WO2024109705A1 - 一种电催化加氢反应装置及方法 - Google Patents

一种电催化加氢反应装置及方法 Download PDF

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WO2024109705A1
WO2024109705A1 PCT/CN2023/132719 CN2023132719W WO2024109705A1 WO 2024109705 A1 WO2024109705 A1 WO 2024109705A1 CN 2023132719 W CN2023132719 W CN 2023132719W WO 2024109705 A1 WO2024109705 A1 WO 2024109705A1
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electrode
electrolyte
reaction
hydrogenation reaction
metal
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French (fr)
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张小龙
王光明
成会明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells

Definitions

  • the present invention relates to the technical field of catalytic hydrogenation reaction, and in particular to an electrocatalytic hydrogenation reaction device and method.
  • Catalytic hydrogenation reaction is one of the most important chemical processes and plays a very important role in human production and life.
  • CO2 , CO, N2 , O2 and other inorganic small molecules as basic raw materials, high value-added fuels or chemical products can be obtained through catalytic hydrogenation reduction;
  • catalytic hydrogenation of unsaturated aromatics is a key process in liquid organic hydrogen storage technology;
  • catalytic hydrogenation of alkynes, aromatic heterocycles, cyanides, aldehydes, ketones, imines, oximes, etc. plays a pivotal role in the production process of pharmaceutical intermediates and bulk chemicals.
  • the catalytic hydrogenation process in industry is mainly achieved by hydrogen reduction under high temperature and high pressure. The reaction often has the problems of harsh conditions, high energy consumption, complex process and high risk factor. Therefore, it is of great scientific and practical significance to develop a catalytic hydrogenation system that can efficiently and directionally obtain the target product under mild conditions.
  • electrochemical reduction has also made great progress.
  • the electrocatalytic reduction process can store renewable "green electricity” energy that is restricted by regionality, seasonality, and intermittency in the form of chemical energy, showing obvious potential competitive advantages.
  • the present invention proposes an electrocatalytic hydrogenation reaction device and method to solve or at least partially solve the problems existing in the prior art.
  • the present invention provides an electrocatalytic hydrogenation reaction device, comprising:
  • a hydrogenation reactor having a hollow interior
  • a proton exchange membrane which is located in the hydrogenation reactor, the inert electrode is located inside the proton exchange membrane, and the proton exchange membrane and the hydrogenation reactor enclose a first electrolysis chamber;
  • a metal membrane electrode is located in the hydrogenation reactor, the proton exchange membrane is located inside the metal membrane electrode, the metal membrane electrode, the hydrogenation reactor and the proton exchange membrane form a second electrolysis chamber, and a reaction chamber is formed between the metal membrane electrode and the inner wall of the hydrogenation reactor;
  • a first electrolyte supply unit configured to provide a first electrolyte to the first electrolysis chamber
  • a second electrolyte supply unit configured to provide a second electrolyte to the second electrolysis chamber
  • reaction substrate supply unit used for providing a reaction substrate to the reaction chamber
  • a power supply unit wherein the positive electrode is electrically connected to the inert electrode and the negative electrode is electrically connected to the metal film electrode;
  • the metal that is easy to form metal hydride includes at least one of La-based metals, Pd, Ru, and transition metals.
  • the metal membrane electrode includes a hydrophobic coating, a metal film layer, and a catalyst layer stacked in sequence, wherein the catalyst layer is close to one side of the reaction chamber, and the hydrophobic coating is close to one side of the second electrolysis chamber; the metal used in the metal film layer is a metal that is easy to form metal hydride.
  • the first electrolyte supply unit comprises:
  • a first liquid inlet pipe one end of which is connected to the first electrolyte storage tank and the other end of which is connected to one side of the first electrolytic chamber;
  • a first peristaltic pump is located on the first liquid inlet pipe or the first liquid outlet pipe.
  • the second electrolyte supply unit comprises:
  • a second liquid inlet pipe one end of which is connected to the second electrolyte storage tank and the other end of which is connected to one side of the second electrolytic chamber;
  • a second peristaltic pump is located on the second liquid inlet pipe or the second liquid outlet pipe.
  • the reaction substrate supply unit comprises:
  • a reaction substrate feeding pipe one end of which is connected to the reaction substrate storage tank and the other end of which is connected to the reaction chamber, is provided with a valve and a flow controller.
  • the first electrolyte and the second electrolyte are both alkaline solutions;
  • the reaction substrate comprises at least one of CO 2 , CO, N 2 , O 2 , alkynes, olefins, aldehydes, carboxylic acids, aromatic hydrocarbons, and aromatic hydrocarbon derivatives;
  • the inert electrode includes one of a graphite electrode, a platinum electrode, and a gold electrode.
  • the alkali 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.
  • the power supply unit is used to provide a voltage of -30V ⁇ 30V.
  • the present invention also provides an electrocatalytic hydrogenation reaction method, comprising the following steps:
  • the positive electrode of the power supply unit is electrically connected to the inert electrode, the negative electrode is electrically connected to the metal film electrode, and the voltage is controlled to perform an electrocatalytic hydrogenation reaction.
  • the electrocatalytic hydrogenation reaction device of the present invention comprises a hydrogenation reactor, an inert electrode, a proton exchange membrane, a metal film electrode and a power supply unit;
  • the metal film electrode can electrically reduce hydrogen ions generated by the anode to hydrogen atoms, and the generated hydrogen atoms can be combined with the metal film electrode to form metal hydrides, and the metal hydrides can improve the electrocatalytic reduction hydrogenation performance of the catalyst surface in the form of active hydrogen transfer, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety caused by avoiding the use of hydrogen;
  • the metal film electrode can avoid the use of hydrogen in the catalytic hydrogenation reaction, improve the reaction safety and reduce the difficulty of selective separation of gas products;
  • the metal film electrode can also promote the generation of active hydrogen atoms and their migration to the catalyst surface, which is beneficial to the improvement of the 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
  • FIG1 is a schematic diagram of the three-dimensional structure of an electrocatalytic hydrogenation reaction device in one embodiment of the present invention.
  • FIG2 is a schematic diagram of the planar structure of an electrocatalytic hydrogenation reaction device in one embodiment of the present invention.
  • FIG3 is a schematic diagram of the structure of a metal film electrode in one embodiment of the present invention.
  • FIG4 is a schematic structural diagram of a second electrolyte supply unit in one embodiment of the present invention.
  • FIG. 5 is a schematic structural diagram of a reaction substrate supply unit in one embodiment of the present invention.
  • the present application embodiment provides an electrocatalytic hydrogenation reaction device, as shown in Figures 1 and 2, comprising:
  • the hydrogenation reactor 1 is hollow inside;
  • a proton exchange membrane 3 is located in the hydrogenation reactor 1, and the inert electrode 2 is located inside the proton exchange membrane 3.
  • the proton exchange membrane 3 and the hydrogenation reactor 1 enclose a first electrolysis chamber 11;
  • the metal membrane electrode 4 is located in the hydrogenation reactor 1, the proton exchange membrane 3 is located inside the metal membrane electrode 4, the metal membrane electrode 4, the hydrogenation reactor 1, and the proton exchange membrane 3 enclose a second electrolysis chamber 12, and a reaction chamber 13 is formed between the metal membrane electrode 4 and the inner wall of the hydrogenation reactor 1;
  • a first electrolyte supply unit which is used to provide a first electrolyte to the first electrolysis chamber 11;
  • a second electrolyte supply unit which is used to provide a second electrolyte to the second electrolysis chamber 12;
  • a reaction substrate supply unit which is used to provide a reaction substrate to the reaction chamber 13;
  • 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 film electrode 4;
  • the metal used for the metal film electrode 4 is a metal that is easy to form metal hydride.
  • 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; wherein the hydrogenation reactor 1 is hollow inside, and its specific shape is determined according to actual conditions, for example, the hydrogenation reactor 1 is a hollow cylindrical shape; the inert electrode 2 is located in the hydrogenation reactor 1, the proton exchange membrane 3 is located in the hydrogenation reactor 1 and is sleeved on the outside of the inert electrode 2, and the proton exchange membrane 3 and the hydrogenation reactor 1 are enclosed to form a first electrolysis chamber 11; specifically, the proton exchange membrane 3 is a hollow cylindrical shape and both ends abut against the inner wall of the hydrogenation reactor 1; The metal membrane electrode 4 is located in the hydrogenation reactor 1 and is sleeved on the outside of the proton exchange membrane 3.
  • the metal membrane electrode 4 is a hollow cylindrical shape and its two ends are abutted against the inner wall of the hydrogenation reactor 1; the metal membrane electrode 4, the hydrogenation reactor 1, and the proton exchange membrane 3 enclose a second electrolysis chamber 12; a reaction chamber 13 is formed between the metal membrane electrode 4 and the inner wall of the hydrogenation reactor 1; a power supply unit 5 is used to provide voltage, and 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 used, the first electrolyte is introduced into the first electrolysis chamber, and the second electrolyte is introduced into the second electrolysis chamber.
  • a second electrolyte is introduced into the 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, the negative electrode is electrically connected to the metal film electrode, and the voltage is controlled to perform an electrocatalytic hydrogenation reaction; the electrocatalytic hydrogenation reaction device of the present application, since the metal used in the metal film electrode 4 is a metal that is easy to form a metal hydride, the metal film electrode can electrically reduce the hydrogen ions generated by the anode (i.e., the inert electrode) to hydrogen atoms, and the generated hydrogen atoms can combine with the metal film electrode to form a metal hydride, and the metal hydride can improve the electrocatalytic reduction hydrogenation performance of the catalyst surface in the form of active hydrogen transfer, thereby having It can effectively improve the activity of catalytic hydrogenation reaction and the safety brought by avoiding the use of hydrogen; the metal film electrode can avoid the use of hydrogen in catalytic hydrogenation reaction, improve the safety of reaction and reduce
  • This device is suitable for the electrocatalytic hydrogenation reduction of substrates such as CO2 , CO, N2 , O2 , alkynes, alkenes, aldehydes, carboxylic acids, and aromatics, and provides important technical support for high-performance, low-cost, long-life, and high-safety sustainable catalytic hydrogenation reaction routes.
  • substrates such as CO2 , CO, N2 , O2 , alkynes, alkenes, aldehydes, carboxylic acids, and aromatics
  • the inert electrode 2 can electrolyze water to produce oxygen and hydrogen ions.
  • the first electrolyte and the second electrolyte are separated by the proton exchange membrane 3.
  • the protons generated on the inert electrode 2 can diffuse to the proton exchange membrane 3 through the first electrolyte, and then pass through the proton exchange membrane 3 into the second electrolyte; the inert electrode 2, the proton exchange membrane 3, the metal membrane electrode 4 and the hydrogenation reactor 1 are all sealed and connected through a seal.
  • the metal that easily forms metal hydride includes at least one of La-based metals, Pd, Ru, and transition metals.
  • the metal film electrode 4 includes a hydrophobic coating 41, a metal film layer 42, and a catalyst layer 43 stacked in sequence, wherein 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 in the metal film layer 42 is a metal that is easy to form metal hydride.
  • the metal film electrode 4 is electrically connected to the negative electrode of the power supply unit 5 through a wire, and can electrically reduce the protons diffused from the second electrolyte to the electrode surface into hydrogen atoms to form metal hydrides, and can transfer the active hydrogen of the metal hydride to the catalyst surface to participate in the hydrogenation reduction reaction;
  • the hydrophobic layer 41 can prevent the second electrolyte solution from penetrating into the hydrogenation reaction system;
  • the metal film layer 42 can be a metal that is easy to form metal hydrides, such as palladium, ruthenium, La-based metals, transition metals, etc., and the thickness of the metal film layer 42 is 10 ⁇ 100 ⁇ m;
  • the metal film layer 42 can electrocatalyze the reduction of hydrogen ions generated by the inert electrode to hydrogen atoms, and the generated hydrogen atoms are combined with the metal film to form metal hydrides, and the active hydrogen atoms of the metal hydride can be transferred to the catalyst surface to induce a high-performance hydrogenation
  • the metal membrane electrode 4 is installed in the hydrogenation reactor 1 by installing a supporting material in the hydrogenation reactor 1 and fixing the metal membrane electrode 4 on the supporting material.
  • the catalyst used in the catalyst layer 43 may be one or more of a palladium-based catalyst and a copper-based catalyst, for example, one or more selected from palladium, copper and its alloys, oxides and hydroxides; preferably, the copper-based catalyst is one or more of Cu nanoparticles, Cu 2 O nanoparticles and a mixture of Cu/Cu 2 O; the hydrophobic material used in the hydrophobic layer 41 may be polytetrafluoroethylene, polycarbonate, etc.
  • the first electrolyte supply unit includes:
  • a first liquid inlet pipe one end of which is connected to the first electrolyte storage tank and the other end of which is connected to one side of the first electrolytic chamber;
  • a first liquid outlet pipe one end of which is connected to the other side of the first electrolytic chamber and the other end of which is connected to the first electrolyte storage tank;
  • the first peristaltic pump is located on the first liquid inlet pipe or the first liquid outlet pipe.
  • the second electrolyte supply unit includes:
  • a second electrolyte storage tank 6 A second electrolyte storage tank 6;
  • the second liquid inlet pipe 61 has one end connected to the second electrolyte storage tank 6 and the other end connected to one side of the second electrolytic chamber 12 .
  • the second electrolyte supply unit further comprises:
  • One end of the second liquid outlet pipe 62 is connected to the other side of the second electrolytic chamber 12 , and the other end is connected to the second electrolyte storage tank 6 .
  • the second electrolyte supply unit further comprises:
  • the second peristaltic pump 63 is located on the second liquid inlet pipe 61 or the second liquid outlet pipe 62 .
  • the second electrolyte storage tank 6 stores the second electrolyte, and after the second electrolyte storage tank 6 is opened, the second electrolyte enters the second electrolysis chamber 12 through the second liquid inlet pipe 61; further, if the second electrolyte supply unit also includes a second liquid outlet pipe 62, the remaining second electrolyte in the second electrolysis chamber 12 can be returned to the second electrolysis chamber 12 through the second liquid outlet pipe 62; at the same time, a second peristaltic pump 63 can be arranged on the second liquid inlet pipe 61 or the second liquid outlet pipe 62, and the second peristaltic pump 63 can be arranged to circulate the second electrolyte at a set flow rate. Specifically, the circulation flow rate of the second peristaltic pump 63 is 5 ⁇ 500 mL/min.
  • the first electrolyte supply unit can be provided 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.
  • the second liquid inlet pipe 61, the second liquid outlet pipe 62 and the second electrolyte storage tank 6 are all sealed and connected through a seal; the first liquid inlet pipe, the first liquid outlet pipe and the first electrolyte storage tank are sealed and connected through a seal.
  • the reaction substrate supply unit comprises:
  • a reaction substrate feeding pipe has one end connected to the reaction substrate storage tank and the other end connected to the reaction chamber.
  • the reaction substrate feeding pipe is provided with a valve and a flow controller.
  • the reaction substrate supply unit includes a liquid reaction substrate supply unit and/or a gaseous reaction substrate supply unit; please refer to FIG5 , the gaseous reaction substrate supply unit includes: a gaseous reaction substrate storage tank 7, in which the gaseous reaction substrate is stored; the gaseous reaction substrate storage tank 7 is connected to the reaction chamber 13 through a gaseous reaction substrate feed pipe 71, and a valve 72 and a flow controller 73 are provided on the gaseous reaction substrate feed pipe 71; 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 to 500 mL/min.
  • the gaseous reaction substrate feed pipe 71 is sealed and connected to the gaseous reaction substrate storage tank 7 and the reaction chamber 13 through a sealing member.
  • the liquid reaction substrate supply unit includes: a liquid reaction substrate storage tank 74, in which the liquid reaction substrate is stored; the liquid reaction substrate storage tank 74 is connected to the reaction chamber 13 through a liquid reaction substrate feed pipe 75, and a valve 72 and a flow controller 73 are provided on the liquid reaction substrate feed pipe 75; 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 sealed and connected with the liquid reaction substrate storage tank 74 and the reaction chamber 13 through a sealing member.
  • a liquid collecting bottle is also included, which is used to collect reaction products and exhaust gases; after catalytic hydrogenation of the gaseous reaction substrate, the product outlet is directly connected to a chromatograph or mass spectrometer for online analysis; after catalytic hydrogenation of the liquid reaction substrate, the product is collected by the liquid collecting bottle and analyzed by nuclear magnetic resonance and other means.
  • a detection and analysis instrument 76 is also included.
  • the detection and analysis instrument 76 is connected to the reaction chamber 13.
  • the product after the electrocatalytic hydrogenation reaction enters the detection and analysis instrument 76 for detection and analysis.
  • the detection and analysis instrument 76 can be a chromatograph, a nuclear magnetic resonance instrument, a mass spectrometer, etc.
  • the first electrolyte and the second electrolyte are both alkaline solutions
  • the reaction substrate comprises at least one of CO 2 , CO, N 2 , O 2 , alkynes, olefins, aldehydes, carboxylic acids, aromatic hydrocarbons, and aromatic hydrocarbon derivatives;
  • the inert electrode 2 includes one of a graphite electrode, a platinum electrode, and a gold electrode.
  • the reaction substrate may be a mixture of CO and N2 , and the mixture may be hydrogenated to produce urea.
  • the aromatic hydrocarbon derivatives include toluene, ethylbenzene, benzaldehyde, benzoic acid, nitrobenzene and the like.
  • 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.
  • the power supply unit 5 is used to provide a voltage of -30V ⁇ 30V.
  • the power supply unit 5 may adopt an electrochemical workstation, which adjusts the peripheral 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 through the wire to form a closed electrolysis circuit.
  • the embodiment of the present application also provides an electrocatalytic hydrogenation reaction method, comprising the following steps:
  • the positive electrode of the power supply unit is electrically connected to the inert electrode, the negative electrode is electrically connected to the metal film electrode, and the voltage is controlled to perform an electrocatalytic hydrogenation reaction.
  • the first electrolyte and the second electrolyte are circulated at a set flow rate through a peristaltic pump; the reaction substrate is introduced into the reaction chamber, and the flow rate of the gas 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 peripheral voltage intensity and the electrolysis mode are adjusted by the electrochemical workstation; the catalyst efficiently catalyzes the hydrogenation reaction under the action of the electric field.
  • the industrial process of catalytic hydrogenation reaction usually requires a temperature of more than 500°C (such as synthetic ammonia).
  • the harsh reaction conditions will lead to huge energy consumption and trigger multiple side reactions to occur simultaneously.
  • the high-temperature reaction environment also has relatively high requirements for equipment.
  • the catalyst is prone to coking and deactivation under high temperature conditions. There are still many problems in many aspects of simple thermal reactions.
  • high-pressure hydrogen is often required in catalytic hydrogenation reactions, which poses a serious threat to safe production.
  • the electrocatalytic hydrogenation reaction method of the present application uses a metal film electrode as a cathode, which can convert the hydrogen ions obtained by electrolysis of water into highly active hydrogen atoms on the metal film electrode, thereby effectively improving the activity of the catalytic hydrogenation reaction and the safety caused by avoiding the use of hydrogen, and thus has broad prospects for industrial application.
  • This embodiment provides an electrocatalytic hydrogenation reaction method, comprising the following steps:
  • 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, and the electrochemical workstation is set to a constant voltage electrolysis mode with a voltage intensity of 0.5 V.
  • the reaction substrate is CO 2 , and CO 2 is introduced for hydrogenation reaction.
  • the reaction gas products enter the chromatograph for quantitative analysis, and the reaction liquid products are collected by a liquid collection bottle and then quantitatively analyzed by nuclear magnetic resonance and mass spectrometry.
  • the electrocatalytic hydrogenation reaction method provided in the embodiments of the present application is the same as that in Embodiment 1, except that the control voltage intensities are respectively -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.
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 1, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 2, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 3, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 4, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 5, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 6, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 7, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in Embodiment 8, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 9, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 10, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 11, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • 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).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 13, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 14, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • the electrocatalytic hydrogenation reaction method provided in the embodiment of the present application is the same as that in embodiment 15, except that CO 2 is adjusted to CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives (specifically toluene).
  • 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).
  • the above embodiments respectively compare the catalytic hydrogenation performance of CO 2 , CO, N 2 , O 2 , acetylene, furfural, benzene and its derivatives under different electrolysis voltage conditions.
  • the electrolysis process is crucial to 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 the hydrogen ions generated by the inert electrode diffuse and transfer to the membrane electrode during the electrolysis process, they can be electrolytically reduced at the membrane electrode to produce metal hydrides, and the active hydrogen atoms of the hydride can be transferred to the catalyst surface, promoting the catalytic hydrogenation process of the reactants, and effectively avoiding the use of hydrogen in conventional catalytic hydrogenation reactions. Therefore, the electrocatalytic hydrogenation reaction device and method of the present application have obvious advantages in catalytic hydrogenation reactions.

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Abstract

本发明提供了一种电催化加氢反应装置及方法。本发明的电催化加氢反应装置，金属膜电极可以将阳极产生的氢离子电还原为氢原子，并且产生的氢原子能够与金属膜电极结合形成金属氢化物，金属氢化物可以通过活性氢转移的形式提高催化剂表面的电催化还原加氢性能，从而有效提高催化加氢反应的活性和因避免氢气使用带来的安全性；金属膜电极能够避免催化加氢反应中氢气的使用，提高反应安全性的同时还能够降低气体产物的选择性分离难度；同时，供电单元提供的电能，不仅能够促进催化剂与反应物分子间的电子转移，还能够打破热力学平衡的限制，促使催化加氢反应能够在温和条件下高活性、高选择性和高稳定性的进行。

Description

一种电催化加氢反应装置及方法 技术领域
本发明涉及催化加氢反应技术领域，尤其涉及一种电催化加氢反应装置及方法。
 背景技术
催化加氢反应是最重要的化学过程之一，在人类的生产生活中发挥着非常重要的作用。以CO 2、CO、N 2、O 2等无机小分子为基础原料，通过催化加氢还原能够得到高附加值的燃料或化工产品；不饱芳烃的催化加氢是液态有机物储氢技术的关键过程；炔烃、芳杂环、氰类、醛类、酮类、亚胺类、肟等的催化加氢过程在医药中间体和大宗化学品的生产过程起到举足轻重的作用。目前工业上的催化加氢过程主要是在高温、高压下通过氢气还原实现，反应中往往存在条件苛刻、能源消耗大、工艺复杂、危险系数高的难题。因此开发温和条件下高效定向得到目标产物的催化加氢体系具有非常重要的科学和现实意义。
尽管自然界中普遍存在着植物的光合作用、固氮生物的自然固氮以及微生物的酶催化加氢等生物转化过程，但是受限于较低的转化效率、较慢的反应速率、局限的反应条件，很难满足人们的实际生产生活需求。相比之下，化学转化过程可以通过催化剂的设计、反应条件的控制以及催化器件的优化高活性和选择性的得到目标产物，因而获得了广泛的研究和应用（如炔烃氢化、工业合成氨、碳氧化物加氢制备甲醇等）。由于升高温度可以明显加快催化反应的速率，目前工业上的化学加氢过程以热催化为主，近年来随着人们对环境污染和能源短缺问题的关注和重视，电化学还原也获得了长足的发展。电催化还原过程能够将受地域性、季节性、间歇性限制的可再生“绿电”能源以化学能的形式储存起来，表现出明显的潜在竞争优势。
但是目前传统的电催化加氢反应面临着高压氢气储存和运输危险系数高、能源效率低、循环稳定性差、选择性分离困难等实际问题，成为限制电催化加氢技术的瓶颈。
基于目前的电催化反应存在的缺陷，有必要对此进行改进。
 技术问题
有鉴于此，本发明提出了一种电催化加氢反应装置及方法，以解决或至少部分解决现有技术中存在的问题。
 技术解决方案
第一方面，本发明提供了一种电催化加氢反应装置，包括：
加氢反应器，其内部中空；
惰性电极，其位于所述加氢反应器内；
质子交换膜，其位于所述加氢反应器内，所述惰性电极位于所述质子交换膜内侧，所述质子交换膜与所述加氢反应器之间围合形成第一电解腔室；
金属膜电极，其位于所述加氢反应器内，所述质子交换膜位于所述金属膜电极内侧，所述金属膜电极、所述加氢反应器、所述质子交换膜之间围合形成第二电解腔室，所述金属膜电极与所述加氢反应器内壁之间形成反应腔室；
第一电解液供应单元，其用于向所述第一电解腔室提供第一电解液；
第二电解液供应单元，其用于向所述第二电解腔室提供第二电解液；
反应底物供应单元，其用于向所述反应腔室提供反应底物；
供电单元，其正极与所述惰性电极电连接、负极与所述金属膜电极电连接；
其中，所述金属膜电极所采用的金属为易于形成金属氢化物的金属。
优选的是，所述的电催化加氢反应装置，所述易于形成金属氢化物的金属包括La系金属、Pd、Ru、过渡金属中的至少一种。
优选的是，所述的电催化加氢反应装置，所述金属膜电极包括依次叠加的疏水涂层、金属薄膜层、催化剂层，其中，所述催化剂层靠近所述反应腔室一侧，所述疏水涂层靠近所述第二电解腔室一侧；所述金属薄膜层所采用的金属为易于形成金属氢化物的金属。
优选的是，所述的电催化加氢反应装置，所述第一电解液供应单元包括：
第一电解液储罐；
第一进液管，其一端与所述第一电解液储罐连通、另一端与所述第一电解腔室一侧连通；
第一出液管，其一端与所述第一电解腔室另一侧连通、另一端与所述第一电解液储罐连通；
第一蠕动泵，其位于所述第一进液管或第一出液管上。
优选的是，所述的电催化加氢反应装置，所述第二电解液供应单元包括：
第二电解液储罐；
第二进液管，其一端与所述第二电解液储罐连通、另一端与所述第二电解腔室一侧连通；
第二出液管，其一端与所述第二电解腔室另一侧连通、另一端与所述第二电解液储罐连通；
第二蠕动泵，其位于所述第二进液管或第二出液管上。
优选的是，所述的电催化加氢反应装置，所述反应底物供应单元包括：
反应底物储罐；
反应底物进料管，其一端与所述反应底物储罐连通、另一端与所述反应腔室连通，所述反应底物进料管设有阀门和流量控制器。
优选的是，所述的电催化加氢反应装置，所述第一电解液、第二电解液均为碱液；
和/或，所述反应底物包括CO 2、CO、N 2、O 2、炔烃、烯烃、醛、羧酸、芳烃、芳烃衍生物中的至少一种；
和/或，所述惰性电极包括石墨电极、铂电极、金电极中的一种。
优选的是，所述的电催化加氢反应装置，所述碱液包括碳酸钠溶液、碳酸钾溶液、碳酸氢钠溶液、碳酸氢钾溶液、氢氧化钠溶液、氢氧化钾溶液中的至少一种。
优选的是，所述的电催化加氢反应装置，所述供电单元用于提供-30V~30V的电压。
第二方面，本发明还提供了一种电催化加氢反应方法，包括以下步骤；
提供所述的电催化加氢反应装置；
向第一电解腔室内通入第一电解液；
向第二电解腔室内通入第二电解液；
向反应腔室通入反应底物；
将供电单元的正极与惰性电极电连接、负极与金属膜电极电连接，控制电压进行电催化加氢反应。
 有益效果
本发明的一种电催化加氢反应装置及方法、相对于现有技术具有以下技术效果：
本发明的电催化加氢反应装置，包括加氢反应器、惰性电极、质子交换膜、金属膜电极以及供电单元；金属膜电极可以将阳极产生的氢离子电还原为氢原子，并且产生的氢原子能够与金属膜电极结合形成金属氢化物，金属氢化物可以通过活性氢转移的形式提高催化剂表面的电催化还原加氢性能，从而有效提高催化加氢反应的活性和因避免氢气使用带来的安全性；金属膜电极能够避免催化加氢反应中氢气的使用，提高反应安全性的同时还能够降低气体产物的选择性分离难度；另外，金属膜电极还能够促进活性氢原子的产生及其向催化剂表面的迁移，有利于催化反应活性的提高；同时，供电单元提供的电能，不仅能够促进催化剂与反应物分子间的电子转移，还能够打破热力学平衡的限制，促使催化加氢反应能够在温和条件下高活性、高选择性和高稳定性的进行。
 附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明其中一个实施例中电催化加氢反应装置的立体结构示意图；
图2为本发明其中一个实施例中电催化加氢反应装置的平面结构示意图；
图3为本发明其中一个实施例中金属膜电极的结构示意图；
图4为本发明其中一个实施例中第二电解液供应单元的结构示意图；
图5为本发明其中一个实施例中反应底物供应单元的结构示意图。
 本发明的最佳实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。
因此，以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步定义和解释。
在本发明的描述中，需要理解的是，如“上”等指示方位或位置的关系为基于附图所示的方位或位置关系，或者是该发明产品使用时惯常摆放的方位或位置关系，或者是本领域技术人员惯常理解的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的设备或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”等仅用于区分描述，而不能理解为指示或暗示相对重要性。
下面将结合本发明实施方式，对本发明实施方式中的技术方案进行清楚、完整的描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本发明保护的范围。
本申请实施例提供了一种电催化加氢反应装置，如图1~2所示，包括：
加氢反应器1，其内部中空；
惰性电极2，其位于加氢反应器1内；
质子交换膜3，其位于加氢反应器1内，惰性电极2位于质子交换膜3内侧，质子交换膜3与加氢反应器1之间围合形成第一电解腔室11；
金属膜电极4，其位于加氢反应器1内，质子交换膜3位于金属膜电极4内侧，金属膜电极4、加氢反应器1、质子交换膜3之间围合形成第二电解腔室12，金属膜电极4与加氢反应器1内壁之间形成反应腔室13；
第一电解液供应单元，其用于向第一电解腔室11提供第一电解液；
第二电解液供应单元，其用于向第二电解腔室12提供第二电解液；
反应底物供应单元，其用于向反应腔室13提供反应底物；
供电单元5，其正极与惰性电极2电连接、负极与金属膜电极4电连接；
其中，金属膜电极4所采用的金属为易于形成金属氢化物的金属。
需要说明的是，本申请的电催化加氢反应装置，包括加氢反应器1、惰性电极2、质子交换膜3、金属膜电极4以及供电单元5；其中，加氢反应器1内部中空，其具体形状根据实际情况确定，例如加氢反应器1为中空的圆柱体状；惰性电极2位于加氢反应器1内，质子交换膜3位于加氢反应器1内且套设在惰性电极2外侧，质子交换膜3与加氢反应器1之间围合形成第一电解腔室11；具体的，质子交换膜3为中空圆柱体状且两端抵接在加氢反应器1内壁上；金属膜电极4位于加氢反应器1内，且套设在质子交换膜3外侧，具体的，金属膜电极4为中空圆柱体状且两端抵接在加氢反应器1内壁上；金属膜电极4、加氢反应器1、质子交换膜3之间围合形成第二电解腔室12；金属膜电极4与加氢反应器1内壁之间形成反应腔室13；供电单元5，其用于提供电压，供电单元5的正极与惰性电极2电连接、负极与金属膜电极4电连接；本申请的电催化加氢反应装置在使用时，向第一电解腔室内通入第一电解液，向第二电解腔室内通入第二电解液；向反应腔室通入反应底物，将供电单元的正极与惰性电极电连接、负极与金属膜电极电连接，控制电压进行电催化加氢反应；本申请的电催化加氢反应装置，由于金属膜电极4所采用的金属为易于形成金属氢化物的金属，金属膜电极可以将阳极（即惰性电极）产生的氢离子电还原为氢原子，并且产生的氢原子能够与金属膜电极结合形成金属氢化物，金属氢化物可以通过活性氢转移的形式提高催化剂表面的电催化还原加氢性能，从而有效提高催化加氢反应的活性和因避免氢气使用带来的安全性；金属膜电极能够避免催化加氢反应中氢气的使用，提高反应安全性的同时还能够降低气体产物的选择性分离难度；另外，金属膜电极还能够促进活性氢原子的产生及其向催化剂表面的迁移，有利于催化反应活性的提高；同时，供电单元提供的电能，不仅能够促进催化剂与反应物分子间的电子转移，还能够打破热力学平衡的限制，促使催化加氢反应能够在温和条件下高活性、高选择性和高稳定性的进行。本装置适用于CO 2、CO、N 2、O 2、炔烃、烯烃、醛、羧酸、芳烃等底物的电催化加氢还原，为高性能、低成本、长寿命、高安全性的可持续催化加氢反应路线提供了重要的技术支持。
本发明的实施方式
上述实施例中，惰性电极2能够电解水产生氧气和氢离子，第一电解液、第二电解液通过质子交换膜3分隔开，惰性电极2上产生的质子可以通过第一电解液扩散到质子交换膜3上，随后穿过质子交换膜3进入第二电解液中；惰性电极2、质子交换膜3、金属膜电极4与加氢反应器1之间均通过密封件实现密封连接。
在一些实施例中，易于形成金属氢化物的金属包括La系金属、Pd、Ru、过渡金属中的至少一种。
在一些实施例中，请参考图3所示，金属膜电极4包括依次叠加的疏水涂层41、金属薄膜层42、催化剂层43，其中，催化剂层43靠近反应腔室13一侧与反应底物接触，疏水涂层41靠近第二电解腔室12一侧与第二电解液接触；金属薄膜层42所采用的金属为易于形成金属氢化物的金属。
在上述实施例中，金属膜电极4通过导线与供电单元5的负极电连接，能够将第二电解液中扩散到电极表面的质子电还原为氢原子形成金属氢化物，并且能够将金属氢化物的活性氢转移到催化剂表面参与加氢还原反应；疏水层41可以防止第二电解液溶液渗入加氢反应体系中；金属薄膜层42可以是钯、钌、La系金属、过渡金属等易于形成金属氢化物的金属，金属薄膜层42厚度为10~100μm；金属薄膜层42能够电催化惰性电极产生的氢离子还原为氢原子，并且生成的氢原子与金属薄膜结合成金属氢化物，金属氢化物的活性氢原子能够转移至催化剂表面引发高性能加氢反应；基于金属氢化物活性氢原子转移引发的氢化反应包括惰性无机小分子和含有不饱和官能团有机小分子的电催化加氢；催化剂层43可以通过沉积、浸渍、喷涂等手段负载在金属薄膜层42上，催化剂层43的用量为2~100 mg。
在一些实施例中，通过在加氢反应器1内安装支撑材料，金属膜电极4固定在支撑材料上，进而将金属膜电极4安装在加氢反应器1内。
具体的，催化剂层43所采用的催化剂可采用钯基催化剂和铜基催化剂的一种或多种，例如为选自钯、铜及其合金、氧化物和氢氧化物的一种或多种；优选地，铜基催化剂为、Cu纳米颗粒、Cu 2O纳米颗粒和Cu/Cu 2O的混合物中的一种或多种；疏水层41所采用的疏水材料可以为聚四氟乙烯、聚碳酸酯等。
在一些实施例中，第一电解液供应单元包括：
第一电解液储罐；
第一进液管，其一端与第一电解液储罐连通、另一端与第一电解腔室一侧连通；
第一出液管，其一端与第一电解腔室另一侧连通、另一端与第一电解液储罐连通；
第一蠕动泵，其位于第一进液管或第一出液管上。
在一些实施例中，请参考图4所示，第二电解液供应单元包括：
第二电解液储罐6；
第二进液管61，其一端与第二电解液储罐6连通、另一端与第二电解腔室12一侧连通。
在一些实施例中，第二电解液供应单元还包括：
第二出液管62，其一端与第二电解腔室12另一侧连通、另一端与第二电解液储罐6连通。
在一些实施例中，第二电解液供应单元还包括：
第二蠕动泵63，其位于第二进液管61或第二出液管62上。
在上述实施例中，第二电解液储罐6中存储有第二电解液，打开第二电解液储罐6后第二电解液则通过第二进液管61进入第二电解腔室12内；进一步的，若第二电解液供应单元还包括第二出液管62，则第二电解腔室12中的残存的第二电解液可通过第二出液管62返回至第二电解腔室12内；同时还可在第二进液管61或第二出液管62上设置第二蠕动泵63，通过设置第二蠕动泵63可使第二电解液以设定的流速循环，具体的，第二蠕动泵63循环流量为5~500 mL/min。
第一电解液供应单元可采用与第二电解液供应单元相同的方式，第一蠕动泵可使第一电解液以设定的流速循环，具体的，第一蠕动泵循环流量为5~500 mL/min。第二进液管61、第二出液管62与第二电解液储罐6之间均通过密封件密封连通；第一进液管、第一出液管与第一电解液储罐之间通过密封件密封连通。
在一些实施例中，反应底物供应单元包括：
反应底物储罐；
反应底物进料管，其一端与反应底物储罐连通、另一端与反应腔室连通，反应底物进料管设有阀门和流量控制器。
具体的，反应底物供应单元包括液态反应底物供应单元和/或气态反应底物供应单元；请参考图5所示，气态反应底物供应单元包括：气态反应底物储罐7，其内存储有气态反应底物；气态反应底物储罐7通过气态反应底物进料管71与反应腔室13连通，气态反应底物进料管71上设有阀门72和流量控制器73；流量控制器73可为质量流量计，质量流量计可以控制气态反应底物流量在5~500 mL/min范围内。气态反应底物进料管71与气态反应底物储罐7、反应腔室13之间均通过密封件密封连通。
液态反应底物供应单元包括：液态反应底物储罐74，其内存储有液态反应底物；液态反应底物储罐74通过液态反应底物进料管75与反应腔室13连通，液态反应底物进料管75上设有阀门72和流量控制器73；流量控制器73可为蠕动泵，蠕动泵可以控制液态反应底物流量在5-500 mL/min范围内。液态反应底物进料管75与液态反应底物储罐74、反应腔室13之间均通过密封件密封连通。
在一些实施例中，还包括集液瓶，集液瓶用于收集反应产物和排出气体；气体反应底物催化加氢后，产物出口直接与色谱或质谱连接，进行在线分析；液态反应底物催化加氢后，产物由集液瓶收集后通过核磁等手段进行分析。
在一些实施例中，还包括检测分析仪器76，检测分析仪器76与反应腔室13连通，电催化加氢反应后的产物进入检测分析仪器76中进行检测分析，例如，检测分析仪器76可为色谱仪、核磁共振仪、质谱仪等。
在一些实施例中，第一电解液、第二电解液均为碱液；
和/或，反应底物包括CO 2、CO、N 2、O 2、炔烃、烯烃、醛、羧酸、芳烃、芳烃衍生物中的至少一种；
和/或，惰性电极2包括石墨电极、铂电极、金电极中的一种。
上述实施例中，反应底物可为CO、N 2的混合物，该混合物氢化可以制备尿素。
具体的，芳烃衍生物采用甲苯、乙苯、苯甲醛、苯甲酸、硝基苯等。
在一些实施例中，碱液包括碳酸钠溶液、碳酸钾溶液、碳酸氢钠溶液、碳酸氢钾溶液、氢氧化钠溶液、氢氧化钾溶液中的至少一种。
在一些实施例中，供电单元5用于提供-30V~30V的电压。
具体的，供电单元5可采用电化学工作站，电化学工作站调节外设电压强度以及电解模式，电化学工作站可以调节施加电压，电化学工作站通过导线能够将惰性电极和金属膜电极通过电解质溶液连接，构成闭合电解回路。
 工业实用性
基于同一构思，本申请实施例还提供了一种电催化加氢反应方法，包括以下步骤；
S1、提供上述的电催化加氢反应装置；
S2、向第一电解腔室内通入第一电解液；
S3、向第二电解腔室内通入第二电解液；
S4、向反应腔室通入反应底物；
S5、将供电单元的正极与惰性电极电连接、负极与金属膜电极电连接，控制电压进行电催化加氢反应。
在上述实施例中，通过蠕动泵使第一电解液、第二电解液以设定的流速循环；向反应腔室中通入反应底物，并通过质量流量计控制气体反应底物流量或通过蠕动泵控制液体反应底物流量；通过电化学工作站调节外设电压强度以及电解模式；催化剂在电场作用下高效催化加氢反应进行。
催化加氢反应的工业过程，通常需要高达500℃以上的温度（如合成氨），苛刻的反应条件将导致巨大的能源消耗，引发多种副反应同时发生，高温的反应环境对设备要求也比较高，再加上高温条件下催化剂容易结焦失活，单纯的热反应在很多方面还存在许多问题。另外，催化加氢反应中往往需要用到高压氢气，这给安全生产带来严重威胁。而本申请的电催化加氢反应方法，采用金属膜电极作为阴极，其能够将电解水获得的氢离子在金属膜电极上转化为高活性的氢原子，从而有效提高催化加氢反应的活性和因避免氢气使用带来的安全性，因而具有广阔的工业化应用前景。
以下进一步以具体实施例说明本申请的电催化加氢反应方法，本部分结合具体实施例进一步说明本发明内容，但不应理解为对本发明的限制。如未特别说明，实施例中所采用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本领域常规试剂、方法和设备。
实施例1
本实施例提供了一种电催化加氢反应方法，包括以下步骤：
S1、提供图1所示的电催化加氢反应装置；
S2、向第一电解腔室内通入第一电解液；
S3、向第二电解腔室内通入第二电解液；
S4、向反应腔室通入反应底物；
S5、将供电单元的正极与惰性电极电连接、负极与金属膜电极电连接，控制电压进行电催化加氢反应；
其中，第一电解液、第二电解液均为碳酸钠溶液，第一电解液、第二电解液的流量为100 mL/min；供电单元为电化学工作站，将电化学工作站设定恒压电解模式，电压强度为0.5V，反应底物为CO 2，通入CO 2进行加氢反应，反应气体产物进入色谱仪，进行定量分析，反应液态产物由集液瓶收集后通过核磁和质谱行定量分析。
实施例2~16
本申请实施例提供的电催化加氢反应方法，同实施例1，不同在于，控制电压强度分别为-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。
实施例17~22
本申请实施例提供的电催化加氢反应方法，同实施例1，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例23~28
本申请实施例提供的电催化加氢反应方法，同实施例2，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例29~34
本申请实施例提供的电催化加氢反应方法，同实施例3，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例35~40
本申请实施例提供的电催化加氢反应方法，同实施例4，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例41~46
本申请实施例提供的电催化加氢反应方法，同实施例5，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例47~52
本申请实施例提供的电催化加氢反应方法，同实施例6，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例53~58
本申请实施例提供的电催化加氢反应方法，同实施例7，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例59~64
本申请实施例提供的电催化加氢反应方法，同实施例8，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例65~70
本申请实施例提供的电催化加氢反应方法，同实施例9，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例71~76
本申请实施例提供的电催化加氢反应方法，同实施例10，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例77~82
本申请实施例提供的电催化加氢反应方法，同实施例11，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例83~88
本申请实施例提供的电催化加氢反应方法，同实施例12，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例89~94
本申请实施例提供的电催化加氢反应方法，同实施例13，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例95~100
本申请实施例提供的电催化加氢反应方法，同实施例14，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例101~106
本申请实施例提供的电催化加氢反应方法，同实施例15，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
实施例107~112
本申请实施例提供的电催化加氢反应方法，同实施例16，不同在于，将CO 2调整为CO、N 2、O 2、乙炔、糠醛、苯及其衍生物（具体为甲苯）。
综上所述，以上实施例分别对比了不同电解电压条件下CO 2、CO、N 2、O 2、乙炔、糠醛、苯及其衍生物催化加氢性能。研究发现：电解过程对基于金属膜电极活性氢转移过程至关重要；本申请的电催化加氢反应在常温下进行，催化剂表现出优异的反应活性、选择性和稳定性；电解过程中惰性电极产生的氢离子扩散转移至膜电极时，能够在膜电极电解还原产生金属氢化物，并且氢化物的活性氢原子能够转移至催化剂表面，促进反应物的催化加氢过程，有效避免了常规催化加氢反应中氢气的使用。因此本申请电催化加氢反应装置及方法具有明显的催化加氢反应优势。
上所述仅为本发明的较佳实施方式而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种电催化加氢反应装置，其特征在于，包括：
    加氢反应器，其内部中空；
    惰性电极，其位于所述加氢反应器内；
    质子交换膜，其位于所述加氢反应器内，所述惰性电极位于所述质子交换膜内侧，所述质子交换膜与所述加氢反应器之间围合形成第一电解腔室；
    金属膜电极，其位于所述加氢反应器内，所述质子交换膜位于所述金属膜电极内侧，所述金属膜电极、所述加氢反应器、所述质子交换膜之间围合形成第二电解腔室，所述金属膜电极与所述加氢反应器内壁之间形成反应腔室；
    第一电解液供应单元，其用于向所述第一电解腔室提供第一电解液；
    第二电解液供应单元，其用于向所述第二电解腔室提供第二电解液；
    反应底物供应单元，其用于向所述反应腔室提供反应底物；
    供电单元，其正极与所述惰性电极电连接、负极与所述金属膜电极电连接；
    其中，所述金属膜电极所采用的金属为易于形成金属氢化物的金属。
  2. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述易于形成金属氢化物的金属包括La系金属、Pd、Ru、过渡金属中的至少一种。
  3. 如权利要求2所述的电催化加氢反应装置，其特征在于，所述金属膜电极包括依次叠加的疏水涂层、金属薄膜层、催化剂层，其中，所述催化剂层靠近所述反应腔室一侧，所述疏水涂层靠近所述第二电解腔室一侧；所述金属薄膜层所采用的金属为易于形成金属氢化物的金属。
  4. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述第一电解液供应单元包括：
    第一电解液储罐；
    第一进液管，其一端与所述第一电解液储罐连通、另一端与所述第一电解腔室一侧连通；
    第一出液管，其一端与所述第一电解腔室另一侧连通、另一端与所述第一电解液储罐连通；
    第一蠕动泵，其位于所述第一进液管或第一出液管上。
  5. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述第二电解液供应单元包括：
    第二电解液储罐；
    第二进液管，其一端与所述第二电解液储罐连通、另一端与所述第二电解腔室一侧连通；
    第二出液管，其一端与所述第二电解腔室另一侧连通、另一端与所述第二电解液储罐连通；
    第二蠕动泵，其位于所述第二进液管或第二出液管上。
  6. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述反应底物供应单元包括：
    反应底物储罐；
    反应底物进料管，其一端与所述反应底物储罐连通、另一端与所述反应腔室连通，所述反应底物进料管设有阀门和流量控制器。
  7. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述第一电解液、第二电解液均为碱液；
    和/或，所述反应底物包括CO 2 、CO、N 2 、O 2 、炔烃、烯烃、醛、羧酸、芳烃、芳烃衍生物中的至少一种；
    和/或，所述惰性电极包括石墨电极、铂电极、金电极中的一种。
  8. 如权利要求7所述的电催化加氢反应装置，其特征在于，所述碱液包括碳酸钠溶液、碳酸钾溶液、碳酸氢钠溶液、碳酸氢钾溶液、氢氧化钠溶液、氢氧化钾溶液中的至少一种。
  9. 如权利要求1所述的电催化加氢反应装置，其特征在于，所述供电单元用于提供-30V~30V的电压。
  10. 一种电催化加氢反应方法，其特征在于，包括以下步骤；
    提供如权利要求1~9任一所述的电催化加氢反应装置；
    向第一电解腔室内通入第一电解液；
    向第二电解腔室内通入第二电解液；
    向反应腔室通入反应底物；
    将供电单元的正极与惰性电极电连接、负极与金属膜电极电连接，控制电压进行电催化加氢反应。
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