CN108892321B - Method for treating pyridine pesticide wastewater by biological-electrochemical coupling technology - Google Patents
Method for treating pyridine pesticide wastewater by biological-electrochemical coupling technology Download PDFInfo
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Abstract
The invention discloses a method for treating pyridine pesticide wastewater by a biological-electrochemical coupling technology, and belongs to the technical field of pesticide wastewater treatment. The processing method comprises the following steps: the pyridine pesticide wastewater is subjected to UBF + O/A/O microorganism strengthening treatment, and biochemical effluent is subjected to sand filtration and then is treated by adopting an electrocatalytic oxidation technology. According to the invention, an exogenous electron acceptor is provided to enhance the anaerobic and anoxic biodegradation effects, the open-loop degradation of pyridine substances is promoted, the wastewater treatment is carried out on biochemical effluent by adopting high-efficiency electrocatalytic oxidation, the high-efficiency stable treatment of pyridine wastewater with high COD, high ammonia nitrogen and difficult biochemical degradation is realized, and the discharge of pyridine pesticide wastewater reaches the standard; the treatment method has the advantages of simple and convenient operation, high efficiency, high stability, convenient maintenance and the like, and no secondary pollution is generated.
Description
Technical Field
The invention belongs to the field of pesticide wastewater treatment processes, and particularly relates to a method for treating pyridine pesticide wastewater by a biological-electrochemical coupling technology.
Background
Pyridine is a low-toxicity organic matter with special odor, has certain biological inhibition, and has the highest concentration of 400mg/L without influence on the operation of a microorganism treatment facility. Unshared electron pairs on N atoms in pyridine molecules do not participate in the formation of a conjugated system of pi electrons on a ring; on the contrary, the structure is called as 'pi-deficient electricity' because the N atom has strong electronegativity and attracts electrons on the ring, so that the electron cloud density on the ring is reduced, and oxygen is prevented from obtaining electrons from the moleculeSubstructure ", and thus pyridine waste water is difficult to biodegrade. In addition, pyridine is difficult to be oxidized under the condition of acid potassium dichromate, and the oxidation efficiency is extremely low. COD detected by national standard GB11914-89crThe value often does not accurately reflect the chemical oxygen demand of the pyridine waste water.
Pyridine and derivatives thereof have the characteristic of causing distortion and have potential hazard to human health, and if the wastewater is directly discharged, the wastewater can form obvious hazard to the ecological environment. The treatment of pyridine and pyridine heterocyclic ring pollutants is basically divided into a physical and chemical method and a biochemical method, wherein the physical and chemical method mainly comprises adsorption, steam stripping, incineration, ozone catalytic oxidation, wet catalytic oxidation, a photocatalytic method, electric flocculation, microwave radiation and the like, wherein the steam stripping, incineration and resin adsorption method has wide and mature application in engineering, but the pollution indexes of the wastewater treated by the method are still high and cannot reach the take-over standard of an industrial park. The biological method has the advantages of mature process, low operation cost and the like, still has important application value in the migration conversion and mineralization processes of pyridine organic substances, and most researches are concentrated on the degradation of pure pyridine substances at present, but the biological method has application researches of engineering on pesticide pyridine wastewater.
The traditional way for treating pyridine-containing wastewater is to place physicochemical pretreatment at the front end of wastewater treatment, which often results in COD in the wastewatercrThe phenomenon of reverse rising is not reduced, and although the pyridine is degraded to a certain degree, the biodegradability of the wastewater cannot be obviously improved. For example, in the fenton oxidation treatment process, the unbound electron pair on the N atom in the pyridine molecule is easily oxidized by hydrogen peroxide to generate N-pyridine oxide, and the purpose of ring opening degradation cannot be effectively achieved. If the pyridine-containing wastewater is directly subjected to electrocatalytic oxidation, the electrocatalytic oxidation is firstly expressed in the ring-opening chain-breaking action of pyridine substances and is expressed as COD in a short timecrIncreased and difficult to achieve 80% conversion to N for total nitrogen removal2The treatment effect ofIf the pyridine-containing wastewater is completely mineralized by an electrocatalytic oxidation method, the operation cost can be greatly increased, and the method is not beneficial to industrial application.
The traditional biochemical treatment process generally adopts an A/O process, and has the advantages that organic pollutants are degraded, and the A/O process also has a certain nitrogen and phosphorus removal function; the heterotrophic bacteria hydrolyze starch, fiber, carbohydrate and other suspended pollutants and soluble organic matters in the sewage into organic acid at an anoxic section, so that macromolecular organic matters are decomposed into micromolecular organic matters, insoluble organic matters are converted into soluble organic matters, and when products after anoxic hydrolysis enter an aerobic tank for aerobic treatment, the biodegradability of the sewage is improved, and the oxygen efficiency is improved; in the anoxic heterotrophic bacteria, protein, fat and other pollutants are ammoniated (N on an organic chain or amino in amino acid) to release ammonia (NH)3、NH4 +) Under the condition of sufficient oxygen supply, the nitrification of autotrophic bacteria can react NH3-N(NH4 +) Oxidation to NO3 -Returning to the anoxic tank under reflux control, and denitrifying to remove NO under anoxic condition3 -Reduced to molecular nitrogen (N)2) C, N, O, the ecological cycle is completed, and the sewage harmless treatment is realized. However, when the A/O process is used for treating pyridine-containing wastewater, as pyridine substances are difficult to degrade and the required degradation time is long, the pyridine substances directly enter the A/O section for treatment, the release of ring nitrogen cannot be ensured, and further ammonia nitrogen cannot enter a nitrification and denitrification treatment stage, and the release of ammonia nitrogen in the wastewater cannot be matched with a biochemical nitrification and denitrification process, so that the ammonia nitrogen cannot reach the standard.
The prior art of Chinese patent publication No. CN102139992A discloses a high-concentration pyridine wastewater treatment process, which comprises the following steps: adjusting the raw water of the wastewater to be acidic, and treating the raw water in an electrocatalytic oxidation device; the effluent is connected into a micro-electrolysis device for treatment, and the acidic and oxygen-enriched conditions of the wastewater are kept in the step; adjusting the effluent to be alkaline, and adding a medicine for coagulating sedimentation; controlling the salt content of the wastewater to be below 2 percent, and then entering an anaerobic hydrolysis and pressurized biological contact oxidation device for biochemical treatment, wherein the effluent reaches the current first-grade sewage discharge standard. The invention adopts a physicochemical treatment process taking electrocatalytic oxidation as a core, can effectively decompose pyridine pollutants, reduce the toxicity of the wastewater and improve the biodegradability of the wastewater; the biochemical treatment adopts a combined process of anaerobic hydrolysis and pressurized biological contact oxidation, so that the organic load, the treatment efficiency and the salt tolerance of the biochemical treatment are improved; the treatment process has the characteristics of strong impact load resistance, good treatment effect and lower operation cost, and can ensure that high-concentration pyridine wastewater is stably discharged after reaching the standard after being treated. The main action of electrocatalytic oxidation in the method is represented by ring opening and chain scission of pyridine substances in the pretreatment process, COD (chemical oxygen demand) and ammonia nitrogen in the wastewater first show a rising trend in the process, and the removal of total nitrogen is completely completed by a biochemical system; the nitrogen removal capability of the biochemical system is greatly related to the air temperature, so that when the temperature is low, although pyridine substances are degraded into chain-shaped substances through electrocatalytic oxidation, the nitrogen removal capability of the biochemical system is weak due to low temperature, so that the COD (chemical oxygen demand) and ammonia nitrogen content of effluent are still high, and the standard is difficult to achieve. Therefore, the process of electrocatalytic oxidation and regeneration treatment is adopted, and the tail end of the treatment lacks control measures which are not influenced by the outside, so that the fluctuation of the temperature on the removal rate of COD and ammonia nitrogen is difficult to resist. Meanwhile, the prior art carries out electrocatalytic oxidation under an acidic condition, has high corrosivity to an electrode and high treatment cost; and under the acidic condition, the oxidation efficiency is reduced due to the fact that the electron-withdrawing effect of nitrogen atoms is enhanced after pyridine salifying.
Therefore, it is an urgent need in the industry to provide a treatment method for efficiently degrading pyridine-containing wastewater, which is suitable for industrial scale application, and which can reduce the treatment cost without affecting the effluent level by temperature.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that COD and total nitrogen removal rate are difficult to meet the requirement of connection pipe when the temperature is low due to the fact that waste water containing pyridine is subjected to electrocatalytic oxidation and then biochemical treatment in the prior art, the invention provides the method for treating pyridine pesticide waste water by the biological-electrochemical coupling technology.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A method for treating pyridine pesticide wastewater by a biological-electrochemical coupling technology comprises the following steps:
(1) pumping the pyridine-containing wastewater in the sewage collection tank into an adjusting tank to adjust the pH value to 7-8, and simultaneously adding an exogenous electron acceptor agent for homogenizing and equalizing;
(2) treating the wastewater in the step (1) in a biochemical treatment working section, and enabling effluent to automatically flow to a secondary sedimentation tank for primary sedimentation;
(3) the effluent of the secondary sedimentation tank flows into a sand filter tank for filtering, and the filtered effluent flows into a buffer tank;
(4) adding electrolyte into the buffer tank and homogenizing;
(5) pumping the effluent of the buffer pool into an electrocatalytic oxidation tank for advanced oxidation reaction, and then discharging the effluent.
Preferably, the pyridine-containing wastewater in the wastewater collection tank in the step (1) is pretreated by one or two of stripping and resin adsorption processes and then enters the wastewater collection tank.
Preferably, the biochemical treatment section in the step (2) comprises a UBF section and a microbial treatment section connected in series with O/A/O.
Preferably, the pyridine-containing wastewater in the step (1) is pyridine wastewater generated by pesticide products containing pyridine, picoline and cyanopyridine, and COD is COD after pretreatmentcrLess than or equal to 3000mg/L, total nitrogen less than or equal to 1000mg/L, TOC less than or equal to 2000mg/L and pyridine less than or equal to 100 mg/L.
Preferably, in step (1), the pH value of the wastewater is adjusted by sodium hydroxide or sodium carbonate.
Preferably, the electron acceptor agent in the step (1) is one or a mixture of nitrate and nitrite, and the addition amount is 30-60 mg/L.
Preferably, the UBF section in step (2) is microbially cured with a polyurethane filler.
Preferably, the hydraulic retention time of the anaerobic biological reaction in the UBF section in the step (2) is 36-72 h.
Preferably, the hydraulic retention time of the two-stage aerobic biological reaction (O section) in the O/A/O section in the step (2) is 60-84 h, and the hydraulic retention time of the anoxic biological reaction (A section) is 16-36 h.
Preferably, the secondary O section in the O/A/O in the step (2) is refluxed to the A section at a reflux ratio of 100-400%.
Preferably, shallow filtration of quartz sand is adopted in the sand filter in the step (3).
Preferably, the electrolyte added in the step (4) is one or a mixture of sodium chloride and sodium sulfate, and the adding amount is 1000-5000 mg/L.
Preferably, the electrocatalytic oxidation in step (5) employs IrO2、RuO2、SnO2A Ti-based coated electrode of a composite of two or more of (1). The electrode has high catalytic performance, and can effectively degrade organic matters and total nitrogen in biochemical effluent of pyridine wastewater.
Preferably, the electrocatalytic oxidation retention time in the step (5) is 60-120 min.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention overcomes the technical problem that COD and total nitrogen content of effluent are too high to reach the standard when the biochemical treatment is greatly influenced by temperature and the temperature is low because the pyridine-containing wastewater is subjected to electrocatalytic oxidation and regeneration treatment in the prior art, firstly, pyridine substances in the wastewater are degraded into organic micromolecules by an open loop through a biochemical treatment working section, then the wastewater is subjected to electrocatalytic oxidation, because the electrocatalytic oxidation process is not influenced by temperature, the step is placed after the biochemical treatment step and used as the control of the biochemical treatment step, when the test conditions are the same, when the environmental temperature is reduced from 20 ℃ to 3 ℃, the treatment capacities of a UBF working section and an O/A/O working section on the COD, the total nitrogen and the pyridine in the pyridine-containing wastewater are greatly reduced, but because the last step of the electrocatalytic oxidation is carried out, the final effluent COD can still be reduced by more than 80 percent, the pyridine concentration is reduced by more than 95%, the total nitrogen is reduced by more than 90%, the TOC is reduced by more than 85%, the effluent meets the requirements of taking over in a garden, and the problems of COD (chemical oxygen demand) and total nitrogen content fluctuation of the effluent caused by the influence of temperature in the biochemical treatment step when the same treatment equipment is used in different seasons are effectively avoided.
(2) In the invention, the biochemical treatment section is provided with a UBF section and a microorganism treatment section connected in series with O/A/O, so that the anaerobic microorganism treatment section, the anoxic microorganism treatment section and the aerobic microorganism treatment section are effectively connected, and the degradation of pyridine substances and the ammoxidation, nitrification and denitrification nitrogen removal of N on a pyridine ring are enhanced; in the steps, firstly, wastewater containing pyridine substances is subjected to a UBF step to remove the biological toxicity of the wastewater, the pyridine is a monocyclic substance and is easy to approach an active center of enzyme, so that the pyridine in the wastewater can be transferred from a wastewater interface to a biological film filled in the UBF, the biodegradation of anaerobic microorganisms on the pyridine can be enhanced, most of the pyridine substances are subjected to ring opening and are broken and further degraded into ammonia nitrogen, and meanwhile, the alkalinity of the wastewater is increased; after the effluent enters an O-section aerobic process, except the process of converting ammonia nitrogen into nitrate nitrogen, part of carbon-containing organic matters are converted into CO2Besides, the nitrification in the stage can consume the alkalinity of the wastewater, so that the pH value of the effluent is maintained at 7-8, which is just the most suitable pH range of the denitrification stage in the next stage; then enters the anoxic process of the A section, the exogenous electron acceptor and the electron acceptor NO generated by the O section3 -The method synergistically enhances the metabolic activity of nitrate reducing bacteria, improves the co-metabolism and mutual benefit symbiosis of microorganisms, thereby enhancing the biodegradation of pyridine substances, on one hand, nitrate nitrogen serving as an electron acceptor further degrades undegraded pyridine substances serving as electron donors under the action of nitroreducing bacteria to release ammonia nitrogen, and on the other hand, the nitrate nitrogen is promoted to be converted into N under the action of denitrifying bacteria2(ii) a The ammonia nitrogen is converted into nitrate nitrogen after entering the O section again, and flows back to the A section to be finally converted into N2(ii) a And a small amount of pyridine substances, organic chain molecules, nitrogen-containing organic molecules and other substances which are not converted in the biochemical treatment process are eliminated in the electrocatalytic oxidation treatment step.
(3) The invention aims at the waste water containing pyridine substances with higher concentration, and the waste water is pretreated by one or two combined processes of steam stripping or resin adsorption and then enters a sewage collecting tank so as to reduce the influence of the pyridine substances on microorganisms in a chemical engineering section.
(4) The invention makes the effluent flow to the secondary sedimentation tank automatically after the biochemical treatment section in order to carry out primary sedimentation and remove most of activated sludge and thalli; the effluent containing a small amount of suspended matters flows to a sand filter automatically to be filtered so as to reduce the backwashing frequency of the sand filter; after SS in the wastewater and substances with larger turbidity are removed by filtering, the gas generated in the electrocatalytic oxidation is prevented from forming foam in the solution, which is more beneficial to engineering.
(5) The UBF section of the invention adopts polyurethane filler to carry out microbial solidification, and has the functions that microbial mucosa can be formed on the surface of a filler gap, wastewater is contacted with the microbial membrane growing on the surface of the filler, and the diffusion and the transfer between the wastewater and the microbial membrane and the adsorption of the microbial mucosa enable pyridine in the wastewater to be transferred from a wastewater interface to the biological membrane, thereby strengthening the material structure change of pyridine substances in the anaerobic treatment process.
(6) According to the invention, the second-stage O section in the O/A/O reflows to the A section at a reflow ratio of 100-400%, so that nitrate nitrogen of the second-stage O section can be ensured to be used as an electron acceptor to reflow to the anoxic section of the A section, and the microorganisms in the A section are supplemented and strengthened with NO3 -Is an electron acceptor, takes pyridine substances as an organic matter degradation function of an electron donor, and simultaneously plays a role in denitrification.
(7) The invention adds electrolyte into the buffer tank before electrocatalytic oxidation, can improve the conductivity of the wastewater and stabilize the tank voltage, and simultaneously generates OH and ClO-、S2O8 2-And oxidizing substances participate in indirect oxidation, so that the electrocatalytic oxidation efficiency is improved.
(8) The hydraulic retention time of anaerobic biological reaction in the UBF section is 36-72 h; the hydraulic retention time of two-stage aerobic biological reaction (O section) in the O/A/O section is 60-84 h, and the hydraulic retention time of anoxic biological reaction (A section) is 16-36 h; under the condition, the reaction time of the action of pollutants and microorganisms in the wastewater is ensured, the structural transformation and further degradation of pyridine substances are ensured, the treatment efficiency of subsequent electrocatalytic oxidation is improved, and the wastewater is ensured to be discharged up to the standard.
(9) IrO is adopted in electrocatalytic oxidation in the invention2、RuO2、SnO2The Ti-based coating electrode of the compound of two or more of the pyridine compounds has higher catalytic performance and can effectively degrade organic matters in biochemical effluent of pyridine wastewater; the electrocatalytic oxidation retention time is 90-120 min; the reasonable residence time can ensure the removal effect of COD and total nitrogen, and simultaneously ensure reasonable engineering applicability, and finally realize that the effluent pyridine content, COD and total nitrogen meet the requirements of taking over in a garden.
(10) The invention adds an exogenous electron acceptor in a biological treatment working section, strengthens the microorganism to take pyridine substances in wastewater as a unique electron donor, improves the ammoniation effect of anaerobic ammonium oxidation bacteria and the denitrification effect of nitrate reducing bacteria in an anoxic section, thereby enhancing the ring-opening degradation of the pyridine substances and solving the problem that the pyridine substances are difficult to open rings and biodegrade.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
As shown in fig. 1, this example provides a method for treating pyridine pesticide wastewater by a bio-electrochemical coupling technique, wherein the pyridine pesticide wastewater is pyridine pesticide wastewater in a workshop of a certain pesticide enterprise in coast of jiangsu, and the treatment steps are as follows at an ambient temperature of 20 ℃:
(1) pyridine wastewater is subjected to steam stripping and resin adsorption in a workshop and then enters a tail end sewage station collecting tank;
(2) pumping the wastewater in the collection tank into a biochemical regulating tank, regulating the pH value to 7 by using sodium carbonate, and simultaneously adding 50mg/L sodium nitrate for homogenizing and homogenizing;
(3) enabling the wastewater in the step (2) to enter a UBF + O/A/O microbial treatment section, enabling UBF to stay for 60 hours in an anaerobic mode, enabling O section to stay for 60 hours, enabling A section to stay for 20 hours, enabling a secondary O section to flow back to the A section at a reflux ratio of 100%, and enabling effluent to flow to a secondary sedimentation tank automatically;
(4) the effluent of the secondary sedimentation tank flows into a sand filter tank for filtering, and the filtered effluent flows into a buffer tank;
(5) adding 1000mg/L sodium chloride into a buffer tank for homogenizing and equalizing;
(6) pumping the effluent of the buffer tank into an IrO2And (3) carrying out advanced oxidation reaction on an electrocatalytic oxidation tank of the titanium-based coating electrode for HRT90min, and accessing effluent to a garden pipe network after the effluent reaches the standard.
TABLE 1 effluent index of each section in the treatment process
As can be seen from Table 1, compared with the wastewater containing pyridine substances after pH adjustment, COD is reduced by 28.6% and pyridine concentration is reduced by 21.1% in the UBF stage; COD of the effluent of the O/A/O section is reduced by 67.8 percent, the concentration of pyridine is reduced by 83.2 percent, and the total nitrogen is reduced by 67.3 percent; compared with the wastewater containing pyridine substances after the pH is adjusted, the COD of the effluent is reduced by 83.9 percent, the pyridine concentration is reduced by 91.8 percent, the total nitrogen is reduced by 97.2 percent, and the TOC is reduced by 89.9 percent.
Comparative example 1
The conditions of the treatment steps in this comparative example were the same as those in example 1 (the pyridine-containing wastewater was the same type of wastewater from the same enterprise, but the COD, total nitrogen, pyridine and TOC contents were slightly different), except that this comparative example was carried out at an ambient temperature of 3 deg.C, the HRT of the high-level oxidation reaction in the electrocatalytic oxidation tank was 120min, and the effluent indexes of the respective sections in the treatment process were as shown in Table 2.
TABLE 2 effluent index of each section in the treatment process
Therefore, when the test conditions are the same, the treatment capacity of the UBF section and the O/A/O section on COD, total nitrogen and pyridine in the pyridine-containing wastewater is greatly reduced due to the reduction of the environmental temperature, but the final electrocatalytic oxidation step is controlled, so that the COD of the final effluent can be reduced by 84.1%, the concentration of the pyridine is reduced by 97.8%, the total nitrogen is reduced by 92.1%, the TOC is reduced by 89.2%, and the effluent meets the requirements of a garden pipe connection standard and meets the treatment requirements.
Example 2
As shown in fig. 1, this example provides a method for treating pyridine pesticide wastewater by a bio-electrochemical coupling technique, where the pyridine pesticide wastewater is picoline pesticide wastewater, and the treatment steps are as follows at an ambient temperature of 15 ℃:
(1) pyridine wastewater is subjected to steam stripping pretreatment in a workshop and then enters a collecting tank of a terminal sewage station;
(2) pumping the wastewater in the collection tank into a biochemical regulating tank, regulating the pH value to 7.5 by using sodium carbonate, and simultaneously adding a mixture of 60mg/L of sodium nitrate and sodium nitrite in a mass ratio of 1:1 for homogenizing and homogenizing;
(3) enabling the wastewater in the step (2) to enter a UBF + O/A/O microbial treatment section, enabling UBF to stay for 72h in an anaerobic manner, enabling O to stay for 72h, enabling A to stay for 16h, enabling a secondary O section to flow back to the A section at a reflux ratio of 200%, and enabling effluent to flow to a secondary sedimentation tank automatically;
(4) the effluent of the secondary sedimentation tank flows into a sand filter tank for filtering, and the filtered effluent flows into a buffer tank;
(5) adding 2500mg/L sodium sulfate into a buffer tank for homogenizing and balancing;
(6) pumping the effluent of the buffer tank into a reactor by adopting RuO2And (3) carrying out advanced oxidation reaction on an electrocatalytic oxidation tank of the titanium-based coating electrode for HRT100min, and accessing effluent to a garden pipe network after the effluent reaches the standard.
TABLE 3 effluent index of each section in the treatment process
As can be seen from Table 3, compared with the wastewater containing pyridine substances after pH adjustment, COD is reduced by 18.3% in the UBF stage, and the pyridine concentration is reduced by 55.1%; COD of effluent of the O/A/O section is reduced by 65.9 percent, the concentration of pyridine is reduced by 79.5 percent, and the total nitrogen is reduced by 53.1 percent; compared with the wastewater containing pyridine substances after the pH is adjusted, the COD of the effluent is reduced by 84.5 percent, the pyridine concentration is reduced by 98.5 percent, the total nitrogen is reduced by 94.2 percent, and the TOC is reduced by 90.8 percent.
Example 3
As shown in fig. 1, this example provides a method for treating pyridine pesticide wastewater by using a bio-electrochemical coupling technique, in which the pyridine pesticide wastewater is 3-cyanopyridine pesticide intermediate wastewater, and the treatment steps are as follows at an ambient temperature of 10 ℃:
(1) pyridine wastewater is adsorbed by resin in a workshop and then enters a collecting tank of a terminal sewage station;
(2) pumping the wastewater in the collection tank into a biochemical regulating tank, regulating the pH value to 8 by using sodium carbonate, and simultaneously adding 30mg/L sodium nitrite for homogenizing and homogenizing;
(3) enabling the wastewater in the step (2) to enter a UBF + O/A/O microbial treatment section, enabling UBF to stay for 36h in an anaerobic manner, enabling O section to stay for 84h, enabling A section to stay for 36h, enabling a secondary O section to flow back to the A section at a reflux ratio of 400%, and enabling effluent to flow to a secondary sedimentation tank automatically;
(4) the effluent of the secondary sedimentation tank flows into a sand filter tank for filtering, and the filtered effluent flows into a buffer tank;
(5) adding a mixture of 5000mg/L sodium chloride and sodium sulfate in a mass ratio of 1:1 into a buffer tank, and homogenizing;
(6) SnO is adopted for pumping the effluent of the buffer tank2Carrying out advanced oxidation reaction on an electrocatalytic oxidation tank of the titanium-based coating electrode, HRT120min, and accessing effluent to a garden pipe network after the effluent reaches the standard.
TABLE 4 effluent index of each section in the treatment process
As can be seen from Table 4, compared with the wastewater containing pyridine substances after pH adjustment, the COD in the UBF stage is increased by 50%, which indicates that the substances in the UBF stage of the wastewater are converted into substances with better degradability, and the pyridine concentration is reduced by 40%; COD of the effluent of the O/A/O section is reduced by 65.2 percent, the concentration of pyridine is reduced by 76 percent, and the total nitrogen is reduced by 63.3 percent; compared with the wastewater containing pyridine substances after the pH is adjusted, the COD of the effluent is reduced by 84.4 percent, the pyridine concentration is reduced by 96.8 percent, the total nitrogen is reduced by 95.9 percent, and the TOC is reduced by 89.4 percent.
The embodiment shows that the biological toxicity of the wastewater is reduced by the UBF section by controlling the biochemical influent water concentration of the pyridine, the pyridine substances are fully degraded and mineralized in the biochemical system O/A/O section, the free ammonia is released, the aim of removing nitrogen is achieved by the system nitrification and denitrification, the tail end is strengthened by the electrocatalytic oxidation process, the treatment capacity of the system is ensured, the method can adapt to the treatment of the wastewater containing the pyridine substances at various environmental temperatures, the high cost caused by overuse of the electrocatalytic oxidation is avoided, the effluent quality fluctuation caused by the temperature change of the biochemical treatment section is avoided, and the method is suitable for industrial scale application.
Claims (5)
1. A method for treating pyridine pesticide wastewater by using a biological-electrochemical coupling technology is characterized by comprising the following steps:
(1) pumping the pyridine-containing wastewater in the sewage collection tank into an adjusting tank to adjust the pH value to 7-8, and simultaneously adding an exogenous electron acceptor agent for homogenizing and equalizing;
(2) treating the wastewater in the step (1) in a biochemical treatment working section, and enabling effluent to automatically flow to a secondary sedimentation tank for primary sedimentation;
(3) the effluent of the secondary sedimentation tank flows into a sand filter tank for filtering, and the filtered effluent flows into a buffer tank;
(4) adding electrolyte into the buffer tank and homogenizing;
(5) pumping the effluent of the buffer pool into an electrocatalytic oxidation tank for advanced oxidation reaction and then discharging the effluent;
the electron acceptor agent in the step (1) is one or a mixture of nitrate and nitrite, and the addition amount is 30-60 mg/L;
the biochemical treatment section in the step (2) comprises a UBF section and a microbial treatment section in series connection with O/A/O;
the hydraulic retention time of two-stage aerobic biological reaction in the O/A/O section in the step (2) is 60-84 h, and the hydraulic retention time of anoxic biological reaction is 16-36 h;
the hydraulic retention time of anaerobic biological reaction in the UBF section in the step (2) is 36-72 h;
and (5) the electrocatalytic oxidation retention time is 60-120 min.
2. The method for treating pyridine pesticide wastewater by using the bio-electrochemical coupling technology as claimed in claim 1, wherein the pyridine wastewater in the wastewater collection tank of step (1) is pretreated by one or a combination of stripping and resin adsorption, and then enters the wastewater collection tank.
3. The method for treating pyridine pesticide wastewater by using the bio-electrochemical coupling technology as claimed in claim 1, wherein in the step (2), the secondary O section in the O/A/O flows back to the A section at a reflux ratio of 100-400%.
4. The method for treating pyridine pesticide wastewater by using the bio-electrochemical coupling technology as claimed in claim 1, wherein the electrolyte added in step (4) is one or a mixture of sodium chloride and sodium sulfate, and the addition amount is 1000-5000 mg/L.
5. The method for treating pyridine pesticide wastewater by using the bio-electrochemical coupling technology as claimed in claim 1, wherein the electrocatalytic oxidation in the step (5) adopts IrO2、RuO2、SnO2A Ti-based coated electrode of a composite of two or more of (1).
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