Electro-oxidation apparatus for treating ammonia nitrogen pollution or micro-organisms in water

Abstract

Disclosed in the present invention is an electro-oxidation apparatus for treating ammonia nitrogen pollution or micro-organisms in water. The apparatus comprises a divided electrolytic cell, an anode cell zone recirculation line, an electrolytic solution pH meter, and a pump tubing liquid flow circulator; the divided electrolytic cell comprises an electrolysis anode, an electrolysis cathode, a cell body, an electrolysis power supply and a cell zone separator, using the cell zone separator to divide the cell body into an anode cell zone and a cathode cell zone; the cell zone separator is an electrolytic cell separator, or a combination of an electrolytic cell separator and an electrolytic cell partition plate; when the cell zone separator is not water-permeable, a partition plate liquid flow through hole and / or an anode electrolytic solution feeder is provided; the anode cell zone recirculation line is a tube connected between the pump tubing liquid flow circulator and the anode cell zone, or the anode cell zone recirculation line is a tube connected to a receiving tank for outflow liquid from the pump tubing liquid flow circulator; a liquid inlet tube of the pump tubing liquid flow circulator is connected to the cathode cell zone.

Description

An electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water. Technical Field

[0001] This invention belongs to the technical field of electrochemical oxidation treatment, specifically relating to an electrochemical oxidation device for treating ammonia nitrogen pollutants or microorganisms in water. Background Technology

[0002] Currently, ammonia-nitrogen-containing wastewater from various sources is commonly found in production and daily life. For example, the circuit board manufacturing industry often uses etching solutions containing ammonia salts, thus generating large quantities of acidic board-washing wastewater containing copper chloride and ammonium chloride, as well as board-washing wastewater containing copper-ammonia complex Cu(NH3)4Cl2, ammonium salts, and ammonia water every day. Another example is the sanitation industry, which needs to treat large amounts of landfill leachate daily. This is a nitrogen-containing organic wastewater and is widely recognized as one of the most difficult wastewaters to treat; the total nitrogen content of landfill leachate is generally close to 3000 mg / L, with ammonia nitrogen accounting for 60-85% of the total nitrogen.

[0003] In the existing technology, the treatment of ammonia nitrogen-containing waste liquid mainly adopts biochemical treatment methods, or a combination of membrane separation purification and biochemical treatment. However, the above methods have disadvantages such as large footprint, high equipment investment, difficulty in treating high-concentration waste liquid, high cost of treating process-escaped waste gas, and low biochemical treatment efficiency.

[0004] In addition, breakpoint chlorination is commonly used in existing technologies to remove ammonia nitrogen pollutants from wastewater, as it is simple to operate and highly efficient. Specifically, this method involves adding chlorine gas and / or sodium hypochlorite to the ammonia nitrogen-containing wastewater to oxidize the pollutants and convert them into nitrogen gas, or directly placing the wastewater containing ammonia nitrogen and chloride ions into an electrolytic cell to electrolyze and generate chlorine gas and / or sodium hypochlorite for oxidation. Existing technologies that directly use breakpoint chlorination in an electrolytic cell employ an electrolytic cell without a separation between the anode and cathode, which often leads to the following two dangerous side reactions during the chemical reaction process.

[0005] The first dangerous side reaction: Due to the use of an unseparated electrolytic cell, during operation, the chlorine gas produced by the anodic electrochemical reaction and other potentially present oxidizing gases (including oxygen produced by decomposition reactions) can mix with the hydrogen gas electrolyzed at the cathode in the electrolytic cell or its circulating pipelines, easily forming an explosive gas mixture that could lead to an explosion. However, due to ion migration during the electrolysis process, simple separation of the electrolytic cell can affect ion migration, thereby impacting the ammonia nitrogen treatment efficiency and overall treatment rate. Currently, there is no technical solution that can effectively separate the gases while maintaining a highly efficient treatment reaction.

[0006] The second hazardous side reaction: The inability to adjust the pH of the ammonia-nitrogen-containing reaction solution in the electrolytic cell during the reaction leads to acidification of the solution. Under acidic conditions, the ammonia-nitrogen waste liquid reacts with chlorine to remove ammonia, easily generating nitrogen trichloride, an explosive hazardous material. The chemical reaction is as follows: NH4Cl + 3Cl2 → 4HCl + NCl3

[0007] Because of the aforementioned safety issues in the existing electrolytic nitrogen removal process, it is necessary to make structural improvements to the electrolytic cells used for treating ammonia nitrogen in order to achieve safe production.

[0008] Modern industrial and agricultural production, as well as daily life, widely employ technologies for treating microorganisms in water bodies. These include: using ultrafiltration membranes to filter microorganisms for seawater purification; using MBR membranes to separate activated sludge from biochemically treated wastewater; adding oxidants to water bodies for deodorization in aquaculture; adding bactericides and algaecides to cooling tower heat exchange water to prevent the growth of algae and microorganisms; and water treatment plants adding chlorine or hypochlorite to treated water for disinfection. Furthermore, because active microorganisms in water bodies have flocculent cross-linking properties, the adhesiveness of these flocs frequently clogs the micropores in filtration equipment. This necessitates regular maintenance cleaning of the equipment using chemicals such as sodium hypochlorite to ensure the filter membrane micropores regain their filtration function. Especially for water spray cooling towers, the heat exchange circulating water is generally tap water with a sodium chloride content of less than 200 mg / L. Because the circulating water has a suitable temperature and sufficient sunlight, and can absorb carbon, nitrogen, and oxygen sources from nature, promoting plant cell division and growth, microbial reproduction, and insect growth, it directly affects the heat exchange operation of the cooling tower. Current solutions to the problems with the heat exchange circulating water in these cooling towers include frequent shutdowns for water changes or the addition of oxidants. However, frequent shutdowns for water changes reduce production efficiency and shorten equipment lifespan. Similarly, using oxidants to inactivate or inhibit the reproduction of microorganisms in the water can corrode and damage the equipment, shortening its lifespan. To better address the toxicity and pollution issues caused by microorganisms in the water, improvements to existing disinfection measures are needed.

[0009] With socio-economic development and the expansion of industrial production, the amount of ammonia nitrogen wastewater discharged daily by urban residents and industrial and mining enterprises is increasing. The demand for water spray cooling towers for temperature control is growing, and there is also a strong preference for membrane equipment technology to treat organic wastewater. Therefore, various industries are urgently seeking new process solutions that are simple, safe, efficient, and cost-effective, hoping to quickly address the hygiene and environmental protection needs of ammonia nitrogen wastewater and the inactivation of microorganisms in water bodies. Summary of the Invention

[0010] The purpose of this invention is to provide an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water, solving the problems existing in the prior art for removing ammonia nitrogen and killing microorganisms; the device eliminates ammonia nitrogen pollutants by combining breakpoint chlorination and ammonium ion discharge, and / or uses breakpoint chlorination combined with electrolytic current to electrolytically inactivate microorganisms in water.

[0011] The objective of this invention is achieved through the following technical solutions:

[0012] An electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water is characterized by comprising at least one partitioned electrolytic cell 1, at least one anode tank reflux pipe 6, at least one electrolyte pH meter 10, and at least one pump pipe liquid flow circulator 11.

[0013] The partitioned electrolytic cell 1 includes an electrolytic anode 2, an electrolytic cathode 3, a cell body 4, an electrolytic power supply 44, and a cell partition. The cell partition divides the cell body 4 into an anode cell area and a cathode cell area. The electrolytic anode 2 is placed in the anode cell area and connected to the positive terminal of the electrolytic power supply 44, and the electrolytic cathode 3 is placed in the cathode cell area and connected to the negative terminal of the electrolytic power supply 44. The cell partition is an electrolytic cell partition 5, or a combination of an electrolytic cell partition 5 and an electrolytic cell partition plate 65. The electrolytic cell partition plate 65 is provided with an electric field line through-hole 9, and the electric field line through-hole 9 is closed by the electrolytic cell partition 5.

[0014] The electrolytic cell separator 5 can effectively prevent bubbles and insoluble solids in the electrolyte from moving between the anode and cathode areas. It can be used as a single layer or in a stacked manner with one or more layers.

[0015] The anode tank return pipe 6 is a pipe connecting the pump tube liquid flow circulator 11 and the anode tank, used to guide the solution flowing out of the pump tube liquid flow circulator 11 back to the anode tank to continue participating in the reaction, or the anode tank return pipe 6 is connected to the receiving tank of the liquid flowing out of the pump tube liquid flow circulator 11, indirectly guiding the liquid containing the liquid flowing out of the pump tube liquid flow circulator 11 back to the anode tank to continue participating in the reaction; the pump tube liquid flow circulator 11 includes a pump and a pipe, or includes a pump, a pipe and a valve to have a flow regulation function, and its inlet is connected to the cathode tank; the pump in the pump tube liquid flow circulator 11 is started and stopped according to the detection data of the electrolyte pH meter 10 and / or the concentration of ammonium ions in the cathode electrolyte and / or the number of active organisms in the cathode electrolyte and / or the electrolysis time and / or the liquid level of the electrolyte in the tank;

[0016] The electrolyte pH meter 10 is installed in the partitioned electrolytic cell 1 and / or in a pipe or container connected to the partitioned electrolytic cell 1, and is used to detect the pH value of the electrolyte.

[0017] The electrolyte in the separate electrolytic cell 1 is ammonia nitrogen pollutant waste liquid containing chloride ions, or treated water containing chloride ions and active microorganisms.

[0018] The electro-oxidation apparatus of the present invention further includes at least one anolyte feeder 61 and / or a liquid flow hole 14 in the spacer plate to help achieve flow balance between the electrolytes in the anode and cathode tank areas. Preferably, at least one anolyte feeder 61 and / or a liquid flow hole 14 is provided when the tank spacer between the anode and cathode tank areas is impermeable to water; the aforementioned impermeability means that the tank spacer does not allow liquid to pass through and completely blocks the liquid exchange between the anode and cathode tank areas.

[0019] The liquid flow hole 14 of the spacer plate is provided on the spacer plate 65 of the electrolytic cell to connect the anode tank area and the cathode tank area, and the liquid flow hole 14 allows the electrolyte to pass through;

[0020] The anolyte feeder 61 consists of a pump and a pipeline, or a pump, a valve and a pipeline. Its inlet is connected to the anode tank area, and its outlet is connected to the cathode tank area. It pumps part of the anolyte into the cathode tank area according to process requirements, or it is connected to the tank into which the loaded solution flows into the cathode tank area and pumps the solution containing the anolyte into the cathode tank area according to process requirements.

[0021] In the electro-oxidation device of the present invention, at least one liquid circulation electrolysis system is established, monitored by a pH meter, in which the anolyte enters the cathode tank and then flows back from the cathode tank to the anode tank. Specifically, the electro-oxidation device of the present invention uses a pump-tube liquid circulation device 11 to stir out a circulating liquid flow during operation, which performs the following three functions: First, it draws a portion of the electrolyte from the cathode tank and adds it to the anode tank to solve the problem of NH4 in the waste liquid during electrolysis. + The first problem is that the alkaline substances, after being subjected to the electric field, accumulate in the cathode tank and cannot participate in the chemical reaction in the anode tank, thus directly affecting the treatment effect. The second solution utilizes the circulating electrolyte flow from the anode tank to the cathode tank to help drive the electrolytic hydrogen gas from the cathode out of the tank. Simultaneously, the electric field established by the electrolytic cathode in the cathode tank is used to electrolytically inactivate microorganisms in the flowing electrolyte. The third solution involves pumping the alkaline substances accumulated in the cathode tank back to the anode tank to participate in the chemical reaction to synthesize hypochlorite, avoiding the formation of hazardous and explosive nitrogen trichloride, and improving the efficiency of treating ammonia nitrogen pollutants and inactivating microorganisms. In summary, by creating a circulating liquid flow to exchange solutions between the two tanks, ammonia nitrogen pollutants in the wastewater can be completely eliminated or microorganisms in the water can be inactivated. This also allows for better recycling of alkaline raw materials, reducing production costs.

[0022] The electrolytic cell separator 5 is divided into a permeable electrolytic cell separator and a non-permeable electrolytic cell separator. The permeable electrolytic cell separator 5 has permeable pores that allow water to pass freely under natural conditions, including a polymer resin permeable plate, a ceramic permeable plate, a filter cloth, and a permeable non-ionic membrane; the non-permeable electrolytic cell separator 5 prevents water from passing through under natural conditions, including a cation exchange membrane, a reverse osmosis membrane, a bipolar membrane, an anion exchange membrane, and a non-permeable non-ionic membrane.

[0023] When the electrolytic cell separator 5 is used alone as the cell zone separator, the electrolytic cell separator 5 is made of polymer resin through-hole plate and / or ceramic through-hole plate and is directly fixed in the cell body 4.

[0024] When a combination of electrolytic cell separator 5 and electrolytic cell partition plate 65 is used as the cell zone spacer, the electrolytic cell partition plate 65 is at least one selected from polymer resin plate, polymer resin perforated plate, and ceramic perforated plate. The electrolytic cell separator 5 is at least one selected from permeable electrolytic cell separator 5 and / or impermeable electrolytic cell separator 5 and is different from the electrolytic cell partition plate 65.

[0025] When an impermeable electrolytic cell separator 5 is used in conjunction with an electrolytic cell partition plate 65 made of polymer resin board to create a watertight barrier between the anode and cathode cell areas, at least one anode electrolyte feeder 61 and / or at least one partition plate liquid flow hole 14 are required to achieve flow balance of the electrolyte in the two cell areas during the reaction. The pump of the anode electrolyte feeder 61 is activated according to process control to draw a portion of the anode electrolyte into the cathode cell area. The partition plate liquid flow hole 14 on the electrolytic cell partition plate 65 is a connecting hole between the anode and cathode cell areas. Utilizing the liquid level difference due to the high potential energy of the anode electrolyte, the anode electrolyte naturally seeps into the cathode cell area through the liquid flow hole 14. The spacer plate liquid flow hole 14 connects the anode and cathode tank areas, allowing the electrolyte in the anode tank area to seep into the cathode tank area and form a circulating liquid flow through the pump pipe liquid flow circulator 11 and the anode tank area return pipe 6. The anode electrolyte adder 61 extracts a portion of the electrolyte from the anode tank area and adds it to the cathode tank area, achieving circulation through the pump pipe liquid flow circulator 11 and the anode tank area return pipe 6. This structural design effectively prevents hydrogen bubbles from the cathode electrolyte from entering the anode tank area and allows the anode electrolyte to flow smoothly into the cathode tank area. Preferably, the spacer plate liquid flow hole 14 is positioned below the electric field line through-hole 9, forming a U-shaped tube structure between the anode and cathode tank areas. This improved structure increases the distance between the spacer liquid flow hole 14 and the electrolytic anode, thereby increasing the chance and extending the reaction time of ammonia nitrogen pollutants or active microorganisms in the water to react with hypochlorite, hypochlorous acid or chlorine in the anode electrolyte during the electrolyte flow process. At the same time, it prevents rising hydrogen bubbles in the cathode electrolyte from passing through the bottom spacer liquid flow hole 14 to the anode tank area.

[0026] When a permeable electrolytic cell separator 5 is used, or a combination of a permeable electrolytic cell separator 5 and an electrolytic cell partition plate 65 is used, or an impermeable electrolytic cell separator 5 is used in combination with a polymer resin perforated plate and / or a ceramic perforated plate as an electrolytic cell partition plate 65 to form a cell area partition, the permeable holes in the electrolytic cell separator 5 and the electrolytic cell partition plate have the water permeability function of the partition plate liquid flow hole 14. Whether or not the anode electrolyte feeder 61 and / or the partition plate liquid flow hole 14 are provided, the anode electrolyte can enter the cathode cell area.

[0027] The outlet of the anode tank return pipe 6 is either inserted into the solution within the anode tank, or positioned above the solution surface within the anode tank, or connected to a pipe or container that returns the solution to the anode tank. Preferably, the outlet of the anode tank pipe 6 is inserted into the solution within the anode tank and faces the electrolytic anode to increase the NH4 content. + The discharge reaction increases the number of microorganisms in the water that enter the electric field and are inactivated by electric shock.

[0028] When a copper-ammonia complex, which is slightly soluble in the electrolyte, is present, copper oxide will be produced when the copper-ammonia complex comes into contact with the electrolytic anode or reacts with the oxidant in the anolyte. In addition, when the copper-ammonia complex comes into contact with the electrolytic cathode, an electrochemical reaction will occur to electrodeposit metallic copper sponge. At this time, the spacer in the tank area plays an insulating role between the electrolytic anode and the electrolytic cathode, avoiding the problem of short circuit between the anode and cathode that is easy to occur when the two electrodes are close together and conductive powder particles are accumulated between them.

[0029] Preferably, the electrolytic cell separator 5 is fixed to the periphery of the electric field line through-hole 9 of the electrolytic cell partition plate 65 using screws and nuts, and is used to seal it.

[0030] The electrolyte pH meter 10 is used to detect the acidity or alkalinity of the reaction solution to be treated or the electrolytic reaction solution. It can be selected to adjust the pH value of the solution participating in the reaction before or during the reaction, so that the pH value of the ammonia nitrogen-containing waste liquid is maintained within the range set by the process throughout the ammonia nitrogen removal process to ensure that no nitrogen trichloride is generated or to reduce chlorine gas evolution by using an alkaline solution for electrolysis.

[0031] The tank 4 is made of an oxidation- and corrosion-resistant material, preferably a polymer resin material. When the working temperature of the electrolytic reaction solution in the set process is greater than 70°C, the tank 4, the pipes through which the high-temperature electrolytic reaction solution flows, and other tanks are preferably made of polytetrafluoroethylene (PTFE). The surface material of the electrolytic anode in contact with the electrolyte is preferably at least one selected from gold, platinum, titanium-based coated insoluble anodes, titanium, and conductive graphite; the surface material of the electrolytic cathode in contact with the electrolyte is preferably at least one selected from gold, platinum, titanium, stainless steel, conductive graphite, and titanium-based coated conductors.

[0032] When the device of this invention is used to treat wastewater containing ammonia nitrogen, it employs breakpoint chlorination and ammonium ion NH4+. + Discharge methods are used to remove ammonia nitrogen pollutants from waste liquids. The ammonium ion discharge method utilizes the movement of NH4+ in the electrolyte. + The NH4+ ions collide with the anode of the electrolysis electrode, thus undergoing an electrochemical reaction. + Elimination. The main chemical reactions in the electrolytic cell are as follows.

[0033] Electrochemical reaction at the anode of electrolysis: 2Cl - +2e - →Cl2 2NH4 + +6e - →8H + +N2↑ (Ammonium ion discharge method)

[0034] Chemical reactions when the electrolyte in the anode tank is alkaline: Cl2 + 2NaOH → NaClO + NaCl + H2O 2NH3 + 3NaClO → 3NaCl + 3H2O + N2↑ (Breakpoint chlorination method)

[0035] Chemical reactions when the electrolyte in the anode tank is acidic: Cl2 + H2O → HCl + HClO 2NH3 + 3HClO → 3HCl + 3H2O + N2↑

[0036] Electrochemical reaction at the cathode of electrolysis: 2H + +2e - →H2↑

[0037] When this invention's device is used to inactivate microorganisms in water, it combines breakpoint chlorination and electrolysis. During operation, the water being treated includes cooling tower heat exchange circulating water and biochemically treated water, which contains trace amounts of chloride ions and is a weak electrolyte solution. During electrolysis, the anolyte produces trace amounts of chlorine gas and hypochlorite ions, which chemically inactivate the microorganisms in the water. The electrolysis method involves the flowing electrolyte carrying the microorganisms into the electric field established between the anode and cathode, causing an electrolytic current to pass through their bodies, disrupting their normal physiological functions and even causing death. By electro-oxidizing the water, the adhesion between the dead microorganisms after they are electrocuted is much lower than that between living organisms. The electro-oxidation treatment not only solves the problem of rapid reproduction of microorganisms in the treated water, but also reduces the phenomenon of membrane equipment being blocked by active microorganisms. As a result, the membrane micropores can be restored to normal water permeability by rinsing the filter membrane with clean water.

[0038] When the device of the present invention is used to inactivate microorganisms in water, as one of the preferred embodiments of the present invention: the output voltage of the electrolysis power supply adopts a safe voltage range of 0.01 to 36V, so as to adopt a treatment scheme that mainly uses electric shock sterilization and supplements it with chemical oxidation reaction inactivation. Preferably, the electrolysis power supply uses an electrolysis decomposition voltage for electrolysis, which can avoid the violent electrochemical reaction at the electrolysis anode that produces a large amount of oxidant that damages water quality and equipment. At the same time, the electrolysis reaction can generate a current that can kill microorganisms in a short time by electric shock. This preferred scheme is particularly suitable for the sterilization and algae removal treatment of heat exchange circulating water in water spray cooling towers. More preferably, when disinfecting large-flow water bodies, the present invention increases the distance between the positive and negative electrodes in the device to establish a wider electric field space, allowing the large-flow water body being treated to pass through the electric field in a concentrated and prolonged manner. The electrolysis power supply still applies the electrolysis decomposition voltage to perform electrolysis, causing the microorganisms in the large-flow water body being treated to be electrolyzed and killed when passing through the electric field, thereby achieving the purpose of efficiently inactivating microorganisms in the water and implementing environmentally friendly production.

[0039] The electrolytic decomposition voltage value is the critical point at which a trace amount of chlorine or hydrogen gas is electrolyzed from the electrolyte in the designed electrolytic cell when the voltage applied between the anode and cathode by the electrolytic power supply under static conditions. The electrolytic decomposition voltage value of the electrolytic cell is related to various factors such as the chemical properties of the electrolyte, its concentration, viscosity, temperature, the materials of the anode and cathode, the electrode contact area, the area of ​​the electrolyte, and the distance between the anode and cathode. Therefore, electrolytic cells of different sizes and shapes will have different electrolytic decomposition voltage values. Under the premise that the structure of the electrolytic cell and the composition of the electrolyte remain unchanged, the electrolytic decomposition voltage of the device of this invention will be a stable value.

[0040] The present invention can be improved as follows: According to process requirements or relevant regulations, a voltage higher than the decomposition voltage is used to electrolyze the water, so that trace amounts of chlorine gas are generated at the electrolysis anode, ensuring that the residual chlorine content of the treated water meets process or regulatory requirements. For example, tap water products obtained by disinfecting purified water must contain 0.3–0.5 mg / L of residual chlorine according to current domestic regulations.

[0041] The present invention can also be improved as follows: To ensure that water containing fewer ions contains residual chlorine after treatment by the device, two or more anode and / or cathode zones are set up in the separate electrolysis cell 1, and a high-density zone structure with alternating anode and cathode zones is adopted. This utilizes the smaller distance between the electrolysis anode and cathode to more easily electrolyze the water and produce trace amounts of chlorine gas, thereby achieving the process requirement of electrolyzing water with residual chlorine. Even when electrolyzing large flows of water containing fewer ions under safe voltage, the goal of retaining residual chlorine can be achieved. In this improvement, two or more electrolytic anodes are connected in parallel to the positive electrode of the electrolytic power supply and / or two or more electrolytic cathodes are connected in parallel to the negative electrode of the electrolytic power supply to form two or more micro-fields. Alternatively, an independent electrolytic unit with two-electrode micro-fields is formed by one electrolytic power supply, one electrolytic anode, and one electrolytic cathode. Two or more independent electrolytic units are then arranged side by side to form two or more independent electric fields with two-electrode micro-fields. Through structural improvement, the distance between the anode and cathode is shortened, and the electrode density is increased. Water containing fewer ions is electrolyzed, and the electrolysis current can meet the requirement of residual chlorine after treatment.

[0042] The present invention can also be improved in the following way: a branch conductor 67 is added to the electrolytic anode 2 to intercept the electrolyte fluid. The branch conductor 67 is made of the same material as the electrolytic anode or other insoluble anode materials. By improving the structure of the electrolytic anode, conditions are created to allow NH4 in the electrolyte to... + Alternatively, microorganisms may have more opportunities to collide with the electrolytic anode and generate discharge, thereby improving processing efficiency and meeting the process requirements of the device of this invention.

[0043] The present invention can also be improved in the following ways: A titanium metal assembly 64 is added to expand the specific surface area of ​​the electrolytic anode 2, increasing the chance of intercepting and colliding with the electrolyte fluid and reducing the manufacturing cost of the precious metal-containing electrolytic anode. The titanium metal assembly 64 is made of sheet-like and / or granular and / or coiled titanium metal. The titanium metal assembly 64 is connected to the electrolytic anode 2, or simultaneously connected to the positive electrode of both the electrolytic anode 2 and the electrolytic power supply 44. Preferably, in industrial electrode catalysis processes, non-precious metals are preferred to control costs. The titanium metal assembly 64 is used to expand the electrolytic anode 2 for the inactivation treatment of microorganisms in water. Although titanium has an extremely low passivation potential and few active sites on its surface, in low-current-density applications involving electrolysis of microorganisms in water, the intensity of its micro-electrolysis current can meet the requirements of the electrolysis process, saving the cost of expensive anode coatings in production. More preferably, a composite electrode is formed by simultaneously adding a titanium metal assembly 64 and a branch conductor 67. The titanium metal assembly 64 and the branch conductor 67 are mixed and hybridized to optimize the structure and expand the specific surface area of ​​the electrolytic anode, which can improve the electrical efficiency.

[0044] The present invention can also be improved in the following ways: a tank cover sealing plate 17 is added to the top of the cathode tank area to seal the tank top, or tank cover sealing plates 17 are respectively installed at the top of the anode tank area and the top of the cathode tank area to seal the tank top. By adding tank cover sealing plates 17 to the electrolytic cell body, the gases emitted from the electrolyte reaction in each tank area can be collected and discharged in a centralized manner. Among them, the tank cover sealing plate 17 of the cathode tank area is provided with at least one hydrogen gas outlet 18, or is provided with at least one hydrogen gas outlet 18 and at least one feed port and / or discharge port.

[0045] The present invention can also be improved in the following ways: the pump in the pump tube liquid flow circulator 11 is a metering pump, which can better return part of the cathode electrolyte to the anode tank area according to the process requirements.

[0046] The present invention can also be improved in the following way: A self-circulating electrolyte flow system is added to the anode tank area, allowing ammonium ions (NH4+) in the anode electrolyte to circulate continuously or intermittently. + In the circulating flow within the anode tank, there is a greater chance of the electrolyte returning to its original position and colliding with the electrolytic anode, thus eliminating the discharge reaction. Alternatively, it may increase the chance of microorganisms in the water entering the electric field and being electrocuted. The self-circulating electrolyte system in the anode tank consists of a liquid flow pump, agitator 47, and its connecting pipes. One end of the pump is connected to the outlet pipe of the anode tank, and the other end is connected to the return pipe 6 of the anode tank and / or the bottom spray pipe 54 located in the anode tank.

[0047] The present invention can also be improved in the following way: a hydrogen-driving spray pipe 13 is installed in the middle or lower part of the cathode tank area, with its nozzle facing upward or obliquely upward, so that the hydrogen gas electrolyzed by the cathode moves upward with the liquid flow sprayed out by the hydrogen-driving spray pipe 13 and is led out of the electrolytic cell from the discharge port or hydrogen outlet 18 of the cathode tank area.

[0048] The present invention can also be improved in the following way: A self-circulating electrolyte system is added to the cathode tank area, which is used to draw the cathode electrolyte after the hydrogen gas has escaped from the bottom of the cathode tank area and spray it onto the electrolytic cathode through the hydrogen-driving spray pipe 13. This improvement utilizes the upward flow of the cathode electrolyte to push the hydrogen bubbles electrolyzed by the cathode upward and out of the liquid surface, so that the hydrogen gas is quickly collected and discharged from the tank. The self-circulating electrolyte system in the cathode tank area consists of a liquid flow pump pipe agitator 47 and its connecting pipes. One end of the agitator is connected to the discharge port of the cathode tank area or the liquid outlet of the gas-liquid separator, and the other end is connected to the hydrogen-driving spray pipe 13 located in the cathode tank area.

[0049] The present invention can also be improved in the following way: a nozzle is installed and connected to the liquid flow hole 14 of the spacer plate, and the outlet of the nozzle faces the electrolytic cathode 3 so that the liquid sprayed during operation helps to guide the electrolytic hydrogen gas to rise and escape more quickly and be collected in a concentrated manner.

[0050] The present invention can also be improved in the following ways: a filter cloth is used to seal the liquid flow hole 14 of the spacer plate, so as to make full use of the water permeability of the filter cloth to allow the anolyte to enter the cathode tank area in a large flow through the large-diameter liquid flow hole 14, while effectively preventing hydrogen bubbles from passing through the liquid flow hole 14 of the spacer plate to the anode tank area.

[0051] The present invention can also be improved in the following ways: the electrolytic cathode 3 is provided with a needle-shaped structure facing the electrolytic anode. By utilizing the needle tip discharge principle of its electrode, hydrogen gas is concentratedly electro-electrolyzed on the cathode needle tip during the reaction, which is convenient for collection. At the same time, the needle-shaped structure on the electrolytic cathode 3 can be closer to the electrolytic anode, making the electrolysis reaction more energy-efficient, thus improving both safety and energy efficiency.

[0052] The present invention can also be improved as follows: a hydrogen bubble collector 66 is added above the electrolytic cathode 3, which includes a solution bubble guide hood, a pipe connected to the solution bubble guide hood, and at least one side solution drain port provided in the pipe, so that the bubble liquid above the electrolytic cathode is guided into the hydrogen bubble collector and can be smoothly separated into gas and liquid; the bubbles escape from the liquid surface in the pipe of the hydrogen bubble collector 66, while the solution flows out and disperses from the side solution drain port of the pipe.

[0053] The present invention can also be improved as follows: a blower 45 and a high-altitude safety emission pipe 46 are added as hydrogen emission devices. The air inlet of the high-altitude safety emission pipe 46 is connected to at least one gas outlet in the device of the present invention where hydrogen escapes, and a branch pipe is provided to connect to the air outlet of the blower 45. The blower 45 is used to pressurize air and inject it into the high-altitude safety emission pipe 46 to dilute the hydrogen drawn into the pipe, so that its concentration is below the hydrogen explosion limit, and to help push the hydrogen to the high altitude for emission.

[0054] The present invention can also be improved in the following ways: a gas-liquid separator 51 is added, the inlet of which is connected to the outlet of the cathode cell, so that the hydrogen-containing overflow liquid from the cathode cell passes through the gas-liquid separator to achieve more thorough separation of hydrogen. When a self-circulating electrolyte system for the cathode cell is provided, the gas-liquid separator 51 is located outside or inside the system.

[0055] The present invention can also be improved as follows: an alkaline pH adjuster feeder 22 is added, which consists of a temporary storage tank, a pump, a switching regulating valve, and a feeding pipe. The outlet of the feeding pipe is connected to the anode tank area of ​​the separate electrolytic cell 1, and / or connected to a pipe and / or container communicating with the anode tank area. The function of the alkaline pH adjuster feeder 22 is to add alkaline pH adjuster to the electrolytic reaction solution during electrolysis, so that the pH value of the anode electrolyte is maintained at no less than pH 5.5. In particular, it is necessary to avoid the production of a large amount of chlorine gas during the electrolysis of the anode electrolyte in the ammonia nitrogen removal reaction, as well as the reaction with acidic ammonium salt solution to generate nitrogen trichloride, an explosive substance. Preferably, the pH value of the anode electrolyte is > pH 7 during the ammonia nitrogen removal electrolysis process. To save raw materials for the production of alkaline pH adjuster, more preferably, the pH value of the anode electrolyte is pH 8.5 to pH 12 during the ammonia nitrogen removal electrolysis process. The alkaline pH adjuster contains at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, alkaline cathode electrolyte, and alkaline ammonia-nitrogen-containing waste liquid.

[0056] The present invention can also be improved as follows: a temperature control system is added at least one of the anode tank area, the pipe connected to the anode tank area, and the container connected to the anode tank area. This system consists of a heat exchanger and a thermometer, enabling the device of the present invention to operate under safe conditions. During electrolysis, both the work done by the current and the decomposition of the oxidant are exothermic reactions, which cause the temperature of the anode electrolyte to rise. The temperature control system ensures that the temperature of the anode electrolyte remains within the process-set temperature range for safe and efficient chemical reactions, reducing errors in instrument readings caused by sensor temperature drift.

[0057] The present invention can also be improved as follows: At least one cathode box 59, which integrates the tank area separator and the tank cover plate, is provided within the tank body 4 to separate the anode tank area and the cathode tank area. The area inside the cathode box 59 is the cathode tank area, and the space inside the tank body 4 and outside the cathode box 59 is the anode tank area. At least one side of the cathode box 59 is equipped with the electrolytic cell separator 5. The cathode box 59 is provided with at least one hydrogen outlet 18 and / or discharge port, and at least one inlet port. When the anode tank area and the cathode tank area are separated by a watertight electrolytic cell separator 5, the cathode box 59 needs to be provided with at least one spacer liquid flow hole 14. The electrolytic cathode 3 is installed inside the cathode box 59. The reactants in the cathode tank area can exchange liquid or gas flow and temperature with the outside environment through at least one of the cathode box 59's discharge port, inlet port, and spacer liquid flow hole 14. Preferably, the electrolytic anode 2 is installed in close contact with the outer side of the spacer surface in the cathode box 59, that is, the electrolytic anode 2 is installed on the outside of the cathode box 59, and the electrolytic cathode 3 is installed inside the cathode box 59. Each is connected to the positive and negative terminals of the electrolytic power supply 44 to form an independent electrolytic cell unit. More preferably, at least one spacer liquid flow hole 14 is added to the bottom of the cathode box 59, so that the anolyte enters the cathode cell area, drives the electrolyzed hydrogen gas to float upward and overflow with the liquid flow.

[0058] The present invention can also be improved in the following way: the discharge port and / or hydrogen escaping port 18 of the cathode box 59 are provided at the top of the cathode box 59 so that the hydrogen gas electrolyzed in the cathode box 59 can be smoothly discharged out of the box.

[0059] The present invention can also be improved as follows: An automatic detection and feeding controller and at least one sensor other than the electrolyte pH meter 10 are added. The automatic detection and feeding controller is used for data processing of the sensor and to achieve partial or fully automatic program control during production. The sensor is selected from at least one of the following: level gauge, barometer, hydrometer, pH meter, photoelectric colorimeter, oxidation-reduction potentiometer (ORP meter), liquid flow sensor, hydrogen concentration detector, chlorine concentration detector, thermometer, ammonia concentration detector, and motor current sensor. The sensor is installed in the pipelines and / or containers of the device of the present invention or in its workshop space, according to process requirements.

[0060] The present invention can also be improved in the following way: an anode tank spray pipe 53 is set in the anode tank area, with its nozzle close to and / or facing the electrolytic anode, so as to spray part or all of the circulating electrolyte that needs to be returned to the anode tank area toward the electrolytic anode and participate in the reaction to improve production efficiency.

[0061] The present invention can also be improved in the following ways: the bottom of the anode and cathode tank is designed as a funnel and is provided with a tank bottom spray pipe 54 for spraying electrolyte to the bottom of the tank, thereby reducing the accumulation of insoluble solid impurities in the electrolyte by spraying and stirring.

[0062] The present invention can also be improved in the following ways: Within the partitioned electrolytic cell 1, two or more electrolytic anodes and / or two or more electrolytic cathodes are arranged in the flow direction of the water being treated. Electrodes of the same type are connected in parallel and then connected to the positive and negative terminals of an electrolytic power source to establish multiple associated electric fields. Alternatively, one electrolytic power source can be combined with one electrolytic anode and one electrolytic cathode to form an independent electrolytic unit, thereby establishing two or more independent electrolytic units along the path of water flow to form two or more independent electric field spatial regions. Through these two improvements in the structure of increasing the electric field spatial region along the fluid flow direction, the water being treated has sufficient time to flow through the electric field of the electrolytic cell, allowing the NH4+ in it to... + There is a greater chance of reacting with oxidants to produce nitrogen gas, or the microorganisms in the water have enough time to be electrocuted in the electric field.

[0063] The present invention can also be improved in the following ways: In the separate electrolysis cell 1, two or more electric fields are installed at a position perpendicular to the flow direction of the water being treated. That is to say, the electric field is established by increasing the electrode density in the structure of alternating positive and negative electrodes on a certain liquid flow pipe diameter. Since shortening the distance between the positive and negative electrodes can reduce the voltage between the positive and negative electrodes under a certain working electrolysis current, the purpose of safe electricity use in production can be achieved.

[0064] This invention can also be improved in the following ways: When using two or more separate electrolytic cells 1 connected together to treat water, there are two connection structure methods. The first method is to connect two or more separate electrolytic cells through pipes; the second method is to separate the separate electrolytic cells with electrolytic cell separators and then directly share the tank body. The direct sharing of the tank body can be achieved by combining yin-yang tank areas or combining similar tank areas. This improvement can enhance the speed and efficiency of treating the substances being processed.

[0065] The present invention can also be improved by adding a temporary storage tank for temporarily storing materials and for use in chemical reactions. The temporary storage tank is connected by a pipe to at least one container and / or device in the apparatus of the present invention.

[0066] The present invention can also be improved in the following ways: an electrolyte discharge pipe with a valve is added at the bottom or near the bottom of the tank 4 to discharge the electrolyte after the electrolytic oxidation operation is completed, or to discharge the electrolyte in the tank according to the process requirements before shutdown to reduce its corrosion of the electrolytic cathode.

[0067] The present invention can also be improved in the following ways: an overflow buffer tank 38 is added, which is connected by a pipe to at least one container or device in the device of the present invention, or is provided on at least one connecting pipe in the device of the present invention, so that the fluid between the containers or devices can be overcome by the fluid potential energy through the delivery of the power pump and flow smoothly into the target device. When the anode tank area and / or the cathode tank area are provided with an electrolyte self-circulation flow system, the overflow buffer tank 38 is provided outside the system or in the system.

[0068] The present invention can also be improved in the following ways: An exhaust gas treatment tank is added, which is connected to the exhaust gas outlet of at least one container and / or device in the device of the present invention via a pipeline, so that the escaping exhaust gas is diverted to the exhaust gas treatment tank for environmental treatment. The exhaust gas treatment tank is a vacuum jet type gas-liquid mixing reaction tank and / or a spray tower type gas-liquid mixing reaction tank. When two or more exhaust gas treatment tanks are set, they are connected by pipelines in series and / or parallel for exhaust gas treatment.

[0069] The present invention can also be improved in the following ways: a chemical reaction tank is added for solution preparation, or for further mixing and reacting the anolyte and / or catholyte treated by the separate electrolytic cell with hypochlorite. The purpose of this improvement is to treat residual trace amounts of ammonia nitrogen impurities or bacterial cells / insects in the electrolyte, and to improve the utilization rate of the separate electrolytic cell by reserving equipment for treating the next batch of treated solution through process scheduling. The chemical reaction tank is piped to at least one container or device in the apparatus of the present invention. Preferably, an ORP meter is installed in the chemical reaction tank, so that the mixture in the chemical reaction tank reacts under the control of the ORP meter, or the ORP meter controls the introduction of external hypochlorite into the chemical reaction tank to participate in the reaction, so that the reaction solution meets the processing standard requirements set by the process.

[0070] The present invention can also be improved as follows: A water-oil separator 29 is added to separate organic impurities (oils) that can form stratified layers or insoluble solid impurities concentrated in a certain part of the waste liquid due to differences in specific gravity from the ammonia-nitrogen-containing waste liquid. Only after separation can the resulting treatment reaction liquid enter the separate electrolytic cell for further processing. The water-oil separator is connected by a pipeline to at least one container or device in the apparatus of the present invention.

[0071] The present invention can also be improved by adding an inclined tube and / or inclined plate sedimentation tank 73 for solid-liquid separation of the solution to be treated before or after electro-oxidation treatment, thereby reducing insoluble solid impurities in the treated water. This sedimentation tank can be connected by pipelines to a separate electrolytic cell and / or membrane treatment equipment and / or other tanks and / or other solid-liquid separators.

[0072] The present invention can also be improved by adding a solid-liquid separator 36 for solid-liquid separation of the solid-liquid mixture. The solid-liquid separator structurally comprises a filter press, a filter, an inclined plate filter, and a centrifuge, which are connected by pipes to the electrolytic cell and / or to at least one container or device in the apparatus of the present invention. The inclined plate filter, in particular, is a device that efficiently achieves solid-liquid separation by utilizing the design of an inclined plate and the theory of gravity settling and shallow pools.

[0073] The device of this invention is safe and simple to operate, has low maintenance and operating costs, and high processing efficiency, meeting market economic applicability requirements. It also improves the efficiency of treating ammonia nitrogen waste liquid or inactivating microorganisms in water. During operation, it can smoothly remove air bubbles from the electrolytic cell, reducing the internal resistance of the electrolyte caused by hydrogen bubbles and quickly eliminating the safety hazard of hydrogen, thus meeting the requirements of safe production and energy-saving and environmentally friendly processes.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] 1. The device of the present invention uses a separate electrolytic cell 1 to effectively avoid the formation of an explosive mixture of hydrogen gas from cathode electrolysis and chlorine gas produced by electrochemical reaction and other possible oxidizing gases, thus avoiding the first dangerous side reaction in the treatment of ammonia nitrogen waste liquid in the prior art.

[0076] 2. The device of the present invention, through a liquid flow circulation electrolysis system, can maintain the pH value of the water within the range set by the process throughout the ammonia nitrogen removal process to ensure that nitrogen trichloride is not generated, thus avoiding the second dangerous side reaction in the existing ammonia nitrogen waste liquid treatment technology.

[0077] 3. The device of the present invention is used to inactivate microorganisms in the circulating water of a cooling tower without the need for external oxidant, thus saving the cost of external oxidant, ensuring the production efficiency of the cooling tower and reducing the maintenance cost of the equipment.

[0078] 4. The device of the present invention is used in membrane treatment processes. Using this device for pretreatment to inactivate microorganisms in water can reduce the number of times membrane equipment needs to be cleaned and extend its service life. Attached Figure Description

[0079] Figure 1 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 1 of the present invention.

[0080] Figure 2 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 2 of the present invention.

[0081] Figure 3 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 3 of the present invention.

[0082] Figure 4 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 4 of the present invention.

[0083] Figure 5 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 5 of the present invention.

[0084] Figure 6 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 6 of the present invention.

[0085] Figure 7 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 7 of the present invention.

[0086] Figure 8 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 8 of the present invention. a is a front view of the device, and b is a right-side cross-section at point AA in a.

[0087] Figure 9 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 9 of the present invention.

[0088] Figure 10 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 10 of the present invention.

[0089] Figure 11 is a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 11 of the present invention.

[0090] Figure labels: 1-Separated electrolytic cell, 2-Electrolytic anode, 3-Electrolytic cathode, 4-Tank body, 5-Electrolytic cell separator, 6-Anode tank area return pipe, 7-Valve, 8-Pump, 9-Electrolyte field line through-hole, 10-Electrolyte pH meter, 11-Pump pipe liquid flow circulator, 12-Electrolyte flow direction guide line, 13-Hydrogen-driving spray pipe, 14-Separator plate liquid flow hole, 15-Anode electrolyte, 16-Cathode electrolyte, 17-Tank cover sealing plate, 18-Hydrogen vent outlet, 19-Tank vent, 20-Acidic 21-Ferrous sulfate solution, 22-Sodium chloride, 23-Alkaline pH adjuster feeder, 24-Alkaline etching and cleaning waste liquid for circuit boards, 25-Hydrochloric acid, 26-Sulfuric acid, 27-Hypochlorite solution, 28-Ammonia-nitrogen-containing waste liquid, 29-Electrolyte mixing tank, 30-Organic oil in waste liquid, 31-Reaction liquid to be treated, 32-Copper oxide powder, 33-Metallic copper powder, 34-Vacuum jet gas-liquid mixer, 35-Bubble-type gas-liquid mixer, 36-Solid-liquid separator, 37-Temporary storage tank, 38-Overflow 39-Buffer tank, 40-Sensor, 41-Automatic detection and feeding controller, 42-Hydrogen, 43-Tap water, 44-Connecting pipe, 45-Electrolysis power supply, 46-Blower, 47-Hydrogen high-altitude discharge pipe, 48-Liquid flow pump pipe and agitator, 49-Waste liquid / filtrate after treatment, 50-Heat and cold exchanger, 51-Impeller agitator, 52-Gas-liquid separator, 53-Insoluble solid impurities, 54-Anode tank area spray pipe, 55-Tank bottom spray pipe, 56-Spray tower, 57-Outer insulation of conductive wire 57-Tail gas treatment tank, 58-Chemical reaction tank, 59-Cathode box, 60-Screw and nut fastener, 61-Anode electrolyte feeder, 62-Inlet pipe, 63-Outlet pipe (or overflow port), 64-Titanium metal assembly, 65-Electrolytic cell partition plate, 66-Hydrogen bubble collector, 67-Branch conductor, 68-Cooling tower, 69-Filtration membrane equipment, 70-Alkaline pH adjuster, 71-Biochemical anaerobic reaction tank, 72-Water-cooled air conditioner, 73-Inclined tube and / or inclined plate sedimentation tank.

[0091] In the accompanying drawings and the following embodiments, the use of reference numerals indicates the use of the same type of material or the same type of component in multiple locations within the apparatus. For example, electrolytic cell separator 5-1 refers to one type of electrolytic cell separator, and electrolytic cell separator 5-2 refers to another type of electrolytic cell separator. Detailed Implementation

[0092] The present invention will be further illustrated by specific embodiments below.

[0093] In the embodiments, the separated electrolytic cell and its electrodes, hydrogen high-altitude emission pipe, liquid flow pump pipe agitator, water-oil separator, gas-liquid separator, temporary storage tank, overflow buffer tank, tail gas treatment tank, vacuum jet, and spray tower used are all products manufactured by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd., Guangdong Province, China. The blower, filter cloth, solid-liquid separator, heat exchanger, electrolysis power supply, various sensors, automatic detection and feeding controller, chemical raw materials, valves, and pumps are all commercially available products. Besides those listed above, those skilled in the art can also choose other products with similar performance to those listed above, based on conventional selection, to achieve the objectives of this invention.

[0094] Example 1

[0095] Figure 1 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 1 of the present invention. It includes a 100-liter partitioned electrolytic cell 1, an anode cell return pipe 6, a pump tube liquid flow circulator 11, an electrolytic power supply 44, a screw and nut fastener 60, an anode electrolyte adder 61, and an electrolytic cell partition plate 65.

[0096] The partitioned electrolytic cell 1 includes a cell body 4; an electrolytic cell partition plate 65 with through holes 9 for electric field lines is welded inside the cell body 4. The partition plate 65 is fixed to the perimeter of the through holes 9 using screws, nuts, and fasteners 60, thus sealing them off. The cell body 4 is divided into a 50-liter anode cell area and a 50-liter closed cathode cell area using the partition plate 65 and the anion exchange membrane 5. The cell body 4 also includes an electrolytic anode 2, an electrolytic cathode 3, and an electrolyte pH meter 10, with the electrolyte pH meter 10 located in the anode cell area.

[0097] Both the electrolytic anode and the electrolytic cathode are graphite electrodes, which are connected to the positive and negative terminals of the electrolytic power supply 44, respectively.

[0098] The pump tube liquid flow circulator 11 includes a pump, pipes and valves. Its inlet is connected to the cathode tank area, and its outlet is connected to the anode tank area return pipe 6 and leads to the anode tank area.

[0099] The anode electrolyte feeder 61 consists of a pump, valves and pipes. Its inlet is connected to the anode tank area and its outlet is connected to the cathode tank area.

[0100] The device used in this embodiment is a basic device structure that uses a waterproof electrolytic cell separator 5 and an anode electrolyte feeder 61 to feed the anode electrolyte into the cathode cell area.

[0101] The device of this embodiment is used to treat ammonia nitrogen-containing waste liquid. Specifically, the ammonia nitrogen-containing waste liquid being treated is a mixed waste liquid 27 containing ammonia water and ammonium chloride, totaling 100 liters, with an ammonia nitrogen (NH3) impurity content of 2700 mg / L.

[0102] 3 kg of sodium chloride and 9 kg of sodium hydroxide were added to 100 liters of ammonia nitrogen-containing waste liquid for mixing and dissolution, resulting in a reaction solution 31 with a pH value greater than pH14.

[0103] The steps for treating ammonia-nitrogen-containing wastewater using the apparatus shown in Figure 1 in this embodiment 1 are as follows:

[0104] 1. Add the reaction solution 31 to be treated to the anode and cathode areas respectively until it is soaked through the electrodes and the electrolyte pH meter 10, as the starting electrolyte.

[0105] 2. Start the pump pipe liquid circulation device 11 and the anode electrolyte adder 61, and turn on the electrolysis power supply 44 to start the electrolysis operation. Set the electrolysis current to 12A and the average cell voltage to 3.4V. During the reaction, hydrogen gas is released from the cathode cell area. The electrolyte pH meter 10 is still greater than pH 14. The following chemical reaction occurs in the anode electrolyte: 2NH4OH+3NaClO→3NaCl+5H2O+N2↑

[0106] 3. After 96 hours of electro-oxidation treatment, the alkalinity of the anolyte decreased. The anolyte was manually sampled for testing, and the results showed that the ammonia nitrogen impurity in the solution was 25 mg / L, which met the process treatment standard requirement of ≥30 mg / L. The unit was then shut down to complete the ammonia nitrogen removal treatment.

[0107] Example 2

[0108] Figure 2 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 2 of the present invention. It includes a 100-liter partitioned electrolytic cell 1, an anode cell return pipe 6, a pump tube liquid flow circulator 11, a cell cover sealing plate 17, a hydrogen outlet 18, an electrolysis power supply 44, a screw and nut fastener 60, and an electrolytic cell partition plate 65.

[0109] The partitioned electrolytic cell 1 includes a cell body 4; an electrolytic cell partition plate 65 with through-holes 9 for electric field lines is welded inside the cell body 4. The partition plate 5 is fixed to the perimeter of the through-holes 9 using screws and nuts 60, thus sealing them off. A cation exchange membrane 5 divides the cell body 4 into a 50-liter anode cell area and a 50-liter closed cathode cell area. Liquid flow holes 14 are provided below the through-holes 9 of the partition plate 65, forming a U-shaped tube structure between the anode and cathode cell areas. The cell body 4 also includes an electrolytic anode 2, an electrolytic cathode 3, and an electrolyte pH meter 10, with the electrolyte pH meter 10 located in the anode cell area.

[0110] The electrolytic anode is a titanium-based coated insoluble anode, and the electrolytic cathode is stainless steel, which are respectively connected to the positive and negative terminals of the electrolytic power supply 44.

[0111] The pump-pipe liquid circulation device 11 includes a pump, pipes, and valves. Its inlet is connected to the cathode tank area, and its outlet is connected to the anode tank area return pipe 6. The outlet of the anode tank area return pipe 6 is located below the liquid surface in the anode tank area and faces the electrolytic anode. The tank cover plate 17 is located at the top of the cathode tank area of ​​the tank body 4, and it has a hydrogen escape outlet 18. The electrolyzed hydrogen is discharged from the hydrogen escape outlet 18.

[0112] The electro-oxidation device used in this embodiment is a basic device structure based on the use of a water-impermeable electrolytic cell separator 5 and a liquid flow hole 14 in the partition plate to allow the anolyte to seep into the cathode cell area.

[0113] The device of this embodiment is used to treat ammonia nitrogen-containing waste liquid. Specifically, the ammonia nitrogen-containing waste liquid being treated is the alkaline etching and cleaning waste liquid of circuit boards. Its components are copper ammonia complex, ammonium chloride, ammonium carbonate, ammonium formate, and ammonia water, totaling 100 liters. Its ammonia nitrogen (NH3) impurity content is 3300 mg / L.

[0114] 3 kg of sodium chloride and 10 kg of sodium hydroxide were added to 100 liters of ammonia nitrogen-containing waste liquid for mixing and dissolution, resulting in a reaction solution 31 with a pH value greater than pH14.

[0115] The steps for treating ammonia-nitrogen-containing wastewater using the apparatus shown in Figure 2 in this embodiment 2 are as follows:

[0116] 1. The electrolyte pH meter 10, which has been immersed in the electrolytic anode 2, is introduced into the anode tank area. The reaction solution 31 to be treated seeps into the cathode tank area through the liquid flow hole 14 of the partition plate and immerses the electrolytic cathode 3.

[0117] 2. Start the pump tube liquid circulation device 11 and turn on the electrolysis power supply 44 to carry out electrolysis. Set the electrolysis current to 50A and the average cell voltage to 3.2V. During the reaction, the hydrogen gas generated by cathode electrolysis is discharged through hydrogen gas outlet 18, and the following chemical reaction occurs in the anolyte: 2NH4OH+3NaClO→3NaCl+5H2O+N2↑ (NH4)2CO3+3NaClO→3NaCl+H2CO3+3H2O+N2↑ 2NH4HCO2+5NaClO→5NaCl+5H2O+2CO2↑+N2↑ 2NH4Cl+3NaClO→3NaCl+2HCl+3H2O+N2↑ 2Cu(NH3)4Cl2+4NaClO→4NaCl+4HCl+10H2O+2CuO↓+N2↑ HCl+NaOH→NaCl+H2O

[0118] 3. After 32 hours of electro-oxidation treatment with flowing electrolyte, the alkalinity of the anolyte decreased. The anolyte was manually sampled for testing, and the results showed that the ammonia nitrogen impurity in the solution was 16 mg / L, which meets the process treatment standard requirement of below 30 mg / L. The unit was then shut down to complete the ammonia nitrogen removal treatment.

[0119] Example 3

[0120] Figure 3 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 3 of the present invention. It includes a 200-liter partitioned electrolytic cell 1, an anode cell return pipe 6, a cell cover sealing plate 17, a hydrogen outlet 18, a pump tube liquid flow circulator 11, an electrolytic power supply 44, a liquid flow pump tube stirrer 47, a branch conductor 67, and a filter membrane device 69.

[0121] The partitioned electrolytic cell 1 includes a cell body 4; within the cell body 4, a polymer resin perforated plate 5 is directly welded to the cell body 4 as a partition, dividing it into a 100-liter anode cell area and a 100-liter closed cathode cell area. The cell body 4 also includes an electrolytic anode 2 with branched conductors 67, an electrolytic cathode 3, and an electrolyte pH meter 10, wherein the electrolyte pH meter 10 is located in the anode cell area.

[0122] Both the electrolytic anode and the electrolytic cathode are platinum metal electrodes, connected to the positive and negative terminals of the electrolytic power supply 44, respectively. The branch conductor 67 is made of the same material as the electrolytic anode. The closest distance between the electrolytic anode 2 and the electrolytic cathode 3 is 250 mm, meaning the closest spatial distance for establishing the electric field between the two electrodes is 250 mm. The electrolytic anode 2 is welded with a homogeneous branch conductor 67.

[0123] The pump pipe liquid flow circulator 11 includes a pump, pipes and valves. Its inlet and outlet are respectively connected to the outlet 63-1 of the cathode tank area and the return pipe 6 of the anode tank area. The return pipe 6 of the anode tank area leads to the anode tank area.

[0124] The hydrogen outlet 18 is located at the top of the cathode tank area of ​​the tank body 4. It has a hydrogen outlet 18, and a small amount of hydrogen gas is discharged from the hydrogen outlet 18 after electrodeposition.

[0125] The aforementioned filtration membrane device 69 is an ultrafiltration membrane device. Its inlet is connected to the outlet pipe 63-2 at the bottom of the anode tank through a pump, valve, and pipeline, so that the oxidized water is pumped into the ultrafiltration device for filtration.

[0126] The device in this embodiment is a basic device structure that uses a permeable electrolytic cell separator 5 and allows the solution in the anode cell to enter the cathode cell through its permeable holes.

[0127] The device of this embodiment is used to inactivate microorganisms in water. The water sample to be treated in this embodiment is 220 liters of seawater taken from a brackish water area. The total number of colonies is 81 CFU / ml and the number of Escherichia coli colonies is 2710 CFU / 100ml. After coarse filtration, 200 liters of reaction solution 31 to be treated is obtained. Its pH value is 7.9 and its electrolytic decomposition voltage is 1.5V when the distance between the positive and negative electrodes is 250mm.

[0128] The steps for inactivating E. coli in water using the device shown in Figure 3 in this embodiment 3 are as follows:

[0129] 1. Add the reaction solution 31 to be treated as the starting electrolyte to the anode tank area and let it permeate through the electrolytic cell separator 5 into the cathode tank area. Start the pump tube liquid flow circulator 11 and turn on the electrolysis power supply 44 to carry out electrolysis operation with an electrolysis decomposition voltage of 1.5V and an electrolysis current of 95mA.

[0130] 2. During the reaction, only a small amount of electrolytic hydrogen bubbles appear at the electrolysis cathode. When the microorganisms in the treated water enter the electric field in the anodic and anode tanks, they are electrocuted.

[0131] 3. After 30 minutes of circulating electro-oxidation treatment, the water body was shut down. 100ml of anolyte was manually extracted for testing. The results showed that the total bacterial count was 17 CFU / ml and the number of live Escherichia coli was 2 CFU / 100ml.

[0132] 4. After obtaining the test results, open valve 7 and start pump 8 and pump pipe liquid flow circulator 11 to pump the treated solution in the electro-oxidation device to the filter membrane equipment 69 for filtration. The filter residue, mainly biological corpses 52, is retained. The filtrate 48 enters the reverse osmosis membrane equipment to produce pure water in the next process.

[0133] Example 4

[0134] Figure 4 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 4 of the present invention. It includes a 100-liter partitioned electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, an electrolytic cell partition 5, a return pipe for the anode cell area 6, an electrolyte pH meter 10, a pump tube liquid flow circulator 11, a hydrogen-driving spray pipe 13, a tank cover sealing plate 17, a hydrogen escape outlet 18, a temporary storage tank 37, an overflow buffer tank 38, an electrolytic power supply 44, two liquid flow pump tube stirrers 47, a gas-liquid separator 51, a screw and nut fastener 60, a titanium metal assembly 64, an electrolytic cell partition plate 65, a branch conductor 67, valves, and pumps.

[0135] The partitioned electrolytic cell 1 includes a cell body 4, in which an electrolytic cell partition plate 65 is welded. The partition plate 65 has electric field line through-holes 9, and a filter cloth 5 is used as a separator 5 to seal the opening using screws and nuts 60, thus dividing the cell body 4 into an anode cell area and a cathode cell area. An electrolyte pH meter 10 is installed in the anode cell area. This embodiment uses a composite anode structure, with a gold-plated electrolytic anode 2 as the main part. A titanium-based coated branch conductor 67 is welded around the electrolytic anode 2, and a titanium metal assembly 64 is wound around the branch conductor 67. The electrolytic anode 2 is connected to the positive terminal of the electrolytic power supply 44 and placed in the anode cell area. The electrolytic cathode 3, a titanium plate, is connected to the negative terminal of the electrolytic power supply 44 and placed in the cathode cell area. A hydrogen-driving spray pipe 13 is installed at the bottom of the electrolytic cathode, and multiple upward-facing spray nozzles are provided. When the liquid is sprayed out, the hydrogen gas electrolyzed by the electrolytic cathode floats upward with the liquid flow and escapes from the liquid surface.

[0136] The gas-liquid separator 51, the liquid flow pump pipe agitator 47-1, the hydrogen-driving liquid spray pipe 13, and the cathode tank overflow port 63-1 form a cathode tank electrolyte self-circulation flow system, which is used to drive out hydrogen gas; specifically, one end of the pipe equipped with the liquid flow pump pipe agitator 47-1 is connected to the liquid outlet of the gas-liquid separator 51, and the other end is connected to the hydrogen-driving liquid spray pipe 13.

[0137] The overflow buffer tank 38, together with the liquid flow pump tube agitator 47-2, the anode tank area return pipes 6-1 and 6-2, and the anode tank area overflow port 63-2, constitutes a self-circulating electrolyte flow system in the anode tank area. Specifically, one end of the pipe equipped with the liquid flow pump tube agitator 47-2 is connected to the outlet of the overflow buffer tank 38, and the other end is connected to the anode tank area return pipes 6-1 and 6-2. The outlets of the anode tank area return pipes 6-1 and 6-2 are both located below the liquid surface in the anode tank area and face the top and bottom of the electrolytic anode, respectively. In this embodiment, the device increases the NH4+ concentration in the flowing anode electrolyte by arranging the anode tank area return pipes 6-1 and 6-2 above and below the electrolytic anode and by adding branch conductors 67 and titanium metal assemblies 64. + Collision with the electrolytic composite anode may cause NH4 to... + A discharge reaction occurs.

[0138] The inlet of the pump tube liquid circulator 11 is connected to the cathode tank area through the gas-liquid separator 51, while the outlet is connected to the overflow buffer tank 38 and leads to the anode tank area.

[0139] The tank cover plate 17 is located at the top of the cathode tank area of ​​the tank body 4, and it is provided with a hydrogen outlet 18, from which the electrolyzed hydrogen is discharged.

[0140] The temporary storage tank 37 is used to load alkaline pH adjuster 70. It is connected to valve 7 and pump 8 to form an alkaline pH adjuster feeder 22. During operation, the electrolyte pH meter 10 in the overflow buffer tank 38 controls the addition of alkaline pH adjuster 70 so that the pH of the anode reaction solution is not lower than 6.8.

[0141] The apparatus of this embodiment is used to treat ammonia-nitrogen-containing wastewater. Specifically, the ammonia-nitrogen-containing wastewater 27 being treated is landfill leachate with an ammonia nitrogen content of 1700 mg / L, totaling 110 liters, and a pH value of pH 6.7. 8% sodium chloride solid is added to wastewater 27 to obtain the reaction solution 31 to be treated.

[0142] The main components of the alkaline pH adjuster 70 are a mixture of 6% sodium hydroxide, 3% potassium hydroxide, 2% sodium carbonate, 1% potassium carbonate, 1% sodium bicarbonate, and 1% potassium bicarbonate.

[0143] The device used in this embodiment for ammonia nitrogen removal has three characteristics: First, the anolyte and catholyte circulate within their respective tank areas, so that the NH4 in the anolyte is removed through the flow of liquid. + Increased opportunities for collisions with the anode accelerate the ammonia nitrogen removal reaction, while the circulating flow of the cathode electrolyte increases the rate at which electrolytic hydrogen escapes from the liquid surface. Secondly, the electrolytic anode 2 is welded with branched conductors 67 and a titanium metal assembly 64, expanding the specific surface area of ​​the electrolytic anode to promote the release of NH4+. + The discharge reaction. The third point is that the electrolyte pH meter 10 is installed in the overflow buffer tank 38 for easy installation and removal.

[0144] The steps for treating ammonia-nitrogen-containing wastewater using the above-described device in this embodiment are as follows:

[0145] 1. Add 110 liters of the reaction liquid 31 to be treated into the tank 4, the gas-liquid separator 51, and the overflow buffer tank 38. Turn on the pump pipe liquid flow circulator 11 and the two liquid flow pump pipe agitators 47-1 and 47-2 to make the electrolyte circulate between the anode tank area and the cathode tank area and to circulate within their respective tank areas.

[0146] 2. Turn on the electrolysis power supply 44 and adjust the electrolysis current to 100A. The average voltage of the electrolytic cell is 5.1V. Under the control of the electrolyte pH meter 10, add alkaline pH adjuster 70 to maintain the pH of the anolyte at pH 6.8. The anolyte reaction produces chlorine and hypochlorite, which react with ammonia nitrogen impurities to produce nitrogen. The hydrogen gas electrolyzed at the cathode is carried to the liquid surface by the circulating liquid flow and escapes. The hydrogen-containing electrolyte is then guided to the gas-liquid separator 51 for gas-liquid separation. The reaction of the anolyte during the process is as follows: Cl2+H2O→HClO+HCl 2NH4OH+3ClO - →3Cl- +5H₂O + N₂↑ 2NH₄ + -6e - →8H + +N2↑

[0147] 3. After 32 hours of treatment, the reaction solution was manually sampled and inspected. The results showed that the ammonia nitrogen impurity in the solution was 6 mg / L, which meets the process standard requirement of less than 30 mg / L.

[0148] 4. Shut down the electrolysis power supply and all operating pumps to complete the electrolysis operation.

[0149] Example 5

[0150] Figure 5 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 5 of the present invention. It includes a 100-liter partitioned electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, a return pipe 6 for the anode tank area, an electrolyte pH meter 10, a pump pipe liquid flow circulator 11, a hydrogen-driving spray pipe 13, two tank cover sealing plates 17 with vent holes, a hydrogen vent outlet 18, a solid-liquid separator 36, a temporary storage tank 37, five sensors 39, an electrolytic power supply 44, four liquid flow pump pipe agitators 47, an impeller agitator 50, a gas-liquid separator 51, a tank bottom spray pipe 54, a tail gas treatment tank 57, a chemical reaction tank 58, screw and nut fasteners 60, an electrolytic cell partition plate 65, a partition plate liquid flow hole 14, valves, and pumps.

[0151] The described partitioned electrolytic cell 1 includes a cell body 4; the bottom of the cell body 4 is a sloping funnel-shaped structure to prevent the accumulation of insoluble solids 52 in the electrolyte. An electrolytic cell partition plate 65 is welded into the cell body 4. The partition plate 65 has electric field line through-holes 9 and liquid flow holes 14 below it. A reverse osmosis membrane, serving as the electrolytic cell partition 5, is used as a screw and nut fastener 60 to seal the electric field line through-holes 9, thus dividing the cell body 4 into an anode cell area and a cathode cell area. An electrolyte pH meter 10 is installed in the anode cell area.

[0152] This embodiment uses a composite anode structure. The main body of the anode is the electrolytic anode 2, which is an insoluble conductive material with a titanium-based coating. A titanium metal assembly 64 is wound around the anode body. The electrolytic anode 2 is connected to the positive terminal of the electrolytic power supply 44 and placed in the anode tank area. The electrolytic cathode 3 is a titanium mesh, which is installed close to the electrolytic cell partition plate 65 and connected to the negative terminal of the electrolytic power supply 44 and placed in the cathode tank area. A hydrogen-driving liquid spray pipe 13 is installed at the bottom of the electrolytic cathode and has multiple upward spray nozzles. When the liquid is sprayed out, the hydrogen gas electrolyzed by the electrolytic cathode floats upward with the liquid flow and escapes.

[0153] The gas-liquid separator 51 is equipped with a sensor 39-1, specifically a level gauge. The gas-liquid separator 51, along with the liquid flow pump pipe agitator 47-1, the hydrogen-driving spray pipe 13, and the cathode tank overflow port 63-1, forms a self-circulating electrolyte flow system A in the cathode electrolytic cell area. Simultaneously, the gas-liquid separator 51, along with the liquid flow pump pipe agitator 47-2, the hydrogen-driving spray pipe 13, and the cathode tank outlet port 63-2, forms a self-circulating electrolyte flow system B in the cathode tank area to drive away hydrogen gas. The liquid flow pump pipe agitator 47-3, along with the tank bottom spray pipe 54 and the anode tank overflow port 63-3, forms a self-circulating anode electrolyte flow system to increase the chance of collision between the anode electrolyte and the electrolytic anode, thus reducing the NH4+ ionization. + A discharge reaction occurs.

[0154] The top of the anode tank area and the cathode tank area of ​​the tank body 4 are respectively equipped with tank cover plates, and each has an escaping port. The escaping port of the cathode tank area is a hydrogen escaping port 18.

[0155] The pump pipe liquid flow circulator 11 is connected to the outlet pipe 63-2 of the cathode tank area and the return pipe 6 of the anode tank area. The pump is a metering pump, which delivers a portion of the cathode electrolyte into the anode tank area through the return pipe 6 of the anode tank area according to the process time and quantity, so as to realize the circulation of electrolyte between the two tank areas.

[0156] The temporary storage tank 37 is equipped with a sensor 39-2, specifically a level gauge. The temporary storage tank 37 is used to load alkaline pH adjuster 70. It, together with valve 7-3 and pump 8-1, forms an alkaline pH adjuster feeder 22. During operation, under the control of electrolyte pH meter 10, it adds alkaline pH adjuster 70 to the anode tank area to maintain the pH value set by the process.

[0157] The chemical reaction tank 58 is equipped with an impeller agitator and a sensor 39-3, which is an ORP meter. The device controls the addition of an external hypochlorite solution 26 to the chemical reaction tank 58 via the ORP meter to participate in the ammonia nitrogen removal reaction. The inlet of the chemical reaction tank 58 is connected to the outlet 63-2 of the tank body 4 and the bottom spray pipe 54. In addition, its outlet is connected to the inlet of the solid-liquid separator 36 via a pipeline.

[0158] The solid-liquid separator 36 is a filter used to filter copper oxide powder in the solution of the chemical reaction tank 58, and the filtrate 48 after filtration can be discharged.

[0159] The exhaust gas treatment tank 57 is used to treat oxidizing gases escaping from the anode tank area, using a mixture of ferrous sulfate and sulfuric acid as the absorption reaction solution. Sensors 39-4 and 39-5 are installed inside the exhaust gas treatment tank 57, respectively, to control the addition of ferrous sulfate solution 20 and the pH meter to control the addition of sulfuric acid 25. The suction pipe of the exhaust gas treatment tank 57 is connected to the exhaust port of the anode tank area and the exhaust port of the chemical reaction tank 58.

[0160] The apparatus of this embodiment is used to treat ammonia-nitrogen-containing wastewater. Specifically, the ammonia-nitrogen-containing wastewater being treated is 110 liters of alkaline etching and cleaning wastewater 23 from circuit boards, wherein the ammonia nitrogen content is 8900 mg / L and the copper ion concentration is 0.4 g / L. 10% sodium chloride solid is added to the wastewater 23 to obtain the reaction solution 31 to be treated.

[0161] The main component of the alkaline pH adjuster 70 is a 30% sodium hydroxide solution.

[0162] The process characteristics of using the device in this embodiment for ammonia nitrogen removal are:

[0163] 1. The electrolyte contains soluble copper salts. During the reaction, some of the copper is electrolyzed at the cathode to form sponge copper, which flows with the reaction solution to the anode tank and is oxidized to copper oxide. The other part of the soluble copper salts reacts with the oxidant sodium hypochlorite in the anode tank to form copper oxide.

[0164] 2. The device uses a reverse osmosis membrane as the separator between the positive and negative cells in the electrolytic cell and has a liquid flow hole 14 drilled at the bottom of the separator plate 65.

[0165] The steps for treating ammonia-nitrogen-containing wastewater using the apparatus shown in Figure 5 in this embodiment are as follows:

[0166] 1. Add 110 liters of the reaction liquid 31 to be treated into the tank 4 and the gas-liquid separator 51. Turn on the pump tube liquid flow circulator 11 and the four liquid flow pump tube agitators 47-1, 47-2 and 47-3 to make the electrolyte circulate between the anode tank area and the cathode tank area and to make self-circulation flow in their respective tank areas. Turn on the liquid flow pump tube agitator 47-4 to make the absorbent liquid in the tail gas treatment tank circulate by vacuum jet.

[0167] 2. Turn on the electrolysis power supply 44 and adjust the electrolysis current to 100A. The average voltage of the electrolytic cell is 5.2V. Use an electrolyte pH meter 10 to control the addition of alkaline pH adjuster 70 to maintain the pH of the reaction solution at 7.7. The anolyte reaction produces sodium hypochlorite, which reacts with ammonia nitrogen impurities and copper salt Cu(NH3)4Cl2 to generate nitrogen gas and copper oxide. The electrolytic cathode mainly electrodeposits hydrogen gas and trace amounts of sponge copper. The anolyte reaction during the process is as follows: 2NH4OH + 3ClO- →3Cl - +5H2O+N2↑ Cu(NH3)4Cl2+6NaClO+2NaOH→8NaCl+CuO+7H2O+2N2↑ 2NH4 + -6e - →8H + +N2↑

[0168] 3. After 26 hours of fluidized electrolyte treatment, the reaction solution was manually sampled and inspected. The results showed that the ammonia nitrogen impurity in the solution was still 56 mg / L, which was below the process treatment standard of 30 mg / L.

[0169] 4. Turn off the electrolysis power supply and open valves 7-1 and 7-2. Pump the oxidized solution in tank 4 into chemical reaction tank 58. Turn on the impeller agitator 50 and add external sodium hypochlorite to the tank under the control of the ORP meter in the tank to continue the ammonia nitrogen removal treatment.

[0170] 5. After 10 hours of reaction in the chemical reaction tank 58, the ammonia nitrogen value is sampled and checked. The solution in the chemical reaction tank 58 is extracted and filtered through the solid-liquid separator 36. The filter residue 52 is retained in the filter, and the filtrate meets the standards and is discharged.

[0171] 6. Throughout the reaction process, the tail gas treatment tank 57 extracts and treats the waste gas escaping from the anode tank area and the chemical reaction tank 58.

[0172] 7. After the process is completed, shut down the equipment and collect the copper oxide powder 32 from the solid-liquid separator 36.

[0173] Note: A test result of ND indicates that the pollutant content in the tested object is less than 0.2 mg / L. The following range of values ​​is set as the detection limit of this testing equipment, hence marked as ND.

[0174] Example 6

[0175] Figure 6 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 6 of the present invention. It includes a 4 cubic meter partitioned electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, electrolytic cell partitions 5-1 and 5-2, a return pipe 6 for the anode cell area, an electrolyte pH meter 10, a pump pipe liquid flow circulator 11, a hydrogen-driving spray pipe 13, two tank cover plates 17, a hydrogen escape outlet 18, a temporary storage tank 37, two sensors 39, an electrolytic power supply 44, a blower 45, a hydrogen high-altitude emission pipe 46, two liquid flow pump pipe agitators 47, a gas-liquid separator 51, a titanium metal assembly 64, an electrolytic cell partition plate 65, a cooling tower 68, a water-cooled air conditioner 72, an inclined tube and / or inclined plate sedimentation tank 73, valves, and pumps.

[0176] The partitioned electrolytic cell 1 includes a cell body 4, in which an electrolytic cell partition plate 65 made of polymer resin material is welded. The electrolytic cell partition plate 65 has an electric field line through hole 9 and a large-diameter partition plate liquid flow hole 14 below it. The filter cloths 5-1 and 5-2, which serve as electrolytic cell separators, are used to seal the two through holes with screws and nuts, so that the cell body 4 is divided into an anode cell area and a cathode cell area.

[0177] This embodiment employs a composite anode structure. The main body of the anode is the electrolytic anode 2, which is a titanium mesh with a platinum-plated surface. The electrolytic anode 2 is placed in the tank 4 at the furthest point from the electrolytic cathode 3 to expand the electric field space. A wound titanium wire ball, serving as a titanium metal assembly 64, is placed in front of the electrolytic anode 2 in the electric field space to increase the specific surface area of ​​the electrolytic anode. The titanium wire ball is also positioned along the path of the anode electrolyte flow. The electrolytic anode 2 and the titanium wire ball 64 are connected to the positive terminal of the electrolytic power supply 44. Below the titanium wire ball 64, an anode tank spray pipe 53 and its nozzles are installed, pointing towards the titanium wire ball 64. The electrolytic cathode 3 is a platinum-plated titanium mesh connected to the negative terminal of the electrolytic power supply 44. A hydrogen-driving spray pipe 13 is installed at the bottom of the electrolytic cathode, with multiple upward-facing spray nozzles. When liquid is sprayed out, the hydrogen gas electrolyzed by the electrolytic cathode drifts upward with the liquid flow and escapes. A sensor 39-2, which is a level gauge, is installed in the anode tank area. The top of the anode tank area and the cathode tank area of ​​the tank body 4 are respectively equipped with tank cover plates, and each has an escaping port. The escaping port of the cathode tank area is a hydrogen escaping port 18.

[0178] The gas-liquid separator 51, the liquid flow pump pipe agitator 47-1, the hydrogen-driving spray pipe 13, and the cathode tank overflow port 63-1 are circulated together to form a cathode tank electrolyte self-circulation system to drive out hydrogen gas. The liquid flow pump pipe agitator 47-2, the inclined tube and / or inclined plate sedimentation tank 73, the temporary storage tank 37, the water-cooled air conditioner 72, the cooling tower 68, the anode tank spray pipe 53, and the anode tank overflow port 63-2 are circulated together to form an anode tank electrolyte self-circulation system. Specifically, the heat exchange water from the cooling tower 68 is diverted to the electric field established by the electrolytic cathode and anode electrodes to electrolyze and kill the microorganisms in the water. During operation, the ORP meter (sensor 39-1) installed in the anode tank electrolyte self-circulation system monitors the work done by the electrolysis power supply 44 and controls its on / off state. The level gauge (sensor 39-2) monitors the level of the anode tank and controls the liquid level by conveying the flow rate through the pump pipe liquid flow circulator 11. An electrolyte pH meter 10 is also installed in the system where the electrolyte in the anode tank area is self-circulating to detect the pH value of the on-site reaction of the anode electrolyte. When the pH value is lower than the process set value of pH 5.5, the equipment will alarm and shut down.

[0179] The inlet of the pump pipe liquid circulator 11 is connected to the cathode tank area through the gas-liquid separator 51, and the outlet is connected to the return pipe 6 of the anode tank area and leads to the anode tank area.

[0180] The inclined tube and / or inclined plate sedimentation tank 73 is used to collect microorganisms and their dead bodies in the heat exchange circulating water overflowing from the electrolytic cell after treatment, and to continuously reduce insoluble solid impurities in the heat exchange circulating water through sedimentation separation.

[0181] The hydrogen high-altitude emission pipe 46 is combined with the blower 45 to guide the produced hydrogen to high altitude after dilution. The hydrogen high-altitude emission pipe 46 is connected to the hydrogen escaping outlet 18 in the cathode tank area and the escaping port of the gas-liquid separator 51.

[0182] The aforementioned sensor 39-3 is a space hydrogen concentration detector, used to monitor equipment operation and ensure safe production.

[0183] The device in this embodiment is also equipped with an automatic detection and feeding controller 40, which is used to collect and process data from various sensors and control the device to operate according to a set program.

[0184] The device used in this embodiment processes the heat exchange circulating water of the cooling tower. The raw water is tap water, which contains microorganisms and trace amounts of chloride ions, and its pH value is 7.1.

[0185] The process characteristics of inactivating microorganisms in water using the device in this embodiment are as follows: a water-cooled air conditioner 72, a cooling tower 68, an inclined tube and / or inclined plate sedimentation tank 73, and a temporary storage tank 37 are installed in the circulating liquid flow system of the anolyte. These components sterilize and kill insects in the heat exchange water of the cooling tower and perform solid-liquid separation of insoluble microorganisms. In particular, the use of inclined tubes and / or inclined plate sedimentation tanks for solid-liquid separation of microorganism corpses 52 removes them from the water, reducing the chance of water decay and odor. To improve the sterilization and algae removal effect, the electrolytic anode body 2 is installed far from the electrolytic cathode 3 to expand the electric field space. Titanium wire balls are placed in the electric field space to intercept the anolyte fluid, causing the microorganisms in the water to be electrocuted or killed by collisions with the electrolytic anode or titanium wire balls during the slow flow. The closest distance between the electrolytic anode and the electrolytic cathode is 1 meter, meaning the closest spatial distance between the two electrodes is 1 meter. The measured electrolytic decomposition voltage of the circulating water entering the cooling tower heat exchange system is 11V.

[0186] The steps for sterilizing and removing algae from the heat exchange circulating water of the cooling tower using the device shown in Figure 6 in this embodiment are as follows:

[0187] 1. Turn on the power to activate the automatic detection and feeding controller 40, and process the data sampled by the field sensors.

[0188] 2. The heat exchange circulating water in the cooling tower 68 is added to the anode tank area, inclined tube and / or inclined plate sedimentation tank, temporary storage tank and cooling tower of the tank body 4. The solution in the anode tank area with high liquid level permeates into the cathode tank area through the sealed filter cloth of the liquid flow hole 14 of the partition plate and overflows into the gas-liquid separator 51. The automatic detection feeding controller 40 issues a command to start the pump pipe liquid flow circulator 11 and the two liquid flow pump pipe agitators 47-1 and 47-2 so that the electrolyte circulates between the anode tank area and the cathode tank area through the electrolytic cell separators 5-1 and 5-2 and the electrolyte in each tank area circulates by itself. The blower 45 and the cooling tower water spray motor are turned on.

[0189] 3. Turn on the electrolysis power supply 44 and adjust the voltage of the electrolysis power supply to 22V, which is above the electrolysis decomposition voltage of 11V, to carry out sterilization and algae removal operations. The electrolysis current is 360mA. The electrolyte pH meter 10 in the connecting pipe 43 of the electrolyte self-circulation system in the anode tank area shows pH 6.9, and the ORP meter shows 230mV. The working status of the electrolysis power supply 44 is controlled accordingly. The anode electrolyte reaction produces trace amounts of chlorine gas and hypochlorous acid.

[0190] When the ORP meter reading reaches the process set value of 250mV, the automatic detection and feeding controller 40 automatically adjusts the electrolysis power supply back to an output of 10V and an electrolysis current of 82mA to continue operation. After the reaction liquid has consumed the oxidant, and the ORP value of the reaction liquid is lower than 230mV, the automatic detection and feeding controller 40 issues a command and adjusts the output voltage of the electrolysis power supply upward to 22V for operation. The trace amount of hydrogen gas electrolyzed by the electrolytic cathode is carried to the liquid surface by the circulating liquid flow and escapes, and the hydrogen-containing cathode electrolyte is guided to the gas-liquid separator 51 for further gas-liquid separation. Finally, the hydrogen gas is discharged into the atmosphere through the high-altitude discharge pipe 46 with the assistance of the blower 45. During the process, the anode electrolyte reaction is as follows: 2Cl - -2e→Cl2↑ Cl2+H2O→HCl+HClO

[0191] 4. During operation, the ORP meter (sensor 39-1) controls the electrolysis power supply 44 to output a voltage between 10V and 22V around the electrolysis decomposition voltage of 11V for sterilization and algae removal. The inclined tube and / or inclined plate sedimentation tank play a role in solid-liquid separation of the heat exchange circulating water. The cooling tower has been running outdoors for 30 consecutive days for heat exchange. No large-scale microbial growth has been found in the heat exchange circulating water. Only the evaporation water needs to be added to keep the cooling tower running normally.

[0192] Example 7

[0193] Figure 7 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 7 of the present invention. It includes a 300-liter partitioned electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, an electrolytic cell partition 5, two anode cell return pipes 6, an electrolyte pH meter 10, a pump pipe liquid flow circulator 11, two hydrogen-driving spray pipes 13, two tank cover plates 17, a hydrogen escape outlet 18, a temporary storage tank 37, seven sensors 39, an automatic detection and feeding controller 40, an electrolytic power supply 44, two liquid flow pump pipe stirrers 47, two heat exchangers 49, a gas-liquid separator 51, a tail gas treatment tank 57, an anode electrolyte feeder 61, a titanium metal assembly 64, an electrolytic cell partition plate 65, a hydrogen bubble collector 66, a branch conductor 67, valves, and pumps.

[0194] The described partitioned electrolytic cell 1 includes a cell body 4, in which an electrolytic cell partition plate 65 is welded. The partition plate 65 has an electric field line through-hole 9, and is sealed with an anion exchange membrane (serving as a separator 5) using screws and nuts, thus dividing the cell body 4 into an anode and a cathode region. This embodiment employs a composite electrolytic anode structure. The main body of the anode is the electrolytic anode 2, which is a titanium-based coated sheet. Branch conductors 67 of the same material are welded around the anode 2, and titanium wires (serving as titanium metal assemblies 64) are wound around it. The electrolytic anode 2 is connected to the positive terminal of the electrolytic power supply 44 and placed in the anode region. The electrolytic cathode 3 is an assembly with titanium needle tips welded onto a titanium sheet. It is connected to the negative terminal of the electrolytic power supply 44 and placed in the cathode region near the electric field line through-hole 9 of the electrolytic cell partition plate 65. Sensors 39-3, 39-4, and 39-5, and a hot / cold temperature exchanger 49-2 are installed in the anode tank area. An anode electrolyte feeder 61, connected to the cathode tank area, is also installed in the anode tank area. Two hydrogen-driving spray pipes 13-1 and 13-2 are installed at the bottom of the electrolytic cathode 3. Hydrogen-driving spray pipe 13-1 is connected to a liquid flow pump and agitator 47-1, while hydrogen-driving spray pipe 13-2 is connected to the anode electrolyte feeder 61. When the liquid is sprayed out, the hydrogen gas electrolyzed by the electrolytic cathode drifts upward with the liquid flow and is guided to the hydrogen bubble collector 66 above the electrolytic cathode for gas release and solution diffusion.

[0195] The gas-liquid separator 51 is equipped with a thermometer (sensor 39-2), a pH meter (sensor 39-3), and a hot and cold temperature exchanger 49-1, enabling the gas-liquid separator 51 to have pH value detection and temperature control functions.

[0196] The gas-liquid separator 51 is connected in a loop with the liquid flow pump pipe agitator 47-1, hydrogen driving liquid spray pipe 13-1, and cathode tank overflow port 63-1 to form a cathode tank electrolyte self-circulation flow system to drive out hydrogen gas.

[0197] The pump pipe liquid flow circulator 11 is connected in a loop with two return pipes 6 flowing into the anode tank area, the discharge port 63-2, the anode electrolyte adder 61, the solid-liquid separator 36, the hydrogen-driving spray pipe 13-2, and the gas-liquid separator 51 to form an electrolyte self-circulation flow system for the anode and cathode tank areas, so that the electrolyte in the anode and cathode tank areas can be exchanged.

[0198] The liquid flow pump tube agitator 47-2 is connected in a loop with two anode tank return pipes 6-1 and 6-2 and the anode tank outlet 63-2 to form an anode tank electrolyte self-circulation flow system, so that the reaction process can proceed stably.

[0199] The temporary storage tank 37 is equipped with a sensor 39-1, specifically a level gauge, for loading alkaline pH adjuster 70. The temporary storage tank 37, valve 7-1, and pump 8 form an alkaline pH adjuster feeder 22. During operation, under the control of electrolyte pH meter 10, alkaline pH adjuster 70 is added to the anode tank area through the anode tank area return pipe 6 to maintain the electrolyte process-set pH 11.

[0200] The hydrogen bubble collector 66 is placed in the cathode tank area, and its hydrogen outlet 18-2 is connected to the hydrogen high-altitude emission pipe 46-2. A blower 45-2 dilutes the hydrogen concentration and assists in pushing it to the upper atmosphere for emission. The hydrogen high-altitude emission pipe 46-1 is connected to the hydrogen outlet 18-1 on the cathode tank cover plate 17-1 and the vent of the gas-liquid separator 51, respectively. A blower 45-1 dilutes the hydrogen concentration and assists in pushing it to the upper atmosphere for emission.

[0201] The exhaust gas treatment tank 57 is used to treat oxidizing gases escaping from the anode tank area, and contains ferrous sulfate 20 as an absorption reaction solution. An ORP meter (sensor 39-7) is installed inside the exhaust gas treatment tank 57 to control the addition of external ferrous sulfate solution 20. The suction pipe of the exhaust gas treatment tank 57 is connected to the exhaust gas outlet of the anode tank area.

[0202] The automatic detection and feeding controller 40 is used to process the data detected by the field sensors and issue instructions according to the program to control the blower, electrolysis power supply, valves and pumps respectively.

[0203] The sensors 39-1 are level gauges, 39-2 are thermometers, 39-3 are pH meters, 39-4 are level gauges, 39-5 are thermometers, 39-6 are ORP meters, and 39-7 are ORP meters.

[0204] The device of this embodiment is used to treat ammonia nitrogen-containing waste liquid. Specifically, the ammonia nitrogen-containing waste liquid 27 is 150 liters of organic nickel plating waste liquid from circuit boards, in which the total nitrogen pollutant content is 6100 mg / L.

[0205] Add 3% sodium chloride solid and 30% sodium hydroxide solution to ammonia nitrogen-containing waste liquid 27 to prepare a reaction solution 31 with a pH value of pH11.

[0206] The initial cathode electrolyte was a mixture of sodium hydroxide and sodium chloride with a pH of 11.

[0207] The main component of the alkaline pH adjuster 70 is a 30% sodium hydroxide solution. The temporary storage tank 37, valve 7-1, pump 8, and pipelines are combined to form the alkaline pH adjuster feeder 22, which is controlled by the electrolyte pH meter 10 for adding the agent.

[0208] The process characteristics of using the apparatus of this embodiment to treat ammonia nitrogen-containing wastewater are as follows:

[0209] a. Raise the pH of the electrolyte to pH 11 so that nickel hydroxide precipitate is generated during the ammonia nitrogen removal process.

[0210] b. The process design uses sensor 39-3 to control the working status of electrolysis power supply 44. By controlling the ORP value of the reaction solution, the entire ammonia nitrogen removal reaction can be carried out safely according to the process design route.

[0211] c. The electrolytic cathode uses a needle-type structure, which can better collect the electrolyzed hydrogen and bring it closer to the electrolytic anode, thus reducing electrolysis energy consumption.

[0212] d. The temperature of the reaction liquid in the process design is greater than 70℃, and all equipment components using polymer resin materials in the device are made of polytetrafluoroethylene high-temperature resistant material.

[0213] e. The initial electrolytes for the cathode and anode tanks are separate, with the cathode electrolyte being a mixture of hydroxide and sodium chloride at pH 11.

[0214] The steps for treating ammonia-nitrogen-containing wastewater using the apparatus shown in Figure 7 in this embodiment are as follows:

[0215] 1. Add 150 liters of the reaction solution to be treated to the anode tank area, add the initial cathode electrolyte to the cathode tank area and the gas-liquid separator 51, turn on the power of the device to enable the automatic detection and feeding controller 40 to process the on-site data, and issue a command to start the pump tube liquid flow circulator 11 and the two liquid flow pump tube agitators 47-1 and 47-2 to make the anode electrolyte circulate in the anode tank area and the cathode electrolyte circulate in the cathode tank area respectively, and turn on the two blowers to generate negative pressure in the cathode tank area and the gas-liquid separator 51 to extract the electrolyzed hydrogen.

[0216] 2. The automatic detection and feeding controller 40 starts two heat exchangers to raise the electrolyte temperature in both tanks to 73℃; the electrolysis power supply 44 is switched on and automatically adjusts the electrolysis current to 230A, with an average electrolysis cell voltage of 5.6V; the electrolyte pH meter 10 detects the reaction solution in the anode tank and transmits the data to the automatic detection and feeding controller 40 for processing. According to the process procedure, it issues an instruction to control pump 8 to add alkaline pH adjuster 70 into the anode tank return pipe 6 to maintain the pH of the anode reaction solution at pH 11. The anode electrolyte reacts to produce sodium hypochlorite, which reacts with ammonia nitrogen impurities, while NH4+ is also produced. + When the anode is touched, a discharge reaction occurs. During the process, nickel hydroxide precipitate appears in the anode electrolyte, which is filtered and retained by the solid-liquid separator 36. Hydrogen gas is mainly electrolyzed out at the electrolytic cathode.

[0217] 3. During the process, the pump pipe liquid flow circulator 11 and the anode electrolyte adder 61 are started to add liquid under the control of the automatic detection and feeding controller 40. Two blowers draw the electrolyzed hydrogen gas to the high altitude for discharge. The tail gas treatment tank 57 is controlled by the sensor 39-7 to add acidic ferrous sulfate solution 20 and to carry out environmental protection treatment on the waste gas escaping from the anode tank area.

[0218] 4. When sensor 39-6 switches the input line from the outside to the electrolysis power supply 44 during the reaction process, it controls the electrolysis power supply to turn on and off, so that the reaction solution in the anode tank is maintained at an ORP value of 250mV for 28 hours. Then, the anode reaction solution is manually sampled and inspected. The inspection result shows that the ammonia nitrogen impurity content in the solution is ND, which meets the requirement of the process treatment standard of less than 30mg / L.

[0219] 5. By manually inputting a signal indicating that the ammonia nitrogen treatment is qualified into the device, the automatic detection and feeding controller 40 issues an instruction to shut down the electrolysis power supply, and extracts the anode reaction liquid containing nickel hydroxide that has completed the ammonia nitrogen removal treatment from the anode tank area for further processing. The nickel hydroxide 52 in the solid-liquid separator 36 is then collected.

[0220] Note: A test result of ND indicates that the pollutant content in the tested object is less than 0.2 mg / L. The following range of values ​​is set as the detection limit of this testing equipment, hence marked as ND.

[0221] Example 8

[0222] Figure 8 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 8 of the present invention. It includes a device with a length of 4 meters, a width of 1 meter, and a height of 1 meter, totaling 4 meters. 3The electrolytic cell includes: 1. Separated electrolytic cell; 2. Six electrolytic anodes; 3. Six electrolytic cathodes; 4. Electrolytic cell separator; 5. Anode cell return pipe; 6. Electrolyte pH meter; 7. Pump pipe liquid flow circulator; 8. Tank cover sealing plate; 9. Hydrogen escape outlet; 10. Two temporary storage tanks; 11. Overflow buffer tank; 22. Sensor; 33. Three electrolytic power supplies; 44. Blower; 5. Hydrogen high-altitude emission pipe; 65. Multiple sets of screw, nut and fasteners; 66. Electrolytic cell partition plate; 77. Inclined tube and / or inclined plate sedimentation tank; 88. Multiple valves and pumps.

[0223] The described partitioned electrolytic cell 1 includes a cell body 4, in which three electrolytic cell partition plates 65 are welded. Each electrolytic cell partition plate 65 has a large electric field line through-hole 9, and a large filter cloth is used as an electrolytic cell separator 5 to seal it using screw and nut fasteners 60. Each electrolytic cell partition plate 65 has a partition plate liquid flow hole 14 at the bottom of its electric field line through-hole 9, creating a combination of four adjacent cell regions with a large internal cavity capacity and divided into alternating anode and cathode cell regions in the water flow direction. Electrolyte pH meter 10-1 and sensor 39-1, and electrolyte pH meter 10-2 and sensor 39-2 are respectively installed in their respective anode cell regions. Sensors 39-1 and 39-2 are ORP meters. The six electrolytic anodes 2 and six electrolytic cathodes are installed in rows of three. The first row of electrolytic anodes 2 is installed in the first anode tank area and is numbered 2-2-1, 2-2-2, and 2-2-3 respectively. The second row of electrolytic anodes 2 behind them is installed in the second anode tank area and is numbered 2-1-1, 2-1-2, and 2-1-3 respectively. The first row of electrolytic cathodes 3 is installed in the first cathode tank area behind the first row of electrolytic anodes 2 and is numbered 3-2-1, 3-2-2, and 3-2-3 respectively. The second row of electrolytic cathodes 3 is installed in the second cathode tank area behind the second row of electrolytic anodes 2 and is numbered 3-1-1, 3-1-2, and 3-1-3 respectively. All six electrolytic anodes 2 are multi-layered grid anodes with a titanium-based coating. Three of these anodes, 2-2-1, 2-2-2, and 2-2-3, are positioned away from the central cathode region (i.e., the first cathode region) and away from the cathodes 3-2-1, 3-2-2, and 3-2-3, respectively. The current-carrying area of ​​each anode 2 is larger than that of each cathode 3. Electrolytic anodes 2-1-1 and 2-2-1 are connected in parallel to the positive terminal of the electrolytic power supply 44-1 and placed in their respective anode regions. The connection method of the other groups of electrolytic anodes to their corresponding electrolytic power supplies is similar to that of the electrolytic power supply 44-1 described above. All six electrolytic cathodes 3 are single-layer titanium meshes. Three of these cathodes, 3-1-1, 3-1-2, and 3-1-3, are positioned away from the electrolytic anodes 2-1-1, 2-1-2, and 2-1-3. Electrolytic cathodes 3-1-1 and 3-2-1 are connected in parallel to the negative electrode of the electrolytic power supply 44-1 and placed in their respective cathode tank areas. The connection method of the other groups of electrolytic cathodes to their corresponding electrolytic power supplies is similar to that of the electrolytic power supply 44-1. This design of the current-carrying area of ​​the anode and cathode in the electrolytic cell not only ensures the smooth escape of hydrogen gas from the electrolytic cathodes but also utilizes the large-area electrolytic anode block to increase the electric field space for killing microorganisms. Placing three independent electrolytic units within the tank 4 along the water flow direction structurally increases the length of the electric field space and simultaneously increases the electrode density radially in the water flow direction, meeting the requirements for large-flow water treatment in large-diameter pipelines. The process creates conditions that allow the microorganisms in the water to have longer electrocution time and a greater chance of being killed by oxidants within tank 4, thereby improving the effectiveness of electrocution to death or chemical killing of the microorganisms.

[0224] The tank cover plate 17 is located at the top of the cathode tank area of ​​the tank body 4, and it is provided with a hydrogen escaping outlet 18.

[0225] The inclined tube and / or inclined plate sedimentation tank 73 is connected to the overflow port 63-2 of the tank body 4, and is used to perform solid-liquid separation on the microbial remains 52 in the water body after treatment by the separate electrolysis cell, thereby improving the water quality of the self-made tap water 42.

[0226] The blower 45 is used for hydrogen concentration dilution and, in combination with the hydrogen high-altitude emission pipe, assists in pushing the hydrogen to the high altitude for emission. The hydrogen vent 18 and the vent of the overflow buffer tank 38 in the device are connected to the hydrogen high-altitude emission pipe 46.

[0227] The overflow buffer tank 38 is used to collect the solution that overflows from the cathode tank due to the high anolyte level, which causes the anolyte to seep through the electrolytic cell separator 5 and the liquid flow hole 14 of the partition plate into the cathode tank to assist in hydrogen removal. The inlet of the overflow buffer tank 38 is connected to the cathode tank, and the outlet is connected to the pump pipe liquid flow circulator 11, which pumps the solution in the cathode tank back to the anode tank through the anode tank return pipe 6 to continue to oxidize and electrolyze the microorganisms in the water.

[0228] In this embodiment, the reaction solution 31 to be treated is pool water that has already undergone flocculant sedimentation treatment and is stored in temporary storage tank 37-1. Its pH value is 7.1, and the total bacterial count is 69 CFU / ml, with an Escherichia coli count of 2280 CFU / 100ml. After treatment and sedimentation by this embodiment, the total bacterial count is 2 CFU / ml, and no Escherichia coli colonies are detected. This meets the requirements for a qualified tap water product prepared according to the national standard GB5749-2022 "Standards for Drinking Water Quality". It is then stored in temporary storage tank 37-2.

[0229] The steps for producing tap water using the device shown in Figure 8 in this embodiment are as follows:

[0230] 1. The reaction solution 31 to be treated is continuously pumped from the temporary storage tank 37-1 into the tank body 4. The anolyte permeates through the filter cloth and passes through the liquid flow hole 14 of the partition plate into the cathode tank area to drive the hydrogen gas in a circulating flow. The three electrolysis power supplies and the blower 45 are turned on. The blower is turned on to create a negative pressure in the cathode tank area and the overflow buffer tank 38 to draw the hydrogen gas to the high air.

[0231] 2. The anode and cathode of the three electrolytic power supplies are spaced 250 mm apart, and their electrolytic decomposition voltage is 6V. When the operation of each electrolytic power supply is adjusted to 24V, the electrolytic operation is carried out. The total electrolytic working current is 5.3A, which causes the anode electrolyte to undergo an electrochemical reaction to produce a trace amount of Cl2, leaving residual chlorine oxidant in the reaction solution, and a trace amount of hydrogen gas is electrodeposited at the cathode.

[0232] 3. The electrolyte pH meter 10 still shows pH 7.1, and the ORP meter reading is 250mV. When the ORP meter reading is higher than 260mV, the output voltage of the three electrolysis power supplies is reduced from 24V to 18V to slow down the electrochemical reaction of the anolyte. When the ORP meter reading drops back to 250mV, the three electrolysis power supplies are adjusted back to their normal operating voltage of 24V.

[0233] 4. Pump 8 has a flow rate of 200 liters / minute. The water being treated is considered as being treated continuously, with an average electro-shock duration of 20 minutes. After 40 minutes of continuous electro-oxidation treatment to remove the initial 20 minutes of overflow, the water flowing from the separate electrolytic cell, after treatment through inclined tubes and / or inclined plate sedimentation tanks, yields 4 m³ of tap water. 3 After the water production process was completed by shutting down the equipment, the solution in the temporary storage tank 37-2 was manually sampled to check for total bacterial count and Escherichia coli contamination. The test results met the national standards, and the residual chlorine in the tap water was 0.3 mg / L.

[0234] Example 9

[0235] Figure 9 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 9 of the present invention. It includes a partitioned electrolytic cell 1, three electrolytic anodes 2, three electrolytic cathodes 3, five electrolytic cell separators 5, three anode cell return pipes 6, an electrolyte pH meter 10, a pump pipe liquid flow circulator 11, a water-oil separator 29, two overflow buffer tanks 38, a thermometer 39, an electrolytic power supply 44, a hot and cold temperature exchanger 49, a gas-liquid separator 51, an outer layer insulator for conductive wires 56, three cathode boxes 59, valves, and a pump.

[0236] The separator electrolytic cell 1 has a tank body 4 with a capacity of 1000 liters and is equipped with a heat exchanger 49. Electrolytic anodes 2-1 and 2-2 are multi-layered titanium-based coated insoluble anodes with mesh plates, while electrolytic anode 2-3 is a single-layered titanium-based coated insoluble anode mesh, to increase the specific surface area of ​​the anode and reduce the concentration of NH4+ in the electrolyte. + To promote the discharge reaction, three cathode boxes, each equipped with a hydrogen exhaust port 18, are fitted with titanium plates as electrolytic cathodes 3. These three cathode boxes are placed inside a tank 4. The space within the tank 4, excluding the volume of the three cathode boxes, serves as the anode tank area, and the internal space of each cathode box serves as its respective cathode tank area. The three electrolytic anodes in the tank 4 are connected in parallel to the positive terminal of the electrolytic power supply 44, and the three electrolytic cathodes are all connected in parallel to the negative terminal of the electrolytic power supply 44, forming a high-efficiency electro-oxidation device with three parallel electrolytic units.

[0237] Each cathode box has an electric field line through-hole 9. The electric field line through-hole 9-1 is sealed with an electrolytic cell separator 5-1. Correspondingly, the electric field line through-holes 9-2, 9-3, 9-4, and 9-5 are sealed with electrolytic cell separators 5-2, 5-3, 5-4, and 5-5, respectively. Electrolytic cell separator 5-1 is a bipolar membrane, electrolytic cell separators 5-2 and 5-3 are impermeable non-ionic membranes, electrolytic cell separator 5-4 is a permeable non-ionic membrane, and electrolytic cell separator 5-5 is a ceramic filter plate. Electrolytic anodes 2-1 and 2-2 are installed between electrolytic cell separators 5-1 and 5-2, and between electrolytic cell separators 5-3 and 5-4, while electrolytic anode 2-3 is installed close to the electric field line through-hole 9-5. Each cathode box has a partition plate liquid flow hole 14 cut at the bottom for electrolyte exchange between the cathode and anode tanks. Each cathode box is equipped with a hydrogen gas outlet 18 and a cathode electrolyte overflow connection pipe 43 at the top, wherein the cathode electrolyte overflow connection pipe 43 leads to the overflow port 63 of the tank body 4.

[0238] The tank 4 contains three anode tank return pipes, all of which are connected to the outlet of the pump tube liquid flow circulator 11. The outlet of pipe 6-1 faces the level sensor 39 and the electrolyte pH meter 10, while the anode tank return pipes 6-2 and 6-3 face the electrolytic anodes 2-1 and 2-2, respectively. The inlet of the pump tube liquid flow circulator 11 is connected to the overflow port 63 of the tank 4 via the gas-liquid separator 51 and the overflow buffer tank 38-2.

[0239] The device in this embodiment is also equipped with a water-oil separator 29, which is connected to the tank body 4 through an overflow buffer tank 38-1.

[0240] The device of this embodiment is used to treat ammonia nitrogen waste liquid. Specifically, the ammonia nitrogen waste liquid 27 being treated is ammonia nitrogen waste liquid containing organic oil, wherein the ammonia nitrogen pollutant is 620 mg / L, and the specific gravity of the organic oil is lighter than that of water.

[0241] The process features of using the device in this embodiment for ammonia nitrogen removal are as follows: 1. An oil-water separator 29 is added to separate the oil-containing ammonia nitrogen waste liquid from the water, reducing the direct impact of the oil film sealing the electrode on the device's production process. 2. A cathode box is used to enhance the management of electro-electrolyzed hydrogen, allowing the hydrogen to be concentrated and rapidly discharged into the upper atmosphere. 3. Because the reaction liquid is controlled at 85℃ according to the process design to perform oxidation-reduction treatment on the oil-containing organic waste liquid to reduce COD, all tanks, pipes, pumps, and valves in the device are made of polytetrafluoroethylene polymer resin material.

[0242] The steps for treating ammonia-nitrogen-containing wastewater using the apparatus shown in Figure 9 in this embodiment are as follows:

[0243] 1. The ammonia-nitrogen-containing waste liquid 27 is put into the water-oil separator 29 for water-oil separation. The oil is trapped in the water-oil separator 29. After the ammonia-nitrogen-containing waste liquid overflows, it is guided into the tank 4 and the gas-liquid separator 51 through the overflow buffer tank 38-1. In addition, 50 kg of sodium chloride and sodium hydroxide are added to the solution in the tank 4 to prepare the reaction solution 31 to be treated, with a pH value of pH 13.5.

[0244] 2. Turn on the pump tube liquid flow circulator 11 to make the electrolyte circulate between the anode tank area and the cathode tank area through the liquid flow holes 14 of each partition plate.

[0245] 3. Turn on the hot and cold temperature exchanger 49 to heat the electrolyte to 85°C, turn on the electrolysis power supply 44 and adjust the electrolysis current to 150A, with the average voltage of the electrolytic cell being 4.8V; the anolyte produces sodium hypochlorite in the electrochemical reaction and reacts with ammonia nitrogen impurities, while NH4+ is also produced. + The discharge reaction occurs when the anode is touched, while the electrolytic cathode mainly produces hydrogen gas through electrolysis.

[0246] 4. After 8 hours of reaction, the reaction solution was manually sampled and inspected. The results showed that the ammonia nitrogen impurity in the solution was 7 mg / L, which meets the process standard requirement of less than 30 mg / L.

[0247] 5. Turn off the electrolysis power supply and pump the oxidized solution from the separate electrolysis cell 1 out of the cell 4 for further processing.

[0248] Example 10

[0249] Figure 10 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 10 of the present invention. It includes a 1000-liter electrolytic cell consisting of two separate electrolytic cells, a return pipe 6 for the anode area, an electrolyte pH meter 10, a pump pipe liquid flow circulator 11, four tank cover plates 17, two hydrogen vents 18, a solid-liquid separator 36, a temporary storage tank 37, two electrolysis power supplies 44, a titanium metal assembly 64, a hydrogen bubble collector 66, a filtration membrane device 69, a biochemical anaerobic reaction tank 71, and an inclined tube and / or inclined plate sedimentation tank 73.

[0250] This embodiment uses an electrolytic cell composed of two separate electrolytic cells 1-1 and 1-2, sharing a single tank body 4. Three electrolytic cell separators 5, directly welded inside the tank body 4, divide it into four tank zones, alternating between anode and cathode zones. Each anode zone and cathode zone has a volume of 250 liters, and each tank is sealed with a tank cover plate 17. The three electrolytic cell separators 5 in the tank body 4 are all perforated polymer resin plates, each with a liquid flow passage 14 at its lower part.

[0251] The electrolytic anode 2-1 is a titanium metal assembly 64, and the electrolytic anode 2-2 is a single-layer grid titanium-based coated insoluble anode. Electrolytic cathodes 3-1 and 3-2 are both made of stainless steel mesh. Electrolytic power supply 44-1 is connected to both electrolytic anode 2-1 and electrolytic cathode 3-1, and electrolytic power supply 44-2 is connected to both electrolytic anode 2-2 and electrolytic cathode 3-2. In the sterilization and algae removal process, the titanium metal assembly 64 is used as the electrolytic anode 2-1. Although the high-resistance passivation film of the electrolytic anode 2-1 increases the interfacial resistance between the anode and the electrolyte, causing an increase in the electrolytic cell voltage, directly using a titanium anode has the advantage of a poor electrolytic chlorine reaction. Therefore, after applying a safe voltage to the electrode, its output micro-electrolytic current can still meet the requirements of the electrolytic technology parameters, while reducing environmental pollution.

[0252] The pump pipe liquid flow circulator 11 is connected to the discharge port 63-2 of the cathode tank area of ​​the electrolytic cell 1-1 and the return pipe 6 of the anode tank area, respectively. The return pipe 6 of the anode tank area is located at the bottom of the anode tank area of ​​the electrolytic cell 1-2.

[0253] The hydrogen bubble collector is placed above the electrolytic cathode 3-1 of the electrolytic cell 1-1 to collect the electrolyzed hydrogen gas and discharge it outward.

[0254] Solid-liquid separator 36 is an inclined plate filter used to separate the solid-liquid mixture in the biochemical anaerobic reactor 71 into activated sludge. The separated activated sludge falls back into the original biochemical reactor, while the filtrate enters the electrolytic cell for sterilization. The inlet of solid-liquid separator 36 is connected to the outlet of biochemical anaerobic reactor 71 via a pipeline, and its outlet is connected to the inlet 62 of the separating electrolytic cell 1-2.

[0255] The inclined tube and / or inclined plate sedimentation tank 72 is used for solid-liquid sedimentation separation of the water overflowing from the separated electrolytic cell after treatment, removing insoluble solid impurities, especially organic microbial remains 52-1, from the water. The inclined tube and / or inclined plate sedimentation tank 72 is connected to the discharge port 63-1 of the separated electrolytic cell 1-1 and the temporary storage tank 37 by pipeline.

[0256] The temporary storage tank 37 is connected to the discharge port 63-1 of the electrolytic cell 1-1 via an inclined tube and / or inclined plate sedimentation tank 72, and is used to store the water after oxidation treatment in the electrolytic cell; the filtration membrane device 69 is an MBR membrane device, and its inlet is connected to the temporary storage tank 37 via a pump, valve and pipe, to perform solid-liquid filtration and water separation on the water after oxidation and sedimentation treatment in the electrolytic cell and the sludge it contains.

[0257] In this embodiment, the electrolytic cell separators 5 are all permeable electrolytic cell separators. The solution in each cell zone enters the adjacent isolation cell zone along the liquid flow direction through the micropores and liquid flow holes 14 in its separators 5. The cells are connected in a series structure with alternating cathode and anode cells.

[0258] The water treated by the device in this embodiment is a solid-liquid mixture reaction liquid containing activated sludge taken from the biochemical reaction tank. It is coarsely filtered by an inclined plate filter. The activated sludge 52-2 separated is returned to the primary anaerobic reaction tank 71. The filtrate is the reaction liquid 31 to be treated, with a pH value of pH 7.1. Solution 31 still contains a certain amount of activated sludge.

[0259] The steps for inactivating activated sludge bacteria in water using the device shown in Figure 10 in this embodiment 10 are as follows:

[0260] 1. Start pump 8-3 to pump the sewage in the anaerobic biological reactor 71 into the inclined plate filter. Most of the activated sludge 52-2 falls back into the biological reactor. The coarsely filtered reaction liquid 31 is used as the starting electrolyte and pumped into the feed port 62 of the partitioned electrolytic cell 1-2 to fill the integrated electrolytic cell. Start the pump pipe liquid circulation device 11 and turn on the electrolysis power supplies 44-1 and 44-2 to carry out the sterilization operation.

[0261] 2. When the amount of water processed by the biochemical reaction tank is small, reduce the flow rate of pumps 8-2 and 8-3, and adjust the electrolysis power supplies 44-1 and 44-2 to 3.5V, which is below the electrolysis decomposition voltage of 4.2V, for electrolysis operation. The electrolysis current of the two electrolysis power supplies is 65mA, the pH value detected by the electrolyte pH meter 10 is 7.1, no hydrogen gas is electrolyzed at the electrolysis cathode, and the microorganisms are electrolyzed by the electric field.

[0262] 3. When the amount of water to be treated in the biochemical reaction tank increases, a large amount of reaction liquid 31 to be treated is prepared by adjusting the flow rate of pump 8-3. During the reaction, the flow rate of pump 8-2 is increased and the voltage of electrolysis power supplies 44-1 and 44-2 is adjusted to 6V. Both electrolysis cathodes electrodeposit a small amount of hydrogen bubbles, and the micro-organisms in the flowing water being treated are electrocuted when they pass through the two electric fields.

[0263] 4. When the flow rate of the treated water is slow and the treatment volume is small, the flow rate is 50 liters / minute, and the treated water is electrolyzed in the electrolysis cell for 20 minutes. When the treatment volume is large, the flow rate is 100 liters / minute, and the treated water is electrolyzed in the separate electrolysis cell 1 for 10 minutes. Both electrolysis methods can kill the active microorganisms in the water.

[0264] 5. The water overflowing from the separate electrolysis cell is treated by inclined tube and / or inclined plate sedimentation tank 73 before being filtered by the MBR membrane equipment. After process improvement, the maintenance cleaning of the membrane equipment with low concentration sodium hypochlorite solution has been extended from once a week to once every two weeks, which still meets the process requirements.

[0265] Example 11

[0266] Figure 11 shows a schematic diagram of an electro-oxidation device for treating ammonia nitrogen pollutants or microorganisms in water according to Embodiment 11 of the present invention. The device is composed of two independent, series-connected electro-oxidation treatment devices, using the separate electrolytic cell from Embodiment 2 and the separate electrolytic cell from Embodiment 3 connected by pipes. Specifically, the cathode area of ​​separate electrolytic cell 1-1 is connected to the anode area of ​​separate electrolytic cell 1-2 via pipes. The reaction solution 31 to be treated is ammonia nitrogen-containing wastewater with a pH of 7.3 and an ammonia nitrogen impurity content of 320 mg / L. After 24 hours of oxidation treatment, the ammonia nitrogen content of the treated solution is reduced to 24 mg / L, meeting the process treatment standard of below 30 mg / L.

Claims

1. An electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water, characterized by The application relates to a separated electrolytic tank, at least one anode tank area backflow pipeline, at least one electrolyte pH meter and at least one pump pipeline liquid flow circulator. The separated electrolytic tank comprises an electrolytic anode, an electrolytic cathode, a tank body, an electrolytic power supply and a tank area separator, the tank body is separated into an anode tank area and a cathode tank area by the tank area separator, the electrolytic anode is arranged in the anode tank area and is connected with the positive pole of the electrolytic power supply, and the electrolytic cathode is arranged in the cathode tank area and is connected with the negative pole of the electrolytic power supply; the tank area separator is an electrolytic tank separator or a combination of the electrolytic tank separator and an electrolytic tank spacing plate, the electrolytic tank spacing plate is provided with an electric field line through hole and is closed by the electrolytic tank separator; the electrolytic tank separator can effectively prevent gas bubbles and insoluble solid matters in electrolyte from moving between the anode tank area and the cathode tank area; when the tank area separator is water-tight, at least one spacing plate liquid flow through hole is arranged to connect the anode tank area and the cathode tank area, and / or an anode electrolyte adding device is arranged to extract electrolyte in part of the anode tank area and add the electrolyte into the cathode tank area, and the circulation is realized through the pump pipeline liquid flow circulator and the anode tank area backflow pipeline; the spacing plate liquid flow through hole is arranged on the electrolytic tank spacing plate to connect the anode tank area and the cathode tank area and allow the electrolyte to pass through; The anode electrolyte adding device is composed of a pump and a pipeline or is composed of a pump, a valve and a pipeline, the liquid inlet of the anode electrolyte adding device is connected with the anode tank area, and the liquid outlet of the anode electrolyte adding device is connected with the cathode tank area or is connected with a tank canister for loading solution into the cathode tank area; The anode tank area backflow pipeline is a pipeline connecting the pump pipeline liquid flow circulator and the anode tank area, and is used for guiding the solution flowed out of the pump pipeline liquid flow circulator back to the anode tank area to continue to participate in the reaction, or the anode tank area backflow pipeline is connected with a receiving tank canister of the solution flowed out of the pump pipeline liquid flow circulator, and indirectly guides the solution containing the solution flowed out of the pump pipeline liquid flow circulator back to the anode tank area to continue to participate in the reaction; The pump pipeline liquid flow circulator comprises a pump and a pipeline or comprises a pump, a pipeline and a valve, and the liquid inlet of the pump pipeline liquid flow circulator is connected with the cathode tank area; the pump in the pump pipeline liquid flow circulator is started or stopped according to the detection data of the electrolyte pH meter, the ammonium ion concentration in the cathode electrolyte, the number of active organisms in the cathode electrolyte, the electrolysis time and the liquid level of the tank area electrolyte; The electrolyte pH meter is arranged in the separated electrolytic tank and / or a pipeline or a container connected with the separated electrolytic tank, and is used for detecting the pH value of the electrolyte. The electrolytic tank separator comprises a water-permeable electrolytic tank separator and a water-impermeable electrolytic tank separator; the water-permeable electrolytic tank separator has a water-permeable through hole allowing water to pass through freely in a natural state, and is at least one selected from a high polymer resin through hole plate, a ceramic through hole plate, filter cloth and a water-permeable non-ionic diaphragm; the water-impermeable electrolytic tank separator prevents water from passing through in a natural state, and is at least one selected from a cation exchange membrane, a reverse osmosis membrane, a bipolar membrane, an anion exchange membrane and a water-impermeable non-ionic diaphragm.

2. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 1, characterized in that, ​ When the combination of the electrolytic cell separator 5 and the electrolytic cell spacer 65 is used as the cell zone spacer, the electrolytic cell spacer 65 is at least one selected from the group consisting of a high polymer resin plate, a high polymer resin through-hole plate, and a ceramic through-hole plate; When the combination of the water-impermeable electrolytic cell separator 5 and the high polymer resin plate is used as the electrolytic cell spacer 65, the cell zone spacer is water-impermeable.

3. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 2, characterized in that, When the water-permeable electrolytic cell separator 5 is used, or the combination of the water-permeable electrolytic cell separator 5 and the electrolytic cell spacer 65 is used, or the combination of the water-impermeable electrolytic cell separator 5 and the high polymer resin through-hole plate and / or the ceramic through-hole plate is used as the cell zone spacer, at least one anode electrolyte adding device and / or the spacer through-hole is further included.

4. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 2, characterized in that, When the electrolytic cell separator is used alone as the cell zone spacer, the electrolytic cell separator is directly fixed in the cell body by using a high polymer resin through-hole plate and / or a ceramic through-hole plate.

5. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 4, characterized in that, The spacer through-hole is arranged at a position below the electric field line through-hole, so that the anode and cathode cell zones form a U-shaped tube structure.

6. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 4, characterized in that, The outlet of the anode cell zone pipeline 6 is inserted into the solution in the anode cell zone and faces the electrolytic anode.

7. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 4, characterized in that, The cell body is made of a high polymer resin material; the surface material of the electrolytic anode in contact with the electrolyte is at least one selected from the group consisting of gold, platinum, a titanium-based coating insoluble anode, titanium, and conductive graphite; and the surface material of the electrolytic cathode in contact with the electrolyte is at least one selected from the group consisting of gold, platinum, titanium, stainless steel, conductive graphite, and a titanium-based coating conductor.

8. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7, characterized in that, When the device is used to inactivate microorganisms in water, the electrolysis power source uses an electrolysis decomposition voltage to perform electrolysis.

9. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7, characterized in that, When the device is used to inactivate microorganisms in water, a voltage higher than the decomposition voltage is used to electrolyze the water, so that the electrolytic anode generates trace amounts of chlorine gas to achieve the residual chlorine content in the treated water to meet the process or regulatory requirements.

10. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7, characterized in that, To make the water containing fewer ions contain residual chlorine after being treated by the device, two or more anode cell zones and / or cathode cell zones are arranged in the separator electrolytic cell, and a high-density cell zone structure with anodes and cathodes arranged alternately is adopted. Two or more electrolytic anodes are connected in parallel to the positive pole of the electrolysis power source, and / or two or more electrolytic cathodes are connected in parallel to the negative pole of the electrolysis power source to form two or more micro-distance electric fields, or two-electrode micro-distance independent electrolytic units are formed by one electrolysis power source, one electrolytic anode, and one electrolytic cathode, and then two or more independent electrolytic units are arranged side by side to form two or more two-electrode micro-distance independent electric fields.

11. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7, characterized in that, A branch conductor is additionally arranged on the electrolytic anode to intercept electrolyte fluid, and the branch conductor is made of the same material as the electrolytic anode or other insoluble anode materials.

12. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7 or 11, characterized in that, A titanium metal assembly is additionally arranged to expand the specific surface area of the electrolytic anode, which is connected to the electrolytic anode or simultaneously connected to the electrolytic anode and the positive pole of the electrolysis power source; the titanium metal assembly is made of sheet blocks and / or granules and / or titanium wire.

13. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7, characterized in that, The top of the cathode groove area is additionally provided with a groove cover sealing plate for sealing the top of the groove, or the top of the anode groove area and the top of the cathode groove area are respectively provided with groove cover sealing plates for sealing the top of the groove; wherein the groove cover sealing plate of the cathode groove area is provided with at least one hydrogen gas escape outlet, or is provided with at least one hydrogen gas escape outlet and at least one feeding pipe opening and / or discharging pipe opening.

14. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, An anode groove area electrolyte self-circulation flow system is additionally provided; the anode groove area electrolyte self-circulation flow system is a liquid flow pump pipe stirrer and its connecting pipeline, one end of which is connected with the discharging pipe opening of the anode groove area, and the other end is connected with the backflow pipeline of the anode groove area and / or the liquid spraying pipe provided in the anode groove area.

15. The electro-oxidation device for treating ammonia-nitrogen pollutants or microorganisms in water according to claim 7 or 14, characterized in that, A hydrogen driving liquid spraying pipe is installed in the middle or lower part of the cathode groove area, the nozzle of which is installed upward or obliquely upward, so that the cathode hydrogen is moved upward along with the liquid flow sprayed by the hydrogen driving liquid spraying pipe and is led out of the electrolytic tank through the discharging pipe opening or the hydrogen gas escape outlet of the cathode groove area.

16. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 15, characterized in that, A cathode groove area electrolyte self-circulation flow system is additionally provided; the cathode groove area electrolyte self-circulation flow system is a liquid flow pump pipe stirrer and its connecting pipeline, one end of which is connected with the discharging pipe opening of the cathode groove area or the liquid outlet opening of the gas-liquid separator, and the other end is connected with the hydrogen driving liquid spraying pipe provided in the cathode groove area.

17. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, A connecting spraying pipe is assembled on the liquid flow through hole of the spacing plate, the liquid outlet of the spraying pipe is directed towards the electrolytic cathode to help guide the electrolytic hydrogen to escape upward and be collected in a concentrated manner.

18. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, The electrolytic cathode is provided with a needle-shaped structure directed towards the electrolytic anode, which utilizes the needle tip discharge principle of the electrode to concentrate the electrolytic hydrogen on the cathode needle tip during the reaction to facilitate collection.

19. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, A hydrogen bubble collector is additionally provided above the electrolytic cathode, which includes a solution bubble flow guide cover, a pipeline connected with the solution bubble flow guide cover, and at least one side branch solution discharge pipe opening provided in the pipeline, so that the bubble liquid flow above the electrolytic cathode enters the hydrogen bubble collector and can be smoothly separated into gas and liquid.

20. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, A gas-liquid separator is additionally provided, the liquid inlet opening of which is connected with the discharging pipe opening of the cathode groove area, so that the cathode groove area overflow liquid containing hydrogen gas passes through the gas-liquid separator to make the hydrogen gas escape more thoroughly.

21. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, An alkaline pH value adjusting agent feeder is additionally provided for adding alkaline pH value adjusting agent to the electrolytic reaction liquid to maintain the pH value of the anode electrolyte at not less than pH 5.5; the alkaline pH value adjusting agent feeder is composed of a temporary storage tank, a pump, an on-off regulating valve and a feeding pipeline, the discharging opening of the feeding pipeline is connected with the spacing electrolytic tank anode groove area, and / or is connected with the pipeline and / or container communicated with the anode groove area.

22. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, A temperature control system is additionally provided in at least one of the anode groove area, the pipeline communicated with the anode groove area, and the container communicated with the anode groove area, which is composed of a cold and hot temperature exchanger and a thermometer.

23. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 13, wherein, At least one cathode box is provided in the groove body to separate the anode groove area and the cathode groove area, the cathode box is provided with an electrolytic cathode and serves as a cathode groove area, and the space in the groove body outside the cathode box is an anode groove area; at least one side of the cathode box is the electrolytic tank spacer, the cathode box is provided with at least one hydrogen gas escape outlet and / or discharging pipe opening, and at least one feeding pipe opening; The electrolytic cathode is provided with a needle-shaped structure directed towards the electrolytic anode, which utilizes the needle tip discharge principle of the electrode to concentrate the electrolytic hydrogen on the cathode needle tip during the reaction to facilitate collection. The outlet and / or hydrogen escape port of the cathode box is arranged at the top of the cathode box, so that the hydrogen generated by electrolysis in the cathode box can be smoothly discharged out of the box; at least one partition plate flow through hole is additionally arranged at the bottom of the cathode box, so that the anode electrolyte enters the cathode groove area to drive the electrolysis hydrogen to float upward and overflow with the flow.

24. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, An anode groove area liquid spraying pipe is arranged in the anode groove area, and the nozzle of the liquid spraying pipe is close to and / or faces the electrolysis anode.

25. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, The groove bottom of the anode and cathode groove areas is designed as a funnel type and is provided with a groove bottom liquid spraying pipe for spraying electrolyte to the groove bottom, so that the accumulation of insoluble solid impurities in the electrolyte is reduced through spraying agitation.

26. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, In the partitioned electrolysis tank, two or more electrolysis anodes and / or two or more electrolysis cathodes are arranged in the flow direction of the water body to be treated, and / or two or more electric fields are arranged at the vertical radial position of the flow direction of the water body to be treated; the same type of electrodes are connected in parallel and then connected to the positive and negative poles of one electrolysis power source to establish multiple associated electric fields, or one electrolysis power source corresponds to one independent electrolysis unit composed of one electrolysis anode and one electrolysis cathode.

27. The electro-oxidation device for treating ammonia-nitrogen contaminants or microorganisms in water according to claim 7, characterized in that, When two or more partitioned electrolysis tanks are connected to treat the water body, the following two connection structure modes are adopted: the first mode is to connect two or more separate partitioned electrolysis tanks through pipelines; the second mode is to separate the separate partitioned electrolysis tanks through electrolysis tank partitions and then directly share the tank body.

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