CN103949033A - Method for degrading hexachloro-cyclohexane soprocide through electrochemical catalytic reduction - Google Patents
Method for degrading hexachloro-cyclohexane soprocide through electrochemical catalytic reduction Download PDFInfo
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- CN103949033A CN103949033A CN201410156020.8A CN201410156020A CN103949033A CN 103949033 A CN103949033 A CN 103949033A CN 201410156020 A CN201410156020 A CN 201410156020A CN 103949033 A CN103949033 A CN 103949033A
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Abstract
The invention relates to a method for degrading organochlorine, and in particular relates to a method for degrading hexachloro-cyclohexane soprocide through electrochemical catalytic reduction. The method is characterized in that the electrochemical reducing method is used for degrading hexachloro-cyclohexane soprocide within certain time under certain control electric potential, wherein platinum nets respectively serves as a working electrode and an assistant electrode, a saturated calomel electrode serves as a reference electrode, pentafluorophenyl porphyrin ferric chloride [(TF5PP)FeCl] serves as an electrocatalyst, tetrabutylammonium perchlorate (TBAP) serves as supporting electrolyte, and N, N-dimethyl formamide (DMF) serves electrolyte. The method is simple and convenient in operation, and high in degrading efficiency.
Description
Technical field
The present invention relates to the method for the organochlorine compound of degrading, particularly, the present invention relates to apply pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl] the electrochemical catalysis deoxidization, degradation BHC method of carrying out.
Background technology
It is the widest and pollute first kinds of pollution matter the most widely that organo-chlorine pesticide is that people are invested in use amount maximum in environment, toxicity; BHC is one wherein, lists one of 12 kinds of persistence organic pollutants (Persistent Organic Pollutants is called for short POPs) in " about the Convention of Stockholm of persistence organic pollutant " in; In 60 ~ eighties of 20th century, BHC is once in a large amount of production of China and use, although be prohibited from using in 1992, the serious environmental consequence causing is difficult to eliminate in a short time.
In recent years, people deepen day by day to the understanding of organochlorine contamination thing harm, and the processing research of organochlorine contamination thing has also been received to more concern; Before for degraded hexachloro cyclohexane, some shortcomings such as the technology of employing mainly contains microbiological treatment, chemical catalysis etc., but these methods length consuming time, and processed in units amount is few, energy consumption is large, equipment cost is large.
Chinese patent 201010158793.1 discloses a kind of method of electrochemical reduction degradation of dichloro-diphenyl-trichloroethane, it is characterized in that: described method is taking platinum net as working electrode and auxiliary electrode, saturated calomel electrode is reference electrode, porphyrin metallic compound is catalyst, and tetrabutylammonium perchlorate (TBAP) is supporting electrolyte, N, dinethylformamide (DMF) is electrolyte, electrolysis DDT, as the porphyrin metallic compound of catalyst, its structure is:
M=Fe
iIIor Mn
iIIm=Fe
iIIor Mn
iII
(TPP) molecular structural formula of MCl molecular structural formula (OEP) MCl
The porphyrin metallic compound of the catalyst that this patent relates to, is applicable to the degraded to DDT, but poor effect while being applied to the degraded to BHC.
Summary of the invention
The object of the invention is, for the deficiencies in the prior art, provide a kind of method of simple to operate, degraded BHC that efficiency is high.
For reaching goal of the invention, adopt disclosed electrolysis unit in Chinese patent 201010158793.1, a kind of method of the BHC of degrading is provided; The method is to be respectively working electrode and auxiliary electrode with platinum net, and saturated calomel electrode is reference electrode, pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl] be catalyst, tetrabutylammonium perchlorate (TBAP) is supporting electrolyte, N, dinethylformamide (DMF) is electrolyte, electrolysis BHC in-1.60V voltage (with respect to saturated calomel electrode) and certain hour, gas chromatograph-mass spectrometer for electrolysate (GC-MS) detects analysis.
The catalyst that the inventive method is used is pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl], said method comprising the steps of:
1, be respectively working electrode and auxiliary electrode with platinum net, taking saturated calomel electrode as reference electrode.
2, the DMF (DMF) that the electrolyte in cathode electrolytic cell is certain volume, contains supporting electrolyte tetrabutylammonium perchlorate (TBAP) 34.15g in every liter of electrolyte (DMF).
3, the DMF (DMF) that the electrolyte in anode electrolytic tank is certain volume, contains supporting electrolyte tetrabutylammonium perchlorate (TBAP) 34.15g in every liter of electrolyte (DMF); In electrolyte, also need to add pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl] as eelctro-catalyst, be BHC by the compound of electrolysis, the ratio of the 1/10(amount of substance that wherein consumption of catalyst is BHC).
4, electrolyte is applied to certain voltage, and the electrolysis regular hour, the Control of Voltage applying at-1.60V(with respect to saturated calomel electrode), electrolysis time is controlled at 3-5 hour.
5, after electrolysis completes, the electrolyte decompression distillation in anode electrolytic tank, to reclaim DMF, then is extracted in cyclohexane or the ether of electrolyte by two volumes, in the residue from extracting, reclaim catalyst and supporting electrolyte cycling and reutilization.
6, electrolysis effectiveness is analyzed by GC-MS technology for detection.
As pentafluorophenyl group porphyrin the iron chloride [(TF of catalyst
5pP) FeCl], its structural formula is:
The present invention is simple to operate, degradation efficiency is high.
Brief description of the drawings
Fig. 1 electrolysis principle schematic diagram of the present invention.
Detailed description of the invention
embodiment 1:
Electrolyte in cathode electrolytic cell contains N-N dimethyl formamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate (TBAP), in every 1L electrolyte (DMF), is 34.15g containing supporting electrolyte.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl], BHC, tetrabutylammonium perchlorate, N-N dimethyl formamide (DMF); In every 1L electrolyte: (TF
5pP) FeCl 0.53g, BHC 1.46g, tetrabutylammonium perchlorate 34.15g.
Apply current potential at-1.60V(with respect to saturated calomel electrode), electrolysis 3 hours.
Pipette the electrolyte in the anode electrolytic tank of 1mL, DMF is removed in decompression distillation, leaches with 2mL cyclohexane or ether, detects by gas chromatography mass spectrometry (GC-MS) technology, and degradation rate is 79.9%.
embodiment 2:
Electrolyte in cathode electrolytic cell contains N-N dimethyl formamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate (TBAP), in every 1L electrolyte (DMF), is 34.15g containing supporting electrolyte.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl], BHC, tetrabutylammonium perchlorate, N-N dimethyl formamide (DMF); In every 1L electrolyte: (TF
5pP) FeCl 0.53g, BHC 1.46g, tetrabutylammonium perchlorate 34.15g.
Apply current potential at-1.60V(with respect to saturated calomel electrode), electrolysis 4 hours.
Pipette the electrolyte in the anode electrolytic tank of 1mL, DMF is removed in decompression distillation, leaches with 2mL cyclohexane or ether, detects by gas chromatography mass spectrometry (GC-MS) technology, and degradation rate is 95.6%.
embodiment 3:
Electrolyte in cathode electrolytic cell contains N-N dimethyl formamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate (TBAP), in every 1L electrolyte (DMF), is 34.15g containing supporting electrolyte.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl], BHC, tetrabutylammonium perchlorate, N-N dimethyl formamide (DMF); In every 1L electrolyte: (TF
5pP) FeCl 0.53g, BHC 1.46g, tetrabutylammonium perchlorate 34.15g.
Apply current potential at-1.60V(with respect to saturated calomel electrode), electrolysis 5 hours.
Pipette the electrolyte in the anode electrolytic tank of 1mL, DMF is removed in decompression distillation, leaches with 2ml cyclohexane or ether, detects by gas chromatography mass spectrometry (GC-MS) technology, and degradation rate is 100.0%.
The degradation results of embodiment
N
l: the amount of substance of BHC when electrolysis; n
p: the amount of substance of used catalyst when electrolysis.
comparative example 1:
Electrolyte in cathode electrolytic cell contains N-N dimethyl formamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate (TBAP), in every 1L electrolyte (DMF), is 34.15g containing supporting electrolyte.
Electrolyte in anode electrolytic tank contains tetraphenylphosphonichloride chloride ferriporphyrin [(TPP) FeCl], BHC, tetrabutylammonium perchlorate, N-N dimethyl formamide (DMF); In every 1L electrolyte: (TPP) FeCl 0. 35g, BHC 1.46g, tetrabutylammonium perchlorate 34.15g.
Apply current potential at-1.60V(with respect to saturated calomel electrode), electrolysis 5 hours.。
Pipette the electrolyte in the anode electrolytic tank of 1mL, DMF is removed in decompression distillation, leaches with 2mL cyclohexane or ether, detects by gas chromatography mass spectrometry (GC-MS) technology, and degradation rate is 91.9%.
comparative example 2:
Electrolyte in cathode electrolytic cell contains N-N dimethyl formamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate (TBAP), in every 1L electrolyte (DMF), is 34.15g containing supporting electrolyte.
Electrolyte in anode electrolytic tank contains octaethylporphyrin iron chloride [(OEP) FeCl], BHC, tetrabutylammonium perchlorate, N-N dimethyl formamide (DMF); In every 1L electrolyte: (OEP) FeCl 0.31g, BHC 1.46g, tetrabutylammonium perchlorate 34.15g.
Apply current potential at-1.60V(with respect to saturated calomel electrode), electrolysis 5 hours.
Pipette the electrolyte in the anode electrolytic tank of 1mL, DMF is removed in decompression distillation, leaches with 2mL cyclohexane or ether, detects by gas chromatography mass spectrometry (GC-MS) technology, and degradation rate is 89.7%.
comparative example 3:
other are identical with comparative example 1, catalyst are changed to (TPP) MnCl, are the amount of substance 1/10 of BHC, and degradation rate is 76.5%.
comparative example 4:
Other are identical with comparative example 2, catalyst are changed to (OEP) MnCl, are the amount of substance 1/10 of BHC, and degradation rate is 67.4%.
Can find out, under identical electrolytic condition, adopt (TF
5pP) FeCl is as the effect of catalyst degradation BHC, is far superior to Chinese patent 201010158793.1 disclosed (TPP) MCl and (OEP) MCl.
The degradation results of comparative example
N
l: the amount of substance of BHC when electrolysis; n
p: the amount of substance of used catalyst when electrolysis.
Claims (6)
1. the method for an electrochemical catalysis deoxidization, degradation BHC, described method is to be respectively working electrode and auxiliary electrode with platinum net, saturated calomel electrode is reference electrode, tetrabutylammonium perchlorate (TBAP) is supporting electrolyte, N, N-dimethyl formyl (DMF) is electrolyte, and electrolysis BHC is characterized in that described catalyst is: pentafluorophenyl group porphyrin iron chloride [(TF
5pP) FeCl], its structural formula is as follows:
。
2. the method for a kind of electrochemical catalysis deoxidization, degradation BHC according to claim 1, is characterized in that: the amount that adds supporting electrolyte tetrabutylammonium perchlorate in every liter of electrolyte is 34.15g.
3. the method for a kind of electrochemical catalysis deoxidization, degradation BHC according to claim 1, is characterized in that: with respect to saturated calomel electrode, Control of Voltage when electrolysis is at-1.60V, and electrolysis time is controlled at 3 to 5 hours.
4. the method for a kind of electrochemical catalysis deoxidization, degradation BHC according to claim 1, is characterized in that: the amount of substance of catalyst pentafluorophenyl group porphyrin iron chloride is BHC 1/10.
5. the method for a kind of electrochemical catalysis deoxidization, degradation BHC according to claim 1, it is characterized in that: after electrolysis completes, by the electrolyte decompression distillation in anode electrolysis pond with reclaim N, dinethylformamide DMF, extract in cyclohexane or the ether of electrolyte by two volumes again, from the residue extraction, reclaim catalyst and supporting electrolyte cycling and reutilization.
6. the method for a kind of electrochemical catalysis deoxidization, degradation BHC according to claim 1, is characterized in that: saturated calomel electrode and salt bridge used for electrolyte separate, and adopts ceramic electrolyte membrane to separate between negative and positive electrolytic cell.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410156020.8A CN103949033B (en) | 2014-04-18 | 2014-04-18 | A kind of method of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane |
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|---|---|---|---|
| CN201410156020.8A CN103949033B (en) | 2014-04-18 | 2014-04-18 | A kind of method of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829651A (en) * | 2015-04-30 | 2015-08-12 | 江苏大学 | Manganese phthalocyanine derivative, and synthetic method and application thereof |
| CN112111756A (en) * | 2020-08-31 | 2020-12-22 | 湖南工程学院 | Method for electrochemically synthesizing cyclic carbonate and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006218071A (en) * | 2005-02-10 | 2006-08-24 | Kobelco Eco-Solutions Co Ltd | Purification method of contamination, and its device |
| CN101053689A (en) * | 2007-05-29 | 2007-10-17 | 广东省生态环境与土壤研究所 | Iron and manganese complex for promoting polyhalogenated organic dehalogenation and detoxification in soil |
| CN101805714A (en) * | 2010-03-22 | 2010-08-18 | 中国科学院动物研究所 | Hexachloro cyclohexane degrading bacteria and application thereof in degraded hexachloro cyclohexane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006218071A (en) * | 2005-02-10 | 2006-08-24 | Kobelco Eco-Solutions Co Ltd | Purification method of contamination, and its device |
| CN101053689A (en) * | 2007-05-29 | 2007-10-17 | 广东省生态环境与土壤研究所 | Iron and manganese complex for promoting polyhalogenated organic dehalogenation and detoxification in soil |
| CN101805714A (en) * | 2010-03-22 | 2010-08-18 | 中国科学院动物研究所 | Hexachloro cyclohexane degrading bacteria and application thereof in degraded hexachloro cyclohexane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829651A (en) * | 2015-04-30 | 2015-08-12 | 江苏大学 | Manganese phthalocyanine derivative, and synthetic method and application thereof |
| CN104829651B (en) * | 2015-04-30 | 2017-11-17 | 江苏大学 | A kind of manganese phthalocyanine derivates and its preparation method and use |
| CN112111756A (en) * | 2020-08-31 | 2020-12-22 | 湖南工程学院 | Method for electrochemically synthesizing cyclic carbonate and application thereof |
| CN112111756B (en) * | 2020-08-31 | 2022-02-11 | 湖南工程学院 | Method for electrochemically synthesizing cyclic carbonate and application thereof |
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