CN103112994A - Method for treating pesticide wastewater - Google Patents

Method for treating pesticide wastewater Download PDF

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Publication number
CN103112994A
CN103112994A CN 201310045939 CN201310045939A CN103112994A CN 103112994 A CN103112994 A CN 103112994A CN 201310045939 CN201310045939 CN 201310045939 CN 201310045939 A CN201310045939 A CN 201310045939A CN 103112994 A CN103112994 A CN 103112994A
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Prior art keywords
waste water
pond
add
aerobic
wastewater
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CN 201310045939
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Chinese (zh)
Inventor
张建鹏
杨晓玲
王伟萍
钟丽云
许嘉龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
Original Assignee
Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
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Priority to CN 201310045939 priority Critical patent/CN103112994A/en
Publication of CN103112994A publication Critical patent/CN103112994A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a method for treating pesticide wastewater. The method comprises the following steps: (1) introducing the pesticide wastewater to a regulating reservoir, and adjusting the pH of the pesticide wastewater to 2-4; (2) introducing a ferrum-carbon reactor, adding scrap iron and hard coke, then adding to H2O2 liquor, and then reacting; (3) conveying the wastewater treated in step (2) to a coagulating sedimentation tank, adding the activation diatomite and NaOH, controlling the pH within 7-9, standing, and conveying the wastewater at the upper layer to a hydrolysis acidification pool from the upper part; (4) introducing the wastewater after carrying out the coagulating sedimentation, adding activated sludge, and standing for 2.5-4.5 hours; and (5) conveying the hydrolytic acidulated waste water into an oxidation pond to implement the aerobic oxidation reaction. The method disclosed by the invention is suitable for treating the pesticide wastewater produced by insecticide factories, and has simple operation and good treating effect; and the outlet water can achieve the national discharge standards.

Description

A kind of method of processing agricultural chemicals waste water
Technical field
The invention belongs to sewage treatment area, particularly a kind of method of processing agricultural chemicals waste water.
Background technology
Agricultural chemicals waste water is a kind of organic chemical waste water of refractory reason, has the characteristics such as COD is high, toxicity large, difficult for biological degradation.Pesticide species is various, and agricultural chemicals waste water water quality is complicated, and its principal feature is: 1. Pollutant levels are higher, and COD (chemical oxygen demand (COD)) can reach every liter of tens thousand of milligram; 2. toxicity is large, except containing agricultural chemicals and intermediate, also contains the material of the toxic substances such as phenol, arsenic, mercury and many biological hard degradations in waste water; 3. foul smelling, irritant to people's respiratory tract and mucous membrane; 4. water quality, the water yield are unstable.The discharging of agricultural chemicals waste water causes pollution of area source widely, longer duration, and residual agricultural chemicals is very large to Health Impact.
Therefore, for this kind waste water COD CrHeight, toxicity is large, and the biodegradability extreme difference has serious inhibiting characteristics to microorganism, needs a kind for the treatment of process of effective removal dragon lantern agricultural chemicals waste water, reduces high COD in waste water CrWith the toxicity of eliminating in waste water, decompose the organism of difficult degradation, add the biodegradability of mcroorganism, make it reach discharging standards (GB8978-1996), and then eliminate the pollution that agricultural chemicals waste water causes surrounding environment with wastewater disposition.
Summary of the invention
The object of the invention is to provide a kind of method of processing agricultural chemicals waste water, exists organism can not reduce in prior art to overcome, and waste water is virose problem also.
Method of the present invention comprises the steps:
(1) agricultural chemicals waste water is introduced equalizing tank, add acidic substance or alkaline matter, regulating described agricultural chemicals waste water pH is 2~4;
Described acidic substance are selected from sulfuric acid;
Described alkaline matter is selected from sodium hydroxide;
(2) above-mentioned waste water is introduced the iron carbon reactor, add iron filings and coke, then add H 2O 2Solution, H 2O 2The add-on of solution is that to make the pH of system be 2~4, then reacts 0.5~2 hour;
The mass ratio of iron filings and coke is 2:1~1:1, iron filings and H 2O 2Mass ratio be 1:2~1:4; The dosage of iron filings is 5~15g/L, in reaction process, passes into air, carries out aeration.
Described agricultural chemicals waste water is from the waste water that produces in insecticide factory's production process, COD in waste water CrBe 1000~5000 mg/L, turbidity is 600~1200 NTU;
Preferably, in reaction process, pass into air, carry out aeration, accelerate speed of reaction;
Above-mentioned iron-carbon micro-electrolysis treatment process is to COD in waste water CrRemoval most effective.Its principle of work is such:
The iron that wherein current potential is low becomes anode, and the carbon that current potential is high becomes negative electrode, and following electrochemical reaction occurs after waste water contacts with iron carbon:
Anode: Fe-2e-→ Fe E 0(Fe 2+/ Fe)=0.4
Negative electrode: 2H++2e-→ H 2E 0(H +/ H 2)=0V
O 2+4H++4e—→2H 2O E 0(O 2/H 2O)=1.22V
O 2+2H 2O+4e—→4OH- E 0(O 2/OH )=0.41V
In reaction, generation the Fe of status nascendi 2+With atom H, they have high chemically reactive, can change many organic structure and characteristics in waste water, make the effects such as organism generation chain rupture, open loop.The nascent state [H] that cathodic reaction generates can with many component generation redox reactions in waste water, destroy the chromophoric group (as azo group) in the dyestuff intermediate molecule, make its decolouring.Little electrolysis has obvious effect to color removal.This is to have stronger reducing power due to nascent state ferrous ion that electrode reaction produces, can make some organic chromophoric group nitro-NO 2, nitroso-group-NO is reduced into amido-NH 2, the biodegradability of another amido type organic is also apparently higher than the nitro type organic; The ferrous ion of nascent state also can make some unsaturated chromophoric group, and (the two keys as carboxyl-COOH, azo-group-N=N-) are opened, chromophoric group destroyed and remove colourity, making part difficult degradation ring-type become the small organic molecule of readily biodegradable and improve biodegradability with the long-chain organic substance decomposing.
By the reaction of iron carbon, consumed a large amount of hydrogen ions, the pH value of waste water is raise, for follow-up catalytic oxidation treatment has been created condition.After the reaction of iron carbon, add appropriate H in waste water 2O 2Solution, the Fe that anodic reaction generates 2+Can be used as the catalyzer of follow-up catalytic oxidation treatment, i.e. Fe 2+With H 2O 2Consist of Fenton reagent oxidation system, it has extremely strong oxidation capacity, is specially adapted to the improvement of organic wastewater with difficult degradation thereby.Why Fenton reagent has extremely strong oxidation capacity, is because HO is produced OH (hydroxyl radical free radical) by the Fe catalytic decomposition.The organic essence hydroxyl radical free radical of Fenton agent treated and organism react.
(3) will send into coagulative precipitation tank by the waste water after step (2) processing, add activation diatomite and NaOH, controlling pH is 7~9, constantly stir simultaneously, its waste water and activation diatomite are mixed, static 0.5~2 hour, upper strata waste water is flowed into hydrolysis acidification pool by top, lower floor's mud,, can be exported mud by mechanical filter press press filtration, dehydration through entering sludge sump by the bottom;
Activation diatomite can adopt 80~200 purpose diatomite of Shengzhou fountain diatomite product company limited.Its main chemical compositions is SiO 2, contain a small amount of Al 2O 3, Fe 2O 3, CaO, MgO and organism.
Described activation diatomite refers to utilize the diatomite after the means such as high temperature sintering or strong acid dissolving are sloughed the interior water of diatomite microvoid and other impurity of part.
Activating diatomaceous dosage is 0.1~1.0g/L;
Contain divalence and ferric ion in waste water in reactor, they are good flocculation agents, particularly newborn ferrous ion has higher absorption-flocculation activity, the pH that regulates waste water can make iron ion become the flocks of oxyhydroxide, the suspension in absorption sewage or molecule and the organic polymer of colloidal attitude.Activation diatomite is larger than diatomaceous aperture, method by physical adsorption, can not bring new material into and enter water body, cause secondary pollution, the flocs unit of producing after reaction is adsorbed onto in the aperture, make its flocculation physical efficiency sink to fast water bottom, reach the colourity of further reduction waste water, remove simultaneously some organic pollutants matter waste water is purified.
(4) waste water after above-mentioned coagulating sedimentation is incorporated into hydrolysis acidification pool, adds active sludge, stop 2.5~4.5h;
Described active sludge is a kind of aerobic sludge, can adopt the thickened sludge of sewage work;
Acidication is mainly used in the sewage treatment process that organic concentration is higher, SS is higher, is an important technique.If rear class accesses aerobic process, can greatly improve the volumetric loading of aerobic section, improve and remove efficient.When in water, organism was complex construction, the acidication bacterium utilized H 2The H of O ionization +With -OH opens the C-C in organic molecule, and an end adds H +, an end adds-OH, long-chain can be hydrolyzed to short chain, side chain and become straight chain, ring junction to consist of straight or branched, improves the biodegradability of sewage.When in water, SS was high, the hydrolysis bacterium caught it by ectoplasm, is hydrolyzed into the molecule part with exoenzyme and enters born of the same parents' intracellular metabolite again, and incomplete metabolism can make SS become dissolved organic matter, and it is limpid that water outlet just becomes.This is hydrolyzed bacterium therebetween is to have utilized covalent linkage energy in the organism of hydrolysis scission of link to complete the activity form of life.
(5) waste water of said hydrolyzed acidifying is sent into oxidation pond, carry out aerobic oxidation;
The method of described aerobic oxidation comprises the steps:
First the pH with the waste water after acidication is controlled at neutral meta-acid, COD in Aerobic Pond CrContent is controlled at 200mg/L, what enter material proportion in the aerobic oxidation pond and be the C:N:P=100:5:1(C representative is glucose, what N represented is urea, what P represented is potassium primary phosphate), active sludge is cultivated in Aerobic Pond and is tamed, and after occurring the active sludge flco in the pond, adds serially the waste water after a small amount of acidication in the pond, and water outlet and backflow continuously, its dosage can be controlled in the pond and to change water degree once every day.Sludge back flow quantity can adopt 50% of flooding quantity.When water temperature during at 15~30 ℃, mud through two week the left and right can cultivate maturation.Just the waste water after acidication can be flowed into when the time comes in the aerobic oxidation pond.
Diatomite waste water is processed by the acidication in early stage, and the non-solubility organism in waste water changes dissolved organic matter into, and the organism of difficult for biological degradation changes the organism of readily biodegradable into, improves the biodegradability of waste water, is beneficial to aerobic treatment.
The present invention is by association response, coagulating sedimentation, acidication, aerobic oxidation and the anaerobic oxidation of the reaction of iron carbon and Fenton reagent, effectively remove the organism of COD, toxicity and the difficult degradation of agricultural chemicals waste water, provide a kind of and can effectively remove agricultural chemicals waste water toxicity, decomposed hardly degraded organic substance, the method of the removal agricultural chemicals waste water that reduction is polluted, environment-friendly type is powerful, the waste water of discharging can reach state sewage emission standard.
Advantage of the present invention: this treatment process be fit to be processed the agricultural chemicals waste water that insecticide factory produces, and processes poisonous, difficult biochemistry, high COD and microorganism is had serious inhibiting waste water; Simple to operate, treatment effect is good, improves the biodegradability of water, decomposes the organism of difficult degradation, eliminates the toxicity of waste water, processes total cost low, can process high-concentration pesticide wastewater, and is economical and practical; Water outlet can reach discharging standards.
Description of drawings
Fig. 1 is process flow sheet.
Embodiment
Referring to Fig. 1, method of the present invention comprises the steps:
(1) agricultural chemicals waste water is introduced equalizing tank 1, added acidic substance or alkaline matter, regulating described agricultural chemicals waste water pH is 2~4;
(2) above-mentioned waste water is introduced iron carbon reactor 2, add iron filings and coke, then add H 2O 2Solution, H 2O 2The add-on of solution is that to make the pH of system be 2-4, then reacts 0.5~2 hour;
(3) will send into coagulative precipitation tank 3 by the waste water after step (2) processing, add activation diatomite and NaOH, controlling pH is 7~9, constantly stir simultaneously, its waste water and activation diatomite are mixed, static 0.5~2 hour, upper strata waste water is flowed into hydrolysis acidification pool by top, lower floor's mud,, can be exported mud by mechanical filter press 8 filter-press dehydrations through entering sludge sump 7 by the bottom;
(4) waste water after above-mentioned coagulating sedimentation is incorporated into hydrolysis acidification pool 4, adds active sludge, stop 2.5-4.5h;
(5) waste water of said hydrolyzed acidifying is sent into oxidation pond 5, carry out aerobic oxidation, then discharging.
Embodiment 1
Processing is from the waste water of agricultural chemicals, COD CrBe 5000 mg/L, turbidity is 1200NTU.
(1) agricultural chemicals waste water is introduced equalizing tank, add sulfuric acid, regulating described agricultural chemicals waste water pH is 4;
(2) above-mentioned waste water is introduced the iron carbon reactor, add iron filings and coke, then add H 2O 2Solution, H 2O 2The add-on of solution is that to make the pH of system be 4, then reacts 2 hours;
The dosage of iron filings is 10g/L;
The mass ratio of iron filings and coke is 2:1, iron filings and H 2O 2Mass ratio be 1:4;
In reaction process, pass into air, carry out aeration;
(3) will send into coagulative precipitation tank by the waste water after step (2) processing, activation diatomite and NaOH, controlling pH is 9, constantly stir simultaneously, its waste water and activation diatomite are mixed, static 2 hours, upper strata waste water is flowed into hydrolysis acidification pool by top, lower floor's mud,, can be exported mud by mechanical filter press press filtration, dehydration through entering sludge sump by the bottom;
Activating diatomaceous dosage is 0.5g/L;
(4) waste water after above-mentioned coagulating sedimentation is incorporated into hydrolysis acidification pool, adds active sludge, stop 4.5h;
Described active sludge adopts aerobic activated sludge;
(5) waste water of said hydrolyzed acidifying is sent into oxidation pond, carry out aerobic oxidation;
The method of aerobic oxidation is as follows: temperature is 20 ℃, and hydraulic detention time is 1 day, and material proportion is C:N:P=100:5:1.
Adopt the method for Hash standard of instruments regulation to detect, concentration of organic wastewater (COD Cr) be 70 mg/L, clearance is 98.6 %, and turbidity is down to 1.5 NTU, and clearance is 99.9 %.
Embodiment 2
Processing is from the waste water of agricultural chemicals: COD CrBe 1000 mg/L, turbidity is 600NTU.
(1) agricultural chemicals waste water is introduced equalizing tank, add acidic substance, regulating described agricultural chemicals waste water pH is 2;
Described acidic substance are sulfuric acid;
(2) above-mentioned waste water is introduced the iron carbon reactor, add iron filings and coke, then add H 2O 2Solution, H 2O 2The add-on of solution is that to make the pH of system be 2, then reacts 0.5 hour;
The dosage of iron filings is 5g/L;
The mass ratio of iron filings and coke is 2:1, iron filings and H 2O 2Mass ratio be 1:4;
In reaction process, pass into air, carry out aeration;
(3) will send into coagulative precipitation tank by the waste water after step (2) processing, activation diatomite and NaOH, controlling pH is 7, constantly stir simultaneously, its waste water and activation diatomite are mixed, static 0.5 hour, upper strata waste water is flowed into hydrolysis acidification pool by top, lower floor's mud,, can be exported mud by mechanical filter press press filtration, dehydration through entering sludge sump by the bottom;
Activating diatomaceous dosage is 0.2g/L;
(4) waste water after above-mentioned coagulating sedimentation is incorporated into hydrolysis acidification pool, adds active sludge, stop 2.5h;
Described active sludge adopts aerobic activated sludge;
(5) waste water of said hydrolyzed acidifying is sent into the aerobic oxidation pond and carried out oxidation;
The method of aerobic oxidation is as follows: temperature is 30 ℃, and hydraulic detention time is 1 day, and material proportion is C:N:P=100:5:1.
Adopt the method for Hash standard of instruments regulation to detect, concentration of organic wastewater (COD Cr) be down to 20 mg/L, clearance is 98 %, and turbidity is down to 1.0 NTU, and clearance is 99.9 %.
Below only expressed embodiments of the present invention, it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (6)

1. a method of processing agricultural chemicals waste water, is characterized in that, comprises the steps:
(1) agricultural chemicals waste water is introduced equalizing tank, add acidic substance or alkaline matter, regulating described agricultural chemicals waste water pH is 2~4;
(2) above-mentioned waste water is introduced the iron carbon reactor, add iron filings and coke, carry out aeration, then add H 2O 2Solution carries out the reaction of Fenton reagent;
(3) will send into coagulative precipitation tank by the waste water after step (2) processing, add activation diatomite and NaOH, and control pH and be 7~9, static, upper strata waste water is flowed into hydrolysis acidification pool by top;
(4) waste water after above-mentioned coagulating sedimentation is incorporated into hydrolysis acidification pool, adds active sludge, stop 2.5-~4.5h;
(5) waste water of said hydrolyzed acidifying is sent into oxidation pond, carry out aerobic oxidation.
2. method according to claim 1, is characterized in that, described acidic substance are selected from sulfuric acid; Described alkaline matter is selected from sodium hydroxide.
3. method according to claim 1, is characterized in that, in step (2), reacted 0.5~2 hour, and the mass ratio of iron filings and coke is 2:1~1:1, iron filings and H 2O 2Mass ratio be that the dosage of 1:2~1:4 iron filings is 5~15g/L, in reaction process, pass into air, carry out aeration.
4. method according to claim 1, it is characterized in that, waste water after processing by step (2) is sent into coagulative precipitation tank, add activation diatomite and NaOH, controlling pH is 7~9, static 0.5~2 hour, upper strata waste water is flowed into hydrolysis acidification pool by top, lower floor's mud,, is exported mud by mechanical filter press press filtration, dehydration through entering sludge sump by the bottom;
Activating diatomaceous dosage is 0.1~1.0g/L.
5. method according to claim 1, is characterized in that, the method for described aerobic oxidation comprises the steps:
First the pH with the waste water after acidication is controlled at neutral meta-acid, COD in Aerobic Pond CrContent is controlled at 200mg/L, what enter material proportion in the aerobic oxidation pond and be the C:N:P=100:5:1(C representative is glucose, what N represented is urea, what P represented is potassium primary phosphate), active sludge is cultivated in Aerobic Pond and is tamed, and after occurring the active sludge flco in the pond, adds serially the waste water after a small amount of acidication in the pond, and water outlet and backflow continuously, its dosage can be controlled in the pond and to change water degree once every day; Sludge back flow quantity can adopt flooding quantity weight 50%, when water temperature during at 15~30 ℃, mud through two week the left and right can cultivate maturation; Just the waste water after acidication can be flowed into when the time comes in the aerobic oxidation pond.
6. according to claim 1~5 described methods of any one, is characterized in that, described agricultural chemicals waste water is from the waste water that produces in insecticide factory's production process, COD in waste water CrBe 1000~5000 mg/L, turbidity is 600~1200 NTU.
CN 201310045939 2013-02-06 2013-02-06 Method for treating pesticide wastewater Pending CN103112994A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274505A (en) * 2013-05-30 2013-09-04 新昌县中发环保材料有限公司 High-COD (Chemical Oxygen Demand) sewage pretreatment method
CN103466885A (en) * 2013-09-12 2013-12-25 安徽省绿巨人环境技术有限公司 Process for treating wastewater generated in solar silicon wafer production process
CN103641230A (en) * 2013-12-02 2014-03-19 哈尔滨工业大学 Method for carrying out organic wastewater pretreatment by using an iron-carbon-Fenton-integrated reactor
CN104150653A (en) * 2014-08-28 2014-11-19 南京大学 Advanced treatment method of VB12 wastewater biochemical treatment effluent
CN104310700A (en) * 2014-10-13 2015-01-28 山东益源环保科技有限公司 Treatment method for wastewater containing high-concentration organic phosphorus
CN105399273A (en) * 2015-11-17 2016-03-16 江苏省嘉庆水务发展有限公司 Pretreatment method of high-concentration organic phosphorus wastewater and device
CN107285435A (en) * 2017-07-05 2017-10-24 山东百川集大环境工程有限公司 Double electrolysis remove the method and apparatus of the phosphorus in organophosphorus pesticide production waste water
CN108911432A (en) * 2018-09-03 2018-11-30 江苏泰源环保科技股份有限公司 The processing unit and treatment process of disperse dyestuff waste water
CN110054348A (en) * 2019-04-11 2019-07-26 江苏禾本生化有限公司 A kind for the treatment of process of fluorine bacterium azoles pesticide wastewater
CN110127939A (en) * 2019-05-15 2019-08-16 江苏禾本生化有限公司 A kind of processing method of clomazone production technology waste water
CN110330154A (en) * 2019-07-17 2019-10-15 中信环境技术(广州)有限公司 A kind of technique pre-processing pesticide waste liquid
CN112062407A (en) * 2020-09-08 2020-12-11 江苏众志新禹环境科技有限公司 Wet oxidation type pesticide wastewater treatment method

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274505B (en) * 2013-05-30 2016-01-20 新昌县中发环保材料有限公司 High-COD sewage pretreatment method
CN103274505A (en) * 2013-05-30 2013-09-04 新昌县中发环保材料有限公司 High-COD (Chemical Oxygen Demand) sewage pretreatment method
CN103466885A (en) * 2013-09-12 2013-12-25 安徽省绿巨人环境技术有限公司 Process for treating wastewater generated in solar silicon wafer production process
CN103641230A (en) * 2013-12-02 2014-03-19 哈尔滨工业大学 Method for carrying out organic wastewater pretreatment by using an iron-carbon-Fenton-integrated reactor
CN104150653A (en) * 2014-08-28 2014-11-19 南京大学 Advanced treatment method of VB12 wastewater biochemical treatment effluent
CN104150653B (en) * 2014-08-28 2016-04-20 南京大学 A kind of VB 12the deep treatment method of wastewater biochemical process water outlet
CN104310700A (en) * 2014-10-13 2015-01-28 山东益源环保科技有限公司 Treatment method for wastewater containing high-concentration organic phosphorus
CN104310700B (en) * 2014-10-13 2016-08-24 山东益源环保科技有限公司 A kind of processing method containing high concentration organism P wastewater
CN105399273A (en) * 2015-11-17 2016-03-16 江苏省嘉庆水务发展有限公司 Pretreatment method of high-concentration organic phosphorus wastewater and device
CN107285435A (en) * 2017-07-05 2017-10-24 山东百川集大环境工程有限公司 Double electrolysis remove the method and apparatus of the phosphorus in organophosphorus pesticide production waste water
CN108911432A (en) * 2018-09-03 2018-11-30 江苏泰源环保科技股份有限公司 The processing unit and treatment process of disperse dyestuff waste water
CN110054348A (en) * 2019-04-11 2019-07-26 江苏禾本生化有限公司 A kind for the treatment of process of fluorine bacterium azoles pesticide wastewater
CN110127939A (en) * 2019-05-15 2019-08-16 江苏禾本生化有限公司 A kind of processing method of clomazone production technology waste water
CN110330154A (en) * 2019-07-17 2019-10-15 中信环境技术(广州)有限公司 A kind of technique pre-processing pesticide waste liquid
CN112062407A (en) * 2020-09-08 2020-12-11 江苏众志新禹环境科技有限公司 Wet oxidation type pesticide wastewater treatment method

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Application publication date: 20130522