CN103288186A - Electrolysis device for treating chlorinated organic wastewater under combined action of multiple electrodes - Google Patents
Electrolysis device for treating chlorinated organic wastewater under combined action of multiple electrodes Download PDFInfo
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- CN103288186A CN103288186A CN2013102716505A CN201310271650A CN103288186A CN 103288186 A CN103288186 A CN 103288186A CN 2013102716505 A CN2013102716505 A CN 2013102716505A CN 201310271650 A CN201310271650 A CN 201310271650A CN 103288186 A CN103288186 A CN 103288186A
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Abstract
The invention discloses an electrolysis device for removing persistent organic pollutants such as chlorinated organic compounds and the like in water under combined action of multiple electrodes, which belongs to the fields of electrochemical and environmental technologies. The main-body structure of the electrolysis device comprises a cathode chamber, an anode chamber, a gas chamber, an air inlet, two cathodes, an anode, a clamp board and a diaphragm, wherein th the two cathodes are of a symmetric structure and distributed on both sides of the anode. According to the invention, chlorinated organic pollutants are degraded by using the electrochemical cathodic reduction and the simultaneous oxidation coupling of the cathodes and the anode, so that the chlorinated organic pollutants are dechlorinated under the reduction action of the cathodes, free chloride ions are oxidated into chlorine gas at the anode and separated from the electrolysis system, and then the chlorinated organic compounds are treated under the combined oxidation coupling action of the cathodes and the anode, so that the chlorinated organic pollutants are degraded. According to the invention, no catalyst is required to be added in the process of dechlorination, and no secondary pollution and material waste are produced, thereby saving resources and reducing the energy consumption; and the electrolysis device is high in dechlorination efficiency, and can be popularized and applied.
Description
Technical field
The present invention relates to the coefficient electrolyzer for persistence organic pollutants such as removal water chlorinatedorganics of a kind of multi-electrode, belong to electrochemistry and environmental technology field.
Background technology
In recent years, along with expanding economy, persistence organic pollutants such as increasing chlorinatedorganic enter in the environment, and ecological and environment have been caused great destruction.Because the amount in the sewage composition of chlorinatedorganic is fewer, and difficult removal, be a difficult problem for the scholar who studies its treatment process.In recent years, electrochemical techniques are used for removing the organic research of waste water to be on the increase, with respect to other method of wastewater treatment, and the electrochemical process simple equipments, easy to control, reaction conditions is less demanding, but it mainly lays particular emphasis on anodic oxidation, when handling organo-chlorine pollutant, the chlorine atom is difficult to thoroughly remove from organic molecule, there is more chloride intermediate product to exist after causing processing, lower to the clearance of organic waste water, and energy consumption is higher.And by the active specy that instead would not directly produce hydroxyl radical free radical and so on of negative electrode to the reduction generation hydrogen peroxide of oxygen, be the focus of studying now.
The patent of Qu Jiuhui (publication number CN1350982A) is a kind of reactor of wastewater treatment, it is characterized in that carrying out earlier oxidation, after reduce processing, or reduce earlier, after carry out oxide treatment, perhaps reduce processing separately, though this reactor can reach the purifying water effect that improves electrochemical process, improve the purpose of energy utilization rate, but because its negative electrode is made by the nickel plate, need not ventilation, so do not have gas compartment and diffuser, not thorough to the processing of waste water, and the anode chamber and the cathode chamber need add manganese sand, fillers such as hard coal, need periodic cleaning, complicated operation, processing efficiency is lower.
The patent of Wang Wenhua (publication number CN1285316A) is a kind of wastewater treatment electrolyzer that adopts compound gas diffusion electrode, anode is placed in reaction cell body bottom, compound gas diffusion electrode places the anode top as negative electrode, has advantage stable, that investment is low, but its need be between diffusion electrode and anode the live catalyzer of semiconductor material particle of loading metal and oxide compound thereof, bring certain difficulty for the operation of technology.
The electrolyzer that the patent of Wang Jianlong (publication number CN101434429A) is narrated carries out electrolysis treatment with two electrode structures to waste water, though it is simple in structure, chloride organic waste water there is treatment effect preferably, and can cut down the consumption of energy, but because its two electrodes structure, treatment capacity is lower, can not take full advantage of, processing efficiency to organic waste water is lower, and the application of can not magnifying.
All things considered, prior art can not thoroughly handle chlorinatedorganic, can produce secondary pollution and material waste, need to add catalyzer or filler, processing efficiency is lower and can not promote the use of.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides the coefficient electrolyzer for persistence organic pollutants such as removal water chlorinatedorganics of a kind of multi-electrode, main body of the present invention comprises cathode compartment (9,11), anolyte compartment (10), gas compartment (1,7), air inlet port (8,13), negative electrode (2,6), anode (4), clamp (12) and barrier film (3,5), wherein, comprise double cathode and single anode, jack to jack adapter is symmetrical structure separation anode both sides very.
The used anode of the present invention is the electrode with oxygenizement, particularly DSA electrode, preferably Ti/IrO
2/ RuO
2Electrode, it has lower chlorine overpotential, the Cl that produces in the organic process of degradating chloro of analysing
-Change into Cl easily
2Separate out, can avoid generating poisonous chloro intermediate product.
The used negative electrode of the present invention is for carrying the carbonaceous gas diffusion electrode of metal, particularly carry palladium carbon nanotube, gac, Graphene electrodes, the preferred palladium Graphene electrodes of carrying, when leading to hydrogen, because electrode has good suction hydrogen dechlorination performance, the reduction dechlorination reaction can fully take place when leading to hydrogen, oxidizing reaction can take place again when leading to oxygen generate H
2O
2, further the intermediate product to reaction carries out oxidation, and chlorinatedorganic is removed completely.
The used barrier film of the present invention is to have the barrier film that the barrier film of separating the two poles of the earth effect, particularly organic synthesis material are made, preferred terylene diaphragm, and its resistance to acids and bases allows ion to pass through, and chemical property is stable, and low cost, is easy to change.
Device of the present invention can feed gas with various when ventilation, preferably lead to hydrogen, then blowing air for the previous period; The sodium sulfate or other the electrolytical concentration that add are 0.01～1.0mol/L, particularly 0.02～0.10mol/L, preferred 0.05mol/L; The time that feeds gas with various is 40～180min, particularly 45～80min, preferred 60min; The control current density is 5～100mA/cm
2, 30～60mA/cm particularly
2, preferred 50mA/cm
2Aeration speed is the preferred 25mL/s of 1～80mL/s, particularly 10～30mL/s; The pH of cathode compartment electrolyte inside reaches 8～13, and particularly 9～11, preferred 10; The pH of anolyte compartment's electrolyte inside reaches 0.5～6.0, and particularly 1～3, preferred 2.
The present invention adopts electrochemistry cathodic reduction regulating YIN and YANG utmost point simultaneous oxidation coupling degradating chloro organic pollutant.Reaction principle is as follows:
1 anodic reaction mechanism
Direct Electrochemistry reaction can take place having in pollutent on the anode of catalytic activity, can also utilize the strong oxidizing property active substance that anode produces (as OH, HO
2Deng) pollutent is changed, thereby make organism generation oxidative degradation, after electrochemical reaction began, the oxygen of anode surface absorption became the hydroxy radical qiao that is adsorbed on anode surface and the Sauerstoffatom that enters in the oxide compound lattice respectively.Control certain anode voltage, can be oxidized to chlorine to the chlorion in the waste water and make waste water obtain certain degraded.
2 cathodic reaction mechanism
Cathodic reaction comprises cathodic reduction and the reaction of negative electrode indirect oxidation:
(1) cathodic reduction reaction
The electrochemical reduction dechlorinating process is to utilize chlorine is removed from the chlorinatedorganic molecule.Compare with additive method, the reaction conditions of electrochemical reduction dechlorinating process is gentleer, and has higher selectivity and exploitativeness.When adopting certain cathode material and controlling proper reaction conditions, at negative electrode evolving hydrogen reaction can take place, be strong reductant with the electronics, realizes the reduction of material by the control electrode electromotive force, chlorinatedorganic dechlorination wholly or in part can be converted into the hydrogenation products of nontoxic or low toxicity.
(2) negative electrode indirect oxidation reaction
The negative electrode indirect oxidation just refers at the hydrogen peroxide or the ferrous ion that produce by the cathodic reduction effect and adds reagent generation class Fenton's reaction.Under the effect of oxygen, generate H in cathode surface generation reduction reaction
2O
2, H
2O
2Under alkaline condition, be converted into HO
2 -, and further be decomposed into OH, O
2 -, because it has very active character, can not have selectively with water in the organism reaction, and it is degraded to CO
2And H
2O can not produce secondary pollution.
Compared with prior art, the invention has the beneficial effects as follows:
1. the reduction dechlorination effect can either take place in the carbonaceous gas diffusion cathode that carries metal of the present invention's employing, indirect oxidation can take place again generate H
2O
2, can take full advantage of the effect of negative electrode, improve the efficient of electrolysis treatment and reduce the energy consumption of reacting.
2. among the present invention, the degraded of chlorinatedorganic in cathode compartment carried out under alkaline condition, and reaction process generates H
2O
2, and need not to add in addition the molysite catalyzer, this has just simplified operation steps, has reduced the expense of technology, has reduced secondary pollution.
3. the present invention adopts electrochemistry cathodic reduction regulating YIN and YANG utmost point simultaneous oxidation coupling degradating chloro organic pollutant, reductive action by negative electrode makes chlorinatedorganic dechlorination detoxification earlier, make its chlorion that from parent, dissociates, and then handle parent jointly by the oxygenizement of anodic oxidation and cathodic reduction product and make its mineralising.This can make chlorinatedorganic effectively be removed, and can improve removal efficient in conjunction with the advantage that can give full play to oxidation, reduction.
4. the present invention adopts three-electrode system, the structure of two negative electrode list anodes can take full advantage of the oxygenizement of the reductive action regulating YIN and YANG utmost point of negative electrode, significantly improve the removal efficient of chlorinatedorganic, and improve the treatment capacity of each run, can also further improve, apply to industrialized wastewater treatment.
Description of drawings
Accompanying drawing is electrolyzer structural representation of the present invention.
As shown in the figure, the reaction cell body horizontal positioned of electrolyzer, cathode compartment (9,11), anolyte compartment (10), gas compartment (1,7), air inlet port (8,13), negative electrode (2,6), anode (4), clamp (12) and barrier film (3,5) are respectively in as shown in the figure position, anode and cathode is fixed by clamp, air inlet port separation gas compartment both sides, jack to jack adapter is symmetrical structure separation anode both sides very.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 1
In this example, with Ti/IrO
2/ RuO
2Electrode is anode, is negative electrode to carry palladium multi-wall carbon nano-tube pipe electrode, adopts terylene diaphragm, and 4-chlorophenol waste water is handled.
The starting condition of example is: the concentration of ionogen sodium sulfate is 0.05mol/L; Initial pH is 7.0; Current density is 50mA/cm
2Aeration speed is 25mL/s; Before 60min feed hydrogen, back 60min aerating oxygen is handled the 4-chlorophenol waste water of the 100mg/L of 100mL.
Through the degraded of 120min electrochemical redox, the 4-chlorophenol transformation efficiency in the anode chamber and the cathode chamber reaches 93.27% (anode), 94.17% (negative electrode 2) and 93.87% (negative electrode 6) at last respectively; The TOC degradation rate reaches 86.5% (anode), 81.8% (negative electrode 2) and 81.3% (negative electrode 6) respectively; The dechlorination rate of 4-chlorophenol is 90.5%.
Embodiment 2
In this example, with Ti/IrO
2/ RuO
2Electrode is anode, is negative electrode to carry palladium Graphene gas diffusion electrode, adopts terylene diaphragm, and 2,4-, two chlorophenol waste water are handled.
The starting condition of example is: the concentration of ionogen sodium sulfate is 0.05mol/L; Initial pH is 7.0; Current density is 50mA/cm
2Aeration speed is 25mL/s; Before 60min feed hydrogen, back 60min aerating oxygen, to 2 of the 100mg/L of 100mL, 4-two chlorophenol waste water are handled.
Through the degraded of 120min electrochemical redox, 2 in the anode chamber and the cathode chamber, 4-two chlorophenol transformation efficiencys reach 94.25% (anode), 95.47% (negative electrode 2) and 95.18% (negative electrode 6) at last respectively; The TOC degradation rate reaches 87.2% (anode), 82.8% (negative electrode 2) and 82.3% (negative electrode 6) respectively; The dechlorination rate of 2,4-, two chlorophenols is 92.8%.
Embodiment 3
In this example, adopt two electrode devicies and multi-electrode device of the present invention that 4-chlorophenol waste water is handled respectively, all with Ti/IrO
2/ RuO
2Electrode is anode, is negative electrode to carry palladium Graphene gas diffusion electrode, adopts terylene diaphragm.
The starting condition of example is: the concentration of ionogen sodium sulfate is 0.05mol/L; Initial pH is 7.0; Current density is 50mA/cm
2Aeration speed is 25mL/s; Before 60min feed hydrogen, back 60min aerating oxygen is handled the 4-chlorophenol waste water of the 100mg/L of 100mL.
Through the degraded of 120min electrochemical redox, two kinds of devices are as shown in table 1 to transformation efficiency, TOC degradation rate and the dechlorination rate result of 4-chlorophenol.
The removal effect of table 1 different device
As can be seen, apparatus of the present invention have treatment effect preferably to chlorinatedorganic, and than two electrode devicies, electrolyzer of the present invention has bigger dechlorination effect to chlorinatedorganic.
More than just the part of the preferred embodiment that can realize according to the present invention is illustrated, as everyone knows, scope of the present invention should not be construed as and is limited to above embodiment, more than Shuo Ming technological thought of the present invention be that the technological thought of sending all should be within the scope of the present invention with this thought.
Claims (5)
1. a multi-electrode is coefficient for the electrolyzer of removing persistence organic pollutant such as water chlorinatedorganic, comprise cathode compartment (9,11), anolyte compartment (10), gas compartment (1,7), air inlet port (8,13), negative electrode (2,6), anode (4), clamp (12) and barrier film (3,5), it is characterized in that it comprises three electrodes, be divided into two negative electrodes and single anode, two negative electrodes are symmetrical structure separation anode both sides; Cathode compartment and anolyte compartment are by separating to have the barrier film of separating the two poles of the earth effect.
2. a kind of multi-electrode according to claim 1 is coefficient for the electrolyzer of removing persistence organic pollutant such as water chlorinatedorganic, it is characterized in that its anode is for having the oxygenizement electrode, negative electrode has gas compartment and air inlet port for carrying the carbonaceous gas diffusion electrode of metal on the device.
3. according to claim 1 and the coefficient electrolyzer for persistence organic pollutants such as removal water chlorinatedorganics of 2 described a kind of multi-electrodes, it is characterized in that air inlet port will lead to 2 kinds of different gases as breather, lead to hydrogen, then blowing air or oxygen for the previous period.
4. according to claim 1, the coefficient electrolyzer for persistence organic pollutants such as removal water chlorinatedorganics of 2 and 3 described a kind of multi-electrodes, it is characterized in that adopting electrochemistry cathodic reduction regulating YIN and YANG utmost point simultaneous oxidation coupling degradating chloro organic pollutant.
5. according to claim 1,2, the coefficient electrolyzer for persistence organic pollutants such as removal water chlorinatedorganics of 3 and 4 described a kind of multi-electrodes, it is characterized in that the sodium sulfate or other the electrolytical concentration that add are 0.01～1.0mol/L, the time that feeds gas with various is 40～180min, and the control current density is 5～100mA/cm
2, aeration speed is 1～80mL/s, and the pH of cathode compartment electrolyte inside reaches 8～13, and the pH of anolyte compartment's electrolyte inside reaches 0.5～6.0.
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| CN201310271650.5A CN103288186B (en) | 2013-07-02 | 2013-07-02 | Electrolysis device for treating chlorinated organic wastewater under combined action of multiple electrodes |
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|---|---|---|---|
| CN201310271650.5A CN103288186B (en) | 2013-07-02 | 2013-07-02 | Electrolysis device for treating chlorinated organic wastewater under combined action of multiple electrodes |
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| CN103288186B CN103288186B (en) | 2015-06-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163478A (en) * | 2014-08-04 | 2014-11-26 | 陈致 | Emergency treatment method and emergency treatment device of organic micro-polluted drinking water |
| CN108439553A (en) * | 2018-04-20 | 2018-08-24 | 武汉大学 | A kind of Electrochemical oxidation device for removing chlorion in water removal |
| CN111153471A (en) * | 2020-01-12 | 2020-05-15 | 大连理工大学 | Integral multi-channel electrode for sequential reduction and oxidation of halogenated organic matters |
| CN114074971A (en) * | 2020-08-20 | 2022-02-22 | 中国石油化工股份有限公司 | electro-Fenton composite oxidation device and method for degrading organic pollutants in high-chlorine sewage |
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| JPS60139384A (en) * | 1983-12-28 | 1985-07-24 | Tatsuo Okazaki | Apparatus for preparing electrolytic water |
| JP2008080217A (en) * | 2006-09-26 | 2008-04-10 | Matsushita Electric Works Ltd | Apparatus for producing electrolytic water |
| CN101434429A (en) * | 2008-12-12 | 2009-05-20 | 清华大学 | Apparatus and method for processing chlorine-containing organic wastewater by electrochemical reduction and oxidation |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60139384A (en) * | 1983-12-28 | 1985-07-24 | Tatsuo Okazaki | Apparatus for preparing electrolytic water |
| JP2008080217A (en) * | 2006-09-26 | 2008-04-10 | Matsushita Electric Works Ltd | Apparatus for producing electrolytic water |
| CN101434429A (en) * | 2008-12-12 | 2009-05-20 | 清华大学 | Apparatus and method for processing chlorine-containing organic wastewater by electrochemical reduction and oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 王辉等: "Pd/C气体扩散电极用于电化学降解五氯酚钠的研究", 《环境科学》, vol. 30, no. 2, 28 February 2009 (2009-02-28) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163478A (en) * | 2014-08-04 | 2014-11-26 | 陈致 | Emergency treatment method and emergency treatment device of organic micro-polluted drinking water |
| CN108439553A (en) * | 2018-04-20 | 2018-08-24 | 武汉大学 | A kind of Electrochemical oxidation device for removing chlorion in water removal |
| CN111153471A (en) * | 2020-01-12 | 2020-05-15 | 大连理工大学 | Integral multi-channel electrode for sequential reduction and oxidation of halogenated organic matters |
| CN114074971A (en) * | 2020-08-20 | 2022-02-22 | 中国石油化工股份有限公司 | electro-Fenton composite oxidation device and method for degrading organic pollutants in high-chlorine sewage |
| CN114074971B (en) * | 2020-08-20 | 2023-05-23 | 中国石油化工股份有限公司 | electro-Fenton composite oxidation device and method for degrading organic pollutants in high-chlorine-content sewage |
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| CN103288186B (en) | 2015-06-17 |
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