CN110981039A - Method for treating organic wastewater by using aluminum carbon-ozone micro-nano bubbles - Google Patents
Method for treating organic wastewater by using aluminum carbon-ozone micro-nano bubbles Download PDFInfo
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- CN110981039A CN110981039A CN201911115990.2A CN201911115990A CN110981039A CN 110981039 A CN110981039 A CN 110981039A CN 201911115990 A CN201911115990 A CN 201911115990A CN 110981039 A CN110981039 A CN 110981039A
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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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- 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
Abstract
The invention discloses a method for treating organic wastewater by using aluminum carbon-ozone micro-nano bubbles, which comprises the following operation steps: 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 dissolving water containing ozone micro-nano bubbles with the wastewater in the step 1); 4) and feeding the mixed solution into an oxidation filter for deep reaction, filling an aluminum-carbon electrode material into the oxidation filter, treating the mixed solution by the aluminum-carbon electrode material, discharging the treated mixed solution after reaching the standard, and simultaneously refluxing part of the effluent to an ozone micro-nano bubble generator to be used as dissolved gas water. According to the invention, the limitation of selective oxidation of ozone is removed by combining the aluminum carbon and ozone micro-nano bubbles, so that the method has higher technical and economic applicability; the method can be used for treating high-concentration organic wastewater in industries such as 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 using aluminum carbon-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. The selective oxidation of ozone causes the residue of organic pollutants and degradation intermediate products thereof, which is difficult to meet the requirement of advanced treatment and even generates secondary pollution.
In recent years, the micro-electrolysis method for treating industrial wastewater has become a hot point for research and application. The conventional microelectrode materials almost belong to iron-carbon load materials, require oxidation-reduction reaction under acidic conditions and cannot be coupled with alkaline environment required by ozone oxidation.
At present, no relevant report of treating wastewater by combining an aluminum carbon microelectrode, ozone and micro-nano bubbles is available.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for treating organic wastewater by using aluminum carbon-ozone micro-nano bubbles.
The invention solves the technical problems by the following technical scheme:
the method for treating organic wastewater by using the aluminum carbon-ozone micro-nano bubbles comprises the following operation steps:
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 dissolving water containing ozone micro-nano bubbles with the wastewater in the step 1);
4) and feeding the mixed solution into an oxidation filter for deep reaction, filling an aluminum-carbon electrode material into the oxidation filter, treating the mixed solution by the aluminum-carbon electrode material, discharging the treated mixed solution after reaching the standard, and simultaneously refluxing part of the effluent to an ozone micro-nano bubble generator to be used as dissolved gas water.
In the step 1), the pH value of the wastewater is adjusted to 8-11.
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 4), the effluent of the oxidation filter 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), the hydraulic retention time of the oxidation filter is 25-60 min.
In the step 4), the aluminum-carbon electrode material is filled in the oxidation filter tank according to 80-90% of the overflow height by taking aluminum powder as an anode material and carbon powder as a cathode material.
In the step 4), the aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: 40-95% of aluminum powder and 5-60% of carbon powder.
The method for treating organic wastewater by using the aluminum carbon-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) the method utilizes the aluminum carbon microelectrode, removes the limitation that the traditional iron carbon microelectrode is only suitable for the acid environment, and can be used for treating high-concentration organic wastewater in industries such as coking, pharmacy, petrifaction, printing and dyeing, chemical engineering and the like;
3) according to the invention, the limitation of selective oxidation of ozone is removed by combining the aluminum carbon and ozone micro-nano bubbles, so that the method has higher technical and economic applicability;
4) the invention adopts the alkaline micro-electrolysis treatment process which can be directly used for micro-electrolysis treatment of the alkaline industrial wastewater without pre-adjusting the alkaline industrial wastewater to be acidic, thereby simplifying the process and saving the cost;
5) the aluminum-carbon electrode material adopted by the method has the advantages of large specific surface area, strong activity, no passivation and no hardening, and because aluminum is amphoteric metal and can react with acid or alkali, the aluminum-carbon electrode material has more advantages than iron when the wastewater is treated under alkaline conditions.
Drawings
FIG. 1 is a schematic process flow diagram of the method for treating organic wastewater by using aluminum carbon-ozone micro-nano bubbles.
In the figure: 1-a regulating tank, 2-a pipeline mixer, 3-an oxidation filter tank, 4-an ozone generator and 5-an ozone micro-nano bubble generator.
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 oxidation filter tank 3, an ozone generator 4 and an ozone micro-nano bubble generator 5, wherein the oxidation filter tank 3 is filled with aluminum carbon electrode materials according to 80-90% of the overflow height.
The aluminum-carbon electrode material takes aluminum powder as an anode material and carbon powder as a cathode material, and the particle diameters of the aluminum powder and the carbon powder are 2-20 nm.
The aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: 40-95% of aluminum powder and 5-60% of carbon powder.
The technical process of the method for treating organic wastewater by using the aluminum carbon-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 8-11, the wastewater is favorable for generating hydroxyl radicals under the alkaline condition, and the pollutant removal effect can be enhanced;
2) ozone generated by an ozone generator 4 and return water of an oxidation filter 3 enter an ozone micro-nano bubble generator 5 together to form gas dissolving water containing a large amount of ozone micro-nano bubbles, and the volume flow ratio of the return water to the ozone liquid is 3.5-8.0: 1;
3) feeding the wastewater in the step 1) and the dissolved gas water in the step 2) into a pipeline mixer 2;
4) the effluent of the pipeline mixer 2 enters an oxidation filter 3 for deep reaction to further degrade organic pollutants in water, and the hydraulic retention time is controlled to be 15-60 min; after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the oxidation filter 3 in an overflowing manner and is discharged after reaching the standard;
5) and (3) refluxing the effluent of the oxidation filter 3 to the ozone micro-nano bubble generator 5 according to the proportion of 5-10% to be used as dissolved air water.
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 pharmaceutical wastewater
The biochemical effluent of a sewage treatment plant of a certain pharmaceutical company is taken as a treatment object, and the advanced treatment effect of the process and the method on the sewage is investigated.
The specific operation is as follows:
1) the initial wastewater enters an adjusting tank 1 to homogenize the water quality, and liquid caustic soda is added to adjust the pH of inlet water to 8-9;
2) ozone generated by the ozone generator 4 and return water of the oxidation filter 3 enter the ozone micro-nano bubble generator 5 together to form gas dissolving water containing a large amount of ozone micro-nano bubbles, and the volume flow ratio of the return water to the ozone is 7.2-8.0: 1;
3) mixing the wastewater and the dissolved air water in a pipeline mixer 2;
4) the effluent of the pipeline mixer 2 enters an oxidation filter 3 for deep reaction to further degrade organic pollutants in water, and the aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: 95% of aluminum powder and 5% of carbon powder are filled in the oxidation filter tank according to 80-90% of the overflow height, and the hydraulic retention time is 30 min;
5) the effluent of the oxidation filter 3 flows back to the ozone micro-nano bubble generator 5 as dissolved gas water according to the proportion of 5-10 percent;
6) and after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the oxidation filter 3 in an overflowing manner 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 128-135mg/L, the COD of the outlet water is 44-48mg/L, the COD is less than or equal to 100mg/L, and the treatment effect meets the first-grade A standard of pollutant discharge Standard of urban wastewater treatment plants (GB 18918-2002).
Example 2: treatment of chemical wastewater
The sewage treatment effect of the process and the method of the invention on the sewage is examined by taking the sewage produced by a certain chemical industry as a treatment object.
The specific operation is as follows:
1) the initial wastewater enters an adjusting tank 1 to homogenize the water quality, and liquid caustic soda is added to adjust the pH of inlet water to 8-9;
2) ozone generated by the ozone generator 4 and backflow outlet water of the oxidation filter 3 enter the ozone micro-nano bubble generator 5 together to form gas dissolving water containing a large amount of ozone micro-nano bubbles, and the liquid-gas volume flow ratio of the backflow outlet water to the ozone is 4.5-5.1: 1;
3) mixing the wastewater and the dissolved air water in a pipeline mixer 2;
4) the effluent of the pipeline mixer 2 enters an oxidation filter 3 for deep reaction to further degrade organic pollutants in water, and the aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: 80% of aluminum powder and 20% of carbon powder are filled in the oxidation filter tank according to 80-90% of the overflow height, and the hydraulic retention time is 40 min;
5) the effluent of the oxidation filter 3 flows back to the ozone micro-nano bubble generator 5 as dissolved gas water according to the proportion of 5-10 percent;
6) and after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the oxidation filter 3 in an overflowing manner 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 273.8-316.4mg/L and the ammonia nitrogen is 31.2-40.8mg/L, the COD of outlet water is 59.9-74.8mg/L, the ammonia nitrogen is 12.5-13.7mg/L, the COD is less than or equal to 100mg/L and the ammonia nitrogen is less than or equal to 15mg/L, and the treatment effect meets the primary standard of the integrated wastewater discharge standard (GB 316.4-1996).
Example 3: treatment of printing and dyeing wastewater
The treatment effect of the process and the method of the invention 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 enters an adjusting tank 1 to homogenize the water quality, and liquid caustic soda is added to adjust the pH of the inlet water to 10-11;
2) ozone generated by the ozone generator 4 and backflow outlet water of the oxidation filter 3 enter the ozone micro-nano bubble generator 5 together to form gas dissolving water containing a large amount of ozone micro-nano bubbles, and the liquid-gas volume flow ratio of the backflow outlet water to the ozone is 3.5-4.1: 1;
3) mixing the wastewater and the dissolved air water in a pipeline mixer 2;
4) the effluent of the pipeline mixer 2 enters an oxidation filter 3 for deep reaction to further degrade organic pollutants in water, and the aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: aluminum powder 40% and carbon powder 60%, and filling in the oxidation filter according to 80-90% of the overflow height, wherein the hydraulic retention time is 60 min;
5) the effluent of the oxidation filter 3 flows back to the ozone micro-nano bubble generator 5 as dissolved gas water according to the proportion of 5-10 percent;
6) and after the wastewater is treated, the wastewater is discharged from an outlet at the tail end of the oxidation filter 3 in an overflowing manner 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 465.3-480.5mg/L and the chroma is 500, the COD of outlet water is 74.4-93.6mg/L, the chroma is 5, the COD is less than or equal to 100mg/L and the chroma 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 the aluminum carbon-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 dissolving water containing ozone micro-nano bubbles with the wastewater in the step 1);
4) and feeding the mixed solution into an oxidation filter for deep reaction, filling an aluminum-carbon electrode material into the oxidation filter, treating the mixed solution by the aluminum-carbon electrode material, discharging the treated mixed solution after reaching the standard, and simultaneously refluxing part of the effluent to an ozone micro-nano bubble generator to be used as dissolved gas water.
2. The method for treating organic wastewater by using the aluminum carbon-ozone micro-nano bubbles according to claim 1, wherein in the step 1), the pH of the wastewater is adjusted to 8-11.
3. The method for treating organic wastewater by using the aluminum carbon-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 the aluminum carbon-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 the aluminum carbon-ozone micro-nano bubbles as claimed in claim 1 or 2, wherein in the step 4), the effluent of the oxidation filter flows back to the ozone micro-nano bubble generator as dissolved air water according to the proportion of 5% -10%.
6. The method for treating organic wastewater by using the aluminum carbon-ozone micro-nano bubbles according to claim 1 or 2, wherein in the step 4), the hydraulic retention time of the oxidation filter is 25-60 min.
7. The method for treating organic wastewater by using the aluminum carbon-ozone micro-nano bubbles as claimed in claim 1 or 2, wherein in the step 4), the aluminum carbon electrode material is filled in the oxidation filter tank according to 80-90% of the overflow height by using aluminum powder as an anode material and carbon powder as a cathode material.
8. The method for treating organic wastewater by using the aluminum-carbon-ozone micro-nano bubbles according to claim 7, wherein in the step 4), the aluminum powder and the carbon powder in the aluminum-carbon electrode material are as follows by mass percent: 40-95% of aluminum powder and 5-60% of carbon powder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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