CN1565982A - Light catalyzed oxidation method for dye wastewater treatment - Google Patents
Light catalyzed oxidation method for dye wastewater treatment Download PDFInfo
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- CN1565982A CN1565982A CNA031375626A CN03137562A CN1565982A CN 1565982 A CN1565982 A CN 1565982A CN A031375626 A CNA031375626 A CN A031375626A CN 03137562 A CN03137562 A CN 03137562A CN 1565982 A CN1565982 A CN 1565982A
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- Prior art keywords
- dyestuff
- wastewater treatment
- oxidation method
- dye wastewater
- photocatalysis oxidation
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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 relates to a light catalyzed oxidation method for dye wastewater treatment, wherein granular TiO2 photochemical catalyst and fluid bed reactor are employed, a low power ultraviolet lamp is used as electric light source for irradiation, and air is blown in to bring the catalyst into a fluidization status in the reactor, and degrade the dyestuff compounds in the dyestuff waste-water into small inorganic molecules.
Description
Technical field
The present invention relates to field of waste water treatment, particularly relate to a kind of photocatalysis oxidation method that is used for dye wastewater treatment.
Technical background
The waste water from dyestuff that DYE PRODUCTION and printing and dyeing industry produce is a kind of professional waste water of very difficult degraded.Wherein common dyestuff kind has toxic substances such as reactive brilliant red k-2G, the pink FG of dye cations, Acid Red B, DISPERSE ORANGE 30 200 149, the emerald green blue GL of direct sun-proof, basic yellow 86, waste water from dyestuff complicated component, changeable and have toxicity uses this type of waste water of routine biochemistry method intractable.The optically catalytic TiO 2 oxidation style is the emerging oxidation technology method of of development in recent years, it is used for dye wastewater treatment is by artificial light or solar light irradiation, excite catalyzer to produce a large amount of active oxygen species, as hydroxyl radical free radical, ultra-oxygen anion free radical etc., attack the chromophoric group of dyestuff, cause the dye composition decolouring, and then to make the dye molecule mineralising be the micromolecular compound of that be easy to remove, nontoxic or low toxicity.The optically catalytic TiO 2 method for oxidation mainly adopts powder TiO
2The packed bed reaction dual mode of suspension reaction and immobilized catalyst (load, plated film etc.).The former uses Powdered TiO
2Be the outstanding slurry system of catalyzer, but fine catalyst can influence the permeability of light, and the Separation and Recovery equipment complexity of fine catalyst, costly and consuming time, when moving continuously, need a large amount of catalyst make-ups.The packed bed reaction of adopting immobilized catalyst then is that catalyzer is fixed on certain carrier as fiber, haydite, and reactor wall etc., the loading process complexity, raw materials cost is high, also can cause the activity of such catalysts reduction during high temperature sintering; And when using immobilized catalyzer to carry out light-catalyzed reaction, can make reaction be subjected to mass transfer limit, and catalyzer stops up easily, and the efficiency of light energy utilization is low; In addition in the reaction process activeconstituents come off and the surface stain problem also directly influence this technology efficient and apply.
Optically catalytic TiO 2 oxidation style light source commonly used mainly contains two kinds of artificial light and sunlights.Sunlight is subject to factor affecting such as season and weather as light source, light distribution is inhomogeneous, poor controllability, and also the reactor floor space of sunlight is big.Artificial light typically uses the high pressure ultraviolet lamp as light source, on the one hand, has a large amount of luminous energy and is converted into heat energy, and energy scatters and disappears, and the efficiency of light energy utilization is low; On the other hand, this light source need dispose stable-pressure device and cooling system, will cause complicated operation like this, and expense increases.
Summary of the invention
The objective of the invention is to overcome the defective that the prior art catalytic activity is low, catalyzer stops up easily, the efficiency of light energy utilization is low, thereby a kind of efficiency of light energy utilization height, the catalyzer photocatalysis oxidation method that is used for dye wastewater treatment cheap and simple to operate are provided.
The objective of the invention is to realize by following technical scheme:
The invention provides a kind of photocatalysis oxidation method that is used for dye wastewater treatment, its concrete steps are as follows:
In fluidized-bed reactor, use wavelength to be 254nm or 365nm, power is that the ultraviolet lamp of 8～36W shines as electric light source, adds particulate state TiO
2Photocatalyst pumps into fluidized-bed reactor with pending waste water from dyestuff, and blasts air simultaneously, at particulate state TiO
2Photocatalyst is under the fluidized state, carries out photocatalysis oxidation reaction 0.5～2 hour continuously or intermittently, discharges the waste water of handling, and is purified water;
Employed particulate state TiO
2Photocatalyst, its particulate specific surface area is 50～194.3m
2/ g, bulk density are 0.85～1kg/L, and iso-electric point is 6.0～6.5, and particle diameter is 16～100 orders;
Its particulate state TiO
2The add-on of photocatalyst is: add 10～30 particulate state TiO that restrain in every liter of pending waste water from dyestuff
2Photocatalyst;
The amount of blasting of described air is 2～10L/min.
The dyestuff kind that contains in the described pending waste water from dyestuff is cationic dyestuff, reactive dyestuffs, matching stain, dispersed dye, substantive dyestuff or basic dyestuff.
Described cationic dyestuff is a cationic pink fg.
Described reactive dyestuffs are reactive brilliant red k-2G.
Described matching stain is an Acid Red B.
Described dispersed dye are DISPERSE ORANGE 30 200 149.
Described substantive dyestuff is the emerald green blue GL of direct sun-proof.
Described basic dyestuff is a basic yellow 86.
The photocatalysis oxidation method advantage that is used for dye wastewater treatment provided by the invention is:
1, the TiO of modification
2The photocatalyst activity height, stable performance, regeneration is simple, can not cause secondary pollution, and application can be mass-produced;
2, the selected low power ultraviolet lamp of the present invention does not need stable-pressure device and cooling system, efficiency of light energy utilization height, and cost and process cost are cheap;
3, in the fluidized-bed, the photocatalyst of fluidized fully contacts with question response solution, can more efficient use luminous energy, to the degradation efficiency height of dye composition; And catalyzer does not flow out with reaction solution, does not have that separation and recovery, activeconstituents come off, problems such as catalyzer stops up, mass transfer limit, and catalyzer is difficult for staining under fluidized state, can play the effect of self-purification;
4, present method is better to the photocatalytic degradation mineralising effect of the dye composition of multiple difficult degradation.
Description of drawings
Fig. 1 is the synoptic diagram of fluidized-bed reactor of the present invention; Wherein
1 stationary tank, 2 pumps, 3 liquid meters, 4 air compressor
5 gas meters, 6 reactors, 7 quartz socket tubes, 8 electric light sources
9 overflow ports, 10 thief holes, 11 thief holes, 12 catalyzer
Embodiment
The present invention's setting drawing of 1 in conjunction with the accompanying drawings is described in further detail method of the present invention.
Fig. 1 is a kind of fluidized-bed reactor synoptic diagram of implementing the inventive method, 1 stationary tank wherein, 2 pumps, 3 liquid meters, 4 air compressor, 5 gas meters, 6 reactors, 7 quartz socket tubes, 8 electric light sources, 9 overflow ports, 10 thief holes, 11 thief holes, 12 catalyzer.The following examples are all carried out in this fluidized-bed reactor.
Embodiment 1, use the inventive method that dye activity bright red k-2G solution is carried out Treatment by Photocatalysis Oxidation dye activity bright red k-2G to be mixed with the aqueous solution of concentration as 120ppm, to place stationary tank (1);
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 36w ultraviolet lamp (8), and predominant wavelength is 254nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
The catalyzer that uses is the modification TiO that Beijing titanium catalyst company limited produces
2, its specific grain surface is long-pending to be 194.3m
2/ g, bulk density are 0.897kg/L, and iso-electric point is 6.12, and particle diameter is 20～40 orders;
Use pump (2), also the above-mentioned dye activity bright red of the 2L k-2G aqueous solution introduced in the reactor (6), and between the quartz socket tube of reactor wall and electric light source, add above-mentioned catalyzer 60g by liquid meter (3);
Use air compressor (4), also pass through gas meter (5), blast air, make catalyzer be fluidized state with 4L/min; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open 40w ultraviolet lamp (8);
After half an hour, told by overflow port (9) and to purify waste water, its percent of decolourization is 70%, and total organic carbon TOC clearance is 50%.
Embodiment 2, use the inventive method are carried out Treatment by Photocatalysis Oxidation to the pink FG solution of dye cations
Experimental technique is with embodiment 1.
The pink FG of dye cations is mixed with the aqueous solution that concentration is 50ppm;
Use commercially available TiO
2, its specific grain surface is long-pending to be 50m
2/ g, bulk density are 0.85kg/L, and iso-electric point is 6.0, and particle diameter is 16～60 orders;
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 8w ultraviolet lamp (8), and predominant wavelength is 365nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
Introduce the pink FG aqueous solution of the above-mentioned dye cations of 2L to reactor, and add photocatalyst 20g, the air capacity that blasts is 10L/min, makes catalyzer be fluidized state; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open the 8w ultraviolet lamp; After 2 hours, tell and purify waste water, its percent of decolourization is 95%, and total organic carbon TOC clearance is 75%.
Embodiment 3, use the inventive method are carried out Treatment by Photocatalysis Oxidation to dyestuff Acid Red B solution
Experimental technique is with embodiment 1.
The dyestuff Acid Red B is mixed with the aqueous solution that concentration is 50ppm;
Modification TiO with the production of Beijing titanium catalyst company limited
2, its specific grain surface is long-pending to be 100m
2/ g, bulk density are 1kg/L, and iso-electric point is 6.5, and particle diameter is 80～100 orders;
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 30w ultraviolet lamp (8), and predominant wavelength is 254nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
Introduce the above-mentioned aqueous solution of 2L to reactor, and add photocatalyst 40g, the air capacity that blasts is 4L/min, makes catalyzer be fluidized state; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open the 30w ultraviolet lamp; After 1 hour, tell and purify waste water, its percent of decolourization is 72%, and total organic carbon TOC clearance is 53%.
Embodiment 4, use the inventive method are carried out Treatment by Photocatalysis Oxidation to dyestuff DISPERSE ORANGE 30 200 149 solution
Experimental technique is with embodiment 1.
Dyestuff DISPERSE ORANGE 30 200 149 is mixed with the aqueous solution that concentration is 50ppm;
Modification TiO with the production of Beijing titanium catalyst company limited
2, its specific grain surface is long-pending to be 179m
2/ g, bulk density are 1kg/L, and iso-electric point is 6.5, and particle diameter is 80～100 orders;
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 30w ultraviolet lamp (8), and predominant wavelength is 254nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
Introduce the above-mentioned aqueous solution of 2L to reactor, and add photocatalyst 40g, the air capacity that blasts is 4L/min, makes catalyzer be fluidized state; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open the 30w ultraviolet lamp; After 1 hour, tell and purify waste water, its percent of decolourization is 70%, and total organic carbon TOC clearance is 50%.
Embodiment 5, use the inventive method are carried out Treatment by Photocatalysis Oxidation to the emerald green blue GL solution of the direct sun-proof of dyestuff
Experimental technique is with embodiment 1.
Emerald green blue GL is mixed with the aqueous solution that concentration is 50ppm with the direct sun-proof of dyestuff;
Modification TiO with the production of Beijing titanium catalyst company limited
2, its specific grain surface is long-pending to be 194.3m
2/ g, bulk density are 1kg/L, and iso-electric point is 6.5, and particle diameter is 80～100 orders;
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 30w ultraviolet lamp (8), and predominant wavelength is 254nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
Introduce the above-mentioned aqueous solution of 2L to reactor, and add photocatalyst 40g, the air capacity that blasts is 4L/min, makes catalyzer be fluidized state; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open the 30w ultraviolet lamp; After 1 hour, tell and purify waste water, its percent of decolourization is 69%, and total organic carbon TOC clearance is 47%.
Embodiment 6, use the inventive method are carried out Treatment by Photocatalysis Oxidation to dyestuff basic yellow 86 solution
Experimental technique is with embodiment 1.
Dyestuff basic yellow 86 is mixed with the aqueous solution that concentration is 50ppm;
Modification TiO with the production of Beijing titanium catalyst company limited
2, its specific grain surface is long-pending to be 194.3m
2/ g, bulk density are 1kg/L, and iso-electric point is 6.5, and particle diameter is 80～100 orders;
Use in the cylindrical flow fluidized bed reactor (6) as shown in Figure 1, its diameter is 150mm, and length is 600mm; Reactor central authorities are 30w ultraviolet lamp (8), and predominant wavelength is 254nm; The light source outside is with quartz socket tube (7), tarnishes in order to avoid light source contacts with reaction solution;
Introduce the above-mentioned aqueous solution of 2L to reactor, and add photocatalyst 40g, the air capacity that blasts is 4L/min, makes catalyzer be fluidized state; Treat aqueous dye solutions after reaching adsorption equilibrium on the catalyzer, open the 30w ultraviolet lamp; After 1 hour, tell and purify waste water, its percent of decolourization is 73%, and total organic carbon TOC clearance is 55%.
Catalyst reactor uses active reduction＜10% after 100 hours in the embodiment of the invention, can recover active substantially with the tap water flushing, successive reaction more than 200 hours catalyzer still can keep greater activity.
Claims (8)
1, a kind of photocatalysis oxidation method that is used for dye wastewater treatment, its concrete steps are as follows:
In fluidized-bed reactor, use wavelength to be 254nm or 365nm, power is that the ultraviolet lamp of 8～36W shines as electric light source, adds particulate state TiO
2Photocatalyst pumps into fluidized-bed reactor with pending waste water from dyestuff, and blasts air simultaneously, at particulate state TiO
2Photocatalyst is under the fluidized state, carries out photocatalysis oxidation reaction 0.5～2 hour continuously or intermittently, discharges the waste water of handling, and is purified water;
Employed particulate state TiO
2Photocatalyst, its particulate specific surface area is 50～194.3m
2/ g, bulk density are 0.85～1kg/L, and iso-electric point is 6.0～6.5, and particle diameter is 16～100 orders;
Its particulate state TiO
2The add-on of photocatalyst is: add 10～30 particulate state TiO that restrain in every liter of pending waste water from dyestuff
2Photocatalyst;
The amount of blasting of described air is 2～10L/min.
2, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 1 is characterized in that: the dyestuff kind that contains in the described pending waste water from dyestuff is cationic dyestuff, reactive dyestuffs, matching stain, dispersed dye, substantive dyestuff or basic dyestuff.
3, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described cationic dyestuff is a cationic pink fg.
4, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described reactive dyestuffs are reactive brilliant red k-2G.
5, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described matching stain is an Acid Red B.
6, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described dispersed dye are DISPERSE ORANGE 30 200 149.
7, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described substantive dyestuff is the emerald green blue GL of direct sun-proof.
8, the photocatalysis oxidation method that is used for dye wastewater treatment as claimed in claim 2 is characterized in that: described basic dyestuff is a basic yellow 86.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031375626A CN1565982A (en) | 2003-06-18 | 2003-06-18 | Light catalyzed oxidation method for dye wastewater treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031375626A CN1565982A (en) | 2003-06-18 | 2003-06-18 | Light catalyzed oxidation method for dye wastewater treatment |
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| Publication Number | Publication Date |
|---|---|
| CN1565982A true CN1565982A (en) | 2005-01-19 |
Family
ID=34470452
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|---|---|---|---|
| CNA031375626A Pending CN1565982A (en) | 2003-06-18 | 2003-06-18 | Light catalyzed oxidation method for dye wastewater treatment |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398455C (en) * | 2006-08-10 | 2008-07-02 | 武汉理工大学 | Technology of circulating purifying dyestuff waste water by reactivating inorganic composite catalytic material |
| CN101805040A (en) * | 2010-04-21 | 2010-08-18 | 桂林理工大学 | Photocatalysis reactor for treating refractory organic substance |
| CN101863524A (en) * | 2010-06-11 | 2010-10-20 | 苏州大学 | Photocatalytic oxidation degradation method of wastewater containing dye |
| CN107892354A (en) * | 2017-09-30 | 2018-04-10 | 天津大学 | A kind of device and method of photocatalytic degradation of dye waste water |
| CN111646536A (en) * | 2020-06-18 | 2020-09-11 | 闽江学院 | Method for directly and photoelectrically degrading basic dye based on FTO conductive glass |
| CN114887660A (en) * | 2022-06-01 | 2022-08-12 | 浙江科技学院 | Preparation of plasma method photocatalytic material and application of material in dye wastewater |
-
2003
- 2003-06-18 CN CNA031375626A patent/CN1565982A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398455C (en) * | 2006-08-10 | 2008-07-02 | 武汉理工大学 | Technology of circulating purifying dyestuff waste water by reactivating inorganic composite catalytic material |
| CN101805040A (en) * | 2010-04-21 | 2010-08-18 | 桂林理工大学 | Photocatalysis reactor for treating refractory organic substance |
| CN101863524A (en) * | 2010-06-11 | 2010-10-20 | 苏州大学 | Photocatalytic oxidation degradation method of wastewater containing dye |
| CN107892354A (en) * | 2017-09-30 | 2018-04-10 | 天津大学 | A kind of device and method of photocatalytic degradation of dye waste water |
| CN111646536A (en) * | 2020-06-18 | 2020-09-11 | 闽江学院 | Method for directly and photoelectrically degrading basic dye based on FTO conductive glass |
| CN114887660A (en) * | 2022-06-01 | 2022-08-12 | 浙江科技学院 | Preparation of plasma method photocatalytic material and application of material in dye wastewater |
| CN114887660B (en) * | 2022-06-01 | 2023-10-24 | 浙江科技学院 | Preparation of photocatalytic material by plasma method and application of photocatalytic material in dye wastewater |
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