CN108423883A - The method and apparatus of hydroxyl radical free radical degradation mineralising quinolone antibiotics - Google Patents

Abstract

The invention discloses a method and device for degrading mineralized quinolone antibiotics by hydroxyl radicals, and relates to quinolone antibiotics. The device is equipped with hydroxyl radical generation equipment, OH oxidation degradation antibiotic reactor, chlorine disinfection unit, flocculation tank, clarification tank, constant pressure filter tank, clear water tank, TRO online detector, mechanical pump, water flow meter, solenoid valve, Unit water outlet valve and sodium hypochlorite storage tank; the hydroxyl radical generation equipment is equipped with an integrated source of atmospheric pressure ionization discharge oxygen plasma, partition excitation type high-frequency high-voltage power supply, Venturi gas-liquid miscible device, booster pump, decompression buffer device, bag filter and cooling water circulation equipment. The processing capacity of the equipment can reach 300-500m ³ /h, the operation is simple, the operation cost is low, and the occupied area is small. It can efficiently and safely mineralize organic pollutants such as antibiotics in water, and provides practical equipment for the engineering application of advanced oxidation technology.

Description

Method and device for degrading mineralized quinolone antibiotics by hydroxyl radicals

technical field

The invention relates to quinolone antibiotics, in particular to a method and a device for degrading mineralized quinolone antibiotics by hydroxyl radicals.

Background technique

Since the discovery of antibiotics in the 20th century, they have made important contributions to the prevention and treatment of human infectious diseases and the improvement of feed conversion rate in animal breeding. However, more than 50% of antibiotics are excreted in intact structures during use and re-enter the aquatic environment through fertilization, discharge, and percolation. Antibiotics have been reported to be detected at concentrations ranging from ng/L to μg/L in different water environments, including wastewater, surface water, groundwater, and even drinking water. Residual antibiotics in water may lead to the emergence of a large number of resistant bacteria, and the metabolites released through biotransformation in the water environment may be more toxic, seriously threatening human health and the ecological environment.

Fluoroquinolone antibiotics are the second most frequently used antibiotics in the world. They can bind to gyrase on bacterial DNA to inhibit bacterial reproduction, and are widely used in the treatment of urinary tract infections and biliary tract infections. The annual discharge of quinolone antibiotics in the environment is as high as 44 million kilograms, resulting in the general detection of quinolone antibiotics in water bodies as 30-50ng/L (K.He, A.D.Soares, H.Adejumo, M.McDiarmid, K.Squibb , L. Blaney, Detection of a wide variety of human and veterinaryfluoroquinolone antibiotics in municipal waste water and waste water-impacted surface water, J. Pharm. Biomed. Anal. 106(2015) 136–143.). The detection of a large number of quinolone antibiotics in the water environment means that conventional water treatment methods such as coagulation-sedimentation, ultraviolet disinfection, microfiltration and other methods cannot effectively remove them from the water body. Therefore, it is urgent to establish a method that can effectively treat water bodies. New approach to antibiotics.

The reported treatment methods for antibiotics in watersheds mainly include physical, chemical and biological methods.

Physical methods mainly use adsorption membranes and filtration to remove antibiotics in water. Vieno et al studied the adsorption effect of Fe ₂ (SO ₄ ) ₃ on norfloxacin (Vieno, NM, Hrkki, H., Tuhkanen, T., Kronberg, L., 2007.Occurrence of pharmaceuticals in river water and their elimination in apilot-scale drinking water treatment plant. Environ. Sci. Technol. 41, 5077～5084.), the research results show that the removal rate of coagulant to antibiotics is only about 10%. Chen Liang disclosed (publication number CN106277166A) a method for removing antibiotics in aquaculture wastewater by using modified biochar. The method needs to be shaken at a constant temperature for 5-20 hours, the reaction time is long, and the treatment capacity is small. Fang Zhanqiang disclosed (publication number CN106622118A) a hydrochloric acid-modified zeolite-loaded cerium material for the degradation of norfloxacin. This method requires a water bath at 70° C. for 2 to 5 hours, which is difficult to implement in practical applications.

The chemical method mainly degrades the antibiotics in the water body through the addition of chemical reagents. Yu Jie et al. disclosed (publication number CN106915885A) a method for oxidatively degrading quinolone antibiotics in water using granular birnessite. In this method, the thermal hydrolysis reaction needs to be carried out in a water environment of 40-90°C. its application in engineering. The patent with the publication number CN105502776A uses the UV/H ₂ O ₂ method to remove antibiotics in water. This method needs to add a large amount of persulfate for pretreatment, and then perform two irradiations. The pH of the treated water sample needs to be adjusted. The treatment time long.

Biological methods mainly degrade antibiotics in water through the metabolites of algae and fungi. Zhang Junwei et al. disclosed (publication number CN103896363A) a method for degrading norfloxacin in water by using active oxygen produced by freshwater algae. The method has strict limits on the pH and temperature of the water. Wei Dongbin disclosed (publication number CN102276101A) a biochemical treatment reactor for removing quinolone antibiotic wastewater. The hydrolytic acidifying bacteria in the anaerobic reactor decompose the pollutants into small molecular compounds, and then the microorganisms in the aerobic reactor It is degraded, and the removal rate after 24 hours of reaction is only 70%-75%.

A comprehensive analysis of the above antibiotic treatment methods in water found that the physical method usually needs to be carried out in a high-temperature water bath, the treatment volume is small, and the removal rate of antibiotics is low. Although the chemical method has a high removal rate, it often requires the addition of high-concentration chemical reagents, which has certain requirements on the pH of the reaction water and is easy to cause secondary pollution, making it difficult to apply on a large scale. The preparation process of biological agents in the biological method is complicated, the reaction cycle is long, and the removal rate of antibiotics is low. Therefore, how to quickly mineralize the antibiotics in the watershed without causing secondary pollution residues is of great significance to the protection of human health and the safety of the ecological environment.

Contents of the invention

The object of the present invention is to provide a device for degrading mineralized quinolone antibiotics by hydroxyl radicals.

Another object of the present invention is to provide a method for degrading mineralized quinolone antibiotics by hydroxyl radicals.

The device for degrading mineralized quinolone antibiotics by hydroxyl radicals is equipped with hydroxyl radical generation equipment, OH oxidation degradation antibiotic reactor, chlorine disinfection unit, flocculation tank, clarification tank, constant pressure filter tank, clear water tank, and the first TRO online Detector, 2nd TRO online detector, 3rd TRO online detector, 4th TRO online detector, 1st mechanical pump, 2nd mechanical pump, 3rd mechanical pump, 4th mechanical pump, 5th mechanical pump, 1st water flow Meter, 2nd water flow meter, 3rd water flow meter, 4th water flow meter, 1st solenoid valve, 2nd solenoid valve, 3rd solenoid valve, 4th solenoid valve, 5th solenoid valve, 6th solenoid valve, The 7th solenoid valve, the 8th solenoid valve, the 9th solenoid valve, the 10th solenoid valve, the 1st unit water outlet valve, the 2nd unit water outlet valve, the 3rd unit water outlet valve, the 4th unit water outlet valve and sodium hypochlorite storage tank;

The hydroxyl radical generation equipment is equipped with an integrated source of atmospheric pressure ionization discharge oxygen plasma, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid miscible device, a booster pump, a decompression buffer, a bag filter and a cooling system. water circulation equipment;

The hydroxyl radical oxidation degradation antibiotic reaction unit is provided with 5 negative pressure jets in parallel, the main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected to the main water pipeline, and the side water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected to At the water outlet of high-concentration hydroxyl radical generating equipment, choose to open 3 to 5 jets to process 300-500m ³ /h of antibiotic solution, which is used for high-efficiency liquid-liquid miscibility of high-concentration hydroxyl radical solution and treated water.

The chlorine disinfection unit is provided with a sodium hypochlorite storage tank, the 8th electromagnetic valve, the 5th mechanical pump, the 4th water flow meter and the 4th TRO online detector, and the chlorine disinfection unit is used to deactivate bacteria, viruses and protozoa in the water, control Microbial regrowth and inhibition of pipe wall biofilm growth during water distribution;

The source water to be treated is connected to the water inlet of the first mechanical pump of the main pipeline, and the first solenoid valve is provided between the source water to be treated and the first mechanical pump, and the outlet of the first mechanical pump is connected to the water inlet of the first water flow meter. 1 There is a first unit water outlet valve between the mechanical pump and the first flow meter, the outlet of the first water flow meter is connected to the water inlet of the flocculation tank, the water outlet of the flocculation tank is connected to the water inlet of the clarification tank, and the second unit is installed between the flocculation tank and the clarification tank The solenoid valve, the water outlet of the clarification tank is connected to the water inlet of the second mechanical pump, and the second unit water outlet valve and the third solenoid valve are arranged between the water outlet of the clarifier tank and the water inlet of the second mechanical pump. The water outlet of the second mechanical pump is connected to the water inlet of the constant pressure filter pool, and the water outlet of the constant pressure filter pool is provided with the water outlet valve of the third unit;

The water outlet of the constant pressure filter tank is divided into two routes, one of which is connected to the water inlet of the third mechanical pump on the branch pipeline, and the fourth electromagnetic valve is arranged between the water outlet of the constant pressure filter tank and the water inlet of the third mechanical pump, and the third mechanical pump The water outlet is connected to the water inlet of the second water flow meter, the water outlet of the second water flow meter is connected to the water inlet of the Venturi gas-liquid mixer of the hydroxyl radical generating equipment, and the water outlet of the Venturi gas-liquid mixer is connected to the hydroxyl radical The first TRO online detector is installed between the branch inlet of the oxidative degradation antibiotic reaction unit, the outlet of the Venturi gas-liquid miscible device and the branch inlet of the hydroxyl radical oxidative degradation antibiotic reaction unit; the outlet of the constant pressure filter pool is connected to another The water inlet of the fourth mechanical pump on the main road, the fifth solenoid valve is installed between the water outlet of the constant pressure filter pool and the water inlet of the fourth mechanical pump, and the water outlet of the fourth mechanical pump is connected to the water inlet of the third water flow meter;

The water outlet of the third water flow meter is divided into two paths, one of which is connected to the main water inlet of the antibiotic reaction unit for oxidation and degradation of hydroxyl radicals, and the sixth solenoid valve is arranged between the third water flow meter and the reaction unit for oxidation and degradation of antibiotics by hydroxyl radicals , the water outlet between the hydroxyl radical oxidative degradation antibiotic reaction unit is connected to the water inlet of the clear water tank, and the second TRO online detector is installed between the hydroxyl radical oxidative degradation antibiotic reaction unit outlet and the clear water tank; the other way of the third water flow meter outlet Connected to the water inlet of the chlorine disinfection unit, the seventh solenoid valve is installed between the water outlet of the third water flowmeter and the water inlet of the chlorine disinfection unit, the water outlet of the chlorine disinfection unit is connected to the water inlet of the clean water pool, and between the water outlet of the chlorine disinfection unit and the water inlet of the clean water pool Equipped with the 3rd TRO online detector;

The water outlet of the clean water pool is provided with a fourth unit water outlet valve, and the water outlet of the clean water pool is divided into two routes, one of which is connected to the external drainage pipeline or the water supply pipe network; the other is connected to the water inlet of the subsequent advanced treatment process.

The method for degrading and mineralizing quinolone antibiotics by the hydroxyl radicals uses the device for degrading the mineralization quinolone antibiotics by the hydroxyl radicals, and the method comprises the following steps:

1) Open the first solenoid valve, turn on the first mechanical pump, use the outlet valve of the first unit to take samples, and detect the COD, turbidity, pH and other water quality parameters and antibiotic concentrations in the raw water. When quinolone antibiotics are detected in the raw water , the hydroxyl radical generating equipment and the hydroxyl radical oxidative degradation antibiotic reaction unit will be turned on; when quinolone antibiotics are not detected in the raw water, the hydroxyl radical generating equipment and the hydroxyl radical oxidative degradation antibiotic reaction unit will be turned off, and the chlorine disinfection unit will be turned on. The water flow is controlled by the first water flow meter, and the raw water to be treated is pumped into the flocculation tank, and the impurities in the water body are removed through the coagulation reaction;

2) Open the second solenoid valve, the effluent from the flocculation tank enters the clarification tank through gravity settlement, and the alum flowers generated in the flocculation tank settle in the clarification tank, and the ratio of the particle sedimentation velocity and the horizontal velocity in the clarification tank is (20～ 40)︰1. The outlet water of the clarification tank is sampled and tested by the outlet valve of the second unit, and the turbidity of the water body is controlled within 3.0NTU;

3) Open the third solenoid valve, turn on the second mechanical pump, pump the water to be treated after passing through the flocculation tank and the clarification tank into the constant pressure filter tank for filtration, the porous medium in the constant pressure filter tank can sieve the solid particles in the water Separation and interception, removal of suspended matter and colloids in the water, the effluent of the constant pressure filter is sampled and tested by the outlet valve of the third unit, and the turbidity of the water is controlled within 0.3NTU;

4) When the detection result in step 1) shows that the source water contains quinolone antibiotics, start the hydroxyl radical generation equipment and the hydroxyl radical oxidation degradation antibiotic reaction unit;

5) Open the valve of the oxygen cylinder, the oxygen passes through the dryer and the mass flow controller, and enters the oxygen plasma integrated source of atmospheric pressure ionization discharge; the partition excitation high-frequency high-voltage power supply forms an atmospheric pressure ionization discharge in a very narrow discharge gap, and the oxygen Ionization and dissociation generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups are detected by the online oxygen active group detector, and then enter the air inlet of the Venturi gas-liquid miscible device;

6) Turn on the cooling water circulation equipment, open the water outlet valve of the cooling water circulation equipment, cool the circulating water cooled to 4°C on the surface of the oxygen active group gas generating equipment, and cool the waste heat generated by the oxygen active group gas generating equipment during operation Transfer to ensure the normal operation of the equipment;

7) Open the fourth solenoid valve and the third mechanical pump, control the water flow of the branch pipeline through the second water flow meter, and filter part of the water passing through the constant pressure filter tank through the bag filter for secondary filtration, and then pressurize The pump is pumped into the water inlet of the Venturi gas-liquid miscible, and the gaseous oxygen active groups generated by the ionization discharge at atmospheric pressure are fully mixed in the Venturi gas-liquid miscible, and the hydroxyl groups generated after gas-liquid miscibility are free The base solution enters the decompression buffer, and the pressure at the outlet of the gas-liquid miscibility equipment is reduced through the decompression buffer, which enhances the hydrodynamic cavitation effect of the gas-liquid miscibility of the oxygen active group gas and the aqueous solution, and prolongs the bursting of the microbubbles and the contact with water. The reaction time is longer, the yield of hydroxyl radical solution is improved, the gas that is not dissolved in water is thermally decomposed into _O2 by the gas eliminator in the gas-liquid separator, and the generated high-concentration hydroxyl radical solution passes through the first TRO online detector After detection, enter the side water inlet of the reaction unit for oxidative degradation of antibiotics by hydroxyl radicals;

8) Turn on the fifth solenoid valve and the sixth solenoid valve, turn on the fourth mechanical pump, control the water flow through the third water flow meter, and pump the filtered water into the main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, according to the treatment capacity According to the demand, you can choose to open 3 to 5 ejectors, and the aqueous solution to be treated will fully mix and react with the high-concentration hydroxyl radical solution inhaled by the side water inlet in the reaction unit for oxidation and degradation of antibiotics by hydroxyl radicals. Mineralization of antibiotics into CO ₂ and H ₂ O. Use the 2nd TRO online detector to detect the concentration of total oxidants in the pipeline, and the water treated with hydroxyl radicals is discharged into the clear water pool;

9) When the test result in step 1) shows that the source water does not contain quinolone antibiotics, the hydroxyl radical generation unit and the hydroxyl radical oxidative degradation antibiotic reaction unit are turned off, and the chlorine disinfection unit is turned on;

10) Close the 6th solenoid valve, open the 7th solenoid valve, open the 8th solenoid valve and the 5th mechanical pump of the chlorine disinfection unit, use the 4th water flow meter to control the flow rate, and use the 3rd TRO online detector to detect the sodium hypochlorite mother liquor , pump the mother liquor of sodium hypochlorite into the main pipeline for mixed reaction with the filtered water, use the 4th TRO on-line detector to detect the total oxidant concentration in the pipeline after chlorine disinfection, and discharge the water after chlorine disinfection into the clear water pool;

11) Open the water outlet valve of Unit 4 to test the water sample after hydroxyl radical or chlorine disinfection. After the treatment, the quinolone antibiotics in the water body are completely degraded and the water quality index reaches the national "Drinking Water Sanitation Standard" (GB5749-2006) , open the 9th solenoid valve, discharge the treated water or enter the water distribution pipe network for subsequent use; when the quinolone antibiotics in the treated water body are not completely degraded, open the 10th solenoid valve for subsequent advanced treatment.

In step 1), polyaluminium chloride is used as a coagulant in the flocculation tank, the dosage of the coagulant is controlled to be 10-15 mg/L, and the stirring rate is 12-15 r/min. Polyaluminum chloride reacts with Ca(HCO ₃ ) ₂ and Ca(OH) ₂ in water to form Al(OH) ₃ colloids, which can absorb impurities in water and cause co-precipitation reactions between colloids and turbidity substances in water, resulting in the formation of Al(OH) 3 colloids. Large particles achieve rapid settling effect.

In step 2), the clarification tank is a slanting plate clarification tank, the length of the sloping plates is 1.5-2.0m, the net distance between the sloping plates is not less than 30mm, and the angle with the horizontal plane is 60°, the water depth of the upper layer of the sloping plate is 0.8m, and the bottom buffer The layer water depth is 1.5m, and the hydraulic retention time can be 2-4h.

In step 3), the filling of the constant pressure filter tank may be a diatomite covering film, and the minimum particle size for removal may be 10-0.3 μm.

In step 5), the oxygen flux can be 5-8 m ³ /h, the concentration of oxygen active groups generated by atmospheric pressure electric field discharge can be 100-150 mg/L, and the gas generation of oxygen active groups can be 300 ~600g/h.

In step 7), the pore size of the bag filter can be 20-50 μm, and the bag filter is used to filter small molecular organic suspended solids and particulate matter in the water body, reducing the consumption of hydroxyl radicals by the turbidity of the water body; The water flow rate in the branch pipeline can be 30-50m ³ /h. Through the Venturi gas-liquid miscible device, the oxygen active group gas in the water undergoes a free radical chain reaction to generate a high-concentration hydroxyl radical solution, and the total oxidant concentration is 5-15mg /L, the generation time of hydroxyl radicals is 0.1-2s.

In step 8), the hydroxyl radical oxidative degradation antibiotic reaction unit can choose to open 3 to 5 negative pressure jets according to the treatment capacity of the water to be treated, the water flow rate is 300 to 500m ³ /h, and the liquid and liquid are miscible The reaction time is 10-25s, and the total oxidant concentration is 0.2-1.0 mg/L; the negative-pressure injection action of the negative-pressure ejector produces violent shock waves, micro jets and water flow agitation, which promotes the high-efficiency of the hydroxyl radical solution and the water to be treated. Mixed, the extreme reaction conditions of high temperature and high pressure at the moment of cavitation bubble rupture can greatly increase the reaction rate of hydroxyl radicals to oxidize and degrade antibiotics, and improve water quality while mineralizing antibiotics.

In step 10), the process of chlorine disinfection can be sterilized with 5% NaClO solution, the dosing concentration is 1.5-2.0 mg/L, and the concentration of residual chlorine in the factory water is controlled to be 0.3 mg/L.

Technical effect of the present invention and advantage are as follows:

1). In the hydroxyl radical generation equipment, the oxygen reactive group gas concentration generated by atmospheric pressure ionization discharge is 100-150mg/L, and the hydroxyl radical solution is efficiently prepared through the extreme reaction conditions formed by the Venturi gas-liquid miscible device , the concentration of the total oxidant mainly composed of hydroxyl radicals is 5-15mg/L, the time for generating hydroxyl radicals is 0.1-2s, and the output of hydroxyl radical solution is 30-50m ³ /h.

2). The negative pressure injection of the reaction unit for the oxidative degradation of antibiotics by hydroxyl radicals produces severe shock waves, micro jets and water flow agitation, which promotes the efficient miscibility of hydroxyl radical solutions and water to be treated, and greatly improves the organic degradation of hydroxyl radicals and antibiotics. Pollutant contact collision probability and efficiency. The concentration of the oxygen free radical solution mainly composed of hydroxyl radicals in the antibiotic reaction unit for the oxidation and degradation of hydroxyl radicals can reach 3 to 6 times the concentration of antibiotics to be treated. Mineralization, the maximum water treatment capacity is 500m ³ /h. The time for the water to be treated to flow through the OH oxidation degradation antibiotic reactor is 10-25s, and the antibiotic concentration after treatment should be undetectable.

3). OH mainly attacks the N atom on the piperazine ring and the double bond on the naphthyridine ring of quinolone antibiotics, opens the piperazine ring and naphthyridine ring, and replaces the fluorine atom, effectively oxidatively degrading the drug of norfloxacin Effect groups, degradation products have no antibacterial activity. ·The further reaction between OH and the oxidized benzene ring cationic radical leads to the cracking of the aromatic ring, which is completely mineralized into CO ₂ , H ₂ O and inorganic ions. ·OH can reduce water turbidity and COD and other parameters while mineralizing antibiotics, improve water quality, and purify water.

4). The processing capacity of the equipment developed by the invention can reach 300-500m ³ /h, and the operation is simple, the operation cost is low, and the occupied area is small. It can efficiently and safely mineralize organic pollutants such as antibiotics in water, and provides practical equipment for the engineering application of advanced oxidation technology.

Description of drawings

Fig. 1 is a schematic diagram of the structure and composition of an embodiment of a device for degrading mineralized quinolone antibiotics by hydroxyl radicals according to the present invention.

Figure 2 is a high performance liquid chromatogram of norfloxacin mineralized by hydroxyl radicals. In Figure 2, curve a is norfloxacin before hydroxyl treatment, and curve b is not detected after hydroxyl treatment.

Figure 3 is the oxidative degradation pathway of norfloxacin mineralized by hydroxyl radicals.

Detailed ways

The following embodiments will further illustrate the present invention in conjunction with the accompanying drawings.

As shown in Figure 1, the device embodiment of the degrading and mineralizing quinolone antibiotics by hydroxyl radicals is provided with hydroxyl radical generating equipment A, OH oxidation degradation antibiotic reactor B, chlorine disinfection unit C, flocculation tank 1, clarification tank 2. Constant pressure filter pool 3, clean water pool 4, first TRO online detector 51, second TRO online detector 52, third TRO online detector 53, fourth TRO online detector 54, first mechanical pump 61, second mechanical pump 62. The third mechanical pump 63, the fourth mechanical pump 64, the fifth mechanical pump 65, the first water flow meter 71, the second water flow meter 72, the third water flow meter 73, the fourth water flow meter 74, the first Solenoid valve 81, 2nd solenoid valve 82, 3rd solenoid valve 83, 4th solenoid valve 84, 5th solenoid valve 85, 6th solenoid valve 86, 7th solenoid valve 87, 8th solenoid valve 88, 9th solenoid valve 89. The tenth solenoid valve 810, the first unit water outlet valve 91, the second unit water outlet valve 92, the third unit water outlet valve 93, the fourth unit water outlet valve 94 and the sodium hypochlorite storage tank 10.

The hydroxyl radical generation equipment A includes an integrated source of atmospheric pressure ionization discharge oxygen plasma, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid miscible device, a booster pump, a decompression buffer, a bag filter and Cooling water circulation equipment.

The OH oxidation degradation antibiotic reactor B is composed of five negative pressure ejectors connected in parallel, the main water inlet is connected to the main water delivery pipeline, and the side water inlet is connected to the outlet of high-concentration hydroxyl radical generating equipment. Selecting to open 3 to 5 jets can process 300 to 500m ³ /h antibiotic solution, which is used for high-efficiency liquid-liquid miscibility of high-concentration hydroxyl radical solution and treated water.

The chlorine disinfection unit C includes a sodium hypochlorite storage tank 10 , an eighth solenoid valve 88 , a fifth mechanical pump 65 , a fourth water flow meter 74 and a fourth TRO on-line detector 54 . Chlorine disinfection unit C is used to inactivate bacteria, viruses, and protozoa in water, control the regrowth of microorganisms in the process of water transportation and distribution, and inhibit the growth of pipe wall biofilm.

The source water to be treated is connected to the water inlet of the first mechanical pump 61 of the main pipeline, and a first electromagnetic valve 81 is provided between the source water to be treated and the first mechanical pump 61 . The water outlet of the first mechanical pump 61 is connected to the water inlet of the first water flow meter 71 , and a first unit water outlet valve 91 is provided between the first mechanical pump 61 and the first flow meter 71 . The water outlet of the first water flow meter 71 is connected to the water inlet of the flocculation tank 1, the water outlet of the flocculation tank 1 is connected to the water inlet of the clarification tank 2, and a second solenoid valve 82 is provided between the flocculation tank 1 and the clarification tank 2. The water outlet of the clarifier tank 2 is connected to the water inlet of the second mechanical pump 62, and the second unit water outlet valve 92 and the third solenoid valve 83 are arranged between the water outlet of the clarifier tank 2 and the water inlet of the second mechanical pump 62. The water outlet of the second mechanical pump 62 is connected to the water inlet of the constant pressure filter tank 3, and the water outlet of the constant pressure filter tank 3 is provided with a third unit water outlet valve 93.

The water outlet of the constant pressure filter pool 3 is divided into two paths, one of which is connected to the water inlet of the third mechanical pump 63 on the branch pipeline, and the fourth electromagnetic valve 84 is arranged between the water outlet of the constant pressure filter pool 3 and the water inlet of the third mechanical pump 63 . The water outlet of the third mechanical pump 63 is connected to the water inlet of the second water flow meter 72, and the water outlet of the second water flow meter 72 is connected to the water inlet of the Venturi gas-liquid miscible device A of the hydroxyl radical generation equipment, and the Venturi gas-liquid miscibility The water outlet of the device is connected to the branch inlet of the reaction unit B for the oxidation and degradation of antibiotics by hydroxyl radicals, and the first TRO online detector is installed between the outlet of the Venturi gas-liquid mixer and the inlet of the reaction unit B for the oxidation and degradation of antibiotics by hydroxyl radicals 51; the other road of the 3 water outlets of the constant pressure filter tank is connected to the water inlet of the 4th mechanical pump 64 on the main road, and the 5th electromagnetic valve 85 is arranged between the 3 water outlets of the constant pressure filter tank and the 4th mechanical pump 64 water inlet. The water outlet of the fourth mechanical pump 64 is connected to the water inlet of the third water flow meter 73 .

The water outlet of the third water flow meter 73 is divided into two paths, one of which is connected to the main water inlet of the oxidative degradation antibiotic reaction unit B of hydroxyl radicals, and a sixth water flow meter 73 and the antibiotic reaction unit B of oxidative degradation of hydroxyl radicals Solenoid valve 86. The water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit B is connected to the water inlet of the clean water tank 4, and the second TRO online detector 52 is installed between the water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit B and the clean water tank 4; the third water flow meter 73 The other way of the water outlet is connected to the water inlet of the chlorine disinfection unit C, and the 7th electromagnetic valve 87 is arranged between the water outlet of the third water flow meter 73 and the water inlet of the chlorine disinfection unit C. The water outlet of the chlorine disinfection unit C is connected to the water inlet of the clean water pool 4, and a third TRO online detector 53 is arranged between the water outlet of the chlorine disinfection unit C and the water inlet of the clean water pool 4.

The 4 water outlets of the clean water pool are provided with a fourth unit water outlet valve 94, and the 4 water outlets of the clean water pool are divided into two paths, one of which is connected to the external drainage pipeline or the water supply pipe network; the other is connected to the water inlet of the subsequent advanced treatment process.

The specific steps of the method for degrading mineralized quinolone antibiotics by hydroxyl radicals are given below:

1) Open the first solenoid valve 81, turn on the first mechanical pump 61, use the first unit outlet valve 91 to take samples, and detect water quality parameters such as COD, turbidity, pH and antibiotic concentration in the raw water. When quinolone antibiotics are detected in the raw water, the hydroxyl radical generation device A and the hydroxyl radical oxidative degradation antibiotic reaction unit B (see steps 4 to 8 for details); when no quinolone antibiotics are detected in the raw water, it will be turned off Hydroxyl radical generation equipment A and hydroxyl radical oxidative degradation antibiotic reaction unit B, turn on chlorine disinfection unit C (see steps 9-10 for details). The water flow rate is controlled by the first water flow meter 71, and the raw water to be treated is pumped into the flocculation tank 1, and impurities in the water body are removed through coagulation reaction.

The flocculation tank 1 uses polyaluminum chloride as a coagulant, the dosage of the coagulant is controlled to be 10-15 mg/L, and the stirring rate is 12-15 r/min. Polyaluminum chloride reacts with Ca(HCO ₃ ) ₂ and Ca(OH) ₂ in water to form Al(OH) ₃ colloids, which can absorb impurities in water and cause co-precipitation reactions between colloids and turbidity substances in water, resulting in the formation of Al(OH) 3 colloids. Large particles achieve rapid settling effect.

2) The second solenoid valve 82 is opened, and the effluent from the flocculation tank 1 enters the clarification tank 2 through gravity settlement. The alum flowers generated in the flocculation tank 1 are settled in the clarification tank 2, and the ratio between the particle sedimentation velocity and the horizontal flow rate in the clarification tank 2 is controlled between 20:1 and 40:1. The outlet water of the clarification tank 2 is sampled and detected by the outlet valve 82 of the second unit, and the turbidity of the water body is controlled within 3.0NTU.

The clarification tank 2 is a slanting plate clarification tank, the length of the sloping plates is 1.5-2.0m, the net distance between the sloping plates is not less than 30mm, and the angle with the horizontal plane is 60°, the water depth of the upper layer of the sloping plate is 0.8m, and the water depth of the bottom buffer layer is 1.5m , The hydraulic retention time is 2 to 4 hours.

3) Open the third solenoid valve 83, turn on the second mechanical pump 62, and pump the water to be treated after passing through the flocculation tank 1 and the clarification tank 2 into the constant pressure filter tank 3 for filtration. The porous medium in the constant pressure filter pool 3 can screen and retain solid particles in the water, and remove suspended matter and colloids in the water. The outlet water of the constant pressure filter tank 3 is sampled and detected by the outlet valve 93 of the third unit, and the turbidity of the water body is controlled within 0.3NTU.

The filler of the constant pressure filter tank 3 is a diatomite covering film, and the minimum particle size for removal is 10-0.3 μm.

4) When the test result in step 1) shows that the source water contains quinolone antibiotics, start the hydroxyl radical generating device A and the hydroxyl radical oxidative degradation antibiotic reaction unit B (steps 5-8).

5) Open the valve of the oxygen cylinder, the oxygen passes through the dryer and the mass flow controller, and enters into the integrated source of the atmospheric pressure ionization discharge oxygen plasma. Partition-excited high-frequency high-voltage power supply forms atmospheric pressure ionization discharge in an extremely narrow discharge gap, ionizes and dissociates oxygen to generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups are detected by an online oxygen active group detector. , into the inlet of the Venturi gas-liquid mixer.

The oxygen flux is 5-8m ³ /h, the concentration of oxygen active groups generated by atmospheric pressure electric field discharge is 100-150mg/L, and the gas generation amount of oxygen active groups is 300-600g/h.

6) Turn on the cooling water circulation equipment, open the water outlet valve of the cooling water circulation equipment, cool the circulating water cooled to 4°C on the surface of the oxygen active group gas generating equipment, and cool the waste heat generated by the oxygen active group gas generating equipment during operation Transfer to ensure the normal operation of the equipment.

7) Turn on the fourth electromagnetic valve 84 and the third mechanical pump 63, control the water flow of the branch pipeline through the second water flow meter 72, and carry out secondary filtration on part of the water passing through the constant pressure filter pool 3 through the bag filter , pumped into the water inlet of the Venturi gas-liquid miscible by the booster pump, and fully mixed with the gaseous oxygen active groups generated by the ionization discharge at atmospheric pressure in the Venturi gas-liquid miscible. The hydroxyl radical solution generated after gas-liquid miscibility enters the decompression buffer, and the pressure at the outlet end of the gas-liquid miscibility equipment is reduced through the decompression buffer to enhance the hydrodynamic cavitation of the gas-liquid miscibility of the oxygen active group gas and the aqueous solution Effect, prolong the reaction time of microbubble bursting and water contact collision, and increase the yield of hydroxyl radical solution. The gas that is not dissolved in water is thermally decomposed into _O2 and discharged through the gas eliminator in the gas-liquid separator. The generated high-concentration hydroxyl radical solution is detected by the first TRO on-line detector 51 and then enters the side water inlet of the reaction unit B for oxidative degradation of antibiotics by hydroxyl radicals.

The pore size of the bag filter is 20-50 μm, which is used for filtering small molecular organic suspended solids and particles in the water body, and reducing the consumption of hydroxyl radicals by the turbidity of the water body. The water flow rate in the branch pipeline is 30-50m ³ /h, through the Venturi gas-liquid miscible device, the oxygen active group gas in the water undergoes free radical chain reaction to generate a high-concentration hydroxyl radical solution, and the total oxidant concentration is 5-50m3/h. 15mg/L, the generation time of hydroxyl radicals is 0.1-2s.

8) Turn on the fifth solenoid valve 85 and the sixth solenoid valve 86, turn on the fourth mechanical pump 64, control the water flow through the third water flow meter 73, and pump the filtered water into the main inlet of the reaction unit B for oxidation and degradation of antibiotics by hydroxyl radicals. Shuikou. According to the demand of processing capacity, you can choose to open 3 to 5 ejectors. The aqueous solution to be treated is fully mixed with the high-concentration hydroxyl radical solution inhaled by the side water inlet in the reaction unit B for the oxidation and degradation of antibiotics by hydroxyl radicals. The hydroxyl radicals will mineralize the antibiotics in the water body into CO ₂ and H ₂ O. The second TRO on-line detector 52 is used to detect the total oxidant concentration in the pipeline, and the water treated with hydroxyl radicals is discharged into the clear water pool 4 .

The hydroxyl radical oxidative degradation antibiotic reaction unit B can select to open 3 to 5 negative pressure injectors according to the processing capacity of the water to be treated, the water flow rate is 300 to 500 m ³ /h, and the liquid-liquid miscible reaction time is 10 to 50 m 3 /h. 25s, the total oxidant concentration is 0.2-1.0mg/L. The negative pressure spraying action of the negative pressure ejector produces severe shock waves, micro jets and water flow agitation, which promotes the efficient mixing of the hydroxyl radical solution and the water to be treated. The extreme reaction conditions of high temperature and high pressure at the moment of cavitation bubble rupture can greatly increase the reaction rate of hydroxyl radicals to oxidize and degrade antibiotics, and improve water quality while mineralizing antibiotics.

9) When the test result in step 1) shows that the source water does not contain quinolone antibiotics, turn off the hydroxyl radical generating device A and the hydroxyl radical oxidative degradation antibiotic reaction unit B, and turn on the chlorine disinfection unit C (step 10).

10) Close the 6th solenoid valve 86, open the 7th solenoid valve 87, open the 8th solenoid valve 88 of the chlorine disinfection unit C, the 5th mechanical pump 65, use the 4th water flow meter 74 to control the flow, pass the 3rd TRO online detector 53. After detecting the sodium hypochlorite mother liquor, pump the sodium hypochlorite mother liquor into the main pipeline for mixed reaction with the filtered water. The 4th TRO online detector 54 is used to detect the total oxidant concentration in the pipeline after chlorine disinfection, and the water after chlorine disinfection is discharged into the clear water pool 4 .

The chlorine disinfection process adopts 5% NaClO solution for disinfection, the dosing concentration is 1.5-2.0 mg/L, and the residual chlorine concentration of the factory water is controlled to be 0.3 mg/L.

11) Open the water outlet valve 94 of the fourth unit to detect the water sample after hydroxyl radical or chlorine disinfection. After the treatment, the quinolone antibiotics in the water body are completely degraded and the water quality index reaches the national "Drinking Water Hygienic Standard" (GB5749-2006) Finally, the ninth solenoid valve 89 is opened to discharge the treated water or enter the water distribution pipe network for subsequent use; when the quinolone antibiotics in the treated water are not completely degraded, the tenth solenoid valve 810 is opened for subsequent advanced treatment.

Provide specific embodiment below:

The water in a river basin polluted by antibiotics needs to be discharged after emergency treatment. The water quality conditions to be treated are as follows: temperature=26.5°C, turbidity=11.8NTU, pH=7.29, oxygen consumption=6.0mg/L. The concentration of sulfadiazine in the water was detected to be 80ng/L, the chlorine disinfection unit was turned off, and the hydroxyl radical mineralization antibiotic unit was started. According to the water quality and the concentration of antibiotics, it is determined that the total oxidant concentration to be added is 0.5 mg/L.

The water containing sulfadiazine is pumped into the main pipeline at a flow rate of 300m ³ /h. In the flocculation tank, the alum flowers formed by the large particles in the water and the flocculant are settled in the clarification tank, and the water is filtered out through a constant pressure filter tank. suspended matter and colloids. The filtered water is pumped into the high-efficiency gas-liquid miscible equipment at a water flow rate of 50m ³ /h to efficiently generate hydroxyl radicals with gaseous oxygen active groups. Fully react in the oxidative degradation antibiotic reaction unit. According to the demand of processing capacity, choose to open 5 negative pressure injectors in the reaction unit of oxidative degradation of antibiotics by hydroxyl radicals, the water flow rate is 300m ³ /h, and the hydraulic retention time of the reaction unit of oxidative degradation of antibiotics by hydroxyl radicals in the water unit to be treated is 15s, the total oxidant concentration after miscibility is 0.5mg/L.

The concentration of norfloxacin in the water treated with hydroxyl radicals was reduced to undetected (see Figure 2), and it can be safely discharged after passing the test. The oxidative degradation pathway of norfloxacin mineralized by hydroxyl radicals is shown in Figure 3.

Claims (10)

1. The device for degrading mineralized quinolone antibiotics by hydroxyl radicals is characterized in that it is provided with hydroxyl radical generating equipment, OH oxidation degradation antibiotic reactor, chlorine disinfection unit, flocculation tank, clarification tank, constant pressure filter tank, clear water tank , 1st TRO online detector, 2nd TRO online detector, 3rd TRO online detector, 4th TRO online detector, 1st mechanical pump, 2nd mechanical pump, 3rd mechanical pump, 4th mechanical pump, 5th mechanical pump, 1st water flow meter, 2nd water flow meter, 3rd water flow meter, 4th water flow meter, 1st solenoid valve, 2nd solenoid valve, 3rd solenoid valve, 4th solenoid valve, 5th solenoid valve, 4th solenoid valve 6 solenoid valves, 7th solenoid valves, 8th solenoid valves, 9th solenoid valves, 10th solenoid valves, 1st unit water outlet valve, 2nd unit water outlet valve, 3rd unit water outlet valve, 4th unit water outlet valve and sodium hypochlorite storage Can; The hydroxyl radical generation equipment is equipped with an integrated source of atmospheric pressure ionization discharge oxygen plasma, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid miscible device, a booster pump, a decompression buffer, a bag filter and a cooling system. water circulation equipment; The hydroxyl radical oxidation degradation antibiotic reaction unit is provided with 5 negative pressure jets in parallel, the main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected to the main water pipeline, and the side water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected to Water outlet of high-concentration hydroxyl radical generating equipment; The chlorine disinfection unit is provided with a sodium hypochlorite storage tank, the 8th electromagnetic valve, the 5th mechanical pump, the 4th water flow meter and the 4th TRO online detector, and the chlorine disinfection unit is used to deactivate bacteria, viruses and protozoa in the water, control Microbial regrowth and inhibition of pipe wall biofilm growth during water distribution; The source water to be treated is connected to the water inlet of the first mechanical pump of the main pipeline, and the first solenoid valve is provided between the source water to be treated and the first mechanical pump, and the outlet of the first mechanical pump is connected to the water inlet of the first water flow meter. 1 There is a first unit water outlet valve between the mechanical pump and the first flow meter, the outlet of the first water flow meter is connected to the water inlet of the flocculation tank, the water outlet of the flocculation tank is connected to the water inlet of the clarification tank, and the first unit is installed between the flocculation tank and the clarification tank 2 Solenoid valves, the outlet of the clarification tank is connected to the water inlet of the second mechanical pump, the second unit outlet valve and the third solenoid valve are installed between the outlet of the clarification tank and the water inlet of the second mechanical pump, the outlet of the second mechanical pump is connected to the constant pressure The water inlet of the filter pool and the water outlet of the constant pressure filter pool are equipped with the third unit water outlet valve; The water outlet of the constant pressure filter pool is divided into two paths, one of which is connected to the water inlet of the third mechanical pump on the branch pipeline, and the fourth solenoid valve is arranged between the water outlet of the constant pressure filter pool and the water inlet of the third mechanical pump. The water outlet of the pump is connected to the water inlet of the second water flow meter, the water outlet of the second water flow meter is connected to the water inlet of the Venturi gas-liquid mixer of the hydroxyl radical generating equipment, and the water outlet of the Venturi gas-liquid mixer is connected to the hydroxyl free radical generator. The first TRO online detector is installed between the branch inlet of the reaction unit for oxidative degradation of antibiotics by hydroxyl radicals, the outlet of the Venturi gas-liquid miscible device and the outlet of the reaction unit for oxidative degradation of antibiotics by hydroxyl radicals; the other channel for the outlet of the constant pressure filter pool Connect the water inlet of the 4th mechanical pump on the main road, the 5th solenoid valve is installed between the water outlet of the constant pressure filter pool and the water inlet of the 4th mechanical pump, and the water outlet of the 4th mechanical pump is connected to the water inlet of the 3rd water flow meter; The water outlet of the third water flow meter is divided into two paths, one of which is connected to the main water inlet of the antibiotic reaction unit for oxidation and degradation of hydroxyl radicals, and the sixth solenoid valve is arranged between the third water flow meter and the reaction unit for oxidation and degradation of antibiotics by hydroxyl radicals , the water outlet between the hydroxyl radical oxidative degradation antibiotic reaction unit is connected to the water inlet of the clear water tank, and the second TRO online detector is installed between the hydroxyl radical oxidative degradation antibiotic reaction unit outlet and the clear water tank; the other way of the third water flow meter outlet Connected to the water inlet of the chlorine disinfection unit, the seventh solenoid valve is installed between the water outlet of the third water flowmeter and the water inlet of the chlorine disinfection unit, the water outlet of the chlorine disinfection unit is connected to the water inlet of the clean water pool, and between the water outlet of the chlorine disinfection unit and the water inlet of the clean water pool Equipped with the 3rd TRO online detector; The water outlet of the clean water pool is provided with a fourth unit water outlet valve, and the water outlet of the clean water pool is divided into two routes, one of which is connected to the external drainage pipeline or the water supply pipe network; the other is connected to the water inlet of the subsequent advanced treatment process. 2. the method for hydroxyl radical degradation mineralization quinolone antibiotics, is characterized in that adopting the device of hydroxyl radical degradation mineralization quinolone antibiotics as claimed in claim 1, described method comprises the following steps: 1) Open the first solenoid valve, turn on the first mechanical pump, use the outlet valve of the first unit to take samples, and detect the COD, turbidity, pH and other water quality parameters and antibiotic concentrations in the raw water. When quinolone antibiotics are detected in the raw water , the hydroxyl radical generating equipment and the hydroxyl radical oxidative degradation antibiotic reaction unit will be turned on; when quinolone antibiotics are not detected in the raw water, the hydroxyl radical generating equipment and the hydroxyl radical oxidative degradation antibiotic reaction unit will be turned off, and the chlorine disinfection unit will be turned on. The water flow is controlled by the first water flow meter, and the raw water to be treated is pumped into the flocculation tank, and the impurities in the water body are removed through the coagulation reaction; 2) Open the second solenoid valve, the effluent from the flocculation tank enters the clarification tank through gravity settlement, and the alum flowers generated in the flocculation tank settle in the clarification tank, and the ratio of the particle sedimentation velocity and the horizontal velocity in the clarification tank is (20～ 40)︰1. The outlet water of the clarification tank is sampled and tested by the outlet valve of the second unit, and the turbidity of the water body is controlled within 3.0NTU; 3) Open the third solenoid valve, turn on the second mechanical pump, pump the water to be treated after passing through the flocculation tank and the clarification tank into the constant pressure filter tank for filtration, the porous medium in the constant pressure filter tank can sieve the solid particles in the water Separation and interception, removal of suspended matter and colloids in the water, the effluent of the constant pressure filter is sampled and tested by the outlet valve of the third unit, and the turbidity of the water is controlled within 0.3NTU; 4) When the detection result in step 1) shows that the source water contains quinolone antibiotics, start the hydroxyl radical generation equipment and the hydroxyl radical oxidation degradation antibiotic reaction unit; 5) Open the valve of the oxygen cylinder, the oxygen passes through the dryer and the mass flow controller, and enters the oxygen plasma integrated source of atmospheric pressure ionization discharge; the partition excitation high-frequency high-voltage power supply forms an atmospheric pressure ionization discharge in a very narrow discharge gap, and the oxygen Ionization and dissociation generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups are detected by the online oxygen active group detector, and then enter the air inlet of the Venturi gas-liquid miscible device; 6) Turn on the cooling water circulation equipment, open the water outlet valve of the cooling water circulation equipment, cool the circulating water cooled to 4°C on the surface of the oxygen active group gas generating equipment, and cool the waste heat generated by the oxygen active group gas generating equipment during operation Transfer to ensure the normal operation of the equipment; 7) Open the fourth solenoid valve and the third mechanical pump, control the water flow of the branch pipeline through the second water flow meter, and filter part of the water passing through the constant pressure filter tank through the bag filter for secondary filtration, and then pressurize The pump is pumped into the water inlet of the Venturi gas-liquid miscible, and the gaseous oxygen active groups generated by the ionization discharge at atmospheric pressure are fully mixed in the Venturi gas-liquid miscible, and the hydroxyl groups generated after gas-liquid miscibility are free The base solution enters the decompression buffer, and the pressure at the outlet of the gas-liquid miscibility equipment is reduced through the decompression buffer, which enhances the hydrodynamic cavitation effect of the gas-liquid miscibility of the oxygen active group gas and the aqueous solution, and prolongs the bursting of the microbubbles and the contact with water. The reaction time is longer, the yield of hydroxyl radical solution is improved, the gas that is not dissolved in water is thermally decomposed into _O2 by the gas eliminator in the gas-liquid separator, and the generated high-concentration hydroxyl radical solution passes through the first TRO online detector After detection, enter the side water inlet of the reaction unit for oxidative degradation of antibiotics by hydroxyl radicals; 8) Turn on the fifth solenoid valve and the sixth solenoid valve, turn on the fourth mechanical pump, control the water flow through the third water flow meter, and pump the filtered water into the main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, according to the treatment capacity According to the demand, choose to open 3 to 5 jets, and the aqueous solution to be treated will fully mix and react with the high-concentration hydroxyl radical solution inhaled by the side water inlet in the hydroxyl radical oxidation degradation antibiotic reaction unit. Antibiotics are mineralized into CO ₂ and H ₂ O; the 2nd TRO online detector is used to detect the concentration of total oxidants in the pipeline, and the water treated with hydroxyl radicals is discharged into the clear water pool; 9) When the test result in step 1) shows that the source water does not contain quinolone antibiotics, the hydroxyl radical generation unit and the hydroxyl radical oxidative degradation antibiotic reaction unit are turned off, and the chlorine disinfection unit is turned on; 10) Close the 6th solenoid valve, open the 7th solenoid valve, open the 8th solenoid valve and the 5th mechanical pump of the chlorine disinfection unit, use the 4th water flow meter to control the flow rate, and use the 3rd TRO online detector to detect the sodium hypochlorite mother liquor , pump the mother liquor of sodium hypochlorite into the main pipeline for mixed reaction with the filtered water, use the 4th TRO on-line detector to detect the total oxidant concentration in the pipeline after chlorine disinfection, and discharge the water after chlorine disinfection into the clear water pool; 11) Open the water outlet valve of Unit 4 to test the water sample after hydroxyl radical or chlorine disinfection. After the treatment, the quinolone antibiotics in the water body are completely degraded and the water quality index reaches the national "Drinking Water Sanitation Standard" (GB5749-2006) , open the 9th solenoid valve, discharge the treated water or enter the water distribution pipe network for subsequent use; when the quinolone antibiotics in the treated water body are not completely degraded, open the 10th solenoid valve for subsequent advanced treatment. 3. the method for hydroxyl radical degradation mineralization quinolone antibiotics as claimed in claim 2, is characterized in that in step 1) in, described flocculation tank uses polyaluminum chloride as coagulant, controls coagulant dosage It is 10~15mg/L, and the stirring rate is 12~15r/min. 4. The method for degrading mineralized quinolone antibiotics by hydroxyl radicals as claimed in claim 2, characterized in that in step 1), polyaluminum chloride reacts with Ca(HCO ₃ ) ₂ and Ca(OH) ₂ in water to generate Al(OH) ₃ colloid can absorb impurities in water, and cause co-precipitation reaction between colloids and turbidity substances in water, resulting in the formation of large particles and rapid sedimentation. 5. the method for hydroxyl free radical degradation mineralization quinolone antibiotics as claimed in claim 2, it is characterized in that in step 2) in, described clarifier is inclined plate type clarifier, and inclined plate length is 1.5～2.0m, and inclined plate The net distance between them is not less than 30mm, and it forms an angle of 60° with the horizontal plane. The water depth of the upper layer of the inclined plate is 0.8m, the water depth of the bottom buffer layer is 1.5m, and the hydraulic retention time is 2 to 4h. 6. the method for hydroxyl free radical degrading mineralization quinolone antibiotics as claimed in claim 2, is characterized in that in step 3) in, the filler of described constant pressure filtration pool is diatomite covering film, and the minimum granularity of removing is 10 ~0.3 μm. 7. The method for degrading mineralized quinolone antibiotics by hydroxyl radicals as claimed in claim 2, characterized in that in step 5), the oxygen flux is 5 to 8 m ³ /h, and oxygen activity is generated by atmospheric pressure electric field discharge The group concentration is 100-150 mg/L, and the gas generation of oxygen-active groups is 300-600 g/h. 8. The method for degrading mineralized quinolone antibiotics by hydroxyl radicals as claimed in claim 2, is characterized in that in step 7), the aperture of the bag filter is 20～50 μm, and the bag filter is used to filter small and medium-sized Molecular organic suspended matter and particulate matter, reducing the consumption of hydroxyl radicals by water turbidity; the water flow rate in the branch pipeline is 30-50m ³ /h, through the Venturi gas-liquid miscible device, the oxygen active group gas is High-concentration hydroxyl radical solution is generated through free radical chain reaction in water, the total oxidant concentration is 5-15mg/L, and the generation time of hydroxyl radical is 0.1-2s. 9. The method for hydroxyl radical degradation mineralization quinolone antibiotics as claimed in claim 2, is characterized in that in step 8), said hydroxyl radical oxidation degradation antibiotic reaction unit selects to open 3 according to the processing capacity of water to be treated ～5 negative pressure ejectors, the water flow rate is 300～500m ³ /h, the liquid-liquid miscible reaction time is 10～25s, and the total oxidant concentration is 0.2～1.0mg/L. 10. The method for degrading mineralized quinolone antibiotics by hydroxyl radicals as claimed in claim 2, characterized in that in step 10), the process of chlorine disinfection adopts 5% NaClO solution for disinfection, and the dosage concentration is 1.5～2.0mg /L, and the concentration of residual chlorine in the factory water is controlled at 0.3mg/L.