CN103288186B - 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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- CN103288186B CN103288186B CN201310271650.5A CN201310271650A CN103288186B CN 103288186 B CN103288186 B CN 103288186B CN 201310271650 A CN201310271650 A CN 201310271650A CN 103288186 B CN103288186 B CN 103288186B
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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 removing the persistence organic pollutant such as chlorinatedorganic in water of a kind of multi-electrode, belonging to electrochemistry and field of environmental technology.
Background technology
In recent years, along with expanding economy, in the persistence organic pollutant entered environments such as increasing chlorinatedorganic, great destruction is caused to ecosystem environment.Because the amount in sewage composition of chlorinatedorganic is fewer, and more difficult removal, the scholar for its treatment process of research is a difficult problem.In recent years, electrochemical techniques are on the increase for removing organic research in waste water, relative to other method of wastewater treatment, and electrochemical process simple equipments, easy to control, reaction conditions is less demanding, but it mainly lays particular emphasis on anodic oxidation, during process organo-chlorine pollutant, chlorine atom is difficult to thoroughly remove from organic molecule, more chloride intermediate product is had to exist after causing process, lower to the clearance of organic waste water, and energy consumption is higher.And directly can not be produced the active specy of hydroxyl radical free radical and so on to the reaction of the reduction Hydrogen Peroxide of oxygen by negative electrode, be the focus of research now.
The patent (publication number CN1350982A) of Qu Jiuhui is a kind of reactor of wastewater treatment, it is characterized in that first being oxidized, after carry out reduction treatment, or first reduce, after carry out oxide treatment, or carry out reduction treatment separately, although this reactor can reach the purifying water effect improving electrochemical process, improve the object of energy utilization rate, but because its negative electrode is made up of nickel plate, without the need to ventilation, so there is no gas compartment and diffuser, not thorough to the process of waste water, and the anode chamber and the cathode chamber needs to add manganese sand, the fillers such as hard coal, need periodic cleaning, complicated operation, processing efficiency is lower.
The patent (publication number CN1285316A) of Wang Wenhua is a kind of wastewater treatment electrolyzer adopting compound gas diffusion electrode, anode is placed bottom reaction cell body, compound gas diffusion electrode is placed in above anode as negative electrode, have stable, invest low advantage, but it needs the catalyzer of loading metal and oxide compound semiconductor material particle alive thereof between diffusion electrode and anode, brings certain difficulty to the operation of technique.
The patent (publication number CN101434429A) of Wang Jianlong the electrolyzer that describes with two electrode structures, electrolysis treatment is carried out to waste water, although its structure is simple, good treatment effect is had to chlorine organic wastewater, and can energy consumption be reduced, but due to its two electrodes structure, treatment capacity is lower, can not make full use of, lower to the processing efficiency of organic waste water, and application of can not magnifying.
All things considered, prior art thoroughly can not process chlorinatedorganic, can produce the waste of secondary pollution and material, need 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 removing the persistence organic pollutant such as chlorinatedorganic in water 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 present invention's anode used is the electrode with oxygenizement, particularly DSA electrode, preferred Ti/IrO
2/ RuO
2electrode, it has lower analyses chlorine overpotential, the Cl produced in the organic process of degradating chloro
-easily change into Cl
2separate out, can avoid generating poisonous chloro intermediate product.
The present invention's negative electrode used is the carbonaceous gas diffusion electrode carrying metal, particularly carry palladium carbon nanotube, gac, Graphene electrodes, preferably carry palladium Graphene electrodes, during logical hydrogen, because electrode has good suction hydrogen dechlorination, fully can there is reduction dechlorination reaction when logical hydrogen, oxidizing reaction can occur again when logical oxygen and generate H
2o
2, further the intermediate product of reaction is oxidized, chlorinatedorganic is removed thoroughly.
The present invention's barrier film used is have the barrier film separating the two poles of the earth effect, the barrier film of particularly organic synthesis material manufacture, preferred terylene diaphragm, and its resistance to acids and bases allows ion to pass through, stable chemical nature, and low cost, is easy to change.
Device of the present invention, when ventilating, can pass into gas with various, preferably leads to hydrogen, then blowing air for the previous period; The sodium sulfate added or other electrolytical concentration are 0.01 ~ 1.0mol/L, particularly 0.02 ~ 0.10mol/L, preferred 0.05mol/L; The time passing into gas with various is 40 ~ 180min, particularly 45 ~ 80min, preferred 60min; Control current density is 5 ~ 100mA/cm
2, particularly 30 ~ 60mA/cm
2, preferred 50mA/cm
2; Aeration rate 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, preferably 10; The pH of anolyte compartment's electrolyte inside reaches 0.5 ~ 6.0, and particularly 1 ~ 3, preferably 2.
The present invention adopts electrochemical cathode reduction regulating YIN and YANG pole simultaneous oxidation coupling degradating chloro organic pollutant.Reaction principle is as follows:
1 anodic reaction mechanism
Can be there is Direct Electrochemistry reaction in pollutent, the strong oxidizing property active substance that anode can also be utilized to produce is (as OH, HO on the anode with catalytic activity
2deng) pollutent is changed, thus make organism generation oxidative degradation, after electrochemical reaction starts, the oxygen of anode surface absorption becomes the hydroxy radical qiao being adsorbed on anode surface and the Sauerstoffatom entered in oxide lattice respectively.Control certain anode voltage, the chlorion in waste water can be oxidized to chlorine 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
Electrochemical reduction dechlorinating process utilizes under the condition of electrochemical reducting reaction, make chlorine remove from chlorinatedorganic molecule.Compared with additive method, the reaction conditions of electrochemical reduction dechlorinating process is gentleer, and has higher selectivity and exploitativeness.When employing certain cathode material when controlling suitable reaction conditions, can evolving hydrogen reaction be there is in negative electrode, take electronics as strong reductant, realized the reduction of material by control electrode electromotive force, by chlorinatedorganic dechlorination wholly or in part, hydrogenation products that is nontoxic or low toxicity can be converted into.
(2) negative electrode indirect oxidation reaction
Negative electrode indirect oxidation is just referred at the hydrogen peroxide produced by cathodic reduction effect or ferrous ion and added regent generation class Fenton's reaction.Under the effect of the oxygen, H is generated in cathode surface generation reduction reaction
2o
2, H
2o
2be converted into HO in the basic conditions
2 -, and be decomposed into OH, O further
2 -, because it has very active character, without selectively reacting with the organism in water, and CO can be degraded to
2and H
2o, can not produce secondary pollution.
Compared with prior art, the invention has the beneficial effects as follows:
1. can either there is reductive dechlorination in the carbonaceous gas dispenser cathode carrying metal that the present invention adopts, indirect oxidation can occur again and generate H
2o
2, the effect of negative electrode can be made full use of, improve the efficiency of electrolysis treatment and reduce the energy consumption of reacting.
2. in the present invention, chlorinatedorganic degraded is in the cathodic compartment carried out in the basic conditions, and reaction process generates H
2o
2, and without the need to separately adding iron salt catalyst, which simplifies operation steps, reduce the expense of technique, decrease secondary pollution.
3. the present invention adopts electrochemical cathode reduction regulating YIN and YANG pole simultaneous oxidation coupling degradating chloro organic pollutant, first make chlorinatedorganic dechlorination detoxification by the reductive action of negative electrode, make its chlorion that dissociates from parent, and then make its mineralising by the oxygenizement co-treatment parent of anodic oxidation and cathode reduction products.This combination can give full play to the advantage of oxidation, reduction, chlorinatedorganic can be made effectively to be removed, and can improve removal efficiency.
4. the present invention adopts three-electrode system, the structure of two negative electrode list anodes can make full use of the oxygenizement of the reductive action regulating YIN and YANG pole of negative electrode, significantly improve the removal efficiency of chlorinatedorganic, and improve the treatment capacity of each run, further can also improve, apply to industrialized wastewater treatment.
Accompanying drawing explanation
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 position as shown in the figure, 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, to carry palladium multi-walled carbon nanotube electrode for negative electrode, adopts terylene diaphragm, processes 4-Chlorophenol.
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
2; Aeration rate is 25mL/s; Front 60min passes into hydrogen, and rear 60min passes into oxygen, processes the 4-Chlorophenol 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 finally reaches 93.27% (anode), 94.17% (negative electrode 2) and 93.87% (negative electrode 6) respectively; 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, to carry palladium Graphene gas diffusion electrode for negative electrode, adopts terylene diaphragm, processes 2,4-Dichlorophenol waste water.
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
2; Aeration rate is 25mL/s; Front 60min passes into hydrogen, and rear 60min passes into oxygen, processes 2, the 4-Dichlorophenol waste water of the 100mg/L of 100mL.
Through the degraded of 120min electrochemical redox, 2,4-Dichlorophenol transformation efficiencys in the anode chamber and the cathode chamber finally reach 94.25% (anode), 95.47% (negative electrode 2) and 95.18% (negative electrode 6) respectively; 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-Dichlorophenol is 92.8%.
Embodiment 3
In this example, two electrode devicies and multi-electrode device of the present invention is adopted to process, all with Ti/IrO 4-Chlorophenol respectively
2/ RuO
2electrode is anode, to carry palladium Graphene gas diffusion electrode for negative 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
2; Aeration rate is 25mL/s; Front 60min passes into hydrogen, and rear 60min passes into oxygen, processes the 4-Chlorophenol of the 100mg/L of 100mL.
Through the degraded of 120min electrochemical redox, two kinds of devices are as shown in table 1 to the transformation efficiency of 4-chlorophenol, TOC degradation rate and dechlorination rate result.
The removal effect of table 1 different device
Can find out, apparatus of the present invention have good treatment effect to chlorinatedorganic, and compared to two electrode devicies, electrolyzer of the present invention has larger dechlorination effect to chlorinatedorganic.
Explanation is with a portion of more than just to the preferred embodiment that can realize according to the present invention, as everyone knows, scope of the present invention should not be construed as and is limited to above embodiment, technological thought of the present invention described above be that the technological thought sent all should be within the scope of the present invention with this thought.
Claims (5)
1. the coefficient electrolyzer for removing chlorinatedorganic in water of multi-electrode, be made up of two cathode compartments (9,11), anolyte compartment (10), two gas compartments (1,7), two air inlet ports (8,13), two negative electrodes (2,6), anode (4), clamp (12) and two barrier films (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 separate by having the barrier film separating the two poles of the earth effect; There is Direct Electrochemistry reaction in described chlorinatedorganic and the strong oxidizing property active substance that utilizes anode to produce makes chlorinatedorganic generation oxidative degradation on anode; The chlorinatedorganic described in hydrogen peroxide degradation that described chlorinatedorganic reductive dechlorination occurs on negative electrode and utilizes cathodic reduction effect to produce.
2. the coefficient electrolyzer for removing chlorinatedorganic in water of a kind of multi-electrode according to claim 1, it is characterized in that its anode is for having oxygenizement electrode, negative electrode is the carbonaceous gas diffusion electrode carrying metal, with gas compartment and air inlet port on device.
3. the coefficient electrolyzer for removing chlorinatedorganic in water of a kind of multi-electrode according to claim 2, is characterized in that air inlet port will lead to 2 kinds of different gases as breather, for the previous period logical hydrogen, then blowing air or oxygen.
4. a kind of multi-electrode coefficient electrolyzer for remove in water chlorinatedorganic described arbitrarily according to claim 1-3, is characterized in that adopting electrochemical cathode reduction regulating YIN and YANG pole simultaneous oxidation coupling degradating chloro organic pollutant.
5. a kind of multi-electrode coefficient electrolyzer for remove in water chlorinatedorganic described arbitrarily according to claim 1-3, it is characterized in that the sodium sulfate that adds or other electrolytical concentration are 0.01 ~ 1.0mol/L, the time passing into gas with various is 40 ~ 180min, and control current density is 5 ~ 100mA/cm
2, aeration rate 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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| CN103288186B true CN103288186B (en) | 2015-06-17 |
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| CN104163478A (en) * | 2014-08-04 | 2014-11-26 | 陈致 | Emergency treatment method and emergency treatment device of organic micro-polluted drinking water |
| CN108439553B (en) * | 2018-04-20 | 2021-04-16 | 武汉大学 | Electrochemical oxidation device for removing chloride ions in water |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JPS60139384A (en) * | 1983-12-28 | 1985-07-24 | Tatsuo Okazaki | Apparatus for preparing electrolytic water |
| JP4899750B2 (en) * | 2006-09-26 | 2012-03-21 | パナソニック電工株式会社 | Electrolyzed water generator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
|---|
| Pd/C气体扩散电极用于电化学降解五氯酚钠的研究;王辉等;《环境科学》;20090228;第30卷(第2期);第601页第2段至第604页最后一段以及图1 * |
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