CN101993129B - Method for treating photoelectrocatalysis of organic wastewater through sharply-structured light anode and photoelectricity rotary disc - Google Patents
Method for treating photoelectrocatalysis of organic wastewater through sharply-structured light anode and photoelectricity rotary disc Download PDFInfo
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- CN101993129B CN101993129B CN2010105283244A CN201010528324A CN101993129B CN 101993129 B CN101993129 B CN 101993129B CN 2010105283244 A CN2010105283244 A CN 2010105283244A CN 201010528324 A CN201010528324 A CN 201010528324A CN 101993129 B CN101993129 B CN 101993129B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a method for treating photoelectrocatalysis of organic wastewater through sharply-structured light anode and photoelectricity rotary disc, comprising the following steps: processing a stainless steel round disc or titanium disc taken as a substrate into an pointed cone structure; loading TiO2 photochemical catalyst on the substrate, forming a photoelectricity rotary disc on a rotary shaft to serve as a light anode, wherein the rotary shaft of the light anode is in connection with a motor; placing a Cu piece taken as a cathode on the inner wall of a reaction slot opposite to the light anode, and connecting the cathode with the cathode of a direct current power supply through a wire; forming a liquid membrane on the surface of the light anode; irradiating the light anode with an excitation light source and irradiating excitation light on the surface of the light anode through the liquid membrane; and sampling and analyzing yielding water, and measuring removal rate of the organic matter in wastewater, thus finishing treatment for the organic wastewater which is hard to degrade. By utilizing the method, absorption of the organic wastewater for light is greatly reduced, the utilization rate of excitation light and the degradation efficiency of the photoelectrocatalysis are improved, the surface size of the light anode is increased, mass transfer is enhanced and the degradation efficiency of photoelectrocatalysis is improved.
Description
Technical field
What the present invention relates to is a kind of photoelectrocatalysis method of chemical technology field, relates in particular to the method that a kind of Wedge structure light anode photoelectric turnplate is handled the organic waste water photoelectrocatalysis.
Background technology
In recent years, TiO
2Be proved to be the semiconductor light-catalyst that a kind of efficient, stable, non-selectivity and material are easy to get.TiO
2Photocatalysis technology almost can make the pollutent permineralization in the sky G&W as a kind of high-level oxidation technology.Find TiO from Fujishima in 1972
2But since the photochemical catalysis splitting water, TiO
2The conductor photocatalysis technology has obtained extensive studies gradually aspect treatment of organic matters of organic.For solving TiO
2Difficulty and the isolating problem of waste water, TiO
2Be fixed on the various carriers, because TiO
2Thereby the immobilization meeting causes its surface-area decline its photocatalytic activity is descended, the investigator is TiO
2Mould material stops the simple composite in light induced electron and hole as anode through adding anodic bias, thereby improves photocatalysis efficiency, and this is that electricity helps photochemical catalysis (abbreviation photoelectrocatalysis), so TiO
2The semiconductor photoelectrocatalysielectrode technology is that a kind of UV-light that utilizes is made excitation light source, makes light induced electron and hole be able to effective the separation through applying bias, produces a kind of oxidation technology that the living radical with strong oxidation capacity comes the oxidative degradation pollutent.At present around increasing TiO
2The surface-area of membrane electrode selects aspects such as suitable electrode base materials and electrode modification to do a large amount of work, but all the time, photo electrocatalysis reactor and efficiency of light energy utilization problem are wherein often ignored by people.Traditional photo electrocatalysis reactor all is that optoelectronic pole is invaded in the reaction solution fully basically, and exciting light need penetrate the surface that thick liquid layer could arrive photocatalyst, the absorption of exciting light is caused the very big loss of exciting light owing to organic solution self.
Retrieval through to prior art is found, Chinese patent document number CN101254961, and open day 2008.9.3 has put down in writing a kind of " TiO
2Film electrode photoelectric turnplate is handled the method for organic wastewater with difficult degradation thereby ", this technology has comprised a kind of dynamic light anodic list composite rotating disk photoelectricity liquid film reactor: with TiO
2Membrane electrode is made into rotating disk, and half of rotating disk is immersed in the water, and is half the in air, utilizes the rotation of rotating disk to make aerial TiO
2The membrane electrode surface portion has formed tens microns liquid film, has solved the exciting light in the traditional reactor and must just can shine the problem on the electrode through the waste water layer of thicker (several centimetres often), has strengthened the utilization ratio and the mass-transfer efficiency of exciting light simultaneously; Thereby can adopt the small power low pressure mercury lamp to make excitation light source, having reduced energy consumption does not need recirculating cooling water system, has simplified device, has practiced thrift valuable excitation light source really.But the same with existing a lot of photoelectrocatalysis anodes, its light anode is a two dimensional structure, and irradiate light only takes place once to absorb to the back, surface, and rest part luminous energy is reflected in the atmosphere, still has the waste of exciting light.So the planar anode structure of disk reactor is expected to further improvement, as makes it to become a kind of surface tissue of inside multiple reflection, claim light trapping again, then can advance one and relate to the utilization ratio that strengthens light.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists, provide a kind of Wedge structure light anode photoelectric turnplate to handle the method for organic waste water photoelectrocatalysis.The present invention is processed as Wedge structure with traditional two dimensional structure light anode, takes place repeatedly to internal reflection when making excitation light irradiation to the surface, and has increased light anodic surface-area, has improved the utilization ratio of exciting light and the degradation efficiency of pollutent.
The present invention realizes through following technical scheme:
The present invention includes following steps:
The first step adopts stainless steel disk or titanium disk as substrate, and substrate is processed as Wedge structure;
Second step is with TiO
2Photocatalyst loads in the substrate, in rotating shaft, forms photoelectric turnplate, and as the light anode, the rotating shaft of light anodic is connected with motor;
The 3rd step, do negative electrode with the Cu sheet, be placed on reactive tank inwall place, light anode opposite, be connected with the negative pole of direct supply through lead;
The 4th step, the voltage of adjusting direct supply; Hotwire, and make photoanode surface form one deck liquid film through the rotating speed of governor control light anode rotation;
The 5th step, adopt excitation light source irradiates light anode, make exciting light see through liquid film and shine photoanode surface;
The 6th step, to the water outlet sampling analysis, measure organic clearance in the waste water, accomplish the processing of organic wastewater with difficult degradation thereby.
Said Wedge structure is bottom width 2-10mm, and end height ratio is 1: 1-1: 4 wedge.
The working method of said Wedge structure is wire cutting method or die stamping method.
Said with TiO
2It is sol-gel method, direct heat oxidation style or anonizing that photocatalyst loads on suprabasil method.
The described photoelectric turnplate of in rotating shaft, forming is in rotating shaft, to form photoelectric turnplate with single chip mode or multi-disc series system as the light anode.
The voltage of said adjusting direct supply is 0.4-3.0V.
Said control rotary speed is meant that the rotating speed through the governor control dial rotation is 20-100rpm.
Said excitation light source is uv lamp or sunshine.
Its back side adopts aluminium foil to reflect to improve the light source utilization ratio when fluorescent tube of the uv lamp that the present invention uses but rotating disk, then places during the multi-disc rotating disk between adjacent two light anodes, does not need aluminium foil, and fluorescent tube does not contact but perpendicular to disk shaft.
The present invention is biasing not, and pointed cone structured light anode promptly of the present invention also can be used as ordinary light catalysis occasion, and good reinforced effects is arranged.
The Wedge structure light anode photoelectric turnplate liquid film reactor that the present invention is unique has the following advantages: multiple internal reflection can take place in excitation light irradiation after on the Wedge structure, improved the utilization ratio of exciting light greatly, has reduced energy consumption; Wedge structure has increased light anodic surface-area greatly, when the light anode rotates, can carry more pollutent, has improved the degradation efficiency of pollutent; Simultaneously Wedge structure light anode has also been accelerated the exchange renewal of electrode surface and main body solution in rotation process, has strengthened mass transfer, has made full use of luminous energy and space, reaches energy-conservation, purpose efficiently.
Description of drawings
Fig. 1 monolithic electrode photoelectric turnplate is handled the experimental installation synoptic diagram of organic wastewater with difficult degradation thereby;
Wherein: (a) side-view; (b) front view;
Fig. 2 multi-disc electrode photoelectric rotating disk is handled the experimental installation synoptic diagram of organic wastewater with difficult degradation thereby;
Among the figure, 1 is SR, and 2 is motor, and 3 are rotating shaft, and 4 is carbon brush, and 5 is reactive tank, and 6 is the light anode, and 7 is negative electrode, and 8 is excitation light source, and 9 is aluminium foil, and 10 is direct supply, and 11 is waste water.
Fig. 3 two dimensional structure and Wedge structure incident light reflection synoptic diagram;
Wherein: (a) plane incident light reflection synoptic diagram; (b) wedge incident light synoptic diagram; (c) Wedge structure synoptic diagram
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment is implemented under with technical scheme prerequisite of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Height ratio wedge anode rotating disk liquid film reactor dye wastewater treatment using of the different ends is made Comparative Examples with the planar light anode.
As depicted in figs. 1 and 2, process object is 30ppm rhodamine B (pH2.5,1.0g/LNa
2SO
4) dye wastewater.Wastewater volume is 120ml.
1) adopting titanium plate disk is substrate, utilizes wire cutting method, and the plane disc substrate is processed as bottom width 2mm, high 2-8mm (be end height ratio 1: 1-1: 4) wedge, with sol-gel method with TiO
2Photocatalyst loads in the substrate, and with single chip mode rotating disk is fixed in the rotating shaft, and as the light anode, the rotating shaft of light anodic is connected with motor.
2) the light anode is placed in the semi arch reactive tank, the rotating shaft of light anodic is in the water surface site of waste water, and half is immersed in the waste water to make the light anode, and the light anode links to each other with the positive pole of direct supply through the carbon brush that links to each other with rotating shaft.
3) make negative electrode with the Cu sheet, be placed on reactive tank inwall place, anode opposite, be connected with the negative pole of direct supply through lead.
4) voltage of adjusting direct supply is 2.0V; Hotwire, and be 60rpm through the rotating speed that governor control light anode rotates, make photoanode surface form one deck liquid film.
5) adopt the 11W254nm low pressure mercury lamp as excitation light source, the irradiates light anode makes exciting light see through liquid film and shines photoanode surface.
6) sampling analysis after 0.5 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%).The result that present embodiment wedge light anode and conventional planar light anode are measured contrasts as follows:
As shown in Figure 3; Can find out that from above result compare with conventional planar structured light anode, Wedge structure light anode obviously improves the percent of decolourization of rhodamine B; This is because Wedge structure light anode can repeatedly utilize exciting light on the one hand, has improved the utilization ratio of exciting light; Be because Wedge structure light anode has increased light anodic surface-area on the other hand, when the light anode rotates, can carry more pollutent and participate in reaction, improved degradation efficiency.
Different processing methods wedge anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is rhodamine B (pH2.5, the 1.0g/LNa of different concns
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, and rotating speed is 100rpm, and sampling analysis after 1 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
| The working method of wedge | Wire cutting method | The die stamping method |
| Rhodamine B chroma removal rate (%) | 98.6 | 96.5 |
Can find out that from above result two kinds of methods can realize effective Wedge structure, but the die stamping method is faster when making in a large number.
Embodiment 3
Different system film mode wedge anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is rhodamine B (pH2.5, the 1.0g/LNa of different concns
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, and rotating speed is 100rpm, and sampling analysis after 1 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
| Different system film modes | Sol-gel method | The direct heat oxidation style | Anonizing |
| Rhodamine B chroma removal rate (%) | 98.6 | 85.5 | 89.3 |
Can find out that from above result different system film modes all have removal effect preferably, just because the different-effect of production method is slightly different.
Embodiment 4
Different rotating speeds wedge light anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is 30ppm rhodamine B (pH2.5,1.0g/LNa
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, shortens the treatment time, and sampling analysis after 0.5 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
| Rotating speed (rpm) | 20 | 40 | 60 | 80 | 100 |
| Rhodamine B chroma removal rate (%) | 86.8 | 89.7 | 91.7 | 94.0 | 95.4 |
Can find out from above result, compare that Wedge structure light anode rotating speed helps the raising of treatment effect greatly with the planar light anode.
Embodiment 5
Different bias voltage wedge light anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is 30ppm rhodamine B (pH2.5,1.0g/LNa
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, and rotating speed is 100rpm, shortens the treatment time, and sampling analysis after 0.5 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
| Bias voltage (V) | 0 | 0.4 | 0.8 | 1.2 | 1.6 | 2.0 | 2.4 | 3.0 |
| Rhodamine B chroma removal rate (%) | 86.8 | 90.8 | 91.2 | 92.9 | 93.0 | 95.4 | 93.1 | 91.1 |
Visible by above result, improve bias voltage and help improving treatment effect, but get final product to 2.0V.
Embodiment 6
Different treatment process wedge anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is rhodamine B (pH2.5, the 1.0g/LNa of different concns
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, and sampling analysis after 0.5 hour is measured the absorbancy of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
| Photoelectrocatalysis (2.0V bias voltage) | Photochemical catalysis (no-bias) | |
| Rhodamine B chroma removal rate (%) | 95.4 | 86.8 |
Visible by above result, common photochemical reaction (i.e. the not light-catalyzed reaction of applying bias) also has the good treatment effect in wedge anode liquid film disk reactor.
Embodiment 7
Different treatment time wedge light anode rotating disk liquid film reactor dye wastewater treatment using
As shown in Figure 1, process object is 30ppm rhodamine B (pH2.5,1.0g/LNa
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1, and wherein using the light anode is 1: 3 wedge light anode, and rotating speed is 100rpm; Bias voltage is 2.0V, and is every at a distance from 50 minutes sampling analysis, measures absorbancy and COD that rhodamine B goes out at 563nm; Ask chroma removal rate (%) and COD clearance (%), the result is following:
| Time (min) | 50 | 100 | 150 |
| Chroma removal rate (%) | 95.3 | 100 | 100 |
| COD clearance (%) | 29.0 | 48.7 | 64.3 |
Embodiment 8
Wedge light anode rotating disk liquid film reactor is handled the different concns waste water from dyestuff
As shown in Figure 1, process object is rhodamine B (pH2.5, the 1.0g/LNa of different concns
2SO
4) dye wastewater.Wastewater volume is 120ml.
Step is with embodiment 1; Wherein using the light anode is 1: 3 wedge light anode, and rotating speed is 100rpm, and bias voltage is 2.0V; Sampling analysis after 150 minutes; Measure rhodamine B at absorbancy and COD that 563nm goes out, ask chroma removal rate (%) and COD clearance (%), and calculate rhodamine B unit surface removal amount (mg/cm
2), and with the planar light anode relatively, the result is following:
From above data, can find out; Compare with conventional planar structured light anode; Wedge structure light anode has remarkable advantages when the treatment of high concentration waste water from dyestuff, colourity and COD clearance are apparently higher than the planar light anode, and unit surface removal amount also is higher than plane electrode.
The foregoing description presentation of results, the foregoing description Wedge structure light anode photoelectric turnplate is handled the method for organic wastewater with difficult degradation thereby can effectively utilize exciting light, makes exciting light at photoanode surface generation multiple internal reflection, improves the utilization ratio of exciting light; Wedge structure has also increased light anodic surface-area greatly simultaneously, when the light anode rotates, can carry more pollutent and participate in reaction, has improved degradation efficiency, reaches efficient low-consume, and the purpose of energy-saving and emission-reduction has very big application prospect in industry.
Claims (8)
1. the method for a Wedge structure light anode photoelectric turnplate processing organic waste water photoelectrocatalysis is characterized in that, comprises the steps:
The first step adopts stainless steel disk or titanium disk as substrate, and substrate is processed as Wedge structure;
Second step is with TiO
2Photocatalyst loads in the substrate, in rotating shaft, forms photoelectric turnplate, and as the light anode, the rotating shaft of light anodic is connected with motor;
The 3rd step, do negative electrode with the Cu sheet, be placed on reactive tank inwall place, light anode opposite, be connected with the negative pole of direct supply through lead;
The 4th step, regulate the voltage of direct supply, hotwire, and make photoanode surface form one deck liquid film through the rotating speed of governor control light anode rotation;
The 5th step, adopt excitation light source irradiates light anode, make exciting light see through liquid film and shine photoanode surface;
The 6th step, to the water outlet sampling analysis, measure organic clearance in the waste water, accomplish the processing of organic wastewater with difficult degradation thereby.
2. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that said Wedge structure is the square of bottom side length 2-10mm, end height ratio is 1: 1-1: 4 wedge.
3. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that the working method of said Wedge structure is lathe in machining method or die stamping method.
4. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that, said with TiO
2It is sol-gel method, direct heat oxidation style or anonizing that photocatalyst loads on suprabasil method.
5. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1; It is characterized in that; The described photoelectric turnplate of in rotating shaft, forming is in rotating shaft, to form photoelectric turnplate with single chip mode or multi-disc series system as the light anode.
6. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that the voltage of said adjusting direct supply is 0.4-3.0V.
7. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that, said photoelectric turnplate, its rotating speed control is 20-100rpm through the rotating speed of governor control dial rotation.
8. handle the method for organic waste water photoelectrocatalysis according to the Wedge structure light anode photoelectric turnplate of claim 1, it is characterized in that said excitation light source is uv lamp or sunshine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104671589A (en) * | 2015-01-23 | 2015-06-03 | 浙江工商大学 | Wastewater nitrogen removal treatment method based on photoelectrocatalysis-autotrophic biofilm |
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| CN104846394B (en) * | 2015-04-15 | 2017-07-11 | 上海交通大学 | Using the photochemical cell device of high chroma containing alcohol waste water cogeneration of hydrogen and electricity |
| CN109467159B (en) * | 2018-11-29 | 2021-10-01 | 长春理工大学 | Self-powered semiconductor photoelectric catalytic device with WSA (Wireless sensor array) position sensitive structure |
| CN116102131B (en) * | 2023-04-14 | 2023-06-06 | 泉州师范学院 | Device and method for recycling phosphorus element in sewage |
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| CN101254961A (en) * | 2008-04-10 | 2008-09-03 | 上海交通大学 | Method for treating refractory organic wastewater by TiO2 film electrode photoelectric turnplate |
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| CN104671589A (en) * | 2015-01-23 | 2015-06-03 | 浙江工商大学 | Wastewater nitrogen removal treatment method based on photoelectrocatalysis-autotrophic biofilm |
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