CN103318990B - Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation - Google Patents
Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation Download PDFInfo
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Abstract
The invention discloses a method for removing organic pollutants in water through electrochemical cathode catalytic ozonation, and relates to a method for degrading organic pollutants in water through electrochemical cathode catalytic ozonation and belonging to the field of water treatment. The method disclosed by the invention aims at solving the problems of an existing catalytic ozonation technology of high loss of catalyst, great influence on water quality, high energy consumption and difficulty in operation. The method comprises the following steps of: pouring the to-be-treated water with organic pollution into an electrochemical cathode catalytic ozonation contact chamber; adding ozone in an ozone aeration mode or ozone saturated solution mode; performing primary treatment at certain ozone dosage; treating at certain ozone dosage and cathode voltage to finish treatment of the to-be-treated water with organic pollution. Compared with independent ozone treatment, the method can be used for improving the removal rate of organic matters by 20-50%, and is mainly used for treating the water with organic pollution.
Description
Technical field
The method that the present invention relates to electrochemistry cathode catalysis ozone oxidation degraded organic pollutants, belongs to water treatment field.
Background technology
In recent years, for the endocrine disrupter, medicine and the personal-care supplies that frequently detect in surface water and Sewage Plant secondary effluent, agricultural chemicals and organic chemical industry's pollutent, ozonation technology widespread use in worldwide owing to effectively removing these organic micro-pollutantses.The hydroxyl radical free radical oxidation that ozonation technology is divided into direct ozone oxidation to the removal of pollutent and indirectly produces in actual water body, for with the higher material of ozone reaction activity as phenol, amine, unsaturated hydro carbons material, the secondary rate constant k>10 of itself and ozone reaction
3m
-1s
-1, mainly by ozone direct oxidation, removed; But for the dysoxidizable material (k<10M of ozone
-1s
-1) as atrazine, MTBE, main by the hydroxyl radical free radical oxidation removal indirectly producing.In order more effectively to remove the difficult oxidizing substance of ozone, a lot of methods are used to promote ozone decomposed to produce hydroxyl radical free radical, as with hydrogen peroxide, use heterogeneous catalyst, UV/O
3, O
3/ ultrasonic etc.
Although existing catalytic ozonation technology can effectively promote ozone decomposed to produce hydroxyl radical free radical, all there are pros and cons.O
3/ H
2o
2technique is widely used in the degraded of hardly degraded organic substance in water, but the hydrogen peroxide adding can not effectively utilize, and is remained in a large number, can affect follow-up BAC process or affect follow-up sterilization process owing to consuming chlorine residue; UV/O
3technique has the advantages such as easy control simple to operate, but UV photon absorption efficiency is subject to water quality impact larger, and has useless consumption O
3etc. problem; Heterogeneous catalyst produces hydroxyl radical free radical as metal oxide can obviously promote ozone decomposed, but can exist metal ion to leak, causes secondary pollution problems; Because ultrasonic energy efficient hardening ozone decomposed proposes O
3/ ultrasonic advanced oxidation processes, but there is the problem of high energy consumption.
In sum, in existing catalytic ozonation technology, have that catalyzer runs off in a large number, water quality impact is large, the problem of high energy consumption and difficult operation.
Summary of the invention
The object of the invention is to solve in existing catalytic ozonation technology, have that catalyzer runs off in a large number, water quality impact is large, the problem of high energy consumption and difficult operation, and provide electrochemistry cathode catalysis ozone oxidation to remove the method for organic pollutants.
Electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, specifically complete according to the following steps: the water of pending Organic pollutants is injected to electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone gas aeration mode or ozone saturated solution mode to add ozone, and be to process 10s～20min under 0.1mg/mgTOC～100mg/mgTOC at the dosage of ozone, then at the dosage of ozone, being 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage processes 2min～40min under+2.0V～-2.5V, complete the water treatment to pending Organic pollutants.
Advantage of the present invention: the present invention utilizes electrochemistry cathode catalysis ozone oxidation exposure chamber, first the dosage at ozone is under 0.1mg/mgTOC～100mg/mgTOC, water body background component carries out oxidative degradation organism as natural humus acid consumes ozone generation free radical fast, then at the dosage of ozone, being 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage completes under+2.0V～-2.5V the organic pollutants process of removing, after material quick in the last stage and ozone reaction is consumed, ozone decomposed is slow, just need to utilize katalysis to promote ozone decomposed to produce hydroxyl radical free radical and strengthen the oxidation removal to organic pollutant.Electrochemistry cathode catalysis ozone oxidation process is to utilize electrochemistry negative electrode that electronics is passed to ozone, produces ozone free radical, and under natural water body condition of water quality, ozone free radical fast decoupled produces hydroxyl radical free radical.This is a kind ofly to take ozone oxidation as basic high-level oxidation technology, can efficiently promote ozone decomposed degradable organic pollutant, and the method applying flexible, cost is cheap, easy and simple to handle, processing efficiency is high (compares with independent ozonize, can obviously promote ozone ozone decomposed to produce hydroxyl radical free radical, organic clearance has been improved to 20%～50%), can in large-scale engineering, promote the use of.
Accompanying drawing explanation
Fig. 1 is the structural representation of the electrochemistry cathode catalysis ozone oxidation exposure chamber described in embodiment two;
Fig. 2 is the structural representation of the electrochemistry cathode catalysis ozone oxidation exposure chamber described in embodiment three;
Fig. 3 is the structural representation of the electrochemistry cathode catalysis ozone oxidation exposure chamber described in embodiment four;
Fig. 4 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test one, in figure, ■ represents to test the atrazine concentration-time curve figure of a simultaneous test;
Fig. 5 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test two, in figure, ■ represents to test the atrazine concentration-time curve figure of two simultaneous tests;
Fig. 6 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test three, in figure, ■ represents to test the atrazine concentration-time curve figure of three simultaneous tests.
Embodiment
Embodiment one: present embodiment is the method that electrochemistry cathode catalysis ozone oxidation is removed organic pollutants, specifically complete according to the following steps: the water of pending Organic pollutants is injected to electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone gas aeration mode or ozone saturated solution mode to add ozone, and be to process 10s～20min under 0.1mg/mgTOC～100mg/mgTOC at the dosage of ozone, then at the dosage of ozone, being 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage processes 2min～40min under+2.0V～-2.5V, complete the water treatment to pending Organic pollutants.
Present embodiment is utilized electrochemistry cathode catalysis ozone oxidation exposure chamber, first the dosage at ozone is that under 0.1mg/mgTOC～100mg/mgTOC, water body background component carries out oxidative degradation organism as natural humus acid consumes ozone generation free radical fast, then at the dosage of ozone, being 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage removes organic pollutants process in the last stage fast and after the material of ozone reaction is consumed for completing under+2.0V～-2.5V, ozone decomposed is slow, just need to utilize katalysis to promote ozone decomposed to produce hydroxyl radical free radical and strengthen the oxidation removal to organic pollutant.Electrochemistry cathode catalysis ozone oxidation process is to utilize electrochemistry negative electrode that electronics is passed to ozone, produces ozone free radical, and under natural water body condition of water quality, ozone free radical fast decoupled produces hydroxyl radical free radical.This is a kind ofly to take ozone oxidation as basic high-level oxidation technology, can efficiently promote ozone decomposed degradable organic pollutant, and the method applying flexible, cost is cheap, easy and simple to handle, processing efficiency is high (compares with independent ozonize, can obviously promote ozone ozone decomposed to produce hydroxyl radical free radical, organic clearance has been improved to 20%～50%), can in large-scale engineering, promote the use of.
Mg/mgTOC is that unit is that every mgTOC adds how many mg ozone, and described TOC refers to total organic carbon.
Embodiment two: in conjunction with Fig. 1, the difference of present embodiment and embodiment one is: described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7 and negative electrode 8, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 interior, negative electrode 8 form is outside arranged on anode 7 and negative electrode 8 in ozone contact chamber 3, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
Negative electrode 8 described in present embodiment is covered with whole space reactor, and such negative electrode has advantages of that specific surface area is large, mass-transfer efficiency is high and current efficiency is high, can promote ozone decomposed degradable organic pollutant, improves processing efficiency.
Embodiment three: in conjunction with Fig. 2, the difference of present embodiment and embodiment one is: described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7, negative electrode 8 and porous barrier 9, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 under, negative electrode 8 is arranged on anode 7 and negative electrode 8 in ozone contact chamber 3 in upper form, porous barrier 9 is arranged in ozone contact chamber 3, between anode 7 and negative electrode 8, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
Negative electrode 8 described in present embodiment is fixed bed electrodes, and such negative electrode has advantages of that specific surface area is large, mass-transfer efficiency is high and current efficiency is high, can promote ozone decomposed degradable organic pollutant, improves processing efficiency.
Embodiment four: in conjunction with Fig. 3, the difference of present embodiment and embodiment one is: described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7 and negative electrode 8, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 outside, negative electrode 8 is arranged on anode 7 and negative electrode 8 in ozone contact chamber 3 in interior form, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
Negative electrode 8 described in present embodiment is thermopnore electrodes, and such negative electrode has advantages of that specific surface area is large, mass-transfer efficiency is high and current efficiency is high, can promote ozone decomposed degradable organic pollutant, improves processing efficiency.
Embodiment five: the difference of present embodiment and embodiment two is: the combined electrode electrode that described anode 7 is modified for one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes.Other are identical with embodiment two.
Embodiment six: the difference of present embodiment and embodiment three is: the combined electrode electrode that described anode 7 is modified for one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes.Other are identical with embodiment three.
Embodiment seven: the difference of present embodiment and embodiment four is: the combined electrode electrode that described anode 7 is modified for one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes.Other are identical with embodiment four.
Embodiment eight: the difference of present embodiment and embodiment two is: electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or combined electrode that described negative electrode 8 is stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.Other are identical with embodiment two.
Embodiment nine: the difference of present embodiment and embodiment three is: electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or combined electrode that described negative electrode 8 is stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.Other are identical with embodiment three.
Embodiment ten: the difference of present embodiment and embodiment four is: electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or combined electrode that described negative electrode 8 is stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.Other are identical with embodiment four.
Adopt following verification experimental verification effect of the present invention:
Test one: in conjunction with Fig. 1, electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, specifically complete according to the following steps: the water of pending Organic pollutants is injected to electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under 2mg/mgTOC at the dosage of ozone, then at the dosage of ozone, being 2mg/mgTOC and cathode electrode voltage processes 13min under+0.5V, completes the water treatment to pending Organic pollutants.
The described electrochemistry cathode catalysis ozone oxidation exposure chamber of this experiment comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7 and negative electrode 8, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 interior, negative electrode 8 form is outside arranged on anode 7 and negative electrode 8 in ozone contact chamber 3, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8, described negative electrode 8 is dendroid electrodes that Stainless Steel Wire is made, and is covered with whole space reactor, described anode 7 is RuO
2/ titanium pipe electrode.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+0.5V, continue to process after 13min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
The water of the pending Organic pollutants that this experiment is described is that atrazine concentration is the water of 100ng/L.
Test a simultaneous test: at the dosage of ozone, be adjusted to the water to pending Organic pollutants under 2mg/mgTOC and process, process 15min.
Because treatment process changes, corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is correlation detection data.
The concentration that is recorded in atrazine concentration in 0～15min, as shown in Figure 4, Fig. 4 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test one, in figure, ■ represents the atrazine concentration-time curve figure of simultaneous test; Test as shown in Figure 4 after 15min, in the water that test one is discharged the Organic pollutants after processing by water outlet 2, the concentration of atrazine is 40.1ng/L; In the water of the Organic pollutants after simultaneous test is processed, the concentration of atrazine is 61.0ng/L, known as calculated: compare with independent ozonize, the clearance of testing a pair of atrazine has improved 20.9%, has greatly improved the removal to atrazine; So proof adopts method provided by the invention to process the water of Organic pollutants, can improve processing efficiency.
Test two: in conjunction with Fig. 2, electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, specifically complete according to the following steps: the water of pending Organic pollutants is injected to electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under 2mg/mgTOC at the dosage of ozone, then at the dosage of ozone, being 2mg/mgTOC and cathode electrode voltage processes 13min under+0.4V, completes the water treatment to pending Organic pollutants.
Ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5 and constant voltage power supply 4, the dosage of ozone is adjusted to 2mg/mgTOC, cathode electrode voltage is adjusted to as+0.4V, in ozone contact chamber 3, process after 15min, the water of being discharged the Organic pollutants after processing by water outlet 2, completes the water treatment to pending Organic pollutants.
The described electrochemistry cathode catalysis ozone oxidation exposure chamber of this experiment comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7, negative electrode 8 and porous barrier 9, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 under, negative electrode 8 is arranged on anode 7 and negative electrode 8 in ozone contact chamber 3 in upper form, porous barrier 9 is arranged in ozone contact chamber 3, between anode 7 and negative electrode 8, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8, described negative electrode 8 is porous graphite fixed bed electrodes, described anode 7 is POROUS TITANIUM PLATE electrode.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+0.4V, continue to process after 13min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
The water of the pending Organic pollutants that this experiment is described is that atrazine concentration is the water of 100ng/L.
Test two simultaneous tests: at the dosage of ozone, be adjusted to the water to pending Organic pollutants under 2mg/mgTOC and process, process 15min.
Because treatment process changes, corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is correlation detection data.
The concentration that is recorded in atrazine concentration in 0～15min, as shown in Figure 5, Fig. 5 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test two, in figure, ■ represents the atrazine concentration-time curve figure of simultaneous test; Test as shown in Figure 5 after 15min, in the water that test two is discharged the Organic pollutants after processing by water outlet 2, the concentration of atrazine is 8.7ng/L; In the water of the Organic pollutants after simultaneous test is processed, the concentration of atrazine is 61.0ng/L, known as calculated: compare with independent ozonize, the clearance of two pairs of atrazines of test has improved 52.3%, has greatly improved the removal to atrazine; And after processing 10min, the clearance of two pairs of atrazines of test just reaches 89% left and right as shown in Figure 5; So proof adopts method provided by the invention to process the water of Organic pollutants, can improve processing efficiency.
Test three: in conjunction with Fig. 3, electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, specifically complete according to the following steps: the water of pending Organic pollutants is injected to electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under 2mg/mgTOC at the dosage of ozone, then at the dosage of ozone, being 2mg/mgTOC and cathode electrode voltage processes 13min under+0.6V, completes the water treatment to pending Organic pollutants.
The described electrochemistry cathode catalysis ozone oxidation exposure chamber of this experiment comprises water-in 1, water outlet 2, ozone contact chamber 3, constant voltage power supply 4, ozone diffuser 5, ozone outlet 6, anode 7 and negative electrode 8, in ozone contact chamber, 3 bottom centre places arrange water-in 1, in ozone contact chamber, 3 side wall upper part set out the mouth of a river 2, in ozone contact chamber, 3 top center places arrange ozone outlet 6, with anode 7 outside, negative electrode 8 is arranged on anode 7 and negative electrode 8 in ozone contact chamber 3 in interior form, ozone diffuser 5 is arranged in ozone contact chamber 3, anode 7 is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode 8, described negative electrode 8 is triflux bed electrodes, described anode 7 is graphite cake electrode, and described negative electrode 8 is carbon fiber electrode.
Principle of work: the ozone contact chamber 3 by the water of pending Organic pollutants by water-in 1 injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser 5, the dosage of ozone is adjusted to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is adjusted to as+0.6V, continue to process after 13min in ozone contact chamber 3, by water outlet 2, discharged the water of the Organic pollutants after processing, by ozone outlet 6, discharge ozone tail gas.
The water of the pending Organic pollutants that this experiment is described is that atrazine concentration is the water of 100ng/L.
Test three simultaneous tests: at the dosage of ozone, be adjusted to the water to pending Organic pollutants under 2mg/mgTOC and process, process 15min.
Because treatment process changes, corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is correlation detection data.
The concentration that is recorded in atrazine concentration in 0～15min, as shown in Figure 6, Fig. 6 is atrazine concentration-time curve figure, in figure ● represent the atrazine concentration-time curve figure of test three, in figure, ■ represents the atrazine concentration-time curve figure of simultaneous test; Test as shown in Figure 6 after 15min, in the water that test three is discharged the Organic pollutants after processing by water outlet 2, the concentration of atrazine is 18.2ng/L; In the water of the Organic pollutants after simultaneous test is processed, the concentration of atrazine is 61.0ng/L, known as calculated: compare with independent ozonize, the clearance of three pairs of atrazines of test has improved 42.8%, has greatly improved the removal to atrazine; And after processing 6min, the clearance of three pairs of atrazines of test just reaches 72% left and right as shown in Figure 6; So proof adopts method provided by the invention to process the water of Organic pollutants, can improve processing efficiency.
Claims (3)
1. electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, the method that it is characterized in that electrochemistry cathode catalysis ozone oxidation removal organic pollutants completes according to the following steps: the ozone contact chamber (3) by the water of pending Organic pollutants by water-in (1) injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser (5), the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber (3), process 10s～20min, restart constant voltage power supply (4), cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber (3), by water outlet (2), discharged the water of the Organic pollutants after processing, by ozone outlet (6), discharge ozone tail gas,
Described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in (1), water outlet (2), ozone contact chamber (3), constant voltage power supply (4), ozone diffuser (5), ozone outlet (6), anode (7) and negative electrode (8), at ozone contact chamber (3) bottom centre place, water-in (1) is set, in ozone contact chamber (3), side wall upper part sets out the mouth of a river (2), in ozone contact chamber (3), top center place arranges ozone outlet (6), with anode (7) interior, negative electrode (8) form is outside arranged on anode (7) and negative electrode (8) in ozone contact chamber (3), ozone diffuser (5) is arranged in ozone contact chamber (3), anode (7) is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode (8),
Described negative electrode (8) is covered with whole space reactor;
Described anode (7) is the combined electrode electrode that one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides is modified, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes,
Described negative electrode (8) is electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or the combined electrode of stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.
2. electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, the method that it is characterized in that electrochemistry cathode catalysis ozone oxidation removal organic pollutants completes according to the following steps: the ozone contact chamber (3) by the water of pending Organic pollutants by water-in (1) injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser (5), the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber (3), process 10s～20min, restart constant voltage power supply (4), cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber (3), by water outlet (2), discharged the water of the Organic pollutants after processing, by ozone outlet (6), discharge ozone tail gas,
Described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in (1), water outlet (2), ozone contact chamber (3), constant voltage power supply (4), ozone diffuser (5), ozone outlet (6), anode (7), negative electrode (8) and porous barrier (9), at ozone contact chamber (3) bottom centre place, water-in (1) is set, in ozone contact chamber (3), side wall upper part sets out the mouth of a river (2), in ozone contact chamber (3), top center place arranges ozone outlet (6), with anode (7) under, negative electrode (8) is arranged on anode (7) and negative electrode (8) in ozone contact chamber (3) in upper form, porous barrier (9) is arranged in ozone contact chamber (3), between anode (7) and negative electrode (8), ozone diffuser (5) is arranged in ozone contact chamber (3), anode (7) is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode (8),
Described negative electrode (8) is fixed bed electrode;
Described anode (7) is the combined electrode electrode that one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides is modified, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes,
Described negative electrode (8) is electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or the combined electrode of stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.
3. electrochemistry cathode catalysis ozone oxidation is removed the method for organic pollutants, the method that it is characterized in that electrochemistry cathode catalysis ozone oxidation removal organic pollutants completes according to the following steps: the ozone contact chamber (3) by the water of pending Organic pollutants by water-in (1) injection electrochemistry cathode catalysis ozone oxidation exposure chamber, then start ozone diffuser (5), the dosage of ozone is adjusted to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber (3), process 10s～20min, restart constant voltage power supply (4), cathode electrode voltage is adjusted to as+2.0V～-2.5V, continuation is processed after 2min～40min in ozone contact chamber (3), by water outlet (2), discharged the water of the Organic pollutants after processing, by ozone outlet (6), discharge ozone tail gas,
Described electrochemistry cathode catalysis ozone oxidation exposure chamber comprises water-in (1), water outlet (2), ozone contact chamber (3), constant voltage power supply (4), ozone diffuser (5), ozone outlet (6), anode (7) and negative electrode (8), at ozone contact chamber (3) bottom centre place, water-in (1) is set, in ozone contact chamber (3), side wall upper part sets out the mouth of a river (2), in ozone contact chamber (3), top center place arranges ozone outlet (6), with anode (7) outside, negative electrode (8) is arranged on anode (7) and negative electrode (8) in ozone contact chamber (3) in interior form, ozone diffuser (5) is arranged in ozone contact chamber (3), anode (7) is connected with negative pole with the positive pole of constant voltage power supply respectively with negative electrode (8),
Described negative electrode (8) is thermopnore electrode;
Described anode (7) is the combined electrode electrode that one or more mixture of diamond film electrode, Graphite Electrodes, metal electrode or metal/metal oxide/metal hydroxides is modified, wherein said Graphite Electrodes is graphite silk electrode, graphite cake electrode, graphite felt electrode, granular graphite electrode or graphite rod electrode, wherein said metal electrode is platinum electrode, titanium electrode, and described titanium electrode is titanium silk electrode, titanium plate electrode or titanium bar electrode, the combined electrode electrode that one or more mixture of wherein said metal/metal oxide/metal hydroxides is modified is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is titanium-matrix electrode or Graphite Electrodes,
Described negative electrode (8) is electrode, carbon fiber electrode, carbon nanomaterial electrode, reticulated vitreous carbon electrodes, Graphite Electrodes or the combined electrode of stainless steel electrode, titanium material electrode, active carbon material, wherein said stainless steel electrode is Stainless Steel Wire electrode, stainless steel plate electrode or stainless steel grit electrode, wherein said titanium material electrode is titanium silk electrode, titanium plate electrode or titanium grain electrode, and the electrode of wherein said active carbon material is active carbon granule electrode, activated carbon/polytetrafluoroethylene electrode, carbon pipe electrode, carbon electrode, carbon sponge electrode or porous active carbon dioxide process carbon electrode, wherein said carbon fiber electrically is carbon fiber cloth electrode, carbon fiber felt electrode, carbon fiber wire electrode, carbon fiber paper electrode or carbon fiber sponge electrode very, wherein said carbon nanomaterial electrode is carbon nanotube electrode, soccerballene electrode, carbon nano-tube/poly tetrafluoroethylene electrode or soccerballene/polytetrafluoroethylene electrode, wherein said Graphite Electrodes is graphite rod electrode, graphite silk electrode, graphite felt electrode, graphite cake electrode, graphite sponge electrode, granular graphite electrode or porous graphite electrode, wherein said combined electrode is for utilizing metal, the combined electrode that one or more mixture of metal oxide and metal hydroxides is modified, and described metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal oxide, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, in described metal hydroxides, metal is ruthenium, tin, plumbous, iridium, titanium, tungsten, manganese, iron, pick, niobium, cobalt, nickel, zinc, silver, palladium, rhodium, molybdenum, platinum, cerium, europium, yttrium, rhenium, neodymium, indium, gadolinium or dysprosium, and in described combined electrode, electrode is carbon fiber electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.
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