CN103949033B - A kind of method of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane - Google Patents
A kind of method of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane Download PDFInfo
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- CN103949033B CN103949033B CN201410156020.8A CN201410156020A CN103949033B CN 103949033 B CN103949033 B CN 103949033B CN 201410156020 A CN201410156020 A CN 201410156020A CN 103949033 B CN103949033 B CN 103949033B
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Abstract
The present invention relates to the method for organochlorine of degrading, specifically, the method that the present invention relates to Gamma Hexaochlorocyclohexane is carried out electrochemical catalysis deoxidization, degradation.Described method is with the method degraded Gamma Hexaochlorocyclohexane of electrochemical reduction, is to be respectively working electrode and auxiliary electrode with platinum net, and saturated calomel electrode is reference electrode, pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl] it is eelctro-catalyst, tetrabutylammonium perchlorate (TBAP) is supporting electrolyte, and N, N dimethylformamide (DMF) is electrolyte, and in the response time is electrolysed Gamma Hexaochlorocyclohexane under certain controlling potential.The present invention is easy and simple to handle, degradation efficiency is high.
Description
Technical field
The present invention relates to the method for organochlorine compound of degrading, specifically, the present invention relates to apply pentafluorophenyl group
Porphyrin iron chloride [(TF5PP) FeCl] method that carries out of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane.
Background technology
Organochlorine pesticide is that the usage amount that people are invested in environment is maximum, toxicity is the widest and it is dirty to pollute a widest class
Dye thing；Gamma Hexaochlorocyclohexane is one therein, holds for 12 kinds listed in " about the Convention of Stockholm of persistence organic pollutant "
One of property organic pollution (Persistent Organic Pollutants is called for short POPs) for a long time；In 60 ~ eighties of 20th century,
Gamma Hexaochlorocyclohexane once produced in a large number in China and used, although be prohibited from using in 1992, but the severe environments consequence caused is short
It is difficult in phase eliminate.
In recent years, the understanding that organochlorine pollutant is endangered by people is deepened day by day, the treatment research to organochlorine pollutant
Also more concern is received；It is front that for degraded hexachloro cyclohexane, the technology of employing mainly has microbial treatments, chemical catalysis etc., but
Some shortcomings such as these methods are the longest, and processed in units amount is few, energy consumption is big, equipment cost is big.
Chinese patent 201010158793.1 discloses a kind of method of electrochemical reduction degradation of dichloro-diphenyl-trichloroethane, and its feature exists
In: described method is with platinum net as working electrode and auxiliary electrode, and saturated calomel electrode is reference electrode, and porphyrin metallizes
Compound is catalyst, and tetrabutylammonium perchlorate (TBAP) is supporting electrolyte, and DMF (DMF) is electrolyte,
Electrolysis clofenotane, as the porphyrin metallic compound of catalyst, its structure is:
M=FeIIIOr MnIII M=FeIIIOr MnIII
(TPP) molecular structural formula of MCl molecular structural formula (OEP) MCl
The porphyrin metallic compound of the catalyst that this patent relates to, it is adaptable to the degraded to clofenotane, but be applied to right
The poor effect during degraded of Gamma Hexaochlorocyclohexane.
Summary of the invention
It is an object of the invention to, for the deficiencies in the prior art, it is provided that a kind of simple to operate, degraded Gamma Hexaochlorocyclohexane that efficiency is high
Method.
For reaching goal of the invention, use the electrolysis unit disclosed in Chinese patent 201010158793.1, it is provided that a kind of
The method of degraded Gamma Hexaochlorocyclohexane；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 [(TF5PP) FeCl] it is catalyst, tetrabutylammonium perchlorate (TBAP) is for supporting electrolysis
Matter, DMF (DMF) is electrolyte, at-1.60V voltage (relative to saturated calomel electrode) with in certain time
Electrolysis Gamma Hexaochlorocyclohexane, electrolysate gas chromatograph-mass spectrometer (GC-MS) carries out detection and analyzes.
The catalyst that the inventive method is used is pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl], described method bag
Include following steps:
1, it is respectively working electrode and auxiliary electrode with platinum net, with saturated calomel electrode as reference electrode.
2, the electrolyte in cathode electrolytic cell is the DMF (DMF) of certain volume, every liter of electrolyte
(DMF) containing supporting electrolyte tetrabutylammonium perchlorate (TBAP) 34.15g in.
3, the electrolyte in anode electrolytic tank is the DMF (DMF) of certain volume, every liter of electrolyte
(DMF) containing supporting electrolyte tetrabutylammonium perchlorate (TBAP) 34.15g in；Electrolyte also needs add pentafluorophenyl group porphyrin
Iron chloride [(TF5PP) FeCl] as eelctro-catalyst, the compound being electrolysed is Gamma Hexaochlorocyclohexane, wherein the consumption of catalyst is six or six
The ratio of the amount of the 1/10(material of six).
4, electrolyte being applied certain voltage, and be electrolysed the regular hour, the Control of Voltage applied is in-1.60V(phase
For saturated calomel electrode), electrolysis time controlled at 3-5 hour.
5, after being electrolysed, the electrolyte in anode electrolytic tank is reduced pressure and distills to reclaim DMF, then by two volumes in electricity
The hexamethylene or the ether that solve liquid extract, and reclaim catalyst and supporting electrolyte cycling and reutilization from the residue after extraction.
6, electrolysis effectiveness GC-MS technology for detection is analyzed.
Pentafluorophenyl group porphyrin iron chloride [(TF as catalyst5PP) FeCl], its structural formula is:
The present invention is simple to operate, degradation efficiency is high.
Accompanying drawing explanation
The electrolysis principle schematic diagram of Fig. 1 present invention.
Detailed description of the invention
Embodiment 1:
Electrolyte in cathode electrolytic cell contains N-N dimethylformamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate
Ammonium (TBAP), containing supporting electrolyte in every 1L electrolyte (DMF) is 34.15g.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl], Gamma Hexaochlorocyclohexane, the tetrabutyl
Ammonium perchlorate, N-N dimethylformamide (DMF)；In every 1L electrolyte: (TF5PP) FeCl 0.53g, Gamma Hexaochlorocyclohexane 1.46g, four fourths
Base ammonium perchlorate 34.15g.
Apply current potential at-1.60V(relative to saturated calomel electrode), it is electrolysed 3 hours.
Pipetting the electrolyte in the anode electrolytic tank of 1mL, decompression is distilled off DMF, soaks with 2mL hexamethylene or ether
Taking, detect by gas chromatography mass spectrometry (GC-MS) technology, degradation rate is 79.9%.
Embodiment 2:
Electrolyte in cathode electrolytic cell contains N-N dimethylformamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate
Ammonium (TBAP), containing supporting electrolyte in every 1L electrolyte (DMF) is 34.15g.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl], Gamma Hexaochlorocyclohexane, the tetrabutyl
Ammonium perchlorate, N-N dimethylformamide (DMF)；In every 1L electrolyte: (TF5PP) FeCl 0.53g, Gamma Hexaochlorocyclohexane 1.46g, four fourths
Base ammonium perchlorate 34.15g.
Apply current potential at-1.60V(relative to saturated calomel electrode), it is electrolysed 4 hours.
Pipetting the electrolyte in the anode electrolytic tank of 1mL, decompression is distilled off DMF, soaks with 2mL hexamethylene or ether
Taking, detect by gas chromatography mass spectrometry (GC-MS) technology, degradation rate is 95.6%.
Embodiment 3:
Electrolyte in cathode electrolytic cell contains N-N dimethylformamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate
Ammonium (TBAP), containing supporting electrolyte in every 1L electrolyte (DMF) is 34.15g.
Electrolyte in anode electrolytic tank contains pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl], Gamma Hexaochlorocyclohexane, the tetrabutyl
Ammonium perchlorate, N-N dimethylformamide (DMF)；In every 1L electrolyte: (TF5PP) FeCl 0.53g, Gamma Hexaochlorocyclohexane 1.46g, four fourths
Base ammonium perchlorate 34.15g.
Apply current potential at-1.60V(relative to saturated calomel electrode), it is electrolysed 5 hours.
Pipetting the electrolyte in the anode electrolytic tank of 1mL, decompression is distilled off DMF, soaks with 2ml hexamethylene or ether
Taking, detect by gas chromatography mass spectrometry (GC-MS) technology, degradation rate is 100.0%.
The degradation results of embodiment
nL: the amount of the material of Gamma Hexaochlorocyclohexane during electrolysis；np: the amount of the material of used catalyst during electrolysis.
Comparative example 1:
Electrolyte in cathode electrolytic cell contains N-N dimethylformamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate
Ammonium (TBAP), containing supporting electrolyte in every 1L electrolyte (DMF) is 34.15g.
Electrolyte in anode electrolytic tank contains tetraphenylphosphonichloride chloride iron porphyrin [(TPP) FeCl], Gamma Hexaochlorocyclohexane, tetrabutyl height chlorine
Acid ammonium, N-N dimethylformamide (DMF)；In every 1L electrolyte: (TPP) FeCl 0. 35g, Gamma Hexaochlorocyclohexane 1.46g, the tetrabutyl are high
Ammonium chlorate 34.15g.
Apply current potential at-1.60V(relative to saturated calomel electrode), it is electrolysed 5 hours..
Pipetting the electrolyte in the anode electrolytic tank of 1mL, decompression is distilled off DMF, soaks with 2mL hexamethylene or ether
Taking, detect by gas chromatography mass spectrometry (GC-MS) technology, degradation rate is 91.9%.
Comparative example 2:
Electrolyte in cathode electrolytic cell contains N-N dimethylformamide (DMF), and supporting electrolyte is tetrabutylammonium perchlorate
Ammonium (TBAP), containing supporting electrolyte in every 1L electrolyte (DMF) is 34.15g.
Electrolyte in anode electrolytic tank contains octaethylporphyrin iron chloride [(OEP) FeCl], Gamma Hexaochlorocyclohexane, tetrabutyl height chlorine
Acid ammonium, N-N dimethylformamide (DMF)；In every 1L electrolyte: (OEP) FeCl 0.31g, Gamma Hexaochlorocyclohexane 1.46g, tetrabutyl height chlorine
Acid ammonium 34.15g.
Apply current potential at-1.60V(relative to saturated calomel electrode), it is electrolysed 5 hours.
Pipetting the electrolyte in the anode electrolytic tank of 1mL, decompression is distilled off DMF, soaks with 2mL hexamethylene or ether
Taking, detect by gas chromatography mass spectrometry (GC-MS) technology, degradation rate is 89.7%.
Comparative example 3:
Other are identical with comparative example 1, and catalyst is changed to (TPP) MnCl, for the amount 1/10 of the material of Gamma Hexaochlorocyclohexane, degradation rate
It is 76.5%.
Comparative example 4:
Other are identical with comparative example 2, and catalyst is changed to (OEP) MnCl, for the amount 1/10 of the material of Gamma Hexaochlorocyclohexane, degradation rate
It is 67.4%.
It can be seen that under identical electrolytic condition, use (TF5PP) FeCl is as the effect of catalyst degradation Gamma Hexaochlorocyclohexane,
It is far superior to disclosed (TPP) MCl and (OEP) MCl of Chinese patent 201010158793.1.
The degradation results of comparative example
nL: the amount of the material of Gamma Hexaochlorocyclohexane during electrolysis；np: the amount of the material of used catalyst during electrolysis.
Claims (6)
1. a method for electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane, described method is to be respectively working electrode and auxiliary with platinum net
Helping electrode, saturated calomel electrode is reference electrode, and tetrabutylammonium perchlorate is supporting electrolyte, and DMF is electricity
Solve liquid, be electrolysed Gamma Hexaochlorocyclohexane, it is characterised in that described catalyst is: pentafluorophenyl group porphyrin iron chloride [(TF5PP) FeCl], its structure
Formula is as follows:
The method of a kind of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane the most according to claim 1, it is characterised in that: every liter of electricity
The amount of addition supporting electrolyte tetrabutylammonium perchlorate in liquid that solves is 34.15g.
The method of a kind of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane the most according to claim 1, it is characterised in that: relative to
Saturated calomel electrode, Control of Voltage during electrolysis is at-1.60V, and electrolysis time controlled at 3 to 5 hours.
The method of a kind of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane the most according to claim 1, it is characterised in that: catalyst
Amount is Gamma Hexaochlorocyclohexane the 1/10 of the material of pentafluorophenyl group porphyrin iron chloride.
The method of a kind of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane the most according to claim 1, it is characterised in that: it has been electrolysed
Cheng Hou, reduces pressure the electrolyte in anode electrolysis pond and distills to reclaim DMF DMF, then by two volumes in electricity
The hexamethylene or the ether that solve liquid extract, and reclaim catalyst and supporting electrolyte cycling and reutilization from the residue after extraction.
The method of a kind of electrochemical catalysis deoxidization, degradation Gamma Hexaochlorocyclohexane the most according to claim 1, it is characterised in that: saturated sweet
Mercury electrode and electrolyte salt bridge separate, and use pottery electrolyte membrane to separate between negative and positive electrolyzer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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