An organic electrochemical synthesis system and method

Abstract

This application discloses an organic electrochemical synthesis system and method, relating to the field of organic electrochemical synthesis technology. The organic electrochemical synthesis system of this application includes a vaporization device, an electrochemical reaction device, and a condensation device connected in sequence. The vaporization device includes an organic vaporization device, a water vaporization device, and a mass flow meter. The organic vaporization device provides vaporized organic raw materials to the electrochemical reaction device; the water vaporization device provides water vapor to the electrochemical reaction device; the mass flow meter controls the flow rate of the carrier gas entering the electrochemical reaction device; and the condensation device condenses the electrochemical reaction products obtained in the electrochemical reaction device. The above-mentioned organic electrochemical synthesis system has high reliability and is easy to operate, helping to reduce the cost of organic electrochemical synthesis and simplify the process.

Description

Technical Field

[0001] This application relates to the field of organic electrochemical synthesis technology, and more specifically, to an organic electrochemical synthesis system and an organic electrochemical synthesis method. Background Technology

[0002] Organic electrochemical synthesis technology is a cutting-edge field that intersects organic chemistry and electrochemistry. Its core lies in driving organic molecules to undergo redox reactions on electrode surfaces using an external electric field, achieving green and efficient preparation of high-value-added chemicals. Most existing organic electrochemical synthesis reactions are carried out in an electrolyte composed of reactants, solvents, and electrolytes. After the reaction, the product needs to be obtained through multiple separation and purification steps. For example, patent CN119592969A uses the electrochemical oxidation of dimethyl sulfide to synthesize dimethyl sulfoxide, with the electrolyte containing dimethyl sulfide, N,N-dimethylacetamide, water, tetrabutylammonium chloride, and trifluoroacetic acid. After the reaction, dimethyl sulfoxide needs to be separated through multiple distillation steps. Patent CN119101938A uses the electrochemical oxidation of cyclohexanone to synthesize adipic acid, with the electrolyte containing cyclohexanone and an aqueous solution of potassium hydroxide. After the reaction, adipic acid needs to be obtained through neutralization, crystallization, and distillation steps.

[0003] The aforementioned organic electrochemical synthesis technology requires the use of expensive electrolytes or organic solvents, and the product recovery and separation process is lengthy and difficult to operate, which restricts the industrial application of organic electrochemical synthesis. Summary of the Invention

[0004] The main objective of this application is to provide an organic electrochemical synthesis system and method to solve the problems of high cost, long product recovery and separation purification process, and high difficulty in the prior art of organic electrochemical synthesis.

[0005] To achieve the above objectives, according to a first aspect of this application, an organic electrochemical synthesis system is provided, comprising a vaporization device, an electrochemical reaction device, and a condensation device connected in sequence; the vaporization device includes an organic vaporization device, a water vaporization device, and a mass flow meter; the organic vaporization device is used to provide vaporized organic raw materials to the electrochemical reaction device; the water vaporization device is used to provide water vapor to the electrochemical reaction device; the mass flow meter is used to control the flow rate of the carrier gas introduced into the electrochemical reaction device; and the condensation device is used to condense the electrochemical reaction products obtained in the electrochemical reaction device.

[0006] Furthermore, the organic vaporization device and the water vaporization device each include the following components: an evaporator, a first fixed plate, a heating rod, a first thermocouple, a first temperature controller, a high-pressure plunger pump, and a solution bottle; the evaporator includes an evaporation chamber, a sealing ring, a sealing gasket, and an evaporation chamber cover plate stacked in sequence, the evaporator is fixed to one side of the first fixed plate, and the evaporation chamber is arranged adjacent to the first fixed plate; the heating rod and the first thermocouple are inserted into the mounting holes of the evaporation chamber; the first temperature controller is used to regulate the temperature inside the evaporator; the high-pressure plunger pump is connected to the solution bottle and the evaporator respectively, and is used to supply liquid to the organic vaporization device and / or the water vaporization device.

[0007] Furthermore, the electrochemical reaction device includes a bipolar plate, an anode, a diaphragm, and a cathode.

[0008] Furthermore, the condensation device includes a cooling fan, a cooling chip, a heat sink, a cold trap, a cold cavity, a second thermocouple, a second temperature controller, a liquid storage bottle, a second fixing plate, and a profile support. The cooling chip, cooling fan, and heat sink are stacked sequentially to form a stacked assembly, which is positioned opposite each other on both sides of the cold cavity, with the cooling chip adjacent to the cold cavity. The cold trap and the second thermocouple are respectively installed in mounting holes at the top of the cold cavity. The second temperature controller regulates the temperature of the cold cavity, and the second fixing plate is located at the bottom of the cold cavity and fixed to the profile support. The liquid storage bottle is located inside the profile support and connected to the cold cavity, and is used to collect electrochemical reaction products.

[0009] According to a second aspect of this application, an organic electrochemical synthesis method is provided, comprising the following steps:

[0010] S1, assemble the bipolar plate, anode, diaphragm and cathode into an electrochemical reaction device;

[0011] S2, vaporizes water and organic raw materials to obtain water vapor and vaporized organic raw materials;

[0012] S3, water vapor and vaporized organic raw materials are introduced into the anode of the electrochemical reactor, liquid water is introduced into the cathode of the electrochemical reactor, voltage is applied to the electrochemical reactor to carry out the electrochemical reaction and obtain the electrochemical reaction products;

[0013] S4 is used to condense the electrochemical reaction products and collect them.

[0014] Furthermore, in S2, the vaporization temperature of water is 60℃~120℃, and the vaporization temperature of organic raw materials is 40℃~200℃.

[0015] Furthermore, in S3, water vapor is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min, and vaporized organic matter is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min.

[0016] Furthermore, in S2, water vapor and vaporized organic feedstock are introduced into the anode of the electrochemical reactor via a carrier gas; the flow rate of the carrier gas is 1 mL / min to 1000 mL / min.

[0017] Furthermore, in S3, liquid water is introduced into the cathode of the electrochemical reaction device at a flow rate of 0.1 mL / min to 1000 mL / min.

[0018] Furthermore, in S3, the voltage is 1V~10V; and / or, the temperature of the electrochemical reaction is 40℃~200℃.

[0019] Furthermore, in S4, the condensation temperature is 0℃~10℃.

[0020] Furthermore, the bipolar plate is made of at least one of graphite, titanium, nickel, and stainless steel.

[0021] Furthermore, the anode includes an anode current collector and an anode catalyst, and the cathode includes a cathode current collector and a cathode catalyst. The materials of the anode current collector and the cathode current collector are each independently at least one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foamed titanium, titanium fiber felt, and powder sintered porous titanium.

[0022] Furthermore, the anode catalyst includes at least one of ruthenium oxide, iridium oxide, lead oxide, manganese oxide, tin oxide, nickel oxide, cobalt oxide, and copper oxide, and the cathode catalyst includes at least one of platinum, ruthenium, nickel, and ruthenium dioxide.

[0023] Furthermore, the membrane includes at least one of cation exchange membranes and anion exchange membranes.

[0024] Furthermore, the organic raw materials include at least one of dimethyl sulfide, cyclohexanol, cyclohexanone, methanol, ethanol, and isopropanol.

[0025] By applying the technical solution of this application, and by separately setting up organic vaporization devices and water vaporization devices, the temperature can be independently controlled to meet the optimal vaporization conditions for water and different organic compounds. This ensures that each reactant can be converted into a gaseous state under the most suitable conditions, improving reaction efficiency and selectivity. It is suitable for the electrochemical synthesis of various organic compounds and is beneficial for industrial applications. The use of a mass flow meter allows for precise control of the carrier gas flow rate, improving the mass transfer efficiency and reaction rate of reactants during electrochemical synthesis, optimizing reaction conditions, and enhancing product selectivity. The design of the aforementioned vaporization devices ensures efficient vaporization of reactants, forming a uniform and high-concentration gas flow into the electrochemical reaction device, greatly improving the efficiency and Faraday efficiency of electrochemical synthesis. The direct collection of products through a condenser greatly simplifies the product separation process. The design of the aforementioned organic electrochemical synthesis system avoids the presence of large amounts of liquid, reducing the risk of leakage and fire, enhancing operational safety, and improving the overall controllability and reliability of the system. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the vaporization device and condensation device in one embodiment of this application;

[0027] Figure 2 This is a schematic diagram of the internal structure of a water vaporization device and / or an organic matter vaporization device according to an embodiment of this application;

[0028] Figure 3 This is a schematic diagram of the internal structure of the water vaporization device in one embodiment of this application;

[0029] Figure 4 This is a schematic diagram of the internal structure of the condensation device in one embodiment of this application;

[0030] Figure 5 This is a process flow diagram of organic electrochemical synthesis in one embodiment of this application;

[0031] The above figures contain the following reference numerals:

[0032] 1. First fixing plate; 2. Heating rod; 3. First thermocouple; 4. First temperature controller; 5. High-pressure plunger pump; 6. Solution bottle; 7. Evaporation chamber; 8. Sealing ring; 9. Sealing gasket; 10. Evaporation chamber cover plate; 11. Compression fitting; 12. Humidity sensor; 21. Cooling fan; 22. Cooling chip; 23. Heat sink; 24. Cold trap; 25. Cold chamber; 26. Second thermocouple; 27. Second temperature controller; 28. Liquid storage bottle; 29. ​​Second fixing plate; 30. Profile bracket; 31. Condensation device; 32. Organic vaporization device; 33. Water vaporization device; 34. Mass flow meter. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0034] As described in the background section of this application, existing technologies suffer from high costs in organic electrochemical synthesis, as well as lengthy and complex product recovery and separation processes. To address these issues, this application provides an organic electrochemical synthesis system in a typical embodiment. This system includes a vaporization device, an electrochemical reaction device, and a condensation device 31 connected in sequence. Schematic diagrams of the vaporization device and the condensation device 31 are shown below. Figure 1 As shown; the vaporization device includes an organic vaporization device 32, a water vaporization device 33, and a mass flow meter 34; the organic vaporization device 32 is used to provide vaporized organic raw materials to the electrochemical reaction device; the water vaporization device 33 is used to provide water vapor to the electrochemical reaction device; the mass flow meter 34 is used to control the flow rate of the carrier gas introduced into the electrochemical reaction device; and the condensation device 31 is used to condense the electrochemical reaction products obtained in the electrochemical reaction device.

[0035] In the embodiments described above, by separately setting up the organic vaporization device 32 and the water vaporization device 33, the temperature can be independently controlled to meet the optimal vaporization conditions for water and different organic compounds. This ensures that each reactant can be converted into a gaseous state under the most suitable conditions, improving reaction efficiency and selectivity. This system is suitable for the electrochemical synthesis of various organic compounds and is beneficial for industrial applications. The mass flow meter 34 allows for precise control of the carrier gas flow rate, improving the mass transfer efficiency and reaction rate of the reactants during electrochemical synthesis, optimizing reaction conditions, and enhancing product selectivity. The design of the vaporization devices ensures efficient vaporization of the reactants, forming a uniform and high-concentration gas flow into the electrochemical reaction device, greatly improving the efficiency and Faraday efficiency of the electrochemical synthesis. The products are directly collected by the condenser, greatly simplifying the product separation process. The design of the above-described organic electrochemical synthesis system avoids the presence of large amounts of liquid, reducing the risk of leakage and fire, enhancing operational safety, and improving the overall controllability and reliability of the system. The embodiments described above in this application directly convert organic raw materials and water into a gaseous state through a vaporization device, avoiding the use of large amounts of organic solvents and electrolytes in traditional liquid-phase electrochemical reactions. This reduces the emission of harmful substances, lowers raw material costs, and simplifies subsequent waste treatment. By setting a condenser 31 after the electrochemical reaction device, the gaseous reaction products can be directly condensed and collected, greatly reducing the energy consumption and cost required for subsequent separation steps and improving production efficiency. In addition, the vaporized organic matter and water vapor can contact the electrodes in a higher concentration, thereby increasing the rate and efficiency of the electrochemical reaction. Furthermore, the transport of gaseous reactants is not limited by liquid viscosity, allowing for higher current densities and thus improving the Faraday efficiency of the products.

[0036] In some embodiments, the internal structural diagrams of the organic vaporization device 32 and the water vaporization device 33 are shown below. Figure 2 As shown, the device comprises the following components: an evaporator, a first fixed plate 1, a heating rod 2, a first thermocouple 3, a first temperature controller 4, a high-pressure plunger pump 5, and a solution bottle 6. The evaporator includes an evaporation chamber 7, a sealing ring 8, a sealing gasket 9, and an evaporation chamber cover plate 10 stacked in sequence. The evaporator is fixed to one side of the first fixed plate 1, and the evaporation chamber 7 is arranged adjacent to the first fixed plate 1. The heating rod 2 and the first thermocouple 3 are inserted into the mounting holes of the evaporation chamber 7. The first temperature controller 4 is used to regulate the temperature inside the evaporator. The high-pressure plunger pump 5 is connected to the solution bottle 6 and the evaporator respectively, and is used to supply liquid to the organic vaporization device 32 and / or the water vaporization device 33.

[0037] The purpose of setting up the first fixing plate 1 is to fix and integrate the evaporator and its components. This modular design facilitates installation and commissioning, simplifies maintenance and troubleshooting, and reduces the total operating cost of the equipment. The evaporator design helps to provide good sealing, reduce leakage of reactants during vaporization, and improve the utilization rate of reactants and the mass transfer efficiency of the reaction. The combination of heating rod 2, first thermocouple 3, and first temperature controller 4 ensures precise control of the internal temperature of the vaporization device, which helps to improve the vaporization efficiency of reactants and the selectivity of the reaction. The use of high-pressure plunger pump 5 can precisely control the flow rate of the solution, thereby controlling the supply rate of vaporized feedstock. The connection method between solution bottle 6 and evaporator, as well as the automated operation of high-pressure plunger pump 5, simplifies the operation process and reduces the difficulty of operation.

[0038] Specifically, but not limitingly, in the organic vaporization device 32 and the water vaporization device 33, each component includes one or more sub-components, which can be adjusted according to actual needs.

[0039] In some implementations, such as Figure 3 As shown, the water vaporization device 33 also includes a humidity sensor 12, which works in conjunction with the high-pressure plunger pump 5 to monitor the amount of water vapor in the water vaporization device so that the organic electrochemical synthesis can proceed efficiently.

[0040] Specifically, but not limitingly, the water vaporization device 33 or the organic vaporization device 32 also includes a compression fitting 11, which is used for fixing and connecting different components. For example, the humidity sensor 12 is fixed to the evaporation chamber cover plate 10 via the compression fitting 11. There can be multiple compression fittings 11.

[0041] In some embodiments, the electrochemical reaction device includes a bipolar plate, an anode, a diaphragm, and a cathode.

[0042] In the above embodiments of this application, the introduction of bipolar plates helps to evenly distribute current and heat energy, while serving as a supporting structure to support the anode and cathode, ensuring close contact and good conductivity between the electrodes, thereby improving current density and energy conversion efficiency. The above electrochemical reaction device is suitable for different types of organic electrochemical reactions.

[0043] In some embodiments, the internal structure of the condenser 31 is shown in the schematic diagram below. Figure 4As shown, the assembly includes a cooling fan 21, a cooling chip 22, a heat sink 23, a cold trap 24, a cold cavity 25, a second thermocouple 26, a second temperature controller 27, a liquid storage bottle 28, a second fixing plate 29, and a profile support 30. The cooling chip 22, cooling fan 21, and heat sink 23 are stacked sequentially to form a stacked assembly, which is positioned opposite each other on both sides of the cold cavity 25. The cooling chip 22 is adjacent to the cold cavity 25. The cold trap 24 and the second thermocouple 26 are respectively installed in the mounting holes at the top of the cold cavity 25. The second temperature controller 27 regulates the temperature of the cold cavity 25. The second fixing plate 29 is located at the bottom of the cold cavity 25 and fixed to the profile support 30. The liquid storage bottle 28 is located inside the profile support 30 and connected to the cold cavity 25, and is used to collect electrochemical reaction products.

[0044] In the above embodiments of this application, by stacking the cooling chip 22, the cooling fan 21, and the heat sink 23, heat exchange during the condensation process is effectively accelerated, ensuring effective cooling of the condensation device 31. Simultaneously, the cooling fan 21 also helps improve the heat dissipation efficiency of the cooling chip 22, maintaining temperature uniformity throughout the device and preventing localized overheating that could lead to efficiency degradation. The cold trap 24 captures and filters condensate and impurities generated during condensation, improving product purity. The precise temperature control of the cold cavity 25 via the second thermocouple 26 and the second temperature controller 27 allows for rapid cooling of other products to a liquid or solid state, improving condensation efficiency. The designed position of the storage bottle 28 automatically collects the condensed product, simplifying the product collection process.

[0045] Specifically, but not limitingly, each component in the condensation device 31 also includes sub-components, and the number of sub-components can be limited according to actual needs. For example, the cold cavity 25 may include two sub-cold cavities to accelerate the product condensation efficiency.

[0046] In another typical embodiment of this application, an organic electrochemical synthesis method is provided, the process flow diagram of which is shown below. Figure 5 As shown, the specific steps include the following:

[0047] S1, assemble the bipolar plate, anode, diaphragm and cathode into an electrochemical reaction device;

[0048] S2, vaporizes water and organic raw materials to obtain water vapor and vaporized organic raw materials;

[0049] S3, water vapor and vaporized organic raw materials are introduced into the anode of the electrochemical reactor, liquid water is introduced into the cathode of the electrochemical reactor, voltage is applied to the electrochemical reactor to carry out the electrochemical reaction and obtain the electrochemical reaction products;

[0050] S4 is used to condense the electrochemical reaction products and collect them.

[0051] In the above embodiments of this application, vaporizing water and organic raw materials can significantly increase the surface area and diffusion rate of the reactants, resulting in more thorough contact between the reactants and the electrodes, faster reaction kinetics, and thus improved reactant utilization. Furthermore, conducting the reaction in the gas phase eliminates the need for large amounts of liquid solvents and electrolytes in organic electrochemical synthesis, reducing the solvent recovery steps in subsequent processing stages, which helps to reduce costs and simplify the process. In addition, by condensing and collecting the product, this invention eliminates the need for complex separation and purification steps, simplifying the production process and reducing energy consumption and operational complexity.

[0052] In some embodiments of this application, in S2, the vaporization temperature of water is 60°C to 120°C, and the vaporization temperature of organic raw materials is 40°C to 200°C.

[0053] By controlling the vaporization temperature of water and organic raw materials within the aforementioned range, it is beneficial to convert water and organic raw materials into a gaseous state, enabling the reaction raw materials to react under gaseous conditions, reducing the energy consumption required for subsequent separation and purification steps, and improving production efficiency. On the other hand, it is beneficial to enable the vaporized organic raw materials and water vapor to contact the electrode in a higher concentration, thereby improving the rate and efficiency of the electrochemical reaction.

[0054] In some embodiments, in S3, water vapor is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min, vaporized organic matter is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min, and liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min.

[0055] In the embodiments described above, by precisely controlling the feed rates of water vapor and organic raw materials, the residence time of the reactants in the electrochemical reactor can be adjusted, thereby affecting the kinetics of the reaction. Appropriate flow rates help to increase the reaction rate, ensure complete reaction of the reactants, reduce the probability of side reactions, promote stable reaction, and improve the purity and Faraday efficiency of the products.

[0056] In some embodiments of this application, in step S3, water vapor and vaporized organic raw materials are introduced into the anode of the electrochemical reaction device via a carrier gas; the flow rate of the carrier gas is 1 mL / min to 1000 mL / min.

[0057] In the embodiments described above, the carrier gas is an inert gas, including at least one of nitrogen, argon, and helium. The carrier gas helps to uniformly disperse and transport water vapor and vaporized organic feedstock to the anode region of the electrochemical reactor, ensuring good contact between the reactants and the electrode surface and improving reaction efficiency. An appropriate carrier gas flow rate ensures that the reactants enter the electrode region at a stable rate, avoiding excessively high or low local concentrations that could reduce Faraday efficiency.

[0058] In some embodiments, in S3, the voltage is 1V to 10V; and / or, the temperature of the electrochemical reaction is 40°C to 200°C.

[0059] In the above embodiments of this application, the magnitude of the voltage and the temperature of the electrochemical reaction directly affect the rate of the electrochemical reaction. By controlling the voltage and the temperature of the electrochemical reaction within the above range, the reaction can be carried out smoothly, ensuring that the reactants make full use of the charge and improving the Faraday efficiency.

[0060] In some implementations, the condensation temperature in S4 is 0°C to 10°C.

[0061] In the above embodiments of this application, controlling the condensation temperature within the above range allows for selective condensation of the target product, thereby improving the purity of the target product. At the same time, condensation under the above conditions also helps to improve condensation efficiency and reduce product loss.

[0062] In some implementations, the bipolar plate is made of at least one of graphite, titanium, nickel, and stainless steel.

[0063] In the above embodiments of this application, the bipolar plate has good conductivity and chemical stability, which can effectively reduce losses in the electrochemical reaction process and improve energy conversion efficiency. In addition, the bipolar plate has good mechanical strength and corrosion resistance, which can withstand the high temperature and strong electric field in the electrochemical synthesis process, extend the service life of the equipment, and reduce maintenance costs.

[0064] In some embodiments, the anode includes an anode current collector and an anode catalyst, and the cathode includes a cathode current collector and a cathode catalyst. The materials of the anode current collector and the cathode current collector are each independently at least one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foamed titanium, titanium fiber felt, and powder sintered porous titanium. The anode catalyst includes at least one of ruthenium oxide, iridium oxide, lead oxide, manganese oxide, tin oxide, nickel oxide, cobalt oxide, and copper oxide. The cathode catalyst includes at least one of platinum, ruthenium, nickel, and ruthenium dioxide. The membrane includes at least one of cation exchange membrane and anion exchange membrane.

[0065] In the embodiments described above, the anode and cathode current collectors possess excellent electrical conductivity and a large surface area, which is beneficial for increasing current density and reactant conversion rate. Furthermore, the porous structure of these materials facilitates uniform gas and liquid distribution, ensuring sufficient contact between the reactants and catalyst, thereby improving reaction selectivity and efficiency. The aforementioned diaphragm is a commonly used diaphragm, effectively maintaining the charge balance of the electrochemical reaction, preventing unnecessary exchange of substances between different electrodes, and improving product purity.

[0066] In some embodiments, the organic raw material includes at least one of dimethyl sulfide, cyclohexanol, cyclohexanone, methanol, ethanol, and isopropanol.

[0067] The above-described organic electrochemical synthesis method of this application enables the above-described organic raw materials to undergo sufficient redox reactions to synthesize the desired organic compounds.

[0068] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0069] The following examples demonstrate the synthesis of organic compounds using the following organic electrochemical synthesis system:

[0070] (1) Vaporization device, schematic diagram of the internal structure of organic matter vaporization device 32 and water vaporization device 33 as shown in the figure Figure 2 As shown, the device comprises the following components: an evaporator, a first fixed plate 1, a heating rod 2, a first thermocouple 3, a first temperature controller 4, a high-pressure plunger pump 5, and a solution bottle 6. The evaporator includes an evaporation chamber 7, a sealing ring 8, a sealing gasket 9, and an evaporation chamber cover plate 10 stacked in sequence. The evaporator is fixed to one side of the first fixed plate 1, and the evaporation chamber 7 is arranged adjacent to the first fixed plate 1. The heating rod 2 and the first thermocouple 3 are inserted into the mounting holes of the evaporation chamber 7. The first temperature controller 4 is used to regulate the temperature inside the evaporator. The high-pressure plunger pump 5 is connected to the solution bottle 6 and the evaporator, respectively, and is used to supply liquid to the organic vaporization device 32 and / or the water vaporization device 33. In addition, the water vaporization device 33 also includes a humidity sensor 12, which is fixed to the evaporation chamber cover plate 10 through a compression fitting 11.

[0071] (2) An electrochemical reaction device, comprising an anode, a diaphragm, and a cathode arranged in sequence, with a bipolar plate arranged on the side of the anode away from the diaphragm and the cathode away from the diaphragm; wherein, the anode includes an anode current collector and an anode catalyst, and the cathode includes a cathode current collector and a cathode catalyst; the diaphragm is a cation exchange membrane Nafion117 (Chemours); the bipolar plate is made of titanium (TA2).

[0072] (3) Condensation device, the structural diagram of which is shown below Figure 4As shown, the assembly includes a cooling fan 21, a cooling chip 22, a heat sink 23, a cold trap 24, a cold cavity 25, a second thermocouple 26, a second temperature controller 27, a liquid storage bottle 28, a second fixing plate 29, and a profile support 30. The cooling chip 22, cooling fan 21, and heat sink 23 are stacked sequentially to form a stacked assembly, which is positioned opposite each other on both sides of the cold cavity 25. The cooling chip 22 is adjacent to the cold cavity 25. The cold trap 24 and the second thermocouple 26 are respectively installed in the mounting holes at the top of the cold cavity 25. The second temperature controller 27 regulates the temperature of the cold cavity 25. The second fixing plate 29 is located at the bottom of the cold cavity 25 and fixed to the profile support 30. The liquid storage bottle 28 is located inside the profile support 30 and connected to the cold cavity 25, and is used to collect electrochemical reaction products.

[0073] Example 1

[0074] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0075] S1, titanium fiber felt is selected as the anode current collector, tin oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and platinum was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0076] S2, dimethyl sulfide is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 80℃; water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0077] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80 °C. A voltage of 2.3 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0078] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condenser. The temperature of the condenser is 5°C. The electrochemical reaction products enter the condenser and are condensed to obtain the product dimethyl sulfoxide.

[0079] The current density of the electrochemical reaction device under the above conditions is 210 mA / cm². 2 The Faraday efficiency of dimethyl sulfoxide is 80%.

[0080] Example 2

[0081] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0082] S1, titanium fiber felt is selected as the anode current collector, ruthenium oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and platinum was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0083] S2, Cyclohexanol is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 160℃; water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0084] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80°C. A voltage of 1.6 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0085] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condensing device. The temperature of the condensing device is 5°C. The electrochemical reaction products enter the condensing device and are condensed to obtain adipic acid.

[0086] The current density of the electrochemical reaction device under the above conditions is 50 mA / cm². 2 The Faraday efficiency of adipic acid is 85%.

[0087] Example 3

[0088] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0089] S1, titanium fiber felt is selected as the anode current collector, ruthenium oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and ruthenium dioxide was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0090] S2, Cyclohexanone is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 160℃; water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0091] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80°C. A voltage of 1.6 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0092] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condensing device. The temperature of the condensing device is 5°C. The electrochemical reaction products enter the condensing device and are condensed to obtain adipic acid.

[0093] The current density of the electrochemical reaction device under the above conditions is 30 mA / cm². 2 The Faraday efficiency of adipic acid is 85%.

[0094] Example 4

[0095] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0096] S1, titanium fiber felt is selected as the anode current collector, manganese oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and ruthenium dioxide was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0097] S2, methanol is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 70℃; water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0098] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80 °C. A voltage of 1.8 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0099] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condenser. The temperature of the condenser is 5°C. The electrochemical reaction product enters the condenser and is condensed to obtain formic acid.

[0100] The current density of the electrochemical reaction device under the above conditions is 350 mA / cm². 2 Formic acid has a Faraday efficiency of 80%.

[0101] Example 5

[0102] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0103] S1, titanium fiber felt is selected as the anode current collector, iridium oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and ruthenium dioxide was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0104] S2, Ethanol is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 80℃; Water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0105] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80 °C. A voltage of 1.8 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0106] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condenser. The temperature of the condenser is 5°C. The electrochemical reaction products enter the condenser and are condensed to obtain acetic acid.

[0107] The current density of the electrochemical reaction device under the above conditions is 300 mA / cm². 2 The Faraday efficiency of acetic acid is 85%.

[0108] Example 6

[0109] One embodiment of the organic electrochemical synthesis method of this application includes the following steps:

[0110] S1, titanium fiber felt is selected as the anode current collector, cobalt oxide is selected as the anode catalyst, and the content of the anode catalyst in the anode is 1 mg / cm³. 2 Titanium fiber felt was selected as the cathode current collector, and ruthenium dioxide was selected as the cathode catalyst. The content of the cathode catalyst in the cathode was 0.5 mg / cm³. 2 ;

[0111] S2, Isopropanol is introduced into the organic raw material vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the organic raw material vaporization device is 80℃; water is introduced into the water vaporization device at a flow rate of 0.5 mL / min, and the temperature of the evaporation chamber in the water vaporization device is 80℃.

[0112] S3, using nitrogen as the carrier gas, water vapor and vaporized organic raw materials are introduced into the electrochemical reactor at a flow rate of 10 mL / min, a water vapor flow rate of 0.5 mL / min, and a vaporized organic raw material flow rate of 0.5 mL / min. Liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 2 mL / min. The temperature of the electrochemical reactor is controlled at 80 °C. A voltage of 1.8 V is applied between the cathode and anode to carry out the electrochemical reaction and obtain the electrochemical reaction products.

[0113] S4, the outlets of the anode and cathode of the electrochemical reaction device are respectively connected to a condenser. The temperature of the condenser is 5°C. The electrochemical reaction products enter the condenser and are condensed to obtain acetone.

[0114] The current density of the electrochemical reaction device under the above conditions is 200 mA / cm². 2 The Faraday efficiency of acetone is 90%.

[0115] Example 7

[0116] One embodiment of the organic electrochemical synthesis method of this application differs from that of Example 1 as follows:

[0117] In S3, the temperature of the electrochemical reaction device is 60℃ and the voltage is 2.3V.

[0118] The current density of the electrochemical reaction device under the above conditions is 180 mA / cm². 2 The Faraday efficiency of dimethyl sulfoxide is 80%.

[0119] Example 8

[0120] One embodiment of the organic electrochemical synthesis method of this application differs from that of Example 1 as follows:

[0121] In S3, the temperature of the electrochemical reaction device is 80℃ and the voltage is 2.1V.

[0122] The current density of the electrochemical reaction device under the above conditions is 170 mA / cm². 2 The Faraday efficiency of dimethyl sulfoxide is 80%.

[0123] Example 9

[0124] One embodiment of the organic electrochemical synthesis method of this application differs from that of Example 1 as follows:

[0125] In S3, the temperature of the electrochemical reaction device is 30℃ and the voltage is 2.3V.

[0126] The current density of the electrochemical reaction device under the above conditions is 110 mA / cm². 2 The Faraday efficiency of dimethyl sulfoxide is 80%.

[0127] Example 10

[0128] One embodiment of the organic electrochemical synthesis method of this application differs from that of Example 1 as follows:

[0129] In S4, the temperature of the condenser is 20°C.

[0130] The current density of the electrochemical reaction device under the above conditions is 210 mA / cm². 2 The Faraday efficiency of dimethyl sulfoxide is 53%.

[0131] Comparative Example 1

[0132] This application provides a comparative example of an organic electrochemical synthesis method. The differences between the organic electrochemical synthesis method described in this comparative example and Example 1 are as follows:

[0133] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0134] The current density of the electrochemical reaction device under the above conditions is 50 mA / cm². 2The Faraday efficiency of dimethyl sulfoxide is 45%.

[0135] Comparative Example 2

[0136] This application provides a comparative example of an organic electrochemical synthesis method. The differences between the organic electrochemical synthesis method described in this comparative example and Example 2 are as follows:

[0137] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0138] The current density of the electrochemical reaction device under the above conditions is 32 mA / cm². 2 The Faraday efficiency of adipic acid is 40%.

[0139] Comparative Example 3

[0140] This application provides a comparative example of an organic electrochemical synthesis method. The differences between the organic electrochemical synthesis method described in this comparative example and Example 3 are as follows:

[0141] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0142] The current density of the electrochemical reaction device under the above conditions is 12 mA / cm². 2 The Faraday efficiency of adipic acid is 42%.

[0143] Comparative Example 4

[0144] This application provides a comparative example of an organic electrochemical synthesis method. The differences between the organic electrochemical synthesis method described in this comparative example and Example 4 are as follows:

[0145] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0146] The current density of the electrochemical reaction device under the above conditions is 152 mA / cm². 2 Formic acid has a Faraday efficiency of 46%.

[0147] Comparative Example 5

[0148] This application provides a comparative example of an organic electrochemical synthesis method. The difference between the organic electrochemical synthesis method described in this comparative example and Example 5 is as follows:

[0149] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0150] The current density of the electrochemical reaction device under the above conditions is 10⁵ mA / cm². 2The Faraday efficiency of acetic acid is 48%.

[0151] Comparative Example 6

[0152] This application provides a comparative example of an organic electrochemical synthesis method. The difference between the organic electrochemical synthesis method described in this comparative example and Example 6 is as follows:

[0153] In S2, the temperature of the evaporation chamber in the organic raw material vaporization device is 25℃; the temperature of the evaporation chamber in the water vaporization device is 25℃.

[0154] The current density of the electrochemical reaction device under the above conditions is 85 mA / cm². 2 The Faraday efficiency of acetone is 52%.

[0155] Performance testing

[0156] Current density = I / A;

[0157] I: Current of the electrochemical reaction device (measured by the electrochemical workstation);

[0158] A: Area of ​​the electrochemical reaction device;

[0159] Faraday efficiency = (n × e × F) / Q;

[0160] n: The number of moles of the product generated (obtained by gas chromatography analysis), in mol;

[0161] e: Number of electrons transferred in the reaction;

[0162] F: Faraday constant (F = 96485), unit is C / mol;

[0163] Q: Electricity consumed (Q=I×t), in C.

[0164] The test results are shown in Table 1.

[0165] Table 1

[0166]

[0167] As shown in Table 1, the organic electrochemical synthesis system and method provided in this application are applicable to various organic electrochemical synthesis reactions, including the oxidation of dimethyl sulfide to prepare dimethyl sulfoxide, the oxidation of cyclohexanol to prepare adipic acid, the oxidation of cyclohexanone to prepare adipic acid, the oxidation of methanol to prepare formic acid, the oxidation of ethanol to prepare acetic acid, and the oxidation of isopropanol to prepare acetone. The Faradaic efficiency and current density of Examples 1-10 are significantly higher than those of Comparative Examples 1-6, indicating that the Faradaic efficiency and current density of gas-phase organic electrochemical synthesis reactions are superior to those of traditional liquid-phase organic electrochemical synthesis reactions.

[0168] Furthermore, comparing the performance test results of Examples 1, 7-8 and 9, it can be seen that the current density is higher when the temperature of the electrochemical reaction is 40℃~200℃.

[0169] Comparing the performance test results of Examples 1, 7-8 and 10, it can be seen that the Faraday efficiency of the product is higher when the temperature of the condensation device is 0-10℃.

[0170] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. An organic electrochemical synthesis system, characterized in that, The device includes a vaporization device, an electrochemical reaction device, and a condensation device (31) connected in sequence. The vaporization device includes an organic vaporization device (32), a water vaporization device (33), and a mass flow meter (34). The organic vaporization device (32) is used to provide vaporized organic raw materials to the electrochemical reaction device. The water vaporization device (33) is used to provide water vapor to the electrochemical reaction device. The mass flow meter (34) is used to control the flow rate of the carrier gas introduced into the electrochemical reaction device. The condensation device (31) is used to condense the electrochemical reaction products obtained in the electrochemical reaction device.

2. The organic electrochemical synthesis system according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The organic vaporization device (32) and the water vaporization device (33) respectively include the following components: evaporator, first fixed plate (1), heating rod (2), first thermocouple (3), first temperature controller (4), high pressure plunger pump (5) and solution bottle (6); the evaporator includes an evaporation chamber (7), sealing ring (8), sealing gasket (9) and evaporation chamber cover plate (10) stacked in sequence, the evaporator is fixed to one side of the first fixed plate (1), and the evaporation chamber (7) is arranged adjacent to the first fixed plate (1); the heating rod (2) and the first thermocouple (3) are inserted into the mounting holes of the evaporation chamber (7); the first temperature controller (4) is used to regulate the temperature inside the evaporator; the high pressure plunger pump (5) is connected to the solution bottle (6) and the evaporator respectively, and is used to supply liquid to the organic vaporization device (32) and / or the water vaporization device (33); (2) The electrochemical reaction device includes a bipolar plate, an anode, a diaphragm, and a cathode; (3) The condensation device (31) includes a cooling fan (21), a cooling chip (22), a heat sink (23), a cold trap (24), a cold cavity (25), a second thermocouple (26), a second temperature controller (27), a liquid storage bottle (28), a second fixing plate (29), and a profile bracket (30); the cooling chip (22), the cooling fan (21), and the heat sink (23) are stacked in sequence to form a stacked component, which is arranged opposite to each other on both sides of the cold cavity (25), and the cooling chip (22) The cold trap (24) and the second thermocouple (26) are respectively disposed in the mounting holes at the top of the cold cavity (25) adjacent to the cold cavity (25); the second temperature controller (27) regulates the temperature of the cold cavity (25); the second fixing plate (29) is disposed at the bottom of the cold cavity (25) and fixed on the profile support (30); the liquid storage bottle (28) is located in the profile support (30) and connected to the cold cavity (25) for collecting the electrochemical reaction products.

3. An organic electrochemical synthesis method, characterized in that, Includes the following steps: S1, assemble the bipolar plate, anode, diaphragm and cathode into an electrochemical reaction device; S2 vaporizes water and organic raw materials to obtain water vapor and vaporized organic raw materials; S3, water vapor and vaporized organic raw material are introduced into the anode of the electrochemical reaction device, liquid water is introduced into the cathode of the electrochemical reaction device, voltage is applied to the electrochemical reaction device to carry out an electrochemical reaction and obtain electrochemical reaction products; S4, the electrochemical reaction products are condensed and collected to obtain the products.

4. The organic electrochemical synthesis method according to claim 3, characterized in that, In step S2, the vaporization temperature of the water is 60℃~120℃, and the vaporization temperature of the organic raw material is 40℃~200℃.

5. The organic electrochemical synthesis method according to claim 3, characterized in that, In step S3, the water vapor is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min, and the vaporized organic matter is introduced into the anode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min; and / or, in step S3, the water vapor and the vaporized organic matter raw material are introduced into the anode of the electrochemical reactor by a carrier gas; the flow rate of the carrier gas is 1 mL / min to 100 mL / min; and / or, in step S3, the liquid water is introduced into the cathode of the electrochemical reactor at a flow rate of 0.1 mL / min to 1000 mL / min.

6. The organic electrochemical synthesis method according to claim 3, characterized in that, In S3, the voltage is 1V~10V; and / or, the temperature of the electrochemical reaction is 40℃~200℃.

7. The organic electrochemical synthesis method according to claim 3, characterized in that, In step S4, the condensation temperature is 0℃~10℃.

8. The organic electrochemical synthesis method according to claim 3, characterized in that, At least one of the following conditions must be met: (1) The material of the bipolar plate is at least one of graphite, titanium, nickel, and stainless steel; (2) The anode includes an anode current collector and an anode catalyst, and the cathode includes a cathode current collector and a cathode catalyst; the materials of the anode current collector and the cathode current collector are each independently at least one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foamed titanium, titanium fiber felt, and powder sintered porous titanium; (3) The membrane includes at least one of cation exchange membrane and anion exchange membrane.

9. The organic electrochemical synthesis method according to claim 8, characterized in that, The anode includes an anode current collector and an anode catalyst, and the cathode includes a cathode current collector and a cathode catalyst; the anode catalyst includes at least one of ruthenium oxide, iridium oxide, lead oxide, manganese oxide, tin oxide, nickel oxide, cobalt oxide, and copper oxide, and the cathode catalyst includes at least one of platinum, ruthenium, nickel, and ruthenium dioxide.

10. The organic electrochemical synthesis method according to claim 3, characterized in that, The organic raw materials include at least one of dimethyl sulfide, cyclohexanol, cyclohexanone, methanol, ethanol, and isopropanol.

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