CN100384751C - Method for treating wastewater of azo dye - Google Patents
Method for treating wastewater of azo dye Download PDFInfo
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- CN100384751C CN100384751C CNB2006100855486A CN200610085548A CN100384751C CN 100384751 C CN100384751 C CN 100384751C CN B2006100855486 A CNB2006100855486 A CN B2006100855486A CN 200610085548 A CN200610085548 A CN 200610085548A CN 100384751 C CN100384751 C CN 100384751C
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- visible light
- azo dye
- light source
- wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000987 azo dye Substances 0.000 title claims abstract description 33
- 239000000975 dye Substances 0.000 claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 16
- 238000002604 ultrasonography Methods 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 13
- 239000010808 liquid waste Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 3
- 230000007096 poisonous effect Effects 0.000 abstract description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention discloses an azo dye wastewater treatment method which comprises the following steps that the azo dye wastewater is drained into a wastewater treatment pool; an ultrasonic generator is installed in an ultrasound radiation mode, and a visible light source is installed in a visible light radiation mode; simultaneously, the ultrasonic generator and the visible light source are turned on, common irradiation by ultrasound and light is carried out to the azo dye wastewater; a dye decomposing result is detected when the wastewater is treated simultaneously; if decomposition reaches saturation, the treatment for the wastewater is stopped. The method has the advantages that most of dye molecules are completely degraded, and poisonous middle products are not generated; the degradation rate and the degradation efficiency of the azo dye are improved greatly; the visible light part in sunlight energy is used sufficiently, and the cost is reduced; other chemistry substances are not added and led, and not only the cost is reduced, but also no secondary pollution occurs; the ultrasonic energy is used sufficiently through leading in visible light energy, which causes the efficiency of ultrasonic for degrading the azo dye to be increased, and large-scale application is realized.
Description
One, technical field
The present invention relates to that a kind of chemical property is stable, difficult degradation and have the improvement method of the novel low energy consumption high-efficiency rate of potential carcinogenesis, azo dye wastewater that the environmental pollution influence is bigger.
Two, background technology
Along with developing rapidly of dyestuff textile industry, a large amount of dischargings of waste water from dyestuff are more and more serious to the pollution problem that ecotope on every side brings.The color of waste water from dyestuff is dark, the molecular structure complexity, and waste water is strongly-acid more or alkaline this makes waste water from dyestuff become one of extremely unmanageable organic industrial sewage.Wherein, azoic dyestuff is most widely used in dyestuff, and in Liu Tong more than the 2000 kind of dyestuff, nearly 2/3 is azoic dyestuff in the market.Azoic dyestuff generally contains the very stable aromatic ring structure of one or more character, and easy reduction decomposition goes out carcinogenic aromatic amine under anaerobic environment, is that the current pollution of China is very serious, one of waste water from dyestuff of demanding urgently administering.
Traditional dye waste water treatment method mainly contains treatment processs such as physics, chemistry, biology such as separation, filtration, oxidation reduction process, activated sludge process etc.These treatment processs in general technical process are long, and the physical reaction process is slow in the wastewater treatment process, and intermediate product is more even may produce deleterious intermediate product, causes secondary pollution easily in treating processes.And generally be difficult to reach complete degrading organic contaminant in wastewater.Conventional process waste water from dyestuff efficiency ratio is lower in addition, and cost is also relatively more expensive.
In recent years, utilize ultrasonic wave to handle the focus that trade effluent becomes domestic and international research.At present the domestic relevant report of ultrasonic degradation phenolic wastewater of utilizing is many, the application of relevant degrading azoic dye waste water and report more rare.And because the stability of limitation of ultrasound and azoic dyestuff molecular structure, speed and the efficient of handling azo dye wastewater with ultrasonic method are not very high, have influenced the practical application of ultrasonic method aspect the improvement azo dye wastewater to a certain extent.Therefore, there is the part scholar to attempt abroad, forms the degraded that the supersonic synergic effect promotes azoic dyestuff in the waste water in conjunction with other existing catalysis process.Mainly comprise ultrasonicly combining, ultrasonicly combine, ultrasonic combine with biotechnology etc. with electrochemistry with Fenton reagent.But these technology are not because the used most price comparison costliness of reagent is suitable for large-scale industrial application.On the other hand, utilizing sunlight to come degrading organic contaminant in wastewater is a kind of very promising method for treating wastewater.But, the inherent degrading waste water of up to the present domestic and international scope aspect, the part that is used effectively in the sunlight mainly is a UV-light, as the ultrasonic degraded Trichlorophenol that combines with UV-light.And the UV-light energy only accounts for 4% of solar energy, thereby causes the efficient of sunlight degrading waste water lower, is difficult to extensive practicability.The report that directly utilizes visible light does not seldom almost have.Generally be to utilize visible light to combine to handle organic pollutant with photocatalyst, combine processing dyestuff sodium alizarinsulfonate (Alizarin Red) with photocatalyst titanium dioxide as visible light, but the photocatalyst cost that common visible light can excite is all very expensive, therefore is not suitable for large-scale industrial application.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide a kind of method of handling azo dye wastewater, this method adopts ultrasonic and energy visible light is coupled, and utilizes the optoacoustic synergistic effect of its generation to realize the degraded of azo dye wastewater.
2, technical scheme: for achieving the above object, of the present inventionly utilize ultrasonic and visible light energy to be coupled to handle the method for azo dye wastewater, may further comprise the steps:
(1) azo dye wastewater is put into purification tank for liquid waste;
(2) according to the ultrasound wave irradiation mode ultrasonic generator is installed, visible light source is installed according to the visible light radiation mode;
(3) open ultrasonic generator and visible light source simultaneously, carry out ultrasonic and the common irradiation of light azo dye wastewater;
Detect the dyestuff decomposition result when (4) waste water being handled, reach capacity, then stop to handle if decompose.
The ultrasonic frequency scope that ultrasonic generator produces in the step (2) is 20KHz-1MHz.
Ultrasound wave irradiation mode in the step (2) can adopt in treating pond side irradiation formula, bottom irradiation formula, downward irradiation formula or ultrasonic generator tool heads are inserted the mode the waste water solution from the top.
Ultrasonic generator in the step (2) is that one group of ultrasonic transducer makes up mutually, as the ultrasound wave irradiation source.Ultrasonic transducer can be one in the ultrasound wave irradiation source, also can be provided with a plurality of as required, for example two, three, four or more ultrasonic transducer, and ultrasonic transducer can be that same frequency is with power, but also can be the different frequency equal-wattage, but also can be the identical power difference of frequency, also can be that frequency is all different with power.
The wavelength region of visible light source is mainly visible light wave range in the step (2).
Visible light radiation mode in the step (2) can adopt the mode of side irradiation, bottom irradiation or top irradiation.
Visible light source in the step (3) is one group of light source, light source can for one, two, three or more, the power of each light source can be the same or different; Visible light source can adopt natural sunlight, also can adopt as electric light sources such as xenon lamp, halogen lamps, also the mode that can adopt sunlight to combine with electric light source.
The present invention is intended to directly make full use of the visible light that accounts for sunlight overwhelming majority energy and handles azo dye wastewater, utilizes ultrasonic wave and visible light irradiation simultaneously, utilizes the optoacoustic synergistic effect to decompose azo dye wastewater.Generally speaking, the molecular structure of azoic dyestuff is very stable, signs of degradation can not take place substantially under the irradiation of light.The present invention is coupled by using ultrasonic and energy visible light, just will be ultrasonic with the visible light acting in conjunction in azo dye wastewater, utilize the optoacoustic synergistic effect of its generation to realize the degraded of azo dye wastewater.This method directly makes full use of the visible light part in the solar energy, greatly reduces the cost of dye wastewater treatment using, and experimental result shows that this method efficiency ratio in handling the waste water process utilizes the efficient of ultrasonic method to be improved largely separately.This method is lower to the requirement of equipment in addition, and easy handling, also can not produce secondary pollution in handling the azo dye wastewater process, is a kind of administration way of environment-protecting clean.
3, beneficial effect:,, realized the degraded of azoic dyestuff in the waste water to handling of azo dye wastewater by the method for the invention:
(1) azo dye wastewater colourity after this method is handled becomes closely colourlessly by original more deeply, and the dye molecule overwhelming majority is degraded fully, and does not produce poisonous intermediate product; As shown in Figure 2, visible Acid Orange II absorption spectrum is along with the increase of irradiation time, and the absorbancy at peak value place is more and more lower, and absorption spectrum is tending towards smooth, and it is more and more lower to have characterized the content of Acid Orange II in solution, and the Acid Orange II overwhelming majority is degraded fully;
(2) degradation rate and the efficient of azoic dyestuff have been improved greatly; As shown in Figure 1, Acid Orange II waste water solution speed of degrading under mode of the present invention is handled and the speed under efficiency ratio conventional ultrasound individual curing and the visible light individual curing and efficient have had significantly and have improved.As shown in Figure 1, the mode of the present invention rate of decomposition of handling Acid Orange II after following 9 hours is respectively and handles more than the twice of rate of decomposition under the conventional ultrasound processing mode of back and 25 times of rate of decomposition under the visible-light treatment through the identical time;
(3) make full use of the visible light part in the solar energy, reduced cost;
(4) additional other chemical substances of introducing had not only reduced cost but also to not bringing secondary pollution;
(5) make full use of ultrasonic energy by introducing visible light energy, made the efficient of ultrasonic degradation azoic dyestuff improve, can realize large-scale application.
Four, description of drawings
The effect comparison diagram that Fig. 1 is a kind of typical waste water from dyestuff Acid Orange II after conventional ultrasound individual curing mode and visible light individual curing mode and mode of the present invention are handled;
Fig. 2 is the change curve synoptic diagram of Acid Orange II waste water solution absorption spectrum under the ultrasonic and common irradiation of visible light.
Five, embodiment
Embodiment 1: present embodiment comprises the following steps:
(1) under the room temperature, be 1.43 * 10 with concentration
-4The Acid Orange II waste water solution of mol/L is put into treating pond, and wherein Acid Orange II is a kind of typical azoic dyestuff;
The ultrasonic frequency of the ultrasonic generator generation of (2) adopting is 1MHz, and the electric power of transverter is 40W, and radiation mode is from purification tank for liquid waste bottom irradiation;
(3) adopt visible light source to adopt xenon lamp (0-300W), average exposure light power is 7.64mW/cm
2, radiation mode is that light source is by the downward irradiation in treating pond top;
(4) open ultrasonic generator and visible light source simultaneously, carry out ultrasonic and the common irradiation of light azo dye wastewater;
Detect the dyestuff decomposition result when (5) waste water being handled, reach capacity, then stop to handle if decompose.
Result shows, reaches rapidly about 70% in two hours in the rate of decomposition of Acid Orange II under the processing of mode of the present invention, after this reaches capacity gradually.The common processing after 9 hours, rate of decomposition reaches about 75%.Solution is shoaled gradually by the orange red of dark shade in the treating processes, and is last near colourless.And finding no poisonous substance matter by the absorption spectrum of measuring solution produces.
In addition, the result who has also done among the embodiment 1 with mode of the present invention under the condition and conventional ultrasound processing mode and visible-light treatment mode contrasts.As shown in Figure 1, after 3 hours, the rate of decomposition of Acid Orange II reaches about 30% Acid Orange II solution through ultrasonic individual curing, after this is tending towards saturated gradually.Supersound process after 9 hours rate of decomposition reach about 35%.And Acid Orange II solution is through the visible light individual curing after 9 hours, almost not degraded of Acid Orange II, and rate of decomposition only is 3%; By comparing result as can be known, the mode of the present invention rate of decomposition of handling down Acid Orange II is respectively 25 times of rate of decomposition under the many and visible-light treatment of the twice of rate of decomposition under the conventional ultrasound processing mode.
Embodiment 2: present embodiment adopts two 20KHz, and the ultrasonic transducer of 150W replaces the ultrasonic transducer among the embodiment 1 as ultrasonic source, and radiation mode adopts the mode in the ultrasonic transducer tool heads insertion waste water solution.Carry out same steps as among the embodiment 1, obtained the result consistent with example 1.
Embodiment 3: use 20KHz, and the ultrasonic transducer of 150W and 1MHz, the ultrasonic transducers incorporate of 40W is as the ultrasound wave irradiation source.The mode that the ultrasonic transducer radiation mode of 20KHz adopts tool heads to immerse waste water solution, 1MHz, the ultrasonic transducer of 40W is from the irradiation of wastewater disposal basin bottom; Visible light source adopts the xenon lamp of two different exposure light power to combine, and the radiation mode of one of them xenon lamp adopts by the downward irradiation formula in treating pond top, and average exposure light power is 7.64mW/cm
2, another xenon lamp radiation mode is from treating pond side irradiation to solution, average exposure light power is 3.80mW/cm
2Carry out same steps as among the embodiment 1, obtained the result consistent with example 1.
Embodiment 4: replace Acid Orange II among the embodiment 1 with the azoic dyestuff reactive black 5, carry out step identical among the embodiment 1, obtained the result consistent with embodiment 1.
Embodiment 5: combine as the light source among the light source replacement embodiment 1 with sunlight and an xenon lamp.The average exposure light power of xenon lamp is 7.64mW/cm
2, radiation mode is that light source is by the downward irradiation in treating pond top.Carry out step identical among the embodiment 1, obtained the result consistent with embodiment 1.
Claims (8)
1. a method for treating wastewater of azo dye is characterized in that, this method comprises the following steps:
(1) azo dye wastewater is put into purification tank for liquid waste;
(2) ultrasonic generator and visible light source are installed;
(3) open ultrasonic generator and visible light source simultaneously, carry out ultrasonic and the common irradiation of light azo dye wastewater;
Detect the dyestuff decomposition result when (4) waste water being handled, reach capacity, then stop to handle if decompose;
Wherein, visible light source radiant light power is 7.64mW/cm
2
2. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, the ultrasonic frequency scope that ultrasonic generator produces in the step (2) is 20KHz-1MHz.
3. method for treating wastewater of azo dye as claimed in claim 1, it is characterized in that, step is installed ultrasonic generator according to the ultrasound wave irradiation mode in (2), and the ultrasound wave irradiation mode adopts in treating pond side irradiation formula, bottom irradiation formula, downward irradiation formula or ultrasonic generator tool heads are inserted the mode the waste water solution from the top.
4. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, the ultrasonic generator in the step (2) is one group of ultrasonic transducer, as the ultrasound wave irradiation source.
5. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, the wavelength region of visible light source is the visible light part in the step (2).
6. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, according to the visible light radiation mode visible light source is installed in the step (2), and the visible light radiation mode adopts the mode of side irradiation, bottom irradiation or top irradiation.
7. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, the visible light source in the step (3) is natural sunlight.
8. method for treating wastewater of azo dye as claimed in claim 1 is characterized in that, the visible light source in the step (3) is one group of light source, as visible light source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100855486A CN100384751C (en) | 2006-06-22 | 2006-06-22 | Method for treating wastewater of azo dye |
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| CNB2006100855486A CN100384751C (en) | 2006-06-22 | 2006-06-22 | Method for treating wastewater of azo dye |
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| CN1872712A CN1872712A (en) | 2006-12-06 |
| CN100384751C true CN100384751C (en) | 2008-04-30 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102887562A (en) * | 2012-11-01 | 2013-01-23 | 浙江师范大学 | Method for ultrasonically degrading dye wastewater by adopting nano piezoelectric material |
| CN110627273B (en) * | 2019-08-20 | 2022-05-31 | 华南理工大学 | Method for degrading methylene blue in rural sewage |
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| WO2002042228A1 (en) * | 2000-11-25 | 2002-05-30 | Questor Technologies Limited | Bioadsoprtion process for the removal of colour from textile effluent |
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2006
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Patent Citations (5)
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|---|---|---|---|---|
| CN1247166A (en) * | 1998-10-22 | 2000-03-15 | 贝德恩·迪林 | Biological treatment process and unit for wate water containing dye in textile and leather industry |
| WO2002042228A1 (en) * | 2000-11-25 | 2002-05-30 | Questor Technologies Limited | Bioadsoprtion process for the removal of colour from textile effluent |
| CN1535249A (en) * | 2001-03-28 | 2004-10-06 | ��ʿͨ��ʽ���� | Method and device for decomposing environmental pollutants |
| CN2641032Y (en) * | 2003-08-26 | 2004-09-15 | 于德贤 | Cooperative high grade oxidation reactor |
| DE102004040353A1 (en) * | 2004-08-20 | 2006-02-23 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Decolorizing process solutions and waste waters from textile and dye industries, by electrolysis in cell with diamond-coated anodes in presence of sulfate, forming peroxodisulfate causing further decolorization |
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