CN110980999A - Method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles - Google Patents
Method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles Download PDFInfo
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- CN110980999A CN110980999A CN201911116016.8A CN201911116016A CN110980999A CN 110980999 A CN110980999 A CN 110980999A CN 201911116016 A CN201911116016 A CN 201911116016A CN 110980999 A CN110980999 A CN 110980999A
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention discloses a method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles, which comprises the following operation steps: 1) firstly, adjusting the wastewater to be alkaline; 2) then sending the ozone generated by the ozone generator into the ozone micro-nano bubble generator to form gas dissolving water containing a large amount of ozone micro-nano bubbles; 3) mixing gas-dissolved water containing ozone micro-nano bubbles with the wastewater in the step 1), and adding hydrogen peroxide to contact the mixed solution to react; 4) and then the mixed solution is sent into an air floatation-oxidation tank for deep reaction, and the reaction treatment is discharged after reaching the standard. The invention utilizes the micro-nano bubbles to improve the utilization rate of ozone; a large amount of hydroxyl radicals are generated by the hydrogen peroxide and the ozone micro-nano bubbles, so that the applicability of the ozone oxidation technology is improved; and other catalysts are not needed to be added, so that the generation of chemical precipitation is avoided, and the method can be used for treating high-concentration organic wastewater in the industries of coking, pharmacy, petrifaction, printing and dyeing, chemical engineering and the like.
Description
Technical Field
The invention relates to the technical field of chemical treatment of industrial wastewater, in particular to a method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles.
Background
In recent years, with the rapid development of industries such as coking, pharmacy, petrifaction, printing and dyeing, chemical industry and the like, the ecological problem caused by wastewater containing various refractory organic matters is more and more serious. The traditional biochemical method is difficult to treat toxic and nondegradable organic matters such as polycyclic aromatic hydrocarbon, halogenated hydrocarbon, heterocyclic compounds, organic pesticides and the like contained in the wastewater. At present, the advanced oxidation technology is one of the most promising methods for treating refractory organic wastewater, and is classified into a photochemical oxidation method, a catalytic wet oxidation method, a sonochemical oxidation method, an ozone oxidation method, an electrochemical oxidation method, a Fenton-like method and the like. Wherein, the ozone oxidation method has the advantages of high organic matter degradation speed, mild conditions, no secondary pollution and wide application in water treatment.
Ozone is an oxidant with strong oxidizing power, the oxidation potential of the ozone is 2.07V, the ozone is soluble in water, and the solubility of the ozone in water at normal temperature and normal pressure is 10 times higher than that of oxygen. The solubility of ozone in water is lower, and meanwhile, the retention time of ozone in mixed liquor is short and the gas-liquid contact area is small in the traditional aeration mode, so that the utilization efficiency of ozone is lower. Has the disadvantages of selective oxidation and incomplete treatment.
The micro-nano bubbles have the characteristics of small volume, high internal pressure, large specific surface area, strong oxidizing property, mass transfer enhancement, no secondary pollution and the like, and compared with bubbles generated by the traditional aeration mode, the micro-nano bubbles can prolong the retention time of ozone in mixed liquid, increase the gas-liquid contact area and ozone solubility and effectively improve the ozone utilization rate.
However, no relevant report of treating wastewater by combining hydrogen peroxide, ozone and micro-nano bubbles is found at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles, which is characterized in that under an alkaline condition, ozone micro-nano bubbles are introduced to oxidize and degrade organic pollutants in the wastewater, and hydroxyl radicals are generated by the hydrogen peroxide and the ozone micro-nano bubbles to perform advanced oxidation so as to intensively degrade the organic pollutants in the wastewater.
The invention solves the technical problems by the following technical scheme:
the method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles comprises the following operation steps:
1) firstly, adjusting the wastewater to be alkaline;
2) then sending the ozone generated by the ozone generator into the ozone micro-nano bubble generator to form gas dissolving water containing a large amount of ozone micro-nano bubbles;
3) mixing gas-dissolved water containing ozone micro-nano bubbles with the wastewater in the step 1), and simultaneously adding hydrogen peroxide to contact with the mixed solution to react so as to degrade partial organic matters in the wastewater;
4) and feeding the mixed solution into an air flotation-oxidation tank for deep reaction, discharging after the reaction treatment reaches the standard, and simultaneously refluxing part of the effluent to an ozone micro-nano bubble generator to be used as dissolved air water.
In the step 1), the pH value of the wastewater is adjusted to 7-11.
In the step 2), the particle size of the ozone micro-nano bubbles is less than 200 nm.
In the step 2), the liquid-gas volume flow ratio of the reflux effluent to the ozone is 3.5-8.0: 1.
In the step 3), the adding amount of the hydrogen peroxide is 0.1-2.5kgH2O2/kg COD。
In the step 4), the hydraulic retention time in the air floatation-oxidation tank is 25-60 min.
In the step 4), the effluent of the air flotation-oxidation tank flows back to the ozone micro-nano bubble generator according to the proportion of 5-10% to be used as dissolved air water.
In the step 4), a mud scraper is arranged at the top of the air floatation-oxidation tank, and the scum is periodically cleaned by the mud scraper.
The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles has the following advantages:
1) according to the invention, the retention time of ozone in the mixed solution is prolonged through the micro-nano bubbles, the gas-liquid contact area and the ozone solubility are increased, and the ozone utilization rate is effectively improved;
2) according to the invention, a large amount of hydroxyl radicals are generated by contacting hydrogen peroxide and ozone, so that the selective oxidation of single ozone oxidation is avoided, the advanced oxidation is realized, the applicability of the ozone oxidation technology is improved, and the method can be used for treating high-concentration organic wastewater in the industries such as coking, pharmacy, petrifaction, printing and dyeing, chemical engineering and the like;
3) the invention does not need to add other metal ion type homogeneous catalysts, thereby avoiding the generation of chemical precipitates such as traditional Fenton iron mud and the like. Compared with the traditional Fenton oxidation method, the method does not need to add Fe2+And the catalyst has no chemical precipitation, avoids secondary pollution, has mild conditions, effectively solves the corrosion protection problem of equipment and saves cost.
Drawings
FIG. 1 is a process flow diagram of the method for treating organic wastewater by hydrogen peroxide-ozone micro-nano bubbles.
In the figure: 1-a regulating tank, 2-a pipeline mixer, 3-an air flotation-oxidation tank, 4-an ozone generator, 5-an ozone micro-nano bubble generator and 6-a mud scraper.
Detailed Description
The invention is further illustrated by the following figures and examples, in which the preparation and use conditions are indicated as typical and not limiting. It is within the scope of the present invention to make simple modifications or alterations to the methods, procedures or conditions of the present invention without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
As shown in figure 1, the equipment adopted for implementing the method mainly comprises a regulating tank 1, a pipeline mixer 2, an air flotation-oxidation tank 3, an ozone generator 4, an ozone micro-nano bubble generator 5 and a mud scraper 6.
The technical process of the method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles comprises the following steps:
1) the initial wastewater enters an adjusting tank 1 to homogenize the water quality, liquid alkali is added to adjust the pH of the wastewater to 7-11, the generation of hydroxyl radicals is facilitated under the alkaline condition of the wastewater, and the pollutant removal effect can be enhanced;
2) ozone generated by an ozone generator 4 and backflow water from an air floatation-oxidation tank 3 enter an ozone micro-nano bubble generator 5 together to form dissolved air water containing a large amount of ozone micro-nano bubbles, and the liquid-air volume flow ratio of the backflow water to the ozone is 3.5-8.0: 1;
3) the wastewater in the step 1) and the dissolved gas water in the step 2) enter a pipeline mixer 2, and the mixing ratio is 0.1-2.5kgH2O2Hydrogen peroxide is added according to the proportion of/kg COD, and the hydrogen peroxide is contacted with ozone in a pipeline mixer to form hydroxyl free radicals, so that advanced oxidation is realized, and partial organic matters are degraded;
4) the effluent of the pipeline mixer 2 enters an air flotation-oxidation tank 3 for deep reaction to further degrade organic pollutants in water, and the hydraulic retention time is 25-60 min;
5) the effluent of the air flotation-oxidation tank 3 is refluxed to an ozone micro-nano bubble generator 5 according to the proportion of 5 to 10 percent to be used as dissolved air water;
6) a mud scraper 6 is matched at the top of the air floatation-oxidation tank 3, the water surface is cleaned periodically according to the accumulated state of scum, and the scum is discharged out of the air floatation-oxidation tank 3 through a scum discharge groove;
7) and after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the air floatation-oxidation tank 3 in an overflowing way and is discharged after reaching the standard.
The ozone micro-nano bubble generator can adopt a membrane aeration device, the membrane aeration device adopts membrane materials in the forms of hollow fiber membranes, plate membranes and tubular membranes, the membrane aperture is 30-50nm, and the diameter of generated micro-nano bubbles is less than 200 nm. The ozone micro-nano bubble generator can also adopt a vortex air pump, and the diameter of the generated micro-nano bubbles is less than 200 nm.
The following are examples of applications of the process of the invention:
example 1: treatment of chemical wastewater
The effluent treated by a centralized sewage plant in a chemical industry park is taken as a treatment object, and the treatment effect of the method on the sewage is examined.
The specific operation steps are as follows:
1) the initial wastewater firstly enters an adjusting tank 1 to homogenize the water quality, NaOH is added, and the pH is adjusted to be 8-9;
2) ozone generated by the ozone generator 4 and backflow water from the air floatation-oxidation tank 3 enter the ozone micro-nano bubble generator 5 together to form dissolved air water containing a large amount of ozone micro-nano bubbles, and the volume flow ratio of the backflow water to the ozone liquid-air is 7.2-8.0: 1;
3) the dissolved air water containing the ozone micro-nano bubbles and the wastewater enter a pipeline mixer 2 together, and H is added simultaneously2O2，H2O2The weight ratio of the water to COD in the wastewater is 0.85kg of H2O2∶1kg COD，H2O2The wastewater is contacted and reacts to degrade partial organic matters in the wastewater;
4) the mixed liquid flows out of the pipeline mixer 2 and enters the air flotation-oxidation tank 3 for deep reaction to further degrade organic matters in the wastewater, the hydraulic retention time of the air flotation-oxidation tank 3 is controlled to be 25min, a mud scraper is matched with the top of the tank, and the water surface is cleaned periodically according to the accumulated condition of scum;
5) the water discharged from the air flotation-oxidation tank 3 flows back to the ozone micro-nano bubble generator 5 according to the proportion of 5-10 percent to be used as dissolved air water.
6) And after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the air floatation-oxidation tank 3 in an overflowing way and is discharged after reaching the standard.
Experiments show that under the condition that the system operates stably, under the condition that the COD of the inlet water is 140mg/L and the COD of the outlet water is 43-47mg/L, the COD is less than or equal to 50mg/L, and the treatment effect meets the first-class A standard of pollutant discharge Standard of urban wastewater treatment plants (GB 18918-2002).
Example 2: treatment of coking wastewater
The treatment effect of the method on the sewage is examined by taking the wastewater of a certain coking plant as a treatment object.
The specific operation steps are as follows:
1) the initial wastewater firstly enters an adjusting tank 1 to homogenize the water quality, NaOH is added, and the pH is adjusted to 10;
2) ozone generated by the ozone generator 4 and backflow water from the air floatation-oxidation tank 3 enter the ozone micro-nano bubble generator 5 together to form dissolved air water containing a large amount of ozone micro-nano bubbles, and the volume flow ratio of the backflow water to the ozone liquid-air is 4.5-5.1: 1;
2) the dissolved air water containing the ozone micro-nano bubbles and the wastewater enter a pipeline mixer 2 together, and H is added simultaneously2O2，H2O2The weight ratio of the water to COD in the wastewater was 1.13kg of H2O2∶1kg COD，H2O2The wastewater is contacted and reacts to degrade partial organic matters in the wastewater;
3) the mixed liquid flows out of the pipeline mixer 2 and then enters the air floatation-oxidation tank 3 for deep reaction to further degrade organic matters in the wastewater, the hydraulic retention time is 30min, a mud scraper is matched with the top of the tank, and the water surface is periodically cleaned according to the accumulated condition of scum;
4) the water discharged from the air flotation-oxidation tank 3 flows back to the ozone micro-nano bubble generator 5 according to the proportion of 5-10 percent to be used as dissolved air water.
6) And after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the air floatation-oxidation tank 3 in an overflowing way and is discharged after reaching the standard.
Experiments show that under the condition that the system operates stably, under the condition that the COD of the inlet water is 183-200mg/L, the COD of the outlet water is 60-67mg/L, the COD is less than or equal to 100mg/L, and the treatment effect meets the discharge standard of pollutants in the coking chemical industry (GB 16171-2012).
Example 3: treatment of printing and dyeing wastewater
The treatment effect of the method on the printing and dyeing wastewater is examined by taking the sewage of a certain printing and dyeing mill as a treatment object.
The specific operation steps are as follows:
1) the initial wastewater firstly enters an adjusting tank 1 to homogenize the water quality, NaOH is added, and the pH is adjusted to 9-10;
2) ozone generated by the ozone generator 4 and backflow water from the air floatation-oxidation tank 3 enter the ozone micro-nano bubble generator 5 together to form dissolved air water containing a large amount of ozone micro-nano bubbles, and the volume flow ratio of the backflow water to the ozone liquid-air is 3.5-4.0: 1;
3) the dissolved air water containing the ozone micro-nano bubbles and the wastewater enter a pipeline mixer 2 together, and H is added simultaneously2O2，H2O2The weight ratio of the water to COD in the wastewater was 2.43kg of H2O2∶1kg COD，H2O2The wastewater is contacted and reacts to degrade partial organic matters in the wastewater;
4) the mixed liquid flows out of the pipeline mixer 2 and then enters the air floatation-oxidation tank 3 for deep reaction to further degrade organic matters in the wastewater, the hydraulic retention time is 60min, a mud scraper is matched with the top of the tank, and the water surface is periodically cleaned according to the accumulated condition of scum;
5) the water discharged from the air flotation-oxidation tank 3 flows back to the ozone micro-nano bubble generator 5 according to the proportion of 5-10 percent to be used as dissolved air water.
6) And after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the air floatation-oxidation tank 3 in an overflowing way and is discharged after reaching the standard.
Experiments show that under the condition that the system operates stably, under the conditions that the COD of inlet water is 460-500mg/L and the chroma is 600, the COD of outlet water is 76-93mg/L and the chroma is 10, the COD is less than or equal to 100mg/L and the chroma treatment is less than or equal to 70, and the effect meets the discharge standard of pollutants for textile dyeing and finishing industry water (GB 4287-2016).
Claims (8)
1. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles is characterized by comprising the following operation steps of:
1) firstly, adjusting the wastewater to be alkaline;
2) sending ozone generated by an ozone generator into an ozone micro-nano bubble generator to form gas dissolving water containing a large amount of ozone micro-nano bubbles;
3) mixing gas-dissolved water containing ozone micro-nano bubbles with the wastewater in the step 1), and simultaneously adding hydrogen peroxide to contact with the mixed solution to react so as to degrade partial organic matters in the wastewater;
4) and feeding the mixed solution into an air flotation-oxidation tank for deep reaction, discharging after the reaction treatment reaches the standard, and simultaneously refluxing part of the effluent to an ozone micro-nano bubble generator to be used as dissolved air water.
2. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1, wherein in the step 1), the pH of the wastewater is firstly adjusted to 7-11.
3. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 2), the particle size of the ozone micro-nano bubbles is less than 200 nm.
4. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 2), the liquid-gas volume flow ratio of the reflux effluent to the ozone is 3.5-8.0: 1.
5. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 3), the adding amount of the hydrogen peroxide is 0.1-2.5kgH2O2/kg COD。
6. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 4), the hydraulic retention time in the air flotation-oxidation tank is 25-60 min.
7. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles as claimed in claim 1 or 2, wherein in the step 4), the effluent of the air flotation-oxidation tank flows back to the ozone micro-nano bubble generator as dissolved air water according to a proportion of 5% -10%.
8. The method for treating organic wastewater by using hydrogen peroxide-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 4), a mud scraper is arranged at the top of the air flotation-oxidation tank, and the scum is periodically cleaned by using the mud scraper.
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Cited By (6)
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| CN111470607A (en) * | 2020-04-27 | 2020-07-31 | 广州市德百顺电气科技有限公司 | Wastewater treatment equipment |
| CN112777722A (en) * | 2021-01-11 | 2021-05-11 | 杭州水处理技术研究开发中心有限公司 | Method and device for efficiently catalyzing ozone for advanced sewage treatment |
| CN113735348A (en) * | 2021-09-17 | 2021-12-03 | 清华大学深圳国际研究生院 | Organic wastewater treatment method |
| CN114180746A (en) * | 2020-09-14 | 2022-03-15 | 北京航天凯恩化工科技有限公司 | Acidic wastewater treatment system and treatment method |
| CN115259554A (en) * | 2022-07-26 | 2022-11-01 | 山东海科创新研究院有限公司 | Treatment method of epoxy resin wastewater |
| CN116589074A (en) * | 2023-06-06 | 2023-08-15 | 上海大学 | Weak cyclone bubble separator and micro-nano bubble reinforced organic pollution wastewater treatment system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111470607A (en) * | 2020-04-27 | 2020-07-31 | 广州市德百顺电气科技有限公司 | Wastewater treatment equipment |
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| CN115259554A (en) * | 2022-07-26 | 2022-11-01 | 山东海科创新研究院有限公司 | Treatment method of epoxy resin wastewater |
| CN116589074A (en) * | 2023-06-06 | 2023-08-15 | 上海大学 | Weak cyclone bubble separator and micro-nano bubble reinforced organic pollution wastewater treatment system and method |
| CN116589074B (en) * | 2023-06-06 | 2024-02-27 | 上海大学 | Weak cyclone bubble separator and micro-nano bubble reinforced organic pollution wastewater treatment system and method |
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Application publication date: 20200410 |