CN106277180A - A kind of intensified by ultrasonic wave photoelectrocatalysis processes containing heavy metal and the device of persistent organic pollutant wastewater - Google Patents
A kind of intensified by ultrasonic wave photoelectrocatalysis processes containing heavy metal and the device of persistent organic pollutant wastewater Download PDFInfo
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- CN106277180A CN106277180A CN201610710214.7A CN201610710214A CN106277180A CN 106277180 A CN106277180 A CN 106277180A CN 201610710214 A CN201610710214 A CN 201610710214A CN 106277180 A CN106277180 A CN 106277180A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 26
- 239000002351 wastewater Substances 0.000 title claims abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 11
- 239000008187 granular material Substances 0.000 claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 33
- 239000003708 ampul Substances 0.000 claims abstract description 23
- 239000010453 quartz Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 239000000463 material Substances 0.000 claims description 18
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- 239000004065 semiconductor Substances 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 16
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- 239000010936 titanium Substances 0.000 claims description 12
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- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 239000010970 precious metal Substances 0.000 description 2
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- 239000010944 silver (metal) Substances 0.000 description 2
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
-
- 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
- C02F2001/46119—Cleaning the electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
nullIt is an object of the invention to provide a kind of intensified by ultrasonic wave photoelectrocatalysis to process containing heavy metal and the device of persistent organic pollutant wastewater，Including electrolysis bath、Ultrasonic generator、DC source、Aerator，Vertically-mounted in electrolysis bath have quartz ampoule、Anode electrode plate and cathode electrode plate，Cloth hole gas plate it is horizontally arranged with in electrolysis bath，The bottom of quartz ampoule is connected with the base plate of electrolysis bath，The top of quartz ampoule is through cloth hole gas plate and stretches out electrolysis bath，Anode electrode plate and cathode electrode plate are positioned at above the gas plate of cloth hole and connect DC source，Uviol lamp or daylight lamp are installed in quartz ampoule，Ultraviolet light stretches out quartz ampoule and is connected with extraneous power supply with daylight lamp，Particle filled composite electrode above the gas plate of cloth hole，The outlet electrolysis bath of aerator is also positioned at the lower section of cloth hole gas plate，Ultrasonic generator is arranged on outside electrolysis bath，The probe of ultrasonic generator stretches in granule electrode.The present invention can efficiently remove water pollutant.
Description
Technical field
The present invention relates to a kind of sewage-treatment plant.
Background technology
Along with the development of industrial technology, heavy metal pollution has become the important pollution problem that water environment faces.Heavy metal-polluted
Dye is essentially from industrial wastewaters such as smelting, electrolysis, pesticide, medicine, paint, dyestuffs.Contaminated by heavy metals water body can cause people
Body and zooblast internal protein and enzyme deformation inactivate.Heavy metal adding up in human organ, can cause serious damage to human body
Evil even threat to life safety.At present, the main removal means of heavy metal ion have absorption method, flocculent precipitation, membrance separation skill
Art, biological method etc., the removal of these methods equal heavy metal ion has certain effect, but absorption method is by heavy metal contaminants
Being enriched in adsorbing material surface, heavy metal contaminants is enriched in mud by flocculent precipitation, and membrane separation technique obtains concentration relatively
High heavy metal contaminants waste water, heavy metal contaminants is enriched with in vivo by biological method.These methods all cannot be real
Reach to remove the purpose of heavy metal contaminants.
At present industrial wastewater and the kind of sanitary sewage and the increase of discharge capacity, in sewage, composition is more complicated, in water not
Only exist heavy metal pollution, there is also the organic pollution of some difficult degradations.The organic pollution of these difficult degradations is conventional
Process technique cannot remove, and these Organic substances have the effects such as carcinogenic, teratogenesis, mutagenesis, have huge to environment and the mankind
Threat.Being the method for advanced oxidation currently for the main removal means of persistent organic pollutants, advanced oxidation is divided into again
Chemical oxidation, electrochemical oxidation, photochemical catalytic oxidation etc., chemical oxidation needs to add oxidant, though effect is good compared with both with rear
But need constantly to add medicament, add investment, have impact on the application in Practical Project.Therefore process in water is heavy metal-polluted
Dye and difficult degradation organic contamination become two current hang-ups.
Photocatalysis technology is a kind of environmentally friendly water technology, is under the effect of semiconductor light-catalyst, utilizes
Organic pollution is decomposed into nontoxic small-molecule substance (such as CO2, H2O etc.) by luminous energy, by toxic heavy metal contamination thing oxidation or
It is reduced to nontoxic or that toxicity is less material.The ultimate principle of photocatalysis technology is: when quasiconductor is by more than its energy gap
During the photon irradiation of energy, the electronics (e-) in valence band will be stimulated and transit to conduction band from valence band, produces in valence band simultaneously
Corresponding hole (h+), part photo-generated carrier (photo-induced hole and electronics) is combined again at inside particles, and remainder then may be used
To diffuse to semiconductor surface.At semiconductor surface, hole can occur at the material (electron donor) of semiconductor surface with absorption
Oxidation reaction, electronics be the most easily attracted to the oxygen of semiconductor surface and other materials (electron acceptor) to be captured generation reduction anti-
Should.Photocatalyst existence form in the reactor can be largely classified into two classes: floating type and support type.Suspension refers to partly lead
Body mainly exists with powder, is suspended in water.The semiconductor grain of powder is trickle, big with pollutant contact area, therefore
Activity is high, and reaction rate is relatively big, but powdered form is prone to inactivation and cohesion, not free settling in aqueous, it is difficult to reclaim so that
Loss of activity composition is relatively big, uses and be very limited in current system.Support type refers to be fixed on carrier quasiconductor.
Simple to operate, water process capable of circulation, catalyst uses continuously, can realize catalysis and isolation integral；Component Vectors can with partly lead
Body interacts, beneficially the separation of electron hole pair increase the absorption of reactant；Sometimes support type quasiconductor also carries
High light source utilization rate.But support type quasiconductor there is also with pollutant contact area by till now, and reaction rate is relatively low
Problem.
Electro-catalysis technology is to utilize the effect of extra electric field, in specific electrochemical reactor, by a series ofization
Learn reaction, electrochemical process or physical process, reach the intended purpose removed water pollutant or reclaim valuable cargo.Whole
Course of reaction can be divided into Direct Electrochemistry process and indirect electrochemical process.Direct Electrochemistry process refers to occur at electrode
Direct oxidation or the process of reduction.Indirect electrochemical process refers to the Strong oxdiative active substance utilizing electrode to produce, such as hydroxyl
Free radicals etc., make the process of pollutant generation redox reaction.Electro-catalysis technical finesse water pollutant also exists two difficulties
Point: the waste water time of staying in the reactor, this is to be determined by the reaction rate of electrochemical reaction；The life problems of electrode,
How the i.e. stability of electrode improves.For the two problem, to enter from the efficient electrode material of development and efficient reactor
Hands.At present, the various new electrode materials developed enhance the treatment effect of two-dimensional electrode, but due to two-dimensional electrode significant surface
The problems such as long-pending little, mass transfer problem etc. can't be solved at all, there is current efficiency low, and energy consumption is high.Three-diemsnional electrode is the most permissible
A certain degree of solution the problems referred to above.Three-diemsnional electrode is a kind of novel electrochemical reactor, and it is at conventional two-dimensional electrolysis bath
Load granular or other clastic working electrode material between electrode, and be that filling working electrode material surface is charged, become the 3rd
Pole, can occur electrochemical reaction on working electrode material surface.
In three dimensional electrode photo electrocatalysis system, photocatalysis and electro-catalysis technical tie-up use, and can reach certain working in coordination with
Effect.During electro-catalysis, inevitably there is the side reaction of electrolysis water, generate hydrogen and oxygen, and at photocatalytic process
Middle oxygen, as a kind of good electron carrier, can well capture photo-generate electron-hole, reduces its recombination velocity, right
Photocatalytic process has facilitation, and generate hydrogen peroxide, it is to avoid hydroxyl radical free radical exists time too short problem.
Three-diemsnional electrode photoelectric reaction system adds ultrasound wave and can play invigoration effect.It is being used alone three-diemsnional electrode light
During electricity reaction system, the reduction reaction of heavy metal ion can form heavy metal simple substance and be deposited on granule electrode surface, cause photoelectricity
The reduction of reaction efficiency.After adding ultrasound wave, the cavitation effect of ultrasound wave itself can produce hydroxyl radical free radical degraded with decomposition water
Organic substance, and the microjet of cavitation effect generation can play the effect of cleaning electrode, accelerates solid-liquid mass transfer.Therefore, ultrasonic
Wave energy is enough has certain invigoration effect for electrical enhanced photocatalysis process, improves the treatment effect of this technology further.
Summary of the invention
A kind of intensified by ultrasonic wave photoelectrocatalysis process that it is an object of the invention to provide efficiently removal water pollutant contains
Heavy metal and the device of persistent organic pollutant wastewater.
The object of the present invention is achieved like this:
The present invention a kind of intensified by ultrasonic wave photoelectrocatalysis processes containing heavy metal and the device of persistent organic pollutant wastewater,
It is characterized in that: include electrolysis bath, ultrasonic generator, DC source, aerator, in electrolysis bath vertically-mounted have quartz ampoule,
Anode electrode plate and cathode electrode plate, be horizontally arranged with cloth hole gas plate, the bottom of quartz ampoule and the base plate of electrolysis bath in electrolysis bath
Being connected, the top of quartz ampoule is through cloth hole gas plate and stretches out electrolysis bath, and anode electrode plate and cathode electrode plate are positioned at cloth hole gas plate
Top also connects DC source, installs uviol lamp or daylight lamp, ultraviolet light and daylight lamp stretch out quartz ampoule and with outward in quartz ampoule
Boundary's power supply is connected, particle filled composite electrode above the gas plate of cloth hole, and the outlet electrolysis bath of aerator is also positioned at cloth hole gas plate
Lower section, ultrasonic generator is arranged on outside electrolysis bath, and the probe of ultrasonic generator stretches in granule electrode.
The present invention can also include:
1, direct current power source voltage is 5～20V, electric current density 10～30mA/m2。
2, anode electrode plate and cathode electrode plate use ti-based coating battery lead plate, and titanio is in titanium plate, titanium net or titanium foam
One, coating use MnO2、PbO2、Pt、SnO2、RuO2In one；Between cathode electrode plate and adjacent anode battery lead plate
Distance is 50～100mm.
3, granule electrode uses area load to have the granular active carbon of photocatalytic activity nano semiconductor material or carbon is received
Mitron, nanometer halfbody material is TiO2、ZnO、SnO2、Cu2One or both in O, ZnS, CdS, the grain diameter of granule electrode
Being 3～4mm, the packing volume of granule electrode is the 1/3～1/2 of reactor.
Present invention have an advantage that the present invention utilizes intensified by ultrasonic wave three dimensional electrode photo electrocatalysis reaction system, electricity is urged
Change reaction, light-catalyzed reaction and ul-trasonic irradiation to combine.There is synergism in electro-catalysis and photocatalysis, in electro-catalysis
Journey inevitably exists the side reaction of electrolysis water, generates hydrogen and oxygen, and oxygen is as one in photocatalytic process
Good electron carrier, can well capture photo-generate electron-hole, reduces its recombination velocity, photocatalytic process is had rush
Enter effect, and generate hydrogen peroxide, it is to avoid hydroxyl radical free radical exists time too short problem.And ultrasonic cavitation produces
Microjet can cleaning electrode surface, it is to avoid the metal simple-substance being reduced out, in the deposition on granule electrode surface, extends
The service life of granule electrode；Ultrasonic cavitation can produce hydroxyl radical free radical by decomposition water, enhances the process of reaction system
Effect.The present invention has and is not required to add oxidant or reducing agent i.e. can get preferable oxidoreduction effect, can remove simultaneously
Heavy metal ion in water and persistent organic pollutants.And this patent can be different according to the character of pollutant to be removed
Different operational factors is used to be controlled, to reach more preferable treatment effect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention.
Detailed description of the invention
Illustrate below in conjunction with the accompanying drawings and the present invention be described in more detail:
In conjunction with Fig. 1, the present invention is mainly by electrolysis bath 1, quartz ampoule 2, uviol lamp 3, DC source 4, anode electrode plate 5, the moon
Pole battery lead plate 6, granule electrode 7, gas distribution orifice plate 8, aerator 10, ultrasonic generator 9, it is positioned at the water inlet below electrolysis bath
With the outlet composition being positioned at above electrolysis bath.
Bottom this quartz ampoule 2, the base plate with electrolysis bath 1 is connected, and upwards sequentially passes through gas distribution orifice plate 8 and granule electrode 7, stone
Electrolysis bath 1 is stretched out at the top of English pipe 2.This uviol lamp 3 is placed in quartz ampoule 2, and uviol lamp 3 and quartz ampoule 2 arrange many groups, Liang Zheyi
One is corresponding.Quartz ampoule 2 is stretched out on uviol lamp 3 top, by being connected to after conductor in parallel on extraneous power supply, it is achieved extraneous power supply is to respectively
The power supply of uviol lamp 3.Uviol lamp 3 selects the gallium lamp of 300W～500W.
Sewage, after preliminary treatment, enters reactor.Preliminary treatment is intended to remove the suspension impurity in sewage, Yi Mianchen
Electro-catalysis and photocatalysis effect is affected on long-pending granule electrode.Pollutant in sewage are under electro-catalysis and light-catalysed synergism
Reach the effect thoroughly removed or toxicity reduces.Appropriate NaCl, Na can be added in sewage2SO4, a kind of conduct in NaClO
Electrolyte, electrolyte concentration is 0.01～0.1mol/L.In this reactor, DC source 4 is to anode electrode plate 5 and cathode electrode
Plate 6 provides voltage, and voltage is 5～20V, electric current density 10～30mA/m2.Anode electrode plate 5 and cathode electrode plate 6 use titanio
Coated electrode plate, titanio can be the one in titanium plate, titanium net or titanium foam, and coating uses MnO2、PbO2、Pt、SnO2、RuO2
In one.Distance between cathode electrode plate and adjacent anode battery lead plate is 50～100mm.Anode electrode plate 5 and negative electrode electricity
Pole plate 6 arranges some groups, and is all disposed with quartz ampoule 2 and uviol lamp 3 between two battery lead plates, and fills with granule electrode 7.Particle
Electrode 7 uses area load to have granular active carbon or the CNT of photocatalytic activity nano semiconductor material, nanometer halfbody
Material is TiO2、ZnO、SnO2、Cu2One in O, ZnS, CdS, it is also possible to be that the compound of two kinds of Nano semiconductor compositions is partly led
Body material.The grain diameter of granule electrode 7 uses 3～4mm.The packing volume of granule electrode is the 1/3～1/2 of reactor.This
Device uses the dispersion of the mode of aeration content beneficially granule electrode to improve oxygen in water, and aeration uses compression empty
Gas aeration, aeration rate uses 0～10L/min.As relatively low in the pollutant load in sewage, this device cannot play one's part to the full,
Pure oxygen aeration or ozonation aerated mode can be used to strengthen reaction effect.This device uses probe type ultrasonic generating means, ultrasonic
Frequency is 20～1000kHz, and power is 20～1000W.Uviol lamp uses the gallium lamp of 300W～500W.
Uviol lamp 3 can also be changed into daylight lamp by the present invention, and daylight lamp uses 300W～500W.Granule electrode 7 is adopted simultaneously
With the TiO after loaded modified on granular active carbon or CNT2Semi-conducting material.Method of modifying has rare-earth metal doped element
(La, Ce, Er, Pr, Gd, Nd, Sm), doped with non-metals element (C, N, S, P, F), doped precious metal (Pt, Ag, Pd, Au, Ru,
Nb) etc..Other parts of device do not change with parameter.Change uviol lamp into visible lamp and reduce operating cost.
Three-diemsnional electrode of the present invention includes ti-based coating battery lead plate and granule electrode.Titanio in ti-based coating battery lead plate
Can be the one in titanium plate, titanium net or titanium foam, coating uses MnO2、PbO2、Pt、SnO2、RuO2In one.Titanio is coated with
The advantages such as it is excellent that layer electrode has catalytic performance compared to conventional graphite electrodes, platinum electrode etc., and electric conductivity is good.Battery lead plate sets
Put some groups, and between two battery lead plates, be all disposed with quartz ampoule and uviol lamp, and fill with granule electrode.Granule electrode employing
On grain activated carbon or CNT, load has the nano semiconductor material of photocatalysis performance, TiO2、ZnO、SnO2、Cu2O、ZnS、
One or both in CdS.Nano semiconductor material is as the theoretical anode in granule electrode, granular active carbon or CNT
As the theoretical negative electrode of granule electrode, at particle surface generation electrocatalytic reaction, increase effectively the reaction effect of electrocatalytic reaction
Rate.The grain diameter of granule electrode controls 3～4mm, and packing volume is the 1/3～1/2 of reactor.
Quartz ampoule of the present invention and uviol lamp one_to_one corresponding, arrange some groups.Quartz ampoule bottom closure and with
Electrolysis bath is connected, and through gas distribution orifice plate, electrolysis bath and open top are stretched out in upper end, it is simple to the placement of uviol lamp and maintenance.Each purple
Outer lamp is unified after top is by conductor in parallel to be received on extraneous power supply.Uviol lamp uses the gallium lamp of 300W～500W.
Light source can make ultraviolet source or visible light source.Radiation of visible light, ti-based coating is changed into as irradiated by ultraviolet light
Battery lead plate is constant, and granule electrode material changes, use loaded modified on granular active carbon or CNT after TiO2Half
Conductor material.Method of modifying has a rare-earth metal doped element (La, Ce, Er, Pr, Gd, Nd, Sm), doped with non-metals element (C, N,
S, P, F), doped precious metal (Pt, Ag, Pd, Au, Ru, Nb) etc..The method of modifying of doping can be at nano semiconductor material lattice table
Face forms defect, becomes the shallow gesture capture trap of photo-generate electron-hole pair, reduces the recombination probability of photo-generate electron-hole, extend light
The existence time of raw electron-hole, reach to strengthen the effect of catalytic performance, and modified, semi-conducting material can be absorbed
The scope of spectrum is extended to visible-range by ultraviolet light range.Uviol lamp is changed into daylight lamp, daylight lamp use 300W～
500W。
DC source of the present invention provides voltage to anode electrode plate and cathode electrode plate, and voltage is 5～20V, electricity
Current density 10～30mA/m2。
Gas distribution orifice plate of the present invention and aerator, use micro-aeration, and aeration rate is 0～10L/min, uses compression
Air carries out aeration, it is possible to use pure oxygen aeration or ozonation aerated.
Ultrasonic generator of the present invention uses sonde-type.Supersonic frequency is 20～1000kHz, power be 20～
1000W。
In the present invention, appropriate NaCl, Na can be added in sewage2SO4, one in NaClO is as electrolyte, electrolysis
The addition of matter can increase electrical conductivity of solution to improve the efficiency of electro-catalysis.Electrolyte concentration is 0.01～0.1mol/L.
A kind of intensified by ultrasonic wave photoelectrocatalysis of the present invention processes containing heavy metal and the side of persistent organic pollutant wastewater
Method is:
Sewage enters reactor, contacts with granule electrode, and granule electrode is charged under electric field action, and theoretical anode (is partly led
Body material) there is direct oxidation process, the Organic substance in oxidation water and part metals ion, theoretical negative electrode (activated carbon) occurs straight
Connecing reduction process, the part metals ion in reductive water to relatively lower valency or direct oxidation are to metal simple-substance；Meanwhile, also can
There is photocatalytic process, due to the irradiation vitalizing semiconductor of ultraviolet light, be allowed to produce photo-generate electron-hole pair, light induced electron-sky
Cave can be more photo-generate electron-hole and water reacts generation hydroxyl with direct oxidation Organic substance or reducing metal ion
Free radical, oxidation of organic compounds；Meanwhile, the cavitation of ultrasound wave can be with decomposition water as H with OH, and hydroxyl radical free radical can be straight
Connect degradation of organic substances, and the microjet that produces of ultrasonic cavitation can cleaning electrode surface, it is to avoid the gold being reduced out
Belong to the simple substance deposition on granule electrode surface, effectively extend the life-span of granule electrode.The method using aeration makes in reactor
Water produces disturbance, it is to avoid gas is in the gathering on granule electrode surface, and aeration can increase the content of the dissolved oxygen in water, dissolves
Oxygen is a kind of more more preferable electron acceptor than water, can preferably capture photo-generate electron-hole, generate hydroxyl radical free radical, enhance
The effect of photochemical catalytic oxidation.
Claims (5)
1. intensified by ultrasonic wave photoelectrocatalysis processes containing heavy metal and a device for persistent organic pollutant wastewater, its feature
It is: include electrolysis bath, ultrasonic generator, DC source, aerator that vertically-mounted in electrolysis bath have quartz ampoule, anode electricity
Pole plate and cathode electrode plate, be horizontally arranged with cloth hole gas plate in electrolysis bath, the bottom of quartz ampoule is connected with the base plate of electrolysis bath, stone
The top of English pipe is through cloth hole gas plate and stretches out electrolysis bath, and anode electrode plate and cathode electrode plate are positioned at above the gas plate of cloth hole and connect
Connect DC source, install in quartz ampoule uviol lamp or daylight lamp, ultraviolet light and daylight lamp stretch out quartz ampoule and with extraneous power supply phase
Even, particle filled composite electrode above the gas plate of cloth hole, the outlet electrolysis bath of aerator is also positioned at the lower section of cloth hole gas plate, ultrasonic
Generating means is arranged on outside electrolysis bath, and the probe of ultrasonic generator stretches in granule electrode.
A kind of intensified by ultrasonic wave photoelectrocatalysis the most according to claim 1 processes containing heavy metal and persistent organic pollutants
The device of waste water, is characterized in that: direct current power source voltage is 5～20V, electric current density 10～30mA/m2。
A kind of intensified by ultrasonic wave photoelectrocatalysis the most according to claim 1 and 2 processes containing heavy metal and the organic dirt of difficult degradation
The device of dye thing waste water, is characterized in that: anode electrode plate and cathode electrode plate use ti-based coating battery lead plate, titanio be titanium plate,
One in titanium net or titanium foam, coating uses MnO2、PbO2、Pt、SnO2、RuO2In one；Cathode electrode plate and adjacent sun
Distance between the battery lead plate of pole is 50～100mm.
A kind of intensified by ultrasonic wave photoelectrocatalysis the most according to claim 1 and 2 processes containing heavy metal and the organic dirt of difficult degradation
Dye thing waste water device, it is characterized in that: granule electrode use area load have photocatalytic activity nano semiconductor material
Grain activated carbon or CNT, nanometer halfbody material is TiO2、ZnO、SnO2、Cu2One or both in O, ZnS, CdS, particle
The grain diameter of electrode is 3～4mm, and the packing volume of granule electrode is the 1/3～1/2 of reactor.
A kind of intensified by ultrasonic wave photoelectrocatalysis the most according to claim 3 processes containing heavy metal and persistent organic pollutants
The device of waste water, is characterized in that: the granule that granule electrode uses area load to have photocatalytic activity nano semiconductor material is lived
Property charcoal or CNT, nanometer halfbody material is TiO2、ZnO、SnO2、Cu2One or both in O, ZnS, CdS, granule electrode
Grain diameter be 3～4mm, the packing volume of granule electrode is the 1/3～1/2 of reactor.
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