CN100546926C - Chlopyrifos pesticides waste water treatment process - Google Patents

Chlopyrifos pesticides waste water treatment process Download PDF

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Publication number
CN100546926C
CN100546926C CNB2007101131645A CN200710113164A CN100546926C CN 100546926 C CN100546926 C CN 100546926C CN B2007101131645 A CNB2007101131645 A CN B2007101131645A CN 200710113164 A CN200710113164 A CN 200710113164A CN 100546926 C CN100546926 C CN 100546926C
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China
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waste water
oxidation
extraction
fenton
acid
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CNB2007101131645A
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Chinese (zh)
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CN101172728A (en
Inventor
宋东升
齐慧芹
孙绪兵
宫振
姚继磊
程翠花
李勇刚
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山东华阳科技股份有限公司
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Abstract

The invention discloses a kind of chlopyrifos pesticides waste water treatment process, comprise processing steps such as acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation.The present invention selects Chlorpyrifos 94 waste water and weedicide pendimethalin waste water combination treatment for use, reached the treatment of wastes with processes of wastes against one another, reduce difficult degradation class organic pollutant load in the waste water, improve biodegradable property of wastewater, remove pollutants in waste water, improve the purpose of the biodegradability of waste water, this process safety, advanced person, cleaning and cost for wastewater treatment are low.

Description

Chlopyrifos pesticides waste water treatment process
Technical field
The present invention relates to a kind of pesticides waste water treatment process, relate in particular to a kind of Chlorpyrifos 94 waste water treatment process, belong to field of environment protection.
Background technology
Chlorpyrifos 94 (chlorpyrifos) is the organophosphorus pesticide of a kind of efficient, wide spectrum, low residue, it is one of pesticide species that output is big in the world at present, in American-European countries's widespread use, also be the improved seeds that current China substitutes the riskiest pesticide acephatemet, market outlook are wide.But the waste water that produces in the Chlorpyrifos 94 production process does not have ripe effectively industrialization improvement method both at home and abroad so far.Contain multiple hazardous contaminants such as heavy metal copper, CN-R, sulfide, organophosphorus and nitrogen heterocyclic ring class in this waste water, B/C ratio is about 0.10, this contaminated wastewater substrate concentration height, saltiness height, colourity height and toxicity height, big to the effect of microorganism toxicity, biological degradability is poor, belongs to high density, difficult degradation organophosphorus agricultural chemicals waste water.
The improvement method of present domestic Chlorpyrifos 94 waste water mainly is a burning method, big energy-consuming, and the cost height, the waste residue generation is big simultaneously, has increased the cost that burns.And mostly the method for Chlorpyrifos 94 waste water treatment be the lab scale Study on Technology, do not see the operation of industrialized unit.
Summary of the invention
For solving the problem of above existence, at the characteristics of Chlorpyrifos 94 waste water, in pre-treatment, its composition is destroyed, make it have biodegradability, the invention provides a kind of chlopyrifos pesticides waste water treatment process, its technical scheme of taking is:
This technology comprises acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation, and its concrete steps are as follows:
1) acid out
Chlorpyrifos 94 waste water and pendimethalin waste water successively enter the acid out pond, and regulating the pH value is to carry out acid precipitation reaction behind the 2-4, filters by plate-and-frame filter press then;
2) complexometric extraction
Waste water and complexing extractant enter and are with the extraction tower that stirs to carry out complexometric extraction behind the acid out, and the back static layering stirs;
3) Fenton oxidation
The waste water that is positioned at extraction tower lower floor after the extraction enters the Fenton pond and carries out the Fenton oxidation, and control Fenton reaction pH value is 2-4, and the mol ratio of hydrogen peroxide and ferrous sulfate is 8-12: 1;
4) catalyzed oxidation
The pond stored in the middle of waste water was introduced into after the Fenton oxidation, entered the catalyzed oxidation tower then and carried out catalyzed oxidation, and the carrying transition metal oxide compound that with the gac is carrier is as catalyzer, ozone oxidation 2 hours, and last water outlet enters biochemical treatment apparatus.
The complexing extractant that is positioned at the extraction tower upper strata behind the complexometric extraction enters extractant regeneration device regeneration back reuse.
Complexing extractant is mixed by A and two kinds of compositions of B, and wherein A is a kind of in N503, TBP, N235, TOA, the trieline, and B is a kind of in kerosene, chloroform, normal hexane, the butylacetate.
The present invention adopts effectively pretreatment technology such as acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation, reduce difficult degradation class organic pollutant load in the waste water significantly, improve biodegradable property of wastewater, remove pollutants in waste water, reach the purpose of the biodegradability that improves waste water.
The present invention is for optimizing the wastewater treatment resource distribution, select Chlorpyrifos 94 waste water and weedicide pendimethalin waste water combination treatment for use, the treatment of wastes with processes of wastes against one another, with the acid waste water of pendimethalin and the alkaline waste water neutralization of Chlorpyrifos 94, the pH value of regulating waste water is to enter extraction treatment behind the 2-4.This technology also makes the COD of waste water reduce by 20% when saving acid and alkali consumption, has reached reduced investment, working cost is low, optimizes the purpose of wastewater treatment structure.
The present invention utilizes reversible network and reaction principle to develop the waste water abstraction technique, by system's phase balance experiment research, designed and be exclusively used in the contrary network extraction agent of this waste water, can form third phase in this extraction system, it is the complexing phase, and this third phase has organic characteristics in the highly enriched processed waste water, handles organic industrial sewage with this, reduces the COD of waste water, have high efficiency and highly selective, lock out operation is simple, and two-phase interface is clear, COD clearance height.
The present invention adopts orthogonal test, and having groped Fenton reaction pH value scope is 2-4, and the mol ratio of hydrogen peroxide and ferrous sulfate is 8-12: 1, make the Fenton oxidation after the COD clearance reach 48%.
The present invention reduces reaction activity by a large amount of orthogonal experiment selecting catalysts, select with the gac be the carrying transition metal oxide compound of carrier as catalyzer, significantly improved oxygenolysis efficient to agricultural chemicals in the water.For improving the efficient of oxidizing reaction, carry out under this catalytic oxidation normal temperature and pressure, reacting balance, easily-controlled operation, and catalyzer can recycle, need not regenerate, and has improved the speed of reaction.Difficult degradation, high stability contaminant removal capacity are surpassed conventional water technology and ozonize technology comprehensively, and compare with traditional ozone technology, the ozone amount that this art breading unit water yield is consumed is low, can reduce cost for wastewater treatment significantly.
The beneficial effect that the present invention had is: the effective organism of chlorpyrifos degradation waste water difficult for biological degradation guarantees the eco-toxicity safety of water outlet and non-secondary pollution; System's water outlet toxicity reduces greatly, and biodegradability brings up to 0.32 by 0.08, and through the biological treatment of A/O method, water outlet reaches country-grade standard after the water outlet dilution; This waste water treatment process safety, advanced person, cleaning, cost for wastewater treatment is low.
Embodiment
Embodiment 1:
The Chlorpyrifos 94 waste water that uses Shandong Huayang Science ﹠. Technology Co., Ltd. adopts acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation technology to handle as pending water.
Concrete processing step is as follows:
1) acid out: utilize pendimethalin acid waste water to regulate the Chlorpyrifos 94 alkaline waste water, Chlorpyrifos 94 waste water is after regulating, and the pH value is controlled at 3, again through the plate-and-frame filter press press filtration;
2) complexometric extraction: waste water and complexing extractant enter the extraction tower that band stirs behind the acid out, after stirring, and layering in static 2 hours.The waste water that is positioned at extraction tower lower floor enters the Fenton pond, and the complexing extractant on upper strata enters the reuse of extractant regeneration device;
3) Fenton oxidation: waste water enters the Fenton pond and carries out the Fenton oxidation, and control Fenton reaction pH value is 3, and adding 30% hydrogen peroxide is 3g/l, and adding ferrous sulfate is 0.4g/l;
4) catalyzed oxidation: the pond stored in the middle of waste water was introduced into after the Fenton oxidation, enter the catalyzed oxidation tower then and carry out catalyzed oxidation, the carrying transition metal oxide compound that with the gac is carrier is as catalyzer, ozone oxidation 2 hours, and last water outlet enters biochemical treatment apparatus.
Fenton oxidation and catalyzed oxidation are collectively referred to as composite catalytic oxidation, and the control air flow is 120m in this process 3/ h, flooding velocity are 5m 3/ h guarantees about 2 hours of retention time of sewage.
Water quality after the Chlorpyrifos 94 wastewater treatment is as shown in table 1 below:
Water-quality guideline contrast before and after the wastewater treatment of table 1 Chlorpyrifos 94
Embodiment 2:
Utilize certain insecticide factory's Chlorpyrifos 94 waste water as pending water, adopt acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation technology to handle.
Concrete processing step is as follows:
1) acid out: utilize pendimethalin acid waste water to regulate the Chlorpyrifos 94 alkaline waste water, Chlorpyrifos 94 waste water is after regulating, and the pH value is controlled at 2, again through the plate-and-frame filter press press filtration;
2) complexometric extraction: waste water and complexing extractant enter the extraction tower that band stirs behind the acid out, after stirring, and layering in static 2 hours.The waste water that is positioned at extraction tower lower floor enters the Fenton pond, and the complexing extractant on upper strata enters the reuse of extractant regeneration device;
3) Fenton oxidation: waste water enters the Fenton pond and carries out the Fenton oxidation, and control Fenton reaction pH value is 3, and adding 30% hydrogen peroxide is 3g/l, and adding ferrous sulfate is 0.4g/l;
4) catalyzed oxidation: the pond stored in the middle of waste water was introduced into after the Fenton oxidation, enter the catalyzed oxidation tower then and carry out catalyzed oxidation, the carrying transition metal oxide compound that with the gac is carrier is as catalyzer, ozone oxidation 2 hours, and last water outlet enters biochemical treatment apparatus.
The control air flow is 100m in the composite catalytic oxidation 3/ h, flooding velocity are 5m 3/ h guarantees about 2 hours of retention time of sewage.
Water quality after the Chlorpyrifos 94 wastewater treatment is as shown in table 2 below:
Water-quality guideline contrast before and after the wastewater treatment of table 2 Chlorpyrifos 94

Claims (3)

1, a kind of chlopyrifos pesticides waste water treatment process comprises acid out, complexometric extraction, Fenton oxidation and catalyzed oxidation, it is characterized in that these technology concrete steps are as follows:
1) acid out
Chlorpyrifos 94 waste water and pendimethalin waste water successively enter the acid out pond, and regulating the pH value is to carry out acid precipitation reaction behind the 2-4, filters by plate-and-frame filter press then;
2) complexometric extraction
Waste water and complexing extractant enter and are with the extraction tower that stirs to carry out complexometric extraction behind the acid out, and the back static layering stirs;
3) Fenton oxidation
The waste water that is positioned at extraction tower lower floor after the extraction enters the Fenton pond and carries out the Fenton oxidation, and control Fenton reaction pH value is 2-4, and the mol ratio of hydrogen peroxide and ferrous sulfate is 8-12: 1;
4) catalyzed oxidation
The pond stored in the middle of waste water was introduced into after the Fenton oxidation, entered the catalyzed oxidation tower then and carried out catalyzed oxidation, and the carrying transition metal oxide compound that with the gac is carrier is as catalyzer, ozone oxidation 2 hours, and last water outlet enters biochemical treatment apparatus.
2, chlopyrifos pesticides waste water treatment process according to claim 1 is characterized in that, the complexing extractant that is positioned at the extraction tower upper strata behind the complexometric extraction enters extractant regeneration device regeneration back reuse.
3, chlopyrifos pesticides waste water treatment process according to claim 1, it is characterized in that, complexing extractant is mixed by A and two kinds of compositions of B, and wherein A is a kind of in N503, TBP, N235, TOA, the trieline, and B is a kind of in kerosene, chloroform, normal hexane, the butylacetate.
CNB2007101131645A 2007-10-16 2007-10-16 Chlopyrifos pesticides waste water treatment process CN100546926C (en)

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CN102603094B (en) * 2011-12-14 2013-06-19 湖北犇星农化有限责任公司 Method for treating waste water during production of chlorpyrifos
CN102701300B (en) * 2012-06-21 2014-01-01 江苏省环境科学研究院 Compound reagent for removing chlorpyrifos in paddy-field drainage and usage method
CN103011455A (en) * 2012-12-12 2013-04-03 湖南海利化工股份有限公司 Method for pretreating 2,4-D pesticide wastewater
CN104098208A (en) * 2014-07-14 2014-10-15 湖南海利常德农药化工有限公司 Pretreatment method for pesticide larvin wastewater
CN104291398B (en) * 2014-09-17 2016-08-10 广东顺德天新环保科技有限公司 A kind of processing method recycling dyeing residual liquid
CN104386852A (en) * 2014-10-23 2015-03-04 浙江卓锦工程技术有限公司 High-concentration surface-active-agent wastewater treating technology
CN105481137A (en) * 2015-12-04 2016-04-13 安徽国星生物化学有限公司 Recycling treatment process for wastewater from chlorpyrifos production
CN106045176A (en) * 2016-07-26 2016-10-26 北京惠宇乐邦环保科技有限公司 Pretreatment method of wastewater generated by trifluralin production
CN106186556B (en) * 2016-08-26 2019-04-16 湖北犇星农化有限责任公司 A kind of method of ozone Oxidation Treatment chlopyrifos production waste water
CN107473974B (en) * 2017-08-23 2020-07-07 山东华阳农药化工集团有限公司 Preparation method of pendimethalin and application of wastewater generated by preparation method in treatment of chlorpyrifos wastewater

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Effective date of registration: 20121221

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Patentee after: Huayang Agricultural Chemicals Group Co., Ltd. Shandong Prov.

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