Gas-liquid mixed electrochemical reaction device for use as methane-to-methanol generator, and method for synthesizing methane and / or methanol using same

Abstract

Disclosed is a gas-liquid mixed electrochemical reaction device for use as a methane-to-methanol generator. The device comprises an electrolytic cell, mainly consisting of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply. The electrolytic anode is connected to a positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to a negative electrode of the electrolytic power supply. The device is characterized in that: the electrolytic cell comprises at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, thereby forming a gas-liquid mixed electrolytic cell; an outlet of the electrolytic cell gas-liquid mixer faces or is located within the electrolytic cell body, and is used to bring a gas-liquid mixture, obtained by mixing an electrolyte in the electrolytic cell with a reaction gas, into contact with the electrocatalytic component. Further disclosed is a method for synthesizing methane and / or methanol using the above device.

Description

A gas-liquid hybrid electrochemical reaction device used as a methane-methanol generator and a method for synthesizing methane and / or methanol thereof Technical Field

[0001] The present invention belongs to the technical field of chemical reactions of substances, and in particular relates to a gas-liquid mixed electrochemical reaction device used as a methane-methanol generator and a method for synthesizing methane and / or methanol thereof. Background Art

[0002] Currently, modern chemical production of methane or methanol requires high-temperature and high-pressure processes, some of which also require the use of catalysts. These existing technologies consume large amounts of energy and are associated with high catalyst costs. A more optimal methane-methanol generator is needed that utilizes an improved atmospheric pressure process to improve production safety, energy efficiency, and return on investment.

[0003] Summary of the Invention

[0004] The first objective of the present invention is to provide a gas-liquid hybrid electrochemical reaction device for use as a methane-methanol generator. This device improves the gas solubility and mass transfer properties of the reactants, enabling electrochemical reactions to synthesize methane and / or methanol and / or other organic substances using carbon dioxide and hydrogen at atmospheric pressure through electrocatalysis. A second objective is to provide a method for synthesizing methane and / or methanol and / or other organic substances using this device, thereby simplifying the process for producing methane and / or methanol and / or other organic substances.

[0005] The first object of the present invention is achieved through the following technical solutions.

[0006] A gas-liquid mixing electrochemical reaction device used as a methane methanol generator includes an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein the electrolytic anode is connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to the negative electrode of the electrolytic power supply; the electrolytic cell is characterized in that it includes at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell; the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body, and is used to bring the gas-liquid mixture obtained by mixing the electrolyte in the electrolytic cell with the reaction gas into contact with the electrocatalytic component; the electrocatalytic component adopts any one or both of the following methods:

[0007] Electrocatalytic method (1): at least one electrocatalytic component is provided in the electrolytic cell, and the outlet of the gas-liquid mixer of the electrolytic cell faces the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode;

[0008] Electrocatalytic method (2): Improve the electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode; that is, at least one of the electrolytic anode and the electrolytic cathode is two or more parallel-connected electrodes, and the outlet of the electrolytic tank gas-liquid mixer faces the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure;

[0009] Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic anode and / or the electrolytic cathode with the improved electrocatalytic performance structure.

[0010] The electrolytic cell gas-liquid mixer described in the present invention has an inlet and at least two outlets, or has a structure with a liquid inlet, an air inlet and an outlet. When the electrolytic cell gas-liquid mixer has an inlet and at least two outlets, the outlet extends into the electrolytic cell body and is used to dispersely input the reaction gas or gas-liquid mixture into the electrolyte in the electrolytic cell for gas-liquid mixing; when the electrolytic cell gas-liquid mixer has a liquid inlet, an air inlet and an outlet, the liquid inlet is connected to the lower pipe of the electrolytic cell body, and the outlet is directed toward or extends into the electrolytic cell body, and is used to input the electrolyte in the electrolytic cell into the gas-liquid mixer so that it is mixed with the reaction gas entering the gas-liquid mixer and then returned to the electrolytic cell.

[0011] The electrocatalytic components in the electrocatalytic method (1) are arranged in the electrolytic cell below the electrolyte level to achieve electrochemical catalytic reaction under the action of the electric field force. The specific electrocatalytic components are bipolar electrodes and / or insoluble conductors, and the specific number and location of the electrocatalytic components can be determined according to the performance of the process setting.

[0012] The bipolar electrode is at least one insoluble conductor located between the electrolytic anode and the electrolytic cathode, not connected to an external power source and immersed in the electrolyte. Its shape and size are not restricted. During electrolysis, the bipolar electrode, when placed in an electric field, can undergo an electrochemical reaction with the substances located there, without requiring direct electrical connection to the electrolytic power source. The end closest to the electrolytic anode acts as a cathode, causing a reduction reaction on some reducible substances in the electrolyte, while the end closest to the electrolytic cathode acts as an anode, causing an oxidation reaction on some oxidizable substances in the electrolyte. When multiple bipolar electrodes are used, each is ideally an independent conductor with no electrical connection to each other. Under the action of the electric field, each bipolar electrode can independently function, forming multiple inductive small cathodes and anodes to enhance the electrocatalytic effect.

[0013] Preferably, as shown in FIG13 , when more than one bipolar electrode is used, the central surface of the conductive member of each bipolar electrode is partially coated with an insulating material to prevent the bipolar electrodes from becoming one large bipolar electrode due to electrical conduction when in contact with each other, thereby reducing the ability of each smaller bipolar electrode to independently perform its electrocatalytic function. Preferably, a powdered conductive member capable of flowing with the electrolyte is used as the bipolar electrode.

[0014] The insoluble conductor is directly connected to the electrolytic anode or electrolytic cathode in a conductive manner, so that the electrolytic anode or electrolytic cathode becomes an irregularly shaped electrode, and the electrochemical reaction between the electrode and the electrolyte is promoted by increasing the surface area of ​​the electrode to achieve the purpose of electrocatalysis. Among them, the insoluble conductor connected to the electrolytic anode is called an insoluble anode conductor, and the insoluble conductor connected to the electrolytic cathode is called an insoluble cathode conductor. The present invention utilizes the characteristics of the insoluble conductor to mix the introduced reaction gas with the electrolyte and then spray it onto the corresponding electrode and insoluble conductor to obtain an electrochemical reaction with high efficiency electrocatalysis. As shown in Figure 14, the insoluble conductor is a conductive material that is insoluble or difficult to dissolve in the electrolyte it contacts, and its shape and size are not limited.

[0015] The device of the present invention requires the mixing of gas and electrolyte to participate in the electrolysis process, and the electrochemical reaction is promoted by the electrocatalytic structure. Common gases that can participate in the reaction include carbon dioxide and hydrogen, among which carbon dioxide gas is an oxidizing gas and hydrogen is a reducing gas. The working principle of the present invention is: the electrolytic cell gas-liquid mixer mixes the gas participating in the reaction into the electrolyte and brings the resulting gas-liquid mixture into contact with at least one of the electrocatalytic components, electrolysis anode, and electrolysis cathode in the gas-liquid mixing electrolytic cell, so that the gas-liquid mixture participates in and undergoes an electrochemical reaction under the promotion of the electrocatalytic structure. Specifically, during the electrolysis operation of the device of the present invention, the gas-liquid mixture containing the oxidizing gas is allowed to contact and react with the negatively charged components in the gas-liquid mixing electrolytic cell, and at the same time, the gas-liquid mixture containing the reducing gas is allowed to contact and react with the positively charged components in the gas-liquid mixing electrolytic cell. The presence of sufficient gas in the gas-liquid mixture promotes electrochemical reactions on components with one electrical property. The resulting electron gain and loss catalyzes active electrochemical reactions on components with the other electrical property, while preventing the substances in the electrolyte to be treated from repeatedly reacting on components with both electrical properties, resulting in consumption and reduced efficiency. Compared with liquid oxidants or reductants, the use of oxidizing or reducing gases can better catalyze electrochemical reactions, is less expensive, and does not increase the amount of electrolyte. When electrolysis is energized, the component with negative charge in the gas-liquid hybrid electrolytic cell is at least one of the electrolytic cathode, the end of the bipolar electrode that acts as the cathode, and an insoluble cathode conductor, and the component with positive charge is at least one of the electrolytic anode, the end of the bipolar electrode that acts as the anode, and an insoluble anode conductor. That is, to achieve the aforementioned electrocatalytic effect, during the electrolysis process, an oxidizing gas is used to conduct an electrochemical reaction in the aforementioned negatively charged components to seal them, thereby ensuring that the reduced substances to be treated can be electrochemically oxidized in the positively charged components; or a reducing gas is used to conduct an electrochemical reaction in the aforementioned positively charged components to seal them, thereby ensuring that the reduced substances to be treated can be electrochemically reduced in the negatively charged components. During the electrolysis process, the positively charged components play a role in converting electrical energy into chemical energy, electrocatalytically oxidizing the reducing substances in the electrolyte. They can also oxidize oxygen, hydroxide ions, and other radicals in the electrolyte to produce a large number of superoxide radicals (O2·), hydroxyl radicals (OH·), and / or chlorine radicals, as well as other oxidizing free radicals, rapidly oxidizing the substances in the electrolyte that require oxidation treatment. In addition, the negatively charged components play a role in converting electrical energy into chemical energy, reducing oxidizing substances in the electrolyte under electrocatalysis, and can also generate a large number of hydrogen radicals (H·) or protons to quickly cause at least one of hydrogenolysis, hydrogenation, and reduction reactions on substances in the electrolyte that need to be reduced.

[0016] When a gas-liquid mixture containing an oxidizing gas, namely carbon dioxide, is sprayed onto a negatively charged component in the electrolysis process, at least one of the following electrochemical reactions occurs: CO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2OCO2+2H + +2e - →CO+H2OCO2+2H + +2e - →HCOOH2CO2+12H + +12e - →C2H4+4H2O2CO2+12H + +12e - →C2H5OH+3H2O

[0017] During the process, CO in the electrolyte also undergoes the following reaction under electrocatalysis: CO+6H + +6e - →CH4+H2OCO+4H + +4e - →CH3OH

[0018] When a gas-liquid mixture containing a reducing gas, namely hydrogen, is sprayed onto a positively charged component during electrolysis, the main electrochemical reaction that occurs is: H2-2e - →2H + H2+2[OH] - -2e - →2H2OCO2+H2-2e→CO+H2OCO2+4H2-8e→CH4+2H2O

[0019] Therefore, during the electrolysis process, under the electrocatalysis of the device of the present invention, CO2 and the generated CO react with H2 to produce at least one of methane, methanol, formic acid, ethylene, ethanol, and other organic substances; in addition to the above-mentioned electrochemical reactions, water may also undergo an electrolysis reaction to produce hydrogen and oxygen during the electrolysis process. The gas-liquid hybrid electrochemical reaction device used as a methane methanol generator of the present invention is produced using a production process improved by a normal pressure process, and one or more products are synthesized by using carbon dioxide gas and hydrogen to undergo an electrochemical reaction under electrocatalysis. Different main products can be produced according to the process design by regulating the ratio of the reaction amounts of carbon dioxide and hydrogen and controlling the reaction conditions. Compared with the complex methane methanol generator equipment currently available in the prior art, the device of the present invention has significant advantages in production safety, energy saving, and equipment investment returns.

[0020] The gas-liquid hybrid electrolytic cell of the present invention can be provided with an electrolytic cell divider in its electrolytic cell body according to the process design to separate it into at least two cell areas. The purpose of providing the electrolytic cell divider in the electrolytic cell body is to prevent the bubbles generated by electrode electrolysis in one of the cell areas from crossing over to other cell areas to cause adverse reactions, or to prevent at least part of the ions and molecules in the electrolyte of one of the cell areas from crossing over and migrating to other cell areas under the action of the electric field force, or to effectively block the catalytic components of the cathode and anode electrodes provided on both sides of the electrolytic cell divider and prevent the two from contacting and causing an electrical short circuit, so that the electrolytic cell meets the process setting requirements. Preferably, the electrolytic cell divider divides the electrolytic cell body into an electrolytic cell including an anode cell area and a cathode cell area, or into a three-cell electrolytic cell including an anode cell area, an intermediate cell area and a cathode cell area.

[0021] When at least two electrolytes with different components and / or concentrations need to exist in the electrolytic cell at the same time during the electrolysis process, at least one layer of electrolytic cell separator 1 is added to the electrolytic cell. # As a partition to effectively block the separation of electrons and water molecules. # The membrane is at least one selected from a bipolar membrane, a reverse osmosis membrane, a cation exchange membrane, an anion exchange membrane, and a proton membrane, as specifically shown in Figures 1, 2, 3, 5, and 6, number 2. When a reverse osmosis membrane is used as the electrolytic cell separator, the pH value of the electrolyte is preferably maintained within a range of 0.05 to 14 to fully utilize the membrane's performance and extend its service life.

[0022] When only one electrolyte is required in the electrolytic cell during the electrolysis process, there is no need to set an electrolytic cell separator in the electrolytic cell, or at least one layer of electrolytic cell separator 2 is added. # The separators are used to allow ions and water molecules to pass through and to ensure that the electrolytic anode, electrolytic cathode, and electrocatalytic components are independently separated. If only one electrolyte is required in the electrolytic cell during the electrolysis process, it is preferred to use a separator-free electrolytic cell structure while effectively avoiding electrical short circuits of the electrodes.

[0023] The electrolytic cell separator 2 # The separator is selected from at least one of a non-ion-selective membrane, a filter cloth, a filter screen, and an insulating through-hole support baffle. The non-ion-selective membrane has micropores that allow ions or molecules to pass through. Specifically, as shown in FIG4 , the electrolytic cell separator uses an insulating through-hole support baffle. The insulating through-hole support baffle is made of an electrically insulating material, has through-holes, and can be designed in any shape according to process requirements.

[0024] The gases involved in the reaction in the present invention are divided into self-electrolyzed gas and externally input gas. The self-electrolyzed gas and the electrolyte it mixes with come from the same cell zone of the same electrolytic cell; the externally input gas and the electrolyte it mixes with come from different cell zones of the same electrolytic cell, or from outside the electrolytic cell. Based on the source of the gas participating in the reaction within the cell, the gas-liquid hybrid electrolytic cell is divided into the following three types.

[0025] (1) Type A tank: The electrolytic tank gas-liquid mixer uses self-electrolyzed gas as the source of gas for the reaction. As shown in Figure 1, the gas inlet of the electrolytic tank gas-liquid mixer is connected to the top of the electrolytic tank area where its outlet is located. The gas electrolyzed by the electrolytic electrodes in this tank area and the electrolyte in this tank area form a gas-liquid mixture through the electrolytic tank gas-liquid mixer and contact the electrolytic electrodes and / or electrocatalytic components in this tank area to undergo an electrochemical reaction. Among them, the electrolyte in the tank area where the electrocatalytic reaction is carried out in the Type A tank with an electrolytic tank partition contains carbon dioxide gas.

[0026] (2) Type B cell: The electrolytic cell gas-liquid mixer uses both self-electrolyzed gas and external input gas as gas sources for the reaction. As shown in Figure 2, the gas inlet of the electrolytic cell gas-liquid mixer is connected to the top of the electrolytic cell tank area where its outlet is located, i.e., the anode tank area. It is also connected to the gas source outside the electrolytic cell. The gas electrolyzed by the electrolytic electrodes in the tank area combines with the gas from outside the tank area and mixes with the electrolyte in the tank area to form a gas-liquid mixture, which contacts the electrolytic electrodes and / or electrocatalytic components in the tank area to undergo an electrochemical reaction.

[0027] (3) C-type cell: The electrolytic cell gas-liquid mixer uses external input gas as the gas source for the reaction. As shown in Figures 3, 4, 5, 6, 10, and 12, the gas inlet of the electrolytic cell gas-liquid mixer is connected to a tank area in the same electrolytic cell that is not connected to the liquid flow and / or a gas source outside the electrolytic cell. The electrolytic cell gas-liquid mixer mixes the gas from the outside of the tank area with the electrolyte in the tank area to form a gas-liquid mixture, which contacts the electrolytic electrodes and / or electrocatalytic components in the tank area to undergo an electrochemical reaction.

[0028] The C-type cell can be further divided into C-1 type cell and C-2 type cell according to the source of the external input gas used. The external input gas used by the C-1 type cell and the electrolyte it mixes with come from different cell zones of the same electrolytic cell, that is, the gas inlet of the electrolytic cell gas-liquid mixer is connected to a cell zone different from the cell zone where the electrolytic cell gas-liquid mixer outlet is located within the same electrolytic cell; the external input gas used by the C-2 type cell comes from outside the electrolytic cell, that is, the gas inlet of the electrolytic cell gas-liquid mixer is connected to a gas source outside the electrolytic cell.

[0029] The C-shaped cell can be operated in an electrolysis process where the voltage applied by the power supply between the anode and cathode is higher than the electrolyte decomposition voltage to obtain external input gas from different cell zones within the same cell. Alternatively, the power supply can be operated in an electrolysis process where the voltage applied by the power supply between the anode and cathode is less than or equal to the decomposition voltage to utilize external input gas from outside the cell and prevent gas deposition from the electrolytic electrodes within the cell. The electrolyte decomposition voltage is the critical value at which the voltage applied by the power supply between the anode and cathode in a static state of the cell electrolyte just produces trace amounts of oxidizing gas or reducing gas. The electrolyte decomposition voltage is dependent on a variety of factors, including the electrolyte concentration, viscosity, temperature, the amount of gas involved in the reaction, the distance between the cathode and anode, and the materials used for the cathode and anode electrodes. Therefore, in order to allow electrolytic gas to be deposited on the electrolysis anode and / or the electrolysis cathode, the voltage value applied between the electrolysis anode and the electrolysis cathode by the electrolysis power supply during operation needs to be higher than the electrolyte decomposition voltage. Specifically, the electrolysis cell structure shown in Figure 6 can be adopted. In order to prevent electrolytic gas from being deposited on the electrolysis anode and / or the electrolysis cathode, the voltage value applied between the electrolysis anode and the electrolysis cathode by the electrolysis power supply during operation needs to be less than or equal to the electrolyte decomposition voltage. Specifically, the gas-liquid hybrid electrolysis cell structure shown in Figures 3, 4, 5, 8, 10, and 12 can be adopted.

[0030] But when having sufficient reducing gases to participate in the electrochemical reaction of electrolysis anode and / or bipolar electrode anode end and make electrolysis anode and bipolar electrode anode end be difficult to electrolysis oxidizing gas, or when having sufficient oxidizing gases to participate in the electrochemical reaction of electrolysis cathode and / or bipolar electrode cathode end and make electrolysis cathode and bipolar electrode cathode end be difficult to electrolysis reducing gas, the electrolysis power supply of described C-2 type groove applies the voltage value between electrolysis anode and the electrolysis cathode and can be slightly higher than the electrolyte decomposition voltage value.When being regulated higher because of the electrolysis power supply applying the voltage value between electrolysis anode and the electrolysis cathode, under these conditions, the reducibility of its electrolysis cathode or the oxidizability of its electrolysis anode can become stronger more.So now, adopt C-2 type groove, under safe situation, electrolysis power supply can be set to apply the voltage value between electrolysis anode and the electrolysis cathode and be slightly higher than the electrolyte decomposition voltage value, to improve electrochemical reaction speed.

[0031] The material of the electrolytic cell body in contact with the electrolyte is selected from polymer resin, or other materials and the contact part with the electrolyte is coated with an insulating anti-corrosion coating or lined with an insulating anti-corrosion material. Preferably, when the electrolyte temperature is high, the electrolytic cell body material is selected from polytetrafluoroethylene.

[0032] The surface of the electrolytic anode is selected from at least one material selected from the group consisting of gold, platinum, nickel, alloys containing at least one of the aforementioned metals, titanium-coated insoluble anodes, and graphite, and its shape and size are not limited. The surface of the electrolytic cathode is selected from at least one material selected from the group consisting of gold, platinum, silver, titanium, copper, nickel, alloys containing at least one of the aforementioned metals, stainless steel, and graphite, and its shape and size are not limited. The electrolytic power supply is a suitable electrolytic power supply that can meet the operating voltage and current density requirements of the gas-liquid hybrid electrolytic cell during the electrolysis process.

[0033] The bipolar electrode can be made of any conductive material that is insoluble or poorly soluble in the electrolyte it contacts, such as a metal, metal oxide, or semiconductor. The appropriate bipolar electrode material is selected based on the conductive material's performance in actual chemical reactions. Preferably, the bipolar electrode surface is made of at least one of the following: gold, platinum, nickel, copper, cobalt, iron, nickel, molybdenum, tin, bismuth, aluminum, ruthenium, titanium, tantalum, alloys containing at least one of the above metals, copper oxide, zinc oxide, aluminum oxide, titanium-coated insoluble electrodes, graphite, or activated carbon. When using a powdered or granular conductive material that flows with the electrolyte as the bipolar electrode, a liquid spray pipe is installed to prevent the powdered or granular bipolar electrode from sinking to the bottom or corners of the tank.

[0034] The material of the insoluble conductor is any conductive material such as a conductive metal, a conductive metal oxide, a semiconductor, etc., and a suitable insoluble conductor material is selected according to the performance of the conductor in an actual chemical reaction. Preferably, the material of the insoluble anode conductor is consistent with the material of the electrolytic anode. When the insoluble conductor is in contact with the electrolytic anode, that is, the surface of the insoluble anode conductor is a material selected from at least one of gold, platinum, nickel, an alloy containing at least one of the above metals, a titanium-based coated insoluble electrode, and graphite. When the insoluble conductor is in contact with the electrolytic cathode, its surface is a material selected from at least one of gold, platinum, silver, titanium, copper, nickel, an alloy containing at least one of the above metals, stainless steel, and graphite.

[0035] The gas-liquid mixture outlet of the electrolytic tank gas-liquid mixer is designed with the number of nozzles and the shape of the liquid spray according to the spraying object, so that the ejected gas-liquid mixture can effectively and fully contact at least one of the electrocatalytic component, the electrolytic anode, and the electrolytic cathode to achieve better catalytic effect. The electrolytic tank gas-liquid mixer is a bubbling electrolytic tank gas-liquid mixer and / or a vacuum jet electrolytic tank gas-liquid mixer. From the perspective of safe production and gas-liquid mixing effect, it is preferred to use a vacuum jet electrolytic tank gas-liquid mixer, or a combination of a bubbling type and a vacuum jet (as shown in numbers 7-1 and 7-2 in Figure 3). The material of the liquid flow surface of the electrolytic tank gas-liquid mixer is selected from at least one of titanium, gold, platinum, nickel, conductive graphite, stainless steel, fiberglass, and polymer resin materials, and is specifically selected according to the chemical properties of the electrolyte and the gas participating in the reaction.

[0036] The present invention can be improved as follows: the electrolytic cell gas-liquid mixer is made of conductive material and electrically connected to the electrolysis power source, and its liquid outlet is directly inserted into the electrolyte, making it an insoluble anode conductor or an insoluble cathode conductor, which serves as an electrocatalytic component to improve the catalytic efficiency; specifically, as shown by number 9 in Figure 5.

[0037] The present invention can also be improved as follows: an air intake branch pipe is added to the air intake pipe of the gas-liquid mixer of the electrolytic cell to introduce multiple or various gases to mix with the electrolyte and then spray them onto the electrolytic anode and / or electrolytic cathode and / or catalytic component to participate in the electrochemical reaction, as specifically shown by number 61 in Figure 4.

[0038] The present invention can also be improved as follows: a sealed tank cover with a gas outlet is added to at least one tank area in the gas-liquid mixing electrolytic cell to seal the tank area with a hole. The gas outlet of the sealed tank cover is connected to the gas inlet of at least one electrolytic cell gas-liquid mixer and / or other common gas-liquid mixer, or is connected to the atmosphere, so that the gas in the sealed tank area is guided through the cover outlet pipe to the electrolytic cell gas-liquid mixer and / or other exhaust gas treatment device and / or a device for recycling the gas, or is directly discharged through the cover outlet; specifically, as shown by reference numeral 30 in FIG5 .

[0039] The present invention can also be improved as follows: when the electrolytic cell separator 1 # When using a cation exchange membrane, a reverse osmosis membrane is added to the electrolytic cell body to form an intermediate tank area between the cation exchange membrane and the reverse osmosis membrane in the electrolytic cell body, and a bipolar electrode is set in the intermediate tank area. # 2-1 is reverse osmosis membrane, electrolytic cell separator 1 # 2-2 is a cation exchange membrane. The electrolyte in the middle tank formed between the two generates a large amount of hydrogen ions H + The electrochemical reaction migrates from the electrolytic anode to the electrolytic cathode. In this process, the bipolar electrode plays an electrocatalytic role, increasing the reduction reaction rate.

[0040] The present invention can also be improved as follows: an adjustable constant voltage electrolysis power supply is used as the electrolysis power supply of the C-2 type cell to ensure a stable output voltage to meet production safety requirements.

[0041] The present invention can also be improved by employing a symmetrical three-zone structure in the gas-liquid hybrid electrolytic cell to improve electrical efficiency. For example, Figure 7 shows a three-zone cell formed by symmetrically arranging one zone of the B-type cell shown in Figure 2 with another zone as the center. The electrolyte in the anode zone can be set to two different concentrations or the same concentration depending on the process. Figure 8 shows a three-zone cell formed by symmetrically arranging one zone of the C-2-type cell shown in Figure 4 with another zone as the center. The electrolyte in the three zones is the same.

[0042] The present invention can also be improved as follows: the gas-liquid hybrid electrolytic cell adopts a circular electrode distribution structure to improve the electrical efficiency of the electrochemical reaction. Specifically, the gas-liquid hybrid electrolytic cell adopts a circular or polygonal electrolytic cell body, with the electrolysis anode or electrolysis cathode positioned at the center of the electrolytic cell body as the central electrode, and one or more corresponding electrodes of another type positioned around the central electrode. Figure 9 shows the circular electrode distribution structure of an A-type cell, where the peripheral electrodes outside the center of the electrolytic cell body share the same electrolyte. Figure 10 shows the circular electrode distribution structure of a C-2 type cell, where the anolyte and cathode electrolytes are the same electrolyte, and the peripheral electrodes outside the center of the electrolytic cell body are separated by insulating partitions and connected to their own electrolysis power sources, forming a combination of multiple independent electrolysis units within the shared central electrode and electrolyte. The electrolysis units include an electrolysis power source, an electrolysis anode, an electrolysis cathode, an electrocatalytic component, and / or at least one electrolysis electrode with improved electrocatalytic performance.

[0043] The present invention can also be improved as follows: an electrolyte ion current cutoff device is added to cut off the short-circuit path of the ion flow in the electrolyte that does not flow through the electrolytic anode and electrolytic cathode during electrolysis operation, so as to avoid the loss of useless work by forming a closed loop circuit with the electrolytic power supply. There are two methods for setting up an electrolyte ion current interrupter: the first is as shown by number 60 in Figure 9, using a tank equipped with a multi-hole drip-type baffle or a pipe with an increased cross-sectional area equipped with a multi-hole drip-type baffle as the electrolyte ion current interrupter, diverting the electrolyte continuously flowing in the pipe into it, and cutting off the path of ion flow and current in the electrolyte in a dripping flow manner; the second is as shown by the temporary storage tanks 2 numbered 20-1 and 20-2 in Figure 10, which use at least two current-breaking temporary storage tanks as electrolyte ion current interrupters, and use them to rotate and interrupt the ion flow in the electrolyte in a rotating manner, and install liquid level gauges in the electrolyte current-breaking temporary storage tanks to control the pumping of each current-breaking temporary storage tank, so that the electrolyte in the tank is pumped into the gas-liquid mixed electrolytic tank for chemical reaction in rotation between the current-breaking temporary storage tanks. The positive rotation pumps the electrolyte in the tank into the current-off temporary storage tank of the electrolytic tank, which does not receive the solution overflowing from the electrolytic tank. The overflow of the gas-liquid mixed electrolytic tank is drained to another current-off temporary storage tank for temporary storage. The electrolyte is pumped into the gas-liquid mixed electrolytic tank in rotation through two or more tanks to achieve a short-circuit channel that cuts off the ion flow.

[0044] The present invention can also be improved as follows: a slot frame metal mesh type bipolar electrode is provided to redistribute the total current passing through the separator to improve the process performance problem of the electrolyte resistance change caused by the different bubble density in the electrolyte. Specifically shown as number 10 in Figure 15. Preferably, the slot frame metal mesh type bipolar electrode is installed between the electrolysis anode and the electrolysis cathode, and close to the electrolytic cell separator. The material selection range of the slot frame metal mesh type bipolar electrode is consistent with that of the conventional bipolar electrode. After such structural improvement, it can evenly disperse the electrolysis current and evenly pass through the separator, avoiding the electrolysis current concentrating at one point to damage the separator. The outer size of the mesh frame of the slot frame metal mesh type bipolar electrode is set according to the size of the electrolytic cell installation cross section.

[0045] The present invention can also be improved as follows: a bubble-containing reaction liquid flow guide is added to the gas-liquid mixing electrolytic cell, and the direction and position of the liquid suction port are determined according to the design process of the gas-liquid mixing electrolytic cell. Preferably, the bubble-containing reaction liquid flow guide is installed on the side of the electrolysis cathode away from and facing away from the electrolysis anode to guide the bubble-containing electrolyte near the electrolysis cathode, or is installed on the side of the electrolysis anode away from and facing away from the electrolysis cathode to guide the bubble-containing electrolyte near the electrolysis anode; specifically as shown in Figure 6, number 62. The main functions of the bubble-containing reaction liquid flow guide include collecting the reaction gas in the electrolyte that does not participate in the electrochemical reaction and re-guiding it together with the electrolyte back to the gas-liquid mixer of the electrolytic cell for gas-liquid mixing again for electrochemical reaction utilization, and keeping the bubbles in the collected liquid absorbed during operation away from the main electric field area to reduce the influence of the bubbles on the uniform distribution of the electrolysis electric field lines.

[0046] The present invention can also be further improved by employing the following: the electrode used in conjunction with the bubble-containing reaction liquid deflector is an insoluble electrode with a through-hole grid structure. The through-holes in the electrode are used to absorb the electrolytic bubbles produced on the electrode and drain the bubble-containing solution into a gas-liquid separator. The electrolytic gas is separated and used from the gas-liquid separator, and the solution is circulated back to the extraction tank area. This improved structure can reduce the impact of the electrolytic gas on the uniform distribution of the electric field lines in the electrolytic cell. This is specifically illustrated by the through-hole grid electrode numbered 4 in Figure 6.

[0047] The present invention can also be improved as follows: the gas-liquid mixing electrolytic cell adopts a vertical structure, and the height of the electrolytic cell body of the electrolytic cell is increased. Since the present invention adopts gas-liquid mixing to carry out the reaction, and since the gas moves vertically upward in the reaction liquid, increasing the vertical reaction chamber helps to improve the reaction efficiency and reduce the waste and loss caused by the unreacted gas escaping from the gas-liquid mixing electrolytic cell. Preferably, the outlet of the electrolytic cell gas-liquid mixer is arranged at the bottom of the gas-liquid mixing electrolytic cell to spray the gas-liquid mixture upward from the bottom to the electrolytic anode and / or electrocatalytic component and / or electrolytic cathode. More preferably, as shown in the vertical structure of Figure 12, at least two groups of independent electrolytic units are arranged in a stacked manner in the gas-liquid mixing electrolytic cell. Among them, it is preferred to arrange the electrolysis electrodes according to the chemical properties of the reaction gases: when the gas participating in the reaction is a reducing gas, they are arranged in the order of electrolysis anode, electrolysis cathode, electrolysis anode, and electrolysis cathode; when the gas participating in the reaction is an oxidizing gas, they are arranged in the order of electrolysis cathode, electrolysis anode, electrolysis cathode, and electrolysis anode, so that the gas-liquid mixed electrolytic cell can fully exert the effect of its electrochemical reaction.

[0048] The present invention can also be improved by adding an ultrasonic generator to the electrolytic cell body and / or the electrolytic cell gas-liquid mixer. This utilizes the ultrasonic cavitation effect to fully disperse and dissolve bubbles in the electrolyte into the solution, thereby improving the efficiency of the oxidation or reduction reaction. Preferably, the ultrasonic generator is mounted on the liquid flow pipe of the electrolytic cell gas-liquid mixer. This simple mounting structure provides improved gas-liquid mixing, as shown in FIG5 , numbered 25. More preferably, the electrolytic cell gas-liquid mixer is made of at least one of stainless steel, titanium, and nickel, enabling the ultrasonic generator mounted on the electrolytic cell gas-liquid mixer to achieve greater energy efficiency during operation.

[0049] The present invention can also be improved as follows: two or more gas-liquid mixed electrolyzers are set up and connected to form a combination of two-stage or multi-stage gas-liquid mixed electrolyzers in series, that is, the gas-liquid mixed electrochemical reaction devices of the front and rear stages are connected by a gas pipeline, and the reaction gas escaping during the reaction of the front-stage gas-liquid mixed electrolyzer is collected and drained to the gas-liquid mixed electrolyzer of the rear stage to be used as a reaction gas raw material, which can reduce production costs and reduce pollution. Preferably, the mixed gas escaping from the reaction of the front-stage electrolyzer is first washed and separated, and the raw gas obtained after the washing and separation treatment is sent to the rear-stage electrolyzer for use as a production raw material. The washing liquid used in the washing and separation treatment is water and / or an electrolyte solution, which is specifically selected according to the properties of the gas.

[0050] The present invention can also be improved as follows: a mixed gas separation tank is added, which is arranged on the gas pipeline of the device of the present invention. Structurally, it is divided into a bubbling type, a spray tower type or a venturi vacuum jet type gas-liquid mixer. The principle is to utilize the gas-liquid mixing process to dissolve the gas components in the mixed gas that are soluble in water or other solvents into water or the solvent, while the other gas components that are insoluble in water or the solvent are separated and discharged from the liquid surface, so as to separate two or more mixed gases. Preferably, the combination of a vacuum ejector and a bubbling gas-liquid mixer is used to inject the mixed gas into the solution for separation, which has a better effect. Preferably, a combination of series-type mixed gas separation tanks is established to perform two-stage or more thorough separation of the mixed gas.

[0051] The present invention can also be improved by adding an insulating bipolar electrode cage or isolation mesh frame. Specifically, an insoluble insulating bipolar electrode cage or isolation mesh frame is used to isolate and securely stack multiple bipolar electrodes during use. This prevents the bipolar electrodes, which are immobilized between the electrolytic anode and the electrolytic cathode, from displacement under the impact of the liquid flow, allowing them to function properly as electrocatalysts. The bipolar electrode cage, shown as 11 in FIG6 , is made of an insulating rubber mesh or porous mesh.

[0052] The present invention can also be improved as follows: when an adaptive electrolytic power supply is selected whose output working voltage is higher than the human body safety voltage (36V), a photoelectric control system or a human body sensing control system is added to the device to set a dangerous working area. When a living thing enters the controlled area, an alarm is immediately triggered and the electrolytic power supply is shut down.

[0053] The present invention can also be improved as follows: a temporary storage tank is added to the device for temporarily storing materials, and the temporary storage tank is connected to other equipment tanks by pipelines for liquid flow or gas flow.

[0054] The present invention can also be improved as follows: an overflow buffer tank is added to the device, which is connected to at least one tank in the device of the present invention to solve the problem of liquid flow between tanks.

[0055] The present invention can also be improved as follows: a polluted exhaust gas treatment tank is added to the device, which is connected to the exhaust gas outlet of at least one of the other polluted exhaust gas treatment tanks such as the gas-liquid mixing electrolytic tank, the temporary storage tank, the overflow buffer tank, the chemical reaction tank, and the mixed gas separation tank through a pipeline, so as to perform environmentally friendly treatment of the polluted exhaust gas; the polluted exhaust gas treatment tank is a gas-liquid mixing treatment tank equipped with a spray-type or Venturi jet-type gas-liquid mixer.

[0056] The present invention can also be improved by adding a hot / cold temperature exchanger to the apparatus, disposed in at least one of the gas-liquid hybrid electrolytic cell, the temporary storage tank, or the chemical reaction tank. The hot / cold temperature exchanger is used to control the temperature of the reaction solution and adjust the temperature of the temporary storage solution, ensuring that the temperature of each solution meets process requirements, thereby achieving safe production and improving reaction efficiency.

[0057] The present invention can also be improved by adding an agitator to the apparatus, located in at least one of the gas-liquid mixing electrolytic cell, the temporary storage tank, or the chemical reaction tank, to achieve uniform temperature and concentration of the reactants, thereby facilitating production process control. Agitators are classified into impeller-type agitators and liquid flow pump tube-type agitators.

[0058] The present invention can also be improved as follows: an automatic detection and feeding controller and a sensor are added to the device, the detection signal output end of the sensor is connected to the detection signal input end of the automatic detection and feeding controller, and the control signal output end of the automatic detection and feeding controller is connected to the control signal input ends of the electrolysis power supply, valves, pumps, ultrasonic generators, hot and cold temperature exchangers, and agitators in the device, so that the device processes sampled data according to a pre-programmed procedure during the production process and controls the addition of chemicals during the reaction process so that the reaction liquid meets the process reaction requirements and operates automatically and safely according to the pre-programmed procedure. The sensor is selected from at least one of a pH meter, a pH meter, a hydrometer, an oxidation-reduction potentiometer (ORP meter), a liquid level gauge, a voltmeter, an ammeter, a thermometer, a photoelectric colorimeter, a methane concentration detector, a hydrogen concentration detector, a carbon monoxide concentration detector, and a carbon dioxide concentration detector, and is installed in at least one of a gas-liquid hybrid electrolytic cell, a temporary storage tank, an overflow buffer tank, a chemical reaction tank, a mixed gas separation tank, and a polluted tail gas treatment tank.

[0059] The present invention can also be improved as follows: an air pressure balance connecting pipe is added, as shown by number 39 in Figure 6, so that at least one tank area in the gas-liquid mixed electrolytic cell is connected to the air channel to achieve pressure balance with the atmosphere according to process requirements.

[0060] The present invention can also be improved as follows: an overflow buffer tank with a gas-liquid mixer is added to circulate carbon dioxide gas into the electrolyte to maintain the stable performance of the weak electrolyte. The overflow buffer tank is connected to the gas-liquid mixing electrolytic tank through a pipeline for circulating liquid flow.

[0061] The present invention can also be improved as follows: a common auxiliary electrolytic cell is added to produce hydrogen for supplying the gas-liquid mixed electrolytic cell, so as to improve the working efficiency of the gas-liquid mixed electrochemical reaction device and reduce production costs.

[0062] The present invention can also be improved as follows: a gas-liquid separation washing tank is added to the gas pipeline of the device of the present invention to separate the bubbles and the solution in the gas-liquid mixture.

[0063] The present invention can also be improved by adding solution guide plates to increase the solution flow area, thereby facilitating the escape of insoluble gases from the electrolyte. These guide plates can be installed in suitable tanks of the present invention according to process requirements. Specifically, as shown in Figure 10 , the two solution guide plates are respectively installed below the liquid inlets of temporary storage tanks 20-1 and 20-2.

[0064] The present invention can also be improved as follows: a condenser is added to the device to separate methanol from methane, carbon dioxide, carbon monoxide and hydrogen by utilizing the boiling point of methanol.

[0065] The present invention can also be improved as follows: a bubble drainage hood is added at the electrode in the electrolytic cell, as shown by number 64 in Figure 17, so that the bubbles in the electrolyte can escape along the drainage pipe and be utilized; preferably, the air outlet of the bubble drainage hood is connected to the air inlet of the gas-liquid mixer of the electrolytic cell.

[0066] The present invention can also be improved as follows: a gas-liquid mixing reaction tank is added to the device; as shown in Figure 11, preferably the gas-liquid mixing reaction tank is composed of a tank body and a gas-liquid mixer combining ordinary vacuum jet type and bubbling type, which is connected to at least one of the gas-liquid mixing electrolytic cell, temporary storage tank, overflow buffer tank, chemical reaction tank, mixed gas separation tank, polluted tail gas treatment tank, and other gas-liquid mixing reaction tanks through a pipeline. This gas-liquid mixing reaction tank can be used to oxidize the substance to be treated with an oxidizing gas.

[0067] The present invention can also be improved as follows: a hydrogen tail gas high altitude discharge pipe is added to at least one gas outlet for discharging hydrogen in the device of the present invention to perform safe discharge treatment on the tail gas containing hydrogen.

[0068] The present invention can also be improved as follows: an electric furnace is added to perform high-temperature treatment on the iron hydroxide precipitate containing only organic impurities, and the iron oxide obtained after the high-temperature treatment is used as other raw materials.

[0069] The second object of the present invention is achieved through the following technical solutions.

[0070] A method for synthesizing methane and / or methanol in the gas-liquid hybrid electrochemical reaction device comprises the following steps:

[0071] (1) Using a gas-liquid hybrid electrochemical reaction device, and adding an aqueous solution containing carbon dioxide as an electrolyte to the gas-liquid hybrid electrolytic cell or at least one cell zone thereof;

[0072] (2) turning on the electrolysis power supply, starting at least one electrolytic cell gas-liquid mixer of the device, and continuously introducing new oxidizing gas and / or reducing gas to be mixed and dissolved in the electrolyte; the oxidizing gas is carbon dioxide gas, and the reducing gas is hydrogen gas;

[0073] Specifically, an oxidizing gas and / or a reducing gas is mixed with an electrolyte to form a gas-liquid mixture, and then brought into contact with at least one of an electrolytic anode, an electrolytic cathode, and an electrocatalytic component. The electrolytic electrode and / or the electrocatalytic component with an improved electrocatalytic structure is used to exert an electrocatalytic effect to cause an electrochemical oxidation and / or reduction reaction between carbon dioxide and hydrogen in the electrolyte to synthesize methane and / or methanol and / or other organic matter.

[0074] When power is applied for electrolysis, the gas-liquid mixture containing the oxidizing gas is brought into contact with the negatively charged components in the gas-liquid hybrid electrolytic cell to react, and the electrolyte is brought into contact with the positively charged components in the gas-liquid hybrid electrolytic cell to cause an oxidation reaction of hydrogen; and / or when power is applied for electrolysis, the gas-liquid mixture containing the reducing gas is brought into contact with the positively charged components in the gas-liquid hybrid electrolytic cell to react, and the electrolyte is brought into contact with the negatively charged components in the gas-liquid hybrid electrolytic cell to cause a reduction reaction of carbon dioxide.

[0075] The gas-liquid mixed electrolytic cell of the present invention can be selected from an electrolytic cell body without partitions or an electrolytic cell body with electrolytic partitions according to process design. When the electrolytic cell body is provided with electrolytic cell partitions, the electrolytic cell body is divided into at least two cell areas.

[0076] In the present invention, the gases involved in the reaction are divided into the combination of self-electrolyzed hydrogen and external carbon dioxide gas, and the miscible combination of external carbon dioxide gas and external hydrogen, thereby setting up the structure of a gas-liquid hybrid electrolytic cell.

[0077] In step (1) and step (2), a gas-liquid hybrid electrochemical reaction device is used to chemically react the oxidizing gas with H2 in the electrolyte under electrocatalysis, and / or to chemically react the reducing gas with carbon dioxide or carbon monoxide in the electrolyte under electrocatalysis to synthesize at least one of methane, methanol, and other organic substances, so that the methane methanol generator achieves the purpose of process production operation.

[0078] When the present invention uses a gas-liquid hybrid electrolyzer to absorb hydrogen and perform at least one of hydrogenolysis, hydrogenation, and reduction reactions on a carbon dioxide aqueous solution, the hydrogen is converted into protons H by electrocatalysis at a component of the gas-liquid hybrid electrolyzer that has positive charge when it is energized for electrolysis. + Participate in the reaction, the electrochemical reaction formula is: H2-2e→2H + and / or hydrogen reacts chemically with oxidizing substances in the electrolyte under the electrocatalysis of negatively charged components of the gas-liquid hybrid electrolyzer when energized for electrolysis. Thanks to the electrocatalytic conditions provided by the gas-liquid hybrid electrolyzer, hydrogen can react with carbon dioxide and carbon monoxide at normal pressure.

[0079] The present invention may also be improved as follows: in order to make the electrolyte safe and controllable during the reaction process, the temperature of the electrolyte is regulated by using a hot and cold temperature exchanger to meet the process temperature requirements.

[0080] The present invention can also be improved as follows: To ensure safe and controllable electrochemical reactions, an automatic detection and feeding controller and detection sensors are used to automatically operate the device for sampling, detection, and controlled feeding of chemical reactants, allowing the device to operate safely according to pre-programmed procedures. The detection sensors include a pH meter, an acidity meter, a thermometer, a liquid level gauge, a hydrometer, a photoelectric colorimeter, an oxidation-reduction potentiometer (ORP meter), a carbon monoxide gas concentration detector, a carbon dioxide gas concentration detector, a methane concentration detector, and a hydrogen concentration detector.

[0081] The present invention can also be improved as follows: a common auxiliary electrolytic cell is used to produce hydrogen to supply the gas-liquid mixed electrolytic cell reaction.

[0082] The present invention can also be improved as follows: an overflow buffer tank with a gas-liquid mixer is used to prepare an aqueous solution containing carbon dioxide and transport it to a gas-liquid mixing electrolytic cell.

[0083] The present invention can also be improved as follows: a condenser is used to separate methane, carbon monoxide, carbon dioxide, hydrogen and the product methanol.

[0084] The present invention can also be improved as follows: in the process of synthesizing methane and / or methanol and / or other organic matter, the output of methane and methanol and the ratio between the selected product outputs can be controlled by adjusting the reaction amount of carbon dioxide gas and / or hydrogen and / or adjusting the output voltage of the electrolysis power supply of the gas-liquid hybrid electrolyzer.

[0085] The present invention can also be improved by setting the reaction temperature of the electrolyte above the boiling point of methanol, so that the methanol produced by the electrolyte reaction can escape from the gas-liquid hybrid electrolytic cell along with methane, carbon dioxide, carbon monoxide, and hydrogen for collection, thereby reducing the organic matter in the electrolyte and maintaining the original electrolytic performance of the electrolytic cell. Preferably, the electrolyte is tested for alkane concentration during the production process to prevent the presence of excessive organic matter in the electrolyte from affecting the normal performance of the gas-liquid hybrid electrolytic cell and to avoid safety accidents caused by changes in the electrolyte composition.

[0086] Compared with the prior art, the present invention has the following beneficial effects.

[0087] 1. The process for synthesizing methane and methanol using a gas-liquid mixed electrochemical reaction device is simple, safe to operate, and requires little equipment investment.

[0088] 2. The gas-liquid hybrid electrochemical reaction device of the present invention has low energy consumption and high economic benefits in synthesizing methane and methanol products.

[0089] 3. The synthetic methane methanol generator of the present invention does not add new pollution sources during the process, and complies with environmental protection regulations.

[0090] 4. The method of the present invention can produce hydrogen through green electricity and produce green methane or methanol from carbon dioxide in the atmosphere, which is an environmentally friendly engineering process with positive significance. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] FIG1 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 6 of the present invention.

[0092] FIG2 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 7 of the present invention.

[0093] FIG3 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 8 of the present invention.

[0094] FIG4 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 9 of the present invention.

[0095] FIG5 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 10 of the present invention.

[0096] FIG6 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 11 of the present invention.

[0097] FIG7 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 12 of the present invention.

[0098] FIG8 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 13 of the present invention.

[0099] FIG9 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 14 of the present invention.

[0100] FIG10 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 15 of the present invention.

[0101] FIG11 is a schematic structural diagram of a gas-liquid mixing reaction tank.

[0102] FIG12 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 16 of the present invention.

[0103] [Corrected 22.07.2024 according to Rule 91] Figure 13 is a schematic diagram of the structure of two bipolar electrodes of different shapes.

[0104] [Corrected 22.07.2024 according to Rule 91] Figure 14 is a schematic diagram of the structures of four different shapes of insoluble conductors.

[0105] FIG15 is a schematic structural diagram of the gas-liquid mixed electrochemical reaction device and the slot-frame metal mesh bipolar electrode of the present invention.

[0106] FIG16 is a schematic diagram of a bipolar electrode insulation cage.

[0107] FIG17 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 1 of the present invention.

[0108] FIG18 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 2 of the present invention.

[0109] FIG19 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 3 of the present invention.

[0110] Figure 20 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator in Example 4 of the present invention; Figure 20-1 is a partial enlarged view of Figure 20, and Figure 20-2 is a partial enlarged view of Figure 20. The two are combined to form a complete gas-liquid hybrid electrochemical reaction device in Example 4.

[0111] FIG21 is a schematic diagram of a gas-liquid hybrid electrochemical reaction device used as a methane methanol generator according to Example 5 of the present invention.

[0112] Reference numerals: 1-electrolytic cell body, 2-electrolytic cell separator 1 #, 3-electrolysis anode, 4-electrolysis cathode, 5-electrolysis power supply, 6-bipolar electrode, 7-vacuum jet electrolytic cell gas-liquid mixer, 8-bubbling electrolytic cell gas-liquid mixer, 9-vacuum jet and bubbling combined electrolytic cell gas-liquid mixer, 10-trough frame metal mesh bipolar electrode, 11-bipolar electrode insulation mesh box, 12-insulating through-hole support baffle, 13-gas-liquid separation washing tank, 14-ordinary bubbling gas-liquid mixer 15-General vacuum jet gas-liquid mixer, 16-General spray tower gas-liquid mixer, 17-cold and hot temperature exchanger, 18-impeller agitator, 19-liquid flow agitator, 20-temporary storage tank, 21-overflow buffer tank, 22-overflow buffer tank with gas-liquid mixer, 23-insoluble anode conductor, 24-insoluble cathode conductor, 25-ultrasonic generator, 26-solid-liquid separator, 27-polluted tail gas treatment Trough, 28-sealed trough cover for collecting escaped gases from the electrolytic cell reaction, 29-carbon dioxide, 30-carbon monoxide, 31-hydrogen, 32-oxygen, 33-reaction liquid containing carbon dioxide, 34-anolyte, 35-catholyte, 36-alkaline solution, 37-pure water, 38-gas pressurizing pump, 39-gas pressure balancing connecting pipe, 40-ordinary auxiliary electrolytic cell, 41-mixed gas, 42-gas escaped after separation of mixed gas, 43-electrical insulator, 44-conductor, 45-conductive connecting line, 46-automatic detection and feeding controller, 47-sensor, 48-solution guide plate, 49-mixed gas gas-liquid separator, 50-refrigerator, 51-condenser, 52-intermediate tank area, 53-intermediate tank electrolyte, 54-safety photoelectric control alarm system, 55-hydrogen cylinder, 56-carbon dioxide cylinder, 57-electrolytic cell partition 2 # Filter cloth, filter screen, water-permeable non-ion selective diaphragm, 58-separator-free gas-liquid mixing electrolytic cell, 59-electrolytic cell electric field line channel, 60-electrolyte ion current interrupter, 61-gas-liquid mixer multi-way air inlet pipe component, 62-bubble reaction liquid guide cover, 63-electrolytic hydrogen, 64-bubble drainage cover in electrolyte, 65-insulating partition plate in electrolytic cell, 66-hydrogen-containing tail gas high-altitude discharge pipe, 67-sulfuric acid solution, 68-valve, 69-pump, 70-overflow buffer tank with gas-liquid mixer, 71-methane, 72-methanol, 73-ethanol, 74-cooling collection bottle, 75-spray pipe.

[0113] In the drawings and the following embodiments, multiple components of the same component type in a device are represented by "reference numerals." For example, electrolytic cell body 1-1 refers to one electrolytic cell body, and electrolytic cell body 1-2 refers to another electrolytic cell body. When there are three or more components of the same component type, "~" is used for abbreviation. For example, electrolytic cell bodies 1-1, 1-2, and 1-3 are referred to as electrolytic cell bodies 1-1 to 1-3, or 1-1 to 3. DETAILED DESCRIPTION

[0114] The present invention will be further described below through specific embodiments.

[0115] The gas-liquid mixing electrolytic cell, mixed gas separation cell, electrolytic anode, electrolytic cathode, bipolar electrode, bipolar electrode insulation cage, electrolytic cell gas-liquid mixer, agitator, temporary storage tank, overflow buffer tank, tail gas treatment tank, insoluble anode conductor, insoluble cathode conductor, and electrolyte ion current interrupter used in the embodiments of the present invention are all manufactured by Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan, Guangdong Province, China. The sensors, automatic detection and feeding controller, valves, pumps, chemical raw materials, and gas detectors used are all commercially available products.

[0116] In addition to the above-mentioned products, those skilled in the art may also select other products with similar properties to the above-mentioned products listed in the present invention according to routine selection, and all of them can achieve the purpose of the present invention.

[0117] Example 1

[0118] As shown in FIG17 , this is Example 1 of the gas-liquid mixing electrochemical reaction device of the present invention used as a methane methanol generator, which includes a gas-liquid mixing electrolytic cell, a safety photoelectric control alarm system 54 , and an overflow buffer tank 70 with a gas-liquid mixer.

[0119] The gas-liquid mixing electrolytic cell is a type A structure electrolytic cell of FIG1, comprising an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and a vacuum jet electrolytic cell gas-liquid mixer 7. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with an electrolytic cell separator 1. # The proton membrane 2 separates the electrolytic anode and cathode sections. The cathode section is equipped with an insoluble cathode conductor 24, directly connected to the electrolytic cathode, and a bubble deflector 64, located above the electrolytic cathode 4 and the insoluble cathode conductor 24, to remove bubbles from the electrolyte. The insoluble cathode conductor 24 serves as an electrocatalytic component. A vacuum jet electrolytic cell gas-liquid mixer 7 is connected to the cathode section of the electrolytic cell via a liquid flow conduit, with its outlet directed toward the electrolytic cathode 4 and the insoluble cathode conductor 24. The electrolytic cell 1 has an effective volume of 60 liters and is equipped with a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction.

[0120] The electrolytic anode is a conductor with a gold-plated surface, and the surfaces of the electrolytic cathode and the bipolar electrode are conductors with a platinum-plated surface.

[0121] The safety photoelectric control alarm system is a production safety measure.

[0122] The overflow buffer tank 70 with a gas-liquid mixer is provided with a common bubbling gas-liquid mixer 14 with a volume of 40 liters, which is used to dissolve carbon dioxide into pure water to produce saturated carbonate electrolyte as the cathode tank electrolyte and the anode tank electrolyte of the gas-liquid mixing electrolytic cell.

[0123] This embodiment uses a type A gas-liquid mixed electrolytic cell to produce methane products through an electrochemical method. The mixed gas 41 escaping from the electrolytic cell body 1 contains methane, carbon dioxide, carbon monoxide, and hydrogen.

[0124] A method for producing methane as a main product in a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0125] 1. Pure water 37 is added to the overflow buffer tank 70 with a gas-liquid mixer, and a saturated carbonic acid solution is prepared and added to the anode tank area and cathode tank area of ​​the gas-liquid mixing electrolytic cell as the electrolyte.

[0126] 2. Start pump 69 to operate electrolytic cell gas-liquid mixer 7, supplying carbon dioxide gas 29 through gas-liquid mixer 14 to dissolve it in pure water 37 to form a gas-liquid mixture, which contacts the electrolytic cathode 4 and insoluble cathode conductor 24 to produce carbonate electrolyte. Then, connect electrolytic power supply 5 to cause the following electrochemical reaction to occur in the gas-liquid mixing electrolytic cell:

[0127] Electrolysis anode: 4[OH] - -4e - →2H2O+O2

[0128] Electrolytic cathode and insoluble cathode conductor: 2H + +2e - →H2CO2+2H + +2e - →CO+H2OCO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2O

[0129] 3. During the reaction, the carbon dioxide input was 0.02 liters / minute, the electrolysis power supply output voltage was 150 V, and the electrolysis current was 1.8 A. The operation was carried out at operating parameters far higher than the electrolyte decomposition voltage value. The mixed gas 41 was detected at the reaction gas escape pipe of the gas-liquid hybrid electrolyzer.

[0130] The detection results of the mixed gas 41 escaping from the electrolytic cell reaction liquid are listed in Table 1.

[0131] Example 2

[0132] As shown in FIG18 , this is Example 2 of the gas-liquid mixed electrochemical reaction device used as a methane methanol generator according to the present invention, wherein the device includes a gas-liquid mixed electrolytic cell.

[0133] The gas-liquid mixing electrolytic cell is a C2 type structure electrolytic cell in FIG3, comprising an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with an electrolytic cell separator 1. # The reverse osmosis membrane 2 is divided into an electrolytic anode tank area and an electrolytic cathode tank area, and an insoluble anode conductor 23 and a bipolar electrode 6-1 are provided in the anode tank area, which are directly conductively connected to the electrolytic anode. An insoluble cathode conductor 24 and a bipolar electrode 6-2 are provided in the cathode tank area, which are directly conductively connected to the electrolytic cathode. The bipolar electrodes 6-1, 6-2, the insoluble anode conductor 23, and the insoluble cathode conductor 24 are electrocatalytic components. The two vacuum jet electrolytic cell gas-liquid mixers 7-1 and 7-2 are each equipped with multi-way air inlet pipes 61-1 and 61-2. These are connected to the electrolytic anode and cathode cell sections, respectively, via pumps 69-1 and 69-2. The outlet of the vacuum jet electrolytic cell gas-liquid mixer 7-1 is directed toward the electrolytic anode 3, insoluble anode conductor 23, and bipolar electrode 6-1, while the outlet of the vacuum jet electrolytic cell gas-liquid mixer 7-1 is directed toward the electrolytic cathode 4, insoluble cathode conductor 24, and bipolar electrode 6-2. The electrolytic cell body 1 has an effective volume of 60 liters and is equipped with two sealed tank covers 28-1 and 28-2 for collecting escaping gases from the electrolytic cell reactions.

[0134] The electrolytic anode is an insoluble titanium-based coating anode, the electrolytic cathode is stainless steel, the insoluble anode conductor is graphite, the insoluble cathode conductor is titanium, and the surface of the bipolar electrode is a platinum-plated conductor.

[0135] This embodiment uses a C-2 type gas-liquid mixed electrolytic cell to produce methane products through an electrochemical method. The mixed gases 41-1 and 41-2 escaping from the electrolytic cell body 1 contain methane, carbon dioxide, carbon monoxide, and hydrogen.

[0136] A method for producing methane as a main product in a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0137] 1. Add pure water 37 to the anode and cathode zones of the gas-liquid mixing electrolytic cell. Start pumps 69-1 and 69-2 to circulate the electrolyte and operate the two electrolytic cell gas-liquid mixers 7-1 and 7-2.

[0138] 2. Hydrogen and carbon dioxide are supplied to the electrolytic cell 1 to form a carbon dioxide-containing aqueous solution as the electrolyte. Valves 68-2 to 68-5 are adjusted to ensure that the two gases react in the anode and cathode regions. The electrolysis power supply 5 is connected and the output voltage and current are adjusted to 4.2V and 410mA, respectively, slightly higher than the electrolyte decomposition voltage of 3.2V. The following main electrochemical reactions occur in the gas-liquid hybrid electrolytic cell:

[0139] Components with positive charge during electrolysis: H2-2e - →2H +

[0140] Negatively charged components during electrolysis: 2H + +2e - →H2CO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2OCO2+2H + +2e - →CO+H2O

[0141] 3. During the reaction, the total input of carbon dioxide is 0.2 liters / minute, and the total input of hydrogen is 0.8 liters / minute. The mixed gases 41-1 and 41-2 are detected respectively.

[0142] The detection results of the mixed gases 41-1 and 41-2 escaping from the electrolytic cell reaction liquid are listed in Table 1.

[0143] Example 3

[0144] As shown in FIG19 , this is Example 3 of the gas-liquid mixed electrochemical reaction device used as a methane methanol generator of the present invention, which includes a gas-liquid mixed electrolytic cell.

[0145] The gas-liquid hybrid electrolytic cell is a C-2 structure electrolytic cell as shown in Figure 5 , comprising an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and a vacuum jet and bubbling electrolytic cell gas-liquid mixer 9. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with a conventional insulating through-hole support baffle 12, an insoluble anode conductor 23 directly electrically connected to the electrolytic anode, and an insoluble cathode conductor 24 directly electrically connected to the electrolytic cathode; the insoluble anode conductor 23 and the insoluble cathode conductor 24 are electrocatalytic components.

[0146] The combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9 is constructed from a conductive material and electrically connected to the positive or negative electrode of the electrolytic power source via a conductive connection line 45. An ultrasonic generator 25 is also provided in its liquid flow conduit. The combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9 is connected to the electrolytic cell body 1 via a pump 69 via a liquid flow conduit. Its outlet faces the electrolytic cathode 4 and insoluble cathode conductor 24, or the electrolytic anode 3 and insoluble anode conductor 23, either towards the same electrode connected to the electrolytic power source via the conductive connection line 45. The electrolytic cell body 1 has an effective volume of 750 liters and is equipped with a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction.

[0147] The electrolytic anode is conductive graphite, the insoluble anode conductor is nickel wire, and the electrolytic cathode and the insoluble cathode conductor are both conductive graphite.

[0148] This embodiment uses a C-2 type gas-liquid mixed electrolytic cell to produce methane products through an electrochemical method. The mixed gas 41 escaping from the electrolytic cell body 1 contains methane, carbon dioxide, carbon monoxide, and hydrogen.

[0149] A method for producing methane as a main product in a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0150] 1. Add pure water 37 to the gas-liquid hybrid electrolytic cell, start the pump 69 and input carbon dioxide gas to prepare a saturated carbonate solution in the water circulation as the electrolyte.

[0151] 2. Turn on the electrolysis power supply 5 and adjust the output voltage to 4.5V and the current to 560mA. Input the hydrogen gas to the electrolytic cell 1. The cell pressure is 4.5V, slightly higher than the electrolyte decomposition voltage value of 3V, and the electrolysis operation is carried out. The hydrogen gas and the electrolyte are mixed as gas and liquid and then contact the electrolytic anode and the insoluble anode conductor, causing the following main electrochemical reactions to occur in the electrolytic cell:

[0152] Components with positive charge during electrolysis: H2-2e - →2H + CO2+H2-2e→CO+H2OCO2+4H2-8e→CH4+2H2O

[0153] Negatively charged components during electrolysis: 2H + +2e - →H2CO2+2H + +2e - →CO+H2OCO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2O

[0154] 3. During the reaction, the carbon dioxide input was 0.2 liters / minute, and the hydrogen input was 0.8 liters / minute. The mixed gas 41 was tested to obtain data on methane, carbon monoxide, carbon dioxide, and hydrogen. The test results of the mixed gas 41 escaping from the electrolytic cell reaction liquid are listed in Table 1.

[0155] Example 4

[0156] As shown in FIG20 , the fourth embodiment of the gas-liquid mixed electrochemical reaction device of the present invention used as a methane methanol generator is shown, and the device includes two gas-liquid mixed electrolytic cells, a gas-liquid separation or washing tank 13, a common auxiliary electrolytic cell 40, an automatic detection and feeding controller 46, a refrigerator 50, two condensers 51 - 1 and 51 - 2, and two cooling and collecting bottles 74 - 1 and 74 - 2.

[0157] One of the gas-liquid hybrid electrolytic cells is a C2 type electrolytic cell of FIG3, comprising an electrolytic cell body 1-1, an electrolytic anode 3-1, an electrolytic cathode 4-1, an electrolytic power supply 5-1, and electrolytic cell gas-liquid mixers 9-1 and 9-2 combining a vacuum jet type and a bubbling type. The electrolytic anode 3-1 is connected to the positive electrode of the electrolytic power supply 5-1, and the electrolytic cathode 4-1 is connected to the negative electrode of the electrolytic power supply 5-1. The electrolytic cell body 1-1 is provided with a cation exchange membrane electrolytic cell separator 1 # 2, which is divided into an electrolytic anode tank area and an electrolytic cathode tank area, and a hot and cold temperature exchanger 17-1, an insoluble anode conductor 23-1 directly conductively connected to the electrolytic anode, and a sensor 47-1 are provided in the anode tank area, and a hot and cold temperature exchanger 17-2, an insoluble cathode conductor 24-1 directly conductively connected to the electrolytic cathode, and a sensor 47-2 are provided in the cathode tank area; wherein the insoluble anode conductor 23-1 and the insoluble cathode conductor 24-1 are electrocatalytic components.

[0158] The electrolytic cell gas-liquid mixer 9-1, which combines the vacuum jet and bubbling types, is connected to the anode tank area of ​​the electrolytic cell body 1-1 by a liquid flow pipeline through the overflow buffer tank 21-1 and the pump 69-2. Its gas inlet is connected to the tail gas outlet of the gas-liquid separation or washing tank 13, the carbon dioxide gas cylinder 56, and the gas outlet of the overflow buffer tank 21-1, and its outlet is directed toward the electrolytic anode 3-1 and the insoluble anode conductor 23-1. The electrolytic cell gas-liquid mixer 9-2, which combines the vacuum jet and bubbling types, is connected to the cathode tank area of ​​the electrolytic cell body 1-1 by a liquid flow pipeline through the overflow buffer tank 21-2 and the pump 69-3. Its gas inlet is connected to the carbon dioxide gas cylinder 56, and its outlet is directed toward the electrolytic cathode 4-1 and the insoluble cathode conductor 24-1. The effective volume of the electrolytic cell body 1-1 is 60 liters, and is provided with a sealed tank cover 28-1 for collecting the escaped gas from the electrolytic cell reaction. Its tail gas outlet and the tail gas outlet of the overflow buffer tank 21-2 are connected to the cooling collection bottle 74-1 through a condenser 51-1 cooled by a refrigerator 50.

[0159] The second gas-liquid hybrid electrolytic cell is a C2-type structure electrolytic cell of Figure 8, including an electrolytic cell body 1-2, an electrolytic anode 3-2, electrolytic cathodes 4-2 and 4-3, electrolytic power supplies 5-2 and 5-3, and an electrolytic cell gas-liquid mixer 9-3 combining vacuum jet and bubbling types. The electrolytic anode 3-2 is connected to the positive poles of the electrolytic power supplies 5-2 and 5-3, and the electrolytic cathodes 4-2 and 4-3 are connected to the negative poles of the electrolytic power supplies 5-2 and 5-3, respectively. The electrolytic cell body 1-2 is provided with bipolar electrolytic cells 6-1 and 6-2, bipolar electrode stacking fixed electrically insulating mesh boxes 11-1 and 11-2 loaded with bipolar electrodes, hot and cold temperature exchangers 17-4 and 17-5, an insoluble anode conductor 23-2 directly conductively connected to the electrolytic anode, insoluble cathode conductors 24-2 and 24-3 directly conductively connected to the electrolytic cathode, and a sensor 47-8; wherein the insoluble anode conductor 23-2, the insoluble cathode conductors 24-2 and 24-3, and the bipolar electrolytic cells 6-1 and 6-2 are electrocatalytic components.

[0160] The electrolytic cell gas-liquid mixer 9-3, a combination of vacuum jet and bubbling, is connected to the electrolytic cell body 1-2 via an electrolyte cutoff ion flow channel 60 and a pump 69-5. Its gas inlet is connected to the exhaust gas outlet of the cooling and collecting bottle 47-1, the exhaust gas outlet of the electrolyte cutoff ion flow channel 60, and the exhaust gas outlet of the gas-liquid separation or washing tank 13. Its outlet faces the electrolytic anode 3-2 and the insoluble anode conductor 23-2. The electrolytic cell body 1-2 has an effective volume of 90 liters and is equipped with a sealed tank cover 28-2 for collecting escaping gases from the electrolytic cell reaction. Its exhaust gas outlet is connected to the cooling and collecting bottle 74-2 via a condenser 51-2 cooled by a refrigerator 50.

[0161] The electrolytic anode 3-1 is a conductor with a gold-plated surface, the electrolytic cathode 4-1 is nickel, the electrolytic anode 3-2 is a conductor with a platinum-plated surface, the electrolytic cathodes 4-2 and 4-3 are titanium, the insoluble anode conductor 23-1 is nickel, the insoluble anode conductor 23-2 is an insoluble electrode with a titanium-based coating, and the insoluble cathode conductors 24-1, 24-2 and 24-3 are all conductive graphite.

[0162] The hydrogen outlet of the conventional auxiliary electrolytic cell 40 is connected to the gas-liquid separation or washing tank 13 through a conventional vacuum jet gas-liquid mixer 15 .

[0163] The electrolyte ion flow channel 60 is provided with a hot and cold temperature exchanger 17 - 3 and a sensor 47 - 4 .

[0164] The two cooling and collecting bottles 74-1 and 74-2 are used to cool and collect methane. Sensors 47-3, 47-4, 47-5, and 47-6 are provided on the tail gas outlet connecting pipe of the cooling and collecting bottle 74-1, and sensors 47-9, 47-10, 47-11, and 47-12 are provided on the tail gas outlet connecting pipe of the cooling and collecting bottle 74-2.

[0165] The hot and cold temperature exchangers 17 - 1 to 5 are used to heat the electrolytic reaction liquid, and the electrolytic reaction liquid is regulated to 78° C. during the process.

[0166] The refrigerator 50 provides cold water for the condenser and the cooling collection bottle.

[0167] The adjustable valves 68-1 and 68-2 are used to adjust the supply of hydrogen to tanks 1-1 and 1-2. The adjustable valves 68-4 and 68-5 are used to adjust the supply of carbon dioxide gas to the cathode and anode regions of tank 1-1.

[0168] This embodiment uses two gas-liquid hybrid electrolytic cells and two sets of condensation and methanol collection systems to produce methane and methanol products through electrochemical reaction methods.

[0169] A method for producing methane and methanol as main products in a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0170] 1. Pure water 37 is added to the two tank areas of the gas-liquid hybrid electrolytic cell 1-1, and pure water 37 is also added to the electrolytic cell body 1-2.

[0171] 2. Turn on the power of the device to enable the automatic detection and feeding controller 46 to process the data detected by each sensor on site, and issue instructions to operate the device under normal conditions.

[0172] 3. Start multiple pumps and open multiple hot and cold temperature exchangers 17 to heat the reaction solution to 78°C, operate the gas-liquid mixers in the two electrolytic cells, start the common auxiliary electrolytic cell 40, and open the carbon dioxide cylinder to supply CO2 and H2 to the electrolytic cell gas-liquid mixer 9-1, respectively. Supply CO2 to the electrolytic gas-liquid mixer 9-2 to participate in the electrochemical reaction in cell 1-1, forming an aqueous solution containing carbon dioxide as the electrolyte in the two cells. Connect the electrolysis power supply 5-1 and adjust it to 4.8V, slightly higher than the electrolyte decomposition voltage of 3.2V in the electrolytic cell body 1-1, and perform the electrolysis operation for two hours, causing the following main electrochemical reactions to occur in the electrolytic cell body 1-1:

[0173] Electrolysis anode and insoluble anode conductor in electrolytic cell 1-1: H2-2e - →2H +

[0174] Electrolytic cathode and insoluble cathode conductor: 2H + +2e - →H2CO2+2H + +2e - →CO+H2OCO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2O

[0175] The main components of the mixed gas 41-1 released from the anode region of electrolytic cell 1-1 are methane, methanol, carbon monoxide, carbon dioxide, and hydrogen. The main components of the mixed gas 41-2 released from the cathode region are methane, methanol, carbon monoxide, carbon dioxide, and hydrogen. Mixed gases 41-1 and 41-2 are condensed and collected to obtain methanol. The remaining mixed gas 41-3 mainly consists of methane, carbon monoxide, carbon dioxide, and hydrogen.

[0176] 4. The mixed gas 41-3 and the supplementary hydrogen are input into the electrolytic cell gas-liquid mixer 9-3 of the electrolytic cell body 1-2 to participate in the electrochemical reaction in the electrolytic cell body 1-2. The electrolysis power supplies 5-2 and 5-3 are adjusted to 4.5V above the electrolyte decomposition voltage value of 3.9V of the electrolyte in the electrolytic cell body 1-2 to carry out the electrolysis operation for two hours. The following main electrochemical reactions occur in the electrolytic cell body 1-2.

[0177] Electrolysis anode and insoluble anode conductor in electrolytic cell 1-2 and anode end of bipolar electrode: H2-2e - →2H +

[0178] Cathode end of bipolar electrode: CO+6H + +6e- →CH4+H2OCO+4H + +4e - →CH3OH

[0179] Electrolytic cathode and insoluble cathode conductor: 2H + +2e - →H2CO2+2H + +2e - →CO+H2OCO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2O

[0180] The CO2 concentration in the electrolyte in the electrolytic cell body 1-2 is low, so the CO product generated by the reaction of carbon dioxide CO2 and hydrogen H2 is small. Therefore, the mixed gas 41-4 mainly becomes methane, methanol, hydrogen and a small amount of carbon dioxide. The mixed gas 41-4 is sent to the condenser for cooling and then collected to obtain methanol. The mixed gas 41-5 is mainly methane and hydrogen and a small amount of carbon dioxide to be used in the next process or separated and collected.

[0181] 5. During the operation, the automatic detection and feeding controller 46 operates according to the pre-programmed control, and various gas concentration detectors automatically record the detection data of the process.

[0182] The detection results of the mixed gases 41-1, 41-2, 41-3, 41-4 and 41-5 produced by the device are listed in Table 1.

[0183] Example 5

[0184] As shown in Figure 21, Example 5 of the gas-liquid mixing electrochemical reaction device of the present invention, used as a methane-methanol generator, comprises two gas-liquid mixing electrolytic cells, two temporary storage tanks 20-1 and 20-2, electrolytic cell bodies 1-1 and 1-2, a vacuum jet electrolytic cell gas-liquid mixer 7, two bubbling electrolytic cell gas-liquid mixers 8, and a combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9, two solution guide plates 48, two gas-liquid mixer multi-way air inlet pipe components 61, a bubble-containing reaction liquid guide cover 62, a liquid spray pipe 75, and multiple valves and pumps.

[0185] One of the gas-liquid mixing electrolytic cells adopts the C2 type electrolytic cell of the structure of Figure 10, including an electrolytic cell body 1-1, electrolytic anodes 3-1 to 3-8, an electrolytic cathode 4-1, electrolytic power supplies 5-1 to 5-8, a vacuum jet electrolytic cell gas-liquid mixer 7, and bubbling electrolytic cell gas-liquid mixers 8-1 and 8-2. The electrolytic anodes 3-1 to 3-8 are connected to the positive poles of the electrolytic power supplies 5-1 to 5-8, and the electrolytic cathode 4-1 is connected to the negative pole of the electrolytic power supplies 5-1 to 5-8. The electrolytic cell body 1-1 is provided with eight insulating partition plates for separating each electrolytic anode therein, thereby forming eight independent electrolytic units in one gas-liquid mixing electrolytic cell. It is also provided with insoluble anode conductors 23-1 to 23-8 directly conductively connected to the electrolytic anodes and an insoluble cathode conductor 24-1 directly conductively connected to the electrolytic cathode. The electrolytic anodes 3-1 to 3-8 and the electrolytic cathode 4-1 are all parallel electrodes connected in parallel, and the angle formed by their parts with the gas-liquid mixture ejection straight line of the electrolytic cell gas-liquid mixer is greater than 0° and less than 90°. After passing through the gas-liquid separation washing tank 13, the electrolytic cell body 1-1 is connected to the temporary storage tanks 20-1 and 20-2 respectively. The liquid inlet of the vacuum jet electrolytic cell gas-liquid mixer 7 is connected to the temporary storage tanks 20-1 and 20-2 respectively, and its outlet is connected to the electrolytic cell body 1-1 through the bubbling electrolytic cell gas-liquid mixers 8-1 and 8-2 respectively. The gas inlet is provided with a gas-liquid mixer multi-way air inlet pipe component 61-1. The outlets of the bubbling electrolytic cell gas-liquid mixers 8-1 and 8-2 are directed toward the electrolytic anodes 3-1 to 3-8 and the insoluble anode conductors 23-1 to 23-8.

[0186] The electrolytic anodes 3-1 to 3-8 are conductive graphite, the insoluble anode conductors 23-1 to 23-8 are nickel wires, the electrolytic cathode 4-1 is nickel, and the insoluble cathode conductor is a conductive wire with a gold-plated surface.

[0187] The second gas-liquid hybrid electrolytic cell adopts the vertical cell shown in Figure 12, which contains three independent electrolysis units. It includes an electrolytic cell body 1-2, electrolytic anodes 3-9 to 3-11, electrolytic cathodes 4-2 to 4-4, electrolytic power supplies 5-9 to 5-11, and an electrolytic cell gas-liquid mixer 9 that combines vacuum jet and bubbling types. The electrolytic anodes 3-9 to 3-11 are respectively connected to the positive electrodes of the electrolytic power supplies 5-9 to 5-11, and the electrolytic cathodes 4-2 to 4-4 are respectively connected to the negative electrodes of the electrolytic power supplies 5-9 to 5-11. The electrolytic cell 1-2 is equipped with insulating through-hole baffles separating each electrode. It also features bipolar electrodes containing conductive powder particles; insoluble anode conductors 23-9 to 23-11 directly conductively connected to the electrolytic anode; insoluble cathode conductors 24-2 to 24-4 directly conductively connected to the electrolytic cathode; a bubble-containing reaction liquid deflector 62 positioned above the terminal electrode of the liquid flow within the electrolytic cell 1-2; and a liquid spray pipe 75 located at the bottom of the electrolytic cell 1-2. The bubble-containing reaction liquid deflector 62 is connected to the liquid spray pipe 75 via a valve 68-3 and a pump 69-3. The electrolytic cell gas-liquid mixer 9, a combination of vacuum jet and bubbling systems, is connected to the electrolytic cell body 1-2 via a pump. Its gas inlet is equipped with a multi-channel gas-liquid mixer inlet pipe assembly 61-2, one of which is connected to the gas outlet of the gas-liquid separation and washing tank. Its outlet is located at the bottom of the electrolytic cell body 1-2, facing the electrolytic electrodes and insoluble conductors. The electrolytic cell body 1-2 has an effective volume of 90 liters and is equipped with a sealed tank cover 28-2 to collect escaping gases from the electrolytic cell reaction. Its exhaust gas outlet is connected to a cooling collection bottle 74-2 via a condenser pipe 51-2.

[0188] The electrolytic anodes 3-9 to 3-11 are all titanium-based coated insoluble anodes, the electrolytic cathodes 4-2 to 4-4 are all graphite, the insoluble anode conductors 23-9 to 23-11 and the insoluble cathode conductors 24-2 to 24-4 are all conductors of different materials that are a mixture of conductive graphite, stainless steel wire and nickel wire, and the bipolar electrode 6 is platinum powder that can flow with the electrolyte and act as a bipolar electrode in the electric field.

[0189] The two temporary storage tanks 20-1 and 20-2 are used to cut off short-circuit paths in the electrolyte ion flow. They are equipped with a solution flow area expansion guide plate 48-1 and a sensor 47-1, and a solution flow area expansion guide plate 48-2 and a sensor 47-2, respectively. Sensors 47-1 and 47-2 are liquid level gauges. The solution flow area expansion guide plate 48 facilitates the decomposition of methane from the electrolyte.

[0190] The liquid spraying pipe 75 is used to take the electrolyte and spray the platinum powder 6 that has settled on the bottom.

[0191] This embodiment utilizes two C2 electrolytic cells and adopts the electrolyte decomposition voltage value to electrochemically synthesize methane products. This process has low production energy consumption and high economic benefits.

[0192] A method for producing methane as a main product in a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0193] 1. Add pure water to temporary storage tanks 20-1 and 20-2, start pump 69-1 to add pure water to electrolytic cell body 1-1, and add pure water to electrolytic cell body 1-2.

[0194] 2. Open the regulating valves and start all pumps to circulate the electrolyte in the two electrolytic cells.

[0195] 3. Carbon dioxide 29 and hydrogen 31 are fed into the electrolytic cell gas-liquid mixer 7 to form a carbon dioxide-containing aqueous solution as the electrolyte, wherein the carbon dioxide is fed at a reaction rate of 0.2 / minute and the hydrogen is fed at a reaction rate of 0.8 / minute. Electrolytic power supplies 5-1 to 8 are started and the output voltage of each electrolytic power supply is adjusted to 4V, which is higher than the electrolyte decomposition voltage of the electrolyte in the electrolytic cell body 1-1, which is 2.8V or more. The two temporary storage tanks, under the control of the liquid level gauge, rotate to pump the electrolyte in the tanks into the electrolytic cell body 1-1 to carry out the following main electrochemical reactions:

[0196] Electrolytic anode and insoluble anode conductor: H2-2e - →2H +

[0197] Electrolytic cathode and insoluble cathode conductor: 2H + +2e - →H2CO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2OCO2+2H + +2e - →CO+H2OCO2+2H + +2e - →HCOOH2CO2+12H + +12e - →C2H4+4H2O2CO2+12H + +12e - →C2H5OH+3H2O

[0198] The main components of the mixed gas 41 - 2 are methane, carbon monoxide, carbon dioxide, and hydrogen.

[0199] 4. The mixed gas 41-2 is drained into the electrolytic cell gas-liquid mixer 9 of the electrolytic cell body 1-2 to form an aqueous solution containing carbon dioxide as the electrolyte, and hydrogen is added to participate in the reaction. The hydrogen reaction amount is supplemented at 0.1 liters / minute. The bubble-containing reaction liquid guide 62 is set on the upper part of the electrolytic cell body to guide the carbon monoxide gas, carbon dioxide gas and hydrogen that have not participated in the reaction back to the bottom of the electrolytic cell body 1-2 to flow upward again and participate in the electrochemical reaction of synthesizing methane again. The platinum powder of the bipolar electrode 6 plays an electrocatalytic role in the electric field to synthesize CH3OH, CH4 and H2O with carbon monoxide CO and hydrogen H2. The following main electrochemical reactions occur in the electrolytic cell body 1-2.

[0200] Electrolytic anode and insoluble anode conductor and anode end of bipolar electrode: H2-2e - →2H +

[0201] Cathode end of bipolar electrode: CO+4H + +4e - →CH3OHCO+6H + +6e - →CH4+H2O

[0202] Electrolytic cathode and insoluble cathode conductor: 2H + +2e - →H2CO2+8H + +8e - →CH4+2H2OCO2+6H + +6e - →CH3OH+H2OCO2+2H + +2e - →CO+H2O

[0203] Since the concentration of carbon dioxide in the electrolyte of the electrolytic cell body 1-2 is low, less CO product is generated by the reaction.

[0204] 5. Use carbon dioxide, carbon monoxide, hydrogen, and methane gas concentration detectors to detect the mixed gas 41-3, obtain detection data of various gas concentrations, and perform COD concentration detection on the solutions in the electrolytic cell body 1-1 and the electrolytic cell body 1-2.

[0205] The concentrations of various gases in the mixed gases 41-2 and 41-3 escaping from the reaction liquids of the two electrolytic cells and the COD detection concentration values ​​of the electrolytes in the electrolytic cell body 1-1 and the electrolytic cell body 1-2 are all listed in Table 1.

[0206] Example 6

[0207] The gas-liquid mixing electrochemical reaction device shown in FIG1 is embodiment 6 of the present invention, which is composed of an electrolytic cell body 1, a sealed tank cover 28 for collecting the escaped gas from the electrolytic cell reaction, an electrolytic cell separator 2, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. # The electrolytic cell body 1 is divided into an anode cell area and a cathode cell area. A sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction covers only the cathode cell area. An electrocatalytic component, namely an insoluble cathode conductor 24, is disposed within the cathode cell area, both immersed in the electrolyte in the cathode cell area. The electrolytic cell gas-liquid mixer is a vacuum jet electrolytic cell gas-liquid mixer 7 having an air inlet, a liquid inlet, and an outlet. The air inlet and liquid inlet are connected to the top and bottom of the cathode cell area, respectively. In other words, in this embodiment, the electrolytic gas generated in the cathode cell area is mixed with the electrolyte in the cathode cell area to form a gas-liquid mixture, which is then ejected through an outlet extending above the electrolyte level in the cathode cell area and toward the electrocatalytic component, namely the insoluble cathode conductor 24.

[0208] Example 7

[0209] The gas-liquid mixing electrochemical reaction device shown in FIG2 is Example 7 of the present invention, which is composed of an electrolytic cell body 1, a sealed tank cover 28-1 and 28-2 for collecting the escaped gas from the electrolytic cell reaction, an electrolytic cell separator 2, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. # The electrolytic cell body 1 is divided into an anode cell area and a cathode cell area. A sealed cell cover 28-1 for collecting escaping gas from the electrolytic cell reaction covers the cathode cell area, while a sealed cell cover 28-2 for collecting escaping gas from the electrolytic cell reaction covers the anode cell area. An electrocatalytic component, namely an insoluble cathode conductor 24, is disposed within the cathode cell area, and both components are immersed in the electrolyte in the cathode cell area. The electrolytic cell gas-liquid mixer is a vacuum jet electrolytic cell gas-liquid mixer 7 having an air inlet, a liquid inlet, and an outlet. The air inlet and liquid inlet are connected to the top and bottom of the cathode cell area, respectively. In other words, this embodiment simultaneously uses external input gas and electrolytic gas generated in the cathode cell area to mix with the electrolyte in the cathode cell area, and then sprays the gas and liquid into the electrolyte through an outlet extending above the electrolyte level in the cathode cell area and toward the electrocatalytic component, namely the insoluble cathode conductor 24.

[0210] Example 8

[0211] The gas-liquid mixing electrochemical reaction device shown in FIG3 is embodiment 8 of the present invention, which is composed of an electrolytic cell body 1, a sealed tank cover 28-1 and 28-2 for collecting the escaped gas of the electrolytic cell reaction, an electrolytic cell separator 2, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer.# , the electrolytic cell body 1 is divided into an anode cell area and a cathode cell area. The sealed cell cover 28-1 for collecting the evolved gas from the electrolytic cell reaction covers the cathode cell area, and the sealed cell cover 28-2 for collecting the evolved gas from the electrolytic cell reaction covers the anode cell area. The electrocatalytic components, namely the bipolar electrode 6-1 and the insoluble anode conductor 23, are arranged in the anode cell area and are immersed in the electrolyte in the anode cell area. The electrocatalytic components, namely the bipolar electrode 6-2 and the insoluble cathode conductor 24, are arranged in the cathode cell area and are immersed in the electrolyte in the cathode cell area. The electrolytic cell gas-liquid mixer adopts vacuum jet type electrolytic cell gas-liquid mixer 7-1 and 7-2, which has an air inlet, a liquid inlet and an outlet. The air inlet and the liquid inlet of the vacuum jet type electrolytic cell gas-liquid mixer 7-1 are respectively connected to the anode cell. The top and bottom of the zone are connected, and the air inlet and liquid inlet of the vacuum jet electrolytic cell gas-liquid mixer 7-2 are connected to the top and bottom of the cathode tank zone, respectively. That is, in this embodiment, external input gas and electrolysis gas generated in the anode tank zone are mixed with the electrolyte in the anode tank zone for gas-liquid mixing, and the mixture is ejected through the outlet extending above the electrolyte surface in the anode tank zone and branching toward the electrocatalytic component, i.e., the bipolar electrode 6-1 and the insoluble anode conductor 23, respectively. At the same time, external input gas and electrolysis gas generated in the cathode tank zone are mixed with the electrolyte in the cathode tank zone for gas-liquid mixing, and the mixture is ejected through the outlet extending above the electrolyte surface in the cathode tank zone and branching toward the electrocatalytic component, i.e., the bipolar electrode 6-2 and the insoluble cathode conductor 24, respectively.

[0212] Example 9

[0213] The gas-liquid hybrid electrochemical reaction device shown in FIG4 is Example 9 of the present invention. The gas-liquid hybrid electrochemical reaction device shown in FIG4 is Example 8 of the present invention. It comprises an electrolytic cell body 1, an electrolytic cell separator, a sealed tank cover 28 for collecting escaped gas from the electrolytic cell reaction, an insulating through-hole support baffle 12, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. Depending on the requirements of the oxidation or reduction reaction, the positions of the electrolytic anode 3 and the electrolytic cathode 4 can be interchanged. Therefore, the electrolytic electrode on the left side of the figure is the electrolytic anode 3 or electrolytic cathode 4, and the electrolytic electrode on the right side is the corresponding other electrode. The electrolytic cell separator adopts electrolytic cell separator 2#-57 to separate the electrolytic cell body 1 into an anode cell area and a cathode cell area; one of the insulating through-hole support baffles 12 12-1 separates the electrolytic anode 3 or the electrolytic cathode 4 and the outlet of the electrolytic cell gas-liquid mixer, and the second insulating through-hole support baffle 12 12-2 overlaps with the electrolytic cell separator 57 to separate the electrolytic anode and the electrolytic cathode. The sealed tank cover 28 for collecting the escaped gas from the electrolytic cell reaction covers the electrolytic cell body 1; when the left electrolytic electrode is the electrolytic anode 3, a conductor 44 is set in the anode cell area as an electrocatalytic component, that is, an insoluble anode conductor and a bipolar electrode 6 and immersed in the electrolyte in the anode cell area, and the electrolytic cathode 4 is a parallel electrode connected in parallel; when the left electrolytic electrode is the electrolytic cathode, a conductor is set in the cathode cell area. The electrolytic body 44 serves as an electrocatalytic component, namely an insoluble cathode conductor and a bipolar electrode 6 and is immersed in the electrolyte in the cathode tank area. The electrolytic anode 3 is a parallel electrode connected in parallel; the electrolytic cell gas-liquid mixer adopts an electrolytic cell gas-liquid mixer 9 that combines a vacuum jet type and a bubbling type, which has an air inlet, a liquid inlet and an outlet. The liquid inlet is connected to the electrolytic cell body, that is, this embodiment uses external input gas from outside the electrolytic cell to mix the electrolyte in the anode tank area or the electrolyte in the cathode tank area for gas-liquid mixing, and sprays it through an outlet extending to the bottom of the electrolyte surface in the anode tank area and toward the electrocatalytic component, namely the bipolar electrode 6 and the insoluble anode conductor 23, or extends to the bottom of the electrolyte surface in the cathode tank area and toward the outlet of the electrocatalytic component, namely the bipolar electrode 6 and the insoluble cathode conductor 24.

[0214] Example 10

[0215] The gas-liquid hybrid electrochemical reaction device shown in FIG5 is Example 10 of the present invention and comprises an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and an insulating through-hole support baffle 12. Depending on the requirements of the oxidation or reduction reaction, the positions of the electrolytic anode 3 and the electrolytic cathode 4 can be interchanged. Therefore, the electrolytic electrode on the left side of the figure is either the electrolytic anode 3 or the electrolytic cathode 4, and the electrolytic electrode on the right side is the corresponding other electrode. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. An electrocatalytic component, namely an insoluble anode conductor 23 and an insoluble cathode conductor 24, is disposed within the electrolytic cell body 1. A sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction covers the electrolytic cell body. The electrolytic cell gas-liquid mixer 9 is a combination of a vacuum jet and bubbling type, electrically connected to the electrolysis power supply and equipped with an ultrasonic generator 25 on its jet tube. The mixer has an air inlet, a liquid inlet, and an outlet. The liquid inlet is connected to the electrolytic cell body. In this embodiment, external gas input from outside the electrolytic cell is mixed with the electrolyte within the electrolytic cell body, and the gas and liquid are ejected through an outlet extending below the electrolytic anode 3 and the electrocatalytic component, namely the insoluble anode conductor 23, or through an outlet extending below the electrolytic cathode 4 and the electrocatalytic component, namely the insoluble cathode conductor 24. An insulating through-hole support baffle 12 is disposed between the electrolytic anode 3 or the electrolytic cathode 4 and the outlet of the electrolytic cell gas-liquid mixer.

[0216] Example 11

[0217] The gas-liquid mixing electrochemical reaction device shown in Figure 6 is Example 11 of the present invention, which consists of an electrolytic cell body 1, one of the electrolytic cell partitions 2-1 and the other 2-2, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, a catalytic component, an electrolytic cell gas-liquid mixer, a gas-liquid separation washing tank 13, and a bubble-containing reaction liquid guide cover 93. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with electrolytic cell dividers 2-1 and 2-2 to divide it into an electrolytic anode cell area, an intermediate cell area and an electrolytic cathode cell area, and an electrocatalytic component, namely a plurality of bipolar electrodes 6, is provided in the intermediate cell area; a bubble-containing reaction liquid flow guide 93 is provided at the electrolytic cathode; the bubble-containing reaction liquid flow guide 93 is connected to the cathode cell area through a gas-liquid separation washing tank 13, and a sealed tank cover 28 for collecting escaping gas from the electrolytic cell reaction only covers the intermediate cell area and the electrolytic cathode cell area, and the part located in the intermediate cell area is provided with a gas-liquid mixed electrolytic cell exhaust pipe port 51, and a gas pressure balance connecting pipe 39 is provided between the electrolytic cathode cell area and the intermediate cell area; the electrolyte in the intermediate cell area is the reaction liquid that needs to be treated. The electrolytic cell gas-liquid mixer adopts a vacuum jet electrolytic cell gas-liquid mixer 7, which has an air inlet, a liquid inlet and an outlet. The air inlet is connected to the air outlet of the gas-liquid separation washing tank 13, and the liquid inlet is connected to the middle tank area. That is, this embodiment uses the electrolysis gas generated in the cathode tank area and the electrolyte in the middle tank area to mix the gas and liquid, and sprays it through the outlet extending above the electrolyte surface in the middle tank area and toward the electrocatalytic component 6, that is, the bipolar electrode.

[0218] Example 12

[0219] The gas-liquid hybrid electrochemical reaction device shown in Figure 7 is Example 12 of the present invention. It is a three-divided gas-liquid hybrid electrolytic cell formed by symmetrically combining the B-type cells of Figure 2. It comprises an electrolytic cell body 1, an electrolytic cell divider 2, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. The electrolytic anode 3 is connected to the positive electrode of the electrolytic power supply 5, and the electrolytic cathode 4 is connected to the negative electrode of the electrolytic power supply 5. The electrolytic cell body 1 is provided with one of the electrolytic cell separators 2-1 and the other 2-2, which divides it into an electrolytic anode cell area and an electrolytic cathode cell area; the two cathode cell areas are respectively provided with an electrocatalytic component bipolar electrode 6-1 and an insoluble anode conductor 24-1 directly conductively connected to the electrolytic cathode, a bipolar electrode 6-2 and an insoluble cathode conductor 24-2; the sealed tank covers 28-1 and 28-2 for collecting the escaped gas of the electrolytic cell reaction are respectively covered on the two electrolytic anode cell areas or the two electrolytic cathode cell areas; the electrolytic cell gas The liquid mixer adopts a vacuum jet electrolytic cell gas-liquid mixer 7-1 and 7-2, which has an air inlet, a liquid inlet and an outlet. The air inlet is connected to the air outlet of the sealing tank cover 28-1 and 28-2 respectively, and the liquid inlet is connected to the two electrolytic anode tank areas or the two electrolytic cathode tank areas respectively. That is, this embodiment simultaneously uses external input gas from outside the electrolytic cell and the electrolytic gas generated in the cathode tank area to mix the gas and liquid with the electrolyte in the cathode tank area and sprays it through the outlet extending above the electrolyte surface of the electrolytic cathode tank area and toward the electrocatalytic component, i.e., the bipolar electrode.

[0220] Example 13

[0221] The gas-liquid hybrid electrochemical reaction device shown in Figure 8 is Example 13 of the present invention. It is a three-divided-tank gas-liquid hybrid electrolytic cell formed by symmetrically combining the C-2-type cells of Figure 4. It comprises an electrolytic cell body 1, a cell divider, a sealed cell cover 28 for collecting escaping gases from the cell reaction, an insulating through-hole support baffle 12, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. Depending on the requirements of the oxidation or reduction reaction, the positions of the electrolytic anode 3 and electrolytic cathode 4 can be interchanged. Thus, the electrolytic electrode located in the middle serves as either the electrolytic anode or the electrolytic cathode, while the electrolytic electrodes located in the cell zones on either side serve as the corresponding other electrode. The electrolytic cell separator adopts one of the electrolytic cell separators 57-1 and 57-2, which are respectively overlapped with the insulating through-hole support baffles 12-2 and 12-3 to separate the electrolytic cell body 1 into the anode cell area and the cathode cell area; the insulating through-hole support baffles 12-1 and 12-4 separate the electrolytic electrodes and the outlet of the electrolytic cell gas-liquid mixer in the two same cell areas, and the sealed cell covers 28 for collecting the escaped gas from the electrolytic cell reaction 28-1, 28-2 and 28-3 are respectively covered on each cell area of ​​the electrolytic cell body 1; an electrocatalytic component, i.e., an insoluble anode conductor 23, is set in the anode cell area and immersed in the electrolyte of the anode cell area, an electrocatalytic component, i.e., an insoluble cathode conductor 24, is set in the cathode cell area and immersed in the electrolyte of the cathode cell area, and electrocatalytic components are respectively set in the two cell areas located on both sides. The components are bipolar electrodes 6-1 and 6-2; the electrolyte in the anode tank area and the electrolyte in the cathode tank area are respectively the reaction liquids to be treated; the electrolytic cell gas-liquid mixer adopts one of the electrolytic cell gas-liquid mixers 9-1 and 9-2 which are a combination of vacuum jet type and bubbling type, which has an air inlet, a liquid inlet and an outlet, and the liquid inlet is connected to the electrolytic cell body, that is, this embodiment uses external input gas from outside the electrolytic cell to mix the electrolyte in the anode tank area or the electrolyte in the cathode tank area for gas-liquid mixing, and sprays it through the outlet extending to the bottom of the electrolyte surface in the anode tank area and toward the electrocatalytic components, namely the bipolar electrodes 6-1 and 6-2, and the insoluble anode conductors 23-1 and 23-3, or extends to the bottom of the electrolyte surface in the cathode tank area and toward the outlet of the electrocatalytic components, namely the bipolar electrodes 6-1 and 6-2, and the insoluble cathode conductors 24-1 and 24-3.

[0222] Example 14

[0223] The gas-liquid mixing electrochemical reaction device shown in Figure 9 is Example 14 of the present invention. It features an A-type cell with a circular electrode distribution structure. It comprises an electrolytic cell body 1, a cell divider 2, an insulating through-hole support baffle 12, an overflow buffer tank 22, a sealed tank cover 28 for collecting escaping gas from the electrolytic cell reaction, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and an electrolyte ion current interrupter 89. Depending on the requirements of the oxidation or reduction reaction, the positions of the electrolytic anode 3 and the electrolytic cathode 4 can be interchanged. Electrode 90-1 represents either the electrolytic anode or cathode, and electrode 90-2 represents the corresponding other electrode. An electrolytic cell separator 2 is provided in the electrolytic cell body 1 to separate it into an electrolytic anode cell area and an electrolytic cathode cell area, and an insulating through-hole support baffle 12 is provided below the electrolytic electrode. The electrolytic cell separator 2 is an anion exchange membrane, and an electrocatalytic component, namely a bipolar electrode 6, is provided in the cell area where the electrolytic electrode 90-1 is located. The electrolytic electrode 90-2 is the central electrode connected to one pole of the eight electrolytic power sources 5 5-1 to 5-8. The electrolytic electrode 90-1 is a plurality of electrodes arranged around the central electrode and is respectively connected to the other pole of each electrolytic power source. The sealed tank cover 28 for collecting the escaped gas from the electrolytic cell reaction covers the electrolytic cell body 1, and the tank area where the electrolytic electrode 90-1 is located is connected to the electrolyte ion current interrupter 89 and the overflow buffer tank 22 through a pipeline; the electrolytic cell gas-liquid mixer is a vacuum jet type and bubbling type combined electrolytic cell gas-liquid mixer 9, which has an air inlet, a liquid inlet and an outlet. The liquid inlet is connected to the overflow buffer tank 22, and the air inlet is connected to the tank area where the electrolytic electrode 90-1 is located. That is, in this embodiment, the gas electrolyzed in the tank area where the electrolytic electrode 90-1 is located is mixed with the electrolyte in the tank area where the electrolytic electrode 90-1 is located, and the gas is ejected through the outlet extending to the bottom of the electrolyte surface and toward the electrolytic electrode 90-1.

[0224] Example 15

[0225] The gas-liquid mixing electrochemical reaction device shown in Figure 10 is Example 15 of the present invention. It is a C-2 type cell with a circular electrode distribution structure. It consists of an electrolytic cell body 1, a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction, a gas-liquid separation and washing tank 13, an electrolytic anode 3 and an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and temporary storage tanks 20-1 and 20-2. Depending on the requirements of the oxidation or reduction reaction, the positions of the electrolytic anode 3 and the electrolytic cathode 4 can be interchanged. Electrolytic electrode 90-1 serves as either the electrolytic anode or cathode, and electrolytic electrode 90-2 serves as the corresponding electrode. Electrolytic electrode 90-2 is the central electrode connected to one of the eight electrolytic power supplies 5, 5-1 to 5-8. Electrolytic electrode 90-1 is a plurality of electrodes arranged around the central electrode and connected to the other electrode of each electrolytic power supply. Multiple electrolysis electrodes 90-1 are separated by insulating partitions, and there is no separation between the electrolysis electrode 90-1 and the electrolysis electrode 90-2. At the same time, the electrolysis anode and the electrolysis cathode are improved in electrocatalytic performance structure: the electrolysis electrode 90-1 and the electrolysis electrode 90-2 are both connected in parallel and the angle formed by the local part of the electrolysis electrode with the gas-liquid mixture ejection straight line of the electrolysis tank gas-liquid mixer is greater than 0° and less than 90°, and an electrocatalytic component is provided, namely an insoluble anode conductor 23 or an insoluble cathode conductor 24 in contact with the electrolysis electrode 90-2; a sealed seal is provided for collecting the escaped gas from the electrolysis tank reaction. The tank cover 28 covers the electrolytic cell body 1, and its gas-liquid mixing electrolytic cell exhaust pipe port 51 is connected to the temporary storage tank 20-1 and the temporary storage tank 20-2 respectively through the gas-liquid separation washing tank 13; the electrolytic cell gas-liquid mixer is a vacuum jet type and bubbling type combined electrolytic cell gas-liquid mixer 9, which has an air inlet, a liquid inlet and an outlet. The liquid inlet is connected to the temporary storage tank 20-1 and the temporary storage tank 20-2. That is, in this embodiment, external input gas from outside the electrolytic cell is used to mix with the electrolyte in the electrolytic cell body 1, and the gas and liquid are ejected through the outlet extending to the bottom of the electrolyte surface and toward the electrolysis electrode 90-1.

[0226] Example 16

[0227] The gas-liquid hybrid electrochemical reaction device shown in Figure 12 is Example 16 of the present invention. It is a vertical gas-liquid hybrid electrolytic cell with three sets of independent electrolytic units installed in layers. It includes an electrolytic cell body 1, three electrolytic anodes 3-1 to 3-3, three electrolytic cathodes 4-1 to 4-3, three electrolytic power supplies 5-1 to 5-3, an electrocatalytic component, and an electrolytic cell gas-liquid mixer. The electrolytic cell gas-liquid mixer is a combination of vacuum jet and bubbling electrolytic cell gas-liquid mixer 9. The electrolytic anode of each independent electrolytic cell is connected to the positive electrode of its corresponding electrolytic power supply, and the electrolytic cathode of each independent electrolytic cell is connected to the negative electrode of its corresponding electrolytic power supply. The electrolytic cell body 1 is externally connected to a liquid flow agitator 19 and internally houses insoluble anode conductors 23-1 through 23-3, which are directly electrically connected to the electrolytic anode, and insoluble cathode conductors 24-1 through 24-3, which are directly electrically connected to the electrolytic cathode. Insulating through-hole baffles 12-1 through 12-6 are also located between the electrolytic electrodes. A combined vacuum jet and bubbling electrolytic cell gas-liquid mixer 9 is connected to the electrolytic cell body via a pump for liquid flow, with its outlet directed toward the electrolytic electrodes and electrocatalytic components. A bubble-containing reaction liquid deflector 93 is installed above the terminal electrode where the electrolyte flow rises within the electrolytic cell body 1. This deflector is connected to the liquid flow agitator 19 and pumps the gas-liquid mixture back to the bottom of the electrolytic cell to re-enter the electrochemical reaction.

[0228] Comparative Example 1

[0229] This comparative example employed the same apparatus and method as Example 1, differing in that a conventional electrolytic cathode was employed without any electrocatalytic structural modifications. Measurements of the mixed gas escaping from the gas-liquid hybrid electrolytic cell revealed only 20 ppm of carbon monoxide and 0.02% methane, indicating a production efficiency significantly lower than that of Example 1.

[0230] Table 1 Test results of methane methanol generator

[0231] The embodiments of the present invention can achieve production with lower energy consumption when the electrochemical reaction is performed at a voltage less than or equal to the electrolyte decomposition voltage, or when the electrochemical reaction is performed at a voltage slightly higher than the electrolyte decomposition voltage when there is sufficient gas participating in the reaction so that it is difficult for electrical components to electrolyze gas.

[0232] Due to experimental conditions, the above embodiments only used a relatively small gas flow rate for the experiment. However, according to experimental rules, increasing the gas flow rate of the reaction gases can effectively improve the product production efficiency.

Claims

1. A gas-liquid hybrid electrochemical reaction device used as a methane methanol generator, comprising an electrolytic cell mainly composed of an electrolytic cell body, an electrolytic anode, an electrolytic cathode, and an electrolytic power supply, wherein: The electrolysis anode is connected to the positive electrode of the electrolysis power supply, and the electrolysis cathode is connected to the negative electrode of the electrolysis power supply. The electrolytic cell is characterized in that it includes at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, forming a gas-liquid mixing electrolytic cell; the outlet of the electrolytic cell gas-liquid mixer is oriented toward or located in the electrolytic cell body, and is used to bring the gas-liquid mixture obtained by mixing the electrolyte in the electrolytic cell with the reaction gas into contact with the electrocatalytic component; the electrocatalytic component adopts any one or both of the following methods: Electrocatalytic method (1): at least one electrocatalytic component is provided in the electrolytic cell, and the outlet of the gas-liquid mixer of the electrolytic cell faces the electrocatalytic component and / or the electrolytic anode and / or the electrolytic cathode; Electrocatalytic method (2): Improve the electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode; that is, at least one of the electrolytic anode and the electrolytic cathode is two or more parallel-connected electrodes, and the outlet of the electrolytic tank gas-liquid mixer faces the electrolytic anode and / or the electrolytic cathode with improved electrocatalytic performance structure; Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle ɑ formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the straight line of the gas-liquid mixture ejected from the outlet of the electrolytic tank gas-liquid mixer is greater than 0° and less than 90°, and the outlet of the electrolytic tank gas-liquid mixer is oriented toward the electrolytic anode and / or the electrolytic cathode with the improved electrocatalytic performance structure.

2. The gas-liquid hybrid electrochemical reaction device according to claim 1, characterized in that: The electrolytic cell gas-liquid mixer has an inlet and at least two outlets, or has a structure with a liquid inlet, an air inlet and an outlet. When the electrolytic cell gas-liquid mixer has an inlet and at least two outlets, the outlet extends into the electrolytic cell body and is used to disperse the reaction gas or gas-liquid mixture into the electrolyte in the electrolytic cell for gas-liquid mixing; when the electrolytic cell gas-liquid mixer has a liquid inlet, an air inlet and an outlet, the liquid inlet is connected to the lower pipe of the electrolytic cell body, and the outlet is directed toward or extends into the electrolytic cell body, and is used to input the electrolyte in the electrolytic cell into the gas-liquid mixer so that it is mixed with the reaction gas entering the gas-liquid mixer and then returned to the electrolytic cell.

3. The gas-liquid hybrid electrochemical reaction device according to claim 2, characterized in that: The electrocatalytic component in the electrocatalytic method (1) is arranged in the electrolytic cell and below the electrolyte level; the electrocatalytic component is a bipolar electrode and / or an insoluble conductor.

4. The gas-liquid hybrid electrochemical reaction device according to claim 3, characterized in that: The bipolar electrode refers to at least one insoluble conductor disposed between the electrolysis anode and the electrolysis cathode, which is not connected to an external power source and is immersed in the electrolyte; the insoluble conductor is directly conductively connected to the electrolysis anode or the electrolysis cathode, so that the electrolysis anode or the electrolysis cathode becomes an electrode of irregular shape, wherein the insoluble conductor connected to the electrolysis anode is called an insoluble anode conductor, and the insoluble conductor connected to the electrolysis cathode is called an insoluble cathode conductor.

5. The gas-liquid hybrid electrochemical reaction device according to claim 4, characterized in that: The gas-liquid hybrid electrolytic cell is divided into the following three types. (1) Type A cell: The electrolytic cell gas-liquid mixer uses self-electrolyzed gas as the gas source for the reaction. The gas inlet of the electrolytic cell gas-liquid mixer is connected to the top of the electrolytic cell area where its outlet is located. The gas electrolyzed by the electrolytic electrodes in the cell area and the electrolyte in the cell area form a gas-liquid mixture through the electrolytic cell gas-liquid mixer and contact the electrolytic electrodes and / or electrocatalytic components in the cell area to carry out electrochemical reaction. (2) Type B cell: The electrolytic cell gas-liquid mixer uses both self-electrolyzed gas and external input gas as gas sources for the reaction. The gas inlet of the electrolytic cell gas-liquid mixer is connected to the top of the electrolytic cell area where its outlet is located, i.e., the anode area. It is also connected to the gas source outside the electrolytic cell. The gas electrolyzed by the electrolytic electrode in the cell area is combined with the gas from outside the cell area and mixed with the electrolyte in the cell area to form a gas-liquid mixture, which contacts the electrolytic electrode and / or electrocatalytic component in the cell area to perform an electrochemical reaction. (3) C-type cell: The electrolytic cell gas-liquid mixer uses external input gas as the gas source for participating in the reaction. The gas inlet of the electrolytic cell gas-liquid mixer is connected to a cell area in the same electrolytic cell that is not connected to the liquid flow and / or a gas source outside the electrolytic cell. The electrolytic cell gas-liquid mixer mixes the gas from the outside of the cell area with the electrolyte in the cell area to form a gas-liquid mixture, and contacts the electrolytic electrodes and / or electrocatalytic components in the cell area to perform an electrochemical reaction.

6. A method for synthesizing methane and / or methanol using the above-mentioned gas-liquid hybrid electrochemical reaction device, characterized in that: The following steps are involved: (1) Using a gas-liquid hybrid electrochemical reaction device, and adding an aqueous solution containing carbon dioxide as an electrolyte to the gas-liquid hybrid electrolytic cell or at least one cell zone thereof; (2) turning on the electrolysis power supply, starting at least one electrolytic cell gas-liquid mixer of the device, and continuously introducing new oxidizing gas and / or reducing gas to be mixed and dissolved in the electrolyte; the oxidizing gas is carbon dioxide gas, and the reducing gas is hydrogen gas; Specifically, an oxidizing gas and / or a reducing gas is mixed with an electrolyte to form a gas-liquid mixture, and then brought into contact with at least one of an electrolytic anode, an electrolytic cathode, and an electrocatalytic component. The electrolytic electrode and / or the electrocatalytic component with an improved electrocatalytic structure is used to exert an electrocatalytic effect to cause an electrochemical oxidation and / or reduction reaction between carbon dioxide and hydrogen in the electrolyte to synthesize methane and / or methanol and / or other organic matter.

7. The method for synthesizing methane and / or methanol according to claim 6, characterized in that: By adjusting the reaction amount of carbon dioxide gas and / or hydrogen and / or adjusting the output voltage of the electrolysis power supply of the gas-liquid hybrid electrolyzer, the output of methane and methanol and the ratio between the selected product outputs are controlled.

Images