CN102921144A - Process for treating chlorinated organic compounds by polyethylene glycol and alkaline substances - Google Patents
Process for treating chlorinated organic compounds by polyethylene glycol and alkaline substances Download PDFInfo
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- CN102921144A CN102921144A CN2012104345990A CN201210434599A CN102921144A CN 102921144 A CN102921144 A CN 102921144A CN 2012104345990 A CN2012104345990 A CN 2012104345990A CN 201210434599 A CN201210434599 A CN 201210434599A CN 102921144 A CN102921144 A CN 102921144A
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- polyethylene glycol
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Abstract
The invention discloses a process for treating chlorinated organic compounds by polyethylene glycol and alkaline substances. Wastes containing chlorinated organic pollutants are added into a reactor, the polyethylene glycol and the alkaline substances are sequentially added into the reactor, and dechlorination degradation reaction can be achieved. The process has the advantages that the reaction time is short, the reaction temperature is low and the reaction materials are easy to obtain.
Description
Technical field
The present invention relates to a kind for the treatment of process to chlorinatedorganic, particularly relate to a kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic.
Background technology
In recent years, persistence organic pollutant (POPs, Persistent Organic Pollutions) harm that human body and environment are brought has become the environment focus that countries in the world are paid close attention to.POPs generally has toxicity, comprises carcinogenicity, genotoxicity, neurotoxicity, endocrine interference characteristic etc., its serious harm organism, and because its persistence, this harm generally all can continue for some time.More seriously, POPs has very strong lipophilic hydrophobicity on the one hand, can in the adipose tissue of biologic-organ, produce biological accumulation, amplify step by step along food chain, thereby make pollutant that in atmosphere, water, soil low concentration exists through the amplification of food chain, and the mankind's of high trophic level health cause serious negative effect to being in; On the other hand, POPs has half volatile, can deposit to the remote arctic regions of the earth in the migration of atmospheric environment middle and long distance and by so-called " global distillation effect " and " grasshopper jumps effect ", thereby cause the pollution spread of global range.Given this passed through in the Stockholm of Switzerland May 22 calendar year 2001 " about the Convention of Stockholm of persistence organic pollutant ", this pact came into effect on May 17th, 2004.Organo-chlorine pollutant mainly includes machine chloro pesticide (OCPs) and Polychlorinated biphenyls (PCBs) is the important POPs material of a class, China also exists at present and a large amount of contains chloro organic matter industrial waste stock and a large amount of contaminated sites is badly in need of repairing, and ecological environment, drinking water safety etc. has been consisted of serious threat.
The technology that is used for the organo-chlorine pollutant processing mainly comprises incineration technology and non-incineration technology two large classes.The dangerous waste incineration technology has the advantages such as treatment effeciency is high, treating capacity is large, but the processing cost of incineration technology is expensive, has simultaneously potential secondary pollution risk, causes incineration technology not accepted by the common people in recent years.Non-incineration technology or be called chemical treatment method, there is certain difference in various chemical technologies according to the difference of its material that adopts and reaction condition, but generally have the advantages such as disposal cost is lower, equipment is flexible.
Base catalysis decomposition technique (BCD, Base-Catalyzed decomposition) is a kind of non-combustion technology that is used for repairing the pollutants such as the liquid that polluted by organochlorine contamination thing (such as PCBs, bioxin, agricultural chemicals etc.), soil, drift, deposit that develop jointly at EPA Risk Reduction engineering experiment chamber and USN Engineering Service center.The BCD technology mainly is in alkaline environment and nitrogen environment, behind the reagent such as adding hydrogen donor catalyst, is heated to more than 300 ℃, after reaction a period of time, realizes cracking organo-chlorine pollutant.The reaction reagent that tradition base catalysis technique adopts is the U.S.P.5019175 patent catalyst of paraffin oil, NaOH and the exploitation of U.S. BCD company, and mainly there is following problem in this technique: the reaction time is long, reaction temperature is higher, the dosage of reaction mass is large, the catalyst patent is held by offshore company.Therefore need the efficient reaction mass prescription of exploitation, realize the high-efficient alkali catalysis dechlorination detoxifcation of chlorinatedorganic.
Summary of the invention
In order to overcome the existing problem of traditional base catalysis decomposition technique, the object of the present invention is to provide a kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, polyethylene glycol and alkaline matter added successively react the dechlorination degraded in the reactor that contains the chloro organic pollution, have the advantages that the reaction time is short, reaction temperature is lower, reaction mass easily obtains.
In order to achieve the above object, technical scheme of the present invention is achieved in that
A kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, the refuse that will contain the chloro organic pollution is added in the reaction vessel, be added to successively polyethylene glycol and alkaline matter in the reactor again, pure chlorinatedorganic: polyethylene glycol (PEG): the mass ratio between the alkaline matter three is 1:1-10:2-5, reaction mass is heated to the 80-250 degree from normal temperature, material is stirred, realize the dechlorination degraded to chlorinatedorganic after the reaction 2-4h.
Described polyethylene glycol (PEG) comprises that molecular weight is polyethylene glycol and the polyethylene glycol monoesters of 200-600, mainly comprises PEG200#, PEG400# or PEGM550#.
Described alkaline matter is alkali-metal hydroxide, comprises NaOH or potassium hydroxide.
The described refuse that contains the chloro organic pollution comprises the former medicine of organo-chlorine pesticide and preparation, contains the transformer oil of Polychlorinated biphenyls (PCBs), by POPs contaminated soil and deposit or contain the industrial waste of POPs.
As the present invention during for the treatment of solid waste (as: by POPs contaminated soil and deposit), at first polyethylene glycol is joined in the aqueous solution of alkaline matter and mix, then the aqueous solution after will mixing is added in the solid waste, when chlorinatedorganic content in the solid waste is low, the dosage of polyethylene glycol and alkaline matter is respectively 10 ~ 20% and 5 ~ 10% of solid waste quality, afterwards solid waste is fully stirred, polyethylene glycol and alkaline matter in the aqueous solution are evenly spread in the solid waste, afterwards solid waste is heated to the 150-250 degree, behind the reaction 2-4h, realization is to the dechlorination degraded of chlorinatedorganic in the solid waste, reacted solid matter, by washing, after the precipitate and separate, the water lotion that contains polyethylene glycol and alkaline matter is recycled, and carries out landfill after the solid matter after the processing is qualified after testing or backfill is disposed.
As the present invention during for the treatment of the organic liquid refuse (as: transformer oil that contains PCBs), at first polyethylene glycol is joined in the aqueous solution of alkaline matter and mix, then the aqueous solution after will mixing joins and contains in the organic organic liquid refuse of chloro, when chlorinatedorganic content in the liquid wastes is low, the dosage of polyethylene glycol and alkaline matter is respectively 10 ~ 20% and 5～10% of liquid wastes quality, heating material after will mixing afterwards is to the 80-150 degree, heat stirring reaction 1-4h, realize the dechlorination degraded to chlorinatedorganic in the organic liquid waste.Reacted material leaves standstill through washing, the liquid-liquid diphase after separating, and organic phase is used for the association area reuse or is used as boiler oil after being up to the standards, and water is recycled through after the evaporation and concentration.
The invention has the advantages that, polyethylene glycol and alkaline matter can form polyethylene glycol salt (to be lower than 150 degree) at a lower temperature, this polyethylene glycol salt is that a kind of efficient nucleopilic reagent and phase transfer catalyst can be transferred to from the aqueous solution of the polyethylene glycol of polarity and alkaline matter in the organic phase and chlorinatedorganic generation nucleophilic substitution, thereby effectively realizes the dechlorination degraded of chlorinatedorganic; Along with reaction temperature is increased to the 150-250 degree, polyethylene glycol and alkaline matter can produce a large amount of hydrogen in addition, and chlorinatedorganic is realized further dechlorination hydrogenation in the reduction atmosphere of hydrogen, thereby realize the complete dechlorination degraded of chlorinatedorganic.The present invention has effectively been lowered the reaction temperature of chlorinatedorganic catalysis dechlorination reaction by the reaction property of polyethylene glycol and alkaline matter, has improved reaction rate and efficient.
The specific embodiment
Embodiment one:
A kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, the refuse hexachloro-benzene 0.1022g that will contain the chloro organic pollution is added in the 10mL reaction vessel, be added to successively 0.6mL polyethylene glycol 0.7g and alkaline matter NaOH 0.3039g in the reactor again, reaction mass is heated to 230 degree from normal temperature, material is stirred, realize the dechlorination degraded to chlorinatedorganic after the reaction 2h.
The present embodiment finds after testing, behind the reaction 2h dechlorination efficiency of hexachloro-benzene greater than 99%, such as the dechlorination efficiency that continues hexachloro-benzene behind the reaction 3h near 100%.
Embodiment two:
A kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, the refuse 5a,6,9,9a-hexahydro-6,9-methano-2,4 0.1135g that will contain the chloro organic pollution is added in the 10mL reaction vessel, be added to successively 0.5405g Macrogol 200 # and alkaline matter NaOH 0.3067g in the reactor again, reaction mass is heated to 250 degree from normal temperature, material is stirred, realize the dechlorination degraded to chlorinatedorganic after the reaction 3h.
By the concentration of chlorion in the silver nitrate titration method mensuration system, the dechlorination efficiency of 5a,6,9,9a-hexahydro-6,9-methano-2,4 is near 100% behind the present embodiment reaction 3h.
Embodiment three:
A kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, PCB126 0 toluene solution of getting 20mL concentration and be 20000ppm places the flask of 50mL, to wherein adding the aqueous solution that contains KOH and PEG400#, dosage is about respectively 2g and 4g(chlorinatedorganic: KOH:PEG400#=1:5:10), behind vigorous stirring reaction 4h under 80 degree, the content that detects Polychlorinated biphenyls in the organic phase with GC/ECD is lower than detectability (1ppm).
Embodiment four:
A kind of technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, to contain the 5a,6,9,9a-hexahydro-6,9-methano-2,4 mass fraction and be 10% octadecane approximately 1g be added in the 10mL reaction vessel, again with approximately 0.1g polyethylene glycol PEG200# and alkaline matter potassium hydroxide 0.2g are added to (5a,6,9,9a-hexahydro-6,9-methano-2,4: PEG200#:KOH=1:1:2) in the reactor successively, reaction mass is heated to 250 degree from normal temperature, material is stirred, after the reaction 3h, measure the content of chlorion in the material, the dechlorination efficiency of 5a,6,9,9a-hexahydro-6,9-methano-2,4 reaches 98.8%.
Claims (6)
1. technique of utilizing polyethylene glycol and alkaline matter for processing chlorinatedorganic, it is characterized in that, the refuse that will contain the chloro organic pollution is added in the reaction vessel, be added to successively polyethylene glycol and alkaline matter in the reactor again, pure chlorinatedorganic: polyethylene glycol (PEG): the mass ratio between the alkaline matter three is 1:1-10:2-5, reaction mass is heated to the 80-250 degree from normal temperature, material is stirred, realize the dechlorination degraded to chlorinatedorganic after the reaction 2-4h.
2. process according to claim 1 the technique of chlorinatedorganic, it is characterized in that, described polyethylene glycol (PEG) comprises that molecular weight is polyethylene glycol and the polyethylene glycol monoesters of 200-600, mainly comprises PEG200#, PEG400# or PEGM550#.
3. process according to claim 1 the technique of chlorinatedorganic, it is characterized in that, described alkaline matter is alkali-metal hydroxide, comprises NaOH or potassium hydroxide.
4. process according to claim 1 the technique of chlorinatedorganic, it is characterized in that, the described refuse that contains the chloro organic pollution comprises the former medicine of organo-chlorine pesticide and preparation, contains the transformer oil of Polychlorinated biphenyls (PCBs), by POPs contaminated soil and deposit or contain the industrial waste of POPs.
5. process according to claim 1 the technique of chlorinatedorganic, it is characterized in that, as the present invention during for the treatment of solid waste, at first polyethylene glycol is joined in the aqueous solution of alkaline matter and mix, then the aqueous solution after will mixing is added in the solid waste, when chlorinatedorganic content in the solid waste is low, the dosage of polyethylene glycol and alkaline matter is respectively 10 ~ 20% and 5～10% of solid waste quality, afterwards solid waste is fully stirred, polyethylene glycol and alkaline matter in the aqueous solution are evenly spread in the solid waste, afterwards solid waste is heated to the 150-250 degree, behind the reaction 2-4h, realization is to the dechlorination degraded of chlorinatedorganic in the solid waste, reacted solid matter, by washing, after the precipitate and separate, the water lotion that contains polyethylene glycol and alkaline matter is recycled, and carries out landfill after the solid matter after the processing is qualified after testing or backfill is disposed.
6. process according to claim 1 the technique of chlorinatedorganic, it is characterized in that, as the present invention during for the treatment of the organic liquid refuse, at first polyethylene glycol is joined in the aqueous solution of alkaline matter and mix, then the aqueous solution after will mixing joins and contains in the organic organic liquid refuse of chloro, when chlorinatedorganic content in the liquid wastes is low, the dosage of polyethylene glycol and alkaline matter is respectively 10 ~ 20% and 5 ~ 10% of liquid wastes quality, heating material after will mixing afterwards is to the 80-150 degree, heat stirring reaction 1-4h, realize the dechlorination degraded to chlorinatedorganic in the organic liquid waste; Reacted material leaves standstill through washing, the liquid-liquid diphase after separating, and organic phase is used for the association area reuse or is used as boiler oil after being up to the standards, and water is recycled through after the evaporation and concentration.
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| CN201210434599.0A CN102921144B (en) | 2012-11-02 | 2012-11-02 | Process for treating chlorinated organic compounds by polyethylene glycol and alkaline substances |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116070A (en) * | 2016-07-29 | 2016-11-16 | 张倩 | A kind of acetone sludge treating agent and preparation method thereof |
| CN106116068A (en) * | 2016-07-29 | 2016-11-16 | 张倩 | A kind of Niran sludge treating agent and preparation method thereof |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
| CN108653970A (en) * | 2018-04-24 | 2018-10-16 | 中国科学院生态环境研究中心 | A kind of method for innocent treatment for discarding halogen drug |
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Patent Citations (8)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116070A (en) * | 2016-07-29 | 2016-11-16 | 张倩 | A kind of acetone sludge treating agent and preparation method thereof |
| CN106116068A (en) * | 2016-07-29 | 2016-11-16 | 张倩 | A kind of Niran sludge treating agent and preparation method thereof |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
| CN106902489B (en) * | 2017-04-16 | 2020-02-07 | 内蒙古佳瑞米精细化工有限公司 | Method for treating CTC (CTC) distillation still residues |
| CN108653970A (en) * | 2018-04-24 | 2018-10-16 | 中国科学院生态环境研究中心 | A kind of method for innocent treatment for discarding halogen drug |
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| CN102921144B (en) | 2015-07-15 |
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Effective date of registration: 20180404 Address after: 510530 B10, No. 11, open source road, Science City, Guangzhou high tech Industrial Development Zone, Guangdong Patentee after: Guangdong Lian Qing environment Co.,Ltd. Address before: 100084 Beijing, Haidian District, 100084 box office box office, Tsinghua University, Patentee before: Tsinghua University |
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Effective date of registration: 20200213 Address after: 100084 Beijing, Haidian District, 100084 box office box office, Tsinghua University, Patentee after: TSINGHUA University Address before: 510530 B10, No. 11, open source road, Science City, Guangzhou high tech Industrial Development Zone, Guangdong Patentee before: Guangdong Lian Qing environment Co.,Ltd. |
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