CN102030387A - Photoelectrocatalysis method of photocathode photoelectric turntable with pointed cone structure for treating organic waste water - Google Patents
Photoelectrocatalysis method of photocathode photoelectric turntable with pointed cone structure for treating organic waste water Download PDFInfo
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Abstract
The invention discloses a potoelectrocatalysis method of a photocathode photoelectric turntable with a pointed cone structure for treating organic waste water, comprising the following steps of: processing a stainless steel disk or a titanium disk as a substrate into a pointed cone structure; loading a TiO2 photocatalyst on the substrate and forming a photoelectric turntable on a rotating shaft to be used as the photocathode, wherein the rotating shaft of the photocathode is connected with a motor; placing a Cu sheet as the cathode at the inner wall of a reaction tank opposite to the photocathode and connecting the Cu sheet with the cathode of a direct current power supply; forming a liquid film on the surface of the photocathode; radiating the photocathode by using an exciting light source to allow the exciting light to radiate to the surface of the photocathode through the liquid film; and sampling and analyzing effluent, measuring the removal rate of organic matters in waste water and finishing the treatment on the organic waste water difficult to degrade. The invention greatly reduces the absorption of the organic waste water on the light, improves the utilization rate of the exciting light and the degradation efficiency of potoelectrocatalysis, increases the surface area of the photocathode, strengthens the mass transfer and improves the degradation efficiency of light (electric) catalysis.
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 pointed cone structured 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 by 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 of utilizing is made excitation light source, makes light induced electron and hole be able to effective the separation by 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.
Find through retrieval prior art, Chinese patent literature CN101254961, 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 half utilizes the rotation of rotating disk to make aerial TiO in air
2The membrane electrode surface portion has formed tens microns liquid film, has solved waste water layer that the exciting light in the traditional reactor must see through thicker (several centimetres often) and just can shine problem on the electrode, 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 saved 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 prior art above shortcomings, provide a kind of pointed cone structured light anode photoelectric turnplate to handle the method for organic waste water photoelectrocatalysis.The present invention is processed as the pointed cone 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 is achieved by the following technical solutions:
The present invention includes following steps:
The first step adopts stainless steel disk or titanium disk as substrate, and substrate is processed as the pointed cone structure;
Second step is with TiO
2Photocatalyst loads in the substrate, forms photoelectric turnplate in rotating shaft, 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 by lead;
The 4th step, regulate the voltage of direct supply, hotwire, and make photoanode surface form one deck liquid film by 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, finish the processing of organic wastewater with difficult degradation thereby.
Described pointed cone structure is the square of bottom side length 2-10mm, and end height ratio is 1: 1-1: 4 pointed cone.
The working method of described pointed cone structure is lathe in machining method or die stamping method.
Described with TiO
2It is sol-gel method, direct heat oxidation style or anonizing that photocatalyst loads on suprabasil method.
The described photoelectric turnplate of forming in rotating shaft is to form photoelectric turnplate with single chip mode or multi-disc series system as the light anode in rotating shaft.
The voltage of described adjusting direct supply is 0.4-3.0V.
Described photoelectric turnplate, its rotating speed control is 20-100rpm by the rotating speed of governor control dial rotation.
Described excitation light source is ultraviolet lamp or sunlight.
Its back side adopts aluminium foil to reflect to improve the light source utilization ratio when fluorescent tube of the ultraviolet 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 present invention has the following advantages: multiple internal reflection can take place in excitation light irradiation after on the pointed cone structure, improved the utilization ratio of exciting light greatly, has reduced energy consumption; The pointed cone structure has increased light anodic surface-area greatly, can carry more pollutent when the light anode rotates, and has improved the degradation efficiency of pollutent; The pointed cone structured light anode exchange of also having accelerated electrode surface and main body solution in rotation process is simultaneously upgraded, and 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 speed regulator, 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 pointed cone structure incident light reflection synoptic diagram;
Wherein: (a) plane incident light reflection synoptic diagram; (b) pointed cone incident light synoptic diagram; (c) pointed cone structural representation.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is implemented under with the technical solution of the present invention prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Height ratio pointed cone 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 the lathe in machining method, and the plane disc substrate is processed as bottom width 2mm, high 2-8mm (be end height ratio 1: 1-1: 4) pointed cone, 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 by 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 by lead.
4) voltage of adjusting direct supply is 1.6V; Hotwire, and be 80rpm by 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 pointed cone light anode and conventional planar light anode are measured contrasts as follows:
As shown in Figure 3, as can be seen from the above results, compare with conventional planar structured light anode, pointed cone structured light anode obviously improves the percent of decolourization of rhodamine B, this is because pointed cone structured light anode can repeatedly utilize exciting light on the one hand, has improved the utilization ratio of exciting light; Be because pointed cone structured 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.
Embodiment 2
Different processing methods pointed cone 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 pointed cone light anode, and rotating speed is 80rpm, 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 as follows:
| The working method of pointed cone | The lathe in machining method | The die stamping method |
| Rhodamine B chroma removal rate (%) | 99.4 | 97.5 |
As can be seen from the above results, two kinds of methods can realize effective pointed cone structure, but the die stamping method is faster when making in a large number.
Embodiment 3
Different system film mode pointed cone 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 120m1.
Step is with embodiment 1, and wherein using the light anode is 1: 3 pointed cone light anode, and rotating speed is 80rpm, 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 as follows:
| Different system film modes | Sol-gel method | The direct heat oxidation style | Anonizing |
| Rhodamine B chroma removal rate (%) | 99.4 | 86.7 | 90.3 |
As can be seen from the above results, 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 pointed cone 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 pointed cone 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 as follows:
| Rotating speed (rpm) | 20 | 40 | 60 | 80 | 100 |
| Rhodamine B chroma removal rate (%) | 82.5 | 88.1 | 91.7 | 93.4 | 92.5 |
As can be seen from the above results, compare with the planar light anode, pointed cone structured light anode rotating speed helps the raising of treatment effect greatly, also can influence to some extent treatment effect when rotating speed is too high simultaneously.
Embodiment 5
Different bias voltage pointed cone 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 pointed cone light anode, and rotating speed is 80rpm, 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 as follows:
| Bias voltage (V) | 0 | 0.4 | 0.8 | 1.2 | 1.6 | 2.0 | 2.4 | 3.0 |
| Rhodamine B chroma removal rate (%) | 86.6 | 87.0 | 89.8 | 90.4 | 92.5 | 92.5 | 92.0 | 91.3 |
By above result as seen, improve bias voltage and help improving treatment effect, but get final product to 1.6V.
Embodiment 6
Different treatment process pointed cone 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 pointed cone 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 as follows:
| Photoelectrocatalysis (1.6V bias voltage) | Photochemical catalysis (no-bias) | |
| Rhodamine B chroma removal rate (%) | 92.5 | 86.6 |
By above result as seen, common photochemical reaction (i.e. the not light-catalyzed reaction of applying bias) also has the good treatment effect in pointed cone anode liquid film disk reactor.
Embodiment 7
Different treatment time pointed cone 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 pointed cone light anode, and rotating speed is 80rpm, bias voltage is 1.6V, every 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 as follows:
| Time (min) | 50 | 100 | 150 |
| Chroma removal rate (%) | 98.1 | 100 | 100 |
| COD clearance (%) | 20.1 | 38.7 | 59.2 |
Embodiment 8
Pointed cone 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 pointed cone light anode, rotating speed is 80rpm, bias voltage is 1.6V, 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 as follows:
From above data as can be seen, compare with conventional planar structured light anode, pointed cone structured light anode has remarkable advantages when handling dye wastewater with high concentration, colourity and COD clearance are apparently higher than the planar light anode, and the unit surface removal amount also is higher than plane electrode.
The foregoing description presentation of results, the foregoing description pointed cone structured 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; Simultaneously the pointed cone structure has also increased light anodic surface-area greatly, can carry more pollutent and participate in reacting when the light anode rotates, has improved degradation efficiency, reaches efficient low-consume, and the purpose of energy-saving and emission-reduction has a very big application prospect industrial.
Claims (8)
1. the method for a pointed cone structured 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 the pointed cone structure;
Second step is with TiO
2Photocatalyst loads in the substrate, forms photoelectric turnplate in rotating shaft, 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 by lead;
The 4th step, regulate the voltage of direct supply, hotwire, and make photoanode surface form one deck liquid film by 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, finish the processing of organic wastewater with difficult degradation thereby.
2. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that described pointed cone structure is the square of bottom side length 2-10mm, end height ratio is 1: 1-1: 4 pointed cone.
3. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that the working method of described pointed cone structure is lathe in machining method or die stamping method.
4. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that, described 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 pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that, the described photoelectric turnplate of forming in rotating shaft is to form photoelectric turnplate with single chip mode or multi-disc series system as the light anode in rotating shaft.
6. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that the voltage of described adjusting direct supply is 0.4-3.0V.
7. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that, described photoelectric turnplate, its rotating speed control is 20-100rpm by the rotating speed of governor control dial rotation.
8. handle the method for organic waste water photoelectrocatalysis according to the pointed cone structured light anode photoelectric turnplate of claim 1, it is characterized in that described excitation light source is ultraviolet lamp or sunlight.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008016671A2 (en) * | 2006-08-01 | 2008-02-07 | Quos, Inc. | Multifunctional filtration and water purification systems |
| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
| CN101307479A (en) * | 2008-01-31 | 2008-11-19 | 上海交通大学 | TiO2 nanometer pore array material preparation method and uses thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008016671A2 (en) * | 2006-08-01 | 2008-02-07 | Quos, Inc. | Multifunctional filtration and water purification systems |
| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
| CN101307479A (en) * | 2008-01-31 | 2008-11-19 | 上海交通大学 | TiO2 nanometer pore array material preparation method and uses thereof |
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