CN105858965B - Method and device for advanced treatment of nitrobenzene wastewater by supergravity-enhanced nano zero-valent iron-ozone method - Google Patents
Method and device for advanced treatment of nitrobenzene wastewater by supergravity-enhanced nano zero-valent iron-ozone method Download PDFInfo
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Abstract
The invention belongs to the technical field of nitrobenzene wastewater treatment, and particularly relates to a method and a device for deeply treating nitrobenzene wastewater by a supergravity-enhanced nano zero-valent iron-ozone method, which solve the problems of complex preparation process of nano zero-valent iron, low ozone utilization rate, large ozone consumption and the like when the nitrobenzene wastewater is directly acted by ozone at present. The method comprises the following steps: waste water solution containing ferrous iron salt nitrobenzene and KBH 4 Or NaBH 4 Reacting the aqueous solution in an impinging stream-rotating packed bed to form aniline-containing wastewater; the aniline-containing wastewater reacts with ozone in a rotating packed bed. The device comprises an impinging stream-rotating packed bed, wherein an upper reaction zone and a lower reaction zone are arranged in the rotating packed bed, the upper reaction zone is a liquid-liquid reaction zone, the lower reaction zone is a gas-liquid reaction zone, a liquid receiving device is arranged between the upper reaction zone and the lower reaction zone, and an air outlet is arranged at the uppermost part of the lower reaction zone. The invention has more sufficient utilization rate of the nano zero-valent iron, improves the utilization rate of ozone and the oxidation efficiency, and is suitable for treating the nitrobenzene wastewater with large batch and heavy treatment task.
Description
Technical Field
The invention belongs to the technical field of nitrobenzene wastewater treatment, and particularly relates to a method and a device for deeply treating nitrobenzene wastewater by a supergravity-enhanced nano zero-valent iron-ozone method.
Background
Nitrobenzene wastewater is extremely difficult to degrade, and is listed in a priority pollutant control list in China at present due to wide source and high toxicity. In recent years, research on the treatment of nitrobenzene waste water is receiving much attention.
The nano zero-valent Iron (NZVI) has the characteristics of large specific surface area, high reaction activity and the like, and has great application potential in the fields of wastewater treatment such as heavy metal ion removal, organic wastewater degradation, groundwater pollution remediation and the like. Research shows that the nanometer zero-valent iron can quickly and efficiently reduce the nitrobenzene compounds which are difficult to degrade into aniline compounds which are easy to biodegrade. However, in the application research of the existing nanoscale zero-valent iron, the preparation process of the nanoscale zero-valent iron is generally as follows: under the protection of nitrogen and continuous stirring, a strong reducing agent is added into a soluble ferrous salt solution containing a certain concentration drop by drop at a certain speed, and then the solution is subjected to multiple times of centrifugation or magnetic separation and washing, and finally the solution is dried or stored in an ethanol or acetone solution. The preparation process has complicated steps and harsh conditions, and part of the nanoparticles are inevitably oxidized and inactivated in the drying and storage processes. In the preparation process of the nano particles, the traditional stirring type reactor has the problems of long mixing time (5-50 ms), uneven mixing, uneven particle size distribution of particles and the like, and is difficult to meet the requirement of mass production.
The ozone is an oxidant which is green, efficient and free of secondary pollution. The oxidation of pollutants by ozone can be divided into direct oxidation, in which the pollutants are attacked directly by ozone molecules, and indirect oxidation, in which the pollutants are attacked indirectly by catalytically generated hydroxyl radicals. The direct oxidation and indirect oxidation of ozone can effectively mineralize organic matters into small molecular substances, thereby improving the biodegradability of the wastewater. The radical hydroxyl free radical is used as a strong oxidizing group, and can degrade organic matters in the wastewater into small molecular compounds without selectivity. Reported in the literature, nano zero-valent iron and Fe 2+ Can catalyze ozone to generate hydroxyl free, thereby degrading pollutants. However, the application of the existing ozone oxidation technology has the problems of poor water solubility of ozone and the like. For nitrobenzene wastewater difficult to degrade, the problem of low ozone utilization rate, large ozone consumption and the like exists when ozone is directly used for treatment.
The High Gravity Technology (High Technology) is a novel process strengthening Technology, and has the advantages of short mixing time, uniform mixing and the like. The high-gravity technology utilizes a high-speed rotating packed bed to simulate a high-gravity field, has the effects of crushing, shearing, tearing and the like on liquid in the high-speed rotating process of the packing, greatly increases the interphase contact area and accelerates the phase interface updating rate, thereby greatly improving the phase boundary mass transfer rate and strengthening the micro mixing process. The hypergravity rotating packed bed has incomparable advantages to the traditional stirrer no matter for micromixing, mass transfer and reaction between liquid-liquid two phases or gas-liquid two-phase flow.
Disclosure of Invention
Aiming at the problems that the existing preparation process of the nano zero-valent iron is complicated and difficult to amplify, and the utilization rate of ozone is not high and the dosage is large when the nitrobenzene wastewater is directly acted by the ozone, the invention aims to provide the method for deeply treating the nitrobenzene wastewater by the supergravity enhanced nano zero-valent iron-ozone method, which can be continuous and is convenient for engineering amplification.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method comprises the following steps:
1) Dissolving soluble ferrous salt in nitrobenzene wastewater to prepare a nitrobenzene wastewater solution containing ferrous iron salt;
2) Taking KBH 4 Or NaBH 4 An aqueous solution;
3) Waste water solution containing ferrous iron salt nitrobenzene and KBH 4 Or NaBH 4 Two streams of liquid of the aqueous solution collide, mix and react in an impinging stream-rotating packed bed, and nitrobenzene is reduced into aniline while nano zero-valent iron is prepared, so that aniline-containing wastewater is formed;
4) And the aniline-containing wastewater is in countercurrent or cross-current contact with ozone in a rotating packed bed to perform oxidative degradation reaction, the degraded wastewater is discharged, and the ozone tail gas is discharged.
The reaction formula for preparing the nano zero-valent iron is as follows:
the reaction formula of reducing nitrobenzene by nano zero-valent iron is as follows:
nano zero-valent iron and Fe 2+ The reaction formula for catalyzing ozone to generate hydroxyl radicals is as follows:
the concentration of the nitrobenzene wastewater is 50-500 mg. L -1 The concentration of ferrous iron in the soluble ferrous salt nitrobenzene wastewater solution is 20-30 times of the concentration of nitrobenzene in the nitrobenzene wastewater; the KBH 4 Or NaBH 4 The concentration of the water solution is 2 to 4 times of the concentration of ferrous iron in the selected soluble ferrite nitrobenzene wastewater solution, and the concentration of the gas-phase ozone is 10 to 100 mg. L -1 The volume flow ratio of the aniline-containing wastewater to the ozone is 500-2000L. M -3 The soluble ferrous salt is ferrous chloride, ferrous nitrate or ferrous sulfate, and the initial pH value of the nitrobenzene wastewater solution containing the ferrous salt is 2.0-9.0.
The ferrous iron salt-containing nitrobenzene wastewater solution and KBH 4 Or NaBH 4 The two liquid streams of the aqueous solution are equal-volume fluid, and the initial impact velocity of the two equal-volume fluid streams is 1-25 m s -1 . The hypergravity dressThe rotation speed is 100-3000 rpm. The reaction temperature is 10-30 ℃.
The device for completing the method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method comprises an impinging stream-rotating packed bed I and a rotating packed bed II, wherein the impinging stream-rotating packed bed I comprises an impinging stream device and the rotating packed bed I, the impinging stream device comprises a feeding pipe I and a feeding pipe II, the bottoms of the feeding pipe I and the feeding pipe II are provided with opposite nozzles, the feeding pipe I and the feeding pipe II are respectively connected with a liquid storage tank I and a liquid storage tank II through a pump I and a pump II, liquid flow meters are arranged between the feeding pipe I and the feeding pipe II and between the pump I and the pump II, and a liquid outlet is arranged at the bottom of the impinging stream-rotating packed bed and is communicated with a liquid storage tank III; the rotary packed bed II is connected with the liquid storage tank III through a pump III and a liquid flowmeter III; the air inlet of the rotary packed bed II is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen cylinder; the gas outlet of the rotary packed bed II is connected with a tail gas treatment device, and the liquid outlet of the rotary packed bed II is connected with a liquid storage groove IV.
The method for deeply treating the nitrobenzene wastewater by the hypergravity-enhanced nano zero-valent iron-ozone method is completed based on the device for deeply treating the nitrobenzene wastewater by the hypergravity-enhanced nano zero-valent iron-ozone method, and contains ferrous iron salt nitrobenzene wastewater solution and KBH 4 Or NaBH 4 The water solution is respectively metered by a pump I and a pump II through a liquid flowmeter I and a liquid flowmeter II and then is pumped into an impinging stream-rotating packed bed from a feeding pipe I and a feeding pipe II, two liquid streams collide, mix and react in the impinging stream-rotating packed bed, nitrobenzene is reduced into aniline while nano zero-valent iron is prepared, and then aniline-containing wastewater is thrown out and discharged into a liquid storage tank III; and pumping the aniline-containing wastewater into a rotary packed bed II by a pump III to perform countercurrent or cross-flow contact with ozone generated by an ozone generator, performing oxidative degradation reaction, discharging the degraded wastewater into a liquid storage tank IV, and discharging ozone tail gas to a tail gas treatment device.
The other device for completing the method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method comprises an impinging stream-rotating packed bed, wherein the impinging stream-rotating packed bed comprises an impinging stream device and a rotating packed bed, and a shell of the rotating packed bed is provided withThe device comprises a liquid inlet, a liquid outlet, an air inlet and an air outlet, wherein an impinging stream device enters a rotary packed bed from a liquid inlet at the top, an upper reaction zone and a lower reaction zone are arranged in the rotary packed bed, and the upper reaction zone is a waste water solution containing ferrous iron salt nitrobenzene and KBH 4 Or NaBH 4 The lower part of the liquid-liquid reaction zone is a gas-liquid reaction zone containing aniline wastewater and ozone, coaxial filler rotors are respectively arranged in the upper part and the lower part of the liquid-liquid reaction zone, a liquid receiving device is arranged between the upper part and the lower part of the liquid-liquid reaction zone, and an air outlet is arranged at the uppermost part of the lower part of the liquid-liquid reaction zone.
The liquid receiving device is a conical liquid receiving plate, the bottom of the conical liquid receiving plate is a circular flat disc, a plurality of liquid distribution holes are uniformly distributed in the flat disc, and the outer edge of the conical liquid receiving plate is connected with the shell of the rotating bed. The inclination angle of the conical liquid receiving plate is 5-45 degrees, and the aperture ratio of the circular flat disc at the bottom of the conical liquid receiving plate is 30-60 percent.
The inner side of the packing rotor of the gas-liquid reaction zone is provided with an inclined plane, and the inclined plane is provided with a plurality of inclined plates with holes which form an angle with the inclined plane. The design angle between the inner inclined plane and the vertical plane is 15-45 degrees, and the design angle between the inclined plate with holes and the inclined plane is 60-90 degrees.
The impinging stream device is a feeding pipe III and a feeding pipe IV, the bottom of the feeding pipe III is provided with a facing nozzle III and a nozzle IV, the feeding pipe III and the feeding pipe IV are respectively connected with a liquid storage tank V and a liquid storage tank VI through a pump IV and a pump V, a liquid flow meter III and a flow meter IV are respectively arranged between the feeding pipe III and the feeding pipe IV and between the pump IV and the pump V, and a liquid outlet is arranged at the bottom of the impinging stream-rotating packed bed III and is communicated with the liquid storage tank VII; the air inlet is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen bottle; the gas outlet is connected with a tail gas treatment device.
The method for the advanced treatment of the nitrobenzene wastewater by the hypergravity-enhanced nano zero-valent iron-ozone method is completed based on the device for the advanced treatment of the nitrobenzene wastewater by the hypergravity-enhanced nano zero-valent iron-ozone method: waste water solution containing ferrous iron salt nitrobenzene and KBH 4 Or NaBH 4 The water solution is respectively metered by a pump IV and a pump V through a liquid flow meter III and a flow meter IV and then is pumped into the impinging stream device from a feed pipe III and a feed pipe IV, and is sprayed out at high speed through a spray nozzle III and a spray nozzle IV of the impinging stream deviceCarrying out primary rapid collision, mixing and reaction, and then enabling the liquid to enter a high-speed rotating packing rotor II for secondary deep mixing reaction; after the liquid-liquid two-phase mixing reaction is finished, aniline-containing wastewater is obtained, thrown to the inner wall of the shell of the rotating bed, flows to a liquid receiving device along the inner wall under the action of gravity, and is redistributed to an inclined plate with holes on the inner side of the packing rotor III through liquid distribution holes; the aniline-containing wastewater is thrown into the filler rotor III under the action of centrifugal force and is thrown out from inside to outside, and ozone enters from the air inlet and is in countercurrent or cross-flow contact with the aniline-containing wastewater in the filler rotor III; after mass transfer and reaction between gas and liquid phases are finished, ozone tail gas is discharged from the gas outlet, and degraded waste water is discharged to the liquid storage tank VII from the liquid outlet.
The invention combines the reduction of nano zero-valent iron and the oxidation of ozone, reduces the nitrobenzene difficult to degrade into aniline easy to degrade, and then utilizes the nano zero-valent iron and Fe generated in the process of reducing the nitrobenzene by the nano zero-valent iron 2+ Catalyzing ozone to generate hydroxyl radicals to degrade aniline, thereby realizing the advanced treatment of the nitrobenzene wastewater. The reduction and oxidation processes are both carried out under the reinforcement of a supergravity device. The characteristics of fast and efficient mixed mass transfer of the supergravity rotating packed bed are utilized to strengthen the reduction and ozone oxidation processes of the nano zero-valent iron, so that the advanced treatment of the nitrobenzene wastewater by the fast, efficient and continuous nano zero-valent iron-ozone oxidation method is realized. The method for treating the nitrobenzene wastewater has the advantages of simple process, low cost, rapidness and high efficiency.
The invention has the beneficial effects that:
1. the method adopts the supergravity technology to prepare the nano zero-valent iron on line and synchronously treat the nitrobenzene wastewater, avoids the feeding of a traditional stirrer in a dripping mode, has the advantages of rapid and uniform mixing, rapid and sufficient reaction, simple and convenient method operation and continuous operation.
2. The method adopts the supergravity technology to prepare the nano zero-valent iron on line and synchronously treat the nitrobenzene wastewater, realizes the reduction of the nitrobenzene wastewater in the preparation process of the nano zero-valent iron, shortens the reaction time, avoids the complex operations of washing, separating, drying, storing and the like in the preparation process of the nano zero-valent iron in the traditional method, changes multiple steps into one step, and greatly simplifies the preparation and use steps; the grain state (as shown in figure 5) of the nano zero-valent iron during the reaction with the nitrobenzene wastewater is changed, the nano zero-valent iron grains are subjected to reduction reaction with nitrobenzene in the initial nucleation stage and the growth process, the nano zero-valent iron in a large grain state in the conventional method is prevented from reacting with nitrobenzene, the utilization rate of the nano zero-valent iron is more sufficient, the dosage concentration of the nano zero-valent iron is 100-200 times of the concentration of nitrobenzene in the nitrobenzene wastewater when the conventional nano zero-valent iron is used for reducing nitrobenzene, and the dosage concentration of the nano zero-valent iron converted in the method is 20-30 times of the concentration of nitrobenzene in the nitrobenzene wastewater.
3. Adopts the supergravity technology to strengthen the mass transfer of ozone in water, and utilizes the nano zero-valent iron and Fe produced in the process of reducing nitrobenzene by using nano zero-valent iron 2+ The ozone oxidation is catalyzed, so that the ozone utilization rate and the oxidation efficiency are improved and the treatment cost is effectively reduced while no extra medicament is added.
4. The super-gravity device is adopted, the device is small in size, simple to install, convenient to start and stop, capable of continuously running and suitable for treating nitrobenzene wastewater which is large in batch and heavy in treatment task.
5. The liquid-liquid two phases are fully mixed and reacted, and then the gas-liquid two-phase reaction is integrated into the same device, so that the integrated design is realized, and the occupied space of equipment is effectively reduced. The inner side inclined plane design of the lower packing rotor is beneficial to receiving liquid distributed from the liquid receiving device as a liquid redistributor. The device can realize the mixed liquid preparation of two original materials and the strengthening of the absorption reaction process. The process of mixing reaction of the raw materials and then mass transfer reaction between the gas phase and the liquid phase can be strengthened.
Drawings
FIG. 1 is a process flow diagram of advanced treatment of nitrobenzene wastewater by a supergravity enhanced nano zero-valent iron-ozone method.
In the figure: 1-liquid storage tank I; 2-pump I; 3-liquid flowmeter I; 4-impinging stream-rotating packed bed i; 5-reservoir II; 6-pump II; 7-liquid flow meter II; 8-motor I; 9-reservoir III; 10-Pump III; 11-liquid flow meter iii; 12-rotating packed bed ii; 13-reservoir IV; 14-motor II; 15-an oxygen cylinder; 16-an ozone generator; 17-a gas flow meter; and 18-a tail gas treatment device.
FIG. 2 is a main body diagram of an impinging stream-rotating packed bed device for advanced treatment of nitrobenzene wastewater by a supergravity enhanced nano zero-valent iron-ozone method.
In the figure: 19-the impact zone; 20-nozzle I; 21-nozzle II; 22-packing rotor I; 23-feeding pipe I; 24-a feed pipe II; 25-liquid inlet; 26-a housing; 27-a liquid outlet; 28-rotating shaft.
FIG. 3 is a process flow diagram of advanced treatment of nitrobenzene wastewater by another supergravity enhanced nano zero-valent iron-ozone method according to the invention.
In the figure: 29-reservoir v; 30-Pump IV; 31-liquid flow meter iii; 32-impinging stream-rotating packed bed iii; 33-a reservoir VI; 34-pump V; 35-liquid flow meter iv; 36-motor III; 37-liquid storage tank VII; 38-an oxygen cylinder; 39-an ozone generator; 40-a gas flow meter; 41-tail gas treatment device.
FIG. 4 is another main body diagram of an impinging stream-rotating packed bed device for deeply treating nitrobenzene wastewater by a supergravity-enhanced nano zero-valent iron-ozone method.
In the figure: 42-a liquid inlet; 43-feed line III; 44-feed pipe IV; 45-nozzle III; 46-nozzle IV; 47-a housing; 48-air outlet; 49-air inlet; 50-a liquid outlet; 51-a rotating shaft; 52-inclined plate with holes; 53-packing rotor III; 54-a liquid receiving device; 55-impact region; 56-packing rotor II.
FIG. 5 is a transmission electron microscope appearance comparison graph of nano zero-valent iron in the reaction process of advanced treatment of nitrobenzene wastewater by a supergravity enhanced nano zero-valent iron-ozone method and nano zero-valent iron in the reaction process of a conventional method.
In the figure: a-hypergravity method; b-conventional methods.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the following detailed description, but the present invention is not limited to the embodiments.
The method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method is characterized by comprising the following steps of: the method comprises the following steps:
1) Dissolving soluble ferrous salt in nitrobenzene wastewater to prepare a nitrobenzene wastewater solution containing ferrous iron salt;
2) Taking KBH 4 Or NaBH 4 An aqueous solution;
3) Ferrous iron salt-containing nitrobenzene wastewater solution and KBH 4 Or NaBH 4 Two streams of liquid of the aqueous solution collide, mix and react in an impinging stream-rotating packed bed, and nitrobenzene is reduced into aniline while nano zero-valent iron is prepared, so as to form aniline-containing wastewater;
4) And the aniline-containing wastewater is in countercurrent or cross-current contact with ozone in a rotating packed bed to perform oxidative degradation reaction, the degraded wastewater is discharged, and the ozone tail gas is discharged.
The concentration of the nitrobenzene wastewater is 50-500 mg. L -1 (ii) a The concentration of ferrous iron in the soluble ferrite nitrobenzene wastewater solution is 20-30 times of the concentration of nitrobenzene in the nitrobenzene wastewater; the KBH 4 Or NaBH 4 The concentration of the water solution is 2 to 4 times of the concentration of ferrous iron in the selected soluble ferrite nitrobenzene wastewater solution, and the concentration of the gas-phase ozone is 10 to 100 mg. L -1 The volume flow ratio of the aniline-containing wastewater to the ozone is 500-2000L. M -3 (ii) a The soluble ferrous salt is ferrous chloride, ferrous nitrate or ferrous sulfate, and the initial pH value of the nitrobenzene wastewater solution containing the ferrous salt is 2.0-9.0. The ferrous iron salt-containing nitrobenzene wastewater solution and KBH 4 Or NaBH 4 The two liquid streams of the aqueous solution are equal-volume fluid, and the initial impact velocity of the two equal-volume fluid streams is 1-25 m s -1 . The rotating speed of the supergravity device is 100-3000 rpm. The reaction temperature is 10-30 ℃.
Examples 1-6 nitrobenzene wastewater was treated using the process scheme shown in figure 1. The device comprises an impinging stream-rotating packed bed I and a rotating packed bed II, wherein the impinging stream-rotating packed bed I comprises an impinging stream device and a rotating packed bed I, the impinging stream device comprises a feeding pipe I and a feeding pipe II, the bottoms of the feeding pipe I and the feeding pipe II are provided with opposite nozzles, the feeding pipe I and the feeding pipe II are respectively connected with a liquid storage tank I and a liquid storage tank II through a pump I and a pump II, liquid flow meters are respectively arranged between the feeding pipe I and the feeding pipe II and between the pump I and the pump II, and a liquid outlet is formed in the bottom of the impinging stream-rotating packed bed and is communicated with a liquid storage tank III; the rotary packed bed II is connected with the liquid storage tank III through a pump III and a liquid flowmeter III; the air inlet of the rotary packed bed II is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen cylinder; the gas outlet of the rotary packed bed II is connected with a tail gas treatment device, and the liquid outlet of the rotary packed bed II is connected with a liquid storage tank IV. In the following examples, the rotating packed bed is a counter-current rotating packed bed.
Dissolving soluble ferrite in nitrobenzene wastewater in a liquid storage tank I1 to prepare nitrobenzene wastewater containing ferrite with a certain concentration, and adjusting the initial pH to 2.0-9.0; mixing KBH with tap water 4 Or NaBH 4 Dissolving in liquid storage tank II 5 to prepare NaBH with certain concentration 4 An aqueous solution. The two liquid streams are respectively metered by a pump I2 and a pump II 6 through a liquid flow meter I3 and a flow meter II 7, and then are sprayed out from a nozzle I20 and a nozzle II 21 of a feeding pipe I23 and a feeding pipe II 24, and are subjected to primary rapid collision, mixing and reaction in an impact area 19. Then, the liquid enters the packing rotor I22 rotating at high speed from the inner direction and the outer direction along the radial direction, and is subjected to secondary deep uniform mixing and reaction. The liquid is then spun off and flows along the inner wall of the rotating packed bed housing 26 to the liquid outlet 27 and is discharged into the reservoir iii 9. The wastewater in the liquid storage tank III 9 is metered by a pump III 10 through a liquid flowmeter III 11 and then is pumped into a rotary packed bed II 12, and the wastewater is treated by nano zero-valent iron and Fe 2+ Under the catalysis of the ozone generator, the ozone is in contact reaction with ozone which is from the ozone generator 16 and metered by the gas flowmeter 17 in the packing rotor I22 rotating at a high speed, after the reaction, waste water is discharged into the liquid storage tank IV 13, and tail gas is discharged from the gas outlet and enters the tail gas treatment device 18. The waste water in the reservoir IV 13 can be pumped into the rotary packed bed 12 by the pump III 10 for circular treatment.
Example 1:
by using the process flow shown in FIG. 1, the mixture is treated at 15 ℃ and has an initial concentration of 250 mg. L -1 The nitrobenzene wastewater. Mixing ferrous sulfate (FeSO) 4 ·7H 2 O) Nitrobenzene wastewater dissolved in liquid storage tank I1, and Fe is prepared 2+ FeSO with concentration 25 times of nitrobenzene concentration 4 Adjusting the initial pH of the nitrobenzene wastewater solution to 9.0; naBH is added to tap water 4 Dissolved in a liquid storage tank II 5 to prepare NaBH 4 At a concentration of FeSO 4 Fe in nitrobenzene waste water solution 2+ NaBH concentration 3 times higher 4 An aqueous solution. The two streams are mixed at 15 m. S -1 The initial impact speed of the mixing device is that the initial rapid collision, mixing and reaction are carried out in an impact area 19, and then the mixture enters a filler rotor I22 with the rotating speed of 100 rpm for secondary deep uniform mixing and reaction. The liquid then drains into reservoir iii 9. The waste water in the liquid storage tank III 9 is metered by a pump III 10 through a liquid flow meter III 11 and then is pumped into a rotary packed bed II 12, and is oxidized by ozone in a packing with 100 rpm, wherein the flow rate of the ozone is 75L. H -1 The concentration of the gas-phase ozone is 50 mg. L -1 The liquid-gas ratio is 1500L. M -3 And discharging the wastewater after reaction into a reservoir IV 13.
Sampling from a liquid storage tank III 9 for analysis, wherein the nitrobenzene removal rate reaches 96% and the COD removal rate reaches 5% after the reduction of the nano zero-valent iron; and (4) sampling from the reservoir IV 13 for analysis, wherein the nitrobenzene removal rate is 99 percent, and the COD removal rate reaches 70 percent. Compared with the traditional method, the method has the advantages of high treatment efficiency, obviously shortened treatment time and obviously reduced ozone consumption.
Example 2:
by using the process flow shown in FIG. 1, the mixture is treated at 30 ℃ and has an initial concentration of 50 mg. L -1 The nitrobenzene wastewater. Mixing ferrous chloride (FeCl) 2 ) Dissolving nitrobenzene wastewater in a liquid storage tank I1 to prepare Fe 2+ FeCl-containing solution with concentration 20 times of nitrobenzene concentration 2 Adjusting the initial pH of the nitrobenzene wastewater solution to 7.0; preparation of KBH 4 At a concentration of FeCl 2 Fe in nitrobenzene wastewater solution 2+ KBH concentration 2.5 times 4 The aqueous solution was placed in reservoir II 5. The two streams are mixed at 25 m. S -1 The initial impinging speed of (2) is that the reaction is carried out in an impinging stream-rotating packed bed I4 with the rotating speed of 1200 rpm and then the reaction product is discharged into a liquid storage tank III 9. The waste water in the reservoir III 9 is pumped into a rotary packed bed II 12 by a pump III 10, oxidized by ozone in a 1200 rpm packing and flows by ozoneThe amount is 40L. H -1 The concentration of the gas-phase ozone is 10 mg. L -1 The liquid-gas ratio is 2000L. M -3 And discharging the wastewater after the reaction into a liquid storage tank IV 13. After single reaction, sampling and analyzing from a liquid storage tank III 9, wherein the removal rate of nitrobenzene is up to 98 percent and the removal rate of COD is up to 7 percent after the reduction of nano zero-valent iron; and (4) sampling from the reservoir IV 13 for analysis, wherein the nitrobenzene removal rate is 100 percent, and the COD removal rate reaches 75 percent.
Example 3:
by using the process flow shown in FIG. 1, the mixture is treated at 20 ℃ and has an initial concentration of 500 mg. L -1 The nitrobenzene wastewater. FeCl is added 2 Dissolving nitrobenzene wastewater in the liquid storage tank I1 to prepare Fe 2+ FeCl-containing solution with concentration 30 times of nitrobenzene concentration 2 Adjusting the initial pH of the nitrobenzene wastewater solution to 2.0; preparation of KBH 4 At a concentration of FeCl 2 Fe in nitrobenzene wastewater solution 2+ KBH concentration 3 times 4 The aqueous solution was placed in reservoir II 5. The two streams are mixed at a pressure of 1 m. S -1 The initial speed of the impact is discharged into a liquid storage tank III 9 after the reaction in an impact flow-rotating packed bed I4 with the rotating speed of 1000 rpm. The waste water in the liquid storage tank III 9 is pumped into a rotary packed bed II 12 by a pump III 10 and is oxidized by ozone in a packing with 1000 rpm, and the flow rate of the ozone is 75L h -1 The concentration of gas-phase ozone is 100 mg. L -1 The liquid-gas ratio is 500L. M -3 And discharging the wastewater after the reaction into a liquid storage tank IV 13. And pumping the wastewater in the liquid storage tank IV 13 into a rotary packed bed II 12 by a pump III 10, and carrying out a circulating reaction for 5min, wherein the nitrobenzene removal rate is 99%, and the COD removal rate is 94%.
Example 4:
by using the process flow shown in FIG. 1, the mixture is treated at 10 ℃ and has an initial concentration of 400 mg. L -1 The nitrobenzene wastewater. FeCl is added 2 Dissolving nitrobenzene wastewater in the liquid storage tank I1 to prepare Fe 2+ FeCl-containing solution with concentration 25 times of nitrobenzene concentration 2 Adjusting the initial pH of the nitrobenzene wastewater solution to 4.0; preparation of NaBH 4 At a concentration of FeCl 2 Fe in nitrobenzene waste water solution 2+ NaBH concentration 4 times higher 4 The aqueous solution was placed in reservoir II 5. Two streams of liquid were mixed at 10 m. S -1 The initial impact speed of the impact is 3000 rpmAnd after the reaction in the flow-rotating packed bed I4, discharging into a liquid storage tank III 9. The wastewater in the liquid storage tank III 9 is pumped into a rotary packed bed II 12 by a pump III 10 and is oxidized by ozone in a packing with 3000 rpm, and the flow rate of the ozone is 50L h -1 The concentration of the gas-phase ozone is 60 mg. L -1 The liquid-gas ratio is 1000L. M -3 And discharging the wastewater after the reaction into a liquid storage tank IV 13. And then pumping the wastewater in the reservoir IV 13 into a rotary packed bed II 12 by a pump III 10, and carrying out a circular reaction for 10min, wherein the nitrobenzene removal rate is 99 percent, and the COD removal rate is 97 percent.
Example 5:
using the process flow shown in FIG. 1, the sample was treated at 25 ℃ to have an initial concentration of 300 mg. L -1 The nitrobenzene wastewater. FeSO (ferric oxide) is added 4 ·7H 2 Dissolving O in nitrobenzene wastewater in a liquid storage tank I1 to prepare Fe 2+ FeSO with concentration 25 times of nitrobenzene concentration 4 Adjusting the initial pH of the nitrobenzene wastewater solution to 7.0; naBH is added with tap water 4 Dissolving in liquid storage tank II 5 to prepare NaBH 4 At a concentration of FeSO 4 Fe in nitrobenzene wastewater solution 2+ NaBH concentration 2.5 times higher 4 An aqueous solution. The two streams were mixed at 20 m. S -1 The initial speed of the impact is discharged into a liquid storage tank III 9 after the reaction in an impact flow-rotating packed bed I4 with the rotating speed of 100 rpm. The waste water in the liquid storage tank III 9 is pumped into a rotary packed bed II 12 by a pump III 10, and is oxidized by ozone in a packing with 100 rpm, and the ozone flow rate is 65L h -1 The concentration of gas-phase ozone is 40 mg. L -1 The liquid-gas ratio is 1500L. M -3 And discharging the wastewater after the reaction into a liquid storage tank IV 13. After single reaction, the nitrobenzene removal rate is 99 percent, and the COD removal rate reaches 79 percent.
Example 6:
by using the process flow shown in FIG. 1, the mixture is treated at 20 ℃ and has an initial concentration of 200 mg. L -1 The nitrobenzene wastewater. FeSO (ferric oxide) is added 4 ·7H 2 Dissolving O in nitrobenzene wastewater in a liquid storage tank I1 to prepare Fe 2+ FeSO with concentration 20 times of nitrobenzene concentration 4 Adjusting the initial pH of the nitrobenzene wastewater solution to 5.0; naBH is added with tap water 4 Dissolving in liquid storage tank II 5 to prepare NaBH 4 At a concentration of FeSO 4 F in nitrobenzene waste water solutione 2+ NaBH concentration 2.5 times higher 4 An aqueous solution. The two streams were mixed at 5 m. S -1 The initial impinging speed of (2) is that the reaction is carried out in an impinging stream-rotating packed bed I4 with the rotating speed of 1200 rpm and then the reaction product is discharged into a liquid storage tank III 9. The waste water in the liquid storage tank III 9 is pumped into a rotary packed bed II 12 by a pump III 10 and is oxidized by ozone in a packing with 1200 rpm, and the flow rate of the ozone is 55L h -1 The concentration of the gas-phase ozone is 30 mg. L -1 The liquid-gas ratio is 1000L. M -3 And discharging the wastewater after reaction into a reservoir IV 13. After single reaction, the nitrobenzene removal rate is 99%, and the COD removal rate reaches 68%.
Example 7 the process of figure 3 was used, the apparatus comprising an impinging stream-rotating packed bed comprising an impinging stream device and a rotating packed bed, the rotating packed bed housing having a liquid inlet, a liquid outlet, a gas inlet and a gas outlet, the impinging stream device entering the rotating packed bed from the top liquid inlet, the rotating packed bed having an upper reaction zone and a lower reaction zone, the upper reaction zone being ferrous iron salt-containing nitrobenzene wastewater solution and KBH 4 Or NaBH 4 The lower part of the aqueous solution liquid-liquid reaction zone is a gas-liquid reaction zone containing aniline wastewater and ozone, coaxial filler rotors are respectively arranged in the upper part and the lower part of the reaction zone, a liquid receiving device is arranged between the upper part and the lower part of the reaction zone, and an air outlet is arranged at the uppermost part of the lower part of the reaction zone.
The liquid receiving device is a conical liquid receiving plate, the bottom of the conical liquid receiving plate is a circular flat disc, a plurality of liquid distribution holes are uniformly distributed in the flat disc, and the outer edge of the conical liquid receiving plate is connected with the shell of the rotating bed. The inclination angle of the conical liquid receiving plate is 5-45 degrees, and the aperture ratio of the circular flat disc at the bottom of the conical liquid receiving plate is 30-60 percent.
The inner side of the packing rotor of the gas-liquid reaction zone is provided with an inclined plane, and the inclined plane is provided with a plurality of inclined plates with holes, which form an angle with the inclined plane. The design angle between the inner inclined plane and the vertical plane is 15-45 degrees, and the design angle between the inclined plate with holes and the inclined plane is 60-90 degrees.
The impinging stream device is a feeding pipe III and a feeding pipe IV, the bottom of the feeding pipe III is provided with a facing nozzle III and a nozzle IV, the feeding pipe III and the feeding pipe IV are respectively connected with a liquid storage tank V and a liquid storage tank VI through a pump IV and a pump V, a liquid flow meter III and a flow meter IV are respectively arranged between the feeding pipe III and the feeding pipe IV and between the pump IV and the pump V, and a liquid outlet is arranged at the bottom of the impinging stream-rotating packed bed III and is communicated with the liquid storage tank VII; the air inlet is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen bottle; the gas outlet is connected with a tail gas treatment device.
Waste water solution containing ferrous iron salt nitrobenzene and KBH 4 Or NaBH 4 The water solution is respectively metered by a pump IV and a pump V through a liquid flowmeter III and a flowmeter IV and then is pumped into the impinging stream device from a feeding pipe III and a feeding pipe IV, the water solution is sprayed out at high speed through a nozzle III and a nozzle IV of the impinging stream device and then is subjected to primary rapid collision, mixing and reaction, and then the liquid enters a filler rotor II rotating at high speed to perform secondary deep mixing reaction; after the liquid-liquid two-phase mixing reaction is finished, aniline-containing wastewater is obtained, the aniline-containing wastewater is thrown to the inner wall of the shell of the rotating bed, flows to a liquid receiving device along the inner wall under the action of gravity, and is redistributed to an inclined plate with holes on the inner side of the packing rotor III through liquid distribution holes; the aniline-containing wastewater is thrown into the filler rotor III under the action of centrifugal force and is thrown out from inside to outside, and ozone enters from the air inlet and is in countercurrent or cross-flow contact with the aniline-containing wastewater in the filler rotor III; after the mass transfer and reaction between the gas phase and the liquid phase are finished, the ozone tail gas is discharged from the gas outlet, and the degraded waste water is discharged to the liquid storage tank VII from the liquid outlet.
Example 7:
using the process flow shown in FIG. 3, the sample was treated at 20 ℃ to have an initial concentration of 250 mg. L -1 The nitrobenzene wastewater. FeSO (ferric oxide) is added 4 ·7H 2 Dissolving O in the nitrobenzene wastewater in a liquid storage tank V29 to prepare Fe 2+ FeSO with concentration 25 times of nitrobenzene concentration 4 Adjusting the initial pH of the nitrobenzene wastewater solution to 4.0; naBH is added with tap water 4 Dissolved in a liquid storage tank VI 33 to prepare NaBH 4 At a concentration of FeSO 4 Fe in nitrobenzene waste water solution 2+ NaBH concentration 3 times higher 4 An aqueous solution. Containing FeSO 4 Nitrobenzene waste water solution and NaBH 4 After being respectively metered by a pump IV 30 and a pump V34 through a liquid flow meter III 31 and a liquid flow meter IV 35, the aqueous solution is pumped into an impinging stream device from a feeding pipe III 43 and a feeding pipe IV 44 and then flows through the impinging stream deviceAfter being discharged from the nozzles III 45 and IV 46, the two streams of liquid are discharged at a flow rate of 20 m · s -1 The initial impact speed of the mixing tank is used for carrying out initial rapid collision, mixing and reaction, and then the liquid enters a filler rotor II 56 with 1000 rpm for carrying out secondary deep mixing reaction; after the liquid-liquid two-phase mixing reaction is finished, aniline-containing wastewater is obtained, the aniline-containing wastewater is thrown to the inner wall of the shell 47 of the rotating bed, flows to a liquid receiving device 54 along the inner wall under the action of gravity, and is redistributed to the inclined plate 52 with holes on the inner side of the packing rotor III 53 through the liquid distribution holes; the aniline-containing wastewater is thrown into the packing rotor III 53 under the action of centrifugal force and thrown out from inside to outside, and is oxidized by ozone entering from the air inlet 49 in the packing rotor III 53 at 1000 rpm, wherein the ozone flow is 50L h -1 The concentration of gas-phase ozone is 40 mg. L -1 The liquid-gas ratio is 1000L. M -3 After the reaction, the ozone tail gas is discharged from the gas outlet 48, and the degraded wastewater is discharged to the liquid storage tank VII 37 from the liquid outlet 50. After single reaction, sampling and detecting from a liquid outlet 50, the nitrobenzene removal rate is 99 percent, and the COD removal rate reaches 71 percent.
Claims (10)
1. A method for advanced treatment of nitrobenzene wastewater by a supergravity enhanced nano zero-valent iron-ozone method is characterized by comprising the following steps: the method comprises the following steps:
1) Dissolving soluble ferrous salt in nitrobenzene wastewater to prepare nitrobenzene wastewater solution containing ferrous iron salt;
2) Taking KBH4 or NaBH4 aqueous solution;
3) The two liquids of ferrous iron salt-containing nitrobenzene wastewater solution and KBH4 or NaBH4 aqueous solution collide, mix and react in an impinging stream-rotating packed bed, and nitrobenzene is reduced into aniline while nano zero-valent iron is prepared, so that aniline-containing wastewater is formed;
4) Carrying out countercurrent or cross-flow contact on the aniline-containing wastewater and ozone in a rotating packed bed of a supergravity device to carry out oxidative degradation reaction, discharging the degraded wastewater and discharging ozone tail gas;
the concentration of the nitrobenzene wastewater is 50-500 mg. L-1; the concentration of ferrous iron in the ferrous salt nitrobenzene wastewater solution is 20-30 times of the concentration of nitrobenzene in the nitrobenzene wastewater;
the concentration of the KBH4 or NaBH4 aqueous solution is 2-4 times of that of ferrous iron in the ferrous salt nitrobenzene wastewater solution, and the concentration of ozone is 10-100 mg.L -1 The volume flow ratio of the aniline-containing wastewater to the ozone is 500-2000L. M -3 ；
The ferrous salt is ferrous chloride, ferrous nitrate or ferrous sulfate, and the initial pH value of the ferrous salt nitrobenzene wastewater solution is 2.0-9.0;
the two streams of liquid of the ferrous salt nitrobenzene wastewater solution and the KBH4 or NaBH4 aqueous solution are isovolumetric fluids, and the initial impact velocity of the two isovolumetric fluids is 1-25 m. S -1 ；
The rotating speed of the supergravity device is 100-3000 rpm; the reaction temperature is 10-30 ℃.
2. The device for implementing the method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method according to claim 1 is characterized in that: the device comprises an impinging stream-rotating packed bed I and a rotating packed bed II, wherein the impinging stream-rotating packed bed I comprises an impinging stream device and a rotating packed bed I, the impinging stream device comprises a feeding pipe I and a feeding pipe II, the bottoms of the feeding pipe I and the feeding pipe II are provided with opposite nozzles, the feeding pipe I and the feeding pipe II are respectively connected with a liquid storage tank I and a liquid storage tank II through a pump I and a pump II, liquid flow meters are arranged between the feeding pipe I and the feeding pipe II and between the pump I and the pump II, and a liquid outlet is formed in the bottom of the impinging stream-rotating packed bed and is communicated with a liquid storage tank III; the rotary packed bed II is connected with the liquid storage tank III through a pump III and a liquid flowmeter III; the air inlet of the rotary packed bed II is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen cylinder; the gas outlet of the rotary packed bed II is connected with a tail gas treatment device, and the liquid outlet of the rotary packed bed II is connected with a liquid storage tank IV.
3. The method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method, which is completed based on the device for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method disclosed by claim 2, is characterized by comprising the following steps of: after being measured by a liquid flow meter I and a liquid flow meter II through a pump I and a pump II respectively, a nitrobenzene wastewater solution containing ferrous salt and a KBH4 or NaBH4 aqueous solution are pumped into an impinging stream-rotating packed bed I from a feeding pipe I and a feeding pipe II, two streams of liquid collide, mix and react in the impinging stream-rotating packed bed I, nitrobenzene is reduced into aniline while nano zero-valent iron is prepared, and then aniline-containing wastewater is thrown out and discharged into a liquid storage tank III; and pumping the aniline-containing wastewater into a rotary packed bed II by a pump III to perform countercurrent or cross-flow contact with ozone generated by an ozone generator, performing oxidative degradation reaction, discharging the degraded wastewater into a liquid storage tank IV, and discharging ozone tail gas to a tail gas treatment device.
4. The device for realizing the method for deeply treating the nitrobenzene wastewater by the supergravity enhanced nano zero-valent iron-ozone method according to claim 3 is characterized in that: the device comprises an impinging stream-rotary packed bed, the impinging stream-rotary packed bed comprises an impinging stream device and a rotary packed bed, a shell of the rotary packed bed is provided with a liquid inlet, a liquid outlet, an air inlet and an air outlet, the impinging stream device enters the rotary packed bed from the liquid inlet at the top, an upper reaction zone and a lower reaction zone are arranged in the rotary packed bed, the upper reaction zone is a liquid-liquid reaction zone containing ferrous iron salt nitrobenzene wastewater solution and KBH4 or NaBH4 aqueous solution, the lower reaction zone is a gas-liquid reaction zone containing aniline wastewater and ozone, coaxial packed rotors are respectively arranged in the upper reaction zone and the lower reaction zone, a liquid receiving device is arranged between the upper reaction zone and the lower reaction zone, and the air outlet is arranged at the uppermost part of the lower reaction zone.
5. The device for advanced treatment of nitrobenzene wastewater by the supergravity enhanced nanoscale zero-valent iron-ozone method according to claim 4, wherein the device comprises: the liquid receiving device is a conical liquid receiving plate, the bottom of the conical liquid receiving plate is a circular flat disc, a plurality of liquid distribution holes are uniformly distributed in the flat disc, and the outer edge of the conical liquid receiving plate is connected with the shell of the rotating bed.
6. The device for deeply treating nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method according to claim 5, is characterized in that: the inclination angle of the conical liquid receiving plate is 5-45 degrees, and the aperture ratio of the circular flat disc at the bottom of the conical liquid receiving plate is 30-60 percent.
7. The apparatus for advanced treatment of nitrobenzene wastewater by the supergravity enhanced nano zero-valent iron-ozone method according to claim 4, 5 or 6, wherein: the inner side of the packing rotor of the gas-liquid reaction zone is provided with an inclined plane, and the inclined plane is provided with a plurality of inclined plates with holes, which form an angle with the inclined plane.
8. The device for deeply treating nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method according to claim 7, is characterized in that: the design angle of the inner side inclined plane and the vertical plane of the packing rotor in the gas-liquid reaction zone is 15-45 degrees, and the design angle of the perforated inclined plate (52) and the inclined plane is 60-90 degrees.
9. The device for deeply treating nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method according to claim 8, is characterized in that: the impinging stream device is provided with a feed pipe III and a feed pipe IV with opposite spray nozzles III and IV at the bottom, the feed pipe III and the feed pipe IV are respectively connected with a reservoir V and a reservoir VI through a pump IV and a pump V, a liquid flow meter III and a flow meter IV are respectively arranged between the feed pipe III and the feed pipe IV and between the pump IV and the pump V, and a liquid outlet is arranged at the bottom of the impinging stream-rotating packed bed III and is communicated with the reservoir VII; the air inlet is connected with an ozone generator through a gas flowmeter, and the ozone generator is connected with an oxygen bottle; the gas outlet is connected with a tail gas treatment device.
10. The method for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method, which is completed based on the device for deeply treating the nitrobenzene wastewater by the supergravity-enhanced nano zero-valent iron-ozone method of claim 9, is characterized in that: after being measured by a liquid flow meter III and a flow meter IV, a ferrous salt-containing nitrobenzene wastewater solution and a KBH4 or NaBH4 aqueous solution are respectively pumped into an impinging stream device from a feeding pipe III and a feeding pipe IV by a pump IV and a pump V, and are sprayed out at a high speed by a nozzle III and a nozzle IV of the impinging stream device to perform primary rapid collision, mixing and reaction, and then the liquid enters a filler rotor II rotating at a high speed to perform secondary deep mixing reaction; after the liquid-liquid two-phase mixing reaction is finished, aniline-containing wastewater is obtained, thrown to the inner wall of the shell of the rotating bed, flows to a liquid receiving device along the inner wall under the action of gravity, and is redistributed to an inclined plate with holes on the inner side of the packing rotor III through liquid distribution holes; the aniline-containing wastewater is thrown into the filler rotor III under the action of centrifugal force and is thrown out from inside to outside, and ozone enters from the air inlet and is in countercurrent or cross-flow contact with the aniline-containing wastewater in the filler rotor III; after mass transfer and reaction between gas and liquid phases are finished, ozone tail gas is discharged from the gas outlet, and degraded waste water is discharged to the liquid storage tank VII from the liquid outlet.
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| CN107081433A (en) * | 2017-05-15 | 2017-08-22 | 轻工业环境保护研究所 | A kind of Nanoscale Iron medicament is prepared and injection synchronous integrated equipment in situ |
| CN108262489A (en) * | 2018-02-02 | 2018-07-10 | 中北大学 | A kind of hypergravity preparation method of chitosan loaded nano zero valence iron and its double metallic composite material |
| CN108217914A (en) * | 2018-03-21 | 2018-06-29 | 河南省化工研究所有限责任公司 | For the micro- mixed reaction unit of second order of ozone deep oxidation processing industrial wastewater |
| CN108706674B (en) * | 2018-04-18 | 2021-08-17 | 中北大学 | Supergravity enhanced extraction of-O3/Fe2+Method and device for treating high-concentration nitrobenzene wastewater by using method |
| CN108911113A (en) * | 2018-09-19 | 2018-11-30 | 南京大学盐城环保技术与工程研究院 | A kind of advanced oxidation device of efficient process organic wastewater with difficult degradation thereby |
| CN113003812B (en) * | 2021-03-09 | 2023-04-07 | 生态环境部南京环境科学研究所 | Purification treatment device and method for organic dirt polluted shallow groundwater |
| CN115215424B (en) * | 2022-07-08 | 2023-05-09 | 九江学院 | Ozone wastewater treatment device and system based on micro-bubble impinging stream |
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