An electrocatalytic hydrogenation reaction device and method

Abstract

The present invention provides an electrocatalytic hydrogenation reaction device and method. In the electrocatalytic hydrogenation reaction device of the present invention, the metal membrane electrode can electrochemically reduce hydrogen ions generated at the anode to hydrogen atoms, and the generated hydrogen atoms can combine with the metal membrane electrode to form metal hydrides. The metal hydrides can improve the electrocatalytic reduction hydrogenation performance on the catalyst surface in the form of active hydrogen transfer, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety due to avoiding the use of hydrogen; the metal membrane electrode can avoid the use of hydrogen in the catalytic hydrogenation reaction, improve the reaction safety and at the same time reduce the difficulty of selective separation of gas products; meanwhile, the electric energy provided by the power supply unit can not only promote the electron transfer between the catalyst and the reactant molecules, but also break the limitation of the thermodynamic equilibrium, enabling the catalytic hydrogenation reaction to proceed with high activity, high selectivity and high stability under mild conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic hydrogenation reactions, and particularly to an electrocatalytic hydrogenation reaction device and method. Background Art

[0002] Catalytic hydrogenation reaction is one of the most important chemical processes and plays a very important role in human production and life. Using inorganic small molecules such as CO 2 、CO、N 2 、O 2 as basic raw materials, high-value-added fuels or chemical products can be obtained through catalytic hydrogenation reduction; the catalytic hydrogenation of unsaturated aromatics is a key process in liquid organic hydrogen storage technology; the catalytic hydrogenation processes of alkynes, heteroaromatics, cyanides, aldehydes, ketones, imines, oximes, etc. play a crucial role in the production processes of pharmaceutical intermediates and bulk chemicals. Currently, the catalytic hydrogenation process in industry is mainly achieved by hydrogen reduction under high temperature and high pressure, and there are often problems such as harsh conditions, high energy consumption, complex processes, and high risk coefficients in the reaction. Therefore, developing a catalytic hydrogenation system that can efficiently and directionally obtain target products under mild conditions has very important scientific and practical significance.

[0003] Although there are generally biological transformation processes in nature such as plant photosynthesis, natural nitrogen fixation by nitrogen-fixing organisms, and enzymatic catalytic hydrogenation by microorganisms, it is difficult to meet the actual production and life needs of people due to limited conversion efficiency, slow reaction rate, and limited reaction conditions. In contrast, chemical transformation processes can obtain target products with high activity and selectivity through catalyst design, reaction condition control, and optimization of catalytic devices, and thus have been widely studied and applied (such as alkyne hydrogenation, industrial ammonia synthesis, hydrogenation of carbon oxides to prepare methanol, etc.). Since increasing the temperature can significantly accelerate the rate of catalytic reactions, the current chemical hydrogenation process in industry is mainly thermal catalysis. In recent years, with the attention and emphasis on environmental pollution and energy shortage problems, electrochemical reduction has also made great progress. The electrocatalytic reduction process can store renewable "green electricity" energy, which is restricted by region, season, and intermittency, in the form of chemical energy, showing obvious potential competitive advantages.

[0004] However, the current traditional electrocatalytic hydrogenation reaction faces practical problems such as high risk coefficients in high-pressure hydrogen storage and transportation, low energy efficiency, poor cycle stability, and difficult selective separation, which have become the bottleneck restricting electrocatalytic hydrogenation technology.

[0005] Based on the defects existing in the current electrocatalytic reaction, it is necessary to improve it. Summary of the Invention

[0006] In view of this, the present invention provides an electrocatalytic hydrogenation reaction device and method to solve or at least partially solve the problems existing in the prior art.

[0007] In a first aspect, the present invention provides an electrocatalytic hydrogenation reaction device, comprising:

[0008] A hydrogenation reactor with a hollow interior;

[0009] An inert electrode located within the hydrogenation reactor;

[0010] A proton exchange membrane located within the hydrogenation reactor, with the inert electrode on the inner side of the proton exchange membrane. A first electrolysis chamber is formed by enclosing between the proton exchange membrane and the hydrogenation reactor;

[0011] A metal membrane electrode located within the hydrogenation reactor, with the proton exchange membrane on the inner side of the metal membrane electrode. A second electrolysis chamber is formed by enclosing between the metal membrane electrode, the hydrogenation reactor, and the proton exchange membrane. A reaction chamber is formed between the metal membrane electrode and the inner wall of the hydrogenation reactor;

[0012] A first electrolyte supply unit for supplying a first electrolyte to the first electrolysis chamber;

[0013] A second electrolyte supply unit for supplying a second electrolyte to the second electrolysis chamber;

[0014] A reaction substrate supply unit for supplying a reaction substrate to the reaction chamber;

[0015] A power supply unit, with its positive electrode electrically connected to the inert electrode and its negative electrode electrically connected to the metal membrane electrode;

[0016] Wherein, the metal used for the metal membrane electrode is a metal that is easy to form metal hydride.

[0017] Preferably, in the electrocatalytic hydrogenation reaction device, the metal that is easy to form metal hydride includes at least one of La series metals, Pd, Ru, and transition metals.

[0018] Preferably, in the electrocatalytic hydrogenation reaction device, the metal membrane electrode includes a hydrophobic coating, a metal thin film layer, and a catalyst layer stacked in sequence. Among them, the catalyst layer is on the side close to the reaction chamber, and the hydrophobic coating is on the side close to the second electrolysis chamber; the metal used for the metal thin film layer is a metal that is easy to form metal hydride.

[0019] Preferably, in the electrocatalytic hydrogenation reaction device, the first electrolyte supply unit includes:

[0020] A first electrolyte storage tank;

[0021] A first liquid inlet pipe, one end of which is communicated with the first electrolyte storage tank and the other end of which is communicated with one side of the first electrolysis chamber;

[0022] A first liquid outlet pipe, one end of which is communicated with the other side of the first electrolysis chamber and the other end of which is communicated with the first electrolyte storage tank;

[0023] A first peristaltic pump, which is located on the first liquid inlet pipe or the first liquid outlet pipe.

[0024] Preferably, for the electrocatalytic hydrogenation reaction device, the second electrolyte supply unit includes:

[0025] A second electrolyte storage tank;

[0026] A second liquid inlet pipe, one end of which is communicated with the second electrolyte storage tank and the other end of which is communicated with one side of the second electrolysis chamber;

[0027] A second liquid outlet pipe, one end of which is communicated with the other side of the second electrolysis chamber and the other end of which is communicated with the second electrolyte storage tank;

[0028] A second peristaltic pump, which is located on the second liquid inlet pipe or the second liquid outlet pipe.

[0029] Preferably, for the electrocatalytic hydrogenation reaction device, the reaction substrate supply unit includes:

[0030] A reaction substrate storage tank;

[0031] A reaction substrate feed pipe, one end of which is communicated with the reaction substrate storage tank and the other end of which is communicated with the reaction chamber, and the reaction substrate feed pipe is provided with a valve and a flow controller.

[0032] Preferably, for the electrocatalytic hydrogenation reaction device, both the first electrolyte and the second electrolyte are alkaline solutions;

[0033] and / or, the reaction substrate includes CO 2 、CO、N 2 、O 2 、alkynes, alkenes, aldehydes, carboxylic acids, aromatic hydrocarbons, aromatic hydrocarbon derivatives or at least one of them;

[0034] and / or, the inert electrode includes one of a graphite electrode, a platinum electrode and a gold electrode.

[0035] Preferably, for the electrocatalytic hydrogenation reaction device, the alkaline solution includes at least one of a sodium carbonate solution, a potassium carbonate solution, a sodium bicarbonate solution, a potassium bicarbonate solution, a sodium hydroxide solution and a potassium hydroxide solution.

[0036] Preferably, in the electrocatalytic hydrogenation reaction device, the power supply unit is used to provide a voltage of -30V to 30V.

[0037] In a second aspect, the present invention also provides an electrocatalytic hydrogenation reaction method, including the following steps;

[0038] Provide the electrocatalytic hydrogenation reaction device described above;

[0039] Introduce a first electrolyte into the first electrolysis chamber;

[0040] Introduce a second electrolyte into the second electrolysis chamber;

[0041] Introduce a reaction substrate into the reaction chamber;

[0042] Electrically connect the positive electrode of the power supply unit to the inert electrode and the negative electrode to the metal membrane electrode, and control the voltage to carry out the electrocatalytic hydrogenation reaction.

[0043] An electrocatalytic hydrogenation reaction device and method of the present invention have the following technical effects compared with the prior art:

[0044] The electrocatalytic hydrogenation reaction device of the present invention includes a hydrogenation reactor, an inert electrode, a proton exchange membrane, a metal membrane electrode, and a power supply unit; the metal membrane electrode can electrochemically reduce hydrogen ions generated at the anode to hydrogen atoms, and the generated hydrogen atoms can combine with the metal membrane electrode to form metal hydrides. The metal hydrides can improve the electrocatalytic reduction hydrogenation performance on the catalyst surface through the form of active hydrogen transfer, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety due to avoiding the use of hydrogen; the metal membrane electrode can avoid the use of hydrogen in the catalytic hydrogenation reaction, improve the reaction safety and at the same time reduce the difficulty of selective separation of gas products; in addition, the metal membrane electrode can also promote the generation of active hydrogen atoms and their migration to the catalyst surface, which is beneficial to the improvement of catalytic reaction activity; at the same time, the electric energy provided by the power supply unit can not only promote the electron transfer between the catalyst and the reactant molecules, but also break the limitation of the thermodynamic equilibrium, enabling the catalytic hydrogenation reaction to proceed with high activity, high selectivity and high stability under mild conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0046] Figure 1 It is a schematic three-dimensional structure diagram of the electrocatalytic hydrogenation reaction device in one embodiment of the present invention;

[0047] Figure 2 It is a schematic plan view of an electrocatalytic hydrogenation reaction device in one embodiment of the present invention;

[0048] Figure 3 It is a schematic structural view of a metal film electrode in one embodiment of the present invention;

[0049] Figure 4 It is a schematic structural view of a second electrolyte supply unit in one embodiment of the present invention;

[0050] Figure 5 It is a schematic structural view of a reaction substrate supply unit in one embodiment of the present invention. Detailed implementation manners

[0051] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. Usually, the components of the embodiments of the present invention described and illustrated in the accompanying drawings here can be arranged and designed in various different configurations.

[0052] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed present invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts fall within the scope of protection of the present invention.

[0053] It should be noted that: similar reference numerals and letters denote similar items in the following drawings. Therefore, once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings.

[0054] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by terms such as "upper" is based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship when the product of this invention is usually placed, or the orientation or positional relationship commonly understood by those skilled in the art. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present invention.

[0055] In addition, terms such as "first" and "second" are only used for descriptive distinction and cannot be understood as indicating or implying relative importance.

[0056] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0057] An electrocatalytic hydrogenation reaction device is provided in an embodiment of the present application, as Figures 1-2 shown, including:

[0058] A hydrogenation reactor 1 with a hollow interior;

[0059] An inert electrode 2 located inside the hydrogenation reactor 1;

[0060] A proton exchange membrane 3 located inside the hydrogenation reactor 1. The inert electrode 2 is located inside the proton exchange membrane 3, and a first electrolysis chamber 11 is formed by enclosing between the proton exchange membrane 3 and the hydrogenation reactor 1;

[0061] A metal membrane electrode 4 located inside the hydrogenation reactor 1. The proton exchange membrane 3 is located inside the metal membrane electrode 4. A second electrolysis chamber 12 is formed by enclosing between the metal membrane electrode 4, the hydrogenation reactor 1, and the proton exchange membrane 3, and a reaction chamber 13 is formed between the metal membrane electrode 4 and the inner wall of the hydrogenation reactor 1;

[0062] A first electrolyte supply unit for supplying a first electrolyte to the first electrolysis chamber 11;

[0063] A second electrolyte supply unit for supplying a second electrolyte to the second electrolysis chamber 12;

[0064] A reaction substrate supply unit for supplying a reaction substrate to the reaction chamber 13;

[0065] A power supply unit 5, whose positive electrode is electrically connected to the inert electrode 2 and whose negative electrode is electrically connected to the metal membrane electrode 4;

[0066] Wherein, the metal used for the metal membrane electrode 4 is a metal that is easy to form metal hydrides.

[0067] It should be noted that the electrocatalytic hydrogenation reaction device of the present application includes a hydrogenation reactor 1, an inert electrode 2, a proton exchange membrane 3, a metal membrane electrode 4, and a power supply unit 5; among them, the interior of the hydrogenation reactor 1 is hollow, and its specific shape is determined according to actual conditions. For example, the hydrogenation reactor 1 is in the shape of a hollow cylinder; the inert electrode 2 is located inside the hydrogenation reactor 1, the proton exchange membrane 3 is located inside the hydrogenation reactor 1 and is sleeved outside the inert electrode 2, and a first electrolysis chamber 11 is formed by enclosing between the proton exchange membrane 3 and the hydrogenation reactor 1; specifically, the proton exchange membrane 3 is in the shape of a hollow cylinder and both ends abut against the inner wall of the hydrogenation reactor 1; the metal membrane electrode 4 is located inside the hydrogenation reactor 1 and is sleeved outside the proton exchange membrane 3. Specifically, the metal membrane electrode 4 is in the shape of a hollow cylinder and both ends abut against the inner wall of the hydrogenation reactor 1; a second electrolysis chamber 12 is formed by enclosing between the metal membrane electrode 4, the hydrogenation reactor 1, and the proton exchange membrane 3; a reaction chamber 13 is formed between the metal membrane electrode 4 and the inner wall of the hydrogenation reactor 1; the power supply unit 5 is used to provide voltage, the positive electrode of the power supply unit 5 is electrically connected to the inert electrode 2, and the negative electrode is electrically connected to the metal membrane electrode 4; when the electrocatalytic hydrogenation reaction device of the present application is in use, a first electrolyte is introduced into the first electrolysis chamber, and a second electrolyte is introduced into the second electrolysis chamber; a reaction substrate is introduced into the reaction chamber, the positive electrode of the power supply unit is electrically connected to the inert electrode, and the negative electrode is electrically connected to the metal membrane electrode, and the voltage is controlled to carry out an electrocatalytic hydrogenation reaction; in the electrocatalytic hydrogenation reaction device of the present application, since the metal used for the metal membrane electrode 4 is a metal that is easy to form metal hydrides, the metal membrane electrode can electrochemically reduce hydrogen ions generated at the anode (i.e., the inert electrode) to hydrogen atoms, and the generated hydrogen atoms can combine with the metal membrane electrode to form metal hydrides. The metal hydrides can improve the electrocatalytic reduction hydrogenation performance on the catalyst surface through the form of active hydrogen transfer, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety due to avoiding the use of hydrogen; the metal membrane electrode can avoid the use of hydrogen in the catalytic hydrogenation reaction, improve the reaction safety and at the same time reduce the difficulty of selective separation of gas products; in addition, the metal membrane electrode can also promote the generation of active hydrogen atoms and their migration to the catalyst surface, which is beneficial to the improvement of catalytic reaction activity; at the same time, the electric energy provided by the power supply unit can not only promote the electron transfer between the catalyst and the reactant molecules, but also break the limitation of the thermodynamic equilibrium, so that the catalytic hydrogenation reaction can proceed with high activity, high selectivity and high stability under mild conditions. This device is applicable to electrocatalytic hydrogenation reduction of substrates such as CO 2 , CO, N 2 , O 2 , alkynes, alkenes, aldehydes, carboxylic acids, aromatic hydrocarbons, etc., providing important technical support for a sustainable catalytic hydrogenation reaction route with high performance, low cost, long life and high safety.

[0068] In the above embodiments, the inert electrode 2 can electrolyze water to generate oxygen and hydrogen ions. The first electrolyte and the second electrolyte are separated by a proton exchange membrane 3. The protons generated on the inert electrode 2 can diffuse through the first electrolyte to the proton exchange membrane 3, and then pass through the proton exchange membrane 3 into the second electrolyte; the inert electrode 2, the proton exchange membrane 3, and the metal film electrode 4 are all hermetically connected to the hydrogenation reactor 1 through seals.

[0069] In some embodiments, the metals that are prone to form metal hydrides include at least one of La series metals, Pd, Ru, and transition metals.

[0070] In some embodiments, please refer to Figure 3 As shown, the metal film electrode 4 includes a hydrophobic coating 41, a metal thin film layer 42, and a catalyst layer 43 stacked in sequence. Among them, the catalyst layer 43 is in contact with the reaction substrate on the side close to the reaction chamber 13, and the hydrophobic coating 41 is in contact with the second electrolyte on the side close to the second electrolysis chamber 12; the metal used for the metal thin film layer 42 is a metal that is prone to form metal hydrides.

[0071] In the above embodiments, the metal film electrode 4 is electrically connected to the negative electrode of the power supply unit 5 through a wire, and can electrochemically reduce the protons diffused to the electrode surface in the second electrolyte to hydrogen atoms to form metal hydrides, and can transfer the active hydrogen of the metal hydrides to the catalyst surface to participate in the hydrogenation reduction reaction; the hydrophobic layer 41 can prevent the second electrolyte solution from seeping into the hydrogenation reaction system; the metal thin film layer 42 can be a metal that is prone to form metal hydrides such as palladium, ruthenium, La series metals, and transition metals, and the thickness of the metal thin film layer 42 is 10-100 μm; the metal thin film layer 42 can electrocatalytically reduce the hydrogen ions generated by the inert electrode to hydrogen atoms, and the generated hydrogen atoms combine with the metal thin film to form metal hydrides, and the active hydrogen atoms of the metal hydrides can be transferred to the catalyst surface to initiate a high-performance hydrogenation reaction; the hydrogenation reaction triggered by the transfer of active hydrogen atoms of metal hydrides includes the electrocatalytic hydrogenation of inert inorganic small molecules and organic small molecules containing unsaturated functional groups; the catalyst layer 43 can be loaded on the metal thin film layer 42 by means of deposition, impregnation, spraying, etc., and the dosage of the catalyst layer 43 is 2-100 mg.

[0072] In some embodiments, by installing a support material in the hydrogenation reactor 1, the metal film electrode 4 is fixed on the support material, and then the metal film electrode 4 is installed in the hydrogenation reactor 1.

[0073] Specifically, the catalyst used for the catalyst layer 43 can be one or more of palladium-based catalysts and copper-based catalysts, such as one or more selected from palladium, copper and their alloys, oxides and hydroxides; preferably, the copper-based catalyst is Cu nanoparticles, Cu 2 O nanoparticles and Cu / Cu2 one or more of the mixture of O; the hydrophobic material used for the hydrophobic layer 41 can be polytetrafluoroethylene, polycarbonate, etc.

[0074] In some embodiments, the first electrolyte supply unit includes:

[0075] a first electrolyte storage tank;

[0076] a first liquid inlet pipe, one end of which is communicated with the first electrolyte storage tank and the other end of which is communicated with one side of the first electrolytic chamber;

[0077] a first liquid outlet pipe, one end of which is communicated with the other side of the first electrolytic chamber and the other end of which is communicated with the first electrolyte storage tank;

[0078] a first peristaltic pump, which is located on the first liquid inlet pipe or the first liquid outlet pipe.

[0079] In some embodiments, please refer to Figure 4 as shown, the second electrolyte supply unit includes:

[0080] a second electrolyte storage tank 6;

[0081] a second liquid inlet pipe 61, one end of which is communicated with the second electrolyte storage tank 6 and the other end of which is communicated with one side of the second electrolytic chamber 12.

[0082] In some embodiments, the second electrolyte supply unit further includes:

[0083] a second liquid outlet pipe 62, one end of which is communicated with the other side of the second electrolytic chamber 12 and the other end of which is communicated with the second electrolyte storage tank 6.

[0084] In some embodiments, the second electrolyte supply unit further includes:

[0085] a second peristaltic pump 63, which is located on the second liquid inlet pipe 61 or the second liquid outlet pipe 62.

[0086] In the above embodiments, the second electrolyte is stored in the second electrolyte storage tank 6. After the second electrolyte storage tank 6 is opened, the second electrolyte enters the second electrolytic chamber 12 through the second liquid inlet pipe 61; further, if the second electrolyte supply unit further includes the second liquid outlet pipe 62, the remaining second electrolyte in the second electrolytic chamber 12 can return to the second electrolytic chamber 12 through the second liquid outlet pipe 62; at the same time, a second peristaltic pump 63 can also be provided on the second liquid inlet pipe 61 or the second liquid outlet pipe 62. By providing the second peristaltic pump 63, the second electrolyte can be circulated at a set flow rate. Specifically, the circulation flow rate of the second peristaltic pump 63 is 5-500 mL / min.

[0087] The first electrolyte supply unit can operate in the same manner as the second electrolyte supply unit. The first peristaltic pump can circulate the first electrolyte at a set flow rate. Specifically, the circulation flow rate of the first peristaltic pump is 5 - 500 mL / min. Both the second liquid inlet pipe 61 and the second liquid outlet pipe 62 are hermetically connected to the second electrolyte storage tank 6 through seals; the first liquid inlet pipe and the first liquid outlet pipe are hermetically connected to the first electrolyte storage tank through seals.

[0088] In some embodiments, the reaction substrate supply unit includes:

[0089] A reaction substrate storage tank;

[0090] A reaction substrate feed pipe, one end of which is connected to the reaction substrate storage tank and the other end is connected to the reaction chamber. The reaction substrate feed pipe is provided with a valve and a flow controller.

[0091] Specifically, the reaction substrate supply unit includes a liquid reaction substrate supply unit and / or a gaseous reaction substrate supply unit; please refer to Figure 5 As shown, the gaseous reaction substrate supply unit includes: a gaseous reaction substrate storage tank 7, which stores a gaseous reaction substrate; the gaseous reaction substrate storage tank 7 is connected to the reaction chamber 13 through a gaseous reaction substrate feed pipe 71. The gaseous reaction substrate feed pipe 71 is provided with a valve 72 and a flow controller 73; the flow controller 73 can be a mass flow meter, and the mass flow meter can control the flow rate of the gaseous reaction substrate within the range of 5 - 500 mL / min. The gaseous reaction substrate feed pipe 71 is hermetically connected to the gaseous reaction substrate storage tank 7 and the reaction chamber 13 through seals.

[0092] The liquid reaction substrate supply unit includes: a liquid reaction substrate storage tank 74, which stores a liquid reaction substrate; the liquid reaction substrate storage tank 74 is connected to the reaction chamber 13 through a liquid reaction substrate feed pipe 75. The liquid reaction substrate feed pipe 75 is provided with a valve 72 and a flow controller 73; the flow controller 73 can be a peristaltic pump, and the peristaltic pump can control the flow rate of the liquid reaction substrate within the range of 5 - 500 mL / min. The liquid reaction substrate feed pipe 75 is hermetically connected to the liquid reaction substrate storage tank 74 and the reaction chamber 13 through seals.

[0093] In some embodiments, a collecting flask is further included. The collecting flask is used to collect the reaction products and discharge gases; after the gaseous reaction substrate is catalytically hydrogenated, the product outlet is directly connected to a chromatograph or a mass spectrometer for on-line analysis; after the liquid reaction substrate is catalytically hydrogenated, the product is collected by the collecting flask and analyzed by means such as NMR.

[0094] In some embodiments, a detection and analysis instrument 76 is further included. The detection and analysis instrument 76 is communicated with the reaction chamber 13, and the product after the electrocatalytic hydrogenation reaction enters the detection and analysis instrument 76 for detection and analysis. For example, the detection and analysis instrument 76 can be a chromatograph, a nuclear magnetic resonance instrument, a mass spectrometer, etc.

[0095] In some embodiments, both the first electrolyte and the second electrolyte are alkaline solutions;

[0096] And / or, the reaction substrate includes CO 2 、CO, N 2 、O 2 、alkynes, alkenes, aldehydes, carboxylic acids, aromatic hydrocarbons, aromatic hydrocarbon derivatives, or at least one of them;

[0097] And / or, the inert electrode 2 includes one of a graphite electrode, a platinum electrode, and a gold electrode.

[0098] In the above embodiments, the reaction substrate can be a mixture of CO and N 2 , and urea can be prepared by hydrogenating this mixture.

[0099] Specifically, the aromatic hydrocarbon derivatives are toluene, ethylbenzene, benzaldehyde, benzoic acid, nitrobenzene, etc.

[0100] In some embodiments, the alkaline solution includes at least one of a sodium carbonate solution, a potassium carbonate solution, a sodium bicarbonate solution, a potassium bicarbonate solution, a sodium hydroxide solution, and a potassium hydroxide solution.

[0101] In some embodiments, the power supply unit 5 is used to provide a voltage of -30V to 30V.

[0102] Specifically, the power supply unit 5 can adopt an electrochemical workstation. The electrochemical workstation adjusts the external voltage intensity and the electrolysis mode. The electrochemical workstation can adjust the applied voltage. The electrochemical workstation can connect the inert electrode and the metal film electrode through the electrolyte solution via a wire to form a closed electrolysis circuit.

[0103] Based on the same concept, the embodiment of the present application also provides an electrocatalytic hydrogenation reaction method, including the following steps;

[0104] S1. Provide the above-mentioned electrocatalytic hydrogenation reaction device;

[0105] S2. Introduce the first electrolyte into the first electrolysis chamber;

[0106] S3. Introduce the second electrolyte into the second electrolysis chamber;

[0107] S4. Introduce the reaction substrate into the reaction chamber;

[0108] S5. Electrically connect the positive electrode of the power supply unit to the inert electrode and the negative electrode to the metal film electrode, and control the voltage to carry out the electrocatalytic hydrogenation reaction.

[0109] In the above embodiments, the first electrolyte and the second electrolyte are circulated at a set flow rate by a peristaltic pump; the reaction substrate is introduced into the reaction chamber, and the flow rate of the gaseous reaction substrate is controlled by a mass flow meter or the flow rate of the liquid reaction substrate is controlled by a peristaltic pump; the external voltage intensity and the electrolysis mode are adjusted by an electrochemical workstation; the catalyst efficiently catalyzes the hydrogenation reaction under the action of an electric field.

[0110] In the industrial process of catalytic hydrogenation reaction, a temperature of usually over 500 °C (such as in ammonia synthesis) is required. The harsh reaction conditions will lead to huge energy consumption, trigger multiple side reactions to occur simultaneously, the high-temperature reaction environment has relatively high requirements for equipment, and in addition, the catalyst is prone to coking and deactivation under high-temperature conditions. There are still many problems in many aspects of simple thermal reaction. In addition, high-pressure hydrogen is often required in the catalytic hydrogenation reaction, which poses a serious threat to safety production. However, in the electrocatalytic hydrogenation reaction method of the present application, a metal film electrode is used as the cathode, which can convert the hydrogen ions obtained by electrolyzing water into highly active hydrogen atoms on the metal film electrode, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety due to avoiding the use of hydrogen, and thus has broad industrial application prospects.

[0111] The following further illustrates the electrocatalytic hydrogenation reaction method of the present application with specific embodiments. This part further illustrates the content of the present invention in combination with specific embodiments, but should not be construed as a limitation to the present invention. Unless otherwise specified, the technical means adopted in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0112] Example 1

[0113] This example provides an electrocatalytic hydrogenation reaction method, including the following steps:

[0114] S1. Provide Figure 1 the electrocatalytic hydrogenation reaction device shown;

[0115] S2. Introduce the first electrolyte into the first electrolysis chamber;

[0116] S3. Introduce the second electrolyte into the second electrolysis chamber;

[0117] S4. Introduce the reaction substrate into the reaction chamber;

[0118] S5. Electrically connect the positive electrode of the power supply unit to the inert electrode and the negative electrode to the metal film electrode, and control the voltage to carry out the electrocatalytic hydrogenation reaction;

[0119] Among them, the first electrolyte and the second electrolyte are both sodium carbonate solutions, and the flow rates of the first electrolyte and the second electrolyte are 100 mL / min; the power supply unit is an electrochemical workstation. Set the electrochemical workstation to the constant voltage electrolysis mode, with a voltage intensity of 0.5 V, and the reaction substrate is CO 2 , and CO 2 is introduced for the hydrogenation reaction. The reaction gas product enters the chromatograph for quantitative analysis, and the reaction liquid product is collected by a liquid collection bottle and then quantitatively analyzed by nuclear magnetic resonance and mass spectrometry.

[0120] Examples 2 to 16

[0121] The electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Example 1, except that the voltage intensities are controlled to be -0.6 V; -0.7 V; -0.8 V; -0.9 V; -1.0 V; -1.1 V; -1.2 V; -1.3 V; -1.4 V; -1.5 V; -1.6 V; -1.7 V; -1.8 V; -1.9 V; -2.0 V respectively.

[0122] Examples 17 to 22

[0123] The electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Example 1, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0124] Examples 23 to 28

[0125] The electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Example 2, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0126] Examples 29 to 34

[0127] The electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Example 3, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0128] Examples 35 to 40

[0129] The electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Example 4, except that CO 2 is adjusted to CO, N 2 , O 2, acetylene, furfural, benzene and its derivatives (specifically toluene).

[0130] Examples 41 - 46

[0131] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 5, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0132] Examples 47 - 52

[0133] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 6, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0134] Examples 53 - 58

[0135] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 7, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0136] Examples 59 - 64

[0137] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 8, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0138] Examples 65 - 70

[0139] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 9, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0140] Examples 71 - 76

[0141] The electrocatalytic hydrogenation reaction method provided by the embodiment of the present application is the same as that of Example 10, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0142] Examples 77 - 82

[0143] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 11, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0144] Examples 83 - 88

[0145] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 12, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0146] Examples 89 - 94

[0147] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 13, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0148] Examples 95 - 100

[0149] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 14, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0150] Examples 101 - 106

[0151] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 15, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0152] Examples 107 - 112

[0153] The electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Example 16, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).

[0154] In summary, the above embodiments respectively compared the catalytic hydrogenation performances of CO 2 , CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives under different electrolytic voltage conditions. It was found that: the electrolysis process is crucial for the active hydrogen transfer process based on the metal membrane electrode; the electrocatalytic hydrogenation reaction of the present application is carried out at room temperature, and the catalyst exhibits excellent reaction activity, selectivity and stability; when hydrogen ions generated by the inert electrode during the electrolysis process diffuse and transfer to the membrane electrode, metal hydrides can be electrolytically reduced on the membrane electrode, and the active hydrogen atoms of the hydrides can transfer to the catalyst surface to promote the catalytic hydrogenation process of the reactants, effectively avoiding the use of hydrogen in the conventional catalytic hydrogenation reaction. Therefore, the electrocatalytic hydrogenation reaction device and method of the present application have obvious advantages in the catalytic hydrogenation reaction.

[0155] The above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An electrocatalytic hydrogenation reaction method, characterized in that, it includes: providing an electrocatalytic hydrogenation reaction device; The electrocatalytic hydrogenation reaction device includes: a hydrogenation reactor with a hollow interior; an inert electrode located inside the hydrogenation reactor; a proton exchange membrane located inside the hydrogenation reactor, the inert electrode is located inside the proton exchange membrane, and a first electrolytic chamber is formed by enclosing between the proton exchange membrane and the hydrogenation reactor; a metal membrane electrode located inside the hydrogenation reactor, the proton exchange membrane is located inside the metal membrane electrode, a second electrolytic chamber is formed by enclosing between the metal membrane electrode, the hydrogenation reactor, and the proton exchange membrane, and a reaction chamber is formed between the metal membrane electrode and the inner wall of the hydrogenation reactor; a first electrolyte supply unit for supplying a first electrolyte to the first electrolytic chamber; a second electrolyte supply unit for supplying a second electrolyte to the second electrolytic chamber; a reaction substrate supply unit for supplying a reaction substrate to the reaction chamber; a power supply unit, whose positive electrode is electrically connected to the inert electrode and whose negative electrode is electrically connected to the metal membrane electrode; wherein, the metal used for the metal membrane electrode is a metal that is easy to form metal hydride; The metal that is easy to form metal hydride includes at least one of La series metals, Pd, Ru, and transition metals; The metal membrane electrode includes a hydrophobic coating, a metal thin film layer, and a catalyst layer stacked in sequence, wherein the catalyst layer is on the side close to the reaction chamber, and the hydrophobic coating is on the side close to the second electrolytic chamber; the metal used for the metal thin film layer is a metal that is easy to form metal hydride; The electrocatalytic hydrogenation reaction method includes: introducing a first electrolyte into the first electrolytic chamber; introducing a second electrolyte into the second electrolytic chamber; introducing a reaction substrate into the reaction chamber; electrically connecting the positive electrode of the power supply unit to the inert electrode and the negative electrode to the metal membrane electrode, and controlling the voltage to carry out an electrocatalytic hydrogenation reaction; Both the first electrolyte and the second electrolyte are alkaline solutions; The reaction substrate includes CO 2 , CO, N 2 , O 2 , at least one of acetylene, furfural, benzene, and toluene; The alkaline solution is a sodium carbonate solution; The power supply unit is used to provide a voltage of -0.6V to 5.0V.

2. The electrocatalytic hydrogenation reaction method according to claim 1, characterized in that, The first electrolyte supply unit includes: a first electrolyte storage tank; a first liquid inlet pipe, one end of which is communicated with the first electrolyte storage tank and the other end is communicated with one side of the first electrolytic chamber; a first liquid outlet pipe, one end of which is communicated with the other side of the first electrolytic chamber and the other end is communicated with the first electrolyte storage tank; a first peristaltic pump located on the first liquid inlet pipe or the first liquid outlet pipe.

3. The electrocatalytic hydrogenation reaction method according to claim 1, characterized in that, The second electrolyte supply unit includes: a second electrolyte storage tank; a second liquid inlet pipe, one end of which is communicated with the second electrolyte storage tank and the other end is communicated with one side of the second electrolytic chamber; a second liquid outlet pipe, one end of which is communicated with the other side of the second electrolytic chamber and the other end is communicated with the second electrolyte storage tank; a second peristaltic pump located on the second liquid inlet pipe or the second liquid outlet pipe.

4. The electrocatalytic hydrogenation reaction method according to claim 1, characterized in that, the reaction substrate supply unit includes: a reaction substrate storage tank; a reaction substrate feed pipe, one end of which is communicated with the reaction substrate storage tank and the other end of which is communicated with the reaction chamber, and the reaction substrate feed pipe is provided with a valve and a flow controller.

5. The electrocatalytic hydrogenation reaction method according to claim 1, characterized in that, the inert electrode includes one of a graphite electrode, a platinum electrode, and a gold electrode.

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