Method and system for oxygenolysis of refractory pollutants based on ozone bubble water

Abstract

The invention relates to the technical field of sewage treatment, and discloses a method and system for oxygenolysis of refractory pollutants based on ozone bubble water. The method comprises the following steps: carrying out grid interception, sand setting and pH regulation pretreatment on sewage; air is compressed, dried and subjected to oxygen generation, and then is introduced into an ozone generator to generate high-concentration ozone gas; enabling the pretreated effluent and ozone gas to form micro-nano bubble water in a shearing spiral-flow type generator; carrying out contact oxidation on the bubble water and the pollutants in a vertical flow reactor; preliminarily oxidized effluent enters a catalytic bed for advanced treatment; and the generated tail gas is absorbed and catalytically decomposed. According to the invention, the solubility and stability of ozone in water are improved, the contact time of ozone and pollutants is prolonged, the oxidation efficiency of ozone is enhanced, and the treatment energy consumption is reduced, so that efficient oxygenolysis of refractory pollutants is realized.

Description

Technical Field

[0001] This application relates to the technical field of sewage treatment, and particularly to a method and system for oxidatively decomposing refractory pollutants based on ozonated water. Background Art

[0002] In existing sewage treatment technologies, refractory organic pollutants such as benzene series compounds, dyes, pesticide residues, drug residues, etc. are usually treated by chemical oxidation methods. Traditional chemical oxidation methods mainly include chlorination, ozonation, and Fenton oxidation, etc. Among them, ozonation is widely used due to its strong oxidizing property and no secondary pollution. Ozone is a strong oxidant with an oxidation potential of 2.07V, second only to fluorine and hydroxyl radicals, and can effectively oxidize and decompose various refractory organic pollutants. Traditional ozonation technologies usually use the aeration method to introduce ozone gas into sewage, or use devices such as Venturi tubes and static mixers to enhance the gas-liquid mixing effect. In addition, there is also the catalytic ozonation technology, which promotes the decomposition of ozone to generate hydroxyl radicals by adding a catalyst to further enhance the oxidation ability.

[0003] However, traditional ozonation technologies have limitations in many aspects: First, the solubility of ozone in water is low and the dissolution rate is slow, resulting in low ozone utilization efficiency, usually only 10 - 30%; Second, the diameter of conventional bubbles is large, the rising speed is fast, the contact time with pollutants is short, and the reaction is not sufficient; Third, ozone itself has poor stability, is easily decomposed in the water environment, has a short half-life, and is difficult to maintain a sufficient oxidation concentration; Fourth, single ozonation is difficult to completely mineralize some organic compounds with complex structures such as halogen-containing compounds and pesticides; Fifth, the traditional process has high energy consumption and high treatment cost, which limits its wide application. These problems lead to low ozonation treatment efficiency and are difficult to meet the increasingly strict sewage treatment requirements. Summary of the Invention

[0004] An object of this application is to provide a method and system for oxidatively decomposing refractory pollutants based on ozonated water, which is used to improve the solubility and stability of ozone in water, extend the contact time between ozone and pollutants, enhance the oxidation efficiency of ozone, reduce the treatment energy consumption, and thus achieve the efficient oxidative decomposition of refractory pollutants.

[0005] To achieve the above object, some embodiments of this application provide the following aspects: In a first aspect, the present application provides a method for oxidatively decomposing refractory pollutants based on ozone microbubble water, including: performing pretreatment of grid interception, grit removal, and pH adjustment on sewage to obtain pretreated effluent; introducing air into an ozone generator for discharge treatment after compression, drying, and oxygen production to obtain high-concentration ozone gas; inputting the pretreated effluent and the high-concentration ozone gas into a shear swirl type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; performing contact reaction treatment on the ozone micro-nano bubble water and refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent; introducing the preliminarily oxidized effluent into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; and performing absorption and catalytic decomposition treatment on the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor.

[0006] In a second aspect, the present application provides a system for oxidatively decomposing refractory pollutants based on ozone microbubble water, including: A treatment module for performing pretreatment of grid interception, grit removal, and pH adjustment on sewage to obtain pretreated effluent; A discharge module for introducing air into an ozone generator for discharge treatment after compression, drying, and oxygen production to obtain high-concentration ozone gas; A mixing module for inputting the pretreated effluent and the high-concentration ozone gas into a shear swirl type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; A reaction module for performing contact reaction treatment on the ozone micro-nano bubble water and refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent; An introduction module for introducing the preliminarily oxidized effluent into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; An absorption module for performing absorption and catalytic decomposition treatment on the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor.

[0007] In a third aspect of the present invention, there is provided a computer device, including: a memory and at least one processor, wherein instructions are stored in the memory; the at least one processor calls the instructions in the memory so that the computer device executes the above-mentioned method for oxidatively decomposing refractory pollutants based on ozone microbubble water.

[0008] In a fourth aspect of the present invention, there is provided a computer-readable storage medium, wherein instructions are stored in the computer-readable storage medium, and when it runs on a computer, it causes the computer to execute the above-mentioned method for oxidatively decomposing refractory pollutants based on ozone microbubble water.

[0009] In the technical solution provided by this application, through the grille interception, grit removal and pH adjustment pretreatment system, stable and high-quality pretreatment effluent is provided, creating an optimal pH environment for subsequent ozone oxidation; the oil-free compression, deep drying and pressure swing adsorption oxygen generation technologies are adopted, combined with dielectric barrier discharge to generate high-concentration and stable ozone gas, ensuring the high purity and stability of the ozone source; the shear swirl type micro-nano bubble generator is innovatively used to uniformly disperse ozone in water in the form of 100-nanometer to 10-micron bubbles, significantly improving the solubility and stability of ozone. The diameter of the micro-nano bubbles is much smaller than that of traditional millimeter-level bubbles, and the specific surface area increases by 100-1000 times, greatly increasing the contact area between ozone and pollutants; the unique zero potential characteristic (-25 mV) of the micro-nano bubbles enhances the adsorption with pollutants, and the long-time suspension characteristic extends the contact time between ozone and pollutants from the minute level to the hour level; the spiral water distribution and multi-layer baffle in the vertical flow reactor design form a "Z" flow path, further optimizing the contact efficiency; the composite catalytic bed reactor combines the dual effects of iron-based catalyst and UV photocatalysis to promote the decomposition of ozone to generate more hydroxyl radicals, forming a synergistic effect of direct ozone oxidation and indirect hydroxyl radical oxidation. The oxidation potential is increased from 2.07V to 2.8V, improving the solubility and stability of ozone in water, extending the contact time between ozone and pollutants, enhancing the oxidation efficiency of ozone, reducing the treatment energy consumption, and thus realizing the efficient oxidation and decomposition of refractory pollutants. Description of the Drawings

[0010] One or more embodiments are exemplarily illustrated by the pictures in the corresponding drawings. These exemplary illustrations do not limit the embodiments. Elements with the same reference numerals in the drawings are represented as similar elements. Unless otherwise stated, the drawings in the figures do not constitute a proportional limitation.

[0011] Figure 1 It is a schematic diagram of an embodiment of the method for oxidizing and decomposing refractory pollutants based on ozone-water in the embodiment of this application; Figure 2 It is a schematic diagram of an embodiment of the system for oxidizing and decomposing refractory pollutants based on ozone-water in the embodiment of this application; Figure 3 It is a schematic block diagram of the structure of the computer device in the embodiment of the present invention. Detailed Embodiments

[0012] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are some, but not all, of the embodiments of this application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in this application without creative efforts shall fall within the scope of protection of this application.

[0013] Please refer to Figure 1 , an embodiment of the method for oxidatively decomposing refractory pollutants based on ozone-enriched bubble water in the embodiments of this application includes: Step S101: Perform pretreatment on the sewage by grille interception, grit removal, and pH adjustment to obtain pretreated effluent; Step S102: After compressing, drying, and oxygen-making treatment of the air, introduce it into an ozone generator for discharge treatment to obtain high-concentration ozone gas; Step S103: Input the pretreated effluent and the high-concentration ozone gas into a shear swirl-type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; Step S104: Perform contact reaction treatment on the ozone micro-nano bubble water and the refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent; Step S105: Introduce the preliminarily oxidized effluent into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; Step S106: Absorb and catalytically decompose the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor.

[0014] It can be understood that the execution subject of this application can be a system for oxidatively decomposing refractory pollutants based on ozone-enriched bubble water, or a terminal or a server. Specifically, it is not limited here. The embodiments of this application will be described by taking the server as the execution subject as an example.

[0015] Specifically, the sewage is subjected to grid interception, grit removal, and pH adjustment treatment through a pretreatment system. In specific implementation, the sewage first passes through a grid device with a spacing of 10 mm, effectively intercepting large-sized solid substances in the wastewater, such as plastic fragments, leaves, and fibers, with an interception efficiency of over 95%. Subsequently, the primary treated water enters an aerated grit chamber with an air-water ratio of 1:8, the horizontal flow velocity is controlled at 0.3 m / s, and the residence time is precisely controlled at 5 minutes to ensure the effective sedimentation and separation of sand particles above 0.2 mm. The secondary treated water enters the adjustment tank, which is equipped with a stirring device with a power density of 20 W / m³. The volume of the adjustment tank is designed according to 25% of the daily sewage treatment volume to ensure the balance of water quality and quantity. Then, the tertiary treated water is transported to the pH adjustment device through a lift pump, and an acid-base regulator is added to stabilize the pH value at 7.5 ± 0.5. This pH value range has been determined through experimental research as the optimal range for the ozone oxidation reaction. In actual operation, when treating a textile printing and dyeing wastewater, the original water pH value is 9.2, and after adding sulfuric acid solution, the pH value drops to 7.5, creating an optimal environment for subsequent ozone micro-nano bubble water treatment.

[0016] The preparation of high-concentration ozone gas is a key link in this method. Air is first compressed to 0.8 MPa by an oil-free air compressor, and the flow rate is maintained at 10 m³ / h to ensure a stable gas source for the system. The compressed air enters a pressure swing adsorption air dryer, and water molecules are forcibly adsorbed by the adsorbent to reduce the dew point to -40°C, preventing water interference during subsequent oxygen production and ozone generation processes. The dried air enters a pressure swing adsorption oxygen generator, using molecular sieve 13X as the adsorbent, and oxygen-nitrogen separation is achieved through pressure changes to produce high-purity oxygen with a purity of over 93% and a production rate of 5 m³ / h. The high-purity oxygen is introduced into an ozone generator using dielectric barrier discharge technology, the discharge frequency is controlled between 600 - 1200 Hz, and the cooling water temperature is precisely maintained in the range of 15 - 20°C to produce high-concentration ozone gas with a concentration of 200 ± 10 g / standard m³. When treating a pharmaceutical wastewater, the system operates stably for 4 hours, and the ozone concentration fluctuation does not exceed ±5 g / standard m³, providing a stable high-concentration ozone source for subsequent micro-nano bubble generation.

[0017] The preparation of ozone micro-nano bubble water adopts the shear swirl flow technology. The pretreated effluent is adjusted in pressure and stabilized at 0.35 MPa, and the pressure of high-concentration ozone gas is adjusted to 0.25 MPa. The two are introduced into a shear swirl flow type micro-nano bubble generator with an internal swirl chamber diameter of 50 mm and a swirl angle of 60 degrees according to a gas-liquid ratio of 1:5. Inside the generator, the tangential inlet flow velocity reaches 15 m / s, generating strong shear force and rotational centrifugal force, which shear the ozone gas into micro-nano bubbles with a diameter of 100 nm - 10 μm. The primary ozone micro-nano bubble water is transported through a polytetrafluoroethylene pipeline made of ozone-resistant material with a pipe diameter of 50 mm and a flow velocity of 1.2 m / s to ensure that the micro-nano bubbles do not coalesce during transportation. After on-line monitoring confirmation, the ozone concentration of the effluent is 15 mg / L and the zero potential is -25 mV, indicating that the bubbles carry a stable negative charge, enhancing the contact adsorption ability with pollutants.

[0018] The contact reaction between ozone micro-nano bubble water and refractory pollutants is carried out in a vertical flow reactor. The height-diameter ratio of this reactor is 3:1, the effective volume is 5 cubic meters, and the material is 316L stainless steel lined with polytetrafluoroethylene. The ozone micro-nano bubble water is evenly distributed through a bottom spiral water distribution device, and the refractory pollutants enter from the top, with a hydraulic retention time of 30 minutes. Three baffle plates with a spacing of 1 m are arranged in the reactor to form a "Z"-shaped flow path, extending the contact time. At the same time, the jacket cooling system precisely controls the temperature at 20 - 25 °C to create the best conditions for the ozone oxidation reaction. On-line monitoring equipment monitors COD, pH value, dissolved oxygen, and redox potential in real time, and automatically adjusts the dosage of ozone micro-nano bubble water according to the monitoring data. When treating a certain dye wastewater, the influent COD is 560 mg / L, and after 30 minutes of reaction, the effluent COD drops to 280 mg / L, showing an obvious initial oxidation effect.

[0019] The effluent from the preliminary oxidation enters the composite catalytic bed reactor for advanced treatment. The reactor adopts a columnar structure with a diameter of 1 meter and a height of 3 meters, filled with a composite catalyst of titanium dioxide supported on an iron-based porous material with a specific surface area greater than 200 m² / g and a pore size distribution in the range of 5 - 10 nm. The effluent from the preliminary oxidation is evenly distributed onto the surface of the catalytic bed through a perforated plate distributor with a pore diameter of 5 mm and an opening rate of 30%, and flows through the catalytic bed at a flow rate of 5 m / h. Ultraviolet lamps are installed in the upper part of the reactor, with a wavelength of 365 nm, a light intensity of 10000 μW / cm², a power density of 100 W / m², and a light uniformity of not less than 85%. Under the catalytic action, the residual ozone decomposes to generate hydroxyl radicals, and titanium dioxide produces a photocatalytic effect under ultraviolet light irradiation, further enhancing the oxidation ability. The treatment system continuously monitors the operating resistance of the catalytic bed. When the resistance increases by 20%, the backwashing program is automatically started, with a backwashing intensity of 15 L / m²·s and a time of 10 minutes to ensure the activity of the catalyst. The tail gas treatment adopts the "high-efficiency absorption + catalytic decomposition" process. The ozone-containing tail gas generated by the vertical flow reactor and the composite catalytic bed reactor is collected and introduced into a packed tower with a height of 3 meters and a diameter of 0.5 meters. The packing is ceramic Raschig rings with a specific surface area of 220 m³ / m³, the absorption liquid is 5% sodium carbonate solution, the liquid-gas ratio is 3:1, the absorption temperature is 25 °C, and the absorption efficiency is over 90%. The primary treated tail gas enters the catalytic decomposition device and is catalytically decomposed at 40 °C through a manganese-based catalyst. The ozone decomposition efficiency is greater than 99.5%, and the outlet ozone concentration is controlled below 0.1 mg / m³, meeting the emission standards. The operating data of the entire system is collected and processed in real time through a distributed control system, including the water quality parameters of each unit, the operating status of equipment, energy consumption data, and chemical consumption data. According to these data, key operating parameters such as ozone generation amount, micro-nano bubble water preparation conditions, reaction time, and catalyst regeneration time are automatically adjusted to ensure the stable treatment effect of the system.

[0020] In a specific embodiment, the process of performing step S101 may specifically include the following steps: The sewage is intercepted by a grid device with a spacing of 10 mm to obtain primary treated water with large-sized solid substances removed; The primary treated water is input into an aerated grit chamber with an air-water ratio of 1:8 for grit removal treatment, and the horizontal flow velocity is controlled at 0.3 m / s to obtain secondary treated water with sand particles larger than 0.2 mm removed; The secondary treated water is homogenized in an adjustment tank with a stirring power density of 20 W / m³. The volume of the adjustment tank is designed according to 25% of the daily sewage treatment volume to obtain tertiary treated water with balanced water quality and quantity; The tertiary treated water is transported to a pH adjustment device through a lift pump for pH adjustment treatment to obtain quaternary treated water with a pH value of 7.5 ± 0.5; Perform real-time monitoring on the fourth-stage treated water. When the suspended solid concentration exceeds 100 mg / L, automatically adjust the chemical dosage to obtain the fifth-stage treated water with stable water quality parameters. Transport the fifth-stage treated water to the ozone micro-nano bubble water preparation unit through a closed pipeline to obtain the pretreated effluent.

[0021] Specifically, when treating sewage, initially separate solid substances from the raw water through the grid interception process. The grid equipment uses stainless steel grid bars with a spacing of 10 mm arranged in parallel to form an interception net. When the sewage flows through the grid, large-sized solid substances such as plastic bags, branches, and fibers are effectively intercepted. Mechanical slag removal is adopted for grid interception. An automatic slag scraper is installed on the upper part of the grid. When the pressure difference sensor detects that the head loss reaches the set value, the slag scraper is automatically started to remove the solid substances accumulated on the grid bars. In actual operation, liquid level difference sensors are set before and after the grid. When the liquid level difference exceeds 10 cm, the control system issues a slag removal command. After treatment by grid interception, large-sized solid substances are effectively removed, forming the primary treated water.

[0022] The primary treated water is transported to the aerated grit chamber for grit removal by gravity flow or a lift pump. The aerated grit chamber adopts a rectangular structure with a length-width ratio of 4:1. An aeration system is set at the bottom of the tank, and the air-water ratio is strictly controlled at 1:8, that is, 1 cubic meter per hour of air volume is equipped for every 8 cubic meters of water volume. The horizontal flow velocity in the tank is precisely adjusted to 0.3 m / s through the inlet gate. This flow velocity can ensure that sand grains with a specific gravity greater than 1.65 and a particle size greater than 0.2 mm settle under the action of gravity, while organic matter is retained under the action of air flotation to avoid loss of organic matter. A spiral sand conveyor is set at the bottom of the grit chamber to regularly transport the deposited sand grains to the sand-water separator. The separated sand grains are regularly removed, and the separated water is returned to the front end of the system. The sand grains that may cause wear to the subsequent treatment equipment have been removed in the secondary treated water produced by this process.

[0023] The secondary treated water enters the regulation tank for water quality and quantity equalization treatment. The volume of the regulation tank is designed according to 25% of the daily sewage treatment volume to ensure that the water volume fluctuation within 8 hours can be effectively regulated. Submersible mixing equipment is installed in the tank, with a mixing power density of 20 W / m³ and a mixing paddle rotation speed of 60 revolutions per minute to ensure complete mixing of the water body in the tank and avoid water quality stratification and local precipitation. Four water level sensors are set in the regulation tank at 25%, 50%, 75%, and 100% water levels respectively. The start and stop of the outlet pump are automatically controlled according to the water level signal to ensure uniform and stable water outlet. The mixing effect in the regulation tank makes water quality parameters such as COD, BOD, and pH tend to be balanced, reducing the impact load on the subsequent treatment units and producing the tertiary treated water with balanced water quality and quantity.

[0024] The tertiary treated water is pumped by the regulating tank lift pump and conveyed to the pH regulating device. The pH regulating device includes an on-line pH meter, a chemical dosing device, and a mixing reaction tank. The on-line pH meter uses a bipolar glass electrode with a measurement accuracy of ±0.1 pH unit and a measurement frequency of once every 10 seconds. When it is detected that the pH of the tertiary treated water deviates from the set value, the control system calculates the required chemical dosage according to the deviation magnitude and adds the acid-base regulator to the mixing reaction tank through the chemical dosing pump. The mixing reaction tank adopts a mechanical stirring method with a stirring intensity of 100 revolutions per minute to ensure sufficient mixing of the regulator and water. The pH control adopts a PID control algorithm with a proportional coefficient Kp = 0.8, an integral time Ti = 30 seconds, and a derivative time Td = 5 seconds. By adjusting the chemical dosage, the pH value is stabilized within the range of 7.5 ± 0.5, and this range is the optimal pH interval for the ozone oxidation reaction. The quaternary treated water after pH adjustment creates favorable conditions for the subsequent ozone micro-nano bubble water oxidation. The quaternary treated water enters the on-line monitoring system for real-time water quality monitoring. The monitoring system includes a suspended solid concentration sensor, a turbidimeter, and an automatic sampler. The suspended solid concentration sensor adopts the light scattering principle with a measurement range of 0 - 1000 mg / L, an accuracy of ±5%, and a measurement frequency of once every 5 minutes. The turbidimeter adopts the 90° scattered light measurement principle with a measurement range of 0 - 100 NTU and an accuracy of ±2%. When it is monitored that the suspended solid concentration exceeds 100 mg / L, the control system starts the automatic adjustment program and calculates the additional coagulant dosage required according to the exceeding degree. The chemical dosage calculation formula is based on a linear relationship, that is, the increased value of the chemical dosage = K × (measured suspended solid concentration - 100), where K is the proportional coefficient determined by experiments according to different coagulants and sewage characteristics. By automatically adjusting the chemical dosage, it is ensured that the suspended solid content in the effluent is stabilized below 100 mg / L, and the quinary treated water with stable water quality parameters is produced.

[0025] The quinary treated water is conveyed to the ozone micro-nano bubble water preparation unit through a closed pipeline system. The closed pipeline is made of PVC material with a diameter of 100 mm and a designed flow rate of 0.8 m / s. The pipeline system includes a flow meter, a pressure gauge, and an automatic control valve. The flow meter is electromagnetic with a measurement range of 0 - 100 cubic meters per hour and an accuracy of ±1% to monitor the conveying flow rate in real time. The pressure gauges are installed at the high and low points of the pipeline to monitor the pressure changes in the pipe network. The automatic control valve automatically adjusts the flow rate according to the requirements of the ozone micro-nano bubble water preparation unit to ensure stable water supply. The conveying pipe network is designed as a fully closed system to prevent external air from entering and causing water quality changes, and at the same time avoid the leakage of odors during the treatment process. The quinary treated water conveyed through the closed pipeline serves as the pre-treated effluent, providing a stable and high-quality water source for the subsequent ozone micro-nano bubble water preparation and ensuring the generation efficiency and quality of the ozone micro-nano bubble water.

[0026] In a specific embodiment, the process of executing step S102 may specifically include the following steps: Compress air through an oil-free air compressor to 0.8 MPa with a flow rate of 10 cubic meters per hour to obtain compressed air; Input the compressed air into a pressure swing adsorption air dryer for drying treatment to reduce the dew point to -40°C to obtain dry air; Carry out oxygen-nitrogen separation treatment on the dry air through an oxygen generator based on the pressure swing adsorption principle. The adsorbent is selected as molecular sieve 13X to obtain high-purity oxygen; Introduce the high-purity oxygen into an ozone generator using dielectric barrier discharge technology for discharge treatment. The discharge frequency is 600 - 1200 Hz, and the cooling water temperature is controlled at 15 - 20°C to obtain ozone gas; Carry out concentration detection treatment on the ozone gas with a detection accuracy of ±2%. Adjust the discharge power through frequency conversion to obtain stable ozone gas with a concentration stabilized at 200 ± 10 g / standard cubic meter; Transport the stable ozone gas through an anti-backflow valve and a flow meter. The accuracy of the flow meter is ±1.5% to obtain high-concentration ozone gas.

[0027] Specifically, an oil-free air compressor is selected to avoid the interference of oil-gas mixing on subsequent ozone generation. The oil-free air compressor uses piston rings and cylinder walls made of polytetrafluoroethylene, and the reciprocating motion of the piston is driven by the rotation of the crankshaft to achieve air compression. An air coarse filter with a filtration accuracy of 10 microns is installed at the compressor inlet to remove dust particles in the air. When the compressor is running, the rotational speed is controlled at 1450 revolutions per minute, and the outlet pressure is monitored in real time. When the pressure reaches 0.85 MPa, the pressure sensor sends a signal, and the frequency converter automatically adjusts the motor power to keep the pressure stable at 0.8 MPa. At the same time, the flow control system maintains a stable flow rate of 10 cubic meters per hour, and the fluctuation range is controlled within ±0.2 cubic meters per hour. To prevent the high temperature generated during the compression process from affecting the gas quality, the compressor is equipped with a water cooling system to maintain the exhaust temperature not exceeding 60°C.

[0028] Compressed air contains a large amount of moisture, which will seriously affect the subsequent ozone generation efficiency. Therefore, deep drying treatment must be carried out. The pressure swing adsorption air dryer contains two adsorption towers in parallel, filled with activated alumina adsorbent with a particle size of 3-5 mm and a bulk density of 700 kg / m³. The drying process uses the pressure swing adsorption principle, and the two towers work alternately. One tower adsorbs while the other tower is regenerated. The adsorption cycle is set to 5 minutes, the regeneration cycle is set to 4 minutes, and the switching time is 1 minute. The adsorption process is carried out at a pressure of 0.8 MPa. In the regeneration process, the pressure is first reduced to atmospheric pressure through a pressure reducing valve, and then a part of the dried air (15% of the total flow) is introduced for backwashing regeneration. A dew point sensor is installed inside the adsorption tower. When the outlet dew point exceeds -35°C, the control system automatically extends the regeneration time. A precision filter is installed at the dryer outlet with a filtration accuracy of 1 μm to ensure that the dew point of the outlet dry air is stably below -40°C and the oil content is less than 0.01 mg / m³. The dried air enters the oxygen generator for oxygen-nitrogen separation treatment. The oxygen generator also uses the pressure swing adsorption principle, but the adsorbent is selected as molecular sieve 13X, which has a three-dimensional pore structure with a pore diameter of 10 Å and a selective adsorption ability for nitrogen that is 3.5 times that of oxygen. The oxygen generator consists of two adsorption columns, a pressure regulating valve, an electromagnetic switching valve, and a control system. The working pressure is 0.6 MPa, the adsorption cycle is 60 seconds, the regeneration cycle is 50 seconds, and the switching time is 10 seconds. To improve the oxygen purity, a two-stage purification process is adopted: the first-stage adsorption mainly removes nitrogen, and the second-stage adsorption further purifies oxygen. An oxygen purity analyzer is set at the system outlet, using paramagnetic analysis method, with a measurement range of 0-100% and an accuracy of ±0.5%. Real-time monitoring shows that the oxygen purity at the outlet of the oxygen generator is stably above 93%, and the output reaches 5 m³ / h.

[0029] High-purity oxygen is introduced into the ozone generator for discharge treatment to generate ozone. The ozone generator uses dielectric barrier discharge technology and consists of a quartz glass tube, stainless steel electrodes, a high-voltage power supply, and a cooling system. The quartz glass tube serves as the dielectric with a thickness of 1.5 mm and a diameter of 25 mm; one stainless steel electrode is set inside the glass tube and the other is set outside the glass tube to form an annular discharge gap with a gap of 2 mm. The high-voltage power supply provides high-frequency high-voltage electricity of 600-1200 Hz with a voltage of 8-12 kV. During the discharge process, high-energy electrons strike oxygen molecules, decomposing them into oxygen atoms, and the oxygen atoms combine with oxygen molecules to form ozone. To prevent the heat generated by the discharge from decomposing ozone, the cooling system continuously circulates cooling water with a flow rate of 2 m³ / h. The inlet water temperature is controlled at 10°C, and the outlet water temperature does not exceed 25°C to ensure that the temperature in the discharge area is stably within the range of 15-20°C. A temperature sensor is installed inside the ozone generator. When the temperature exceeds 22°C, the cooling water flow rate is automatically increased.

[0030] After the ozone gas is generated, it is continuously monitored by an on-line ozone concentration detection system. The detection system uses the ultraviolet absorption method. Based on the ultraviolet light intensity absorption characteristics of ozone at a wavelength of 254 nm, the measurement range is 0 - 300 g / standard cubic meter, and the detection accuracy is ±2%. The detection system collects data every 10 seconds and calculates the control signal according to the deviation between the measurement result and the set value. The control system uses the PID control algorithm (proportional coefficient Kp = 0.5, integral time Ti = 20 s, derivative time Td = 3 s), and adjusts the discharge power through a frequency converter. When the detected ozone concentration is lower than 190 g / standard cubic meter, the system automatically increases the discharge power; when the concentration is higher than 210 g / standard cubic meter, the system automatically reduces the discharge power to ensure that the ozone concentration is stable at 200 ± 10 g / standard cubic meter. At the same time, the system continuously records the ozone production and the change trend of the concentration, providing data support for the adjustment of equipment operation.

[0031] The stable ozone gas is transported to the micro-nano bubble generator through a dedicated transportation system. The transportation system consists of a polytetrafluoroethylene pipe made of ozone-resistant material, a non-return valve, a flow meter, and a pressure gauge. The inner diameter of the pipe is 15 mm, the wall thickness is 3 mm, and the pressure resistance is 1.5 MPa to ensure no ozone leakage and decomposition during transportation. The non-return valve is of the spring-loaded type with an opening pressure of 0.02 MPa to prevent the reverse flow of air caused by system pressure fluctuations. The flow meter is a thermal mass flow meter with a measurement range of 0 - 6 cubic meters per hour, an accuracy of ±1.5%, and a display resolution of 0.01 cubic meters per hour. The outlet pressure of the system is accurately controlled at 0.25 MPa to ensure that the ozone gas enters the micro-nano bubble generator at a stable pressure. To ensure operation safety, the system is equipped with an ozone leakage detector. When the ambient ozone concentration exceeds 0.1 mg / cubic meter, the emergency shutdown procedure is automatically started and the exhaust system is turned on.

[0032] In a specific embodiment, the process of performing step S103 may specifically include the following steps: Perform pressure adjustment on the pretreated effluent to 0.35 MPa to obtain a stabilized pretreated water; Perform intake pressure adjustment on the high-concentration ozone gas to 0.25 MPa to obtain a stabilized ozone gas; Input the stabilized pretreated water and the stabilized ozone gas into a shear swirl type micro-nano bubble generator with an inner swirl chamber diameter of 50 mm and a swirl angle of 60 degrees at a gas-liquid ratio of 1:5, and the tangential inlet flow rate reaches 15 m / s to obtain primary ozone micro-nano bubble water; Transport the primary ozone micro-nano bubble water through a polytetrafluoroethylene pipeline made of ozone-resistant material with a pipe diameter of 50 mm and the flow rate controlled at 1.2 m / s to obtain ozone micro-nano bubble water with stable transmission; Parameter monitoring and processing are carried out on the ozone micro-nano bubble water with stable transmission, including ozone concentration, bubble diameter, and zero potential, to obtain optimized ozone micro-nano bubble water with an ozone concentration of 15 mg / L, a bubble number density of not less than 1×10 8 pieces / ml, and a zero potential of -25 mV; The optimized ozone micro-nano bubble water is input into a buffer tank with a volume of 1 cubic meter for buffering treatment to obtain ozone micro-nano bubble water.

[0033] Specifically, the pretreatment effluent pressure regulation treatment is a key link to ensure the stable generation of micro-nano bubble water. The pretreatment effluent is pressurized and transported by a centrifugal pump. The pump selected is a single-stage centrifugal pump with Q = 30 cubic meters per hour and H = 45 meters, a motor power of 5.5 kilowatts, and a speed of 2900 revolutions per minute. A pressure transmitter is set at the pump outlet, with a measurement range of 0 - 1 MPa and an accuracy class of 0.5. The measurement signal is transmitted to the PLC control system through 4 - 20 mA current. The control system adopts a pressure PID control algorithm (proportional coefficient Kp = 0.6, integral time Ti = 15 seconds, derivative time Td = 2 seconds). According to the deviation between the real-time pressure and the set value of 0.35 MPa, the pump speed is adjusted through a frequency converter to achieve precise pressure control. The system sets a pressure fluctuation alarm limit of ±0.03 MPa. When the range is exceeded, the system automatically issues an alarm signal and makes adjustments. To prevent water hammer phenomenon, an airbag-type buffer tank is set in the pipeline, with a volume of 100 liters and a pre-charging pressure of 0.2 MPa, effectively reducing pressure fluctuations. The inlet pressure regulation of high-concentration ozone gas uses a special gas pressure reducing valve. The pressure reducing valve selected is a diaphragm-type precision pressure reducing valve, with a diaphragm made of polytetrafluoroethylene and a spring made of stainless steel. The inlet pressure range of the pressure reducing valve is 0.5 - 1.0 MPa, and the outlet pressure adjustable range is 0.1 - 0.4 MPa. A pressure gauge is set at the outlet of the pressure reducing valve, with a measurement range of 0 - 0.6 MPa and an accuracy class of 1.0, and a scale value of 0.01 MPa. The operator manually adjusts the adjusting bolt on the pressure reducing valve according to production requirements to make the outlet pressure stable at 0.25 MPa. The system is also equipped with a safety relief valve, with a set pressure of 0.35 MPa, which automatically opens to relieve pressure when the system pressure exceeds the set value to prevent the system from overpressuring. A demister is also set in the gas pipeline to remove possible trace moisture in the pipeline, ensure the ozone gas is dry and pure, prevent the decomposition of ozone by moisture, and ensure the stability of the ozone gas concentration.

[0034] The pressure-stabilized pre-treated water and the pressure-stabilized ozone gas enter the shear cyclone-type micro-nano bubble generator at a gas-liquid ratio of 1:5. The core component of the generator is the cyclone chamber with an inner diameter of 50 mm, made of 316L stainless steel. The inner wall is precision machined with a roughness Ra ≤ 0.4 μm. The pressure-stabilized pre-treated water enters from the tangential direction of the side wall of the cyclone chamber, with an inlet pipe diameter of 20 mm and the flow rate strictly controlled at 15 m / s. The pressure-stabilized ozone gas enters axially from the center of the cyclone chamber, with an inlet pipe diameter of 10 mm. The swirl angle is designed to be 60 degrees, which can produce the best shearing effect. A strong spiral flow is formed in the cyclone chamber, with the tangential velocity of the water reaching 20 m / s and the radial velocity gradient exceeding 2000 / s, generating a huge shearing force to shear the ozone gas into micro-nano bubbles with a diameter of 100 nm - 10 μm. A back-pressure valve is set at the outlet of the generator, and the back-pressure value is set at 0.15 MPa to ensure an appropriate pressure is maintained in the cyclone chamber, which is beneficial to the stable formation of micro-nano bubbles.

[0035] The primary ozone micro-nano bubble water is transported to the subsequent treatment unit through a dedicated pipeline system. The pipeline is made of polytetrafluoroethylene, which has excellent ozone resistance to avoid ozone being absorbed and decomposed by the pipe material. The pipe diameter is designed to be 50 mm, the wall thickness is 4 mm, and the pressure-bearing capacity is 1.0 MPa. The flow rate during transportation is controlled at 1.2 m / s, which can not only ensure that the micro-nano bubbles do not coalesce but also avoid the increase in energy consumption caused by too high a flow rate. The pipeline system is designed to be fully enclosed to reduce ozone escape. The pipeline joints are connected by flanges, and the sealing gasket is made of polytetrafluoroethylene material. A bracket is set every 10 m to fix the pipeline and prevent pipeline vibration. Flow meters and pressure gauges are set at key points of the system to monitor the flow rate and pressure changes in real time. The flow meter is electromagnetic, with a measurement range of 0 - 50 m³ / h and an accuracy of ±1%; the pressure gauge has a measurement range of 0 - 1 MPa and an accuracy class of 1.0.

[0036] The ozone micro-nano bubble water parameter monitoring system includes ozone concentration, bubble diameter, and zero potential monitoring equipment. The ozone concentration is monitored by the indigo colorimetric method. After the water sample is mixed with the indigo reagent, the absorbance is measured at a wavelength of 600 nm by a spectrophotometer, and the ozone concentration is calculated according to the standard curve, with a measurement range of 0 - 30 mg / L and an accuracy of ±3%. The bubble diameter is monitored by dynamic light scattering technology, with a measurement range of 1 nm - 100 μm. The wavelength of the instrument's laser light source is 650 nm, the scattering angle is 90 degrees, and the acquisition time is 30 s to obtain the bubble diameter distribution and number density data. The zero potential is monitored by the potentiometer method, with the electrode material being platinum and the reference electrode being a saturated calomel electrode, with a measurement range of ±100 mV and an accuracy of ±1 mV. After the monitored parameters reach the set values (ozone concentration of 15 mg / L, bubble number density not less than 1×10 8 pieces / mL, zero potential of -25 mV), it is confirmed as the optimized ozone micro-nano bubble water.

[0037] Optimize the input buffer tank for ozone micro-nano bubble water for temporary buffering. The volume of the buffer tank is 1 cubic meter, and the material is stainless steel lined with polytetrafluoroethylene. The design pressure is 0.6 MPa. The tank body adopts a vertical structure, and the height-diameter ratio is 2:1. An exhaust valve is set at the top of the tank to discharge the gas that may accumulate; a drain valve is set at the bottom of the tank to regularly discharge the sediment. A liquid level sensor is set inside the tank, which adopts the magnetostrictive principle, with a measurement accuracy of ±5 mm. The measurement signal is transmitted to the control system. When the liquid level is lower than 20%, water replenishment is automatically started; when the liquid level is higher than 90%, the water outlet mode is automatically switched. A temperature sensor is also set in the buffer tank to control the temperature within the range of 15 - 25 °C to prevent the accelerated decomposition of ozone caused by too high temperature. A flow regulating valve is set at the outlet of the buffer tank to adjust the water outlet flow according to the subsequent treatment requirements, ensuring that the ozone micro-nano bubble water is transported to the treatment unit for refractory pollutants at a stable flow rate and guaranteeing the stability of the treatment effect.

[0038] In a specific embodiment, the process of executing step S104 may specifically include the following steps: Input the ozone micro-nano bubble water into the bottom of a vertical flow reactor with a height-diameter ratio of 3:1, an effective volume of 5 cubic meters, and a material of 316L stainless steel lined with polytetrafluoroethylene through a spiral water distribution device to obtain uniformly distributed active oxidants; Introduce the refractory pollutants from the top of the reactor to contact and treat with the uniformly distributed active oxidants. The hydraulic retention time is 30 minutes to obtain a preliminarily mixed reaction liquid; Perform a Z-shaped flow treatment on the preliminarily mixed reaction liquid through 3 baffle plates with a spacing of 1 meter to extend the contact time and obtain a fully reacted mixed liquid; Perform temperature control treatment on the fully reacted mixed liquid, and maintain the temperature at 20 - 25 °C through a jacket cooling system to obtain an oxidation mixed liquid under the optimal reaction conditions; Perform real-time monitoring treatment on the oxidation mixed liquid under the optimal reaction conditions, including COD analysis, pH value, dissolved oxygen, and redox potential measurement. When the COD removal rate is insufficient, automatically adjust the dosage of ozone micro-nano bubble water to obtain a treatment liquid with a stable oxidation effect; Discharge the treatment liquid with a stable oxidation effect from the water outlet of the reactor to obtain the preliminarily oxidized effluent.

[0039] Specifically, the ozone micro-nano bubble water enters the bottom of the vertical flow reactor through a dedicated delivery system. The vertical flow reactor adopts a cylindrical structure with a height-to-diameter ratio of 3:1, a height of 3.6 meters, a diameter of 1.2 meters, and an effective volume of 5 cubic meters. The reactor is made of 316L stainless steel lined with polytetrafluoroethylene, and the lining thickness is 2 millimeters to ensure the inner wall of the reactor is resistant to ozone corrosion. A spiral water distribution device is set at the bottom of the reactor. The device consists of a main pipe and four spiral branch pipes distributed at 90 degrees. The branch pipes are evenly drilled with small holes with a diameter of 6 millimeters, the hole spacing is 50 millimeters, and the total number of small holes is 96. The ozone micro-nano bubble water is evenly distributed at the bottom of the reactor through the water distribution device at a flow rate of 1.5 cubic meters per hour, forming an upward flow of active oxidants. The spiral structure of the water distribution device generates a rotating flow to prevent local short-circuiting, and the distribution uniformity coefficient is greater than 0.9, ensuring the uniform distribution of the ozone micro-nano bubble water across the cross-section of the reactor. The refractory pollutants are introduced from the center of the top of the reactor. The inlet pipe is made of stainless steel with a diameter of 80 millimeters. A porous distributor is set at the end of the pipe, with a pore diameter of 10 millimeters and 36 holes, evenly distributed in a ring shape. The refractory pollutants are introduced at a flow rate of 3 cubic meters per hour, forming a convective contact with the ozone micro-nano bubble water rising from the bottom. The two fluids are fully mixed under the complex flow field in the reactor to form a preliminarily mixed reaction solution. The reactor volume is designed to precisely control the hydraulic retention time at 30 minutes, which is the optimal reaction time determined through bench-scale and pilot-scale experiments. The formula for the retention time is t = V / Q, where V is the effective volume of the reactor, which is 5 cubic meters, and Q is the total flow rate of 4.5 cubic meters per hour (including the flow rate of the ozone micro-nano bubble water of 1.5 cubic meters per hour and the pollutant flow rate of 3 cubic meters per hour).

[0040] The preliminarily mixed reaction solution is guided in the reactor through three layers of baffle plates. The baffle plates are made of polytetrafluoroethylene, with a thickness of 8 mm and a width of 0.9 m (75% of the inner diameter of the reactor). The distance between the baffle plates is 1 m, and the three layers of baffle plates are sequentially arranged at 0.8 m, 1.8 m, and 2.8 m from the bottom of the reactor. The first and third layers of baffle plates extend from the left side to the right side of the reactor, leaving a 0.3 m channel in the middle; the second layer of baffle plates extends from the right side to the left side, also leaving a 0.3 m channel. This setting makes the mixed solution form a "Z"-shaped flow path, effectively extending the contact time between ozone micro-nano bubbles and pollutants and increasing the reaction time. Through computational fluid dynamics analysis, this design extends the theoretical contact time from 30 minutes to an actual contact time of about 45 minutes, and the flow uniformity coefficient is increased to 0.94, significantly improving the reaction effect. Temperature control is extremely important during the reaction process, directly affecting the stability of ozone and the oxidation reaction rate. A jacket cooling system is set on the outer wall of the reactor. The height of the jacket is 3.4 m and the width is 10 cm. The cooling water forms a spiral upward flow in the jacket to ensure uniform heat exchange. The inlet temperature of the cooling water is controlled at 15°C, and the flow rate is 10 m³ / h. The cooling water flow rate is controlled by a three-way regulating valve to achieve precise temperature control. Three PT100 temperature sensors are set in the reactor, located at the bottom, middle, and top respectively, with a temperature measurement accuracy of ±0.1°C. The measurement signals are transmitted to the temperature controller. The controller adopts a PID temperature control algorithm (proportional coefficient Kp = 1.2, integral time Ti = 120 s, derivative time Td = 30 s). According to the deviation between the actual temperature in the reactor and the set temperature (22.5°C), it automatically adjusts the cooling water flow rate to stably control the reaction temperature within the range of 20 - 25°C to ensure the best oxidation reaction conditions.

[0041] Real-time monitoring of the water quality parameters of the oxidation mixture is crucial to ensure the treatment effect. The monitoring system includes an online COD analyzer, a pH meter, a dissolved oxygen meter, and an oxidation-reduction potential meter. The online COD analyzer uses the potassium dichromate oxidation-colorimetric method, with a measurement range of 0-2000 mg / L, an accuracy of ±5%, and a measurement period of 30 minutes; the pH meter uses a composite glass electrode, with a measurement range of 0-14 and an accuracy of ±0.1 pH for continuous measurement; the dissolved oxygen meter uses the fluorescence method, with a measurement range of 0-20 mg / L and an accuracy of ±0.2 mg / L, and a measurement interval of 5 minutes; the oxidation-reduction potential meter uses a platinum electrode, with a measurement range of -2000 to +2000 mV and an accuracy of ±5 mV for continuous measurement. The monitoring data is transmitted to the control system in real time through an industrial communication network, and the system automatically calculates the dosage of ozone micro-nano bubble water based on the COD removal rate. When the detected COD removal rate is lower than the preset value (usually 50%), the control system automatically increases the dosage of ozone micro-nano bubble water, and the increment calculation formula is ΔQ = K×(target removal rate - actual removal rate), where K is the proportionality coefficient, determined according to the characteristics of the sewage, and the typical value is 0.05 m³ / h / percentage point.

[0042] The stabilized oxidation effect treatment liquid after comprehensive treatment is discharged from the outlet on the upper side wall of the reactor. The height of the outlet is 0.3 m below the top of the reactor, with a diameter of 100 mm, and an overflow weir is set to ensure the stability of the liquid level in the reactor. A flow meter and a sampling port are set on the outlet pipeline. The flow meter is electromagnetic, with a measurement range of 0-10 m³ / h and an accuracy of ±1% for real-time monitoring of the effluent flow; the sampling port automatically collects water samples every 4 hours and sends them to the laboratory for water quality analysis. The effluent is discharged into the next treatment unit after passing through a U-shaped water seal with a height of 30 cm to prevent gas escape. To monitor the reaction effect, the system sets an automatic comparison function to calculate the change rates of indicators such as COD, chromaticity, and pH of the influent and effluent, and generates a trend chart to provide data support for process adjustment. The COD removal rate in the preliminary oxidation effluent usually reaches over 50%, and the chromaticity removal rate reaches over 70%.

[0043] In a specific embodiment, the process of executing step S105 may specifically include the following steps: The effluent from the preliminary oxidation is introduced into a catalytic bed filled with an iron-based porous material supported titanium dioxide composite catalyst with a specific surface area greater than 200 m² / g and a pore size distribution in the range of 5-10 nm through a perforated plate distributor. The pore diameter of the distributor is 5 mm, and the porosity is 30%, to obtain uniformly distributed influent; The uniformly distributed influent is subjected to permeation treatment in the catalytic bed, with the flow rate controlled at 5 m / h, and a catalytic reaction occurs on the surface of the catalyst to obtain primary catalytic oxidation water; The primary catalytic oxidation water is treated by ultraviolet light irradiation with a wavelength of 365 nm, a light intensity of 10000 μW / cm², a lamp power density of 100 W / m², and a light uniformity of not less than 85% to obtain photocatalytically enhanced treated water; The photocatalytically enhanced treated water is subjected to water quality parameter monitoring, including COD, turbidity, and flow rate monitoring. When the catalytic effect decreases, the ultraviolet lamp irradiation intensity is automatically increased or the flow rate is adjusted to obtain advanced treated water with a stable catalytic effect; The operating resistance of the catalytic bed is monitored. When the resistance increases by 20%, the backwashing procedure is started. The backwashing intensity is 15 L / m²·s, and the backwashing time is 10 minutes to obtain a regenerated catalytic bed and backwash water; The backwash water is collected and returned to the regulation tank for recycling, and the advanced treated water with a stable catalytic effect is discharged as the advanced treatment effluent.

[0044] Specifically, the effluent from the preliminary oxidation enters the composite catalytic bed reactor for advanced treatment. The effluent is first introduced into the catalytic bed filled with the composite catalyst through a perforated plate distributor. The perforated plate distributor is made of 316L stainless steel with a thickness of 8 mm, a diameter of 1 m, the same as the inner diameter of the catalytic bed. It is evenly provided with round holes with a diameter of 5 mm, and the hole opening rate is precisely controlled at 30%. The number of holes is about 1145, and the hole spacing is 25 mm. This design enables the liquid to pass through each hole at a uniform flow rate, avoiding local short-circuiting, and the distribution uniformity coefficient reaches more than 0.95. The catalytic bed is filled with a composite catalyst of iron-based porous material supported by titanium dioxide. The catalyst is prepared by the impregnation method, using activated carbon as the carrier, loading iron oxide and titanium dioxide, with a specific surface area greater than 200 m² / g, the pore size distribution concentrated in the range of 5-10 nm, a filling height of 1.5 m, a packing density of 500 kg / m³, and a total filling amount of about 590 kg. The catalyst is in the form of 3-5 mm particles to ensure an appropriate porosity (about 40%) of the bed layer and reduce the water flow resistance.

[0045] The uniformly distributed influent flows through the catalytic bed in a downward direction for infiltration treatment. The flow rate is strictly controlled at 5 m / h, which is determined by experiments as the optimal treatment speed, ensuring both sufficient contact time and not causing excessive head loss. Differential pressure gauges are installed on both sides of the catalytic bed to monitor the head loss in real time. The head loss during normal operation is about 0.3 m water column. Multiple catalytic reactions occur on the surface of the catalyst: on the one hand, the iron-based material promotes the decomposition of ozone to generate more hydroxyl radicals (•OH); on the other hand, the residual ozone molecules in the water directly react with the pollutants. Ozone and hydroxyl radicals oxidize and decompose the refractory pollutants, decomposing the macromolecular organic matter into small molecular organic matter or inorganic matter.

[0046] The primary catalytic oxidation water enters the ultraviolet photocatalytic region for photocatalytic enhanced treatment. An ultraviolet lamp array is set above the catalytic bed. Forty ultraviolet lamps with a wavelength of 365 nanometers are used, each with a power of 40 watts, a length of 1.2 meters, and a spacing of 10 centimeters, and they are evenly distributed on the top of the reactor. The lamp tubes use quartz glass shells with a light transmittance greater than 90%. The depth of ultraviolet penetration into the water is about 30 centimeters. The total power of the ultraviolet lamp tubes is 1600 watts, the irradiation area is 16 square meters, the power density is 100 watts per square meter, and the light intensity is 10000 microwatts per square centimeter. Reflectors are set for the lamp tubes to enhance the lighting effect, and the lighting uniformity is not less than 85%. The ultraviolet light irradiates the surface of the titanium dioxide catalyst, exciting electron-hole pairs to generate reactive oxygen species and hydroxyl radicals, further oxidizing and decomposing residual pollutants. The water treated by photocatalytic enhancement enters the on-line monitoring system for real-time water quality monitoring. The monitoring system includes a COD analyzer, a turbidimeter, and a flowmeter. The COD analyzer uses the ultraviolet digestion-colorimetric method, with a measurement range of 0-1000 milligrams per liter, an accuracy of ±3%, and a detection period of 15 minutes; the turbidimeter uses the 90° scattered light principle, with a measurement range of 0-100 NTU, an accuracy of ±2%, and continuous measurement; the flowmeter uses an electromagnetic type, with a measurement range of 0-10 cubic meters per hour, an accuracy of ±0.5%, and continuous measurement. The monitoring data is transmitted to the control system through the RS-485 communication interface, and the system automatically adjusts the treatment conditions according to the water quality parameters. When it is detected that the catalytic effect decreases (the COD removal rate decreases by more than 5%), the system first increases the irradiation intensity of the ultraviolet lamp by 10-30%, which is achieved through the dimming module; if the irradiation intensity has reached the maximum value and the effect is still not good, the flow rate is automatically reduced by 20% to extend the contact time. After adjustment, the system continuously monitors for 5 detection cycles to confirm that the catalytic effect returns to stability, and the advanced treated water with a COD removal rate reaching more than 70% is produced.

[0047] The long-term operation of the catalytic bed will cause pollutants and sediments to accumulate on the surface of the catalyst, resulting in an increase in resistance and a decrease in treatment efficiency. A differential pressure sensor is set in the system to monitor the operating resistance of the catalytic bed in real time, with a measurement range of 0-1 meter of water column and an accuracy of ±1%. The initial resistance value is recorded as the reference value. When it is monitored that the resistance increases by 20%, the control system automatically starts the backwashing procedure. The backwashing adopts the combined air-water backwashing method. First, the inlet valve and the outlet valve are closed, and the backwashing water valve and the backwashing air valve are opened. The backwashing water flows upward from the bottom of the catalytic bed at a flow rate of 15 liters per square meter per second, and the backwashing air flow rate is 60 liters per square meter per second. The backwashing lasts for 10 minutes to fully expand the catalyst bed layer and remove the pollutants attached to the surface of the catalyst. An observation window is set during the backwashing process to observe the expansion of the bed layer, and the expansion height is controlled at about 50%. After the backwashing is completed, the system automatically enters the normal operating state, and the resistance of the catalytic bed returns to the initial level.

[0048] Backwashing water is collected into a collection tank through a dedicated pipeline. The volume of the collection tank is 10 cubic meters, and the residence time is 2 hours to preliminarily settle suspended solids. The supernatant is transported back to the regulation tank for cyclic treatment by a lift pump. The pump flow rate is 5 cubic meters per hour, the head is 20 meters, and the power is 1.5 kilowatts. The sediment at the bottom of the collection tank is cleaned once a month and sent to the sludge treatment system. Cyclic treatment not only saves water resources but also avoids environmental pollution that may be caused by the direct discharge of backwashing water. At the same time, the advanced treated water with stable catalytic effect is discharged from the lower outlet of the reactor. A flow control valve is set at the outlet to adjust the water discharge according to the subsequent treatment requirements.

[0049] In a specific embodiment, the process of executing step S106 may specifically include the following steps: Collect and aggregate the ozone-containing tail gas generated by the vertical flow reactor and the composite catalytic bed reactor for treatment to obtain the tail gas to be treated; Introduce the tail gas to be treated into a packed tower with a height of 3 meters and a diameter of 0.5 meters for absorption treatment. The packing uses ceramic Raschig rings with a specific surface area of 220 square meters per cubic meter. The absorption liquid is 5% sodium carbonate solution, the liquid-gas ratio is 3:1, and the absorption temperature is controlled at 25°C to obtain the primary treated tail gas with an absorption efficiency of not less than 90%; Catalytically decompose the primary treated tail gas through a manganese oxide-based catalyst. The catalytic temperature is 40°C, and the space velocity is 5000 h -1 , to obtain the qualified tail gas with an ozone decomposition efficiency greater than 99.5%; Conduct ozone concentration detection treatment on the qualified tail gas to ensure that the ozone concentration is less than 0.1 mg / m³ to obtain the safe tail gas meeting the emission standards; Collect and process the operation data during the treatment process through a distributed control system, including water quality parameters, equipment status, energy consumption data, and chemical consumption data, to obtain the system operation database; Automatically adjust the system operation parameters according to the system operation database, including ozone generation amount, micro-nano bubble water preparation conditions, reaction time, and catalyst regeneration time, to obtain the optimized system operation parameters.

[0050] Specifically, ozone-containing tail gas will be generated during the operation of the vertical flow reactor and the composite catalytic bed reactor, which needs to be properly treated before being discharged. The tail gas collection system consists of a gas collection hood, a pipe and a negative pressure fan. A gas collection hood with a diameter of 1.5 meters and a height of 0.5 meters is set on the top of the vertical flow reactor. It is made of polypropylene; multiple gas collection ports are set on the top and side of the composite catalytic bed reactor, each with a diameter of 100 mm. The collected tail gas is merged into the main pipeline through a pipeline. The main pipe is made of polyvinyl chloride with a diameter of 200 mm. A flow meter and a pressure gauge are set on the pipeline. The flow meter uses a thermal mass flow meter with a measurement range of 0-100 cubic meters / hour and an accuracy of ±2%; the pressure gauge has a measurement range of -5000 to +1000 Pa, an accuracy of ±20 Pa, and real-time monitoring of the tail gas flow and pressure. The negative pressure fan is centrifugal, with an air volume of 100 cubic meters per hour, an air pressure of 2000 Pa, a motor power of 1.1 kilowatts, a speed of 2900 rpm, and adopts frequency conversion control to automatically adjust the speed according to the pipeline pressure to maintain a stable negative pressure environment and ensure that the exhaust gas does not leak.

[0051] The tail gas to be treated is introduced into the packed absorption tower for wet absorption treatment. The packed tower adopts a cylindrical structure, with a height of 3 meters and a diameter of 0.5 meters. It is made of fiberglass and has a design pressure of ±5000 Pa. The tower is filled with ceramic Raschig ring packing, with a packing specification of 25 mm × 25 mm × 3 mm, a specific surface area of ​​220 square meters / cubic meter, a porosity of 92%, and a filling height of 2.5 meters. The absorption liquid adopts a 5% sodium carbonate solution, which is evenly sprayed on the top of the packing through a liquid distributor. The distributor is rotary, with a rotation speed of 3 rpm, 16 nozzles, a diameter of 2 mm, and uniform distribution. The liquid-gas ratio is strictly controlled at 3:1, that is, 3 liters of absorption liquid are equipped for every cubic meter of tail gas. A temperature sensor is set in the tower, using a PT100 type, with a measurement accuracy of ±0.2℃, and the temperature of the absorption tower is controlled to be stable at 25℃ through a circulating water jacket. The absorption liquid reacts with ozone. The primary treated tail gas enters the catalytic decomposition device for deep treatment. The catalytic decomposition device uses a fixed bed reactor with an inner diameter of 300 mm and a height of 600 mm, and is made of 304 stainless steel. The reactor is filled with a manganese oxide-based catalyst with a particle size of 3-5 mm, a filling height of 400 mm, and a filling volume of about 28 kg. The catalyst is prepared by the impregnation method. As carrier, load 20% and 5% CuO, and activated by roasting at 600℃ for 4 hours. The reactor is equipped with an electric heating device, which is wound with electric belts and has a power of 2 kW. It is equipped with a temperature controller and uses a PID control algorithm (proportional coefficient Kp=0.8, integral time Ti=60 seconds, differential time Td=15 seconds) to control the catalytic temperature to be stable at 40±1℃. The primary treatment tail gas is heated at a space velocity of 5000 hours. -1 Through the catalyst bed, the gas flow rate per hour is 5000 times the catalyst volume. On the catalyst surface, ozone decomposes into oxygen: , the decomposition efficiency is greater than 99.5%, and the up-to-standard tail gas with extremely low ozone concentration is obtained.

[0052] To ensure the up-to-standard discharge of the tail gas, an on-line ozone concentration detection system is set up. The detection system uses the ultraviolet absorption method, with a measurement range of 0 - 1 mg / m³, an accuracy of ±0.01 mg / m³, and a detection interval of 30 seconds. The detection device is installed at the outlet of the catalytic decomposition device to monitor the ozone concentration of the outlet gas in real time. When the detected ozone concentration is greater than 0.08 mg / m³, the system issues a warning signal; when the concentration is greater than 0.1 mg / m³, the system automatically adjusts the treatment parameters - first reducing the treatment air volume by 20%. If the requirements are still not met, the catalytic temperature is increased to 45°C, and at the same time, the concentration of the absorption liquid is increased to 6%. The system is equipped with 16 levels of ozone leakage alarms distributed around the equipment. When the ambient ozone concentration exceeds 0.1 mg / m³, it gives an audible and visual alarm and automatically starts the emergency fan to ensure the safety of the operating environment. The up-to-standard tail gas is discharged through a 15-meter-high exhaust stack, meeting the requirements of the Comprehensive Emission Standard for Air Pollutants.

[0053] The entire treatment system is monitored and data is collected in real time through a distributed control system (DCS). The DCS system consists of a field device layer, a control layer, and a management layer. The field device layer includes various sensors and actuators, which communicate with the control layer through I / O modules; the control layer uses redundant-configured controllers to run real-time monitoring software; the management layer includes operator stations, engineer stations, and historical data servers. The data collected by the system includes: the water quality parameters (COD, pH, turbidity, chromaticity, etc.) of the inlet and outlet water of each treatment unit (collection frequency: once every 15 minutes); the operating status of the equipment (current, rotation speed, pressure, temperature, etc., collection frequency: once every 1 minute); energy consumption data (power consumption, power factor, etc., collection frequency: once every 1 hour); chemical consumption data (ozone production, absorption liquid usage, etc., collection frequency: once every 1 hour). All data is preprocessed and then stored in the historical database to establish a tagged data model to support data mining and trend analysis.

[0054] Based on the collected operation data, the DCS system automatically optimizes and adjusts the system operation parameters through the built-in analysis module. The optimization algorithm adopts fuzzy neural network control, and a water quality characteristic - treatment parameter model is established through training with a large amount of historical data. The system first calculates the deviation between the current treatment effect and the target effect, and then selects an appropriate parameter adjustment strategy according to the classification of water quality characteristics. The specific adjustment parameters include: ozone generation amount (adjusted by regulating the discharge power, adjustment range ±20%); preparation conditions of micro-nano bubble water (mainly adjusting the gas-liquid ratio and swirl velocity, adjustment range ±15%); reaction time (adjusted by regulating the influent flow rate, adjustment range ±25%); catalyst regeneration time (advanced or postponed according to the pollutant characteristics and the change trend of the catalytic bed resistance, adjustment range ±2 days). The system evaluates the parameter adjustment effect every 12 hours and generates an optimization report, and the operator can perform manual intervention according to the report suggestions.

[0055] The method for oxidizing and decomposing refractory pollutants based on ozone micro-bubble water in the embodiments of the present application has been described above. Next, the system for oxidizing and decomposing refractory pollutants based on ozone micro-bubble water in the embodiments of the present application will be described. Please refer to Figure 2 One embodiment of the system for oxidizing and decomposing refractory pollutants based on ozone micro-bubble water in the embodiments of the present application includes: A treatment module for performing pretreatment such as grid interception, grit removal, and pH adjustment on sewage to obtain pretreated effluent; A discharge module for introducing air into an ozone generator for discharge treatment after compression, drying, and oxygen production to obtain high-concentration ozone gas; A mixing module for inputting the pretreated effluent and the high-concentration ozone gas into a shear swirl-type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; A reaction module for performing contact reaction treatment on the ozone micro-nano bubble water and the refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent; An introduction module for introducing the preliminarily oxidized effluent into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; An absorption module for absorbing and catalytically decomposing the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor.

[0056] Refer to Figure 3 In the embodiments of the present invention, a computer device is further provided. The computer device may be a server, and its internal structure may be as Figure 3As shown in the figure. The computer device includes a processor, a memory, a display screen, an input device, a network interface, and a database connected through a system bus. Among them, the processor of the computer design is used to provide computing and control capabilities. The memory of the computer device includes a non-volatile storage medium and an internal memory. The non-volatile storage medium stores an operating system, a computer program, and a database. The internal memory provides an environment for the operation of the operating system and the computer program in the non-volatile storage medium. The database of the computer device is used to store the corresponding data in this embodiment. The network interface of the computer device is used to communicate with an external terminal through a network connection. When the computer program is executed by the processor, the above method is implemented.

[0057] Those skilled in the art can understand that Figure 3 the structure shown in the figure is only a block diagram of a part of the structure related to the solution of the present invention, and does not constitute a limitation on the computer device to which the solution of the present invention is applied.

[0058] An embodiment of the present invention also provides a computer-readable storage medium, on which a computer program is stored. When the computer program is executed by a processor, the above method is implemented. It can be understood that the computer-readable storage medium in this embodiment can be a volatile readable storage medium or a non-volatile readable storage medium.

[0059] Those skilled in the art can clearly understand that for the convenience and simplicity of description, the specific working processes of the above-described systems, systems, and units can refer to the corresponding processes in the foregoing method embodiments and will not be described herein again.

[0060] If the integrated unit is implemented in the form of a software functional unit and sold or used as an independent product, it can be stored in a computer-readable storage medium. Based on this understanding, the technical solution of the present invention, in essence, or the part that contributes to the prior art, or all or part of the technical solution, can be embodied in the form of a software product. The computer software product is stored in a storage medium and includes several instructions for causing a computer device (which can be a personal computer, a server, or a network device, etc.) to execute all or part of the steps of the methods described in various embodiments of the present invention. The foregoing storage medium includes: USB flash drives, mobile hard disks, read-only memories (ROMs), random access memories (RAMs), magnetic disks, or optical discs, etc., which can store program codes.

[0061] As described above, the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for decomposing refractory pollutants by oxidation using ozone bubble water, characterized in that: include: The sewage is pre-treated by screen interception, sand settling and pH adjustment to obtain pre-treated effluent; The air is compressed, dried and oxygenated, then introduced into the ozone generator for discharge treatment to obtain high-concentration ozone gas; The pretreated water and the high-concentration ozone gas are input into a shear cyclone type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; The ozone micro-nano bubble water is contacted with the refractory pollutants for reaction treatment in a vertical flow reactor to obtain initially oxidized effluent; The effluent from the preliminary oxidation is introduced into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; The tail gas generated by the vertical flow reactor and the composite catalytic bed reactor is subjected to absorption and catalytic decomposition treatment.

2. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The sewage is pretreated by grid interception, sand settling and pH adjustment to obtain pretreated effluent, including: The sewage is intercepted and treated by a screen device with a spacing of 10 mm to obtain primary treated water with large-sized solid matter removed; The primary treated water is input into an aerated grit chamber with an air-water ratio of 1:8 for grit treatment, and the horizontal flow rate is controlled at 0.3 m / s to obtain secondary treated water with sand particles larger than 0.2 mm in diameter removed; The secondary treated water is homogenized in a regulating tank with a stirring power density of 20 watts / cubic meter, and the volume of the regulating tank is designed according to 25% of the daily sewage treatment volume, to obtain tertiary treated water with balanced water quality and quantity; The tertiary treated water is transported to a pH adjusting device through a lift pump for pH adjustment treatment to obtain quaternary treated water with a pH value of 7.5±0.5; The four-stage treated water is monitored in real time, and when the suspended matter concentration exceeds 100 mg / L, the dosage is automatically adjusted to obtain the five-stage treated water with stable water quality parameters; The five-stage treated water is transported to the ozone micro-nano bubble water preparation unit through a closed pipeline to obtain the pretreated effluent.

3. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The air is compressed, dried and oxygenated and then introduced into an ozone generator for discharge treatment to obtain high-concentration ozone gas, including: The air is compressed by an oil-free air compressor to 0.8 MPa with a flow rate of 10 cubic meters per hour to obtain compressed air; The compressed air is input into a pressure swing adsorption air dryer for drying, and the dew point is reduced to -40°C to obtain dry air; The dry air is subjected to oxygen-nitrogen separation treatment by a pressure swing adsorption oxygen generator, with molecular sieve 13X being selected as the adsorbent, to obtain high-purity oxygen; The high-purity oxygen is introduced into an ozone generator using dielectric barrier discharge technology for discharge treatment, the discharge frequency is 600-1200 Hz, and the cooling water temperature is controlled at 15-20° C. to obtain ozone gas; The ozone gas is subjected to concentration detection processing with a detection accuracy of ±2%, and the discharge power is adjusted by frequency conversion to obtain a stable ozone gas with a concentration of 200±10 g / standard cubic meter; The stable ozone gas is transported through an anti-backflow valve and a flow meter with an accuracy of ±1.5% to obtain the high-concentration ozone gas.

4. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The pre-treated water and the high-concentration ozone gas are input into a shear cyclone type micro-nano bubble generator for mixing to obtain ozone micro-nano bubble water, comprising: The pre-treated water is subjected to pressure regulation to a value of 0.35 MPa to obtain stabilized pressure pre-treated water; The high-concentration ozone gas is subjected to an inlet pressure adjustment process to be adjusted to 0.25 MPa to obtain a pressure-stabilized ozone gas; The stabilized pressure pretreated water and the stabilized pressure ozone gas are input into a shear swirl micro-nano bubble generator with an internal swirl chamber diameter of 50 mm and a swirl angle of 60 degrees at a gas-liquid ratio of 1:5, and the tangential inlet flow velocity reaches 15 m / s to obtain primary ozone micro-nano bubble water; The primary ozone micro-nano bubble water is transported through an ozone-resistant polytetrafluoroethylene pipe with a pipe diameter of 50 mm and a flow rate controlled at 1.2 m / s to obtain stably transmitted ozone micro-nano bubble water; The parameters of the stably transmitted ozone micro-nano bubble water were monitored, including ozone concentration, bubble particle size and zero potential, and the ozone concentration was 15 mg / L and the bubble number density was not less than 1×10 8 Optimized ozone micro-nano bubble water with 1000 g / ml and zero potential of -25 mV; The optimized ozone micro-nano bubble water is input into a buffer tank with a volume of 1 cubic meter for buffering treatment to obtain the ozone micro-nano bubble water.

5. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The step of subjecting the ozone micro-nano bubble water to contact reaction with the refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent water comprises: The ozone micro-nano bubble water is input into the bottom of a vertical flow reactor having a height-to-diameter ratio of 3:1, an effective volume of 5 cubic meters, and a material of 316L stainless steel lined with polytetrafluoroethylene through a spiral water distribution device to obtain a uniformly distributed active oxidant; Introducing the refractory pollutants from the top of the reactor and contacting them with the uniformly distributed active oxidants for a hydraulic retention time of 30 minutes to obtain a preliminarily mixed reaction solution; The preliminarily mixed reaction liquid is subjected to a Z-shaped flow treatment through three layers of baffles with a spacing of 1 meter to extend the contact time and obtain a fully reacted mixed liquid; The fully reacted mixed solution is subjected to temperature control treatment, and the temperature is maintained at 20-25° C. by a jacket cooling system to obtain an oxidized mixed solution under optimal reaction conditions; The oxidation mixed liquid under the optimal reaction conditions is subjected to real-time monitoring and treatment, including COD analysis, pH value, dissolved oxygen and redox potential measurement, and when the COD removal rate is insufficient, the dosage of ozone micro-nano bubble water is automatically adjusted to obtain a treatment liquid with a stable oxidation effect; The treated liquid with stable oxidation effect is discharged from the water outlet of the reactor to obtain the effluent of the preliminary oxidation.

6. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The step of introducing the effluent from the preliminary oxidation into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent comprises: The effluent from the preliminary oxidation is introduced into a catalytic bed filled with a titanium dioxide composite catalyst supported by an iron-based porous material with a specific surface area greater than 200 square meters / gram and a pore size distribution in the range of 5-10 nanometers through a porous plate distributor, the pore size of the distributor is 5 mm, and the opening rate is 30%, so as to obtain uniformly distributed influent; The uniformly distributed influent water is subjected to permeation treatment in a catalytic bed, the flow rate of which is controlled at 5 m / h, and a catalytic reaction occurs on the catalyst surface to obtain primary catalytic oxidation water; The primary catalytic oxidation water is subjected to ultraviolet irradiation treatment, with a wavelength of 365 nanometers, a light intensity of 10,000 microwatts per square centimeter, a lamp power density of 100 watts per square meter, and a light uniformity of not less than 85%, to obtain photocatalytically enhanced treated water; The photocatalytically enhanced treated water is subjected to water quality parameter monitoring, including COD, turbidity and flow rate monitoring, and when the catalytic effect decreases, the ultraviolet light irradiation intensity is automatically increased or the flow rate is adjusted to obtain deeply treated water with a stable catalytic effect; The catalyst bed is monitored for operating resistance. When the resistance increases by 20%, the backwashing procedure is started. The backwashing intensity is 15 L / m2·sec and the backwashing time is 10 minutes to obtain a regenerated catalyst bed and backwashing water. The backwash water is collected and returned to the regulating tank for circulation treatment, and the deep-treated water with a stable catalytic effect is discharged as the deep-treated effluent.

7. The method for decomposing refractory pollutants by oxidation using ozone bubble water according to claim 1, characterized in that: The process of absorbing and catalytically decomposing the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor comprises: The ozone-containing tail gas generated by the vertical flow reactor and the composite catalytic bed reactor is collected and processed to obtain tail gas to be treated; The tail gas to be treated is introduced into a packed tower with a height of 3 meters and a diameter of 0.5 meters for absorption treatment, the packing is a ceramic Raschig ring with a specific surface area of ​​220 square meters / cubic meter, the absorption liquid is a 5% sodium carbonate solution, the liquid-gas ratio is 3:1, and the absorption temperature is controlled at 25°C to obtain a primary treated tail gas with an absorption efficiency of not less than 90%; The primary treated tail gas is catalytically decomposed by a manganese oxide-based catalyst at a catalytic temperature of 40°C and a space velocity of 5000 h / h. -1 , obtaining tail gas that meets the standards with an ozone decomposition efficiency greater than 99.5%; Perform ozone concentration detection on the exhaust gas that meets the emission standards to ensure that the ozone concentration is less than 0.1 mg / m3, thereby obtaining safe exhaust gas that meets emission standards; The operation data in the treatment process is collected and processed through the distributed control system, including water quality parameters, equipment status, energy consumption data and reagent consumption data, to obtain the system operation database; The system operation parameters are automatically adjusted according to the system operation database, including the amount of ozone generated, micro-nano bubble water preparation conditions, reaction time and catalyst regeneration time, to obtain optimized system operation parameters.

8. A system for decomposing refractory pollutants by oxidation with ozone bubble water, used to implement the method for decomposing refractory pollutants by oxidation with ozone bubble water as described in any one of claims 1 to 7, characterized in that: include: A treatment module is used to pre-treat the sewage by grid interception, sand settling and pH adjustment to obtain pre-treated effluent; The discharge module is used to introduce the air into the ozone generator for discharge treatment after compression, drying and oxygen production to obtain high-concentration ozone gas; A mixing module, used for inputting the pretreated water and the high-concentration ozone gas into a shear cyclone type micro-nano bubble generator for mixing treatment to obtain ozone micro-nano bubble water; A reaction module, used for contacting and reacting the ozone micro-nano bubble water with refractory pollutants in a vertical flow reactor to obtain preliminarily oxidized effluent; An introduction module is used to introduce the effluent from the preliminary oxidation into a composite catalytic bed reactor for catalytic oxidation treatment to obtain deeply treated effluent; The absorption module is used for absorbing and catalytically decomposing the tail gas generated by the vertical flow reactor and the composite catalytic bed reactor.

9. A computer device comprising a memory and a processor, wherein the memory stores a computer program executable on the processor, wherein: When the processor executes the computer program, the method for decomposing refractory pollutants based on ozone bubble water oxidation according to any one of claims 1 to 7 is implemented.

10. A computer-readable storage medium having a computer program stored thereon, wherein when the computer program is executed by a processor, the processor is enabled to execute the method for decomposing refractory pollutants by oxidation using ozone bubble water as claimed in any one of claims 1 to 7.

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