CN103408185A - Advanced treatment method for organic phosphorus pesticide wastewater - Google Patents
Advanced treatment method for organic phosphorus pesticide wastewater Download PDFInfo
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- CN103408185A CN103408185A CN2013102947711A CN201310294771A CN103408185A CN 103408185 A CN103408185 A CN 103408185A CN 2013102947711 A CN2013102947711 A CN 2013102947711A CN 201310294771 A CN201310294771 A CN 201310294771A CN 103408185 A CN103408185 A CN 103408185A
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Abstract
The invention discloses an advanced treatment method for organic phosphorus pesticide wastewater, which comprises the following steps of performing pre-catalytic oxidation on the organic phosphorus wastewater with the COD (chemical oxygen demand) of 200-800mg/l and TP (total phosphorus) of 0.5-100, removing precipitates after the pre-oxidation, and treating the supernatant by a 'directional biological domestication reactor'; and performing secondary post-oxidation reaction by use of hydrogen peroxide and ferrous sulphate. By making full use of the advantage of low treatment cost of a biochemical method and since further biochemical treatment on the existing biochemical effluent with the COD of about 300 is difficult to implement, the biochemical performance can be improved through proper pre-chemical oxidation in the case of exceeding TP, and the COD and TP are removed through secondary oxidation after efficient biochemical treatment, so that the organic phosphorus wastewater reaches the national first-level discharge standard; and enough upgrading space is provided in combination with the existing physical-chemical technology.
Description
Technical field
The present invention relates to a kind of waste water advanced improvement method of Organophosphorus pesticides.
Background technology
The organic phosphine waste water treatment is a worldwide difficult problem for a long time, for the impact alleviated environment, the way of taking products production to shift is arranged abroad, and in the organic phosphine kind world's tonnage maximum be glyphosate, external still the reservation, account for production capacity over half in the world, to the final management goal of the waste water produced in glyphosate production, be discrepant both at home and abroad, this is mainly to determine due to employing technology and national conditions.External discharge of wastewater is according to environmental permission and manufacturing enterprise's production capacity is large and a strongly professional for example external glyphosate production business discharge of wastewater COD is less than 200mg/l, and total phosphorus TP is less than the way that 20PPM implements to enter ocean.And domestic enterprise little and distribute more scattered have be located in interior ground implement at present country directly discharge must COD be less than 100 mg/l or the country-level discharge mark COD that carries out according to locality is less than 80,60 or 50 mg/l, total phosphorus TP is less than 0.5PPM. or has the environmentally sensitive area requirement harsher.This determines mainly due to the area environmental requirement of domestic production enterprise.Enterprise practical is administered the general COD80-500 mg/l of result at present, total phosphorus TP3-50PPM, do to such an extent that three grades of (letter connects) emission compliance COD<500 can be accomplished by better enterprise, if even TP<8 so also give the municipal wastewater treatment plant that receives waste water or the garden sewage work amount of receiving more greatly to the TP that implements first grade discharging administer bring administer difficulty cause the major cause of this problem be exactly in total phosphorus (TP) by analysis test more than at least 30%, be not biodegradable organic phosphine, the depositing of organic phosphine not only makes TP higher but also bring the COD value, make to contain organic phosphine waste water and be difficult to main aspect up to standard, current enterprise faces the enforcement of the strictest National Environmental policy and the effective execution of supervision, it is the selection of Sustainable Development of Enterprises that enterprise payes attention to waste water treatment.
Summary of the invention
The object of the present invention is to provide that a kind for the treatment of effect is good, the waste water advanced improvement method of Organophosphorus pesticides easily.
Technical solution of the present invention is:
A kind of waste water advanced improvement method of Organophosphorus pesticides, it is characterized in that: comprise the following steps: thing is levied to the organic phosphine waste water into COD200-800 mg/l, TP0.5-100, by pre-catalyzed oxidation, after preoxidation, remove the rear supernatant water of precipitation and go " biochemical reactor " to carry out biochemical treatment; With hydrogen peroxide and ferrous sulfate, carrying out the secondary rear oxidation again reacts.
Described pre-catalyzed oxidation is to adopt hydrogen peroxide and ferrous sulfate, the ratio control of hydrogen peroxide and sewage is 0.5 ~ 2. 5 ‰, and the ferrous sulfate dosage is 2 ~ 5 ‰, controls the PH of its reaction environment between 3.5 ~ 5.5, under the environment of temperature 20-35 ℃, react, with alkali, recall to PH to 7.5 ~ 8.5 after reaction.
During the reaction of secondary rear oxidation, the ratio control of hydrogen peroxide and sewage is 0.2 ~ 1.5 ‰, and the ferrous sulfate dosage is 1 ~ 3 ‰, controls the PH of its reaction environment between 4.5-6.5, reacts under the environment of temperature 20-35 ℃, with alkali, recalls to PH to 7.5 ~ 8.5 after reaction.
The present invention takes full advantage of the advantage that the biochemical process processing cost is low, for existing bio-chemical effluent COD300 left and right characteristics regenerationization difficulty, TP exceeds standard and carries out the pre-chemical oxidation of appropriateness and promote biodegradability and can pass through efficient biochemical, after again secondary oxidation remove COD and TP make organic phosphine waste water reach national grade one discharge standard also supporting existing materialization technology can have enough carrying to mark space.
The invention will be further described below in conjunction with embodiment.
Embodiment
A kind of waste water advanced improvement method of Organophosphorus pesticides, comprise the following steps: thing is levied to the mg/l into COD200-800, is generally 300-500 mg/l; TP0.5-100, be generally 3-50PPM; The organic phosphine waste water of cl content<2%, by pre-catalyzed oxidation (being the Fenton oxidation method with hydrogen peroxide and ferrous sulfate oxidized waste water), organic phosphine is converted into to tertiary iron phosphate and has improved the biodegradability energy, control COD clearance 40-70%, the TP clearance > 60%, through removal, precipitate to obtain waste water COD 120-450 after oxidation, TP<8; After after preoxidation, removing precipitation, supernatant water goes " biochemical reactor " to carry out biochemical treatment, processed waste water COD80-150; With hydrogen peroxide and ferrous sulfate, carry out the secondary rear oxidation again and react, control the rear effluent index COD30-70 of precipitation, TP<0.3; Further the water outlet charcoal bed of flowing through is guaranteed lower effluent index.
Described pre-catalyzed oxidation is to adopt hydrogen peroxide and ferrous sulfate, the ratio control of hydrogen peroxide and sewage is 0.5 ~ 2. 5 ‰, and the ferrous sulfate dosage is 2 ~ 5 ‰, controls the PH of its reaction environment between 3.5 ~ 5.5, under the environment of temperature 20-35 ℃, react, with alkali, recall to PH to 7.5 ~ 8.5 after reaction.
During the reaction of secondary rear oxidation, the ratio control of hydrogen peroxide and sewage is 0.2 ~ 1.5 ‰, and the ferrous sulfate dosage is 1 ~ 3 ‰, controls the PH of its reaction environment between 4.5-6.5, reacts under the environment of temperature 20-35 ℃, with alkali, recalls to PH to 7.5 ~ 8.5 after reaction.
Described " biochemical reactor " is the commercially available prod " directed biological domestication reactor " of adopting Beijing Selfway Environmental Engineering Technology Co., Ltd..In the reaction tank of this reactor, add the commercially available prod " Industrial Wastewater Treatment specific bacteria " of Beijing Selfway Environmental Engineering Technology Co., Ltd. or speed how quick series of high efficiency composite anaerobic bacterium or bio-synergistic preparation Enviro-BZ-501, Enviro-BZ-AC, Bio-T100, Enviro-BZ-AB etc.
Described " biochemical reactor " processed can be also to adopt Chinese patent CN201120380539.6, CN201110197616.9 technology contents to carry out.
Described " biochemical reactor " processed can be also to add commercially available biological inoculum (as: commercially available prod of Beijing Selfway Environmental Engineering Technology Co., Ltd. " Industrial Wastewater Treatment specific bacteria " etc.) in treating pond, to carry out biochemical treatment.Or according to the routine biochemistry disposal methods.
Claims (3)
1. waste water advanced improvement method of Organophosphorus pesticides, it is characterized in that: comprise the following steps: thing is levied to the organic phosphine waste water into COD200-800 mg/l, TP0.5-100, by pre-catalyzed oxidation, after preoxidation, remove the rear supernatant water of precipitation and go " biochemical reactor " to carry out biochemical treatment; With hydrogen peroxide and ferrous sulfate, carrying out the secondary rear oxidation again reacts.
2. the waste water advanced improvement method of Organophosphorus pesticides according to claim 1, it is characterized in that: described pre-catalyzed oxidation is to adopt hydrogen peroxide and ferrous sulfate, the ratio control of hydrogen peroxide and sewage is 0.5 ~ 2. 5 ‰, the ferrous sulfate dosage is 2 ~ 5 ‰, control the PH of its reaction environment between 3.5 ~ 5.5, under the environment of temperature 20-35 ℃, react, with alkali, recall to PH to 7.5 ~ 8.5 after reaction.
3. the waste water advanced improvement method of Organophosphorus pesticides according to claim 1 and 2, it is characterized in that: during the reaction of secondary rear oxidation, the ratio control of hydrogen peroxide and sewage is 0.2 ~ 1.5 ‰, the ferrous sulfate dosage is 1 ~ 3 ‰, control the PH of its reaction environment between 4.5-6.5, under the environment of temperature 20-35 ℃, react, with alkali, recall to PH to 7.5 ~ 8.5 after reaction.
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| CN2013102947711A CN103408185A (en) | 2013-07-15 | 2013-07-15 | Advanced treatment method for organic phosphorus pesticide wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826854A (en) * | 2015-05-07 | 2015-08-12 | 环境保护部南京环境科学研究所 | Regeneration processing method of dangerous solid waste containing organic phosphor pesticide |
| CN108947122A (en) * | 2018-07-23 | 2018-12-07 | 安徽华星化工有限公司 | A kind of organic phosphorus pesticide waste water recycling process |
| CN108996822A (en) * | 2018-08-01 | 2018-12-14 | 深圳市深投环保科技有限公司 | Reach the three-dimensional industrial organic waste water processing method of ground Table IV discharge standard |
| CN109775891A (en) * | 2019-03-08 | 2019-05-21 | 南通江山农药化工股份有限公司 | The method and device thereof of acid out and oxidation combination processing thiophosphoric acid diester waste water |
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| JPH04349997A (en) * | 1991-05-28 | 1992-12-04 | Ebara Infilco Co Ltd | Treatment of organic waste water |
| CN1227191A (en) * | 1998-02-24 | 1999-09-01 | 化学工业部北京化工研究院 | Method for treating waste water from developing and printing photographic film |
| CN101186402A (en) * | 2007-11-27 | 2008-05-28 | 华泰集团有限公司 | Fenton two-stage method oxidation processing technique for paper-making pulping waste water |
| CN101659483A (en) * | 2008-08-29 | 2010-03-03 | 中国石油化工股份有限公司 | Method for treating high-concentrated non-degradable wastewater by using wastewater containing hydrogen peroxide |
| CN102616977A (en) * | 2011-01-27 | 2012-08-01 | 上海彰华膜净化有限公司 | Fenton oxidation wastewater processing system |
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2013
- 2013-07-15 CN CN2013102947711A patent/CN103408185A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04349997A (en) * | 1991-05-28 | 1992-12-04 | Ebara Infilco Co Ltd | Treatment of organic waste water |
| CN1227191A (en) * | 1998-02-24 | 1999-09-01 | 化学工业部北京化工研究院 | Method for treating waste water from developing and printing photographic film |
| CN101186402A (en) * | 2007-11-27 | 2008-05-28 | 华泰集团有限公司 | Fenton two-stage method oxidation processing technique for paper-making pulping waste water |
| CN101659483A (en) * | 2008-08-29 | 2010-03-03 | 中国石油化工股份有限公司 | Method for treating high-concentrated non-degradable wastewater by using wastewater containing hydrogen peroxide |
| CN102616977A (en) * | 2011-01-27 | 2012-08-01 | 上海彰华膜净化有限公司 | Fenton oxidation wastewater processing system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826854A (en) * | 2015-05-07 | 2015-08-12 | 环境保护部南京环境科学研究所 | Regeneration processing method of dangerous solid waste containing organic phosphor pesticide |
| CN108947122A (en) * | 2018-07-23 | 2018-12-07 | 安徽华星化工有限公司 | A kind of organic phosphorus pesticide waste water recycling process |
| CN108996822A (en) * | 2018-08-01 | 2018-12-14 | 深圳市深投环保科技有限公司 | Reach the three-dimensional industrial organic waste water processing method of ground Table IV discharge standard |
| CN109775891A (en) * | 2019-03-08 | 2019-05-21 | 南通江山农药化工股份有限公司 | The method and device thereof of acid out and oxidation combination processing thiophosphoric acid diester waste water |
| CN109775891B (en) * | 2019-03-08 | 2023-06-16 | 南通江山农药化工股份有限公司 | Method and device for treating phosphorothioate diester wastewater by combination of acid precipitation and oxidation |
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Application publication date: 20131127 |