CN209906422U - Device for advanced oxidation of degradation-resistant industrial wastewater by ozone/hydrogen peroxide - Google Patents
Device for advanced oxidation of degradation-resistant industrial wastewater by ozone/hydrogen peroxide Download PDFInfo
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- CN209906422U CN209906422U CN201822272193.2U CN201822272193U CN209906422U CN 209906422 U CN209906422 U CN 209906422U CN 201822272193 U CN201822272193 U CN 201822272193U CN 209906422 U CN209906422 U CN 209906422U
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Abstract
The utility model discloses a device for high-grade oxidation of refractory industrial wastewater by ozone/hydrogen peroxide. The device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide comprises a water inlet pipeline, a water outlet pipeline, a hydrogen peroxide adding device, a pipeline mixer, an ozone generator, a reaction device, a tail gas treatment device, a first ejector and a second ejector; wherein, the water inlet pipeline and the hydrogen peroxide adding device are respectively connected with the pipeline mixer, and the pipeline mixer is sequentially connected with the first ejector and the reaction device; the reaction device is respectively connected with the water outlet pipeline and the tail gas treatment device; the water outlet pipeline is also connected with the reaction device through a second ejector; the ozone generator is respectively connected with the first ejector and the second ejector. The utility model discloses a processing apparatus combines together ozone and hydrogen peroxide solution advanced oxidation, can effectively improve the utilization ratio of ozone, reduces ozone input volume, strengthens the advanced treatment effect when reducing treatment cost, has high-efficient clear advantage.
Description
Technical Field
The utility model relates to a device for high-grade oxidation of refractory industrial wastewater by ozone/hydrogen peroxide.
Background
In recent years, the advanced treatment technology commonly used for refractory organic wastewater is widely applied to the processes including modified Fenton process, ozone + BAF, ozone + activated carbon, ozone/hydrogen peroxide advanced oxidation and the like.
Fenton and Fenton-like processes: the Fenton reagent can effectively oxidize and remove refractory organic matters which cannot be removed by the traditional wastewater treatment technology, and the essence is H2O2In Fe2+The catalyst of (2) can generate OH with high reaction activity, and the oxidizing property of the OH is not selective, so the catalyst can be degraded by the action of most organic matters. In the Fenton process, raw water firstly enters a pH adjusting tank to be adjusted to be acidic and then enters a catalytic reaction tank, and Fe is added in an acidic environment2+Catalysis H2O2Generating hydroxyl radical, further oxidatively decomposing organic matter, and further Fe3+The existing of (2) can also generate flocculation to accelerate the removal of pollutants, the pollutants enter a neutralization tank to adjust the pH back, and are discharged after solid-liquid separation is carried out in a sedimentation tank, the Fenton process easily generates a large amount of sludge, and the sludge is also discharged through concentration, filter pressing and other treatments. Therefore, for the Fenton process, the acidic environment is ensured, and H is controlled and optimized2O2And Fe2+The adding proportion is the key of the success of the high-efficiency application of the technology. Meanwhile, the Fenton process has the defects of large occupied area, high manufacturing cost, large sludge yield, high operating cost, large management and maintenance amount and the like, and the development of the Fenton process in the field of advanced treatment of refractory organic wastewater is restricted.
Ozone + BAF process: the combined process of ozone and biological aerated filter combines the advantages of ozone oxidation and biological aerated filter, can give full play to the advantages of each treatment, and can remove COD with the best effect. The ozone pre-oxidation is utilized to remove the chroma, the turbidity and part of COD, the biodegradability of the wastewater is improved, then the wastewater enters the aeration biological filter, and the metabolism of microorganisms is utilized to achieve the advanced treatment of COD and chroma, thereby having higher treatment effect. However, the process has large occupied area, high operating cost and high manufacturing cost, and the water outlet effect is difficult to stably control below 50mg/L and difficult to popularize.
The ozone and active carbon process comprises the following steps: the ozone biological activated carbon process is a wastewater advanced treatment process developed on the basis of the biological activated carbon process, and comprises ozonization and activated carbon adsorption. And the biodegradation of the microorganisms growing on the surface of the activated carbon is utilized. The device can effectively remove organic pollutants in water, integrates the functions of ozone oxidation, sterilization, physical adsorption of activated carbon and microbial oxidation, fully exerts respective characteristics, promotes each other, and obtains multiple effects of removing organic pollutants, thereby achieving the purpose of deeply purifying water. Although the ozone-biological activated carbon filter advanced treatment technology plays a good role in controlling the advanced treatment of wastewater, the ozone-biological activated carbon filter advanced treatment technology also has limitations which are mainly reflected in that: ozone can effectively degrade unsaturated bonds or partial aromatic organic pollutants, and is difficult to oxidize and degrade partial stable organic pollutants such as pesticides, halogenated organic matters, nitro compounds and the like; ozone can oxidize macromolecular organic matters into micromolecular organic matters. The research shows that the activated carbon adsorption has a good effect of removing organic substances with molecular mass of 500-3000 Da, and has a poor effect of removing organic substances with large molecules and small molecules. The molecular mass of the organic matters after the ozone oxidation is reduced, which is not beneficial to the adsorption of the active carbon. In addition, for the wastewater deep treatment system with higher concentration, the penetration time of the activated carbon is shorter, continuous regeneration and supplement are needed, and the operation difficulty and the cost are relatively higher.
The existing ozone oxidation process has the problems of low ozone treatment efficiency, large dosage and higher operation cost, and because the oxidation potential of ozone is relatively low, the ozone oxidation process has higher selectivity for removing pollutants and is difficult to remove various organic matters which are difficult to degrade; for catalytic oxidation of ozone, although the utilization rate of ozone can be effectively improved through the action of the catalyst, the catalyst has the problems of easy poisoning, loss of active ingredients and the like, the replacement period of the catalyst is short, and the problems of higher later-stage operation cost and the like exist.
Advanced oxidation technology is an emerging water treatment technology in recent years, and hydroxyl radicals (. OH) with strong oxidizing property can be generated in the treatment process, and the strong oxidizing property can easily degrade and mineralize macromolecular dye molecules which are difficult to degrade. However, in the currently applied process, the problems of low oxidation utilization rate of ozone molecules, high operation cost, oxidation barriers, difficulty in completely degrading partial refractory organic matters and the like generally exist.
SUMMERY OF THE UTILITY MODEL
In order to overcome the problems existing in the prior art, the utility model aims to provide a device for the advanced oxidation of the industrial wastewater difficult to degrade by ozone/hydrogen peroxide, which is suitable for the advanced treatment of the effluent of the industrial wastewater difficult to degrade, such as printing and dyeing, fine chemical engineering, pharmacy, papermaking or coking wastewater, after secondary biochemical treatment.
The utility model adopts the technical proposal that:
a device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide comprises a water inlet pipeline, a water outlet pipeline, a hydrogen peroxide adding device, a pipeline mixer, an ozone generator, a reaction device, a tail gas treatment device, a first ejector and a second ejector; wherein, the water inlet pipeline and the hydrogen peroxide adding device are respectively connected with the pipeline mixer, and the pipeline mixer is sequentially connected with the first ejector and the reaction device; the reaction device is respectively connected with the water outlet pipeline and the tail gas treatment device; the water outlet pipeline is also connected with the reaction device through a second ejector; the ozone generator is respectively connected with the first ejector and the second ejector.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide, the first ejector and the second ejector are respectively provided with a water inlet end, a gas inlet end and a water outlet end; the water inlet end is used for feeding water, the air inlet end is used for feeding ozone, and the water outlet end is used for outputting a mixed gas-liquid mixture.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by using the ozone/hydrogen peroxide, the first ejector and the second ejector are both venturi ejectors.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide, the hydrogen peroxide adding device is connected with the pipeline mixer through a diaphragm metering pump.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide, the top end of the reaction device is provided with an exhaust valve, and the exhaust valve is connected with a tail gas treatment device.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by using the ozone/hydrogen peroxide, a demister is arranged at the top of the reaction device.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide, the reaction device is a vertical cylindrical storage tank with an upper end enclosure and a lower end enclosure.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide, the water outlet pipeline is connected with the second ejector through a circulating pump.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by using the ozone/hydrogen peroxide, the tail gas treatment device is an electric heating tail gas destructor or a thermal catalysis tail gas destructor.
Preferably, in the device for the advanced oxidation of the degradation-resistant industrial wastewater by using the ozone/hydrogen peroxide, the ozone generator is an air source ozone generating device or an oxygen-rich source ozone generating device.
The utility model has the advantages that:
the utility model discloses a processing apparatus combines together ozone and hydrogen peroxide solution advanced oxidation, can effectively improve the utilization ratio of ozone, reduces ozone input volume, strengthens the advanced treatment effect when reducing treatment cost, has high-efficient clear advantage.
Drawings
FIG. 1 is a schematic diagram of an apparatus for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials/apparatus used in the examples were obtained from conventional commercial sources unless otherwise specified. The term "connected" or "connection" between the devices/apparatuses in the embodiments refers to the connection through pipes, pipelines or pumps.
FIG. 1 is a schematic diagram of an apparatus for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide. In FIG. 1, 1-the water inlet pipe; 2-hydrogen peroxide feeding device; 3-diaphragm metering pump; 4-a line mixer; 5-a first ejector; 6-an ozone generator; 7-a reaction device; 8-a water outlet pipeline; 9-a demister; 10-an exhaust valve; 11-a tail gas treatment device; 12-a circulation pump; 13-second ejector.
An example of an apparatus for advanced oxidation of refractory industrial wastewater with ozone/hydrogen peroxide is described below with reference to fig. 1. The device for the advanced oxidation of the degradation-resistant industrial wastewater by ozone/hydrogen peroxide comprises a water inlet pipeline 1, a water outlet pipeline 8, a hydrogen peroxide adding device 2, a pipeline mixer 4, an ozone generator 6, a reaction device 7, a tail gas treatment device 11, a first ejector 5 and a second ejector 13. The first ejector 5 and the second ejector 13 are provided with a water inlet end, a gas inlet end and a water outlet end. The water inlet pipeline 1 is connected with the water inlet end of the pipeline mixer 4, and the hydrogen peroxide adding device 2 is connected with the pipeline mixer 4 through the diaphragm metering pump 3. The water outlet end of the pipeline mixer 4 is connected with the water inlet end of the first ejector 5, and the water outlet end of the first ejector 5 is connected with the water inlet end of the reaction device 7. The water outlet end of the reaction device 7 is connected with a water outlet pipeline 8, the water outlet pipeline 8 is connected with the water inlet end of a second ejector 13 through a circulating pump 12, and the water outlet end of the second ejector 13 is connected with the bottom of the reaction device 7. The top of reaction unit 7 is equipped with defroster 9, and reaction unit 7's top is equipped with discharge valve 10, and discharge valve 10 links to each other with tail gas processing apparatus 11. The ozone generator 6 is respectively connected with the air inlet ends of the first ejector 5 and the second ejector 13.
The hydrogen peroxide adding device inputs hydrogen peroxide into the pipeline mixer through a diaphragm metering pump to be mixed with the wastewater from the water inlet pipeline, and the adding amount of the hydrogen peroxide is 50mL/m3～200mL/m3The mass concentration of the hydrogen peroxide can be 24%, 27.5% or 30%.
The first ejector and the second ejector both adopt a Venturi water ejector for adding ozone. The parts of the first ejector and the second ejector, which are contacted with ozone, are made of titanium alloy or polytetrafluoroethylene materials. In the first jet device, the air inlet end is connected with an ozone generator through an ozone inlet pipeline, the water inlet end is used for accessing mixed liquid from the pipeline mixer, and the water outlet end is connected with the reaction device. In the first ejector, the gas-water ratio of ozone addition is (0.5-3): 1. the ozone generator is an air source or oxygen-enriched source ozone generator, and the concentration of the generated ozone is 60 mg/L-150 mg/L.
The main structure of the reaction device is a vertical cylindrical storage tank with an upper end socket and a lower end socket, the vertical cylindrical storage tank is made of 304 stainless steel, and the reaction residence time is 30-150 min. The gas-liquid mixture composed of ozone and raw water to be treated enters the reaction device along the longitudinal direction, and enters the water outlet pipeline after full reaction. One end of the water outlet pipeline is connected with a water drainage pipeline, and the treated wastewater is directly discharged; the other end of the water outlet pipeline is connected into the second ejector through a circulating pump, and ozone can be added for supplement according to the water quality condition. The gas-water ratio of ozone addition of the second ejector is (0.5-1): 1. and the gas-liquid mixture flows back to the bottom of the reaction device through the second ejector and is recycled.
After the ozone gas in the reaction device reacts, the tail gas is demisted, then enters a tail gas treatment device through an exhaust valve at the top end of the reaction device, is subjected to tail gas destruction by adopting an electric heating or thermal catalysis process, and then is discharged.
The following further illustrates an example of applying the device of the present invention to perform advanced oxidation treatment of wastewater ozone/hydrogen peroxide through a specific application example.
Application example 1
The device shown in FIG. 1 is used for treating the effluent of a secondary sedimentation tank of a certain printing and dyeing enterprise in Guangzhou white cloud area, and the treatment process is as follows:
1) mixing wastewater with 50L/h of treated water with hydrogen peroxide in a pipeline mixer, wherein the adding amount of the hydrogen peroxide is 120mL/m3The obtained mixed liquid enters a first ejector to be mixed with ozone, the gas-water ratio of the first ejector to the ozone is 1:1, the obtained gas-liquid mixture enters a reaction device to carry out oxidation reaction, and the hydraulic retention time of the reaction device is 60 min;
2) one part of effluent of the reaction device is directly discharged to a drainage pipeline, the other part of effluent returns to a second jet device to be mixed with ozone, the gas-water ratio of the feeding is 1:1, the obtained gas-liquid mixture flows back to the reaction device, and the internal circulation ratio of the system is 2:1 (the ratio of the water yield of the backflow to the water yield of the discharge);
3) and after demisting the tail gas of the reaction device, destroying the tail gas by an electric heating device, and then discharging.
Wherein, the ozone generator adopts an air source, and the adding amount of ozone is 60 mg/L.
The treated raw water and the effluent quality are shown in table 1. After advanced treatment, the effluent of the system reaches the five-class water standard of surface water.
TABLE 1 comparison of Water quality before and after advanced treatment of dyeing wastewater
| Item | CODCr(mg/L) | SS(mg/L) |
| Quality of raw water | 80～90 | ～20 |
| Quality of effluent water | ≤40 | ≤10 |
Application example 2
Treating the effluent of Shandong Yanzhou certain papermaking enterprise in the secondary sedimentation tank by using the device shown in FIG. 1, wherein the treatment process is as follows:
1) mixing wastewater with 50L/h of treated water with hydrogen peroxide in a pipeline mixer, wherein the adding amount of the hydrogen peroxide is 150mL/m3The obtained mixed liquid enters a first ejectorMixing with ozone, adding gas-water ratio of 0.8:1, and allowing the obtained gas-liquid mixture to enter a reaction device for oxidation reaction, wherein the hydraulic retention time of the reaction device is 120 min;
2) one part of effluent of the reaction device is directly discharged to a drainage pipeline, the other part of effluent returns to a second jet device to be mixed with ozone, the gas-water ratio of the feeding is 0.8:1, the obtained gas-liquid mixture flows back to the reaction device, and the internal circulation ratio of the system is 2:1 (the ratio of the water yield of the backflow to the water yield of the discharge);
3) and after demisting the tail gas of the reaction device, destroying the tail gas by a thermal catalytic device, and then discharging.
Wherein, the ozone generator adopts an oxygen-rich source, and the adding amount of ozone is 90 mg/L.
The treated raw water and the effluent quality are shown in Table 2. After advanced treatment, the effluent of the system reaches the five-class water standard of surface water.
TABLE 2 comparison of water quality before and after deep treatment of paper making
| Item | CODCr(mg/L) | SS(mg/L) |
| Quality of raw water | ≤150 | ≤20 |
| Quality of effluent water | ≤50 | ≤10 |
The utility model discloses the O of development3/H2O2The advanced oxidation device provides a method for solving the problems of deep decolorization and difficult biodegradation of organic matters, and provides a feasible choice for developing the research of a sewage deep treatment method. Under the catalytic action of O3/H2O2Chain reaction occurs to generate a great amount of hydroxyl free radicals with strong oxidation effect and other active intermediates such as active free radicals and the like, so that the oxidation property of the ozone can be further improved. O is3/H2O2The advanced oxidation process can improve the degradation rate of organic matters in the organic wastewater difficult to degrade in the degradation process, increase the utilization rate of ozone molecules, overcome the embarrassing defect that the self-decomposition efficiency is higher than the actual oxidation efficiency in the ozone oxidation process, promote ozone to generate more hydroxyl radicals with oxidation activity after entering the wastewater, reduce the selectivity of degradation components, improve the overall effect of applying the ozone to wastewater treatment, and realize deep oxidation of residual organic pollutants and chromaticity.
Compared with other ozone oxidation methods, O3/H2O2The advanced oxidation process has the advantages of high pollutant removal efficiency, stable operation effect, small occupied area, low manufacturing cost, simple management and maintenance, low operation cost and the like, and has wide prospect in the treatment of the refractory organic wastewater of various scales.
The utility model discloses develop the O that agrees with current difficult degradation organic waste water field actual demand3/H2O2The catalytic oxidation device can treat the organic wastewater difficult to degrade to reach the national standard even stricter with lower cost, and has obvious technical and economic advantages.
Claims (7)
1. The utility model provides a device of difficult degradation industrial waste water of ozone hydrogen peroxide advanced oxidation which characterized in that: comprises a water inlet pipeline, a water outlet pipeline, a hydrogen peroxide adding device, a pipeline mixer, an ozone generator, a reaction device, a tail gas treatment device, a first ejector and a second ejector; wherein, the water inlet pipeline and the hydrogen peroxide adding device are respectively connected with the pipeline mixer, and the pipeline mixer is sequentially connected with the first ejector and the reaction device; the reaction device is respectively connected with the water outlet pipeline and the tail gas treatment device; the water outlet pipeline is also connected with the reaction device through a second ejector; the ozone generator is respectively connected with the first ejector and the second ejector.
2. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1, characterized in that: the first ejector and the second ejector are both venturi ejectors.
3. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1, characterized in that: the hydrogen peroxide adding device is connected with the pipeline mixer through a diaphragm metering pump.
4. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1, characterized in that: the top end of the reaction device is provided with an exhaust valve which is connected with a tail gas treatment device.
5. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1 or 4, characterized in that: the top of the reaction device is provided with a demister.
6. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1 or 4, characterized in that: the tail gas treatment device is an electric heating tail gas destructor or a thermal catalysis tail gas destructor.
7. The device for advanced oxidation of refractory industrial wastewater by ozone/hydrogen peroxide according to claim 1, characterized in that: the water outlet pipeline is connected with the second ejector through a circulating pump.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851025A (en) * | 2018-12-29 | 2019-06-07 | 广州市金龙峰环保设备工程股份有限公司 | A kind of device and method of ozone/hydrogen peroxide solution advanced oxidation indegradable industrial effluent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851025A (en) * | 2018-12-29 | 2019-06-07 | 广州市金龙峰环保设备工程股份有限公司 | A kind of device and method of ozone/hydrogen peroxide solution advanced oxidation indegradable industrial effluent |
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