CN108658373B - Combined system for removing antibiotics in pharmaceutical wastewater by using hydroxyl radicals - Google Patents

Combined system for removing antibiotics in pharmaceutical wastewater by using hydroxyl radicals Download PDF

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CN108658373B
CN108658373B CN201810477540.7A CN201810477540A CN108658373B CN 108658373 B CN108658373 B CN 108658373B CN 201810477540 A CN201810477540 A CN 201810477540A CN 108658373 B CN108658373 B CN 108658373B
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CN108658373A (en
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田一平
张芝涛
白敏冬
余忆玄
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Dalian Maritime 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
    • C02F1/52—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
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Physical Water Treatments (AREA)

Abstract

Anti-resistance in pharmaceutical wastewater removed by hydroxyl radicalsA combined system of biotin relates to free radical chemistry and water treatment application. The device is provided with a hydroxyl radical solution generating device, a 1 st liquid hydrodynamic cavitation mixing device, a 2 nd liquid hydrodynamic cavitation mixing device, a grid pool, an adjusting pool, a coagulation pool, a primary sedimentation pool, a secondary sedimentation pool, an SBR biochemical reaction pool, 1 st to 3 rd mechanical pumps, 1 st to 4 th water flow meters, 1 st to 10 th electromagnetic valves and 1 st to 5 th unit water outlet valves. While removing antibiotics in the wastewater, the method can reduce the chroma, COD, total organic carbon and the like of the water body, and the chroma of the treated wastewater<30 degree, BOD5<10mg/L、COD<50mg/L ammonia nitrogen<5mg/L, total organic carbon<15mg/L, and each index reaches the requirements of the discharge standard of pharmaceutical industry water pollutants. The system has the advantages of good pollutant treatment effect, high degradation speed, small occupied area, high automation degree and the like.

Description

Combined system for removing antibiotics in pharmaceutical wastewater by using hydroxyl radicals
Technical Field
The invention relates to free radical chemistry and water treatment application, in particular to a combined system for removing antibiotics in pharmaceutical wastewater by using hydroxyl free radicals.
Background
With the development of the modernization of the pharmaceutical technology, the pharmaceutical industry in China is rapidly developed. In the aspect of antibiotic pharmacy, China is in the leading position of the world, more than 300 enterprises in China produce antibiotics of more than 70 varieties accounting for 20% -30% of the world output, and the antibiotics become one of the main antibiotic preparation producing countries in the world.
With the rapid development, the problem of discharging pharmaceutical wastewater is more and more prominent. The antibiotic pharmaceutical wastewater is one of the main types, and is high-concentration organic wastewater which is discharged by the pharmaceutical industry of China and has high chroma, difficult biodegradation and more biological toxic substances. The antibiotic pharmaceutical wastewater is mainly characterized by containing high-concentration organic pollutants and suspended matters, having large changes of acidity and alkalinity and temperature, and a large amount of residual antibiotics, and having obvious microbial inhibition effect. At present, the state has already provided the discharge standard of pharmaceutical industry pollutants, and the environmental pollution degree of the industry is further controlled by adopting a mandatory means.
The domestic method mainly adopts a combined process of pretreatment-hydrolysis (or anaerobic) -aerobic biochemical treatment to treat the high-concentration refractory pharmaceutical wastewater, or mixes the high-concentration pharmaceutical wastewater after the pretreatment and anaerobic biochemical stages with the low-concentration wastewater to carry out the aerobic biochemical treatment together. The physicochemical pretreatment technology mainly comprises an air floatation method, a coagulating sedimentation method, an oxidation flocculation method and the like, and the biochemical treatment mainly adopts an activated sludge method, a biological contact oxidation method, a sequencing batch activated sludge method and the like, so that the treatment effect on pollutants is good. However, antibiotic pharmaceutical wastewater has poor biodegradability, contains high-concentration residual antibiotics, and has strong bacteriostatic activity, required strains are difficult to culture and domesticate, aerobic or anaerobic treatment is difficult, and treatment load is low, so that many existing related wastewater treatment systems cannot achieve the standard treatment. Therefore, the research on the technical process suitable for the treatment of antibiotic pharmaceutical wastewater is urgent.
The advanced oxidation technology is a treatment process with high removal efficiency, no secondary pollution, small selectivity and wide development prospect, and can improve the degradation efficiency of pharmaceutical wastewater aiming at the characteristics of difficult degradation, poor biodegradability and the like. At present, many researchers at home and abroad try to treat high-concentration refractory organic pharmaceutical wastewater by adopting an advanced oxidation technology and obtain a good treatment effect. Compared with the traditional biotechnology, the advanced oxidation technology not only has good effect on removing the COD in the wastewater, but also can effectively degrade the organic pollutants which are difficult to degrade in the wastewater by the characteristics of high oxidation capability, small selectivity, high efficiency and the like of hydroxyl free radicals, and can obviously improve the biodegradability of the wastewater. However, the advanced oxidation technology has the characteristics of high treatment cost, complex part of process equipment and the like, so that the application of the advanced oxidation technology in the practical wastewater treatment engineering is influenced. Most of the domestic products still stay in the laboratory stage, and still many problems need to be solved for realizing industrialization of the advanced oxidation technology.
Disclosure of Invention
The invention aims to provide a combined system for removing antibiotics in pharmaceutical wastewater by using hydroxyl radicals, which can be used as a pretreatment process to improve the biodegradability of the pharmaceutical wastewater, can also be used for further performing advanced treatment on the antibiotic wastewater, removes the antibiotics in the wastewater by using the strong oxidizing property of the hydroxyl radicals, and simultaneously oxidizes organic pollutants which are difficult to biodegrade in the wastewater, thereby providing a new way for efficiently, quickly and industrially treating the antibiotic pharmaceutical wastewater.
The second purpose of the invention is to provide a method for removing antibiotics in pharmaceutical wastewater by hydroxyl radicals.
The combined system for removing antibiotics from pharmaceutical wastewater by using hydroxyl radicals is provided with a hydroxyl radical solution generating device, a 1 st liquid hydrodynamic cavitation mixing device, a 2 nd liquid hydrodynamic cavitation mixing device, a grid pool, an adjusting pool, a coagulation pool, a primary sedimentation pool, a secondary sedimentation pool, an SBR biochemical reaction pool, an online monitor, 1 st to 3 rd mechanical pumps, 1 st to 4 th water flow meters, 1 st to 10 th electromagnetic valves and 1 st to 5 th unit water outlet valves.
The hydroxyl radical solution generating device is used for generating a high-concentration hydroxyl radical solution;
the liquid-liquid hydrodynamic cavitation mixing and dissolving device 1 and the liquid-liquid hydrodynamic cavitation mixing and dissolving device 2 are used for mixing and dissolving high-concentration hydroxyl radical solution and high-efficiency liquid of treated water, so that the preoxidation and advanced treatment of antibiotics and other organic pollutants are realized;
the water inlet of the grating pool is externally connected with the antibiotic pharmaceutical wastewater to be treated through a 1 st mechanical pump, the water outlet of the grating pool is connected with the water inlet of an adjusting pool, the water outlet of the adjusting pool is connected with the water inlet of a coagulation pool, the water outlet of the coagulation pool is connected with the water inlet of a primary sedimentation pool, the water outlet of the primary sedimentation pool is divided into two paths, one path is directly connected with the water inlet of the side end of an SBR biochemical reaction pool, the other path is connected with the water inlet of the side end of a 1 st liquid hydrodynamic cavitation mixing device through a 2 nd mechanical pump, the water outlet of the 1 st liquid hydrodynamic cavitation mixing device is connected with the water inlet of the SBR biochemical reaction pool, the water outlet of the SBR biochemical reaction pool is connected with the water inlet of the side end of a 2 nd liquid hydrodynamic cavitation mixing device, the water outlet of a hydroxyl radical solution generating device is respectively connected with the water inlet of the upper ends of the 1 st liquid hydrodynamic cavitation mixing device and the 2 nd liquid hydrodynamic cavitation mixing device through a 3 rd mechanical pump, and the water outlet of the 2 nd liquid hydrodynamic cavitation mixing device is connected with the water inlet of a secondary sedimentation pool, the water outlet of the secondary sedimentation tank is conveyed to a sewage pipe network through a 4 th mechanical pump;
a 1 st electromagnetic valve is arranged between the 1 st mechanical pump and the antibiotic pharmaceutical wastewater to be treated; a 1 st water flow meter is arranged between the 1 st mechanical pump and the water inlet of the grid pool; a 2 nd electromagnetic valve is arranged between the water outlet of the grating tank and the water inlet of the regulating tank; a 3 rd electromagnetic valve is arranged between the water outlet of the regulating tank and the water inlet of the coagulation tank; a 4 th electromagnetic valve is arranged between the water outlet of the coagulation tank and the water inlet of the primary sedimentation tank; a 1 st water outlet valve and a 6 th electromagnetic valve are arranged between the water outlet of the primary sedimentation tank and the 2 nd mechanical pump, and a 2 nd water flow meter is arranged between the 2 nd mechanical pump and the water inlet at the side end of the 1 st liquid-liquid hydrodynamic cavitation mixing device; a 2 nd water outlet valve is arranged between the water outlet of the 1 st liquid-liquid hydrodynamic cavitation mixing device and the water inlet of the SBR biochemical reaction tank; a 5 th electromagnetic valve is arranged between the pipeline directly connecting the water outlet of the primary sedimentation tank and the water inlet of the SBR biochemical reaction tank; a 9 th electromagnetic valve and a 3 rd water outlet valve are arranged between the water outlet of the SBR biochemical reaction tank and the water inlet at the side end of the 2 nd liquid hydrodynamic cavitation mixing device; an online monitor is arranged between the water outlet of the hydroxyl radical solution generating device and the No. 3 mechanical pump; a 7 th electromagnetic valve and a 3 rd water flow meter are sequentially arranged between the 3 rd mechanical pump and the water inlet at the upper end of the 1 st liquid-liquid hydrodynamic cavitation mixing device; a 4 th water flowmeter and an 8 th electromagnetic valve are sequentially arranged between the 3 rd mechanical pump and the water inlet at the upper end of the 2 nd liquid-liquid hydrodynamic cavitation mixing device; a 4 th water outlet valve is arranged between the water outlet of the 2 nd liquid-liquid hydrodynamic cavitation mixing device and the water inlet of the secondary sedimentation tank; a 5 th water outlet valve and a 10 th electromagnetic valve are sequentially arranged between the water outlet of the secondary sedimentation tank and the 4 th mechanical pump.
The hydroxyl radical solution generating device can be 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 circulation equipment.
The water flow of the first liquid hydrodynamic cavitation mixing device 1 and the second liquid hydrodynamic cavitation mixing device 2 can be 100-200 t/h.
A method for removing antibiotics in pharmaceutical wastewater by hydroxyl radicals comprises the following steps:
1) opening a 1 st electromagnetic valve and a 1 st mechanical pump, controlling the water quantity through a 1 st water flow meter, and pumping the antibiotic pharmaceutical wastewater to be treated into a grid pool.
2) The grid adopts a rotary mechanical grid, the depth of water in front of the grid is 1m, the flow velocity in front of the grid is 0.4m/s, the flow velocity through the grid is 0.4m/s, the width of the grid bars is 0.01m, the width of the gaps of the grid bars is 0.04m, the number of the gaps of the grid bars is 80, and the inclination angle of the grid is 60 degrees. The main function of the grating is to remove larger suspended or floating substances in the wastewater so as to reduce the treatment load of the subsequent water treatment process.
3) And opening the 2 nd electromagnetic valve to convey the effluent of the grating tank to the regulating tank. Effective volume of regulating pool is 1000m3The effective water depth is 3.5m, the hydraulic retention time is 6h, and two reaction stirrers are arranged below the regulating reservoir to uniformly mix the wastewater.
4) And opening the 3 rd electromagnetic valve, and enabling the effluent of the adjusting tank to enter the coagulation tank. The surface load of the coagulation basin is 0.8m3/m2And d, selecting iron salt as a coagulant, optimally adding 800mg/L, stirring at the rotating speed of 10-15 r/min, and controlling the pH value to be 7.5-8.
5) And opening the 4 th electromagnetic valve, and enabling the effluent of the coagulation tank to enter the primary sedimentation tank. The primary sedimentation tank adopts inclined tube type sedimentation with the surface load of 2.8m3/m2d, the pipe diameter of the inclined pipe is 25-35mm, and the length of the inclined pipe>50cm, the inclination angle of the counter current is 60 degrees, the flow rate of the counter current is 10mm/s, and the interception speed is 0.3 mm/s; and sampling the effluent of the primary sedimentation tank by a No. 1 water taking valve, detecting the concentrations of organic pollutants such as antibiotics and the like in the effluent, and determining the amount of the hydroxyl radical solution to be added for water body preoxidation according to the concentrations.
6) If the antibiotics in the effluent of the primary sedimentation tank are easily biodegradable, opening a 5 th electromagnetic valve, and directly feeding the effluent of the primary sedimentation tank into an SBR biochemical reaction tank to carry out biochemical degradation process of the antibiotics; if the antibiotics in the effluent of the primary sedimentation tank are of a type difficult to biodegrade, the antibiotics enter a hydroxyl radical pre-oxidation process; the amount of the hydroxyl radical solution to be added for water pre-oxidation is determined by the water sample of the No. 1 water intake valve.
7) The hydroxyl radical generating device is used for preparing high-concentration hydroxyl solution, and the specific process is as follows: a) oxygen in the OH generating device passes through a subarea excitation plasma generator and is ionized and dissociated into oxygen active groups by the discharge of an atmospheric pressure electric field; b) starting a water diversion pump in the OH generation device to pump clean water from a clean water well to a filter in the OH generation device for coarse filtration; c) the oxygen active groups are efficiently dissolved in the filtered water body through a gas-liquid mixing device in the OH generating device, and after sufficient plasma reaction is carried out in a pressure reduction reactor, a high-concentration hydroxyl radical solution is generated;
in the preparation process of the high-concentration hydroxyl solution, the oxygen flux of the OH generation device is 8-10 m3The concentration of oxygen active groups generated by atmospheric pressure electric field discharge is controlled to be 60-100 mg/L, the yield is 480-800 g/h, and the power of the whole machine is controlled<20 kw; through a gas-liquid miscibility vessel and a pressure reduction reactor, oxygen active groups react in water through a free radical chain to generate a high-concentration hydroxyl free radical solution, and the concentration of a total oxidant is 10-20 mg/L; the flow rate of the generated high-concentration hydroxyl radical solution is 30-50 m3H; the cooling water temperature in the OH generating apparatus is less than 5 ℃.
8) Opening a 6 th electromagnetic valve and a 7 th electromagnetic valve, conveying effluent of a primary sedimentation tank and part of high-concentration hydroxyl solution to a 1 st liquid-liquid mixed-dissolution hydraulic cavitation device, introducing the effluent of the primary sedimentation tank through a side water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device of a 2 nd mechanical pump, introducing part of high-concentration hydroxyl solution through a side water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device of a 3 rd mechanical pump, and performing sufficient mixing reaction on the high-concentration hydroxyl solution and the effluent of the primary sedimentation tank through hydraulic cavitation to realize the oxidative degradation of antibiotics and other organic pollutants; sampling the effluent of the 1 st liquid-liquid mixing and dissolving hydrodynamic cavitation device by a 2 nd water taking valve, and detecting the concentration of organic pollutants such as antibiotics in the pretreated water;
the process of the hydroxyl radical preoxidation of the antibiotic wastewater comprises the following steps: the preoxidation can destroy the drug property groups of the antibiotics, so that the antibiotics lose the drug effect, the influence of the antibiotics on microorganisms in a next biochemical reaction tank is reduced, and meanwhile, macromolecular organic pollutants (or pollutants difficult to biodegrade) in water are degraded into micromolecular substances (or biodegradable substances), so that the biodegradability of the water body is improved, and the next biochemical reaction effect is promoted; efficient liquid-liquid mixing and dissolving of the hydroxyl solution and sand filtration effluent is the core of oxidative degradation of antibiotics and other organic pollutants, the concentration of a total oxidant in water after liquid-liquid mixing and dissolving is 5-10 mg/L, and the liquid-liquid mixing and dissolving reaction time is 6-20 s;
the Venturi ejector in the liquid-liquid mixing and hydraulic cavitation device can generate cavitation flow containing a large number of micro bubbles, so that the collision probability of organic pollutants such as hydroxyl radicals, antibiotics and the like is increased; the local instantaneous high temperature and high pressure generated at the moment of cavitation bubble collapse improve the reaction rate between hydroxyl radicals and organic pollutants, and realize the degradation of the organic pollutants.
9) And (3) leading the effluent of the 1 st liquid-liquid mixing and dissolving hydrodynamic cavitation device to enter an SBR biochemical reaction tank. The water filling ratio of the SBR biochemical reaction tank is 30 percent, and the effective volume of the reaction tank is 500m3The sludge concentration is 4000mg/L, and the sludge load is 0.17kgBOD5/(kgMLSS d); the SBR biochemical reaction tank is internally provided with blast aeration, the air diffuser is an air aerator, and the drainage adopts a buoyancy valve type decanter. And sampling the effluent of the SBR biochemical reaction tank by a 3 rd water taking valve, detecting the concentration of organic pollutants such as antibiotics and the like in the effluent, and determining the amount of the hydroxyl radical solution required to be added for the advanced treatment of the water body according to the concentration.
10) Opening an 8 th electromagnetic valve and a 9 th electromagnetic valve, conveying the effluent of the SBR biochemical reaction tank and part of the high-concentration hydroxyl solution to a 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, enabling the effluent of the SBR biochemical reaction tank to enter through a side water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, enabling part of the high-concentration hydroxyl solution to enter through a 3 rd mechanical pump from an upper end water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, and enabling the high-concentration hydroxyl solution and the effluent of the SBR biochemical reaction tank to perform full mixed reaction through a hydraulic cavitation effect, so that efficient oxidative degradation of residual antibiotic mineralization and other organic pollutants is realized; sampling the outlet water of the 2 nd liquid-liquid mixing and dissolving hydrodynamic cavitation device by a 4 th water taking valve, wherein the antibiotics in the treated water sample are not detected;
the step 9) is a hydroxyl radical advanced treatment process of the antibiotic wastewater, and can carry out mineralization treatment on the residual antibiotic in the water after biochemical treatment and simultaneously carry out further oxidative degradation treatment on other organic pollutants which are not completely subjected to biochemical treatment; after the liquid and the liquid are mixed and dissolved, the concentration of the total oxidant in the water is 1-5 mg/L, and the reaction time of the liquid and the liquid mixing and dissolving is 6-20 s.
11) The 2 nd liquid-liquid mixing and dissolving hydraulic cavitation device discharges and feeds waterAnd (5) putting the mixture into a secondary sedimentation tank for secondary sedimentation treatment. The diameter of the secondary sedimentation tank is 40m, the height of the clear water area is 0.8m, the height of the separation area is 1.5m, the height of the tank edge is 0.3m, and the diameter-depth ratio>6, surface load 0.75m3/m2h, water flow rate 900m3And/h, the settling time is 2h, the settling efficiency is 60 percent, and mechanical sludge discharge is adopted.
12) And opening a 5 th water taking valve to detect the treated water sample. And when the index of the treated wastewater reaches the national discharge standard of pharmaceutical industry water pollutants, opening a 4 th mechanical pump and a 10 th electromagnetic valve, and inputting the treated water in the secondary sedimentation tank into a sewage pipe network.
The invention has the following technical effects and advantages:
1) antibiotic pharmacy waste water system is handled to hydroxyl free radical: the method comprises the steps of grating-adjustment-coagulation-primary sedimentation-OH pretreatment-SBR biochemical reaction-OH oxidation antibiotics-secondary sedimentation-sewage pipe network, wherein the treatment amount is 100-200 t/h, and the antibiotics in the pharmaceutical wastewater after treatment are not detected;
2) the hydroxyl radical solution generating device is used for preparing a total oxidant with the concentration of 10-20 mg/L and the output of more than 30m3The power of the whole machine is less than 20kW, the volume of the container is 3.5m multiplied by 1.5m multiplied by 2m, and the container can be transported on a vehicle;
3) the liquid-liquid hydrodynamic cavitation mixing and dissolving device realizes the mixing and dissolving of the strong-oxidation hydroxyl radical solution and the treated water high-efficiency liquid, enhances the efficiency of organic pollutants such as antibiotics in advanced oxidation treatment wastewater, and has water flow of 100-200 t/h;
4) OH pretreatment of antibiotic pharmaceutical wastewater: OH solution is injected into the antibiotic pharmaceutical wastewater after primary precipitation, so that medicinal groups of the antibiotic in the wastewater are destroyed by pre-oxidation, the antibiotic loses medicinal effect, the influence of the antibiotic on microorganisms in a next biochemical reaction tank is reduced, and meanwhile, macromolecular organic pollutants (or pollutants difficult to biodegrade) in the water are degraded into micromolecular substances (or biodegradable substances), so that the biodegradability of the water body is improved, and the next biochemical reaction effect is promoted; the pre-oxidation treatment time is 6-20 s, and the adding dosage of the OH solution is 5-10 mg/L;
5) OH advanced treatment of antibiotic pharmaceutical wastewater: injecting OH solution into the antibiotic pharmaceutical wastewater after SBR biochemical treatment, mineralizing the residual antibiotic in the water after biochemical treatment, and simultaneously performing further oxidative degradation treatment on other organic pollutants which are not subjected to biochemical treatment; the advanced treatment time is 6-20 s, and the adding dosage of the OH solution is 1-5 mg/L;
6) the treatment system can reduce the chroma, COD, total organic carbon and the like of the water body while removing the antibiotics in the wastewater, and the chroma of the treated wastewater<30 degree, BOD5<10mg/L、COD<50mg/L ammonia nitrogen<5mg/L, total organic carbon<15mg/L, and each index reaches the requirements of the discharge standard of pharmaceutical industry water pollutants. The system has the advantages of good pollutant treatment effect, high degradation speed, small occupied area, high automation degree and the like.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of the combined system for removing antibiotics from pharmaceutical wastewater by hydroxyl radicals according to the present invention.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings.
As shown in FIG. 1, the embodiment of the combined system for removing antibiotics in pharmaceutical wastewater by hydroxyl radicals is provided with: the device comprises a hydroxyl radical solution generating device 1, a liquid-1 hydrodynamic cavitation mixing device 21, a liquid-2 hydrodynamic cavitation mixing device 2122, an SBR biochemical reaction tank 3, a grid tank 4, an adjusting tank 5, a coagulation tank 6, sedimentation tanks 71-72, an online monitor 8, mechanical pumps 91-94, water flow meters 101-104, electromagnetic valves 111-1110 and unit water outlet valves 121-125.
The invention combines the conventional wastewater treatment process and the hydroxyl radical (. OH) oxidation treatment process of pharmaceutical factories, and is provided with a hydroxyl radical solution generating device 1, liquid-liquid hydrodynamic cavitation mixing devices 21-22, an SBR biochemical reaction tank 3, a grid tank 4, an adjusting tank 5, a coagulation tank 6, sedimentation tanks 71-72, an online monitor 8, mechanical pumps 91-94, water flow meters 101-104, electromagnetic valves 111-1110 and unit water outlet valves 121-125.
The hydroxyl radical solution generating device 1 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 and is used for generating a high-concentration hydroxyl radical solution;
the liquid-liquid hydrodynamic cavitation mixing and dissolving device is 21-22, the water flow is 100-200 t/h, and the device is used for mixing and dissolving the high-concentration hydroxyl radical solution and the high-efficiency liquid of the treated water, so that the preoxidation and advanced treatment of antibiotics and other organic pollutants are realized.
The water inlet of the grid pond 4 is externally connected with the antibiotic pharmaceutical wastewater A to be treated through a 1 st mechanical pump 91, the water outlet of the grid pond 4 is connected with the water inlet of an adjusting pond 5, the water outlet of the adjusting pond 5 is connected with the water inlet of a coagulating pond 6, the water outlet of the coagulating pond 6 is connected with the water inlet of a primary sedimentation pond 71, the water outlet of the primary sedimentation pond 71 is divided into two paths, one path is directly connected with the water inlet of an SBR biochemical reaction pond 3, the other path is connected with the water inlet at the side end of a 1 st liquid hydrodynamic cavitation mixing device 21 through a 2 nd mechanical pump 92, the water outlet of the 1 st liquid hydrodynamic cavitation mixing device 21 is connected with the water inlet of an SBR biochemical reaction pond 3, the water outlet of the SBR biochemical reaction pond 3 is connected with the water inlet at the side end of a 2 nd liquid hydrodynamic cavitation mixing device 22, the water outlet of a hydroxyl radical solution generating device 1 is respectively connected with the water inlets at the upper ends of the 1 st liquid hydrodynamic cavitation mixing device 21 and the 2 nd liquid cavitation mixing device 22 through an online mechanical pump 8 and a 3 rd mechanical pump 93, the side water outlet of the 2 nd liquid hydrodynamic cavitation mixing device 22 is connected with the water inlet of the secondary sedimentation tank 72, and the water outlet of the secondary sedimentation tank 72 is conveyed to the sewage pipe network B through the 4 th mechanical pump 94.
A 1 st electromagnetic valve 111 is arranged between the 1 st mechanical pump 91 and the antibiotic pharmaceutical wastewater to be treated; a 1 st water flow meter 101 is arranged between the 1 st mechanical pump 91 and the water inlet of the grating pool 4; a 2 nd electromagnetic valve 112 is arranged between the water outlet of the grating tank 4 and the water inlet of the adjusting tank 5; a 3 rd electromagnetic valve 113 is arranged between the water outlet of the regulating tank 5 and the water inlet of the coagulation tank 6; a 4 th electromagnetic valve 114 is arranged between the water outlet of the coagulation tank 6 and the water inlet of the primary sedimentation tank 71; a 1 st water outlet valve 121 and a 6 th electromagnetic valve 116 are arranged between the water outlet of the primary sedimentation tank 71 and the 2 nd mechanical pump 92, and a 2 nd water flow meter 102 is arranged between the 2 nd mechanical pump 92 and the water inlet at the side end of the 1 st liquid-liquid hydrodynamic cavitation mixing and dissolving device 21; a 2 nd water outlet valve 122 is arranged between the water outlet of the 1 st liquid-liquid hydrodynamic cavitation mixing device 21 and the water inlet of the SBR biochemical reaction tank 3; a 5 th electromagnetic valve 115 is arranged between the pipeline directly connecting the water outlet of the primary sedimentation tank 71 and the water inlet of the SBR biochemical reaction tank 3; a 9 th electromagnetic valve 119 and a 3 rd water outlet valve 123 are arranged between the water outlet of the SBR biochemical reaction tank 3 and the water inlet at the side end of the 2 nd liquid hydrodynamic cavitation mixing device 22; a TRO online detector 8 is arranged between the water outlet of the hydroxyl radical solution generating device 1 and the 3 rd mechanical pump 93; a 7 th electromagnetic valve 117 and a 3 rd water flow meter 103 are sequentially arranged between the 3 rd mechanical pump 93 and the water inlet at the upper end of the 1 st liquid-liquid hydrodynamic cavitation mixing device 21; a 4 th water flowmeter 104 and an 8 th electromagnetic valve 118 are sequentially arranged between the 3 rd mechanical pump 93 and the water inlet at the upper end of the 2 nd liquid-liquid hydrodynamic cavitation mixing device 22; a 4 th water outlet valve 124 is arranged between the water outlet of the 2 nd liquid-liquid hydrodynamic cavitation mixing device 22 and the water inlet of the secondary sedimentation tank 72; a 5 th water outlet valve 125 and a 10 th electromagnetic valve 1110 are sequentially arranged between the water outlet of the secondary sedimentation tank 72 and the 4 th mechanical pump 94.
A method for removing antibiotics in pharmaceutical wastewater by hydroxyl radicals comprises the following steps:
1) opening the 1 st electromagnetic valve 111 and the 1 st mechanical pump 91, controlling the water quantity through the 1 st water flow meter 101, and pumping the antibiotic pharmaceutical wastewater to be treated into the grid pond 4.
2) The grid pool 4 adopts a rotary mechanical grid, the depth of water before the grid is 1m, the flow velocity before the grid is 0.4m/s, the flow velocity through the grid is 0.4m/s, the width of grid bars is 0.01m, the width of grid bar gaps is 0.04m, the number of grid bar gaps is 80, and the grid inclination angle is 60 degrees. The main function of the grating is to remove larger suspended or floating substances in the wastewater so as to reduce the treatment load of the subsequent water treatment process.
3) And opening the 2 nd electromagnetic valve 112 to convey the effluent of the grating tank 4 to the regulating tank 5. The effective volume of the adjusting tank 5 is 1000m3The effective water depth is 3.5m, the hydraulic retention time is 6h, and two reaction stirrers are arranged below the regulating reservoir to uniformly mix the wastewater.
4) And opening a 3 rd electromagnetic valve 113, and leading the effluent of the regulating reservoir 5 to enter a coagulation basin 6. The surface load of the coagulation tank 6 is 0.8m3/m2And d, selecting iron salt as a coagulant, optimally adding 800mg/L, stirring at the rotating speed of 10-15 r/min, and controlling the pH value to be 7.5-8.
5) The 4 th electromagnetic valve 114 is opened, and the coagulation tank 6 discharges waterEnters a primary sedimentation tank 71. The primary sedimentation tank 71 adopts inclined tube type sedimentation with the surface load of 2.8m3/m2d, the pipe diameter of the inclined pipe is 25-35mm, and the length of the inclined pipe>50cm, the inclination angle of the counter current is 60 degrees, the flow rate of the counter current is 10mm/s, and the interception speed is 0.3 mm/s; the effluent of the primary sedimentation tank 71 is sampled by a No. 1 water intake valve 121, and the concentration of organic pollutants such as antibiotics in the effluent is detected.
6) If the antibiotics in the effluent of the primary sedimentation tank 71 are easily biodegradable, opening a 5 th electromagnetic valve 115, and directly feeding the effluent of the primary sedimentation tank 71 into the SBR biochemical reaction tank 3 to perform biochemical degradation process of the antibiotics; if the antibiotics in the effluent of the primary sedimentation tank 71 are of a type difficult to biodegrade, the antibiotics enter a hydroxyl radical pre-oxidation process; the amount of the hydroxyl radical solution to be added for water pre-oxidation is determined by the water sample of the No. 1 water intake valve 121.
7) The hydroxyl radical generating apparatus 1 prepares a high-concentration hydroxyl solution by the following procedure: a) oxygen in the OH generating device passes through a subarea excitation plasma generator and is ionized and dissociated into oxygen active groups by the discharge of an atmospheric pressure electric field; b) starting a water diversion pump in the OH generation device to pump clean water from a clean water well to a filter in the OH generation device for coarse filtration; c) the oxygen active groups are efficiently dissolved in the filtered water body through a gas-liquid mixing device in the OH generating device, and after sufficient plasma reaction is carried out in a pressure reduction reactor, a high-concentration hydroxyl radical solution is generated;
in the preparation process of the high-concentration hydroxyl solution, the oxygen flux of the OH generation device is 8-10 m3The concentration of oxygen active groups generated by atmospheric pressure electric field discharge is controlled to be 60-100 mg/L, the yield is 480-800 g/h, and the power of the whole machine is controlled<20 kW; through a gas-liquid miscibility vessel and a pressure reduction reactor, oxygen active groups react in water through a free radical chain to generate a high-concentration hydroxyl free radical solution, and the concentration of a total oxidant is 10-20 mg/L; the flow rate of the generated high-concentration hydroxyl radical solution is 30-50 m3H; the cooling water temperature in the OH generating apparatus is less than 5 ℃.
8) Opening a 6 th electromagnetic valve 116 and a 7 th electromagnetic valve 117, conveying effluent of a primary sedimentation tank and part of high-concentration hydroxyl solution to a 1 st liquid-liquid mixed-dissolution hydraulic cavitation device 21, introducing effluent of the primary sedimentation tank 71 through a 2 nd mechanical pump 92 through a side water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device 21, introducing part of high-concentration hydroxyl solution through a 3 rd mechanical pump from an upper water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device 21, and performing sufficient mixing reaction on the high-concentration hydroxyl solution and effluent of the primary sedimentation tank 71 through a hydraulic cavitation effect to realize oxidative degradation of antibiotics and other organic pollutants; the effluent of the 1 st liquid-liquid mixing and dissolving hydrodynamic cavitation device 21 is sampled by a 2 nd water intake valve 122, and the concentration of organic pollutants such as antibiotics and the like in the pretreated water is detected;
the process of the hydroxyl radical preoxidation of the antibiotic wastewater comprises the following steps: the preoxidation can destroy the drug property groups of the antibiotics, so that the antibiotics lose the drug effect, the influence of the antibiotics on microorganisms in a next biochemical reaction tank is reduced, and meanwhile, macromolecular organic pollutants (or pollutants difficult to biodegrade) in water are degraded into micromolecular substances (or biodegradable substances), so that the biodegradability of the water body is improved, and the next biochemical reaction effect is promoted; the efficient liquid-liquid mixing of the hydroxyl solution and the effluent of the primary sedimentation tank 71 is the core of the oxidative degradation of antibiotics and other organic pollutants, the concentration of the total oxidant in water after the liquid-liquid mixing is 5-10 mg/L, and the liquid-liquid mixing reaction time is 6-20 s.
The Venturi ejector in the first liquid-liquid mixing and dissolving hydrodynamic cavitation device 21 can generate cavitation flow containing a large number of micro bubbles, so that the collision probability of organic pollutants such as hydroxyl radicals, antibiotics and the like is increased; the local instantaneous high temperature and high pressure generated at the moment of cavitation bubble collapse improve the reaction rate between hydroxyl radicals and organic pollutants, and realize the degradation of the organic pollutants.
9) The effluent of the 1 st liquid-liquid mixing and dissolving hydrodynamic cavitation device 21 enters an SBR biochemical reaction tank 3. The water filling ratio of the SBR biochemical reaction tank 3 is 30 percent, and the effective volume of the SBR biochemical reaction tank 3 is 500m3The sludge concentration is 4000mg/L, and the sludge load is 0.17kgBOD5/(kgMLSS d); the SBR biochemical reaction tank 3 is internally provided with blast aeration, an air aerator is arranged as an air diffuser, and a buoyancy valve type decanter is adopted for drainage. And the effluent of the SBR biochemical reaction tank 3 is sampled by a 3 rd water taking valve 123, the concentrations of organic pollutants such as antibiotics and the like in the effluent are detected, and the amount of the hydroxyl radical solution to be added for the water body advanced treatment is determined accordingly.
10) Opening an 8 th electromagnetic valve 118 and a 9 th electromagnetic valve 119, conveying the effluent of the SBR biochemical reaction tank 3 and part of the high-concentration hydroxyl solution to a 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device 22, introducing the effluent of the SBR biochemical reaction tank 3 through a side water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device 22, introducing part of the high-concentration hydroxyl solution from an upper water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device 22 through a 3 rd mechanical pump 93, and performing sufficient mixed reaction on the high-concentration hydroxyl solution and the effluent of the SBR biochemical reaction tank 3 through a hydraulic cavitation effect to realize efficient oxidative degradation of residual antibiotic mineralization and other organic pollutants; the outlet water of the 2 nd liquid-liquid mixing and hydraulic cavitation device 22 is sampled by a 4 th water taking valve 124, and the antibiotics in the processed water sample are not detected;
the step 9) is a hydroxyl radical advanced treatment process of the antibiotic wastewater, and can carry out mineralization treatment on the residual antibiotic in the water after biochemical treatment and simultaneously carry out further oxidative degradation treatment on other organic pollutants which are not completely subjected to biochemical treatment; after the liquid and the liquid are mixed and dissolved, the concentration of the total oxidant in the water is 1-5 mg/L, and the reaction time of the liquid and the liquid mixing and dissolving is 6-20 s.
11) And the effluent of the 2 nd liquid-liquid mixing and dissolving hydrodynamic cavitation device 22 enters a secondary sedimentation tank 72 for secondary sedimentation treatment. The diameter of the secondary sedimentation tank 72 is 40m, the height of the clear water area is 0.8m, the height of the separation area is 1.5m, the height of the tank edge is 0.3m, and the diameter-depth ratio>6, surface load 0.75m3/m2h, water flow rate 900m3And/h, the settling time is 2h, the settling efficiency is 60 percent, and mechanical sludge discharge is adopted.
12) And opening the 5 th water taking valve 125 to detect the processed water sample. When the index of the treated wastewater reaches the national discharge standard of pharmaceutical industry water pollutants, the 4 th mechanical pump 94 and the 10 th electromagnetic valve 1110 are started, and the treated water in the secondary sedimentation tank 72 is input into a sewage pipe network.

Claims (1)

1. A method for removing antibiotics in pharmaceutical wastewater by hydroxyl radicals is characterized in that: the system is provided with a hydroxyl radical solution generating device, a 1 st liquid hydrodynamic cavitation mixing device, a 2 nd liquid hydrodynamic cavitation mixing device, a grid pool, an adjusting pool, a coagulation pool, a primary sedimentation pool, a secondary sedimentation pool, an SBR biochemical reaction pool, an online monitor, 1 st to 3 rd mechanical pumps, 1 st to 4 th water flow meters, 1 st to 10 th electromagnetic valves and 1 st to 5 th unit water outlet valves;
the hydroxyl radical solution generating device is used for generating a high-concentration hydroxyl radical solution;
the liquid-liquid hydrodynamic cavitation mixing and dissolving device 1 and the liquid-liquid hydrodynamic cavitation mixing and dissolving device 2 are used for mixing and dissolving high-concentration hydroxyl radical solution and high-efficiency liquid of treated water, so that preoxidation and advanced treatment of organic pollutants of antibiotics are realized;
the water inlet of the grating pool is externally connected with the antibiotic pharmaceutical wastewater to be treated through a 1 st mechanical pump, the water outlet of the grating pool is connected with the water inlet of an adjusting pool, the water outlet of the adjusting pool is connected with the water inlet of a coagulation pool, the water outlet of the coagulation pool is connected with the water inlet of a primary sedimentation pool, the water outlet of the primary sedimentation pool is divided into two paths, one path is directly connected with the water inlet of the side end of an SBR biochemical reaction pool, the other path is connected with the water inlet of the side end of a 1 st liquid hydrodynamic cavitation mixing device through a 2 nd mechanical pump, the water outlet of the 1 st liquid hydrodynamic cavitation mixing device is connected with the water inlet of the SBR biochemical reaction pool, the water outlet of the SBR biochemical reaction pool is connected with the water inlet of the side end of a 2 nd liquid hydrodynamic cavitation mixing device, the water outlet of a hydroxyl radical solution generating device is respectively connected with the water inlet of the upper ends of the 1 st liquid hydrodynamic cavitation mixing device and the 2 nd liquid hydrodynamic cavitation mixing device through a 3 rd mechanical pump, and the water outlet of the 2 nd liquid hydrodynamic cavitation mixing device is connected with the water inlet of a secondary sedimentation pool, the water outlet of the secondary sedimentation tank is conveyed to a sewage pipe network through a 4 th mechanical pump;
a 1 st electromagnetic valve is arranged between the 1 st mechanical pump and the antibiotic pharmaceutical wastewater to be treated; a 1 st water flow meter is arranged between the 1 st mechanical pump and the water inlet of the grid pool; a 2 nd electromagnetic valve is arranged between the water outlet of the grating tank and the water inlet of the regulating tank; a 3 rd electromagnetic valve is arranged between the water outlet of the regulating tank and the water inlet of the coagulation tank; a 4 th electromagnetic valve is arranged between the water outlet of the coagulation tank and the water inlet of the primary sedimentation tank; a 1 st water outlet valve and a 6 th electromagnetic valve are arranged between the water outlet of the primary sedimentation tank and the 2 nd mechanical pump, and a 2 nd water flow meter is arranged between the 2 nd mechanical pump and the water inlet at the side end of the 1 st liquid-liquid hydrodynamic cavitation mixing device; a 2 nd water outlet valve is arranged between the water outlet of the 1 st liquid-liquid hydrodynamic cavitation mixing device and the water inlet of the SBR biochemical reaction tank; a 5 th electromagnetic valve is arranged between the pipeline directly connecting the water outlet of the primary sedimentation tank and the water inlet of the SBR biochemical reaction tank; a 9 th electromagnetic valve and a 3 rd water outlet valve are arranged between the water outlet of the SBR biochemical reaction tank and the water inlet at the side end of the 2 nd liquid hydrodynamic cavitation mixing device; an online monitor is arranged between the water outlet of the hydroxyl radical solution generating device and the No. 3 mechanical pump; a 7 th electromagnetic valve and a 3 rd water flow meter are sequentially arranged between the 3 rd mechanical pump and the water inlet at the upper end of the 1 st liquid-liquid hydrodynamic cavitation mixing device; a 4 th water flowmeter and an 8 th electromagnetic valve are sequentially arranged between the 3 rd mechanical pump and the water inlet at the upper end of the 2 nd liquid-liquid hydrodynamic cavitation mixing device; a 4 th water outlet valve is arranged between the water outlet of the 2 nd liquid-liquid hydrodynamic cavitation mixing device and the water inlet of the secondary sedimentation tank; a 5 th water outlet valve and a 10 th electromagnetic valve are sequentially arranged between the water outlet of the secondary sedimentation tank and the 4 th mechanical pump;
the hydroxyl radical solution generating device 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 water flow of the 1 st liquid-liquid hydrodynamic cavitation mixing device and the 2 nd liquid-liquid hydrodynamic cavitation mixing device is 100-200 t/h;
the hydroxyl radical solution generating device is used for preparing the total oxidant with the concentration of 10-20 mg/L and the output of more than 30m3The operation is automatically controlled, the power of the whole machine is less than 20kW, the volume of the container is 3.5m multiplied by 1.5m multiplied by 2m, and the container is transported on a vehicle;
the method comprises the following steps:
1) opening a 1 st electromagnetic valve and a 1 st mechanical pump, controlling the water quantity through a 1 st water flow meter, and pumping the antibiotic pharmaceutical wastewater to be treated into a grid pool;
2) the method comprises the following steps that a rotary mechanical grid is selected as the grid, the depth of water in front of the grid is 1m, the flow rate in front of the grid is 0.4m/s, the flow rate of passing through the grid is 0.4m/s, the width of a grid bar is 0.01m, the width of a grid bar gap is 0.04m, the number of the grid bar gaps is 80, and the grid dip angle is 60 ℃;
3) opening the 2 nd electromagnetic valve to convey the effluent of the grating tank to the regulating tank, wherein the regulating tank is effectiveVolume 1000m3The effective water depth is 3.5m, the hydraulic retention time is 6h, and two reaction stirrers are arranged below the regulating reservoir to uniformly mix the wastewater;
4) opening the 3 rd electromagnetic valve, and enabling the effluent of the adjusting tank to enter a coagulation tank; the surface load of the coagulation basin is 0.8m3/m2d, selecting iron salt as a coagulant, optimally adding 800mg/L, stirring at the rotating speed of 10-15 r/min, and controlling the pH value to be 7.5-8;
5) opening the 4 th electromagnetic valve, leading the effluent of the coagulation tank to enter a primary sedimentation tank, adopting inclined tube type sedimentation in the primary sedimentation tank, and leading the surface load to be 2.8m3/m2d, the pipe diameter of the inclined pipe is 25-35mm, and the length of the inclined pipe>50cm, a different directional flow inclination angle of 60 degrees, a different directional flow velocity of 10mm/s and a interception velocity of 0.3 mm/s; sampling the effluent of the primary sedimentation tank by a No. 1 water intake valve, detecting the concentration of the antibiotic organic pollutants in the effluent, and determining the amount of the hydroxyl radical solution added for water body preoxidation according to the concentration;
6) if the antibiotics in the effluent of the primary sedimentation tank are easily biodegradable, opening a 5 th electromagnetic valve, and directly feeding the effluent of the primary sedimentation tank into an SBR biochemical reaction tank to carry out biochemical degradation process of the antibiotics; if the antibiotics in the effluent of the primary sedimentation tank are of a type difficult to biodegrade, the antibiotics enter a hydroxyl radical pre-oxidation process; the amount of the hydroxyl radical solution added for water preoxidation is determined by the water sample of the No. 1 water intake valve;
7) the hydroxyl radical generating device is used for preparing high-concentration hydroxyl solution, and the specific process is as follows: a) oxygen in the OH generating device passes through a subarea excitation plasma generator and is ionized and dissociated into oxygen active groups by the discharge of an atmospheric pressure electric field; b) starting a water pump in the OH generating device to pump clean water from a clean water well to a filter in the OH generating device for coarse filtration; c) the oxygen active groups are efficiently dissolved in the filtered water body through a gas-liquid mixing device in the OH generating device, and after full plasma reaction is carried out in a pressure reduction reactor, a high-concentration hydroxyl radical solution is generated;
in the preparation process of the high-concentration hydroxyl solution, the oxygen flux of the OH generation device is 8-10 m3The concentration of oxygen active groups generated by atmospheric pressure electric field discharge is controlled to be 60-100 mg/L, and the yield is480-800 g/h, total machine power<20 kw; through a gas-liquid miscibility vessel and a pressure reduction reactor, oxygen active groups react in water through a free radical chain to generate a high-concentration hydroxyl free radical solution, and the concentration of a total oxidant is 10-20 mg/L; the flow rate of the generated high-concentration hydroxyl radical solution is 30-50 m3H; cooling water temperature in the OH generating device is less than 5 ℃;
8) opening a 6 th electromagnetic valve and a 7 th electromagnetic valve, conveying effluent of a primary sedimentation tank and part of high-concentration hydroxyl solution to a 1 st liquid-liquid mixed-dissolution hydraulic cavitation device, introducing the effluent of the primary sedimentation tank from a side water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device through a 2 nd mechanical pump, introducing part of high-concentration hydroxyl solution from an upper end water inlet of the 1 st liquid-liquid mixed-dissolution hydraulic cavitation device through a 3 rd mechanical pump, and performing sufficient mixing reaction on the high-concentration hydroxyl solution and the effluent of the primary sedimentation tank through hydraulic cavitation to realize oxidative degradation of antibiotic organic pollutants; sampling the effluent of the 1 st liquid-liquid mixing and dissolving hydrodynamic cavitation device by a 2 nd water taking valve, and detecting the concentration of antibiotic organic pollutants in pretreated water;
the process of the hydroxyl radical preoxidation of the antibiotic wastewater comprises the following steps: preoxidation can destroy the drug property groups of antibiotics, so that the antibiotics lose the drug effect, the influence of the antibiotics on microorganisms in a next biochemical reaction tank is reduced, and meanwhile, macromolecular organic pollutants or pollutants difficult to biodegrade in water are degraded into micromolecular substances or biodegradable substances; carrying out liquid-liquid mixing and dissolving on the hydroxyl solution and the sand filtration effluent, wherein the concentration of the total oxidant in water after the liquid-liquid mixing and dissolving is 5-10 mg/L, and the reaction time of the liquid-liquid mixing and dissolving is 6-20 s;
a Venturi ejector in the liquid-liquid mixing and hydraulic cavitation device generates cavitation flow containing a large number of micro bubbles;
9) the effluent of the 1 st liquid-liquid mixing hydrodynamic cavitation device enters an SBR biochemical reaction tank, the water filling ratio of the SBR biochemical reaction tank is 30 percent, and the effective volume of the reaction tank is 500m3The sludge concentration is 4000mg/L, and the sludge load is 0.17kgBOD 5/(kgMLSS.d); the SBR biochemical reaction tank is internally provided with blast aeration, the air diffuser is an air aerator, and the drainage adopts a buoyancy valve type decanter; the effluent of the SBR biochemical reaction tank is sampled by a 3 rd water taking valve to detect the concentration of the antibiotic organic pollutants in the effluentDetermining the amount of hydroxyl radical solution to be added for the advanced treatment of the water body;
10) opening an 8 th electromagnetic valve and a 9 th electromagnetic valve, conveying the effluent of the SBR biochemical reaction tank and part of the high-concentration hydroxyl solution to a 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, enabling the effluent of the SBR biochemical reaction tank to enter through a side water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, enabling part of the high-concentration hydroxyl solution to enter through a 3 rd mechanical pump from an upper end water inlet of the 2 nd liquid-liquid mixed-dissolution hydraulic cavitation device, and enabling the high-concentration hydroxyl solution to perform mixed reaction with the effluent of the SBR biochemical reaction tank through a hydraulic cavitation effect to realize oxidative degradation of residual antibiotics and mineralized organic pollutants; sampling the outlet water of the 2 nd liquid-liquid mixing and dissolving hydrodynamic cavitation device by a 4 th water taking valve, wherein the antibiotics in the treated water sample are not detected;
the hydroxyl radical advanced treatment process of the antibiotic wastewater comprises the following steps: carrying out mineralization treatment on antibiotics remained in the water after biochemical treatment, and simultaneously carrying out further oxidative degradation treatment on organic pollutants which are not completely subjected to biochemical treatment; after the liquid and the liquid are mixed and dissolved, the concentration of the total oxidant in the water is 1-5 mg/L, and the reaction time of the liquid and the liquid mixing and dissolving is 6-20 s;
11) the effluent of the 2 nd liquid-liquid mixing hydrodynamic cavitation device enters a secondary sedimentation tank for secondary sedimentation treatment, the diameter of the secondary sedimentation tank is 40m, the height of a clear water zone is 0.8m, the height of a separation zone is 1.5m, the height of the tank edge is 0.3m, and the diameter-depth ratio>6, surface load 0.75m3/m2h, water flow rate 900m3The precipitation time is 2 hours, the precipitation efficiency is 60 percent, and mechanical sludge discharge is adopted;
12) and opening a 5 th water taking valve, detecting the treated water sample, and after the treated wastewater index reaches the national pharmaceutical industry water pollutant discharge standard, opening a 4 th mechanical pump and a 10 th electromagnetic valve, and inputting the treated water in the secondary sedimentation tank into a sewage pipe network.
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CN102689974A (en) * 2010-11-20 2012-09-26 大连海事大学 Device for treating sewage by using reactive oxygen species
CN205398398U (en) * 2016-03-08 2016-07-27 马越 Circulation recirculating aquaculture system based on advanced oxidation technologies
CN106977048A (en) * 2017-03-31 2017-07-25 厦门大学 A kind of combined system of hydroxyl radical free radical processing plant recirculating aquaculture water
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102689974A (en) * 2010-11-20 2012-09-26 大连海事大学 Device for treating sewage by using reactive oxygen species
CN205398398U (en) * 2016-03-08 2016-07-27 马越 Circulation recirculating aquaculture system based on advanced oxidation technologies
CN106977048A (en) * 2017-03-31 2017-07-25 厦门大学 A kind of combined system of hydroxyl radical free radical processing plant recirculating aquaculture water
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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