CN108191158B - Tebuconazole pesticide production wastewater treatment and potassium sulfate resource recovery method - Google Patents
Tebuconazole pesticide production wastewater treatment and potassium sulfate resource recovery method Download PDFInfo
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Abstract
The invention discloses a tebuconazole pesticide production wastewater treatment and potassium sulfate resource recovery method, belonging to the technical field of pesticide wastewater treatment. The processing method comprises the following steps: separately collecting and treating ketene, condensation production section wastewater and epoxy production section wastewater in the tebuconazole pesticide production process, wherein the ketene and the condensation production section wastewater are treated by stripping, micro-electrolysis, Fenton oxidation, neutralization and precipitation, the epoxy production section wastewater is treated by resin adsorption and potassium sulfate is recovered, and finally effluent water treated by the two modes is combined to enter biochemical treatment. The treatment method solves the problem of poor subsequent treatment effect in the mixed treatment of degradable wastewater generated in the ketene condensation production section and the nondegradable wastewater generated in the epoxy production section in the prior art, and realizes resource recycling of potassium sulfate in the wastewater.
Description
Technical Field
The invention belongs to the field of pesticide wastewater treatment processes, and particularly relates to a tebuconazole pesticide production wastewater treatment and potassium sulfate resource recovery method.
Background
Tebuconazole belongs to triazole bactericides and is a sterol demethylation inhibitor. At present, the bactericide can be used as a high-efficiency bactericide for seed treatment or foliage spraying of important economic crops worldwide. The pesticide has the advantages of wide bactericidal spectrum, high activity and long lasting period, and can effectively prevent and treat various rust diseases, powdery mildew, net blotch, root rot, scab, smut, seed-borne wheel spot and the like of cereal crops. Tebuconazole is registered and widely applied in more than 50 countries and more than 60 crops in the world, and is the fastest-developing and largest-selling variety of triazole bactericides.
The tebuconazole is produced by taking p-chlorobenzaldehyde as a starting material and carrying out ketene synthesis, catalytic hydrogenation, epoxy reaction, condensation reaction and other steps. The tebuconazole production process mainly produces three-step waste water, namely the waste water of ketene process, epoxy process and condensation process, and mainly contains the waste water of substances such as p-chlorobenzaldehyde, pinacolone, pyrrolidone, methanol, dimethyl sulfide, toluene, triazole, potassium sulfate and the like. Because the pollutants have high solubility in the wastewater and great toxic effect on microorganisms, the pollutants are high-concentration pesticide wastewater which is difficult to degrade and can cause serious harm to the ecological environment and human health if the pollutants are directly discharged without treatment.
In the traditional treatment process, the product process wastewater is comprehensively treated in a tail end treatment device, and the physicochemical treatment rate and the biochemical degradability of substances in the wastewater are not strictly distinguished. The components of the wastewater are complex, various physicochemical pretreatment methods have certain applicability, and the problem of removing all wastewater can not be solved by one physicochemical treatment technology. Once the process wastewater is integrated, if some wastewater containing substances which are difficult to damage and degrade exists, the operation cost is increased, and the overall treatment efficiency is reduced. When the biological method treatment is carried out, once the standard is not reached, the tracing is difficult.
At present, no effective treatment method is available for tebuconazole pesticide production wastewater. The biochemical treatment is a method for treating industrial wastewater with broad spectrum and strong applicability due to the characteristics of low operation cost, simple operation method and the like, but the tebuconazole pesticide production wastewater contains certain toxic and harmful substances and has high salt property, so that the biochemical treatment system can be inhibited, the aim of biodegradation of the wastewater is difficult to achieve, and even the biological treatment system is crashed due to death of microorganisms.
Through retrieval, the prior art also discloses a related technical scheme, and the application of Chinese patent No. CN201210493745.7, published as 2013.02.13 discloses a tebuconazole pesticide wastewater treatment process, the method of the application adopts Fenton oxidation, chlorine dioxide oxidation and iron carbon-coagulation processes to treat wastewater, the total removal rate of COD in a treated water sample reaches about 84%, and simultaneously, the load of organic pollutants difficult to degrade in the wastewater can be reduced to a certain extent, the biodegradability of the wastewater is improved, and the aim of improving the biodegradability of the wastewater is fulfilled. However, the technology needs to carry out three oxidation and separation processes respectively, and is complex to operate; meanwhile, the selected oxidant chlorine dioxide can cause strong stimulation and corrosion, and is unsafe and environment-friendly.
The characteristics of the wastewater generated in the tebuconazole production section are as follows: 1) the toxicity is high, and the waste water contains a large amount of raw materials, intermediates, metabolites and the like with high toxicity; 2) the pollutants are difficult to degrade, are persistent organic pollutants, have long residual time after being discharged into the environment and are difficult to naturally degrade. In the literature of Tebuconazole pesticide wastewater resource treatment technology research, the treatment method comprises the following steps: firstly, recovering N-methyl pyrrolidone in the wastewater, and then treating the wastewater by adopting an iron-carbon micro-electrolysis and ozone catalytic oxidation method, wherein after the wastewater is pretreated by adopting the method, the recovery rate of the N-methyl pyrrolidone in the wastewater is 82%, the COD (chemical oxygen demand) removal rate of the wastewater reaches 95%, and meanwhile, the B/C ratio is increased from the original 0.19 to 0.45, so that the content of substances which are difficult to biodegrade in the wastewater is reduced, and the biodegradability of the wastewater is improved. However, this solution has the following problems: the method comprises the following steps of (1) adopting a distillation-reduced pressure rectification method to recover N-methyl pyrrolidone in wastewater generated in a tebuconazole condensation process, strictly controlling the distillation temperature in the process, carrying out reduced pressure distillation after distillation, and accurately controlling the pressure, the temperature and the reflux ratio, so that the problems of complex process, high operation cost and the like exist; in addition, other pollutants such as dimethyl sulfide and toluene still exist in the epoxy process wastewater, and can not be effectively removed by using the iron-carbon micro-electrolysis and ozone catalytic oxidation methods independently; the pretreatment method of tebuconazole pesticide production wastewater does not solve the problem of high salt content in the wastewater, and directly enters biochemical treatment, so that a large amount of dilution water is needed to meet the requirement of the biochemical treatment.
Therefore, in order to overcome the drawbacks of the prior art, it is necessary to provide a comprehensive treatment method with low cost, good comprehensive treatment effect and effective resource recovery.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the tebuconazole pesticide wastewater treatment effect is poor and the resources in the tebuconazole pesticide wastewater cannot be effectively recycled in the prior art, the invention aims to provide the tebuconazole pesticide wastewater treatment method which has low cost and good comprehensive treatment effect and can recycle the potassium sulfate salt resources.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
The invention provides a potassium sulfate resource recovery method, which comprises the steps of separately collecting epoxy production workshop section wastewater in tebuconazole pesticide production wastewater, standing for precipitation, filtering, and performing adsorption treatment by using resin; adjusting the pH of the effluent liquid after resin adsorption treatment to be neutral, then, introducing the effluent liquid into MVR for evaporation crystallization, and performing centrifugal treatment, drying and granulation on the mother liquid after evaporation crystallization to obtain the refined potassium sulfate salt.
As a further improvement of the invention, the height-diameter ratio of the resin in the adsorption column filling column is (3-5): 1; the resin material is amino modified ultrahigh cross-linked adsorption resin, the volume exchange capacity is more than or equal to 0.5mmol/L, the effective particle size is 350-600 mu m, and the specific surface area is 450-650 m2(ii)/g; the flow rate of the waste water after resin adsorption treatment is 0.5-2.0 BV/h.
As a further improvement of the invention, the temperature of the evaporative crystallization is 85-95 ℃.
As a further improvement, the invention provides a tebuconazole pesticide production wastewater treatment method, which comprises a potassium sulfate resource recovery method, and the treatment method comprises the following steps:
1) mixing and collecting ketene in tebuconazole pesticide production wastewater and condensation production section wastewater, and carrying out air stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment;
2) independently collecting epoxy production section wastewater in tebuconazole pesticide production wastewater, standing for precipitation, filtering, and performing resin adsorption treatment; adjusting the pH of the effluent liquid after resin adsorption treatment to be neutral, then, introducing the effluent liquid into MVR for evaporation crystallization, and performing centrifugal treatment, drying and granulation on the mother liquid after evaporation crystallization to obtain refined potassium sulfate;
3) when the COD value of condensed effluent after evaporation crystallization is more than 10000mg/L, mixing the condensed effluent with the effluent treated in the step 1) and low-concentration wastewater, and performing subsequent biochemical reaction treatment; the low-concentration wastewater has a COD value less than or equal to 500 mg/mL; when the COD value of the condensed effluent is less than or equal to 10000mg/L, the condensed effluent is applied to the production water of the tebuconazole epoxy workshop section, and the generated wastewater is subjected to the process of the step 2).
As a further improvement of the invention, an adsorption column regeneration treatment step is further included between the step 2) and the step 3), wherein in the adsorption column regeneration treatment step, a regeneration liquid is obtained, and the regeneration liquid is mixed with the MVR condensed effluent in the step 3) and the effluent and the low-concentration wastewater treated in the step 1) and then enters the subsequent biochemical reaction treatment.
As a further improvement of the invention, the subsequent biochemical reaction in the step 3) is an anaerobic and aerobic combined treatment, wherein the anaerobic and aerobic combined treatment is an aerobic biological reaction in an aerobic activated sludge system after an anaerobic biological reaction in a UASB system; the hydraulic retention time of the anaerobic biological reaction is 48-72 h; the hydraulic retention time of the aerobic biological reaction is 72-96 h.
As a further improvement of the invention, in the regeneration treatment step of the adsorption column, two times of desorption treatment are carried out, the desorption liquid during the first desorption is a mixture of sodium hydroxide with the mass concentration of 4-10% and methanol with the mass concentration of 90-100%, and the volume ratio of the sodium hydroxide to the methanol solution in the mixture is (0.5-2): 1; and tap water is adopted as desorption liquid during secondary desorption.
As a further improvement of the invention, the desorption flow during the first desorption is 1-2 BV, the flow rate is 0.5-1.0 BV/h, and the elution temperature is 40-60 ℃; the desorption flow during the secondary desorption is 2-4 BV, the flow rate is 1.0-2.0 BV/h, and the elution temperature is 30-50 ℃.
As a further improvement of the invention, the regeneration treatment during the first desorption is to put the desorbed first desorption liquid into a rectifying tower for rectifying and recovering methanol, then re-compound the methanol recovered by rectification to prepare the first desorption liquid again, and incinerate the rectified residual liquid; the compounding method is to prepare the first desorption solution from the methanol and sodium hydroxide aqueous solution recovered by rectification.
As a further improvement of the invention, the specific steps of the stripping-microelectro-Fenton oxidation-neutralization precipitation treatment are as follows:
a) stripping treatment: blowing off the ketene and the wastewater of the condensation production section at the temperature of 60-70 ℃ for 2-4 h;
b) micro-electrolysis treatment: firstly adjusting the pH value of effluent water from the blow-off treatment to 2-4, then adding cast iron powder and mechanically stirring for reaction for 2-4 h, wherein the particle size of the cast iron powder is 50-100 meshes, the carbon content in the cast iron powder is 10-25%, and the adding amount of the cast iron powder is 0.5-1.0 per mill of the mass of ketene and wastewater from a condensation production section; iron carbide particles are dispersed in the cast iron material in the cast iron powder, wherein the particle size of the iron carbide particles is 50-100 meshes, and under the condition, hydrogen peroxide and ferrous ions generated by micro-electrolysis treatment form a Fenton oxidant;
c) fenton oxidation treatment: adding 30% of hydrogen peroxide by mass into the effluent after micro-electrolysis treatment, and carrying out aeration stirring for 2-4 h, wherein the adding amount of the hydrogen peroxide is 2-3% of the volume of the effluent after the micro-electrolysis treatment; and adjusting the pH value of the effluent after the Fenton oxidation treatment to 8-9, and performing neutralization and precipitation.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the potassium sulfate resource recovery method, resin adsorption treatment is carried out according to the characteristic that the tebuconazole pesticide production wastewater epoxy workshop section wastewater contains refractory organic pollutants such as dimethyl sulfide, toluene and the like, the removal rate of COD (chemical oxygen demand) in the wastewater of the workshop section is less than 10% by the traditional micro-electrolysis-Fenton oxidation treatment, and the biodegradability of the wastewater cannot be obviously improved; the resin adsorption can effectively adsorb organic pollutants such as dimethyl sulfide, methylbenzene and the like in the wastewater, the COD removal rate of the wastewater can reach more than 40%, the biodegradability is improved, and the subsequent biochemical treatment is combined, so that the higher COD removal rate is realized; in addition, after MVR evaporation crystallization and salt precipitation are carried out on the wastewater pre-purified by the resin, the purity of the potassium sulfate can reach more than 95%, and the TOC content in the potassium sulfate is less than or equal to 1.0 mg/g.
(2) The tebuconazole pesticide production wastewater treatment method separately collects ketene, condensation production workshop section wastewater and epoxy production workshop section in the tebuconazole pesticide production process, overcomes the problem of poor subsequent treatment effect when the degradable wastewater generated in the ketene and condensation production workshop section and the difficultly-degradable wastewater in the epoxy production workshop section are mixed for treatment in the prior art, independently treats the wastewater which is difficult to be biochemically degraded and has high salt content, ensures the excellent treatment effect, and can refine and recycle the prepared potassium sulfate resource, thereby realizing the recycling and utilization.
(3) According to the tebuconazole pesticide production wastewater treatment method, according to the characteristic that ketene and condensation production section wastewater mainly contain organic pollutants such as pinacolone, triazole, methanol and the like, the cost-low treatment mode is adopted for the ketene and the condensation production section wastewater to improve the biodegradability of the wastewater, the air stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment is adopted, the COD removal rate of the wastewater is stabilized at 30-40%, meanwhile, the B/C value of the wastewater can be improved to be more than 0.3, and the COD removal rate of the wastewater can reach more than 90% by combining with the subsequent biochemical treatment, so that the tebuconazole pesticide production wastewater treatment method has an excellent removal effect on the ketene and condensation production section wastewater.
(4) The tebuconazole pesticide production wastewater treatment method selects different treatment modes for condensed effluent in the wastewater treatment process of the epoxy production section according to the COD value, when the COD value is more than 10000mg/L, the condensed effluent is subjected to subsequent biochemical treatment, and when the COD value is less than 10000mg/L, the condensed effluent can be applied to production water of the tebuconazole epoxy section; experiments show that when the COD value of the effluent is less than 10000mg/L, the application mode has no influence on the purity of the synthesized tebuconazole product, the method reduces the treatment capacity of the wastewater, simultaneously does not introduce new substances, does not generate secondary pollution, has high and stable treatment process, and avoids the defect that the biochemical degradation process of the wastewater is slow and is not beneficial to engineering.
(5) According to the tebuconazole pesticide production wastewater treatment method, resin adsorption treatment is adopted in the wastewater of the epoxy production section, high-boiling-point substances in the wastewater can be effectively adsorbed to achieve the purpose of water purification, the COD value of the wastewater can be effectively reduced from 25000-30000 mg/L to 12000-15000 mg/L, and the adsorbed effluent is mainly low-boiling-point micromolecular substances; the resin adsorption treatment effectively carries out the pre-purification treatment, ensures the normal and efficient operation of the MVR device, prevents the problem of blockage caused by coking of organic pollutants at high temperature, and can realize the recycling and the repeated use of the resin adsorption column by periodically carrying out the regeneration treatment on the resin adsorption column material by using desorption liquid.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The embodiment provides a method for treating tebuconazole pesticide production wastewater, potassium sulfate resource is effectively recycled in the method, the treated object is tebuconazole pesticide wastewater in a workshop of a certain pesticide enterprise in coastal areas of Jiangsu, a process flow chart of the invention is shown in figure 1, and the treatment steps are as follows:
(1) treating wastewater of ketene and condensation production workshop section: the method comprises the steps of air stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment, and the treatment process comprises the following specific steps:
a) stripping by blowing: separately collecting ketene in a tebuconazole pesticide preparation process in a workshop and wastewater in a condensation production section into a collecting tank, pumping the wastewater into a stripping tower by using a pump, and stripping for 2 hours at 60 ℃.
b) Micro-electrolysis: and pumping the wastewater into an iron-carbon micro-electrolysis kettle by using a pump, firstly adjusting the pH value of the wastewater to 2 by using sulfuric acid, then adding cast iron powder into the wastewater and mechanically stirring for 2 hours, wherein the micro-electrolysis treatment is in the optimal reaction time range, and the number of ferrous ions can be effectively controlled by proper reaction time, so that the cost is reduced.
The particle size of the cast iron powder is 50-100 meshes, the carbon content in the cast iron powder is 10%, the adding amount of the cast iron powder is 0.5 per thousand of the mass of the ketene and the wastewater in the condensation production section, a large amount of iron carbide is dispersed in the cast iron material in the cast iron powder, wherein the iron carbide is extremely small particles, the particle size is 50-100 meshes, and thousands of tiny iron-carbon micro primary batteries are formed when the cast iron material is immersed in an acidic wastewater solution, so that internal electrolysis reaction is carried out, and the structure and the form in wastewater pollutants can be changed.
c) Fenton oxidation: hydrogen peroxide with the mass fraction of 30% is continuously added into the effluent after the micro-electrolysis treatment, and the effluent is aerated and stirred for 2 hours, and the Fenton oxidation treatment tank adopts perforation aeration, so that the hydrogen peroxide and the wastewater can be fully mixed; meanwhile, the removal rate of COD in the range of the aeration stirring reaction time is high, the biodegradability of the wastewater is also improved, the adding amount of the hydrogen peroxide is 2% of the volume of the effluent after the micro-electrolysis treatment, under the condition, the hydrogen peroxide and ferrous ions generated by the micro-electrolysis treatment form a Fenton oxidant, and the hydrogen peroxide generates OH free radicals with strong oxidizing capability under the catalysis of the ferrous ions, so that the structure of organic pollutants in the wastewater can be effectively destroyed, the organic pollutants in the wastewater are oxidized and further mineralized, and the B/C value of the wastewater is improved; and the Fenton oxidation treatment effluent is subjected to neutralization and precipitation, and the pH value of the effluent is adjusted to 8 by using lime milk before the neutralization and precipitation.
(2) Epoxy workshop section wastewater treatment: separately collecting the waste water of the tebuconazole production section in a workshopAnd the other collecting tank is kept stand for precipitation, filtered by a bag filter and then enters a resin adsorption tower for treatment, the temperature of the resin adsorption treatment is controlled at 25 ℃, and the height-diameter ratio of the resin subjected to the resin adsorption treatment in a packed column in the adsorption column is 3: 1; the volume exchange capacity of the resin material of the resin adsorption column is 0.5mmol/L, and the effective particle size is 350-400 mu m; the specific surface area is 450m2The flow rate of the waste water after resin adsorption treatment is 0.5BV/h, the flow rate is controlled by a high-pressure pump, and the treatment capacity of the waste water is 10 BV. The resin adsorption column subjected to resin adsorption treatment is filled with amino modified ultrahigh cross-linked adsorption resin, and the resin is independently developed by Jiangsu national Innovation Material research center, Inc., and has the model of GC-8.
The resin adsorption process is essentially a surface adsorption phenomenon caused by high dispersion of objects or uneven application of force to surface molecules, and the adsorption force is a result of van der waals force or hydrogen bonding, wherein van der waals force is an intermolecular force including an orienting force, a dispersion force, an inducing force, and the like, and has a screening effect on substances having different molecular sizes due to the porous structure of the adsorption filler. Therefore, the organic compounds are separated and enriched under the action of the adsorption mechanism and the screening principle of the adsorption filler according to different adsorption forces and molecular weights, and the amino modified ultra-high cross-linked adsorption resin of the GC-8 model adopted in the embodiment has stronger adsorption force on refractory organic matters such as dimethyl sulfide, toluene and the like contained in the wastewater of the epoxy workshop section, so that the resin is suitable for removing organic pollutants in the epoxy workshop section and has excellent treatment effect.
The operation process of resin adsorption comprises the following steps: loading the resin into an adsorption column, and continuously passing the solution; the volume of resin loaded in the resin column is called bed volume, abbreviated as BV, and therefore represents the volume of wastewater 10 times the volume of the resin bed; the flow rate of the solution through the resin column was 0.5BV/h, i.e.the volume of wastewater passing through the column per hour was 0.5 times the volume of the resin bed.
Adding sulfuric acid into the effluent liquid after resin adsorption treatment in a pH adjusting tank until the pH value is stabilized at 7, neutralizing acidic components in the wastewater to form salt, recovering potassium sulfate in the wastewater, then, feeding the wastewater into an MVR (mechanical vapor recompression) tank for evaporation and crystallization, wherein the temperature of the evaporation and crystallization is 85 ℃, the mother liquor after the evaporation and crystallization is subjected to centrifugal treatment, the centrifugal device for centrifugal treatment adopts a closed centrifugal device, the drying equipment for centrifugal treatment adopts an air flow dryer, waste gas generated in the working section is connected into a waste gas collecting pipe network and is dried and granulated to prepare refined potassium sulfate, the purity of the precipitated potassium sulfate reaches 95%, the TOC content in the potassium sulfate reaches 1.0mg/g, the refined potassium sulfate can be used as resources such as potassium fertilizer, and the MVR is a mechanical vapor recompression technology.
(3) Regeneration treatment of the adsorption column: the resin adsorption column after resin adsorption treatment is regenerated by adopting a twice desorption mode, the first desorption liquid is a sodium hydroxide compound agent with the mass concentration of 4% and a methanol compound agent with the mass concentration of 90% during first desorption, and the volume ratio of the sodium hydroxide to the methanol solution in the compound agent is 0.5: 1, the desorption flow during the first desorption is 1BV, the flow rate is 0.5BV/h, and the elution temperature is controlled at 40 ℃; during secondary desorption, tap water is adopted as secondary desorption liquid, the secondary desorption liquid is recovered after secondary desorption and is used as secondary desorption liquid after secondary desorption, the desorption flow during secondary desorption is 2BV, the flow rate is 1.0BV/h, and the elution temperature is controlled at 30 ℃; the regeneration treatment during the first desorption is to put the desorbed first desorption liquid into a rectifying tower for rectifying and recovering methanol, then re-compound the rectified and recovered methanol to prepare the first desorption liquid again, and incinerate the rectified residual liquid; the compounding method is that the methanol recovered by rectification is added with sodium hydroxide to prepare the first desorption solution; the above method realizes the reuse of methanol, and the purity of the methanol obtained by adopting the rectification method is higher.
(4) And (3) when the COD value of the condensate generated by evaporative crystallization in the step (2) is lower than 10000mg/L, applying the condensate to the production water in a tebuconazole epoxy working section, repeating the process in the step (2) on the generated wastewater, mixing the condensate with the effluent after the air stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment, the secondary desorption solution after the secondary desorption and other low-concentration wastewater until the COD value of the condensate is higher than 10000mg/L, performing biochemical regulation, and performing UASB and aerobic activated sludge combined treatment, wherein the COD concentration of the wastewater with other concentration is 300mg/L in the embodiment, including initial rainwater and domestic sewage, wherein the initial rainwater refers to the precipitation of surface runoff formed by the thickness of 10-15 mm on the ground.
The reason for choosing the initial rain is as follows: in the early stage of rainfall, a large amount of acid gas, automobile exhaust, factory waste gas and other pollutant gases in the air are dissolved in the rainwater, and after the rainwater falls to the ground, the rainwater in the early stage contains a large amount of pollutants due to scouring of roofs, asphalt concrete roads and the like, so that the pollution degree of the rainwater in the early stage is higher and even exceeds that of common urban sewage;
the reason why domestic sewage is selected is as follows: a large amount of domestic sewage in cities has complex components and high COD value, and the capacity of treating by only a special sewage treatment plant is limited.
The UASB and the aerobic activated sludge are jointly treated, namely, after anaerobic biological reaction is carried out in the structure or equipment of the UASB, the UASB and the aerobic activated sludge enter the structure or equipment of the aerobic activated sludge for aerobic biological reaction; in the embodiment, the hydraulic retention time of anaerobic biological reaction in the UASB equipment is 48h, the hydraulic retention time of aerobic biological reaction in the aerobic activated sludge-containing equipment is 72h, and the reaction time of the action of pollutants and microorganisms ensures the thorough mineralization of degradable substances and the standard reaching of wastewater.
(5) Effluent after the combined treatment of the UASB and the aerobic activated sludge is merged and connected into a garden pipe network for unified treatment; the standard of the garden pipe connection is that the COD value of the effluent in a garden pipe network is less than or equal to 500mg/L, the ammonia nitrogen concentration is less than or equal to 35mg/L, and the total salt concentration is less than or equal to 5000 mg/L. Table 1 shows the effluent index in the treatment of example 1.
TABLE 1 treatment Process effluent index
As can be seen from Table 1, after the treatment by the method of example 1, the salt recovery effect is very significant, especially the total salt content in the wastewater of the epoxy production section is reduced from 90000mg/L to 700mg/L, and the salt recovery is 92.2%; in the treatment step of the epoxy production section, resin adsorption treatment is mainly adopted, and tests show that under the same conditions, evaporation crystallization treatment is directly carried out without resin adsorption treatment, and salts can be recovered by 73.5%.
After the wastewater treatment of the epoxy production section, the COD value is reduced to 7500mg/L from 29500mg/L, the condensed effluent is used as the production water of the epoxy production section, the generated wastewater is subjected to UASB and aerobic activated sludge combined treatment after the wastewater treatment of the epoxy production section is repeated, the COD value is reduced to 480mg/L from 10300mg/L, and the removal rate of COD is 95.3%.
After the combined treatment of air stripping, micro-electrolysis, Fenton oxidation, neutralization and precipitation and UASB and aerobic activated sludge, the COD value is reduced from 28000mg/L to 480mg/L, and the removal rate of the COD is 98.2 percent; tests show that under the same conditions, the removal rate of COD is only 70-82% without blowing-off-micro-electrolysis-Fenton oxidation-neutralization precipitation treatment or UASB and aerobic activated sludge combined treatment.
If the traditional method in the prior art is adopted to hardly treat ketene and wastewater in a condensation production section, the treatment effect of the wastewater in a tebuconazole production section is extremely poor, the removal rate of COD (chemical oxygen demand) is only 30-58% under the same condition, and simultaneously, salts in the wastewater are directly discharged into the environment without being treated, thereby causing inevitable harm to the environment.
Example 2
The embodiment provides a tebuconazole pesticide production wastewater treatment method, potassium sulfate resource is effectively recovered in the method, the treated object is tebuconazole pesticide wastewater in a workshop of a certain pesticide enterprise in Jiangsu coastal areas, and the combined treatment process comprises the following steps:
(1) ketene and wastewater treatment in a condensation production section, wherein the treatment process comprises the following steps:
a) stripping by blowing: separately collecting ketene and wastewater in a condensation production section in a tebuconazole pesticide preparation process in a workshop into a collecting tank, pumping the wastewater in the collecting tank into a stripping tower by using a pump, and stripping for 4 hours at the temperature of 70 ℃.
b) Micro-electrolysis: and pumping water into an iron-carbon micro-electrolysis kettle by using a pump, firstly adjusting the pH value of the wastewater to 3 by using sulfuric acid, then adding cast iron powder into the wastewater, and mechanically stirring for 4 hours, wherein the particle size of the cast iron powder is 50-100 meshes, the carbon content in the cast iron powder is 25%, the adding amount of the cast iron powder is 1.0 per mill of the total mass of ketene and wastewater in a condensation production section, and a large amount of iron carbide is dispersed in the cast iron material in the cast iron powder in the micro-electrolysis process, wherein the iron carbide is extremely small particles (50-100 meshes).
c) Fenton oxidation treatment: adding 30% by mass of hydrogen peroxide into the effluent obtained in the step b), and carrying out aeration stirring for 4 hours, wherein the adding amount of the hydrogen peroxide is 3% of the volume of the effluent after micro-electrolysis treatment; adjusting the pH value of the effluent after Fenton oxidation treatment to 9 by using lime milk, and then performing neutralization and precipitation treatment.
(2) Epoxy workshop section wastewater treatment: separately collecting tebuconazole production section wastewater in a workshop into another collecting tank, standing, precipitating and filtering, and then performing resin adsorption treatment, wherein the temperature of the resin adsorption treatment is controlled at 25 ℃, and the height-diameter ratio of resin subjected to resin adsorption treatment in a packed column of the adsorption column is 5: 1; the volume exchange capacity of the resin material of the resin adsorption column is 1.2mmol/L, and the effective particle size is 400-600 mu m; the specific surface area is 650m2The flow rate of the waste water after resin adsorption treatment is 2.0BV/h, and the treatment capacity of the waste water is 10 BV; the resin material was the same as in example 1; and adding sulfuric acid into the effluent liquid after the resin adsorption treatment until the pH value of the effluent liquid is stabilized at 7, then, carrying out evaporative crystallization in MVR at the temperature of 95 ℃, carrying out centrifugal treatment on the mother liquid after the evaporative crystallization, introducing waste gas generated in the working section into a waste gas collecting pipe network, drying and granulating to obtain the refined potassium sulfate, wherein the purity of the precipitated potassium sulfate reaches 97%, and the TOC content in the potassium sulfate is 0.5 mg/g.
(3) Regeneration treatment of the adsorption column: performing regeneration treatment by adopting a twice desorption mode, wherein the first desorption solution is a sodium hydroxide compound agent with the mass concentration of 10% and a methanol compound agent with the mass concentration of 100% during the first desorption, and the volume ratio of the sodium hydroxide to the methanol solution in the compound agent is 2: 1, the desorption flow during the first desorption is 2BV, the flow rate is 1.0BV/h, and the elution temperature is controlled at 60 ℃; tap water is adopted as secondary desorption liquid during secondary desorption, the secondary desorption liquid is recovered after secondary desorption and is used as secondary desorption liquid after secondary desorption, the desorption flow during secondary desorption is 4BV, the flow rate is 2.0BV/h, and the elution temperature is controlled at 50 ℃.
(4) When the COD value of the condensate generated by evaporative crystallization in the step (2) is lower than 10000mg/L, the condensate is applied to the production water in the tebuconazole epoxy working section, the generated wastewater is subjected to the process in the step (2) until the COD value of the condensate is higher than 10000mg/L, and is mixed with the effluent after the stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment, the secondary desorption solution and other low-concentration wastewater for biochemical regulation, and then the effluent is subjected to UASB and aerobic activated sludge combined treatment; in the embodiment, the COD concentration of other low-concentration wastewater is 500mg/L, the hydraulic retention time of anaerobic biological reaction in the UASB equipment in the embodiment is 72h, and the hydraulic retention time of aerobic biological reaction in the aerobic activated sludge-containing equipment is 96 h.
(5) Effluent after the combined treatment of the UASB and the aerobic activated sludge is merged and connected into a garden pipe network for unified treatment; table 2 shows the effluent indexes in the treatment process of example 2.
Table 2 effluent index in example 2 treatment process
As can be seen from Table 2, after the treatment by the method of example 2, the salt recovery effect is very significant, especially the total salt content in the wastewater of the epoxy production section is reduced from 85000mg/L to 600mg/L, and the salt recovery is 94.6%; in the treatment step, resin adsorption treatment is mainly adopted, and tests show that under the same conditions, evaporation crystallization treatment is directly carried out without resin adsorption treatment, and salts can be recovered by only 71.5%.
After the combined treatment of air stripping, micro-electrolysis, Fenton oxidation, neutralization and precipitation and UASB and aerobic activated sludge, the COD value is reduced from 26000mg/L to 455mg/L, and the removal rate of the COD is 98.2 percent; tests show that under the same conditions, the removal rate of COD is only 68-79% without blowing-off-micro-electrolysis-Fenton oxidation-neutralization precipitation treatment or UASB and aerobic activated sludge combined treatment.
The COD value in the wastewater in the epoxy production section is reduced from 25500mg/L to 6200mg/L, and after the wastewater is mechanically applied and is subjected to combined treatment by UASB and aerobic activated sludge, the COD value can be reduced from 10500mg/L to 455mg/L, and the removal rate of the COD is 95.7%.
If the traditional method in the prior art is adopted to hardly treat the ketene and condensation production section wastewater, the treatment effect of the tebuconazole production section wastewater is extremely poor, and the removal rate of COD under the same condition is only 32-56%.
Example 3
The embodiment provides a tebuconazole pesticide production wastewater treatment method, potassium sulfate resource is effectively recycled in the method, the treatment object is the same as the embodiment 2, and the combined treatment process comprises the following steps:
(1) ketene and wastewater treatment in a condensation production section, wherein the treatment process comprises the following steps:
a) stripping by blowing: separately collecting ketene and wastewater in a condensation production section in a tebuconazole pesticide preparation process in a workshop into a collecting tank, pumping the wastewater in the collecting tank into a stripping tower by using a pump, and stripping for 3 hours at the temperature of 65 ℃.
b) Micro-electrolysis: and pumping water into an iron-carbon micro-electrolysis kettle by using a pump, firstly adjusting the pH value of the wastewater to be 4 by using sulfuric acid, then adding cast iron powder into the wastewater and mechanically stirring for 3 hours, wherein the particle size of the cast iron powder is 50-100 meshes, the carbon content in the cast iron powder is 20 percent, the adding amount of the cast iron powder is 8 per mill of the total mass of ketene and wastewater in a condensation production section, and a large amount of iron carbide is dispersed in the cast iron material in the cast iron powder in the micro-electrolysis process, wherein the iron carbide is extremely small particles (50-100 meshes).
c) Fenton oxidation treatment: adding 30% by mass of hydrogen peroxide into the effluent obtained in the step b), and carrying out aeration stirring for 3 hours, wherein the adding amount of the hydrogen peroxide is 2.5% of the volume of the effluent after micro-electrolysis treatment; adjusting the pH value of the effluent after Fenton oxidation treatment to 8.5 by using lime milk, and then performing neutralization and precipitation treatment.
(2) Epoxy workshop section wastewater treatment: separately collecting tebuconazole production section wastewater in a workshop into another collecting tank, standing, precipitating and filtering, and then performing resin adsorption treatment, wherein the temperature of the resin adsorption treatment is controlled at 25 ℃, and the height-diameter ratio of the resin subjected to the resin adsorption treatment in a packed column of the adsorption column is 4: 1; the volume exchange capacity of the resin material of the resin adsorption column is 1.5mmol/L, and the effective particle size is 350-600 mu m; the specific surface area is 550m2The flow rate of the waste water after resin adsorption treatment is 1.5BV/h, and the treatment capacity of the waste water is 10 BV; the resin material was the same as in example 1; adding sulfuric acid into the effluent liquid after the resin adsorption treatment until the pH value is stabilized at 7, then, carrying out evaporative crystallization in MVR at the temperature of 90 ℃, carrying out centrifugal treatment on the mother liquid after the evaporative crystallization, introducing waste gas generated in the working section into a waste gas collecting pipe network, drying and granulating to obtain the refined potassium sulfate, wherein the purity of the refined potassium sulfate reaches 96.5%, and the TOC content in the potassium sulfate is 0.8 mg/g.
(3) Regeneration treatment of the adsorption column: performing regeneration treatment by adopting a twice desorption mode, wherein the first desorption solution is a sodium hydroxide compound agent with the mass concentration of 6% and a methanol compound agent with the mass concentration of 95% during the first desorption, and the volume ratio of the sodium hydroxide to the methanol solution in the compound agent is 1.5: 1, the desorption flow during the first desorption is 1.5BV, the flow rate is 0.8BV/h, and the elution temperature is controlled at 50 ℃; tap water is adopted as secondary desorption liquid during secondary desorption, the secondary desorption liquid is recovered after secondary desorption and is used as secondary desorption liquid after secondary desorption, the desorption flow during secondary desorption is 3BV, the flow rate is 1.5BV/h, and the elution temperature is controlled at 40 ℃.
(4) When the COD value of the condensate generated by evaporative crystallization in the step (2) is lower than 10000mg/L, the condensate is applied to the process water in the tebuconazole epoxy working section, the generated wastewater is subjected to the process in the step (2) until the COD value of the condensate is higher than 10000mg/L, and is mixed with the effluent after the stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment, the secondary desorption solution and other low-concentration wastewater for biochemical regulation, and then the effluent is subjected to UASB and aerobic activated sludge combined treatment; in the embodiment, the COD concentration of other low-concentration wastewater is 500mg/L, the hydraulic retention time of anaerobic biological reaction in the UASB equipment in the embodiment is 60h, and the hydraulic retention time of aerobic biological reaction in the aerobic activated sludge-containing equipment is 84 h.
(5) Effluent after the UASB and aerobic activated sludge combined treatment is combined and connected into a garden pipe network for unified treatment, and a table 3 shows effluent indexes in the treatment process of the embodiment 3.
Table 3 water output index in example 3 treatment process
As can be seen from Table 3, after the treatment by the method of example 3, the salt recovery effect is very significant, especially the total salt content in the wastewater of the epoxy production section is reduced from 80000mg/L to 650mg/L, and the salt recovery is 95.8%; in the treatment step, resin adsorption treatment is mainly adopted, and tests show that under the same conditions, evaporation crystallization treatment is directly carried out without resin adsorption treatment, and salts can be recovered by 72.6%.
After the combined treatment of air stripping, micro-electrolysis, Fenton oxidation, neutralization and precipitation and UASB and aerobic activated sludge, the COD value is reduced from 27500mg/L to 470mg/L, and the removal rate of COD is 98.3%; tests show that under the same conditions, the removal rate of COD is only 65-74% without blowing-off-micro-electrolysis-Fenton oxidation-neutralization precipitation treatment or UASB and aerobic activated sludge combined treatment.
The COD value in the wastewater in the epoxy production section is reduced from 26500mg/L to 6800mg/L, the COD value can be reduced to 455mg/L after the wastewater is mechanically applied and then subjected to combined treatment of UASB and aerobic activated sludge, and the removal rate of the COD is 95.6 percent.
If the traditional method in the prior art is adopted to hardly treat the ketene and condensation production section wastewater, the treatment effect of the tebuconazole production section wastewater is extremely poor, and the removal rate of COD under the same condition is only 30-52%.
While the invention has been described in further detail in connection with specific embodiments thereof, it will be understood that the invention is not limited thereto, and that various other modifications and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be considered to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A tebuconazole pesticide production wastewater treatment method is characterized in that: the processing method comprises the following steps: 1) mixing and collecting ketene in tebuconazole pesticide production wastewater and condensation production section wastewater, and carrying out air stripping-microelectrolysis-Fenton oxidation-neutralization precipitation treatment; 2) Independently collecting epoxy production section wastewater in tebuconazole pesticide production wastewater, standing for precipitation, filtering, and performing resin adsorption treatment; adjusting the pH of the effluent liquid after resin adsorption treatment to be neutral, then, introducing the effluent liquid into MVR for evaporation crystallization, and performing centrifugal treatment, drying and granulation on the mother liquid after evaporation crystallization to obtain refined potassium sulfate; 3) When the COD value of condensed effluent after evaporation crystallization is more than 10000mg/L, mixing the condensed effluent with effluent treated in the step 1) and low-concentration wastewater, and performing subsequent biochemical reaction treatment, wherein the low-concentration wastewater is wastewater with the COD value of less than or equal to 500 mg/L; when the COD value of the condensed water is less than or equal to 10000mg/L, the condensed water is used as the production water for the tebuconazole epoxy workshop section.
2. The tebuconazole pesticide production wastewater treatment method of claim 1, characterized in that: the height-diameter ratio of the resin in the adsorption column is (3-5): 1; the resin material is amino-modified ultrahigh cross-linked adsorption resin, the volume exchange capacity of the resin material is more than or equal to 0.5mmol/L, the effective particle size is 350-600 mu m, and the specific surface area is 450-650 m2(ii)/g; the flow rate of the waste water after resin adsorption treatment is 0.5-2.0 BV/h; and a regeneration treatment step of the adsorption column is also included between the step 2) and the step 3).
3. The tebuconazole pesticide production wastewater treatment method of claim 2, characterized in that: the subsequent biochemical reaction in the step 3) is anaerobic and aerobic combined treatment, and the hydraulic retention time of the anaerobic treatment is 48-72 h; the hydraulic retention time of the aerobic treatment is 72-96 h.
4. The tebuconazole pesticide production wastewater treatment method of claim 3, characterized in that: in the regeneration treatment step of the adsorption column, two times of desorption treatment are carried out, desorption liquid during the first desorption is a mixture of sodium hydroxide with the mass concentration of 4% -10% and methanol with the mass concentration of 90% -100%, and the volume ratio of the sodium hydroxide to the methanol solution in the mixture is (0.5-2): 1; and tap water is adopted as desorption liquid during secondary desorption.
5. The tebuconazole pesticide production wastewater treatment method of claim 4, characterized in that: the desorption flow during the first desorption treatment is 1-2 BV, the flow rate is 0.5-1.0 BV/h, and the elution temperature is 40-60 ℃; the desorption flow during the secondary desorption treatment is 2-4 BV, the flow rate is 1.0-2.0 BV/h, and the elution temperature is 30-50 ℃.
6. The tebuconazole pesticide production wastewater treatment method according to claim 4 or 5, characterized in that: the first desorption treatment is that the desorbed first desorption liquid is put into a rectifying tower to be rectified and recycled methanol, then the rectified and recycled methanol is re-compounded to prepare the first desorption liquid, and the rectified residual liquid is burned; the compounding method is to prepare the first desorption solution from the methanol and sodium hydroxide aqueous solution recovered by rectification.
7. The tebuconazole pesticide production wastewater treatment method of claim 1, characterized in that: the air stripping-micro-electrolysis-Fenton oxidation-neutralization precipitation treatment comprises the following specific steps: a) Stripping treatment: blowing off the ketene and the wastewater of the condensation production section at the temperature of 60-70 ℃ for 2-4 h; b) Micro-electrolysis treatment: adjusting the pH value of effluent water from the blow-off treatment to 2-4, adding cast iron powder, mechanically stirring and reacting for 2-4 hours, wherein the particle size of the cast iron powder is 50-100 meshes, the carbon content in the cast iron powder is 10-25%, and the adding amount of the cast iron powder is 0.5-1.0 per mill of the mass of ketene and wastewater from a condensation production section; iron carbide particles are dispersed in the cast iron material in the cast iron powder, and the particle size of the iron carbide particles is 50-100 meshes; c) Fenton oxidation treatment: adding 30% of hydrogen peroxide by mass into the effluent after micro-electrolysis treatment, and aerating and stirring for 2-4 h, wherein the adding amount of the hydrogen peroxide is 2-3% of the volume of the effluent after the micro-electrolysis treatment; and adjusting the pH value of the effluent after the Fenton oxidation treatment to 8-9, and performing neutralization and precipitation.
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