Gas-liquid mixing type electrochemical reaction device and usage method therefor

Abstract

Disclosed in the present invention is a gas-liquid mixing type electrochemical reaction device, comprising an electrolytic cell, which mainly consists of an electrolytic cell body, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein 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 electrolytic cell comprises at least one electrolytic cell gas-liquid mixer and an electrocatalytic component, which form a gas-liquid mixing type electrolytic cell; and an outlet of the electrolytic cell gas-liquid mixer faces or is located in the electrolytic cell body for bringing a gas-liquid mixture, which is obtained after an electrolytic solution in the electrolytic cell is mixed with a reaction gas, into contact with the electrocatalytic component. Further disclosed in the present invention is a method for performing, by using the device, electrochemical reaction treatment on a substance needing to be oxidized and / or reduced.

Description

A gas-liquid mixed electrochemical reaction device and its use method Technical Field

[0001] The present invention belongs to the technical field of electrochemical reactions, and in particular relates to a gas-liquid mixed electrochemical reaction device and a method for using the same. Background Art

[0002] In modern chemical production and environmental treatment industries, common processes include oxidation and / or reduction reactions, processes for removing nitrogen pollutants, and processes for degrading organic pollutants. These processes often involve high-temperature, high-pressure chemical reaction conditions and / or corrosive chemicals, requiring the use of reactors that are resistant to high temperatures, high pressures, and / or corrosion. Reactors used for high-temperature, high-pressure chemical reactions are pressure-bearing equipment with high production and management costs. Corrosion-resistant reactors also typically require higher material costs. Therefore, in addition to meeting the requirements for high-temperature, high-pressure, and / or corrosion resistance, users of these reactors typically also require high reaction efficiency and better economic benefits for the investment equipment.

[0003] Summary of the Invention

[0004] The first object of the present invention is to provide a gas-liquid hybrid electrochemical reaction device that utilizes a gas-liquid hybrid electrolytic cell to improve the gas solubility and mass transfer properties of reactants, enabling electrochemical reactions on substances requiring treatment using oxidizing or reducing gases under electrocatalysis at atmospheric pressure. A second object is to provide a method for using the gas-liquid hybrid electrochemical reaction device, specifically a method for using the gas-liquid hybrid electrochemical reaction device to perform electrochemical reactions on substances requiring oxidation and / or reduction, thereby simplifying the currently complex oxidation and / or reduction treatment processes.

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

[0006] A gas-liquid mixing electrochemical reaction device comprises 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 more of the following methods:

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

[0009] Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the gas-liquid mixture ejection straight line of the electrolytic tank gas-liquid mixer is greater than 0° and less than or equal to 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 electrolytic cell body by a pipeline, 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 located within the electrolytic cell and below the electrolyte level, and are used to achieve electrochemical catalytic reaction capabilities under the action of electric field forces. Specific electrocatalytic components are bipolar electrodes and / or insoluble conductors, and the specific number and location of the components can be determined based on the performance of the process settings.

[0012] The bipolar electrode is an insoluble conductor placed between the electrolytic anode and cathode, not connected to an external power source, and immersed in the electrolyte. Its shape and size are not limited. During electrolysis, the end of the bipolar electrode closest to the anode acts as a cathode, causing a reduction reaction on the reducible components of the electrolyte, while the end closest to the cathode acts as an anode, causing an oxidation reaction on the oxidizable components. When multiple bipolar electrodes are used, ideally, each bipolar electrode is an independent conductor with no electrical connection to the others. Under the action of an electric field, each bipolar electrode can independently function, forming multiple inductive small cathodes and anodes to enhance the electrocatalytic effect. Preferably, as shown in Figure 13, when more than one bipolar electrode is used, the central surface of the conductor of the bipolar electrode is partially coated with an insulating material to prevent the bipolar electrodes from contacting each other, resulting in the electrodes becoming one large bipolar electrode and losing the independent electrocatalytic function of the small bipolar electrodes. Preferably, a powdered conductor that can flow with the electrolyte is used as the bipolar electrode.

[0013] 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 with the electrolyte is promoted by increasing the surface area of ​​the electrode to achieve the purpose of catalysis. 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 to obtain an electrochemical reaction with high efficiency electrocatalysis. As shown in Figure 14, the insoluble conductor is a conductor that is insoluble or difficult to dissolve in the electrolyte it contacts, and its shape and size are not limited.

[0014] The electrolysis process using the device of the present invention requires the mixing of gases and electrolytes, with the electrocatalytic structure promoting the chemical reaction. Common gases that can participate in the reaction include at least one of ozone, oxygen, chlorine, and hydrogen. Ozone, oxygen, and chlorine are oxidizing gases, while hydrogen is a reducing gas.

[0015] The specific principle of the present invention is as follows: the electrolytic cell gas-liquid mixer mixes the gas involved in the reaction into the electrolyte and contacts the resulting gas-liquid mixture with at least one of the electrocatalytic components, electrolytic anode, and electrolytic cathode in the gas-liquid mixing electrolytic cell, causing the gas-liquid mixture containing the oxidizing gas to react with the negatively charged components in the gas-liquid mixing electrolytic cell, and / or causing the gas-liquid mixture containing the reducing gas to react with the positively charged components in the gas-liquid mixing electrolytic cell; the presence of sufficient gas in the gas-liquid mixture promotes an electrochemical reaction on the components with one of the electrical properties, and the resulting electron gain and loss catalyzes a positive electrochemical reaction on the components with the corresponding other electrical property, while preventing the substances to be treated in the electrolyte from repeatedly reacting on the components with both electrical properties, causing consumption and reducing efficiency. Compared with liquid oxidants or reducing agents, the use of oxidizing or reducing gases mixed with the electrolyte can better produce a catalytic effect on the electrochemical reaction, is less expensive, and does not increase the amount of electrolyte. In the gas-liquid hybrid electrolytic cell, when electrolysis is carried out, the negatively charged component is at least one of the electrolysis cathode, the end of the bipolar electrode that functions as the cathode, and an insoluble cathode conductor, and the positively charged component is at least one of the electrolysis anode, the end of the bipolar electrode that functions as the anode, and an insoluble anode conductor. That is, to achieve the aforementioned electrocatalytic effect, during the electrolysis process, the present invention employs an oxidizing gas to conduct an electrochemical reaction in the negatively charged component to seal the electrolysis, thereby ensuring that the reducing substance to be treated can be electrochemically oxidized in the positively charged component without being reduced by the negatively charged component; or employs a reducing gas to conduct an electrochemical reaction in the positively charged component to seal the electrolysis, thereby ensuring that the oxidizing substance to be treated can be electrochemically reduced in the negatively charged component without being oxidized by the positively charged component. During the electrolysis process, the positively charged component plays a role in converting electrical energy into chemical energy, oxidizing the reducing substances in the electrolyte under electrocatalysis, and can also oxidize the oxygen, hydroxide ions, chloride ions, etc. in the electrolyte to produce a large number of superoxide radicals (O2·), hydroxyl radicals (OH·) and / or chlorine radicals (Cl·), chloroxyl radicals (ClO·) and other oxidizing free radicals, so that the substances in the electrolyte that need to be oxidized are quickly oxidized, such as oxidizable organic matter and inorganic ammonia in landfill leachate; the negatively charged component plays a role in converting electrical energy into chemical energy, reducing the oxidizing substances in the electrolyte under electrocatalysis, and can also produce a large number of hydrogen radicals (H·) or protons to quickly cause at least one of hydrogenolysis reaction, hydrogenation reaction, and reduction reaction on the substances in the electrolyte that need to be reduced, such as reducible organic matter and nitrogen oxides in landfill leachate.

[0016] When a gas-liquid mixture containing an oxidizing gas is sprayed onto a negatively charged component in the electrolysis process, taking sufficient oxygen as an example, the main electrochemical reaction that occurs is: O2+4H + +4e - →H2O.

[0017] When a gas-liquid mixture containing reducing gas is sprayed onto a positively charged component in the electrolysis process, taking sufficient hydrogen as an example, when the electrolyte contains organic matter, in addition to the organic matter reduction reaction, the main electrochemical reaction is: H2-2e - →2H + , or H2+2[OH] - -2e - →2H2O.

[0018] The electrolytic cell of the present invention can be provided with an electrolytic cell separator in the cell according to the process design to separate the electrolytic cell into at least two cell areas. The purpose of providing the electrolytic cell separator in the electrolytic cell is to prevent the bubbles generated by the electrode electrolysis in one cell area of ​​the electrolytic cell 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 cell area 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 separator 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 separator 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.

[0019] 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, and an anion exchange 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 the range of 0.05 to 14 to fully utilize the membrane's performance and extend its service life.

[0020] 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.

[0021] 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 Figure 4, the electrolytic cell separator is 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 based on process requirements.

[0022] 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.

[0023] (1) Type A tank: The electrolytic tank gas-liquid mixer uses self-electrolyzed gas as the gas source for the reaction. As shown in Figures 1 and 2, 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 sprayed into this tank area to undergo an electrochemical reaction. Among them, a bipolar electrode is placed in the tank area where the electrocatalytic reaction occurs in the A-type tank with an electrolytic tank partition.

[0024] (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 3, 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 of the tank to undergo an electrochemical reaction.

[0025] (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 4 to 7, the gas inlet of the electrolytic cell gas-liquid mixer is connected to a cell area within 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 cell area with the electrolyte in the cell area to form a gas-liquid mixture, which contacts the electrolytic electrodes and / or electrocatalytic components in the cell area to undergo an electrochemical reaction.

[0026] 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 in the C-1 type cell and the electrolyte it is mixed 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 in 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.

[0027] The C-shaped cell can be operated in an electrolysis process where the voltage applied by the electrolysis power source 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 electrolysis process can be performed with the voltage applied by the electrolysis power source between the anode and cathode being less than or equal to the decomposition voltage to utilize external input gas from outside the cell and prevent gas deposition from the electrolysis electrodes within the cell. The electrolyte decomposition voltage is the critical value at which the voltage applied by the electrolysis power source between the anode and cathode in a static state of the electrolytic 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, amount of gas involved in the reaction, distance between the anode and cathode electrodes, and the materials used for the 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 Figures 5 and 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 4 and 7 can be adopted.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] The bipolar electrode is 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 conductor's performance in actual chemical reactions. Preferably, the surface of the bipolar electrode is made of at least one of gold, platinum, nickel, copper, cobalt, iron, nickel, molybdenum, tin, bismuth, aluminum, ruthenium, titanium, tantalum, an alloy containing at least one of the above metals, copper oxide, zinc oxide, aluminum oxide, an insoluble electrode with a titanium-based coating, graphite, or activated carbon. More preferably, the surface of the bipolar electrode used in acidic electrolytes is made of at least one of gold, platinum, graphite, and activated carbon. When using a powdered or granular conductive material that can flow 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.

[0032] The material of the insoluble conductor is any conductive material such as conductive metal, conductive metal oxide, semiconductor, etc., and the appropriate insoluble conductor material is selected according to the performance of the conductor in the 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 selected from at least one material selected from gold, platinum, nickel, an alloy containing at least one of the above metals, a titanium-based coated insoluble electrode, and graphite. More preferably, when the anode electrolyte is alkaline, the surface of the insoluble anode conductor arranged in the anode tank area is made of nickel material. When the insoluble conductor is in contact with the electrolytic cathode, that is, the surface of the insoluble cathode conductor is selected from at least one material selected from gold, platinum, silver, titanium, copper, nickel, an alloy containing at least one of the above metals, stainless steel, and graphite.

[0033] 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 adopt a vacuum jet electrolytic tank gas-liquid mixer, or an electrolytic tank gas-liquid mixer combining a bubbling type and a vacuum jet type (as shown in number 9 in Figure 4). The material of the surface of the electrolytic tank gas-liquid mixer in contact with the electrolyte 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.

[0034] The present invention can be improved as follows: the electrolytic cell gas-liquid mixer is made of a conductive material and is electrically connected to at least one of the electrolysis power source, the electrolysis anode or the electrolysis cathode, and the connecting conductive wire between the electrolysis power source and the electrolysis anode or the electrolysis cathode, and its 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 catalytic efficiency; specifically, this is shown as number 9 in Figure 7.

[0035] 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, 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; specifically shown as number 92 in Figure 5.

[0036] 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 the 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 .

[0037] The present invention can also be improved as follows: when the electrolytic cell separator 1 # When an anion exchange membrane or cation exchange membrane is used, a reverse osmosis membrane is added to the electrolytic cell body to form an intermediate tank area between the anion exchange membrane or 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 an anion exchange membrane, electrolytic cell separator 1 # 2-2 is a reverse osmosis membrane. A large amount of [OH] - The electrochemical reaction of ions migrating from the electrolytic cathode to the electrolytic anode, in this process, the bipolar electrode plays an electrocatalytic role and increases the oxidation reaction rate. # 2-1 is reverse osmosis membrane, electrolytic cell separator 1 # 2-2 is a cation exchange membrane, and the electrolyte in the middle tank generates a large amount of hydrogen ions H + The electrochemical reaction migrates from the electrolytic anode to the electrolytic cathode, during which the bipolar electrode plays an electrocatalytic role and increases the reduction reaction rate.

[0038] 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.

[0039] The present invention can also be improved by employing a symmetrical three-zone structure in a gas-liquid hybrid electrolytic cell to improve electrical efficiency. For example, Figure 8 shows a three-zone cell structure in which one zone of the A-type cell in Figure 1 is symmetrically arranged with another zone as the center. The electrolytes in the two symmetrical zones can be set to two different electrolytes or the same electrolyte depending on the process. Figure 9 shows a three-zone cell structure in which one zone of the C-2-type cell in Figure 4 is symmetrically arranged with another zone as the center, and the electrolytes in the three zones are the same.

[0040] The present invention can also be improved as follows: the gas-liquid hybrid electrolytic cell is improved by using a circular electrode distribution structure to increase the electrical efficiency of the electrochemical reaction. Specifically, the gas-liquid hybrid electrolytic cell uses 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 11 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-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.

[0041] 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 89 in Figure 11, 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 temporary storage as shown by numbers 20-1 and 20-2 in Figure 10, which uses at least two current-breaking temporary storage tanks as electrolyte ion current interrupters, and uses a rotation operation method to rotate the ion flow in the electrolyte, and installs a liquid level meter in the electrolyte current-breaking temporary storage tank to control the pump 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.

[0042] 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 structural improvement, it can evenly disperse the electrolysis current and evenly distribute it through the separator, avoiding the electrolysis current from being concentrated at one point and damaging 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.

[0043] 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 shown as No. 93 in Figure 6. 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.

[0044] 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.

[0045] 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 17, 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.

[0046] 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, utilizing the ultrasonic cavitation effect to fully disperse and dissolve the bubbles in the electrolyte into the solution, thereby improving the efficiency of the oxidation or reduction reaction. Preferably, the ultrasonic generator is installed on the liquid flow pipeline of the electrolytic cell gas-liquid mixer. Its installation structure is simple and can achieve better gas-liquid mixing effect, as shown in Figure 7. More preferably, the electrolytic cell gas-liquid mixer is made of at least one of stainless steel, titanium, and nickel, so that the ultrasonic generator installed on the electrolytic cell gas-liquid mixer can achieve greater energy efficiency during operation.

[0047] The present invention can also be improved as follows: two or more gas-liquid mixed electrolytic cells are set up, and connected to form a combination of two-stage or multi-stage gas-liquid mixed electrolytic cells connected in series with gas pipelines, that is, the gas-liquid mixed electrochemical reaction devices of the front and rear stages are connected by gas pipelines, and the reaction gas escaping during the reaction of the front-stage gas-liquid mixed electrolytic cell is collected and drained to the gas-liquid mixed electrolytic cell 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 electrolytic cell is first washed and separated, and the raw gas obtained after the washing and separation treatment is sent to the rear-stage electrolytic cell 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 selected specifically according to the properties of the gas.

[0048] 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, and its structure is divided into a bubbling type, a spray tower type or a venturi vacuum ejector 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, and to separate the other gas components that are insoluble in water or the solvent 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.

[0049] 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 FIG5 , is made of an insulating rubber mesh or porous mesh.

[0050] 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.

[0051] The present invention can also be improved as follows: a temporary storage tank is added to the device for temporarily storing materials.

[0052] 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 system of the present invention to solve the problem of liquid flow between tanks.

[0053] The present invention can also be improved as follows: a chemical reaction tank is added to the device, which is connected to at least one of the gas-liquid mixed electrolytic tank, temporary storage tank, overflow buffer tank, mixed gas separation tank, and other chemical reaction tanks through a pipeline, and is used to perform chemical reaction treatment on the reactants or adjust the pH value of the solution.

[0054] The present invention can also be improved by adding a polluted exhaust gas treatment tank to the apparatus, which is connected to the exhaust gas outlet of at least one of the gas-liquid mixing electrolytic cell, temporary storage tank, overflow buffer tank, chemical reaction tank, mixed gas separation tank, or other polluted exhaust gas treatment tanks via a pipeline, for environmentally friendly treatment of the polluted exhaust gas. The structure of the gas-liquid mixing treatment tank is a spray-type or Venturi-jet-type gas-liquid mixing treatment tank.

[0055] The present invention can also be improved as follows: a solid-liquid separator is added to the device, connected to at least one of the gas-liquid mixed electrolytic cell, temporary storage tank, overflow buffer tank, chemical reaction tank, mixed gas separation tank, polluted exhaust gas treatment tank, and other solid-liquid separators via a pipeline, for solid-liquid separation of the solid-liquid mixture. Specifically, these include filters, filter presses, and centrifuges.

[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 end of the electrolysis power supply, valve, pump, ultrasonic generator, hot and cold temperature exchanger and stirrer in the device, so that the device performs sampling data processing according to a pre-programmed program 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 program. The sensor is selected from at least one of 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 chlorine concentration detector, a hydrogen concentration detector, an ammonia concentration detector, a nitric oxide concentration detector, a nitrogen dioxide concentration detector and a spectrophotometer, and is arranged 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 56 in Figure 5, so that at least one tank area in the gas-liquid mixing 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: additional conventional electrolytic cells are provided to produce oxidizing gas and / or hydrogen for use in the gas-liquid mixed electrolytic cell, thereby improving the working efficiency of the gas-liquid mixed electrochemical reaction device and reducing production costs.

[0061] The present invention can also be improved as follows: a gas-liquid separator is added to the gas pipeline of the device of the present invention to separate the bubbles from the solution in the gas-liquid mixture.

[0062] 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 within a suitable tank of the present invention according to process requirements. Specifically, as shown by reference numbers 67-1 and 67-2 in FIG10 , two solution guide plates are positioned below the liquid inlets of temporary storage tanks 20-1 and 20-2, respectively.

[0063] 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 95 in Figure 5, 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.

[0064] The present invention can also be improved by adding a gas-liquid mixing reaction tank to the apparatus, as shown in Figure 12 , and connecting it 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 via a pipeline. The present invention utilizes the gas-liquid mixing reaction tank to oxidize the substance to be treated using an oxidizing gas.

[0065] 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.

[0066] 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.

[0067] The second object of the present invention is achieved through the following technical solutions.

[0068] A method for electrochemically treating a substance requiring oxidation and / or reduction using the gas-liquid hybrid electrochemical reaction device comprises the following steps:

[0069] (1) Using a gas-liquid hybrid electrochemical reaction device, using the substance to be treated as an electrolyte or one of its components or mixed in the electrolyte in the form of an insoluble substance, and adding the electrolyte to the gas-liquid hybrid electrolytic cell or its cell area of ​​the device; the substance to be treated is a substance that needs to participate in electrochemical oxidation and / or reduction reaction;

[0070] (2) turning on the electrolysis power supply and starting at least one electrolytic cell gas-liquid mixer of the device, mixing the oxidizing gas and / or reducing gas with the electrolyte to form a gas-liquid mixture, and contacting the mixture with at least one of the electrolysis anode, the electrolysis cathode, and the electrocatalytic component, and utilizing the electrolysis electrode and / or the electrocatalytic component with an improved electrocatalytic structure to exert an electrocatalytic effect to oxidize and / or reduce the substance to be treated in the electrolyte.

[0071] Among them, when power is applied for electrolysis, the gas-liquid mixture containing the oxidizing gas is allowed to contact and react with the negatively charged components in the gas-liquid mixed electrolytic cell, and the electrolyte is allowed to contact with the positively charged components in the gas-liquid mixed electrolytic cell to cause the substance to be treated to undergo an oxidation reaction; and / or when power is applied for electrolysis, the gas-liquid mixture containing the reducing gas is allowed to contact and react with the positively charged components in the gas-liquid mixed electrolytic cell, and the electrolyte is allowed to contact with the negatively charged components in the gas-liquid mixed electrolytic cell to cause the substance to be treated to undergo at least one of a hydrogenolysis reaction, a hydrogenation reaction, and a reduction reaction.

[0072] The gas-liquid mixing electrolytic cell of the present invention can be an electrolytic cell without a partition or an electrolytic cell with an electrolytic partition according to the process design. When an electrolytic cell partition is provided in the gas-liquid mixing electrolytic cell, it is divided into at least two cell areas.

[0073] The substance to be treated in step (1) may be an electrolyte solution, an insoluble solid substance, or a solid-liquid mixture.

[0074] The oxidizing gas described in step (2) is at least one selected from ozone, oxygen, and chlorine. The reducing gas is hydrogen. The gases participating in the reaction in the present invention are divided into self-electrolysis gas and external input gas. The self-electrolysis gas and the electrolyte it is mixed with are all from the same tank area of ​​the same electrolytic cell; the external input gas and the electrolyte it is mixed with are from different tank areas of the same electrolytic cell, or from outside the electrolytic cell. Among them, ozone and carbon dioxide are external input gases, while oxygen, chlorine, and hydrogen can be both external input gases and self-electrolysis gases.

[0075] In step (1) and step (2), a gas-liquid hybrid electrolytic cell is used in combination with an oxidizing gas to perform an electrochemical oxidation reaction on the substance to be treated in the electrolyte, so that the valence of the substance to be treated increases under electrocatalysis or the organic matter therein is oxidized and degraded; and / or the gas-liquid hybrid electrolytic cell is used in combination with a reducing gas to perform an electrocatalytic reduction on the substance to be treated or the organic matter therein undergoes a hydrogenolysis reaction and / or a hydrogenation reaction and / or a reduction reaction; thereby achieving the purpose of process treatment of the substance to be treated.

[0076] When the present invention uses a gas-liquid hybrid electrochemical reaction device to absorb oxidizing gas to perform an oxidation reaction on the substance to be treated, during the electrolysis process, in addition to the electrochemical oxidation reaction of the substance to be treated under electrocatalysis, it also undergoes an oxidation reaction with the newly generated oxidant in the gas-liquid hybrid electrolytic cell.

[0077] The present invention uses a gas-liquid hybrid electrochemical reaction device to absorb hydrogen to perform at least one of hydrogenolysis, hydrogenation, and reduction reactions on the substance to be treated; when the gas-liquid hybrid electrolytic cell is energized for electrolysis, the hydrogen is converted into protons H by electrocatalysis at the positively charged components. + Participate in the reaction, the electrochemical reaction formula is: H2-2e→2H + , and / or hydrogen reacts chemically with the oxidizing substances in the electrolyte under the electrocatalysis of the negatively charged components when the gas-liquid hybrid electrolyzer is powered on for electrolysis. Thanks to the electrocatalytic conditions provided by the gas-liquid hybrid electrolyzer, hydrogen can react with the substances to be treated under normal pressure by hydrogenolysis and / or hydrogenation, promoting the reductive decomposition of organic impurities and the reduction of NO2 - 、NO3 - electrochemical reduction reaction.

[0078] The present invention can also be improved as follows: when the substance to be treated is a solution, if it contains other insoluble substances that do not need to be treated, these solid substances that do not need to be treated should be separated and removed by solid-liquid separation, and the filtrate that needs to be treated should be fed into the gas-liquid hybrid electrolytic cell for reaction treatment. Preferably, when the substance to be treated is a solution, ferrous carbonate and ferrous hydroxide water purifiers are added to the solution to precipitate calcium, magnesium ions, heavy metal ions and phosphate PO4 3- More preferably, while adding ferrous carbonate and ferric hydroxide, the pH value is adjusted and hydrogen peroxide is added to the organic waste liquid to be treated to undergo a Fenton reaction, so that the organic impurities in the waste liquid are oxidized and degraded.

[0079] The present invention can be improved as follows: When the electrolyte is a viscous liquid, a gap-connected structure is used in the gas-liquid hybrid electrolytic cell to separate the anode and cathode zones. Specifically, the anode and cathode zones within the electrolytic cell are connected only by the gap structure, i.e., the cathode and anode zones are only connected over a small area, thereby effectively separating the anolyte and cathode electrolyte without hindering ion migration. By utilizing the gap-connected structure to separate the anode and cathode zones, the present invention improves the Type A gas-liquid hybrid electrolytic cell that uses self-electrolyzed gas as the source of the reacting gas, thereby resolving the problem of viscous liquid blocking the electrolytic cell divider within the Type A cell of the present invention, as shown in FIG18 . Preferably, an overflow buffer tank is added, and newly generated precipitates in the electrolytes of the anode and cathode zones separated by the gap-connected structure are removed by solid-liquid separation. The filtered electrolyte is then pumped back to the electrolytic cell gas-liquid mixer to continue mixing with the reacting gas and sprayed onto the electrodes for electrochemical reaction. More preferably, during the electrolysis process, the positive and negative poles of the electrolysis power supply are swapped at set intervals according to the process settings, so that the material adhering to the electrodes is dissolved through the electrochemical reaction caused by reverse polarity electrolysis. Even more preferably, the electrolysis reaction is carried out using a reverse pulse electrolysis power supply, so that the viscous liquid can continuously undergo oxidation reaction and hydrogenolysis-hydrogenation-reduction polarity change reaction to reduce the insulation sealing of the electrodes by the viscous liquid, thereby achieving a normal electrochemical reaction.

[0080] The present invention can also be improved as follows: during the entire electrochemical reaction process, if waste gases of different properties are generated and need to be treated, two or more waste gas environmental protection treatment tanks are added to perform environmental protection treatment of the corresponding waste gases.

[0081] To effectively treat the substance to be treated, an oxidizing gas is used for oxidation and a reducing gas is used for hydrogenolysis, hydrogenation, or reduction. The oxidation reaction using an oxidizing gas can be performed by absorbing the oxidizing gas in a gas-liquid hybrid electrolytic cell, or by directly adding the oxidizing gas for oxidation. Furthermore, the two oxidation methods can be used sequentially. The treatment method of the present invention does not require the order in which the oxidizing gas is used for oxidation of the substance to be treated and the hydrogenolysis and / or hydrogenation and / or reduction of the organic waste liquid using a reducing gas are treated, and these can be flexibly arranged according to the process.

[0082] A preferred solution in the treatment method of the present invention is to directly add ozone and / or chlorine to the substance to be treated in a solution state or a solution containing the substance to be treated (hereinafter referred to as the solution to be treated) to carry out an oxidation reaction, and use a gas-liquid hybrid electrolytic tank to perform an electrochemical reduction reaction on it, which not only achieves the purpose of oxidation treatment but also reduces equipment investment and simplifies the process of reduction reaction. There is no requirement for the order of the above-mentioned oxidation reaction and the use of reducing gas for hydrogenolysis reaction and / or hydrogenation reaction and / or reduction reaction, and they can be flexibly arranged according to the process. Preferably, the gas-liquid hybrid reaction tank of the existing technology is used to directly mix ozone and / or chlorine into the solution to be treated for oxidation reaction.

[0083] Among them, compared with chlorine, ozone shows higher oxidation performance in the oxidation reaction of the substance to be treated under the same conditions. The ozone is obtained by using an ozone generator to convert oxygen or air into ozone gas through the action of a high-frequency and high-voltage electric field. Preferably, ozone is produced using oxygen, and its oxygen source is one or more of commercial oxygen, oxygen produced by ordinary chemical reactions, and oxygen produced by electrolysis reactions, and oxygen from one oxygen source is used alone or oxygen from more than one oxygen source is mixed and used. When ozone is produced by an ozone generator using oxygen produced by electrolysis, the oxygen is first pre-washed and condensed and dried to avoid affecting the normal operation of the ozone generator.

[0084] The chlorine gas may be one or more of commercial chlorine, chlorine produced by common chemical reaction, and chlorine produced by electrolytic reaction, and the chlorine gas from one chlorine source may be used alone or after mixing the chlorine gas from more than one chlorine source.

[0085] The substance to be treated can react with ozone under acidic, alkaline, or neutral conditions. However, when reacting with chlorine in an acidic environment, nitrogen trichloride, which is an explosive substance, is easily generated. Therefore, it is preferably reacted with chlorine in an alkaline environment.

[0086] In the ozone reaction treatment process, when the substance to be treated is an organic waste liquid containing nitrogen pollutants, the treatment process generates carbon dioxide, water, nitrogen and / or nitrogen oxide gas and / or nitrate, and may be accompanied by the generated oxygen and residual trace ozone escaping from the reaction liquid. The chemical reaction equation of the above reaction is shown below, where R-NH X Refers to organic amines.

[0087] R-NH X +O3→CO2↑+N2↑+O2↑+H2O

[0088] 6NH3+7O3→9H2O+6NO2↑

[0089] 3NO+O3→3NO2↑

[0090] 2NO+O2→2NO2↑

[0091] NO2 - +O3→NO3 - +O2↑

[0092] When the substance to be treated is a solution containing hypophosphite, it also reacts with ozone in the following ways:

[0093] PO2 3- +O3→PO3 3- +O2↑

[0094] PO3 3- +O3→PO4 3- +O2↑

[0095] When chloride ions are present in the solution to be treated and react with ozone under acidic conditions, in addition to the above reactions, nitrogen trichloride, an explosive substance, will also be generated. 2- ions and also release hydrogen sulfide.

[0096] Cl - +O3→ClO - +O2↑

[0097] HCl+HClO→Cl2↑+H2O

[0098] NH4Cl+3Cl2→NCl3+4HCl

[0099] Oxidation of the solution to be treated using an oxidizing gas under alkaline conditions can prevent the generation of explosive and highly toxic substances such as nitrogen trichloride and hydrogen sulfide due to the presence of chlorine compounds and sulfur compounds in the acidic reaction solution during the reaction, effectively ensuring production safety. Therefore, the pH value of the reaction solution during the oxidation reaction is preferably not less than 7. More preferably, the pH value of the reaction solution is controlled within the range of 8 to 14; even more preferably, the pH value of the reaction solution is controlled within the range of pH 8.5 to pH 11. When adding an alkaline substance to the solution to be treated to adjust its pH value, the alkaline substance is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0100] When the solution contains chloride ions Cl - and / or sulfide ions S 2- When reacting with ozone under alkaline conditions, the generation of nitrogen trichloride and hydrogen sulfide can be avoided, and the following chemical reaction occurs, where M represents a metal element:

[0101] Cl - +O3→ClO - +O2↑

[0102] NaCl + HClO → NaOH + Cl2↑

[0103] 2NH3+3ClO - →3Cl - +3H2O+N2↑

[0104] S 2- +O3+H2O→H2SO4

[0105] M +n +n(OH) - →M(OH)n↓

[0106]

[0107] When using chlorine to oxidize the solution to be treated under alkaline conditions, if the NH3, NO2 - Impurities mainly undergo the following chemical reactions:

[0108] Cl2 + NaOH → NaClO + HCl

[0109] 2NH3+3NaClO→3NaCl+3H2O+N2↑

[0110] NO2 - +ClO - →NO3 - +Cl -

[0111] When the solution to be treated contains hypophosphite, the following reaction also occurs:

[0112] PO2 3- +ClO - →PO3 3- +Cl -

[0113] PO3 3- +ClO - →PO4 3- +Cl -

[0114] When removing inorganic NH3 from the solution to be treated, it is preferred to use chlorine gas to directly oxidize it under alkaline conditions to reduce the treatment cost.

[0115] The present invention can also be improved as follows: after the solution to be treated is oxidized using chlorine gas under alkaline conditions, the following two schemes are used to remove the residual chlorine gas and hypochlorite in the reaction solution so that the reaction solution can smoothly proceed to the next chemical reaction:

[0116] Option 1: Add a ferrous compound to the reaction solution to remove residual chlorine and hypochlorite therein, and then perform solid-liquid separation under the condition that the pH value of the reaction solution is greater than pH 7. Preferably, the ferrous compound used to remove residual chlorine and hypochlorite in the reaction solution is at least one selected from ferrous hydroxide, ferrous carbonate, ferrous sulfate, and ferrous chloride. Preferably, the pH value of the reaction solution is set to no less than 10.5 after the addition of the ferrous compound, so as to utilize the added Fe 2+ This reduces the high-valent chromium or manganese ions in the reaction solution to low-valent ions, converting most of the heavy metal ions in the reaction solution into insoluble hydroxides and / or carbonate precipitates. Solid-liquid separation is then performed to remove the heavy metal ions from the reaction solution. This solid-liquid separation process also removes insoluble phosphates from the reaction solution, achieving phosphorus removal. The resulting filter residue contains organic impurities in addition to the aforementioned pollutants and should be treated as hazardous waste.

[0117] Option 2: Add hydrochloric acid and / or sulfuric acid to the reaction solution to lower its pH to below 7, converting the hypochlorite in the reaction solution into hypochlorous acid and continuing the effective acidic oxidation degradation of the organic pollutants in the reaction solution. Under acidic conditions, chlorine reacts with water to produce hydrochloric acid and hypochlorous acid. Any hypochlorous acid that does not react with the organic pollutants gradually decomposes into hydrochloric acid and oxygen.

[0118] The present invention can also be improved as follows: when the substance to be treated is an organic waste liquid containing protein, a protein removal step is added. Hydrochloric acid and / or sulfuric acid is added to the organic waste liquid to adjust its pH to below 6, preferably within the range of pH 1 to pH 3.5, so that the protein in the organic waste liquid coagulates and can be removed through solid-liquid separation. The filter residue obtained from this solid-liquid separation should be treated as hazardous waste. Preferably, before adding hydrochloric acid and / or sulfuric acid to the organic waste liquid for protein removal, a small amount of hydrogen peroxide is added to kill pathogens in the organic waste liquid to ensure occupational safety and health.

[0119] The present invention can also be improved as follows: after the solution to be treated is subjected to at least one of hydrogenolysis, hydrogenation and reduction reactions in a gas-liquid hybrid electrolytic cell, the resulting solution contains trace amounts of NO3 - To remove pollutants, add ferrous compounds to the reaction solution under acidic conditions and NO3 - The pollutants react to reduce NO3 in the reaction solution - Concentration. The method is used to eliminate NO3 in the reaction solution. - The ferrous compound of the pollutant is at least one selected from ferrous sulfate, ferrous chloride, ferrous hydroxide, and ferrous carbonate. The chemical reaction formula is as follows:

[0120] 3Fe 2+ +NO3 -+4H + →3Fe 3+ +2H2O+NO↑

[0121] Preferably, ferrous compounds are used to remove NO3 in the reaction solution. - Afterwards, the pH of the reaction solution is adjusted to within the appropriate range set by the process, and ferrous compounds and hydrogen peroxide are added multiple times or continuously to carry out a Fenton oxidation reaction, thereby oxidatively degrading the organic pollutants in the reaction solution. More preferably, an alkaline substance is added to the reaction solution after the Fenton reaction to adjust the pH of the reaction solution, so that ferric hydroxide, heavy metal hydroxides and / or heavy metal carbonates, and phosphate precipitates are generated in the reaction solution. Solid-liquid separation is then performed to obtain a ferric hydroxide filter residue containing heavy metals, organic pollutants, and phosphorus compounds. The resulting filtrate is then processed in the next step. This filter residue should be treated as hazardous waste.

[0122] The present invention can also be improved as follows: the iron hydroxide precipitate filter residue obtained during the process, which does not contain heavy metals and phosphorus compounds but only contains organic pollutants, is subjected to high-temperature treatment to decompose the organic pollutants therein at high temperature, and an iron oxide product is obtained which can be used as other raw materials.

[0123] The present invention can also be improved by adding an inorganic ammonia removal step. The ammonia-rich solution to be treated is heated and stirred under alkaline conditions, converting the inorganic ammonia NH₄OH therein into ammonia gas NH₃, which is then driven out and removed. The escaped ammonia gas NH₃ can be centrally disposed of for environmentally friendly treatment.

[0124] The present invention can also be improved as follows: in order to make the reaction liquid safe and controllable during the reaction process, the temperature of the reaction liquid is regulated by using a hot and cold temperature exchanger to meet the process temperature requirements.

[0125] The present invention can also be improved as follows: to ensure safe and controllable chemical reactions, an automatic detection and feeding controller and sensors are used to operate the device for sampling and detection and control of the feeding of chemical reactants, so that the device can 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 nitric oxide gas concentration detector, a nitrogen dioxide gas concentration detector, an ozone flowmeter, a chlorine flowmeter, a chlorine concentration detector, and a hydrogen concentration detector.

[0126] Compared with the prior art, the present invention has the following beneficial effects.

[0127] 1. The gas-liquid hybrid electrochemical reaction device of the present invention achieves efficient electrocatalysis by providing an electrolytic cell gas-liquid mixer and improving the electrocatalytic method. Therefore, the device of the present invention can be used in the process production of oxidation and / or reduction reactions of inorganic substances, and can also remove nitrogen pollutants and degrade organic pollutants in organic waste liquids, simplifying the more complex treatment processes in the existing technology and reducing the large amount of space occupied by production equipment and the consumption of resources.

[0128] 2. The process equipment of the present invention has a simple structure, small economic investment, and is safe to operate because it is used under normal pressure.

[0129] 3. The process of the present invention does not add any new pollution sources during the production process, and complies with environmental protection regulations.

[0130] 4. The process of the present invention has low energy consumption, fast reaction speed and high economic benefit. BRIEF DESCRIPTION OF THE DRAWINGS

[0131] FIG1 is a schematic diagram of a type A gas-liquid hybrid electrochemical reaction device according to Example 6 of the present invention.

[0132] FIG2 is a schematic diagram of a type A device of a gas-liquid mixing electrochemical reaction device according to Example 7 of the present invention.

[0133] FIG3 is a schematic diagram of a type B device of a gas-liquid mixing electrochemical reaction device according to Example 8 of the present invention.

[0134] FIG4 is a schematic diagram of a C-2 type device of a gas-liquid hybrid electrochemical reaction device according to Example 9 of the present invention.

[0135] FIG5 is a schematic diagram of a C-1 type device of a gas-liquid hybrid electrochemical reaction device according to Example 10 of the present invention.

[0136] FIG6 is a schematic diagram of a C-1 type device of a gas-liquid mixed electrochemical reaction device according to Example 11 of the present invention.

[0137] FIG7 is a schematic diagram of a C-2 type device of a gas-liquid hybrid electrochemical reaction device according to Example 12 of the present invention.

[0138] FIG8 is a schematic structural diagram of a gas-liquid mixed electrochemical reaction device according to Example 132 of the present invention.

[0139] FIG9 is a schematic structural diagram of a gas-liquid hybrid electrochemical reaction device according to Example 14 of the present invention.

[0140] FIG10 is a schematic structural diagram of a gas-liquid hybrid electrochemical reaction device according to Example 15 of the present invention.

[0141] FIG11 is a schematic structural diagram of a gas-liquid hybrid electrochemical reaction device according to Example 16 of the present invention.

[0142] FIG12 is a schematic structural diagram of a gas-liquid mixing reaction tank.

[0143] FIG13 is a schematic diagram of the structures of two bipolar electrodes of different shapes.

[0144] FIG14 is a schematic diagram of the structures of four insoluble conductors of different shapes.

[0145] 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.

[0146] FIG16 is a schematic diagram of a bipolar electrode electrically insulating cage.

[0147] Figure 17 is a schematic structural diagram of the gas-liquid mixed electrochemical reaction device of Example 17 of the present invention.

[0148] FIG18 is a schematic structural diagram of a gas-liquid mixed electrochemical reaction device according to Example 18 of the present invention.

[0149] FIG19 is a schematic diagram of a gas-liquid mixing electrochemical reaction device according to Example 1 of the present invention.

[0150] FIG20 is a schematic structural diagram of a gas-liquid mixed electrochemical reaction device according to Example 2 of the present invention.

[0151] FIG21 is a schematic structural diagram of a gas-liquid mixed electrochemical reaction device according to Example 3 of the present invention.

[0152] FIG22 is a schematic structural diagram of a gas-liquid mixed electrochemical reaction device according to Example 4 of the present invention.

[0153] Figure 23 is a structural schematic diagram of the gas-liquid hybrid electrochemical reaction device of Example 5 of the present invention, wherein Figure 23-1, Figure 23-2, Figure 23-3, Figure 23-4, and Figure 23-5 are respectively partial enlarged views of Figure 23, and the five are combined to form the complete gas-liquid hybrid electrochemical reaction device of Example 5.

[0154] Reference numerals:

[0155] 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 electrolytic cell gas-liquid mixer, 10-trough frame metal mesh bipolar electrode, 11-bipolar electrode electrical insulation box, 12-insulating through-hole support baffle, 13-gas-liquid separation washing tank, 14-ordinary bubbling gas-liquid mixer, 15-ordinary vacuum jet gas-liquid mixer, 16-ordinary spray tower gas-liquid mixer, 17-cold and hot temperature exchanger, 18-impeller agitator, 19- Liquid flow agitator, 20-temporary storage tank, 21-chemical reaction tank, 22-overflow buffer tank, 23-insoluble anode conductor, 24-insoluble cathode conductor, 25-ultrasonic generator, 26-solid-liquid separator, 27-polluted tail gas treatment tank, 28-sealed tank cover for collecting escaped gas from electrolytic cell reaction, 29-sealed tank cover plate hydrogen discharge pipe port, 30-sealed tank cover plate oxidizing gas discharge pipe port, 31-hydrogen, 32-oxidizing gas, 33-oxygen, 34-chlorine, 35-nitric oxide, 36-nitrogen dioxide, 37-nitrogen, 38-carbon dioxide gas, 39-ammonia, 4 0-Ammonia, 41-Ozone, 42-Solution to be treated, 43-Coagulated protein solid, 44-Solid material to be treated, 45-Solid-liquid mixture to be treated, 46-Reaction solution to be treated, 47-Anolyte, 48-Cathode electrolyte, 49-Alkaline solution, 50-Acidic solution, 51-Gas-liquid mixed electrolytic cell exhaust pipe, 52-Valve, 53-Pump, 54-Sealing screw, 55-Gas booster pump, 56-Gas pressure balance connecting pipe, 57-Ordinary electrolytic cell, 58-Water, 59-Mixed gas, 60-Gas escaping after separation of mixed gas, 61 - Reaction products soluble in water, 62 - Electrical insulator, 63 - Conductor, 64 - Conductive connecting wire, 65 - Automatic detection and feeding controller, 66 - Sensor, 67 - Solution flow area expansion guide plate, 68 - Support frame, 69 - Mixed gas gas-liquid separator, 70 - Refrigerator, 71 - Hydrogen peroxide, 72 - Ferrous material, 73 - Filter residue, 74 - Filtrate, 75 - Intermediate tank area, 76 - Intermediate tank electrolyte, 77 - Safety photoelectric control alarm system, 78 - Heater, 79 - Oxygen cylinder, 80 - Chlorine cylinder, 81 - Hydrogen cylinder, 82 - Nitrogen cylinder, 83 - Electrolytic cell partition 2 #Filter cloth, filter screen, water-permeable non-ion selective diaphragm, 84-separator-free gas-liquid mixing electrolytic cell, 85-electrolytic cell electric field line channel, 86-solid sediment baffle, 87-nozzle, 88-discharge liquid, 89-electrolyte ion current interrupter, 90-electrolysis electrode, 91-reducing gas, 92-gas-liquid mixer multi-way air inlet pipe component, 93-bubble reaction liquid guide cover, 94-electrolysis gas, 95-bubble drainage cover in electrolyte, 96-insulating partition plate in electrolytic cell, 97-ozone generator, 98-hydrogen-containing tail gas high-altitude discharge pipe, 99-sodium chloride solution, 100-titanium basket, 101-electric heating furnace.

[0156] 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

[0157] The present invention will be further described below through specific embodiments.

[0158] The gas-liquid mixing electrolytic cell, mixed gas separation cell, electrolytic anode, electrolytic cathode, bipolar electrode, bipolar electrode insulating mesh box, 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 solid-liquid separator, sensor, automatic feed controller, valve, pump, chemical raw materials, and gas detectors for ammonia, hydrogen, and chlorine used in these processes are all commercially available products.

[0159] 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.

[0160] Example 1

[0161] As shown in FIG19 , this is Example 1 of the gas-liquid mixing chemical reaction device of the present invention, which includes a gas-liquid mixing electrolytic cell.

[0162] The gas-liquid mixing electrolytic cell is an electrolytic cell of the structure shown in 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 reverse osmosis membrane 2 separates the electrolytic cell into an anode and cathode compartments, and a bipolar electrode 6 is located in the anode compartment. A vacuum jet electrolytic cell gas-liquid mixer 7 is connected to the anode compartment of the electrolytic cell body via a pump 53 via a liquid flow conduit, with its outlet directed toward the electrolytic anode 3 and bipolar electrode 6. The electrolytic cell body 1 is also equipped with a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction.

[0163] The electrolytic anode is a conductor with a gold-plated surface, the electrolytic cathode and the bipolar electrode are conductors with a platinum-plated surface, and platinum metal conductive powder is used as another bipolar electrode to float with the electrolyte during electrolysis operation.

[0164] The solution 42 to be treated is waste liquid from alkaline etching and washing of circuit boards, and its main components are a small amount of ammonium chloride, cuprammonium chloride, ammonia water, and sodium hydroxide, wherein the copper ion concentration is 0.3 g / L, the NH3 concentration is 3.7 g / L, and the pH value is pH 12. The cathode electrolyte 48 is a sodium hydroxide solution.

[0165] This embodiment uses a gas-liquid mixed electrochemical reaction device to remove NH3.

[0166] A method for removing NH3 using a gas-liquid hybrid electrochemical reaction device, the operating steps are as follows:

[0167] 1. A solution 42 to be treated with a pH of 12 is added to the anode tank area of ​​the electrolytic cell 1, and a cathode electrolyte 48 is added to the cathode tank area.

[0168] 2. Start the pump 53 to operate the gas-liquid mixer, and connect the electrolysis power supply 5 to cause the following electrochemical reaction to occur in the electrolytic cell. During the electrolysis process, the chlorine gas precipitated from the anode tank is mixed with the electrolyte in the electrolytic cell gas-liquid mixer and sprayed onto the bipolar electrode to contact it, causing an oxidation reaction:

[0169] Electrolysis anode and bipolar electrode anode end: 2Cl - -2e - →Cl2

[0170] Electrolysis cathode: 2H + +2e - →H2↑

[0171] Cathode end of bipolar electrode: Cl2+2H + +2e - →2HCl

[0172] The following oxidation reactions occur simultaneously in the anolyte, i.e. the solution to be treated:

[0173] Cl2+2NaOH→NaCl+NaClO+H2O

[0174] 2NH3+3NaClO→3NaCl+3H2O+N2↑

[0175] 3. After 10 hours of oxidation reaction, a sample was taken for testing. The test result of the reaction solution 46 showed that the NH3 content was still 320 mg / L.

[0176] Example 2

[0177] As shown in FIG20 , this is Example 2 of the gas-liquid mixing chemical reaction device of the present invention, which includes a gas-liquid mixing electrolytic cell, two temporary storage tanks 20 - 1 and 20 - 2 , a chemical reaction tank 21 , and two solid-liquid separators 26 - 1 and 26 - 2 .

[0178] The gas-liquid mixing electrolytic cell is the electrolytic cell of Figure 3, 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 bipolar membrane 2 separates the electrolytic anode and cathode regions. The anode region is equipped with an insoluble anode conductor 23, directly electrically connected to the electrolytic anode, a bipolar electrode 6, and an insulating through-hole support plate 12. The electrolytic cell gas-liquid mixer 7 is connected to the anode region of the electrolytic cell body via a pump 53-2 via a liquid flow conduit, with its outlet directed toward the electrolytic anode 3, the insoluble anode conductor 23, and the bipolar electrode 6. The electrolytic cell body 1 is also equipped with a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction.

[0179] The electrolytic anode is an insoluble anode with a titanium-based coating, the insoluble anode conductor is gold-plated on the surface, the electrolytic cathode is titanium metal, and the surface of the bipolar electrode is a platinum-plated conductor.

[0180] The chemical reaction tank 21 is provided with an impeller stirrer 18 and a sensor 66. The sensor 66 is a pH meter.

[0181] The solution to be treated is wastewater from nickel deposition on circuit boards, whose main components are small amounts of nickel sulfate, hypophosphite, and organic amines. Sodium hydroxide and sodium carbonate are added to the wastewater, with a COD of 31,000 mg / L and a total phosphorus of 9,400 mg / L. The pH of the solution to be treated is adjusted to 14 with sodium hydroxide, serving as the anolyte. The catholyte 48 is sodium hydroxide.

[0182] The external gas input to participate in the reaction is chlorine.

[0183] This embodiment uses a gas-liquid mixed electrochemical reaction device to remove NH3 and phosphorus and degrade organic impurities from the nickel precipitation wastewater.

[0184] A method for treating nickel precipitation waste liquid using a gas-liquid mixed electrochemical reaction device, the operating steps are as follows:

[0185] 1. A solution 42 to be treated with a pH of 14 is added to the anode tank of the electrolytic cell 1, and a sodium hydroxide solution 48 is added to the cathode tank.

[0186] 2. Turn on the electrolysis power supply 5 and start the pump 53-2 to operate the electrolytic cell gas-liquid mixer 7, which absorbs external and electrolyzed chlorine gas, mixes it with the electrolyte, and sprays it onto the electrolysis anode 3, the insoluble anode conductor 23, and the bipolar electrode 6, where they come into contact. The following electrochemical reaction occurs:

[0187] Electrolytic anode, insoluble anode conductor and bipolar electrode anode end:

[0188] 2Cl - -2e - →Cl2

[0189] Electrolysis cathode: 2H + +2e - →H2↑

[0190] Cathode end of bipolar electrode: Cl2+2H + +2e - →2HCl

[0191] In the anolyte, i.e. the solution to be treated, there is simultaneous oxidative degradation of organic impurities and the following oxidation reactions:

[0192] Cl2+2NaOH→NaCl+NaClO+H2O

[0193] 2NH3+3NaClO→3NaCl+3H2O+N2↑

[0194] ClO - +PO3 3- →Cl - +PO4 3-

[0195] 2ClO - +PO2 3- →2Cl - +PO4 3-

[0196] 3. After the oxidation reaction is completed for 6 hours, the electrolytic cell is shut down and the pump 53 - 1 is started to extract the reaction liquid 46 for filtration. The filter residue 73 - 1 is nickel hydroxide, and the filtrate 74 - 1 is drained into the chemical reaction tank 21 .

[0197] 4. Add ferrous sulfate 72 into tank 21 to absorb residual chlorine and make Fe 2+ to Fe 3+And with PO4 3- The insoluble FePO4 is combined and controlled by the pH meter sensor 66 to add 50% sulfuric acid to the tank 21 until the pH value of the solution is 7.

[0198] 5. Start pump 53-3 for filter pressing to produce filter residues of ferric phosphate and ferric hydroxide and filter residue 74-2, and temporarily store the filter residue in tank 20-1 and drain the filtrate into tank 20-2 for temporary storage.

[0199] 6. The solution 74-2 in the tank 20-2 was tested and found to contain 38 mg / L of total nitrogen, 3700 mg / L of COD, and 0.4 mg / L of total phosphorus.

[0200] Example 3

[0201] As shown in FIG21 , this is Example 3 of the gas-liquid mixing chemical reaction device of the present invention, which includes a gas-liquid mixing electrolytic cell.

[0202] The gas-liquid mixing electrolytic cell is an electrolytic cell of the structure shown in FIG6, 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 electrolytic cell comprises a reverse osmosis membrane 2-1 and a cation exchange membrane 2-2, which are divided into an electrolytic anode cell zone, an intermediate cell zone, and an electrolytic cathode cell zone. A pressure-balancing connection pipe 56 is provided between the intermediate and cathode cell zones, and a bipolar electrode 6 is located in the intermediate cell zone. The electrolytic cell gas-liquid mixer 7 is connected to the intermediate cell zone via a liquid flow conduit through a bubble-containing reaction liquid guide 93, a pump 53-1, and a gas-liquid separation and washing tank 13, with its outlet facing the bipolar electrode 6. The electrolytic cell 1 also has a sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction.

[0203] The electrolytic anode is an insoluble anode with a titanium-based coating, the electrolytic cathode is stainless steel, and the surface of the bipolar electrode is a platinum-plated conductor.

[0204] The solution to be treated 42 is a waste nitric acid solution containing 0.11 M / L nitric acid. The anolyte 47 and the catholyte 48 are both sulfuric acid solutions at pH 2.

[0205] This embodiment uses a gas-liquid mixed electrochemical reaction device to treat the waste nitric acid solution. The electrolytic cell using the structure of Figure 6 can prevent the waste nitric acid from corroding the electrolytic anode, allowing the equipment to operate normally.

[0206] A method for treating waste nitric acid using a gas-liquid hybrid electrochemical reaction device, the operating steps are as follows:

[0207] 1. The waste nitric acid solution 42 to be treated is added to the middle tank area of ​​the electrolytic cell 1, and the dilute sulfuric acid is added to the anode tank area and the cathode tank area respectively.

[0208] 2. Start pumps 53-1 and 53-2 to operate the electrolytic cell gas-liquid mixer 7. Connect the electrolysis power supply 5 to cause the electrolytic cell to electrolyze oxygen and hydrogen. The hydrogen is drained into the electrolytic cell gas-liquid mixer 7 and mixed with the electrolyte before being sprayed onto the bipolar electrode 6 to participate in the electrochemical reaction in the intermediate cell. The electrochemical reaction formula is as follows:

[0209] Bipolar electrode anode end in the middle tank area: H2-2e - →2H +

[0210] Cathode end of the bipolar electrode in the middle tank area:

[0211] HNO3+8H + +8e - →3H2O+NH3

[0212] 2HNO3+10H + +10e - →6H2O+N2

[0213] HNO3+3H + +3e - →2H2O+NO

[0214] 3. After 8 hours of oxidation reaction, a sample was taken for total nitrogen detection, and the detection result of the reaction solution 46 was 0.03M / L.

[0215] Example 4

[0216] As shown in FIG22, it is a process flow chart of Example 4 of the gas-liquid hybrid electrochemical reaction device of the present invention, wherein the device includes a gas-liquid hybrid electrolytic cell, four temporary storage tanks 20-1 to 20-4, a chemical reaction tank 21, two overflow buffer tanks 22-1 and 22-2, a common electrolytic cell 57, an electric heating furnace 101,

[0217] The gas-liquid mixing electrolytic cell adopts the electrolytic cell structure shown in Figure 4 and includes an electrolytic cell body 1, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, and a combined 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 insulating through-hole support baffles 12-1 and 12-2, and is equipped with 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 electrolytic cell gas-liquid mixer 9 is connected to the electrolytic cell body 1 via a liquid flow conduit, with its outlet facing the electrolytic anode 3 and the insoluble anode conductor 23.

[0218] The gas-liquid hybrid electrolytic cell is used to remove nitrate nitrogen NO3 in the reaction solution. - The electrolytic anode is nickel, the insoluble anode conductor is conductive graphite, and the electrolytic cathode and insoluble cathode conductor are stainless steel.

[0219] The cathode of the common electrolytic cell is used for electrolysis of hydrogen gas to supply the gas-liquid hybrid electrolytic cell, and the electrolytic anode is an insoluble anode, and the electrolyte is a sodium sulfate solution.

[0220] The solution to be treated is the water from a fish pond used for bottom treatment, which contains feed residues and fish excrement. The pH value of the water is 7.2, and the total nitrogen content is 2 mg / L.

[0221] The solid-liquid separator 26-1 is used to separate the mud and water mixture in the fish pond. The solid-liquid separator 26-2 is used to filter the sludge produced by the solid-liquid separator 26-1. The solid-liquid separator 26-3 is used to separate the solid-liquid mixture after the reaction in the chemical reaction tank 21.

[0222] The ferrous substance 72 is ferrous hydroxide.

[0223] The chemical reaction tank 21 is equipped with a common bubbling gas-liquid mixer 14, an impeller stirrer 18, and an ORP meter 66, which uses ozone to sterilize and convert NH3 into NO3 - Then the NO3 - The purpose of adding ferrous hydroxide is to react with ozone to generate new oxidative free radicals and new ferric hydroxide colloids, which will be co-precipitated together with the organic impurities and heavy metal ions in the reaction solution.

[0224] This embodiment uses a new chemical method to improve the bottom of an aquaculture fish pond. The steps for using a gas-liquid hybrid electrochemical reaction device to improve the bottom of an aquaculture fish pond water are as follows:

[0225] 1. The bottom mud of the aquaculture fish pond to be treated is pumped into the solid-liquid inclined tube separation tank 26-1 together with the pond water 42 to separate the water from the bottom mud. The bottom mud slurry is then passed through the filter press 26-2 to dehydrate the bottom mud, and the filtrate 74-1 is drained into the chemical reaction tank 21.

[0226] 2. Start the impeller stirrer 18 and add ferrous hydroxide to the chemical reaction tank 21 and inject ozone 41 through the common bubbling gas-liquid mixer 14 to react. During the process, the ORP meter of the sensor 66 controls the injected ozone.

[0227] 3. After the reaction liquid in the chemical reaction tank 21 has reacted for 0.5 hours, the impeller agitator is turned off and the pump 53-4 is turned on to separate the solid-liquid mixture in the chemical reaction tank 21 through the solid-liquid separator 26-3, and the filtrate 74-2 is drained into the temporary storage tank 20-3.

[0228] 4. Open the ordinary electrolytic cell 57 and its cathode electrolyzes hydrogen to supply the gas-liquid hybrid electrolytic cell for NO3 removal. - In use, hydrogen is mixed with the electrolyte through the electrolytic cell gas-liquid mixer 9 to form a gas-liquid mixture, which is then sprayed onto the electrolytic anode 3 and the insoluble anode conductor 23 to contact them. At the same time, the electrolytic power supply 5 of the gas-liquid mixing electrolytic cell is turned on, and the output voltage of the electrolytic power supply is adjusted to the electrolyte decomposition voltage value of 1.3V to remove NO3 in the reaction solution. - electrolysis operation.

[0229] 5. After two hours of treatment in the gas-liquid mixed electrolytic cell, the reaction liquid was pumped to the temporary storage tank 20-4 for temporary storage and testing. The total nitrogen content was measured to be 0.7 mg / L.

[0230] 6. The ferric hydroxide containing organic impurities in the filter residue 73-2 is sent to the electric heating furnace 101 for thermal decomposition of the organic impurities, and the obtained pure iron oxide is reused.

[0231] Example 5

[0232] FIG23 shows Example 5 of a gas-liquid hybrid electrochemical reaction device according to the present invention. The device includes two gas-liquid hybrid electrolytic cells, four solid-liquid separators 26, three polluted tail gas treatment tanks 27, a conventional electrolytic cell 57, an automatic detection and feeding controller 65, two electric heating furnaces 101, a gas-liquid separator 13, three spray towers 16, eleven temporary storage tanks 20, five chemical reaction tanks 21, three overflow buffer tanks 22, and a safety photoelectric control alarm system 77.

[0233] One of the gas-liquid mixing electrolytic cells is the electrolytic cell of the structure of Figure 10, which includes an electrolytic cell body 1-1, eight electrolytic anodes 3-1 to 3-8, an electrolytic cathode 4-1, eight electrolytic power supplies 5-1 to 5-8, a vacuum jet electrolytic cell gas-liquid mixer 7, and two bubbling electrolytic cell gas-liquid mixers 8-1 and 8-2. The electrolytic cathode 4-1 serves as a central electrode and is connected to the negative electrodes of the eight electrolytic power supplies 5-1 to 5-8. The eight electrolytic anodes 3-1 to 3-8 are arranged around the central electrode and are respectively connected to the positive electrodes of their respective electrolytic power supplies 5-1 to 5-8. The electrolytic anodes 3-1 in the electrolytic cell body 1-1 are separated by insulating partitions, and the electrolytic anodes and electrolytic cathodes are structurally improved for electrocatalytic performance: the electrolytic anodes 3-1 and electrolytic cathodes 4-1 are both parallel-connected electrodes, and the angle formed by their parts with the straight line of gas-liquid mixture ejection from the electrolytic cell gas-liquid mixer is greater than 0° and less than 90°. In addition, insoluble anode conductors 23-1 to 23-8 are directly conductively connected to the electrolytic anodes, and an insoluble cathode conductor 24-1 is directly conductively connected to the electrolytic cathode. The vacuum jet electrolytic cell gas-liquid mixer 7 is connected to the electrolytic cell body 1-1 via two bubbling electrolytic cell gas-liquid mixers 8-1 and 8-2 as a liquid flow conduit, and its outlet faces the electrolytic anodes 3-1 to 3-8.

[0234] The second gas-liquid mixing electrolytic cell is the electrolytic cell of the structure of Figure 18, including an electrolytic cell body 1-2, an electrolytic anode 3-9, an electrolytic cathode 4-2, an electrolytic power supply 5-9, and electrolytic cell gas-liquid mixers 9-1 and 9-2 that combine vacuum jet and bubbling types. The electrolytic anode 3-9 is connected to the positive pole of the electrolytic power supply 5-9, and the electrolytic cathode 4-2 is connected to the negative pole of the electrolytic power supply 5-9. The electrolytic cell body 1-2 is provided with insulating through-hole support baffles 12-1 and 12-2, and is provided with two sets of bipolar electrodes 6-1 and 6-2, an insoluble anode conductor 23-9 directly conductively connected to the electrolytic anode, and an insoluble cathode conductor 24-2 directly conductively connected to the electrolytic cathode; electrolytic cell gas-liquid mixers 9-1 and 9-2, which are a combination of vacuum jet and bubbling types, are respectively connected to the electrolytic cell body 1-2 by liquid flow pipes, with the outlet of the electrolytic cell gas-liquid mixer 9-1 facing the electrolytic anode 3-9, the insoluble anode conductor 23-9 and the bipolar electrode 6-1, and the outlet of the electrolytic cell gas-liquid mixer 9-2 facing the electrolytic cathode 4-2, the insoluble cathode conductor 24-2 and the bipolar electrode 6-2.

[0235] The second gas-liquid hybrid electrolytic cell adopts reverse polarity electrolysis and combines the electrolyte with acidic electrolysis first and then adjusting the pH value to be greater than pH7 for alkaline electrolysis treatment to accelerate the degradation of organic waste liquid and the removal of ammonia nitrogen.

[0236] The electrolytic anodes 3-1 to 8 are all conductors with platinum-plated surfaces, the electrolytic cathode 4-1 is conductive graphite, and the insoluble anode conductors 23-1 to 8 and the insoluble cathode conductor 24-1 are all conductive graphite.

[0237] The conventional electrolytic cell has a cation exchange membrane as its separator, a sodium chloride solution as its anolyte, a sodium hydroxide solution as its catholyte, an insoluble titanium-coated anode as its anode, and titanium as its cathode. The electrolysis produces chlorine gas for oxidation in the chemical reaction tank 21-3 and produces hydrogen gas for electrochemical reaction in the electrolysis cell body 1-1.

[0238] The sensors 66-1, 66-5, 66-9, 66-12, 66-16 and 66-18 are pH meters, the sensors 66-3, 66-4, 66-7, 66-8, 6-11, 66-14, 66-15 and 66-17 are liquid level meters, and the sensors 66-2, 66-6, 66-10, 66-13 and 66-19 are ORP meters.

[0239] The automatic detection and feeding controller 65 is used for the device to perform pre-programmed automatic control operation.

[0240] Chemical reaction tank 21-1 is used for protein coagulation. Chemical reaction tank 21-2 is used for the Fenton reaction of the treated solution. Chemical reaction tank 21-3 is used for chlorine oxidation to remove NH3. Chemical reaction tank 21-4 uses residual chlorine to perform an acidic oxidation reaction on the reaction solution. Tank 21-5 is used for the Fenton reaction.

[0241] The temporary storage tanks 20-7 and 20-8 are a set of combined tanks for interrupting the flow of electrolyte ions.

[0242] There are three polluted tail gas treatment tanks: the polluted tail gas treatment tank 27-1 is used to treat sulfur-containing polluted gas G, the polluted tail gas treatment tank 27-2 is used to treat chlorine-containing polluted tail gas G2, and the polluted tail gas treatment tank 27-3 is used to treat NO and hydrogen-containing tail gas G3.

[0243] The alkaline substance is sodium hydroxide solution 49, and the acidic substance is sulfuric acid 50.

[0244] The ferrous substance is a mixture of ferrous sulfate and ferrous chloride 72.

[0245] The solution to be treated is pig farm wastewater, in which the CCD is 11000 mg / L and the total nitrogen is 2200 mg / L.

[0246] This embodiment uses a new electrochemical reaction method to treat farm wastewater, replacing the currently used biochemical treatment process that takes up a lot of space and has low efficiency. Through the improvement of the process, the wastewater treatment achieves better results.

[0247] The operating steps of a method for treating farm wastewater using a gas-liquid mixed electrochemical reaction device are as follows:

[0248] 1. Connect the power supply of the device to enable the automatic detection and feeding controller 65 to process the on-site detection data of each sensor, and issue a command to operate the device under normal circumstances.

[0249] 2. The pig farm wastewater 42 in the temporary storage tank 20-1 is pumped into the solid-liquid separator 26-1 using pump 53-1 for pressure filtration. The resulting filter residue 73-1 is retained in the temporary storage tank 20-2 for processing. The filtrate is then fed into the chemical reaction tank 21-1, where hydrogen peroxide is added for disinfection and sulfuric acid is added for acidification to coagulate the protein. The exhaust gas G1 emitted from the reaction is discharged into tank 27-1 for environmental treatment.

[0250] 3. The solid-liquid mixture in the chemical reaction tank 21-1 is passed through the filter press 26-2 for solid-liquid separation to obtain protein hazardous waste residue 73-2. The filtrate 74-2 is drained to the temporary storage tank 20-4 for temporary storage.

[0251] 4. The solution 74-2 in the temporary storage tank 20-4 is fed into the chemical reaction tank 21-2 for Fenton reaction to achieve the purpose of oxidative degradation of COD, removal of heavy metals and removal of phosphorus compounds. The waste gas escaping from the reaction is discharged to the tank 27-1 for treatment. After the reaction, the solid-liquid separation is carried out through the filter press 26-3 to obtain the iron hydroxide hazardous waste filter residue 73-3 containing heavy metal compounds, phosphates and organic impurities. The filtrate 74-3 is drained to the temporary storage tank 20-6 for temporary storage.

[0252] 5. The waste liquid 74-3 containing NH3630mg / L in the temporary storage tank 20-6 is put into the chemical reaction tank 21-3 for the breakpoint chlorination method to remove NH3. After 6 hours of reaction, the NH3 value is detected to be below 50mg / L. The reaction is considered to be completed when the NH3 value is 50mg / L. The waste liquid is pumped into the chemical reaction tank 21-4, acid is added, and the residual chlorine is used to continue the oxidation reaction for 5 hours.

[0253] 6. The solution in the chemical reaction tank 21-4 is pumped into the temporary storage tanks 20-7 and 20-8 respectively. The ordinary electrolytic tank 57 and the electrolytic tank body 1-1 are started. The eight electrolytic power supplies 5 of the electrolytic tank body 1-1 are adjusted to output voltage of 1.4V, which is slightly higher than the electrolyte decomposition voltage of 0.5V, to perform electrolysis to remove NO3 in the electrolyte. - The hydrogen gas released from the cathode tank area of ​​the ordinary electrolytic cell 57 is directed to the electrolytic cell gas-liquid mixers 8-1 and 8-2 to mix with the electrolyte to form a gas-liquid mixture, which is then sprayed toward the electrolytic anodes 3-1 to 3-8 to contact them.

[0254] Temporary storage tanks 20-7 and 20-8 are operated in turn to pump the electrolyte into the electrolytic cell body 1-1 to short-circuit the ion flow and perform a reduction reaction for 5 hours. Subsequently, sampling and testing show that the nitrate nitrogen NO3 is less than 40 mg / L. This value is considered to be the completion of the reaction in terms of process. The solutions in temporary storage tanks 20-7 and 20-8 are pumped to temporary storage tank 20-9 for temporary storage.

[0255] 7. The solution in the temporary storage tank 20-9 is pumped into the electrolytic cell body 1-2 via pump 53-17 for electrochemical reaction. The electrolytic cell body 1-2 operates as follows: the connector of the electrolytic power supply 5-9 is interchanged every 10 minutes to reverse the polarity of the high voltage and high current (cell voltage 140V, electrolysis current 56A) to perform electrolysis in a self-electrolyzed gas A-type electrolytic cell under the electrocatalysis of the electrolytic electrodes, insoluble electrode conductors, and bipolar electrodes. That is, the self-electrolyzed gas is mixed with the electrolyte in a vacuum jet and bubbling electrolytic cell gas-liquid mixer and then sprayed onto the electrolytic anode, electrolytic cathode, insoluble anode conductor, insoluble cathode conductor, and bipolar electrodes, so that the gas-liquid mixture contacts the above-mentioned electrodes. The electrolysis process is carried out in the first 2 hours using an acidic electrolyte to allow the NO3 in the acidic cathode electrolyte to be dissolved in the electrolyte. - Further removal, after 2 hours, sodium hydroxide is added to adjust the electrolyte to pH 7.2 under the control of the pH meter of sensor 66-16. Since the anolyte contains chloride ions, hypochlorite is generated during the electrolysis operation to continue to remove NH3 and electrochemically oxidize organic impurities. The catholyte undergoes hydrogenolysis, hydrogenation and electrochemical reduction reactions under the electrocatalysis of the electrolysis cathode, the insoluble cathode conductor and the cathode end of the bipolar electrode.

[0256] During the operation, the safety photoelectric control system 77 is turned on to monitor the working area of ​​the electrolytic cell 1-2. When someone enters the working area of ​​the electrolytic cell body 1-2, the electrolytic power supply 5-9 is temporarily shut down and an audible and visual alarm is issued.

[0257] The reaction escaped gas of the electrolytic cell body 1-2 is discharged into the polluted tail gas treatment tank 27-3 for treatment by switching to the escaped gas of the anode tank area according to G2, and the escaped gas of the cathode tank area is treated according to G3.

[0258] 8. The solution after the reaction in the electrolytic cell 1-2 is pumped to the chemical reaction tank 21-5 for Fenton reaction and neutralization treatment after the Fenton reaction, and the escaping gas is discharged to the polluted tail gas treatment tank 27-2 for treatment.

[0259] 9. After the solution reaction in the chemical reaction tank 21-5 is completed, solid-liquid separation is performed through the filter press of the solid-liquid separator 26-4 to obtain iron hydroxide residue 73-4 containing organic impurities and filtrate 74-4, which are then drained into the temporary storage tank 20-11 for temporary storage.

[0260] 10. The solution 88 in the temporary storage tank 20-11 was extracted for testing. The test results showed that the COD value was 72 mg / L, the total nitrogen value was 27 mg / L, and the total phosphorus value was 0.3 mg / L, which met the process treatment index requirements.

[0261] 11. The filter residue 73-1 is put into the electric heating furnace 101-1 for sterilization and drying at 130°C to be used as organic fertilizer. The filter residue 73-4 is put into the electric heating furnace 101-2 for high temperature decomposition of organic impurities at 600°C and reaction to produce iron oxide powder for other raw materials.

[0262] 12. According to the process, the solution to be treated is automatically tested after treatment, and the feeding controller 65 detects and shuts down each running device.

[0263] Example 6

[0264] The gas-liquid hybrid electrochemical reaction device shown in Figure 1 is Example 6 of the present invention. It is a Type A gas-liquid hybrid electrolytic cell, comprising an electrolytic cell body 1, a sealed cell cover 28 for collecting escaping gases 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 7. 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. Thus, electrolytic electrode 90-1 serves as either the electrolytic anode or the electrolytic cathode, and electrolytic electrode 90-2 serves as the corresponding electrode. The electrolytic cell separator 2, which is electrolytic cell separator 1#, separates the electrolytic cell body 1 into an anode cell area and a cathode cell area. When the electrolysis electrode 90-1 is an electrolysis anode, the sealed tank cover 28 for collecting the escaped gas from the electrolysis cell reaction only covers the anode tank area, and two electrocatalytic components, namely bipolar electrodes 6, are set in the anode tank area, and both of them are immersed in the electrolyte in the anode tank area; when the electrolysis electrode 90-1 is an electrolysis cathode, the sealed tank cover 28 for collecting the escaped gas from the electrolysis cell reaction only covers the cathode tank area, and two electrocatalytic components, namely bipolar electrodes 6, are set in the cathode tank area, and both of them are immersed in the electrolyte in the cathode tank area; the electrolyte in the anode tank area and the electrolyte in the cathode tank area are the reaction liquids to be treated respectively; the electrolysis cell gas-liquid mixer 7 adopts The vacuum jet electrolytic cell gas-liquid mixer has an air inlet, a liquid inlet and an outlet, and the air inlet and the liquid inlet are respectively connected to the top and the bottom of the anode tank area, or to the top and the bottom of the cathode tank area. That is, in this embodiment, the electrolysis gas generated in the anode tank area is mixed with the electrolyte in the anode tank area for gas-liquid mixing, and is ejected through an outlet extending above the electrolyte surface in the anode tank area and toward the electrocatalytic component, i.e., the bipolar electrode 6. Alternatively, the electrolysis gas generated in the cathode tank area is mixed with the electrolyte in the cathode tank area for gas-liquid mixing and is ejected through an outlet extending above the electrolyte surface in the cathode tank area and toward the electrocatalytic component, i.e., the bipolar electrode 6. Due to the presence of sufficient gas, this gas-liquid mixture can promote active electrochemical reactions in the solution being treated. The positively charged components play a role in converting electrical energy into chemical energy, oxidizing the reducing substances in the electrolyte under electrocatalysis. They can also oxidize oxygen, hydroxide ions, chloride ions, etc. in the electrolyte to produce a large number of superoxide radicals (O2·), hydroxyl radicals (OH·) and / or chlorine radicals (Cl·), chloroxyl radicals (ClO·), and other oxidizing free radicals, rapidly oxidizing substances in the electrolyte that require oxidation treatment, such as oxidizable organic matter and inorganic ammonia in the solution being treated. The negatively charged components play a role in converting electrical energy into chemical energy, reducing oxidizable substances in the electrolyte under electrocatalysis, and can also produce a large number of hydrogen radicals (H·) or protons to rapidly cause at least one of hydrogenolysis, hydrogenation, and reduction reactions on substances in the electrolyte that require reduction treatment, such as reducible organic matter and nitrogen oxides in the solution being treated.

[0265] Example 7

[0266] The gas-liquid mixing electrochemical reaction device shown in Figure 2 is Example 7 of the present invention, which is also a type A gas-liquid mixing electrochemical reaction device. Unlike the device in Figure 1, the anode tank area and the cathode tank area are both covered by a sealed tank cover 28 for collecting the escaped gas from the electrolytic cell reaction. Its electrocatalytic components adopt two components of the electrocatalytic method (1) in both tank areas, that is, several bipolar electrodes 6 and two insoluble anode conductors 23 directly connected to the electrolytic anode and two insoluble cathode conductors 24 connected to the electrolytic cathode are arranged in both tank areas, and they are all immersed in the electrolyte; an electrolytic cell gas-liquid mixer 7 is provided in the anode tank area and the cathode tank area, which adopts a vacuum jet electrolytic cell gas-liquid mixer, and the outlet of each electrolytic cell gas-liquid mixer 7 extends above the electrolyte surface of the corresponding tank area and forks towards the bipolar electrode 6 and the electrolytic electrode respectively.

[0267] Example 8

[0268] The gas-liquid mixing electrochemical reaction device shown in Figure 3 is Example 8 of the present invention, which is a Type B device. Unlike the Type A device shown in Figure 1, the anode tank area and the cathode tank area are both covered by a sealed tank cover 11. In addition to the bipolar electrolysis 6, the electrocatalytic component arranged in the anode tank area also adopts two insoluble anode conductors or insoluble cathode conductors directly electrically connected to the electrolysis anode or electrolysis cathode. The air inlet of the vacuum jet electrolytic tank gas-liquid mixer 7 adopts not only the self-generated gas connected to the tank area where its outlet is located, but also external input gas.

[0269] Example 9

[0270] The gas-liquid hybrid electrochemical reaction device shown in FIG4 is Example 9 of the present invention. It is a C-2 type gas-liquid hybrid electrolytic cell, comprising an electrolytic cell body 1, an electrolytic cell separator, a sealed cell cover 28 for collecting escaping 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. Thus, electrolytic electrode 90-1 serves as either the electrolytic anode or the electrolytic cathode, while electrolytic electrode 90-2 serves as the corresponding other electrode. The electrolytic cell separator adopts electrolytic cell separator 2#83, which divides 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 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 2 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 electrolytic electrode 90-1 is the electrolytic anode, an electrocatalytic component, i.e., an insoluble anode conductor 23, is set in the anode cell area and immersed in the electrolyte in the anode cell area, and the electrolytic cathode 4 is a parallel electrode connected in parallel; when the electrolytic electrode 90-1 is the electrolytic cathode, an electrocatalytic component, i.e., an insoluble cathode conductor 23, is set in the anode cell area. The electrode conductor 24 is immersed in the electrolyte in the anode tank area, and the electrolytic anode 3 is a parallel electrode connected in parallel; the electrolyte in the anode tank area and the electrolyte in the cathode tank area are respectively the solutions to be treated; the electrolytic tank gas-liquid mixer adopts an electrolytic tank 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, and the liquid inlet is connected to the electrolytic tank body, that is, this embodiment uses external input gas from outside the electrolytic tank 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 component, that is, the insoluble anode conductor 23, or extends to the bottom of the electrolyte surface in the cathode tank area and toward the electrocatalytic component, that is, the insoluble cathode conductor 24.

[0271] Example 10

[0272] The gas-liquid hybrid electrochemical reaction device shown in Figure 5 is Example 10 of the present invention, and is a C-1 type gas-liquid hybrid electrolytic cell. It comprises an electrolytic cell body 1, one of the electrolytic cell separators 2-1 and 2-2, an electrolytic anode 3, an electrolytic cathode 4, an electrolytic power supply 5, an electrocatalytic component, an electrolytic cell gas-liquid mixer, and a bipolar electrode electrically insulating mesh box 11. 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 separators 2-1 and 2-2 to divide it into an electrolytic anode cell area, an intermediate cell area, and an electrolytic cathode cell area. A bipolar electrode electrically insulating mesh box 11 is provided in the intermediate cell area and loaded with electrocatalytic components, namely multiple bipolar electrodes 6. The electrolytic cell separator 2-1 is an anion exchange membrane, and the electrolytic cell separator 2-2 is a reverse osmosis membrane. A bubble drainage cover 95 is provided at the electrolytic anode. The sealed tank cover 28 for collecting escaping gases from the electrolytic cell reaction only covers the electrolytic anode cell area and the intermediate cell area. The portion of the sealed tank cover 28 located in the anode cell area is provided with an oxidizing gas discharge pipe port 30, and the portion of the sealed tank cover 28 located in the intermediate cell area is provided with a gas-liquid mixed electrolytic cell exhaust pipe port 51. A gas pressure equalization connecting pipe 56 is provided between the electrolytic anode cell area and the intermediate cell area. The electrolyte in the intermediate cell area is the reaction liquid 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 provided with an air inlet branch pipe, and the liquid inlet is connected to the middle tank area. That is, this embodiment simultaneously uses external input gas from outside the electrolytic cell and electrolysis gas generated in the anode tank area to mix gas and liquid with the electrolyte in the middle tank area, and sprays it through the outlet extending above the electrolyte surface in the middle tank area and toward the electrocatalytic component 6, i.e., the bipolar electrode.

[0273] Example 11

[0274] The gas-liquid hybrid electrochemical reactor shown in Figure 6 is Example 11 of the present invention, a C-1 type gas-liquid hybrid electrochemical reactor. It comprises an electrolytic cell body 1, one of the electrolytic cell dividers 2-1 and two of the electrolytic cell dividers 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 and washing tank 13, and a bubble-containing reaction liquid deflector 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 separators 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; the electrolytic cell separator 2-3 is an anion exchange membrane, the electrolytic cell separator 2-4 is a reverse osmosis membrane, and 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 the sealed tank cover 28 for collecting the escaped 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 56 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.

[0275] Example 12

[0276] The gas-liquid hybrid electrochemical reaction device shown in Figure 7 is Example 12 of the present invention, and is a C-2 type gas-liquid hybrid electrolytic cell. It 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. Thus, electrolytic electrode 90-1 serves as either the electrolytic anode or the electrolytic cathode, while electrolytic electrode 90-2 serves as 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 provided in the electrolytic cell body 1. When the electrolytic electrode 90-1 is the electrolytic anode, the conductor 63-1 is the insoluble anode conductor 23 and the conductor 63-2 is the insoluble cathode conductor 24. When the electrolytic electrode 90-1 is the electrolytic cathode, the opposite is true. A sealed tank cover 28 for collecting the escaped gas from the electrolytic cell reaction is covered on the electrolytic cell body. The electrolytic cell gas-liquid mixer adopts a vacuum jet type and bubbling type combined electrolytic cell gas-liquid mixer 9, which is electrically connected to the electrolytic power supply and has a jet tube. An ultrasonic generator 25 is installed, which has an air inlet, a liquid inlet and an outlet. The liquid inlet is connected to the electrolytic cell body. That is, in this embodiment, external input gas from outside the electrolytic cell is mixed with the electrolyte in the electrolytic cell body to mix gas and liquid, and is ejected through an outlet extending below the electrolytic anode 3 and the electrocatalytic component, i.e., the insoluble anode conductor 23, or through an outlet extending below the electrolytic cathode 4 and the electrocatalytic component, i.e., the insoluble cathode conductor 24; an insulating through-hole support baffle 12 is arranged between the electrolytic anode 3 or the electrolytic cathode 4 and the outlet of the electrolytic cell gas-liquid mixer.

[0277] Example 13

[0278] The gas-liquid hybrid electrochemical reaction device shown in FIG8 is Example 13 of the present invention. It is a three-divided gas-liquid hybrid electrolytic cell symmetrically assembled from the A-type cell of FIG1 . 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. 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. Thus, electrolytic electrodes 90-1 and 90-3 serve as either the electrolytic anode or the electrolytic cathode, while electrolytic electrode 90-2 serves as the corresponding alternative 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. The electrolytic cell body 1 is provided with one of the electrolytic cell separators 2-1 and the other 2-2, which divide it into two electrolytic anode cell areas and one electrolytic cathode cell area, or one electrolytic anode cell area and one electrolytic cathode cell area; when the electrolytic electrodes 90-1 and 90-3 are electrolytic anodes, the two anode cell areas are respectively provided with an electrocatalytic component bipolar electrode 6-1 and an insoluble anode conductor 23-1 directly conductively connected to the electrolytic anode, a bipolar electrode 6-2 and an insoluble anode conductor 23-2; or when the electrolytic electrodes 90-1 and 90-3 are electrolytic cathodes, 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 escaped gas from the electrolytic cell reaction is collected The sealing tank covers 28-1 and 28-2 cover the two electrolytic anode tank areas or the two electrolytic cathode tank areas respectively; the electrolytic tank gas-liquid mixer adopts a vacuum jet electrolytic tank 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 covers 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, in this embodiment, the electrolysis gas generated in the anode tank area is mixed with the electrolyte in the anode tank area for gas-liquid mixing and is ejected through the outlet extending above the electrolyte surface of the electrolytic anode tank area and toward the electrocatalytic component, i.e., the bipolar electrode, or the electrolysis gas generated in the cathode tank area is mixed with the electrolyte in the cathode tank area for gas-liquid mixing and is ejected through the outlet extending above the electrolyte surface of the electrolytic cathode tank area and toward the electrocatalytic component, i.e., the bipolar electrode.

[0279] Example 14

[0280] The gas-liquid hybrid electrochemical reaction device shown in Figure 9 is Example 14 of the present invention. It is a three-divided-tank gas-liquid hybrid electrolytic cell formed by symmetrically combining the C-2-type cell of Figure 4. It comprises an electrolytic cell body 1, a cell divider, a sealed cell cover 28 for collecting escaping gas 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 the electrolytic cathode 4 can be interchanged. Therefore, electrolytic electrodes 90-1 and 90-3 serve as either the electrolytic anode or the electrolytic cathode, while electrolytic electrode 90-2 serves as the corresponding other electrode. The electrolytic cell separators are electrolytic cell separators 2#83, one 83-1 and two 83-2, which are respectively superimposed on insulating through-hole support baffles 12#12-2 and three 12-3 to separate the electrolytic cell body 1 into an anode cell area and a cathode cell area. The insulating through-hole support baffles 12#12-1 and four 12-4 separate the electrolytic electrodes 90-1 and 90-3 and the outlet of the electrolytic cell gas-liquid mixer in two identical cell areas. The sealed tank covers 28#28-1, two 28-2 and three 28-3 for collecting the escaped gas from the electrolytic cell reaction are respectively covered on each cell area of ​​the electrolytic cell body 1. When the electrolytic electrode 90-1 is an electrolytic anode, an electrocatalytic component, i.e., an insoluble anode conductor 23, is provided in the anode cell area and immersed in the electrolyte in the anode cell area. The electrolytic cathode 4 is a parallel electrode connected in parallel. When the electrolytic electrode 90-1 is an electrolytic cathode, the electrolytic cathode 4 is a parallel electrode connected in parallel. During the electrolysis, an electrocatalytic component, i.e., an insoluble cathode conductor 24, is arranged in the anode tank area and immersed in the electrolyte in the anode tank area. The electrolytic anode 3 is a parallel electrode connected in parallel; 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 tank gas-liquid mixer adopts one 9-1 and the other 9-2 of the electrolytic tank gas-liquid mixers which are a combination of vacuum jet type and bubbling type, which have an air inlet, a liquid inlet and an outlet, and the liquid inlet is connected to the electrolytic tank body. That is, this embodiment uses external input gas from outside the electrolytic tank 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 component, i.e., the insoluble cathode conductor 23, or extends to the bottom of the electrolyte surface in the cathode tank area and toward the outlet of the electrocatalytic component, i.e., the insoluble cathode conductor 24.

[0281] Example 15

[0282] 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.

[0283] Example 16

[0284] The gas-liquid mixing electrochemical reaction device shown in Figure 11 is Example 16 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 electrolytic cathode 4 can be interchanged, with 90-1 representing either the electrolytic anode or cathode, and electrolytic electrode 90-2 representing 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.

[0285] Example 17

[0286] The gas-liquid mixing electrochemical reaction device shown in Figure 17 is Example 17 of the present invention. It is a vertical gas-liquid mixing 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.

[0287] Example 18

[0288] The gas-liquid mixing electrochemical reaction device shown in Figure 18 is Example 18 of the present invention, which includes an electrolytic cell body 1, 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 cell gas-liquid mixer is an electrolytic cell gas-liquid mixer 9-1 and 9-2 that combines vacuum jet and bubbling types. The electrolytic anode 3-1 or 3-2 is connected to the positive pole of the electrolytic power supply 5, and the electrolytic cathode 4-1 or 4-2 is connected to the negative pole of the electrolytic power supply 5. The electrolytic cell body 1 is provided with insulating through-hole support baffles 12-1, 12-2, 12-3 and 12-4, and is provided with electrocatalytic components, namely two sets of bipolar electrodes 6-1 and 6-2, an insoluble anode conductor 23-1 or 23-2 directly conductively connected to the electrolytic anode, and an insoluble cathode conductor 24-1 or 24-2 directly conductively connected to the electrolytic cathode; vacuum jet and bubbling type combined electrolytic cell gas-liquid mixers 9-1 and 9-2 They are respectively connected to the electrolytic cell body 1 as liquid flow pipelines, and the outlet of the electrolytic cell gas-liquid mixer 9-1 is directed toward the electrolytic anode 3-1 or the electrolytic cathode 4-1, the insoluble anode conductor 23-1 or the insoluble cathode conductor 24-1, and the bipolar electrode 6-1; the outlet of the electrolytic cell gas-liquid mixer 9-2 is directed toward the electrolytic anode 3-2 or the electrolytic cathode 4-2, the insoluble anode conductor 23-2 or the insoluble cathode conductor 24-2, and the bipolar electrode 6-2.

Claims

1. A gas-liquid hybrid electrochemical reaction device, 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 more of the following methods: Electrocatalytic method (1): at least one electrocatalytic component is provided in the electrolytic cell body, and the outlet of the electrolytic cell gas-liquid mixer 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; Electrocatalytic method (3): The electrocatalytic performance structure of the electrolytic anode and / or the electrolytic cathode is improved, and the angle formed by a part or the whole of at least one of the electrolytic anode and the electrolytic cathode and the gas-liquid mixture ejection straight line of the electrolytic tank gas-liquid mixer is greater than 0° and less than or equal to 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 electrolytic cell body by a pipeline, 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 located inside the electrolytic cell and below the electrolyte level, and is used to achieve electrochemical catalytic reaction under the action of an electric field force; 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 an insoluble conductor disposed between the electrolysis anode and the electrolysis cathode, not connected to an external power source, and 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 electrolyzer 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 electrode 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 electrode and / or electrocatalytic component sprayed into 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 a gas source outside the electrolytic cell. The gas electrolyzed by the electrolytic electrodes in the cell area combines with the gas from outside the cell area and mixes with the electrolyte in the cell area to form a gas-liquid mixture, which contacts the electrolytic electrodes and / or electrocatalytic components of the cell to undergo 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 outside 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. The gas-liquid hybrid electrochemical reaction device according to claim 4, characterized in that: The surface of the electrolytic anode is selected from at least one material selected from gold, platinum, nickel, alloys containing at least one of the above metals, titanium-based coated insoluble anodes, and graphite; the surface of the electrolytic cathode is selected from at least one material selected from gold, platinum, silver, titanium, copper, nickel, alloys containing at least one of the above metals, stainless steel, and graphite; The material of the bipolar electrode is any conductive material that is insoluble or poorly soluble in the electrolyte it contacts, such as metal, metal oxide, semiconductor, etc. The material of the insoluble conductor is conductive metal, conductive metal oxide, or conductive semiconductor material.

7. A method for electrochemically treating a substance requiring oxidation and / or reduction using the gas-liquid hybrid electrochemical reaction device according to claim 1, characterized in that: The following steps are involved: (1) Using a gas-liquid hybrid electrochemical reaction device, using the substance to be treated as an electrolyte or one of its components or mixed in the electrolyte in the form of an insoluble substance, and adding the electrolyte to the gas-liquid hybrid electrolytic cell or its cell area of the device; the substance to be treated is a substance that needs to participate in electrochemical oxidation and / or reduction reaction; (2) turning on the electrolysis power supply and starting at least one of the electrolytic tank gas-liquid mixers of the device, mixing the oxidizing gas and / or reducing gas with the electrolyte to form a gas-liquid mixture and contacting the mixture with at least one of the electrolysis anode, electrolysis cathode, and electrocatalytic component, and utilizing the electrolysis electrode and / or electrocatalytic component with improved electrocatalytic structure to exert electrocatalytic effect on the electrolyte. The substance to be treated undergoes oxidation and / or reduction reaction.

8. The method for electrochemically treating a substance requiring oxidation and / or reduction according to claim 7, wherein: 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 the substance to be treated to undergo an oxidation reaction; 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 the substance to be treated to undergo at least one of a hydrogenolysis reaction, a hydrogenation reaction, and a reduction reaction.

9. The method for electrochemically treating a substance requiring oxidation and / or reduction according to claim 8, wherein: The oxidizing gas in step (2) is at least one selected from ozone, oxygen, and chlorine; and the reducing gas is hydrogen.

10. The method for electrochemically treating a substance requiring oxidation and / or reduction according to claim 9, wherein: The substances to be treated are subjected to oxidation reaction using oxidizing gas and at least one of hydrogenolysis reaction, hydrogenation reaction and reduction reaction using reducing gas in a step-by-step manner.

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