CN108423883B - Method and device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals - Google Patents

Method and device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals Download PDF

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CN108423883B
CN108423883B CN201810477051.1A CN201810477051A CN108423883B CN 108423883 B CN108423883 B CN 108423883B CN 201810477051 A CN201810477051 A CN 201810477051A CN 108423883 B CN108423883 B CN 108423883B
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water
hydroxyl radical
tank
electromagnetic valve
water outlet
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CN108423883A (en
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白敏冬
余忆玄
张芝涛
黄凌风
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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  • Hydrology & Water Resources (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract

A method and a device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals relate to quinolone antibiotics. The device is provided with hydroxyl free radical generating equipment, an OH oxidative degradation antibiotic reactor, a chlorine disinfection unit, a flocculation tank, a clarification tank, a constant pressure filter tank, a clean water tank, a TRO on-line detector, a mechanical pump, a water flow meter, an electromagnetic valve, a unit water outlet valve and a sodium hypochlorite storage tank; the hydroxyl radical generating equipment is provided with an atmospheric pressure ionization discharge oxygen plasma integrated source, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid mixing and dissolving device, a booster pump, a decompression buffer, a bag filter and cooling water circulating equipment. The equipment throughput can reach 300-500 m3The method has the advantages of simple operation, low operation cost and small occupied area. Can efficiently and safely mineralize organic pollutants such as antibiotics and the like in the water body, and provides practical equipment for the engineering application of the advanced oxidation technology.

Description

Method and device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals
Technical Field
The invention relates to quinolone antibiotics, in particular to a method and a device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals.
Background
Antibiotics have been found to make important contributions to the control of infectious diseases in humans and the improvement of feed conversion rates in animal breeding since the 20 th century. However, more than 50% of the antibiotics are expelled from the body as a complete structure during use and re-enter the water environment by fertilization, drainage, percolation, and the like. Antibiotics with the detection concentration of ng/L to mug/L are reported in different water environments including waste water, surface water, underground water and even drinking water. Residual antibiotics in water bodies can cause a large number of drug-resistant bacteria to appear, and metabolites released by biotransformation in water environments can have stronger toxicity, thereby seriously threatening human health and ecological environment.
Fluoroquinolone antibiotics, which are the antibiotics with high frequency of use in the world at 2, 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 amount of the quinolone antibiotics discharged in the environment is up to 4400 kilo per year, which results in the universal Detection amount of the quinolone antibiotics in water bodies being 30-50 ng/L (K.He, A.D. Soares, H.Adejumo, M.McDiamid, K.Squibb, L.Blanky, Detection of a wireless of human and veterinary fluorimetric antibiotics in a microbial water and water-infected surface water, J.Pharm.biomed.Anal.106(2015) 136-143.). The detection of a large amount of quinolone antibiotics in the water environment means that the quinolone antibiotics cannot be effectively removed from the water body by the conventional water treatment methods such as coagulation-precipitation, ultraviolet disinfection, microfiltration and the like, so that a new method for effectively treating the antibiotics in the water body needs to be established.
The treatment methods for antibiotics in the fluid field that have been reported so far are mainly physical methods, chemical methods, and biological methods.
The physical method mainly utilizes an adsorption membrane and a filtration mode to remove antibiotics in the water body. Vieno et al studied Fe2(SO4)3The adsorption effect on norfloxacin (Vieno, N.M., Hrkki, H., Tuhkanen, T., Kronberg, L.,2007. Occurence of pharmaceuticals in river water and the interference in anode-scale drying water treatment plant. environ. Sci. Technol.41, 5077-5084.) the result of the study shows that the removal rate of the coagulant on antibiotics is only about 10%. Chenlian discloses (publication number CN106277166A) a method for removing antibiotics in aquaculture wastewater by using modified biochar, and the method needs to shake for 5-20 hours under constant temperature conditions, and has long reaction time and small treatment capacity. The Fangshiqiang discloses (publication No. CN106622118A) that a hydrochloric acid modified zeolite cerium-loaded material is used for degradation of norfloxacin, and the method needs to be carried out in a water bath at 70 ℃ for 2-5 hours, and is difficult to realize in practical application.
The chemical method mainly degrades antibiotics in the water body by adding chemical reagents. In Jie et al (publication No. CN106915885A), a method for oxidative degradation of quinolone antibiotics in water by using granular birnessite is disclosed, wherein the thermal hydrolysis reaction needs to be carried out in a water environment at 40-90 ℃, and the application of the method in engineering is limited. Publication No. CN105502776A uses UV/H2O2The method for removing the antibiotics in the water needs to add a large amount of persulfate for pretreatment and then carry out irradiation twice, and needs to treat a water sampleThe pH of the solution is adjusted, and the treatment time is long.
Biological methods degrade antibiotics in water bodies mainly through metabolites of algae and fungi. Zhang Junwei et al (publication No. CN103896363A) discloses a method for degrading norfloxacin in water by using active oxygen generated by freshwater algae, wherein the method has strict limits on the pH and temperature of the water. Wei-bin discloses (publication No. CN102276101A) a biochemical treatment reactor for removing quinolone antibiotic wastewater, wherein pollutants are decomposed into micromolecular compounds by hydrolytic acidification bacteria of an anaerobic reactor, and the micromolecular compounds are degraded by microorganisms in an aerobic reactor, and the removal rate after 24 hours of reaction is only 70-75%.
The comprehensive analysis of the above methods for treating antibiotics in water finds that: the physical method usually needs to be carried out in a high-temperature water bath, the treatment amount is small, and the removal rate of antibiotics is low. Although the chemical method has high removal rate, a high-concentration chemical reagent is often required to be added, certain requirements are required on conditions such as pH of a reaction water body, secondary pollution is easily caused, and large-scale application is difficult. The preparation process of the biological agent in the biological method is complex, the reaction period is long, and the removal rate of antibiotics is low. Therefore, how to rapidly mineralize antibiotics in the fluid area and not generate secondary pollution residue has important significance for protecting human body health and ecological environment safety.
Disclosure of Invention
The invention aims to provide a device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals.
Another object of the present invention is to provide a method for degrading and mineralizing quinolone antibiotics by hydroxyl radicals.
The device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals is provided with hydroxyl radical generating equipment, an OH oxidation degradation antibiotic reactor, a chlorine disinfection unit, a flocculation tank, a clarification tank, a constant pressure filter tank, a clean water tank, a 1 st TRO on-line detector, a 2 nd TRO on-line detector, a 3 rd TRO on-line detector, a 4 th TRO on-line detector, a 1 st mechanical pump, a 2 nd mechanical pump, a 3 rd mechanical pump, a 4 th mechanical pump, a 5 th mechanical pump and a 1 st water flow meter, the water flow meter comprises a 2 nd water flow meter, a 3 rd water flow meter, a 4 th water flow meter, a 1 st electromagnetic valve, a 2 nd electromagnetic valve, a 3 rd electromagnetic valve, a 4 th electromagnetic valve, a 5 th electromagnetic valve, a 6 th electromagnetic valve, a 7 th electromagnetic valve, an 8 th electromagnetic valve, a 9 th electromagnetic valve, a 10 th electromagnetic valve, a 1 st unit water outlet valve, a 2 nd unit water outlet valve, a 3 rd unit water outlet valve, a 4 th unit water outlet valve and a sodium hypochlorite storage tank;
the hydroxyl radical generating equipment is provided with an atmospheric pressure ionization discharge oxygen plasma integrated source, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid mixing and dissolving device, a booster pump, a decompression buffer, a bag filter and cooling water circulating equipment;
the hydroxyl radical oxidation degradation antibiotic reaction unit is provided with 5 negative pressure ejectors which are connected in parallel, a main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with a main water delivery pipeline, a side water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with a water outlet of high-concentration hydroxyl radical generation equipment, and 3-5 ejectors are selectively opened to process 300-500 m3The antibiotic solution is used for mixing the high-concentration hydroxyl radical solution and the high-efficiency liquid of the water to be treated.
The chlorine disinfection unit is provided with a sodium hypochlorite storage tank, an 8 th electromagnetic valve, a 5 th mechanical pump, a 4 th water flowmeter and a 4 th TRO online detector, and is used for inactivating bacteria, viruses and protozoa in water, controlling the regrowth of microorganisms in the water delivery and distribution process and inhibiting the growth of a pipe wall biofilm;
treat the water inlet of the 1 st mechanical pump of source water connection main pipeline of treatment, be equipped with the 1 st solenoid valve between source water and the 1 st mechanical pump of treatment, the 1 st water flowmeter water inlet is connected to the delivery port of the 1 st mechanical pump, be equipped with the 1 st unit outlet valve between the 1 st mechanical pump and the 1 st water flowmeter, the flocculation basin water inlet is connected to the 1 st water flowmeter delivery port, the clarification tank water inlet is connected to the flocculation basin delivery port, be equipped with the 2 nd solenoid valve between flocculation basin and clarification tank, the 2 nd mechanical pump is connected to the clarification tank delivery port and is gone into the mouth of a river, be equipped with the 2 nd unit outlet valve and the 3 rd solenoid valve between the mouth of a river. The 2 nd mechanical pump water outlet is connected with the constant pressure filter tank water inlet, and the constant pressure filter tank water outlet is provided with a 3 rd unit water outlet valve;
the water outlet of the constant pressure filter tank is divided into two paths, one path is connected with the water inlet of a 3 rd mechanical pump on the branch pipeline, a 4 th electromagnetic valve is arranged between the water outlet of the constant pressure filter tank and the water inlet of the 3 rd mechanical pump, the water outlet of the 3 rd mechanical pump is connected with the water inlet of a 2 nd water flow meter, the water outlet of the 2 nd water flow meter is connected with the water inlet of a venturi gas-liquid mixing and dissolving device in the hydroxyl radical generating equipment, the water outlet of the venturi gas-liquid mixing and dissolving device is connected with the branch water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, and a 1 st TRO online detector is arranged between the water outlet of the venturi gas-liquid mixing and; the other path of the water outlet of the constant-pressure filter tank is connected with the water inlet of a 4 th mechanical pump on the main pipeline, a 5 th electromagnetic valve is arranged between the water outlet of the constant-pressure filter tank and the water inlet of the 4 th mechanical pump, and the water outlet of the 4 th mechanical pump is connected with the water inlet of a 3 rd water flowmeter;
the water outlet of the 3 rd water flow meter is divided into two paths, one path is connected with a main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, a 6 th electromagnetic valve is arranged between the 3 rd water flow meter and the hydroxyl radical oxidation degradation antibiotic reaction unit, the water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with the water inlet of the clean water tank, and a 2 nd TRO online detector is arranged between the water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit and the clean water tank; the other path of the water outlet of the 3 rd water flowmeter is connected with a water inlet of a chlorine disinfection unit, a 7 th electromagnetic valve is arranged between the water outlet of the 3 rd water flowmeter and the water inlet of the chlorine disinfection unit, the water outlet of the chlorine disinfection unit is connected with the water inlet of a clean water pool, and a 3 rd TRO on-line detector is arranged between the water outlet of the chlorine disinfection unit and the water inlet of the clean water pool;
the water outlet of the clean water tank is provided with a 4 th unit water outlet valve, and the water outlet of the clean water tank is divided into two paths, wherein one path is connected with an external discharge pipeline or a water supply pipe network; the other path is connected with a water inlet of a subsequent advanced treatment process.
The method for degrading and mineralizing quinolone antibiotics by hydroxyl radicals and the device for degrading and mineralizing quinolone antibiotics by the hydroxyl radicals comprise the following steps:
1) opening a 1 st electromagnetic valve, opening a 1 st mechanical pump, sampling by using a 1 st unit water outlet valve, detecting water quality parameters such as COD (chemical oxygen demand), turbidity and pH (potential of hydrogen) in raw water and antibiotic concentration, and opening a hydroxyl radical generating device and a hydroxyl radical oxidation degradation antibiotic reaction unit when quinolone antibiotics are detected in the raw water; when no quinolone antibiotics are detected in the raw water, closing the hydroxyl radical generating equipment and the hydroxyl radical oxidation degradation antibiotic reaction unit, starting the chlorine disinfection unit, controlling the water flow through the No. 1 water flow meter, pumping the raw water to be treated into a flocculation tank, and removing impurities in the water body through coagulation reaction;
2) opening the 2 nd electromagnetic valve, enabling the effluent of the flocculation tank to enter a clarification tank through gravity settling, settling alum floc generated in the flocculation tank in the clarification tank, wherein the ratio of the particle settling speed to the horizontal flow speed in the clarification tank is (20-40): 1, sampling and detecting the effluent of the clarification tank through the 2 nd unit effluent valve, and controlling the turbidity of the water body within 3.0 NTU;
3) opening a 3 rd electromagnetic valve, opening a 2 nd mechanical pump, pumping the water to be treated which passes through the flocculation tank and the clarification tank into a constant pressure filter tank for filtering, wherein the porous medium in the constant pressure filter tank can sieve and intercept solid particles in the water, so as to remove suspended substances and colloids in the water, the effluent of the constant pressure filter tank is sampled and detected by a 3 rd unit water outlet valve, and the turbidity of the water body is controlled within 0.3 NTU;
4) when the detection result in the step 1) shows that the source water contains the quinolone antibiotics, starting hydroxyl radical generating equipment and a hydroxyl radical oxidation and degradation antibiotic reaction unit;
5) opening an oxygen cylinder valve, and allowing oxygen to enter an atmospheric pressure ionization discharge oxygen plasma integrated source through a dryer and a mass flow controller; the high-frequency high-voltage power supply of the partition excitation type forms atmospheric pressure ionization discharge in an extremely narrow discharge gap, oxygen is ionized and dissociated to generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups enter an air inlet of the Venturi gas-liquid mixing and dissolving device after the concentration of the gaseous oxygen active groups is detected by an online oxygen active group detector;
6) starting cooling water circulation equipment, opening a water outlet valve of the cooling water circulation equipment, cooling the surface of the oxygen active group gas generation equipment by circulating water cooled to 4 ℃, transferring waste heat generated by the oxygen active group gas generation equipment in the operation, and ensuring the normal operation of the equipment;
7) opening a 4 th electromagnetic valve and a 3 rd mechanical pump, controlling the water flow of the branch pipeline through a 2 nd water flow meter, performing secondary filtration on part of water passing through a constant pressure type filter tank through a bag filter, pumping the water into a water inlet of a Venturi gas-liquid mixing device through a booster pump, fully mixing the water with gaseous oxygen active groups generated by atmospheric pressure ionization discharge in the Venturi gas-liquid mixing device, allowing a hydroxyl radical solution generated after gas-liquid mixing and dissolving to enter a decompression buffer, reducing the pressure at the outlet end of the gas-liquid mixing and dissolving device through the decompression buffer, enhancing the hydraulic cavitation effect of the gas-liquid mixing and dissolving of the oxygen active group gas and the water solution, prolonging the reaction time of the contact and collision of micro bubbles of the oxygen active group gas and the water, improving the yield of the hydroxyl radical solution, thermally decomposing the gas not dissolved in the water into O through a gas eliminator in a2Discharging, wherein the generated high-concentration hydroxyl radical solution enters a side water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit after being detected by a 1 st TRO on-line detector;
8) opening a 5 th electromagnetic valve and a 6 th electromagnetic valve, opening a 4 th mechanical pump, controlling water flow through a 3 rd water flow meter, pumping filtered water into a main water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit, optionally opening 3-5 ejectors according to the requirement of treatment capacity, fully mixing and reacting the water solution to be treated in the hydroxyl radical oxidation degradation antibiotic reaction unit with high-concentration hydroxyl radical solution sucked by a side water inlet, and mineralizing the antibiotics in the water body into CO by the hydroxyl radical2And H2And O. Detecting the concentration of the total oxidant in the pipeline by using a 2 nd TRO on-line detector, and discharging water treated by hydroxyl radicals into a clean water tank;
9) when the detection result in the step 1) shows that the source water does not contain quinolone antibiotics, closing the hydroxyl radical generating unit and the hydroxyl radical oxidation degradation antibiotic reaction unit, and opening the chlorine disinfection unit;
10) closing the 6 th electromagnetic valve, opening the 7 th electromagnetic valve, opening the 8 th electromagnetic valve and the 5 th mechanical pump of the chlorine disinfection unit, controlling the flow by using a 4 th water flow meter, pumping sodium hypochlorite mother liquor into the main pipeline to perform a mixing reaction with filtered water after detecting the sodium hypochlorite mother liquor by using a 3 rd TRO online detector, detecting the concentration of a total oxidant in the chlorine disinfection pipeline by using the 4 th TRO online detector, and discharging the chlorine disinfection water into a clean water tank;
11) opening the 4 th unit water outlet valve to detect the water sample after hydroxyl radical or chlorine disinfection, opening the 9 th electromagnetic valve when the quinolone antibiotics in the treated water body are completely degraded and the water quality index reaches the national sanitary Standard for Drinking Water (GB5749-2006), and discharging or inputting the treated water into a water distribution network for subsequent use; and when the quinolone antibiotics in the treated water body are not completely degraded, opening the 10 th electromagnetic valve for subsequent advanced treatment.
In the step 1), polyaluminium chloride is used as a coagulant in the flocculation tank, the coagulant adding amount is controlled to be 10-15 mg/L, and the stirring speed is 12-15 r/min. Polyaluminium chloride with Ca (HCO) in water3)2、Ca(OH)2Wait for reaction to produce Al (OH)3The colloid can adsorb impurities in water, so that the colloid and the turbidity substances in the water are subjected to coprecipitation reaction, large particles are generated, and the effect of rapid sedimentation is achieved.
In the step 2), the clarification tank is an inclined plate type clarification tank, the length of inclined plates is 1.5-2.0 m, the clear distance between the inclined plates is not less than 30mm, an angle of 60 degrees is formed between the clear distance and the horizontal plane, the water depth of the upper layer of the inclined plates is 0.8m, the water depth of the bottom buffer layer is 1.5m, and the hydraulic retention time can be 2-4 h.
In the step 3), the filler of the constant-pressure filter tank can be a diatomite covering film, and the removal minimum particle size can be 0.3-10 μm.
In the step 5), the oxygen flux can be 5-8 m3The concentration of the oxygen active groups generated by the atmospheric pressure electric field discharge can be 100-150 mg/L, and the gas generation amount of the oxygen active groups can be 300-600 g/h.
In the step 7), the aperture of the bag filter can be 20-50 μm, and the bag filter is used for filtering small-molecular organic suspended matters and particles in the water body and reducing the consumption of the turbidity of the water body on hydroxyl radicals; what is needed isThe flow rate of water in the branch pipeline can be 30-50 m3And h, enabling the oxygen active group gas to generate a high-concentration hydroxyl radical solution through a free radical chain reaction in water through a Venturi gas-liquid mixing and dissolving device, wherein the total oxidant concentration is 5-15 mg/L, and the hydroxyl radical generation time is 0.1-2 s.
In the step 8), the hydroxyl radical oxidation degradation antibiotic reaction unit can selectively start 3-5 negative pressure ejectors according to the treatment capacity of water to be treated, and the water flow is 300-500 m3The reaction time of liquid-liquid mixing and dissolving is 10-25 s, and the total oxidant concentration is 0.2-1.0 mg/L; the negative pressure jet action of the negative pressure jet device generates violent shock waves, micro jet and water flow stirring, promotes the efficient mixing of the hydroxyl radical solution and the water to be treated, and under the extreme reaction condition of high temperature and high pressure at the moment of cavitation bubble collapse, the reaction rate of the hydroxyl radical oxidation degradation antibiotics is greatly improved, and the water quality is improved while the antibiotics are mineralized.
In the step 10), 5% NaClO solution can be adopted for disinfection in the chlorine disinfection process, the adding 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.
The invention has the following technical effects and advantages:
1) in hydroxyl radical generating equipment, the concentration of oxygen active group gas generated by atmospheric pressure ionization discharge is 100-150 mg/L, hydroxyl radical solution is efficiently prepared under the extreme reaction condition formed by a Venturi gas-liquid mixing and dissolving device, the concentration of total oxidants mainly containing hydroxyl radicals is 5-15 mg/L, the time for generating the hydroxyl radicals is 0.1-2 s, and the yield of the hydroxyl radical solution is 30-50 m3/h。
2) The negative pressure jetting effect of the hydroxyl radical oxidation degradation antibiotic reaction unit generates violent shock waves, micro jet flow and water flow stirring, promotes the efficient mixing and dissolution of the hydroxyl radical solution and the water to be treated, and greatly improves the contact collision probability and efficiency of the hydroxyl radical, the antibiotic and other organic pollutants. The concentration of the oxygen radical solution mainly containing the hydroxyl radical in the hydroxyl radical oxidation degradation antibiotic reaction unit can reach 3-6 times of the concentration of the antibiotic to be treated, and the hydroxyl radical oxidation degradation antibiotic reaction unitThe mineralization of organic pollutants such as antibiotics is completed, and the maximum water treatment capacity is 500m3H is used as the reference value. The time for the water to be treated to flow through the OH oxidation degradation antibiotic reactor is 10-25 s, and the concentration of the antibiotic after treatment is not detected.
3) OH is mainly used for opening a piperazine ring and a naphthyridine ring by attacking an N atom on the piperazine ring and a double bond on the naphthyridine ring of the quinolone antibiotic to replace fluorine atoms, so that the pharmacophore of norfloxacin is effectively degraded in an oxidizing way, and the degraded product has no antibacterial activity. Further reaction of OH with the oxidized radical of the benzene ring cation leads to cleavage of the aromatic ring, completely mineralizing it as CO2、H2O and inorganic ions. OH can reduce parameters such as turbidity, COD and the like of the water body, improve the water quality and purify the water body while mineralizing the antibiotics.
4) The processing capacity of the equipment developed by the invention can reach 300-500 m3The method has the advantages of simple operation, low operation cost and small occupied area. Can efficiently and safely mineralize organic pollutants such as antibiotics and the like in the water body, and provides practical equipment for the engineering application of the advanced oxidation technology.
Drawings
Fig. 1 is a schematic structural composition diagram of an embodiment of the device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals according to the invention.
FIG. 2 is a high performance liquid chromatogram of a hydroxyl radical mineralized norfloxacin. In FIG. 2, curve a shows norfloxacin before the hydroxyl treatment, and curve b shows no detection after the hydroxyl treatment.
FIG. 3 is a graph showing the oxidative degradation pathway of hydroxyl radical mineralized norfloxacin.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
As shown in FIG. 1, the embodiment of the device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals is provided with a hydroxyl radical generating device A, an OH oxidative degradation antibiotic reactor B, a chlorine disinfection unit C, a flocculation tank 1, a clarification tank 2, a constant pressure filtration tank 3, a clean water tank 4, a 1 st TRO on-line detector 51, a 2 nd TRO on-line detector 52, a 3 rd TRO on-line detector 53, a 4 th TRO on-line detector 54, a 1 st mechanical pump 61, a 2 nd mechanical pump 62, a 3 rd mechanical pump 63, a 4 th mechanical pump 64, a 5 th mechanical pump 65, a 1 st water flow meter 71, a 2 nd water flow meter 72, a 3 rd water flow meter 73, a 4 th water flow meter 74, a 1 st electromagnetic valve 81, a 2 nd electromagnetic valve 82, a 3 rd electromagnetic valve 83, a 4 th electromagnetic valve 84, a 5 th electromagnetic valve 85, a 6 th electromagnetic valve 86, a 7 th electromagnetic valve 87, an 8 th electromagnetic valve 88, a 9 th electromagnetic valve 89, a 10 th, A unit 1 water outlet valve 91, a unit 2 water outlet valve 92, a unit 3 water outlet valve 93, a unit 4 water outlet valve 94 and a sodium hypochlorite storage tank 10.
The hydroxyl radical generating equipment A comprises an atmospheric pressure ionization discharge oxygen plasma integrated source, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid mixing and dissolving device, a booster pump, a decompression buffer, a bag filter and cooling water circulating equipment.
The OH oxidative degradation antibiotic reactor B is formed by connecting five negative pressure jet devices in parallel, a main water inlet is connected with a main water delivery pipeline, and a side water inlet is connected with a water outlet of high-concentration hydroxyl radical generating equipment. Selectively starting 3-5 ejectors capable of processing 300-500 m3The antibiotic solution is used for mixing and dissolving the high-concentration hydroxyl radical solution and the high-efficiency liquid of the treated water.
The chlorine disinfection unit C comprises a sodium hypochlorite storage tank 10, an 8 th electromagnetic valve 88, a 5 th mechanical pump 65, a 4 th water flow meter 74 and a 4 th TRO online detector 54. The chlorine disinfection unit C is used for inactivating bacteria, viruses and protozoa in water, controlling the regrowth of microorganisms in the water delivery process and inhibiting the growth of a pipe wall biofilm.
The source water to be treated is connected with the water inlet of the 1 st mechanical pump 61 of the main pipeline, and a 1 st electromagnetic valve 81 is arranged between the source water to be treated and the 1 st mechanical pump 61. The water outlet of the 1 st mechanical pump 61 is connected with the water inlet of the 1 st water flow meter 71, and a 1 st unit water outlet valve 91 is arranged between the 1 st mechanical pump 61 and the 1 st flow meter 71. The water outlet of the 1 st water flowmeter 71 is connected with the water inlet of the flocculation tank 1, the water outlet of the flocculation tank 1 is connected with the water inlet of the clarification tank 2, and a 2 nd electromagnetic valve 82 is arranged between the flocculation tank 1 and the clarification tank 2. The water outlet of the clarification tank 2 is connected with the water inlet of the 2 nd mechanical pump 62, and a 2 nd unit water outlet valve 92 and a 3 rd electromagnetic valve 83 are arranged between the water outlet of the clarification tank 2 and the water inlet of the 2 nd mechanical pump 62. The water outlet of the No. 2 mechanical pump 62 is connected with the water inlet of the constant pressure filtering tank 3, and the water outlet of the constant pressure filtering tank 3 is provided with a No. 3 unit water outlet valve 93.
The water outlet of the constant pressure filter tank 3 is divided into two paths, one path is connected with the water inlet of the 3 rd mechanical pump 63 on the branch pipeline, and a 4 th electromagnetic valve 84 is arranged between the water outlet of the constant pressure filter tank 3 and the water inlet of the 3 rd mechanical pump 63. The water outlet of the 3 rd mechanical pump 63 is connected with the water inlet of a 2 nd water flow meter 72, the water outlet of the 2 nd water flow meter 72 is connected with the water inlet of a venturi gas-liquid mixing device in the hydroxyl radical generating device A, the water outlet of the venturi gas-liquid mixing device is connected with the branch water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit B, and a 1 st TRO online detector 51 is arranged between the water outlet of the venturi gas-liquid mixing device and the branch water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit B; the other path of the water outlet of the constant pressure filter tank 3 is connected with the water inlet of the 4 th mechanical pump 64 on the main pipeline, and a 5 th electromagnetic valve 85 is arranged between the water outlet of the constant pressure filter tank 3 and the water inlet of the 4 th mechanical pump 64. The 4 th mechanical pump 64 water outlet is connected with the 3 rd water flow meter 73 water inlet.
The water outlet of the 3 rd water flow meter 73 is divided into two paths, one path is connected with the main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit B, and a 6 th electromagnetic valve 86 is arranged between the 3 rd water flow meter 73 and the hydroxyl radical oxidation degradation antibiotic reaction unit B. A 2 nd TRO online detector 52 is arranged between the water outlet of the hydroxyl radical oxidation and degradation antibiotic reaction unit B and the clean water tank 4; the other path of the water outlet of the 3 rd water flow meter 73 is connected with the water inlet of the chlorine disinfection unit C, and a 7 th electromagnetic valve 87 is arranged between the water outlet of the 3 rd 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 with the water inlet of the clean water tank 4, and a 3TRO on-line detector 53 is arranged between the water outlet of the chlorine disinfection unit C and the water inlet of the clean water tank 4.
The water outlet of the clean water tank 4 is provided with a unit 4 water outlet valve 94, the water outlet of the clean water tank 4 is divided into two paths, and one path is connected with an external discharge pipeline or a water supply pipe network; the other path is connected with a water inlet of a subsequent advanced treatment process.
The specific steps of the method for degrading and mineralizing the quinolone antibiotics by the hydroxyl radicals are given as follows:
1) the 1 st electromagnetic valve 81 is opened, the 1 st mechanical pump 61 is started, the 1 st unit water outlet valve 91 is used for sampling, and water quality parameters such as COD, turbidity and pH in the raw water and the antibiotic concentration are detected. When quinolone antibiotics are detected in raw water, starting a hydroxyl radical generating device A and a hydroxyl radical oxidation degradation antibiotic reaction unit B (see steps 4-8 for details); when no quinolone antibiotics are detected in the raw water, the hydroxyl radical generating equipment A and the hydroxyl radical oxidation degradation antibiotic reaction unit B are closed, and the chlorine disinfection unit C is started (see steps 9-10 for details). The water flow is controlled by a 1 st water flow meter 71, 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 polyaluminium chloride as a coagulant, the adding amount of the coagulant is controlled to be 10-15 mg/L, and the stirring speed is 12-15 r/min. Polyaluminium chloride with Ca (HCO) in water3)2、Ca(OH)2Wait for reaction to produce Al (OH)3The colloid can adsorb impurities in water, so that the colloid and the turbidity substances in the water are subjected to coprecipitation reaction, large particles are generated, and the effect of rapid sedimentation is achieved.
2) The 2 nd electromagnetic valve 82 is opened, and the effluent of the flocculation tank 1 enters the clarification tank 2 through gravity settling. The alum floc generated in the flocculation tank 1 is settled in the clarification tank 2, and the ratio of the particle settling speed to the horizontal flow speed in the clarification tank 2 is controlled to be 20: 1-40: 1. The effluent of the clarification tank 2 is sampled and detected by a 2 nd unit effluent valve 92, and the turbidity of the water body is controlled within 3.0 NTU.
The clarification tank 2 is an inclined plate type clarification tank, the length of inclined plates is 1.5-2.0 m, the clear distance between the inclined plates is not less than 30mm, an angle of 60 degrees is formed between the inclined plates and the horizontal plane, the water depth of the upper layer of each inclined plate is 0.8m, the water depth of the bottom buffer layer is 1.5m, and the hydraulic retention time is 2-4 h.
3) And opening the 3 rd electromagnetic valve 83, starting the 2 nd mechanical pump 62, and pumping the water to be treated which passes through the flocculation tank 1 and the clarification tank 2 into the constant-pressure filtration tank 3 for filtration. The porous medium in the constant pressure filter tank 3 can sieve and intercept solid particles in water to remove suspended substances and colloids in the water. The effluent of the constant pressure filter tank 3 is sampled and detected by a 3 rd unit effluent valve 93, and the turbidity of the water body is controlled within 0.3 NTU.
The filler of the constant-pressure filter tank 3 is a diatomite covering film, and the minimum removal particle size is 10-0.3 mu m.
4) And (2) when the detection result in the step 1) shows that the source water contains the quinolone antibiotics, starting the hydroxyl radical generating equipment A and the hydroxyl radical oxidation and degradation antibiotic reaction unit B (step 5-8).
5) And opening an oxygen cylinder valve, and introducing oxygen into the atmospheric pressure ionization discharge oxygen plasma integrated source through a dryer and a mass flow controller. The high-frequency high-voltage power supply of the partition excitation type forms atmospheric pressure ionization discharge in an extremely narrow discharge gap, oxygen is ionized and dissociated to generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups enter an air inlet of the Venturi gas-liquid mixing and dissolving device after the concentration of the gaseous oxygen active groups is detected by the on-line oxygen active group detector.
The oxygen flux is 5-8 m3The concentration of oxygen active groups generated by atmospheric pressure electric field discharge is 100-150 mg/L, and the generation amount of oxygen active group gas is 300-600 g/h.
6) And starting cooling water circulation equipment, opening a water outlet valve of the cooling water circulation equipment, cooling the surface of the oxygen active group gas generation equipment by circulating water cooled to 4 ℃, transferring waste heat generated by the oxygen active group gas generation equipment in the running process, and ensuring the normal running of the equipment.
7) And opening the 4 th electromagnetic valve 84 and the 3 rd mechanical pump 63, controlling the water flow of the branch pipeline through the 2 nd water flow meter 72, performing secondary filtration on part of the water passing through the constant pressure type filter tank 3 through a bag filter, pumping the water into a water inlet of the Venturi gas-liquid mixing and dissolving device through a booster pump, and fully mixing the water with gaseous oxygen active groups generated by atmospheric pressure ionization discharge in the Venturi gas-liquid mixing and dissolving device. The hydroxyl radical solution generated after gas-liquid mixing enters a decompression buffer, the pressure at the outlet end of the gas-liquid mixing equipment is reduced through the decompression buffer, the hydrodynamic cavitation effect of the gas-liquid mixing of the oxygen active radical gas and the water solution is enhanced, the reaction time of the contact collision of the burst micro bubbles and the water is prolonged, and the yield of the hydroxyl radical solution is improved. Gas not dissolved in waterThermal decomposition into O by gas eliminator in gas-liquid separator2And (5) discharging. The generated high-concentration hydroxyl radical solution is detected by a 1 st TRO on-line detector 51 and then enters a side water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit B.
The bag filter has the aperture of 20-50 microns, and is used for filtering small-molecular organic suspended matters and particles in a water body and reducing the consumption of hydroxyl radicals caused by the turbidity of the water body. The flow rate of water in the branch pipeline is 30-50 m3And h, enabling the oxygen active group gas to generate a high-concentration hydroxyl radical solution through a free radical chain reaction in water through a Venturi gas-liquid mixing and dissolving device, wherein the total oxidant concentration is 5-15 mg/L, and the hydroxyl radical generation time is 0.1-2 s.
8) And opening a 5 th electromagnetic valve 85 and a 6 th electromagnetic valve 86, opening a 4 th mechanical pump 64, controlling the water flow through a 3 rd water flow meter 73, and pumping the filtered water into a main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit B. According to the requirement of the treatment capacity, 3-5 ejectors can be selected to be started. The water solution to be treated is fully mixed and reacted with the high-concentration hydroxyl radical solution sucked from the side water inlet in the hydroxyl radical oxidation degradation antibiotic reaction unit B, and the hydroxyl radical mineralizes the antibiotic in the water body into CO2And H2And O. The total oxidant concentration in the pipeline is detected by using a 2 nd TRO on-line detector 52, and the water treated by the hydroxyl radicals is discharged into the clean water tank 4.
The hydroxyl radical oxidation degradation antibiotic reaction unit B can selectively start 3-5 negative pressure ejectors according to the treatment capacity of water to be treated, and the water flow is 300-500 m3The reaction time of the liquid-liquid mixing and dissolving is 10-25 s, and the total oxidant concentration is 0.2-1.0 mg/L. The negative pressure jetting effect of the negative pressure jet device generates violent shock waves, micro jet flow and water flow stirring, and the efficient mixing of the hydroxyl radical solution and the water to be treated is promoted. The cavitation bubble breaks the extreme reaction condition of high temperature high pressure in the moment, raise the reaction rate of hydroxy radical oxidation degradation antibiotic greatly, improve the water quality while mineralizing the antibiotic.
9) And (3) when the detection result in the step 1) shows that the source water does not contain the quinolone antibiotics, closing the hydroxyl radical generating device A and the hydroxyl radical oxidation degradation antibiotic reaction unit B, and opening the chlorine disinfection unit C (step 10).
10) Closing the 6 th electromagnetic valve 86, opening the 7 th electromagnetic valve 87, opening the 8 th electromagnetic valve 88 of the chlorine disinfection unit C, using the 4 th water flowmeter 74 to control the flow, detecting the sodium hypochlorite mother liquor through the 3 rd TRO on-line detector 53, and pumping the sodium hypochlorite mother liquor into the main pipeline to perform mixed reaction with the filtered water. The total oxidant concentration in the chlorine-disinfected pipeline is detected by using a 4 th TRO on-line detector 54, and the water disinfected by chlorine is discharged into the clean water tank 4.
In the chlorine disinfection process, 5% NaClO solution is adopted for disinfection, the adding 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) Opening the 4 th unit water outlet valve 94 to detect the water sample after hydroxyl radical or chlorine disinfection, opening the 9 th electromagnetic valve 89 after the quinolone antibiotics in the treated water body are completely degraded and the water quality index reaches the national sanitary Standard for Drinking Water (GB5749-2006), and discharging or inputting the treated water into a water distribution network for subsequent use; when the quinolone antibiotics in the treated water body are not completely degraded, the 10 th electromagnetic valve 810 is opened for subsequent advanced treatment.
Specific examples are given below:
the water in a certain basin polluted by antibiotics needs to be discharged after emergency treatment. The water quality conditions of the water to be treated are as follows: temperature 26.5 ℃, turbidity 11.8NTU, pH 7.29, oxygen consumption 6.0 mg/L. And (3) detecting that the concentration of sulfadiazine in the water is 80ng/L, closing the chlorine disinfection unit, and starting the hydroxyl radical mineralized antibiotic unit. And determining the concentration of the total oxidant to be added to be 0.5mg/L according to the water quality condition and the antibiotic concentration.
The sulfadiazine-containing water is mixed with water of 300m3Pumping into a main pipeline at a flow speed of/h, settling large particles in a water body and alum floc generated by a flocculating agent in a settling pond, and filtering out suspended substances and colloids in water through a constant-pressure filtering pond. At 50m3The filtered water is pumped into a high-efficiency gas-liquid mixing and dissolving device at the water flow speed/h to efficiently generate hydroxyl radicals with gaseous oxygen active groupsThe total oxidant concentration is 4mg/L, and the total oxidant and the filtered water in the main pipeline fully react in the hydroxyl radical oxidation degradation antibiotic reaction unit. According to the requirement of treatment capacity, 5 negative pressure ejectors in the hydroxyl radical oxidative degradation antibiotic reaction unit are selectively started, and the water flow rate is 300m3The hydraulic retention time of the hydroxyl radical oxidation and degradation antibiotic reaction unit of the water unit to be treated is 15s, and the total oxidant concentration after mixing and dissolving is 0.5 mg/L.
The concentration of norfloxacin in the water treated by the hydroxyl free radicals is reduced to be not detected (see figure 2), and the norfloxacin can be safely discharged after being detected to be qualified. The oxidative degradation pathway of hydroxyradical mineralized norfloxacin is shown in fig. 3.

Claims (10)

1. The device for degrading and mineralizing quinolone antibiotics by hydroxyl radicals is characterized by being provided with hydroxyl radical generating equipment, an OH oxidation degradation antibiotic reactor, a chlorine disinfection unit, a flocculation tank, a clarification tank, a constant pressure filtration tank, a clean water tank, a 1 st TRO online detector, a 2 nd TRO online detector, a 3 rd TRO online detector, a 4 th TRO online detector, a 1 st mechanical pump, a 2 nd mechanical pump, a 3 rd mechanical pump, a 4 th mechanical pump, a 5 th mechanical pump and a 1 st water flow meter, the water flow meter comprises a 2 nd water flow meter, a 3 rd water flow meter, a 4 th water flow meter, a 1 st electromagnetic valve, a 2 nd electromagnetic valve, a 3 rd electromagnetic valve, a 4 th electromagnetic valve, a 5 th electromagnetic valve, a 6 th electromagnetic valve, a 7 th electromagnetic valve, an 8 th electromagnetic valve, a 9 th electromagnetic valve, a 10 th electromagnetic valve, a 1 st unit water outlet valve, a 2 nd unit water outlet valve, a 3 rd unit water outlet valve, a 4 th unit water outlet valve and a sodium hypochlorite storage tank;
the hydroxyl radical generating equipment is provided with an atmospheric pressure ionization discharge oxygen plasma integrated source, a partition excitation type high-frequency high-voltage power supply, a Venturi gas-liquid mixing and dissolving device, a booster pump, a decompression buffer, a bag filter and cooling water circulating equipment;
the hydroxyl radical oxidation degradation antibiotic reaction unit is provided with 5 negative pressure jet devices which are connected in parallel, a main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with a main water delivery pipeline, and a side water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with a water outlet of the high-concentration hydroxyl radical generation equipment;
the chlorine disinfection unit is provided with a sodium hypochlorite storage tank, an 8 th electromagnetic valve, a 5 th mechanical pump, a 4 th water flowmeter and a 4 th TRO online detector, and is used for inactivating bacteria, viruses and protozoa in water, controlling the regrowth of microorganisms in the water delivery and distribution process and inhibiting the growth of a pipe wall biofilm;
the water outlet of the 1 st mechanical pump is connected with the water inlet of a 1 st mechanical pump of the main pipeline, a 1 st electromagnetic valve is arranged between the water source to be treated and the 1 st mechanical pump, the water outlet of the 1 st mechanical pump is connected with the water inlet of a 1 st water flowmeter, a 1 st unit water outlet valve is arranged between the 1 st mechanical pump and the 1 st water flowmeter, the water outlet of the 1 st water flowmeter is connected with the water inlet of a flocculation basin, the water outlet of the flocculation basin is connected with the water inlet of a clarification basin, a 2 nd electromagnetic valve is arranged between the flocculation basin and the clarification basin, the water outlet of the clarification basin is connected with a 2 nd mechanical pump water inlet, a 2 nd unit water outlet valve and a 3 rd electromagnetic valve are arranged between the water outlet of the clarification basin and the 2 nd mechanical pump;
the water outlet of the constant pressure filter tank is divided into two paths, one path is connected with the water inlet of a 3 rd mechanical pump on the branch pipeline, a 4 th electromagnetic valve is arranged between the water outlet of the constant pressure filter tank and the water inlet of the 3 rd mechanical pump, the water outlet of the 3 rd mechanical pump is connected with the water inlet of a 2 nd water flow meter, the water outlet of the 2 nd water flow meter is connected with the water inlet of a venturi gas-liquid mixing and dissolving device in the hydroxyl radical generating equipment, the water outlet of the venturi gas-liquid mixing and dissolving device is connected with the branch water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, and a 1 st TRO online detector is arranged between the water outlet of the venturi gas-liquid mixing and; the other path of the water outlet of the constant-pressure filter tank is connected with the water inlet of a 4 th mechanical pump on the main pipeline, a 5 th electromagnetic valve is arranged between the water outlet of the constant-pressure filter tank and the water inlet of the 4 th mechanical pump, and the water outlet of the 4 th mechanical pump is connected with the water inlet of a 3 rd water flowmeter;
the water outlet of the 3 rd water flow meter is divided into two paths, one path is connected with a main water inlet of the hydroxyl radical oxidation degradation antibiotic reaction unit, a 6 th electromagnetic valve is arranged between the 3 rd water flow meter and the hydroxyl radical oxidation degradation antibiotic reaction unit, the water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit is connected with the water inlet of the clean water tank, and a 2 nd TRO online detector is arranged between the water outlet of the hydroxyl radical oxidation degradation antibiotic reaction unit and the clean water tank; the other path of the water outlet of the 3 rd water flowmeter is connected with a water inlet of a chlorine disinfection unit, a 7 th electromagnetic valve is arranged between the water outlet of the 3 rd water flowmeter and the water inlet of the chlorine disinfection unit, the water outlet of the chlorine disinfection unit is connected with the water inlet of a clean water pool, and a 3 rd TRO on-line detector is arranged between the water outlet of the chlorine disinfection unit and the water inlet of the clean water pool;
the water outlet of the clean water tank is provided with a 4 th unit water outlet valve, and the water outlet of the clean water tank is divided into two paths, wherein one path is connected with an external discharge pipeline or a water supply pipe network; the other path is connected with a water inlet of a subsequent advanced treatment process.
2. Process for the degradation of mineralized quinolone antibiotics with hydroxyl radicals, characterized in that with the device for the degradation of mineralized quinolone antibiotics with hydroxyl radicals according to claim 1,. OH opens the piperazine ring and the naphthyridine ring by attacking the N atom on the piperazine ring and the double bond on the naphthyridine ring of quinolone antibiotics, replacing fluorine atoms, effectively oxidatively degrading the pharmacophore of norfloxacin, the degradation products are free from antibacterial activity, further reaction of OH with the benzene ring cation free radicals leads to cleavage of the aromatic ring, completely mineralizing it to CO2、H2O and inorganic ions; the method comprises the following steps:
1) opening a 1 st electromagnetic valve, opening a 1 st mechanical pump, sampling by using a 1 st unit water outlet valve, detecting COD, turbidity, pH water quality parameters and antibiotic concentration in raw water, and opening a hydroxyl radical generating device and a hydroxyl radical oxidation degradation antibiotic reaction unit when quinolone antibiotics are detected in the raw water; when no quinolone antibiotics are detected in the raw water, closing the hydroxyl radical generating equipment and the hydroxyl radical oxidation degradation antibiotic reaction unit, starting the chlorine disinfection unit, controlling the water flow through the No. 1 water flow meter, pumping the raw water to be treated into a flocculation tank, and removing impurities in the water body through coagulation reaction;
2) opening the 2 nd electromagnetic valve, enabling the effluent of the flocculation tank to enter a clarification tank through gravity settling, settling alum floc generated in the flocculation tank in the clarification tank, wherein the ratio of the particle settling speed to the horizontal flow speed in the clarification tank is (20-40): 1, sampling and detecting the effluent of the clarification tank through the 2 nd unit effluent valve, and controlling the turbidity of the water body within 3.0 NTU;
3) opening a 3 rd electromagnetic valve, opening a 2 nd mechanical pump, pumping the water to be treated which passes through the flocculation tank and the clarification tank into a constant pressure filter tank for filtering, wherein the porous medium in the constant pressure filter tank can sieve and intercept solid particles in the water, so as to remove suspended substances and colloids in the water, the effluent of the constant pressure filter tank is sampled and detected by a 3 rd unit water outlet valve, and the turbidity of the water body is controlled within 0.3 NTU;
4) when the detection result in the step 1) shows that the source water contains the quinolone antibiotics, starting hydroxyl radical generating equipment and a hydroxyl radical oxidation and degradation antibiotic reaction unit;
5) opening an oxygen cylinder valve, and allowing oxygen to enter an atmospheric pressure ionization discharge oxygen plasma integrated source through a dryer and a mass flow controller; the high-frequency high-voltage power supply of the partition excitation type forms atmospheric pressure ionization discharge in an extremely narrow discharge gap, oxygen is ionized and dissociated to generate high-concentration oxygen active groups, and the generated gaseous oxygen active groups enter an air inlet of the Venturi gas-liquid mixing and dissolving device after the concentration of the gaseous oxygen active groups is detected by an online oxygen active group detector;
6) starting cooling water circulation equipment, opening a water outlet valve of the cooling water circulation equipment, cooling the surface of the oxygen active group gas generation equipment by circulating water cooled to 4 ℃, transferring waste heat generated by the oxygen active group gas generation equipment in the operation, and ensuring the normal operation of the equipment;
7) opening the 4 th electromagnetic valve and the 3 rd mechanical pump, controlling the water flow of the branch pipeline through the 2 nd water flow meter, performing two-stage filtration on part of water passing through the constant pressure type filter tank through a bag filter, pumping the water into a water inlet of a Venturi gas-liquid mixing and dissolving device through a booster pump, fully mixing the water and gaseous oxygen active groups generated by atmospheric pressure ionization discharge in the Venturi gas-liquid mixing and dissolving device, allowing a hydroxyl radical solution generated after gas-liquid mixing and dissolving to enter a decompression buffer, and reducing the gas-liquid flow through the decompression bufferThe pressure at the outlet end of the mixing and dissolving equipment enhances the hydrodynamic cavitation effect of gas-liquid mixing and dissolving of the oxygen active group gas and the aqueous solution, prolongs the reaction time of contact and collision of micro bubbles and water, improves the yield of the hydroxyl radical solution, and the gas which is not dissolved in the water is thermally decomposed into O through a gas eliminator in a gas-liquid separator2Discharging, wherein the generated high-concentration hydroxyl radical solution enters a side water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit after being detected by a 1 st TRO on-line detector;
8) opening a 5 th electromagnetic valve and a 6 th electromagnetic valve, opening a 4 th mechanical pump, controlling water flow through a 3 rd water flow meter, pumping filtered water into a main water inlet of a hydroxyl radical oxidation degradation antibiotic reaction unit, selectively opening 3-5 ejectors according to the requirement of treatment capacity, fully mixing and reacting the water solution to be treated with high-concentration hydroxyl radical solution sucked from a side water inlet in the hydroxyl radical oxidation degradation antibiotic reaction unit, and mineralizing the antibiotics in the water into CO by the hydroxyl radical2And H2O; detecting the concentration of the total oxidant in the pipeline by using a 2 nd TRO on-line detector, and discharging water treated by hydroxyl radicals into a clean water tank;
9) when the detection result in the step 1) shows that the source water does not contain quinolone antibiotics, closing the hydroxyl radical generating unit and the hydroxyl radical oxidation degradation antibiotic reaction unit, and opening the chlorine disinfection unit;
10) closing the 6 th electromagnetic valve, opening the 7 th electromagnetic valve, opening the 8 th electromagnetic valve and the 5 th mechanical pump of the chlorine disinfection unit, controlling the flow by using a 4 th water flow meter, pumping sodium hypochlorite mother liquor into the main pipeline to perform a mixing reaction with filtered water after detecting the sodium hypochlorite mother liquor by using a 3 rd TRO online detector, detecting the concentration of a total oxidant in the chlorine disinfection pipeline by using the 4 th TRO online detector, and discharging the chlorine disinfection water into a clean water tank;
11) opening the 4 th unit water outlet valve to detect the water sample after hydroxyl radical or chlorine disinfection, opening the 9 th electromagnetic valve when the quinolone antibiotics in the treated water body are completely degraded and the water quality index reaches the national sanitary Standard for Drinking Water (GB5749-2006), and discharging or inputting the treated water into a water distribution network for subsequent use; and when the quinolone antibiotics in the treated water body are not completely degraded, opening the 10 th electromagnetic valve for subsequent advanced treatment.
3. The method for degrading and mineralizing a quinolone antibiotic by using a hydroxyl radical according to claim 2, wherein in the step 1), polyaluminum chloride is used as a coagulant in the flocculation tank, the addition amount of the coagulant is controlled to be 10-15 mg/L, and the stirring rate is controlled to be 12-15 r/min.
4. The method of claim 3, wherein the polyaluminum chloride is mixed with Ca (HCO) in water3)2、Ca(OH)2Reaction to form Al (OH)3The colloid can adsorb impurities in water, so that the colloid and the turbidity substances in the water are subjected to coprecipitation reaction, large particles are generated, and the effect of rapid sedimentation is achieved.
5. The method for degrading and mineralizing quinolone antibiotics by using hydroxyl radicals according to claim 2), wherein in the step 2), the clarification tank is a sloping plate clarification tank, the length of the sloping plates is 1.5-2.0 m, the clear distance between the sloping plates is not less than 30mm, the angle between the sloping plates and the horizontal plane is 60 degrees, the water depth of the upper layer of the sloping plates is 0.8m, the water depth of the bottom buffer layer is 1.5m, and the hydraulic retention time is 2-4 h.
6. The method for degrading and mineralizing a quinolone antibiotic by using a hydroxyl radical according to claim 2, wherein in the step 3), the filler of the constant pressure filter tank is a diatomite covering film, and the removal minimum particle size is 0.3-10 μm.
7. The method for degrading and mineralizing a quinolone antibiotic by using hydroxyl radicals according to claim 2, wherein in step 5), the oxygen flux is 5-8 m3The concentration of oxygen active groups generated by atmospheric pressure electric field discharge is 100-150 mg/L, and the gas generation amount of the oxygen active groups is 300-600 g/h.
8. The method for degrading and mineralizing a quinolone antibiotic by using hydroxyl radicals as claimed in claim 2, wherein in step 7), the pore size of the bag filter is 20-50 μm, and the bag filter is used for filtering small-molecule organic suspended matters and particles in water to reduce the consumption of hydroxyl radicals caused by turbidity of the water; the flow rate of water in the branch pipeline is 30-50 m3And h, enabling the oxygen active group gas to generate a high-concentration hydroxyl radical solution through a free radical chain reaction in water through a Venturi gas-liquid mixing and dissolving device, wherein the total oxidant concentration is 5-15 mg/L, and the hydroxyl radical generation time is 0.1-2 s.
9. The method for degrading mineralized quinolone antibiotics with hydroxyl radicals according to claim 2, wherein in step 8), the hydroxyl radical oxidation degradation antibiotic reaction unit selectively starts 3 to 5 negative pressure ejectors according to the treatment capacity of water to be treated, and the water flow rate is 300 to 500m3The reaction time of the liquid-liquid mixing and dissolving is 10-25 s, and the total oxidant concentration is 0.2-1.0 mg/L.
10. The method for degrading and mineralizing quinolone antibiotics by hydroxyl radicals according to claim 2, wherein in the step 10), 5% NaClO solution is adopted for disinfection in the chlorine disinfection process, the adding 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.
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CN107758927A (en) * 2017-11-23 2018-03-06 大连海事大学 A kind of advanced oxidation drinking water water preparation process optimizes checking system

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