CN103318990A - 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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- CN103318990A CN103318990A CN201310279516XA CN201310279516A CN103318990A CN 103318990 A CN103318990 A CN 103318990A CN 201310279516X A CN201310279516X A CN 201310279516XA CN 201310279516 A CN201310279516 A CN 201310279516A CN 103318990 A CN103318990 A CN 103318990A
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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 present invention relates to the method for electrochemistry cathode catalysis ozone oxidation degraded organic pollutants, belong 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 the Sewage Plant secondary effluent, agricultural chemicals and organic chemical industry's pollutent, ozonation technology is owing to can effectively remove these organic micro-pollutantses and widespread use in worldwide.The hydroxyl radical free radical oxidation that ozonation technology is divided into direct ozone oxidation and indirectly produces removal of pollutants in actual water body, for with the higher material of ozone reaction activity such as phenol, amine, unsaturated hydro carbons material, the secondary rate constant k of itself and ozone reaction 10
3M
-1s
-1, mainly removed by the ozone direct oxidation; But for the dysoxidizable material (k＜10M of ozone
-1s
-1) such as atrazine, MTBE, then main by the indirect hydroxyl radical free radical oxidation removal that produces.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 both 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 the water, but the hydrogen peroxide that adds 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 efficient is subjected to water quality impact larger, and has useless consumption O
3Etc. problem; Heterogeneous catalyst such as metal oxide can obviously promote ozone decomposed to produce hydroxyl radical free radical, cause secondary pollution problems but can exist metal ion to leak; Owing to ultrasonic energy efficient hardening ozone decomposed proposes O
3/ ultrasonic advanced oxidation processes, but have the problem of high energy consumption.
In sum, have in the existing catalytic ozonation technology 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 objective of the invention is to solve have in the existing catalytic ozonation technology that catalyzer runs off in a large number, water quality impact is large, the problem of high energy consumption and difficult operation, and provides 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 finish according to the following steps: the water of pending Organic pollutants is injected 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 the dosage of ozone be 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage for+2.0V～-process 2min～40min under the 2.5V, namely finish the water treatment to pending Organic pollutants.
Advantage of the present invention: the present invention utilizes electrochemistry cathode catalysis ozone oxidation exposure chamber, dosage at ozone is under 0.1mg/mgTOC～100mg/mgTOC first, water body background component such as natural humus acid consume fast the ozone generation free radical and carry out the oxidative degradation organism, then the dosage of ozone be 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage for+2.0V～-finish the organic pollutants process of removing under the 2.5V, 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 generation hydroxyl radical free radical to strengthen the oxidation removal to organic pollutant.Electrochemistry cathode catalysis ozone oxidation process is to utilize the electrochemistry negative electrode that electronics is passed to ozone, produces the ozone free radical, and under the natural water body condition of water quality, ozone free radical fast decoupled produces hydroxyl radical free radical.This is a kind of take the high-level oxidation technology of ozone oxidation as the basis, can efficiently promote the 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 the ozone ozone decomposed to produce hydroxyl radical free radical, the organic matter removal rate has been improved 20%～50%), can in large-scale engineering, promote the use of.
Description of drawings
Fig. 1 is the structural representation of embodiment two described electrochemistry cathode catalysis ozone oxidation exposure chambers;
Fig. 2 is the structural representation of embodiment three described electrochemistry cathode catalysis ozone oxidation exposure chambers;
Fig. 3 is the structural representation of embodiment four described electrochemistry cathode catalysis ozone oxidation exposure chambers;
Fig. 4 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test one, and ■ represents to test the atrazine concentration-time curve figure of a simultaneous test among the figure;
Fig. 5 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test two, and ■ represents to test the atrazine concentration-time curve figure of two simultaneous tests among the figure;
Fig. 6 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test three, ■ represents to test the atrazine concentration-time curve figure of three simultaneous tests among the figure.
Embodiment
Embodiment one: present embodiment is the method that electrochemistry cathode catalysis ozone oxidation is removed organic pollutants, specifically finish according to the following steps: the water of pending Organic pollutants is injected 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 the dosage of ozone be 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage for+2.0V～-process 2min～40min under the 2.5V, namely finish the water treatment to pending Organic pollutants.
Present embodiment is utilized electrochemistry cathode catalysis ozone oxidation exposure chamber, be that water body background component such as natural humus acid consume fast the ozone generation free radical and carry out the oxidative degradation organism under 0.1mg/mgTOC～100mg/mgTOC at the dosage of ozone first, then the dosage of ozone be 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage for+2.0V～-finish under the 2.5V and remove the organic pollutants process in last stage fast and after the material of ozone reaction is consumed, ozone decomposed is slow, just need to utilize katalysis to promote ozone decomposed generation hydroxyl radical free radical to strengthen the oxidation removal to organic pollutant.Electrochemistry cathode catalysis ozone oxidation process is to utilize the electrochemistry negative electrode that electronics is passed to ozone, produces the ozone free radical, and under the natural water body condition of water quality, ozone free radical fast decoupled produces hydroxyl radical free radical.This is a kind of take the high-level oxidation technology of ozone oxidation as the basis, can efficiently promote the 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 the ozone ozone decomposed to produce hydroxyl radical free radical, the organic matter removal rate has been improved 20%～50%), can in large-scale engineering, promote the use of.
Mg/mgTOC is that unit is that how much mg ozone every mgTOC adds, 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, at ozone contact chamber 3 bottom centre place water-in 1 is set, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, with anode 7 interior, negative electrode 8 form outside is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, with cathode electrode voltage transfer to into+2.0V～-2.5V, continuation is processed 2min～40min in ozone contact chamber 3 after, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
The described negative electrode 8 of 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 the 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, at ozone contact chamber 3 bottom centre place water-in 1 is set, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, descending with anode 7, negative electrode 8 is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3 in upper form, porous barrier 9 is arranged in the ozone contact chamber 3, between anode 7 and the negative electrode 8, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, with cathode electrode voltage transfer to into+2.0V～-2.5V, continuation is processed 2min～40min in ozone contact chamber 3 after, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
The described negative electrode 8 of 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 the 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, at ozone contact chamber 3 bottom centre place water-in 1 is set, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, with anode 7 outside, negative electrode 8 is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3 in interior form, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively.Other are identical with embodiment one.
Principle of work: the ozone contact chamber 3 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 0.1mg/mgTOC～100mg/mgTOC, in ozone contact chamber 3, process 10s～20min, restart constant voltage power supply 4, with cathode electrode voltage transfer to into+2.0V～-2.5V, continuation is processed 2min～40min in ozone contact chamber 3 after, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
The described negative electrode 8 of 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 the 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.Other are identical with embodiment four.
Embodiment eight: the difference of present embodiment and embodiment two is: 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined 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: 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined 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: 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined 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 finish according to the following steps: the water of pending Organic pollutants is injected electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under the 2mg/mgTOC at the dosage of ozone, then being 2mg/mgTOC and cathode electrode voltage at the dosage of ozone processes 13min under+the 0.5V, namely finishes the water treatment to pending Organic pollutants.
This is tested described electrochemistry cathode catalysis ozone oxidation exposure chamber and 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, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, with anode 7 interior, negative electrode 8 form outside is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively; 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 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is transferred to be+0.5V, after continuing in ozone contact chamber 3, to process 13min, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
This water of testing described pending Organic pollutants is that atrazine concentration is the water of 100ng/L.
Test a simultaneous test: transfer under the 2mg/mgTOC water to pending Organic pollutants at the dosage of ozone and process, process 15min.
Because treatment process changes, then corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is the correlation detection data.
Be recorded in the concentration of atrazine concentration in 0～15min, as shown in Figure 4, Fig. 4 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test one, and ■ represents the atrazine concentration-time curve figure of simultaneous test among the figure; After testing 15min as shown in Figure 4, the concentration of atrazine is 40.1ng/L in the water of the Organic pollutants after test one is processed by water outlet 2 discharges; The concentration of atrazine is 61.0ng/L in the water of the Organic pollutants after simultaneous test is processed, and as calculated as can be known: 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 finish according to the following steps: the water of pending Organic pollutants is injected electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under the 2mg/mgTOC at the dosage of ozone, then being 2mg/mgTOC and cathode electrode voltage at the dosage of ozone processes 13min under+the 0.4V, namely finishes the water treatment to pending Organic pollutants.
The water of pending Organic pollutants is injected the ozone contact chamber 3 of electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5 and constant voltage power supply 4, the dosage of ozone is transferred to 2mg/mgTOC, cathode electrode voltage transfers to and is+0.4V, after in ozone contact chamber 3, processing 15min, discharged the water of the Organic pollutants after processing by water outlet 2, namely finish the water treatment to pending Organic pollutants.
This is tested described electrochemistry cathode catalysis ozone oxidation exposure chamber and 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, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, descending with anode 7, negative electrode 8 is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3 in upper form, porous barrier 9 is arranged in the ozone contact chamber 3, between anode 7 and the negative electrode 8, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively; Described negative electrode 8 is porous graphite fixed bed electrodes; Described anode 7 is the POROUS TITANIUM PLATE electrode.
Principle of work: the ozone contact chamber 3 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is transferred to be+0.4V, after continuing in ozone contact chamber 3, to process 13min, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
This water of testing described pending Organic pollutants is that atrazine concentration is the water of 100ng/L.
Test two simultaneous tests: transfer under the 2mg/mgTOC water to pending Organic pollutants at the dosage of ozone and process, process 15min.
Because treatment process changes, then corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is the correlation detection data.
Be recorded in the concentration of atrazine concentration in 0～15min, as shown in Figure 5, Fig. 5 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test two, and ■ represents the atrazine concentration-time curve figure of simultaneous test among the figure; After testing 15min as shown in Figure 5, the concentration of atrazine is 8.7ng/L in the water of the Organic pollutants after test two is processed by water outlet 2 discharges; The concentration of atrazine is 61.0ng/L in the water of the Organic pollutants after simultaneous test is processed, and as calculated as can be known: 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 about 89% 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 finish according to the following steps: the water of pending Organic pollutants is injected electrochemistry cathode catalysis ozone oxidation exposure chamber, then adopt ozone saturated solution mode to add ozone, and be to process 2min under the 2mg/mgTOC at the dosage of ozone, then being 2mg/mgTOC and cathode electrode voltage at the dosage of ozone processes 13min under+the 0.6V, namely finishes the water treatment to pending Organic pollutants.
This is tested described electrochemistry cathode catalysis ozone oxidation exposure chamber and 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, 3 side wall upper part set out the mouth of a river 2 in the ozone contact chamber, 3 top center places arrange ozone outlet 6 in the ozone contact chamber, with anode 7 outside, negative electrode 8 is arranged on anode 7 and negative electrode 8 in the ozone contact chamber 3 in interior form, ozone diffuser 5 is arranged in the ozone contact chamber 3, and anode 7 is connected with negative electrode and is connected with negative pole with the positive pole of constant voltage power supply respectively; Described negative electrode 8 is triflux bed electrodes; Described anode 7 is the graphite cake electrode, and described negative electrode 8 is carbon fiber electrode.
Principle of work: the ozone contact chamber 3 of the water of pending Organic pollutants being injected electrochemistry cathode catalysis ozone oxidation exposure chamber by water-in 1, then start ozone diffuser 5, the dosage of ozone is transferred to 2mg/mgTOC, in ozone contact chamber 3, process 2min, restart constant voltage power supply 4, cathode electrode voltage is transferred to be+0.6V, after continuing in ozone contact chamber 3, to process 13min, discharged the water of the Organic pollutants after processing by water outlet 2, discharge ozone tail gas by ozone outlet 6.
This water of testing described pending Organic pollutants is that atrazine concentration is the water of 100ng/L.
Test three simultaneous tests: transfer under the 2mg/mgTOC water to pending Organic pollutants at the dosage of ozone and process, process 15min.
Because treatment process changes, then corresponding atrazine concentration-time curve figure also should change, and therefore please revise detection figure is the correlation detection data.
Be recorded in the concentration of atrazine concentration in 0～15min, as shown in Figure 6, Fig. 6 is atrazine concentration-time curve figure, among the figure ● the atrazine concentration-time curve figure of expression test three, and ■ represents the atrazine concentration-time curve figure of simultaneous test among the figure; After testing 15min as shown in Figure 6, the concentration of atrazine is 18.2ng/L in the water of the Organic pollutants after test three is processed by water outlet 2 discharges; The concentration of atrazine is 61.0ng/L in the water of the Organic pollutants after simultaneous test is processed, and as calculated as can be known: 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 about 72% 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 (10)
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 is finished according to the following steps: the water of pending Organic pollutants is injected 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 the dosage of ozone be 0.1mg/mgTOC～100mg/mgTOC and cathode electrode voltage for+2.0V～-process 2min～40min under the 2.5V, namely finish the water treatment to pending Organic pollutants.
2. electrochemistry cathode catalysis ozone oxidation according to claim 1 is removed the method for organic pollutants, it is characterized in that 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, side wall upper part sets out the mouth of a river (2) in ozone contact chamber (3), the top center place arranges ozone outlet (6) in ozone contact chamber (3), with anode (7) interior, negative electrode (8) form outside is arranged on anode (7) and negative electrode (8) in the ozone contact chamber (3), ozone diffuser (5) is arranged in the ozone contact chamber (3), and anode (7) is connected 8 with negative electrode) be connected with negative pole with the positive pole of constant voltage power supply respectively.
3. electrochemistry cathode catalysis ozone oxidation according to claim 1 is removed the method for organic pollutants, it is characterized in that 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, side wall upper part sets out the mouth of a river (2) in ozone contact chamber (3), the top center place arranges ozone outlet (6) in ozone contact chamber (3), descending with anode (7), negative electrode (8) is arranged on anode (7) and negative electrode (8) in the ozone contact chamber (3) in upper form, porous barrier (9) is arranged in the ozone contact chamber (3), between anode (7) and the negative electrode (8), ozone diffuser (5) is arranged in the ozone contact chamber (3), and anode (7) is connected 8 with negative electrode) be connected with negative pole with the positive pole of constant voltage power supply respectively.
4. electrochemistry cathode catalysis ozone oxidation according to claim 1 is removed the method for organic pollutants, it is characterized in that 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, side wall upper part sets out the mouth of a river (2) in ozone contact chamber (3), the top center place arranges ozone outlet (6) in ozone contact chamber (3), with anode (7) outside, negative electrode (8) is arranged on anode (7) and negative electrode (8) in the ozone contact chamber (3) in interior form, ozone diffuser (5) is arranged in the ozone contact chamber (3), and anode (7) is connected 8 with negative electrode) be connected with negative pole with the positive pole of constant voltage power supply respectively.
5. electrochemistry cathode catalysis ozone oxidation according to claim 2 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.
6. electrochemistry cathode catalysis ozone oxidation according to claim 2 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.
7. electrochemistry cathode catalysis ozone oxidation according to claim 3 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.
8. electrochemistry cathode catalysis ozone oxidation according to claim 3 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined electrode, reticulated vitreous carbon electrodes, Graphite Electrodes, carbon nanotube electrode, active carbon electrode, activated carbon/polytetrafluoroethylene electrode, titanium-matrix electrode or stainless steel electrode.
9. electrochemistry cathode catalysis ozone oxidation according to claim 4 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is titanium-matrix electrode or Graphite Electrodes in the described combined electrode.
10. electrochemistry cathode catalysis ozone oxidation according to claim 4 is removed the method for organic pollutants, it is characterized in that 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, metal is ruthenium in the described metal oxide, 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, metal is ruthenium in the described metal hydroxides, 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 electrode is carbon fiber electrode in the described combined 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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