CN104326530A - Device and method for performing oxidation treatment on sewage by cooperating pipeline type electric catalysis with ozone - Google Patents
Device and method for performing oxidation treatment on sewage by cooperating pipeline type electric catalysis with ozone Download PDFInfo
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- CN104326530A CN104326530A CN201410645142.3A CN201410645142A CN104326530A CN 104326530 A CN104326530 A CN 104326530A CN 201410645142 A CN201410645142 A CN 201410645142A CN 104326530 A CN104326530 A CN 104326530A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
The invention belongs to the technical field of electrochemical sewage treatment and particularly relates to a device and a method for performing oxidation treatment on sewage by cooperating pipeline type electric catalysis with ozone. In a sealed pipeline type reactor, the device is equipped with a tubular anode electrode, a cathode electrode and an aerator tube from the outside to the inside in sequence, wherein the anode electrode, the cathode electrode and the aerated tube are respectively arranged along the axial direction of a pipeline of the closed pipeline type reactor, so that the aeration in the closed pipeline type reactor is uniformly distributed. According to the device and the method disclosed by the invention, the cathode electrode is used for converting Cl<-> in the sewage into other strong oxidant particles, such as HClO and ClO<-> to perform direct or indirect oxidization treatment on sewage organic substances; O2 in aeration reacts with water on the cathode electrode to produce H2O2, the H2O2 reacts with the O3 in the aeration to produce a hydroxyl free group.OH which cooperates with the anode electrode to degrade organic substances. The device and the method disclosed by the invention can be applied to a pipeline sewage conveying process, small in floor space, high in efficiency, free of secondary pollution, and capable of improving the biochemical property of degradation-resistant sewage and has a relatively high denitrification function.
Description
Technical field
The invention belongs to electrochemistry technical field of sewage, particularly the device and method of a kind of duct type electrocatalysis and ozone cooperative oxidation sewage treatment.
Background technology
In China's industrial park development rapidly, the centralized biochemical process pattern of the many employings in industrial park processes garden waste water.Be difficult to up to standard containing the effluent quality after the organic sewage disposal of bio-refractory, complicated water quality, cause the water pollutions in China basin day by day serious, therefore, industrial park waste water advanced treatment becomes environment difficulties urgently to be resolved hurrily.
In recent years, ozone and the high-level oxidation technology based on ozone are applied to the research of biochemical tailrace advanced process aspect by extensive concern, and it mainly applies O
3oxidisability (2.07Vs) oxidation of organic compounds itself or based on the advanced oxidation of ozone (as O
3-H
2o
2) react the stronger oxidisability particle of generation oxidisability as OH oxidative degradation organism.But O
3oxidation capacity limited and to organic oxidation, there is certain selectivity, with H
2o
2reaction produces hydroxyl radical free radical and is subject to as the restriction of the envrionment conditions such as concentration, pH, therefore, and O
3oxidation sewage treatment is also subject to certain development restriction.
Have scholar electrochemistry and ozone coupling to be disposed of sewage, it mainly utilizes O
2or O
3electric negative electrode and near the strong hydroxyl radical free radical of generation oxidisability dispose of sewage, equality people as few in child utilizes oil of mirbane in electrochemistry and ozone coupling degradation of sewage, and Fourier Series expansion technique degrading nitrobenzene clearance reaches 96%; In addition, Amada Co., Ltd. has applied for electrochemistry and ozone coupling sewage treatment, but these researchs mainly only utilize electric cathode excitation O
2-O
3react and produce single oxidisability particle hydroxyl radical free radical, the advantage of the multiple oxidisability particle that electricity anode can produce is not exploited, in addition, these institutes adopt electrode to be all small-scale flat type, be not suitable for very much with needing the reaction unit of airtight aeration, engineering industry's application is restricted.
Summary of the invention
In order to overcome the shortcoming of above-mentioned technology, the invention provides the device and method of a kind of duct type electrocatalysis and ozone cooperative oxidation sewage treatment, electric cathode excitation O can be utilized
2-O
3produce strong oxidizing property particle hydroxyl radical free radical, on electric anode, produce multiple oxidisability particle simultaneously, make full use of electric positive pole and negative pole, improve the treatment effect of the sewage quality to industrial park complexity; In addition, electric anodic-cathodic changes system into the cylindrical of sewer line shape, is convenient to can dispose of sewage in sewage transport process, saves process space, is convenient to the popularization of through engineering approaches.
A device for duct type electrocatalysis and ozone cooperative oxidation sewage treatment, arranges sheath electrode, sleeve cathode electrode and aeration tube successively respectively from outside to inside in sealed pipe type reactor; Anode electrode, cathode electrode and aeration tube are arranged along the pipeline axial of sealed pipe type reactor respectively; The end winding support that anode electrode, cathode electrode are corresponding with sealed pipe type reactor respectively with the two ends of aeration tube is connected; Tubular housing is formed respectively between the two ends of adjacent component and sealed pipe type reactor; Anode electrode and cathode electrode make tubular reactor form closed system by inner cased type connection insulated from each other; Anode electrode is connected with direct supply respectively with cathode electrode; The bottom tube wall of sealed pipe type reactor arranges water-in, the top tube wall of sealed pipe type reactor sets out the mouth of a river and ozone tail gas venting port.
Described sealed pipe type reactor one end is by inner cased type connection insulated from each other, and the other end forms closed system by tongued and grooved flanges.
Described anode electrode and cathode electrode to be connected with the insulating disc at sealed pipe type reactor (1) two ends respectively by internal and external screw mode and to be fixed.
Inner sleeve layer by layer each other between described anode electrode and cathode electrode, the number of plies is installed according to sealed pipe type reactor inside diameter size and water quality multilayer.
Described anode electrode and cathode electrode are respectively reticulated structure.
The spacing of described anode electrode and cathode electrode is 10mm ~ 20mm.
The material of described anode electrode is titanium, and its surface-coated has inert matrix material, and in described inert matrix material, the mol ratio of Sn, Ru and Sb is Sn:Ru:Sb=80 ~ 90:5 ~ 10:5 ~ 10.
On described anode electrode, the method for coated inert matrix material is: by removing the oxide compound on surface, dirt and grease to titanium-base polishing, ultrasonic, alkali cleaning (massfraction is the NaOH aqueous solution of 30% ~ 50%), then removed zone of oxidation by pickling (massfraction is the HCl aqueous solution of 40% ~ 60%), improved its electroconductibility; SnCl4, SbCl3 and RuCl3 (are soaked in Virahol by coating liquid according to the above ratio that configure according to the mol ratio of above-mentioned Sn, Ru and Sb, drip the HCl aqueous solution that massfraction is 40% ~ 60%, and constantly stir until dissolve) apply, first dry at 100 DEG C ~ 110 DEG C, after carry out thermolysis at 450 DEG C ~ 550 DEG C; Above-mentioned coating, oven dry, thermal decomposition process repeat more than 20 times successively.
The material of described cathode electrode is carbon.
Described aeration tube is arranged multiple wire aeration opening.
Use the method that the device of above-mentioned duct type electrocatalysis and ozone cooperative oxidation sewage treatment is disposed of sewage, the device of described duct type electrocatalysis and ozone cooperative oxidation sewage treatment is energized by direct supply and carries out sewage disposal in sewage transport process; The aeration that described aeration tube produces is the O that ozonizer produces
2and O
3mixed gas, wherein O
3volume fraction is approximately 5% ~ 10%; Aeration diffuses to cathode electrode surface, wherein O
2h is obtained by cathode electrode reduction of dissolved
2o
2, gained H
2o
2with O
3reaction generates the stronger OH of oxidisability, and then oxidative degradation organic matter of sewage; Described anode electrode surface direct oxidation degradation of sewage organism, or generation dithizone carries out oxidative degradation to organic matter of sewage, and the chlorion wherein contained in sewage is oxidized to ClO
-oxidative degradation is carried out to organic matter of sewage.
The dithizone that described anode electrode surface produces is O
3, OH, ClO
-and O.
Beneficial effect of the present invention is:
Apparatus of the present invention in electrocatalytic method, O
2carbon cathode can produce H
2o
2, can with O
3there is synergistic oxidation effect.The present invention is in conjunction with sewage running piping, and devising anodic-cathodic is mesh duct formula electric catalysis reactor, in sewage transport process, just directly can carry out oxide treatment to sewage.Make full use of to produce O
3for the purpose of the mixed gas that produces be reactant gases, utilize O
2and O
3o in mixed gas
2on the carbon cathode of electric catalysis reactor, there is catalyzed reaction, produce H
2o
2, and H
2o
2again with the O in mixed gas
3reaction produces the strong OH hydroxyl radical free radical particle of oxidisability, thus oxidation removal bio-refractory organism; The electric anode had compared with oxygen evolution potential and lower chlorine evolution potential is utilized to produce dithizone O
3, OH, O etc. and HClO, ClO
-etc. chloride oxidisability particle Simultaneous Oxidation degraded biorefractory organic, thus effectively realize electrocatalysis and O
3, Cl
-deng synergy.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of the electrocatalysis of inventive pipeline formula and ozone cooperative oxidation sewage treatment;
Fig. 2 is the transverse cross-sectional view of the device of the electrocatalysis of inventive pipeline formula and ozone cooperative oxidation sewage treatment;
Fig. 3 is the longitudinal sectional drawing of the device of the electrocatalysis of inventive pipeline formula and ozone cooperative oxidation sewage treatment;
Number in the figure: 1-sealed pipe type reactor, 2-cathode electrode, 3-anode electrode, 4-tongued and grooved flanges, 5-direct supply, 6-aeration tube.
Embodiment
The invention provides the device and method of a kind of duct type electrocatalysis and ozone cooperative oxidation sewage treatment, below in conjunction with the drawings and specific embodiments, detailed, complete description explanation is carried out to concrete technological method of the present invention and device, described embodiment is only part example of the present invention, instead of whole example.The every other example that those skilled in the art obtain under not making creative work prerequisite, all belongs to protection scope of the present invention.
A device for duct type electrocatalysis and ozone cooperative oxidation sewage treatment, arranges sheath electrode 3, sleeve cathode electrode 2 and aeration tube 6 successively respectively from outside to inside in sealed pipe type reactor 1; Anode electrode 3, cathode electrode 2 and aeration tube 6 are arranged along the pipeline axial of sealed pipe type reactor 1 respectively; The end winding support that anode electrode 3, cathode electrode 2 are corresponding with sealed pipe type reactor 1 respectively with the two ends of aeration tube 6 is connected; Tubular housing is formed respectively between the two ends of adjacent component and sealed pipe type reactor 1; Anode electrode 3 and cathode electrode 2 make tubular reactor 1 form closed system by inner cased type connection insulated from each other; Anode electrode 3 is connected with direct supply 5 respectively with cathode electrode 2; The bottom tube wall of sealed pipe type reactor 1 arranges water-in, the top tube wall of sealed pipe type reactor 1 sets out the mouth of a river and ozone tail gas venting port.
Described sealed pipe type reactor 1 one end is by inner cased type connection insulated from each other, and the other end forms closed system by tongued and grooved flanges 4.
Described anode electrode 3 and cathode electrode 2 to be connected with the insulating disc at sealed pipe type reactor 1 two ends respectively by internal and external screw mode and to be fixed.
Inner sleeve layer by layer each other between described anode electrode 3 and cathode electrode 2, the number of plies can multilayer be installed according to sealed pipe type reactor 1 internal diameter size and water quality.
Described anode electrode 3 and cathode electrode 2 are respectively reticulated structure.
The spacing of described anode electrode 3 and cathode electrode 2 is 10mm ~ 20mm.
The material of described anode electrode 3 is titanium, and its surface-coated has inert matrix material, and in described inert matrix material, the mol ratio of Sn, Ru and Sb is Sn:Ru:Sb=80 ~ 90:5 ~ 10:5 ~ 10.。
On described anode electrode 3, the method for coated inert matrix material is: by removing the oxide compound on surface, dirt and grease to titanium-base polishing, ultrasonic, alkali cleaning (massfraction is the NaOH aqueous solution of 30% ~ 50%), then removed zone of oxidation by pickling (massfraction is the HCl aqueous solution of 40% ~ 60%), improved its electroconductibility; SnCl4, SbCl3 and RuCl3 (are soaked in Virahol by coating liquid according to the above ratio that configure according to the mol ratio of above-mentioned Sn, Ru and Sb, drip the HCl aqueous solution that massfraction is 40% ~ 60%, and constantly stir until dissolve) apply, first dry at 100 DEG C ~ 110 DEG C, after carry out thermolysis at 450 DEG C ~ 550 DEG C; Above-mentioned coating, oven dry, thermal decomposition process repeat more than 20 times successively.
The material of described cathode electrode 2 is carbon.
Described aeration tube 6 arranges multiple wire aeration opening.
The device of described duct type electrocatalysis and ozone cooperative oxidation sewage treatment is energized by direct supply 5 and carries out sewage disposal in sewage transport process, thus saves sewage disposal space; Described aeration tube 6 produce aeration be ozonizer produce O
2and O
3mixed gas; Aeration diffuses to carbon cathode electrode 2 surface, and in DC electric field, carbon cathode electrode 2 forms solid-liquid-gas three phase boundary in sewage solution, O
2h is obtained by carbon cathode electrode 2 reduction of dissolved
2o
2, gained H
2o
2with O
3reaction generates the stronger OH of oxidisability, oxidative degradation organic matter of sewage; Described Ni―Ti anode electrode 3 surperficial direct oxidation degradation of sewage organism, or generation dithizone carries out oxidative degradation to organic matter of sewage, and the chlorion wherein contained in sewage is oxidized to HCLO, ClO
-oxidative degradation is carried out to organic matter of sewage.
The O that ozonizer manufactures
2and O
3mixed gas through aeration tube 6 uniform aeration, gained aeration and carbon cathode electrode 2 uniform contact react, and the oxidisability particle of generation is evenly distributed in pipeline, is conducive to oxidative degradation organism.
Claims (11)
1. a device for duct type electrocatalysis and ozone cooperative oxidation sewage treatment, is characterized in that: in sealed pipe type reactor (1), arrange sheath electrode (3), sleeve cathode electrode (2) and aeration tube (6) from outside to inside successively respectively; Anode electrode (3), cathode electrode (2) and aeration tube (6) are arranged along the pipeline axial of sealed pipe type reactor (1) respectively; The end winding support that anode electrode (3), cathode electrode (2) are corresponding with sealed pipe type reactor (1) respectively with the two ends of aeration tube (6) is connected; Tubular housing is formed respectively between the two ends of adjacent component and sealed pipe type reactor (1); Anode electrode (3) and cathode electrode (2) make tubular reactor (1) form closed system by inner cased type connection insulated from each other; Anode electrode (3) is connected with direct supply (5) respectively with cathode electrode (2); The bottom tube wall of sealed pipe type reactor (1) arranges water-in, the top tube wall of sealed pipe type reactor (1) sets out the mouth of a river and ozone tail gas venting port.
2. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, it is characterized in that: described sealed pipe type reactor (1) one end is by inner cased type connection insulated from each other, and the other end forms closed system by tongued and grooved flanges (4).
3. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, is characterized in that: described anode electrode (3) and cathode electrode (2) to be connected with the insulating disc at sealed pipe type reactor (1) two ends respectively by internal and external screw mode and to be fixed.
4. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, is characterized in that: described anode electrode (3) and cathode electrode (2) are respectively reticulated structure.
5. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, is characterized in that: the spacing of described anode electrode (3) and cathode electrode (2) is 10mm ~ 20mm.
6. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, it is characterized in that: the material of described anode electrode (3) is titanium, its surface-coated has inert matrix material, and in described inert matrix material, the mol ratio of Sn, Ru and Sb is Sn:Ru:Sb=80 ~ 90:5 ~ 10:5 ~ 10.
7. the device of a kind of duct type electrocatalysis according to claim 6 and ozone cooperative oxidation sewage treatment, it is characterized in that, on described anode electrode 3, the method for coated inert matrix material is: by removing the oxide compound on surface, dirt and grease to titanium-base polishing, ultrasonic, alkali cleaning, then remove zone of oxidation by pickling; The coating liquid configured according to the mol ratio of Sn, Ru and Sb according to claim 6 applies, and first dries at 100 DEG C ~ 110 DEG C, after carry out thermolysis at 450 DEG C ~ 550 DEG C; Above-mentioned coating, oven dry, thermal decomposition process repeat more than 20 times successively.
8. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, is characterized in that: the material of described cathode electrode (2) is carbon.
9. the device of a kind of duct type electrocatalysis according to claim 1 and ozone cooperative oxidation sewage treatment, is characterized in that: described aeration tube (6) arranges multiple wire aeration opening.
10. the method using the device of the duct type electrocatalysis described in claim 1 ~ 9 any one claim and ozone cooperative oxidation sewage treatment to dispose of sewage, is characterized in that: the device of described duct type electrocatalysis and ozone cooperative oxidation sewage treatment is energized by direct supply (5) and carries out sewage disposal in sewage transport process; The aeration that described aeration tube (6) produces is the O that ozonizer produces
2and O
3mixed gas; Aeration diffuses to cathode electrode (2) surface, wherein O
2h is obtained by cathode electrode (2) reduction of dissolved
2o
2, gained H
2o
2with O
3reaction generates OH, oxidative degradation organic matter of sewage; Described anode electrode (3) surperficial direct oxidation degradation of sewage organism, or generation dithizone carries out oxidative degradation to organic matter of sewage, and the chlorion wherein contained in sewage is oxidized to HClO, ClO
-oxidative degradation is carried out to organic matter of sewage.
11. methods according to claim 10, is characterized in that: the dithizone that described anode electrode (3) surface produces is O
3, OH, HClO, ClO
-and O.
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|---|---|---|---|
| CN201410645142.3A CN104326530B (en) | 2014-11-06 | 2014-11-06 | The device and method of a kind of duct type electro-catalysis and ozone cooperative oxidation sewage treatment |
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Cited By (21)
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| CN104773916A (en) * | 2015-04-01 | 2015-07-15 | 傅水娟 | Chemical engineering wastewater treatment method |
| CN105286991A (en) * | 2015-10-13 | 2016-02-03 | 南方医科大学 | Electric snare |
| CN106335998A (en) * | 2016-10-21 | 2017-01-18 | 北京交通大学 | Method for anode and cathode synergistic oxidized electro-catalysis-ozonation |
| CN107200394A (en) * | 2017-07-18 | 2017-09-26 | 中国科学院生态环境研究中心 | A kind of electro-catalysis ozone high grade oxidation membrane reactor wastewater treatment equipment and method |
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