severely limits the reaction rate, resulting in generally low current density. The generated methanol cannot be quickly removed from the reaction zone, causing it to remain in the chamber for too long and easily undergo continuous deep oxidation on the catalyst surface. Existing experimental devices are usually "assembled" from multiple independent units such as reactors, material conveying, and product collection, with complex external pipeline connections between the units. Therefore, this invention provides an integrated device for electrocatalytic methane to methanol production.

[0008] To achieve the above objectives, this utility model employs the following technical solution:

[0009] An integrated device for the electrocatalytic production of methanol from methane includes a methane supply and collection unit, an argon supply and collection unit, an electrolyte supply and circulation unit, an electrocatalytic reaction unit, and a product collection and separation unit.

[0010] The methane supply and collection unit includes a high-pressure methane cylinder, a first flow-adjustable sampling pump, and a methane collection bag. The high-pressure methane cylinder is connected to the inlet of the first flow-adjustable sampling pump, the outlet of the first flow-adjustable sampling pump is connected to the inlet of the anode plate, and the methane collection bag is connected to the outlet of the anode plate.

[0011] The argon gas supply and collection unit includes an argon gas cylinder, a second flow-adjustable sampling pump, and an argon gas collection bag. The argon gas cylinder is connected to the inlet of the second flow-adjustable sampling pump, the outlet of the second flow-adjustable sampling pump is connected to the inlet of the cathode plate, and the argon gas collection bag is connected to the outlet of the cathode plate.

[0012] The electrolyte supply and circulation unit includes an electrolyte storage tank and a peristaltic pump. The electrolyte storage tank is connected to the inlet via the peristaltic pump.

[0013] The electrocatalytic reaction unit includes a shell, an anode plate, and a cathode plate. Gas ports are provided on both sides of the shell. The left side of the shell is sealed to the anode plate, and the right side of the shell is sealed to the cathode plate. A liquid inlet is provided at the upper end of the shell, and a liquid outlet is provided at the lower end. A reference electrode is inserted into the liquid outlet. An anode plate electrode clamp is provided on the anode plate, and a cathode plate electrode clamp is provided on the cathode plate. The liquid outlet is connected to the inlet of the gas-liquid separator.

[0014] The product collection and separation unit includes a rotary evaporator and a gas-liquid separator. The rotary evaporator is equipped with a feeding valve, and the outlet of the gas-liquid separator is connected to the feeding valve.

[0015] Furthermore, the electrolyte storage tank contains electrolyte, which is a weakly alkaline electrolyte. The flow rate of the peristaltic pump ranges from 0.1 to 10.0 mL / min, with an accuracy of ±1%.

[0016] Furthermore, a serpentine flow field is provided inside the shell, with a flow channel width of 1.0-2.0 mm and a flow channel depth of 0.5-1.0 mm.

[0017] Furthermore, the housing contains a membrane electrode, which is formed by pressing together a cathode gas diffusion layer, a cathode catalyst layer, an anion exchange membrane, a reference electrode plate, an anode catalyst layer, and an anode porous current collector stacked from top to bottom.

[0018] Furthermore, the cathode gas diffusion layer is made of hydrophobically treated carbon paper or carbon cloth, with a thickness of 200-400 μm and a porosity of 70-80%. The cathode catalyst layer is composed of Pt / C nanoparticles supported on a carbon support, with a platinum loading of 0.5-2.0 mg / cm³. 2 The anion exchange membrane is a perfluorosulfonic acid membrane with a thickness of 50-180 μm, and the anode catalyst layer is composed of vanadium pentoxide-based catalyst or cerium oxide-based catalyst with a loading of 1.0-4.0 mg / cm³. 2 The porous current collector for the anode is made of carbon cloth or nickel foam material with a porosity of ≥85%.

[0019] Furthermore, the reference electrode is an Ag / AgCl or saturated calomel reference electrode, and the anode plate electrode clamp and cathode plate electrode clamp are connected to the computer via an electrochemical workstation.

[0020] The beneficial effects of this utility model are as follows:

[0021] 1. Compact structure and high space efficiency

[0022] This invention integrates multiple functional units, including methane supply, electrolyte circulation, electrocatalytic reaction, and product collection, into a single unit through optimized piping design, breaking away from the traditional layout of separate equipment and complex piping. This highly compact physical structure significantly reduces the overall footprint of the device and improves the efficiency of laboratory space utilization.

[0023] 2. Operational safety and reliability are significantly improved.

[0024] The closed-loop circulation pipeline design of the methane supply and circulation unit of this invention confines flammable methane gas within a fixed flow path, effectively avoiding the leakage risks that may arise from open or simple venting systems. All connections between units utilize standard sealed interfaces. This integrated sealing structure fundamentally reduces potential leakage points caused by multiple temporary connections, improving the overall reliability and safety of the device operation.

[0025] 3. Physical means to effectively suppress side reactions

[0026] This invention integrates a continuous electrolyte circulation and a rapid product removal structure. A liquid flow system consisting of a peristaltic pump and connecting pipelines actively forces the generated methanol product out of the reaction zone and transports it to an external collection unit. This physical flow mechanism significantly shortens the product's residence time in the reaction zone, providing a guarantee for suppressing excessive oxidation from the device's operating principle.

[0027] 4. Proprietary reactor structure for enhanced mass transfer

[0028] The core electrocatalytic reaction unit of this invention adopts a planar membrane electrode configuration. This structure, through precise shell design, physically creates independent gas and liquid channels. This unique flow channel structure allows the reactant methane to be directly and efficiently transported to the catalyst surface in gaseous form, thus physically solving the mass transfer bottleneck problem of slow gas dissolution and diffusion in traditional devices.

[0029] 5. Enables continuous online concentration and high-purity recovery of products; the equipment boasts strong functional integrity.

[0030] This invention innovatively integrates the rotary evaporator with the product collection tank via pipelines and valves, making it a built-in functional module of the device. This design allows the low-concentration methanol solution flowing from the reactor to be directly transported to the rotary evaporator for online concentration without manual transfer. This continuous-flow concentration structure not only avoids product volatilization loss and potential contamination during intermediate transfer, but also fundamentally solves the problems of cumbersome operation, low efficiency, and large batch-to-batch variability caused by the need for batch, offline sample processing in traditional experiments, achieving full-process integration and automation from reaction to product concentration and recovery. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the structure of this utility model.

[0032] In the diagram, 1-high-pressure methane cylinder; 2-first flow adjustable sampling pump; 3-methane gas collection bag; 4-anode plate inlet; 5-anode plate outlet; 6-anode plate electrode clamp; 7-anode plate; 8-argon cylinder; 9-second flow adjustable sampling pump; 10-argon gas collection bag; 11-cathode plate inlet; 12-cathode plate outlet; 13-cathode plate electrode clamp; 14-cathode plate; 15-shell; 16-liquid inlet; 17-liquid outlet; 18-reference electrode; 19-electrolyte storage tank; 20-peristaltic pump; 21-gas-liquid separator; 22-inlet; 23-outlet; 24-rotary evaporator; 25-feed valve. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this utility model clearer, the present utility model is described below with reference to specific embodiments shown in the accompanying drawings. However, it should be understood that these descriptions are merely exemplary and not intended to limit the scope of the present utility model. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concept of the present utility model.

[0034] Example:

[0035] like Figure 1 As shown, this embodiment provides an integrated device for the electrocatalytic production of methanol from methane, including a methane supply and collection unit, an argon supply and collection unit, an electrolyte supply and circulation unit, an electrocatalytic reaction unit, and a product collection and separation unit.

[0036] An integrated apparatus for the electrocatalytic production of methanol from methane, characterized in that it includes a methane supply and collection unit, an argon supply and collection unit, an electrolyte supply and circulation unit, an electrocatalytic reaction unit, and a product collection and separation unit.

[0037] The methane supply and collection unit includes a high-pressure methane cylinder 1, a first flow adjustable sampling pump 2, and a methane collection bag 3. The high-pressure methane cylinder 1 is connected to the inlet of the first flow adjustable sampling pump 2, and the outlet of the first flow adjustable sampling pump 2 is connected to the inlet 4 of the anode plate. The methane collection bag 3 is connected to the outlet 5 of the anode plate.

[0038] The argon gas supply and collection unit includes an argon gas cylinder 8, a second flow-adjustable sampling pump 9, and an argon gas collection bag 10. The argon gas cylinder 8 is connected to the inlet of the second flow-adjustable sampling pump 9, and the outlet of the second flow-adjustable sampling pump 9 is connected to the cathode plate inlet 11. The argon gas collection bag 10 is connected to the cathode plate outlet 12.

[0039] The electrolyte supply and circulation unit includes an electrolyte storage tank 19 and a peristaltic pump 20. The electrolyte storage tank 19 is connected to the inlet 16 through the peristaltic pump 20.

[0040] The electrocatalytic reaction unit includes a shell 15, an anode plate 7, and a cathode plate 14. Gas ports are provided on both sides of the shell 15. The left side of the shell 15 is sealed to the anode plate 7, and the right side of the shell 15 is sealed to the cathode plate 14. A liquid inlet 16 is provided at the upper end of the shell 15, and a liquid outlet 17 is provided at the lower end. A reference electrode 18 is inserted into the liquid outlet 17. An anode plate electrode clamp 6 is provided on the anode plate 7, and a cathode plate electrode clamp 13 is provided on the cathode plate 14. The liquid outlet 17 is connected to the inlet 22 of the gas-liquid separator 21.

[0041] The product collection and separation unit includes a rotary evaporator 24 and a gas-liquid separator 21. The rotary evaporator 24 is equipped with a feeding valve 25, and the outlet 23 of the gas-liquid separator 21 is connected to the feeding valve 25.

[0042] The product collection and separation unit includes a rotary evaporator 24 and a gas-liquid separator 21. The rotary evaporator 24 is equipped with a feeding valve 25, and the gas-liquid separator 21 is equipped with an inlet 22 and an outlet 23. The feeding valve 25 is connected to the outlet 23.

[0043] Specifically, the electrolyte storage tank 19 contains electrolyte, which is a weakly alkaline electrolyte, and the flow rate of the peristaltic pump 20 is in the range of 0.1-10.0 mL / min with an accuracy of ±1%.

[0044] Specifically, a serpentine flow field is provided inside the housing 15, with a flow channel width of 1.0-2.0 mm and a flow channel depth of 0.5-1.0 mm.

[0045] Specifically, the housing 15 contains a membrane electrode, which is formed by pressing together a cathode gas diffusion layer, a cathode catalyst layer, an anion exchange membrane, a reference electrode plate, an anode catalyst layer, and an anode porous current collector stacked from top to bottom.

[0046] Specifically, the cathode gas diffusion layer is hydrophobically treated carbon paper or carbon cloth with a thickness of 200-400 μm and a porosity of 70-80%. The cathode catalyst layer is composed of Pt / C nanoparticles supported on a carbon support, with a platinum loading of 0.5-2.0 mg / cm³. 2 The anion exchange membrane is a perfluorosulfonic acid membrane with a thickness of 50-180 μm, and the anode catalyst layer is composed of a vanadium pentoxide-based catalyst or a cerium oxide-based catalyst with a loading of 1.0-4.0 mg / cm³. 2 The porous anode current collector is made of carbon cloth or nickel foam material with a porosity ≥85%.

[0047] Specifically, the reference electrode 18 is an Ag / AgCl or saturated calomel reference electrode, and the anode plate electrode clamp 6 and the cathode plate electrode clamp 13 are connected to a computer via an electrochemical workstation.

[0048] The present invention has been described in detail above. However, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, any modifications or improvements that do not depart from the spirit of the present invention are within the protection scope of the present invention.

Claims

1. An integrated apparatus for the electrocatalytic production of methanol from methane, characterized in that, It includes a methane supply and collection unit, an argon supply and collection unit, an electrolyte supply and circulation unit, an electrocatalytic reaction unit, and a product collection and separation unit; The methane supply and collection unit includes a high-pressure methane cylinder (1), a first flow adjustable sampling pump (2), and a methane collection bag (3). The high-pressure methane cylinder (1) is connected to the inlet of the first flow adjustable sampling pump (2), the outlet of the first flow adjustable sampling pump (2) is connected to the anode plate inlet (4), and the methane collection bag (3) is connected to the anode plate outlet (5). The argon gas supply and collection unit includes an argon gas cylinder (8), a second flow adjustable sampling pump (9), and an argon gas collection bag (10). The argon gas cylinder (8) is connected to the inlet of the second flow adjustable sampling pump (9), the outlet of the second flow adjustable sampling pump (9) is connected to the cathode plate inlet (11), and the argon gas collection bag (10) is connected to the cathode plate outlet (12). The electrolyte supply and circulation unit includes an electrolyte storage tank (19) and a peristaltic pump (20). The electrolyte storage tank (19) is connected to the inlet (16) through the peristaltic pump (20). The electrocatalytic reaction unit includes a shell (15), an anode plate (7), and a cathode plate (14). Gas ports are provided on both sides of the shell (15). The left side of the shell (15) is sealed to the anode plate (7), and the right side of the shell (15) is sealed to the cathode plate (14). A liquid inlet (16) is provided at the upper end of the shell (15), and a liquid outlet (17) is provided at the lower end. A reference electrode (18) is inserted into the liquid outlet (17). An anode plate electrode clamp (6) is provided on the anode plate (7), and a cathode plate electrode clamp (13) is provided on the cathode plate (14). The liquid outlet (17) is connected to the inlet (22) of the gas-liquid separator (21). The product collection and separation unit includes a rotary evaporator (24) and a gas-liquid separator (21). The rotary evaporator (24) is equipped with a feeding valve (25), and the outlet (23) of the gas-liquid separator (21) is connected to the feeding valve (25).

2. The integrated apparatus for electrocatalytic methane-to-methanol production according to claim 1, characterized in that, The electrolyte storage tank (19) contains electrolyte, which is a weakly alkaline electrolyte. The flow rate of the peristaltic pump (20) is 0.1-10.0 mL / min with an accuracy of ±1%.

3. The integrated apparatus for electrocatalytic methane-to-methanol production according to claim 1, characterized in that, The shell (15) is provided with a serpentine flow field, with a flow channel width of 1.0-2.0 mm and a flow channel depth of 0.5-1.0 mm.

4. The integrated apparatus for electrocatalytic methane-to-methanol production according to claim 1, characterized in that, The housing (15) contains a membrane electrode, which is formed by pressing together a cathode gas diffusion layer, a cathode catalyst layer, an anion exchange membrane, a reference electrode plate, an anode catalyst layer and an anode porous current collector.

5. The integrated apparatus for electrocatalytic methane-to-methanol production according to claim 4, characterized in that, The cathode gas diffusion layer is made of hydrophobically treated carbon paper or carbon cloth, with a thickness of 200-400 μm and a porosity of 70-80%. The cathode catalyst layer is composed of Pt / C nanoparticles supported on a carbon support, with a platinum loading of 0.5-2.0 mg / cm³. 2 The anion exchange membrane is a perfluorosulfonic acid membrane with a thickness of 50-180 μm, and the anode catalyst layer is composed of a vanadium pentoxide-based catalyst or a cerium oxide-based catalyst with a loading of 1.0-4.0 mg / cm³. 2 The porous anode current collector is made of carbon cloth or nickel foam material with a porosity ≥85%.

6. The integrated apparatus for electrocatalytic methane-to-methanol production according to claim 1, characterized in that, The reference electrode (18) is an Ag / AgCl or saturated calomel reference electrode, and the anode plate electrode clamp (6) and the cathode plate electrode clamp (13) are connected to a computer via an electrochemical workstation.

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