CN102887562A - Method for ultrasonically degrading dye wastewater by adopting nano piezoelectric material - Google Patents
Method for ultrasonically degrading dye wastewater by adopting nano piezoelectric material Download PDFInfo
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- CN102887562A CN102887562A CN2012104300720A CN201210430072A CN102887562A CN 102887562 A CN102887562 A CN 102887562A CN 2012104300720 A CN2012104300720 A CN 2012104300720A CN 201210430072 A CN201210430072 A CN 201210430072A CN 102887562 A CN102887562 A CN 102887562A
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Abstract
The invention discloses a method for ultrasonically degrading dye wastewater by adopting a nano piezoelectric material. The method comprises the steps of: firstly pouring dye wastewater into an ultrasonic cleaner; then adding a proper quantity of nano piezoelectric material as a catalyst; and finally selecting a proper ultrasonic frequency for degrading the dye wastewater. The method has the advantages of low processing cost, good industrialized application prospect, high wastewater degrading efficiency, mild reaction conditions, environmental friendliness and wide application range.
Description
Technical field
The invention belongs to the dye wastewater treatment field, particularly a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff.
Background technology
Dyeing is the discharging rich and influential family of trade effluent, and according to incompletely statistics, the dyeing waste water of China's discharging every day is approximately
Cubic meter.Dyeing waste water is high because of its organic content, complicated component, colourity is dark, change of water quality is large, becomes one of difficult waste water of generally acknowledging both at home and abroad.In recent years, along with the development of printing and dyeing chemical engineering industry, the widespread use of PVA slurry, artificial silk alkaline hydrolysis thing (main component is O-phthalic acids material) and other New-type adjuvants is so that the organic substance of a large amount of difficult degradations has been sneaked in the dyeing waste water.Simultaneously, new dye is towards the future development of anti-oxidant, anti-photodissociation, acid-alkali-corrosive-resisting and antimicrobial degraded, and this has just increased intractability and the processing cost of dyeing waste water greatly.
At present, the method for the treatment of of dyeing and printing mainly contains photocatalytic oxidation, chemical method, biological degradation method and electrolytic process both at home and abroad.Wherein photocatalytic oxidation is low owing to efficient, degradation time is long fails to be widely used; The chemical method degradation efficiency is higher, but since high cost and easily polluting fail to be used widely; The biological degradation method degradation efficiency is high, cost is low, but contains a large amount of compounds that is difficult to biological degradation or even has bio-toxicity in the waste water from dyestuff, therefore directly adopts biological degradation method treatment effect and speed unsatisfactory; Adopt the degradation efficiency of electrolytic process high, but energy consumption is huge, fails to be used widely.Under this background, develop a kind of degradation efficiency high, processing cost is low, environmental nonpollution, degradation conditions is gentle, acid-alkali-corrosive-resisting, the treatment process that the industrial applications prospect is large comes degradation of dye waste water to be necessary.
Summary of the invention
To the objective of the invention is in order addressing the above problem, to provide a kind of degradation efficiency high, the method for the employing nanometer piezoelectric ultrasonic degradation waste water from dyestuff that processing cost is low.
Under ultrasonication, the microbubble in the waste water is because ultrasonic cavatition can extremely blast of instantaneous expansion.When the masterpiece of this generation because microbubble explodes is used on the piezoelectric with special appearance structure, can make the nanometer piezoelectric produce deformation.Because the crystal symmetry of nanometer piezoelectric is lower, when being subject to External Force Acting generation deformation, the relative displacement of negative ions no longer overlaps the positive and negative charge center in the structure cell, causes crystal generation macroscopic polarization, thereby makes the nanometer piezoelectric material surface produce heterocharge.The electric charge that the nanometer piezoelectric produces impels water decomposition, produce some active particles that are conducive to the dyestuff degraded (as:
,
,
), these active ions make the organic dye molecule degraded in the waste water from dyestuff.
The mechanism of nanometer piezoelectric generation electric charge degradation of dye waste water is as follows:
The nanometer piezoelectric is applying under the cavatition that ultrasonic vibration produces, the surface produce heterocharge (as:
,
).
Anode:
Negative electrode:
The dyestuff degraded:
+ dye molecule → dye molecule degraded
Based on this research, technical scheme of the present invention is: a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff, it is characterized in that: at first waste water from dyestuff is poured in the ultrasonic cleaner, add subsequently an amount of nanometer piezoelectric as catalyzer, select at last suitable ultrasonic frequency that waste water from dyestuff is degraded.
Say further, being shaped as of described nanometer piezoelectric is bar-shaped, a kind of in the wire, tubulose, band shape, dendroid; The length of described nanometer piezoelectric is that 0.1～100 micron, diameter are 1～1000 nanometers.
Say further, the quality of described interpolation nanometer piezoelectric and the volume ratio of waste water from dyestuff are 0.002～0.4 g/ml.
Say further, the ultrasonic frequency that the ultrasonic degradation waste water from dyestuff adopts is 20～100 kHz.
Say further, described nanometer piezoelectric is selected from one or more in zinc oxide, barium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, the PMN-PT.
Say further, the waste water from dyestuff of described ultrasonic degradation can be a kind of in acid, alkalescence, the neutral waste water from dyestuff.
Say further, described waste water from dyestuff increases UV-light or radiation of visible light in applying the process of ultrasonic vibration, photocatalytic degradation of dye waste water together is combined with the ultrasonic degradation waste water from dyestuff.
When the present invention applies ultrasonic vibration to the waste water from dyestuff that has added the nanometer piezoelectric, ultrasonic vibration produces cavitation effect, cavitation effect is so that the blast of microbubble in the waste water, piezoelectric nano rod (or nano wire, nanotube, nano belt, dendritic crystalline substance) produced reactive force, so that it produces deformation.Because piezoelectric effect, piezoelectric nano rod (or nano wire, nanotube, nano belt, dendritic crystalline substance) two ends produce electric charge, under electrochemical action, and the dye molecule in the degradation of dye waste water.
The present invention has following advantage: (1) processing cost is low, and the industrial applications prospect is large.It is simple that piezoelectric of the present invention prepares technique, and cost of material is cheap.(2) efficient of degrading waste water is high, and reaction conditions is gentle.Adopt the method dye wastewater treatment using to discolor effective, degradation of dye waste water efficient is up to more than 80%.(3) environmental friendliness.(4) applied widely.Can process acidity, alkalescence or neutral waste water from dyestuff.
Description of drawings
Be described in further details below in conjunction with accompanying drawing and embodiments of the present invention.
Fig. 1 is the degradation efficiency curve of different concns acid orange 7 waste water from dyestuff after the ultrasonic vibration that applies different time that has added zinc oxide nano rod;
Fig. 2 is the degradation efficiency curve of acid orange 7 waste water from dyestuff after the ultrasonic vibration that applies different time that has added the same concentrations different PH of zinc oxide nano rod;
Fig. 3 only adds zinc oxide nano rod, does not apply ultrasonic vibration; Only apply ultrasonic vibration, do not add zinc oxide nano rod; Both added zinc oxide nano rod, applied again under the ultrasonic vibration condition, the degradation efficiency graphic representation of different time waste water from dyestuff.
Embodiment
In the present embodiment, with 20 ml concentration be
Mol/L (perhaps
Mol/L or
Mol/L) acid orange 7 waste water from dyestuff (pH value of waste water can be adjusted to 3.2,5.4,6.8,9.4 or 10.5) is poured in the ultrasonic cleaning tank, ratio according to 0.02 g/ml adds zinc oxide nano rod in the acid orange 7 waste water from dyestuff again, adopt subsequently the ultrasonic frequency of 40 kHz that the acid orange 7 waste water from dyestuff is applied ultrasonic vibration, applying the ultrasonic vibration time is 10～60 minutes.The degradation efficiency of acid orange 7 is shown in table 1 after the reaction.
Table 1 add zinc oxide nano rod as the result of catalyzer ultrasonic degradation acid orange 7 waste water from dyestuff (dye strength:
Mol/L; The waste water pH value is 6.8).
Transverse axis represents the time (min) among Fig. 1, and the longitudinal axis represents dyestuff degradation efficiency (%).The A curve represents strength of solution
Mol/L, B curve represent strength of solution and are
Mol/L, C curve represent strength of solution
Mol/L.As shown in Figure 1, the acid orange 7 waste water from dyestuff of different concns is adding a certain amount of zinc oxide nano rod, and behind the ultrasonic cleaning different time, the concentration of waste water from dyestuff is larger, and degradation effect is poorer.
Transverse axis represents the time (min) among Fig. 2, and the longitudinal axis represents dyestuff degradation efficiency (%).It is that to represent solution PH be that to represent solution PH be that to represent solution PH be that to represent solution PH be 10.5 to 3.2, H curve to 9.4, G curve to 5.4, F curve to 6.8, E curve that the D curve represents solution PH.As shown in Figure 2, the acid orange 7 waste water from dyestuff of same concentrations different PH is adding a certain amount of zinc oxide nano rod, behind the ultrasonic cleaning different time, best near neutral dye wastewater degradation effect, the acid excessive or alkaline metropolitan of crossing affects degradation effect greatly.
Transverse axis represents the time (min) among Fig. 3, and the longitudinal axis represents dyestuff degradation efficiency (%).The I curve represents waste water from dyestuff and is adding zinc oxide nano rod, apply the degradation efficiency under the condition of ultrasonic vibration, the J curve represents waste water from dyestuff and is adding zinc oxide nano rod, do not apply the degradation efficiency under the condition of ultrasonic vibration, the K curve represents waste water from dyestuff and is not adding zinc oxide nano rod, applies the degradation efficiency under the condition of ultrasonic vibration.As shown in Figure 3, waste water from dyestuff only adding zinc oxide nano rod, applies under the condition of ultrasonic vibration, just can degrade.
Claims (7)
1. method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff, it is characterized in that: at first waste water from dyestuff is poured in the ultrasonic cleaner, add subsequently an amount of nanometer piezoelectric as catalyzer, select at last suitable ultrasonic frequency that waste water from dyestuff is degraded.
2. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1 is characterized in that: being shaped as of described nanometer piezoelectric is bar-shaped, a kind of in the wire, tubulose, band shape, dendroid; The length of described nanometer piezoelectric is that 0.1～100 micron, diameter are 1～1000 nanometers.
3. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1, it is characterized in that: the quality of described interpolation nanometer piezoelectric and the volume ratio of waste water from dyestuff are 0.002～0.4 g/ml.
4. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1 is characterized in that: the ultrasonic frequency that the ultrasonic degradation waste water from dyestuff adopts is 20～100 kHz.
5. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1 or 2, it is characterized in that: described nanometer piezoelectric is selected from one or more in zinc oxide, barium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, the PMN-PT.
6. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1 is characterized in that: the waste water from dyestuff of described ultrasonic degradation can be a kind of in acid, alkalescence, the neutral waste water from dyestuff.
7. a kind of method that adopts nanometer piezoelectric ultrasonic degradation waste water from dyestuff as claimed in claim 1, it is characterized in that: described waste water from dyestuff is in applying the process of ultrasonic vibration, increase UV-light or radiation of visible light, photocatalytic degradation of dye waste water together is combined with the ultrasonic degradation waste water from dyestuff.
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| CN103977798A (en) * | 2014-06-04 | 2014-08-13 | 山东大学 | Silver oxide/barium titanate ultrasonic photo-catalyst and preparation method thereof |
| CN105000626A (en) * | 2015-06-26 | 2015-10-28 | 中山大学 | Method for reinforcing piezoelectric effect to improve organic pollutant degradation efficiency and application thereof |
| CN108479748A (en) * | 2018-02-09 | 2018-09-04 | 南方科技大学 | Organic pollutant degradation piezoelectricity photoelectron material and biodegrading process |
| CN108545805A (en) * | 2018-04-09 | 2018-09-18 | 沈阳化工大学 | A kind of method of efficient degradation methyl orange |
| CN108855073A (en) * | 2018-06-29 | 2018-11-23 | 上海交通大学 | A kind of niobium lead codope, the preparation method of the titanium dioxide/titanium acid barium nano heterojunction photocatalysis agent of palladium load |
| CN109529807A (en) * | 2018-12-23 | 2019-03-29 | 上海师范大学 | Enhance the piezoelectricity-photochemical catalyst and its preparation method and application that photocatalytic degradation reacts |
| CN109607739A (en) * | 2018-12-13 | 2019-04-12 | 中山大学 | A kind of application of piezoelectric material barium titanate Ultrasound-activated persulfate in processing waste water |
| CN110002574A (en) * | 2019-04-25 | 2019-07-12 | 淮海工学院 | Applications catalyst and aeration removal pollutant system under a kind of dark condition |
| CN110510701A (en) * | 2019-08-16 | 2019-11-29 | 南京理工大学 | The method for bending Electrocatalysis Degradation waste water containing dye |
| CN110614102A (en) * | 2019-10-25 | 2019-12-27 | 福州大学 | Preparation and application of chlorine-doped zinc oxide nano-rod |
| CN112209476A (en) * | 2020-10-21 | 2021-01-12 | 新疆大学 | Method for degrading organic dye by applying low-dimensional zinc oxide nano material through piezoelectric catalysis |
| CN113877516A (en) * | 2021-11-08 | 2022-01-04 | 佛山(华南)新材料研究院 | Preparation method of germanium selenide nano material and application of germanium selenide nano material |
| CN114538504A (en) * | 2022-02-28 | 2022-05-27 | 江苏科技大学 | PbTiO 23Flower-like particles, their preparation and use |
| WO2022167915A1 (en) * | 2021-02-02 | 2022-08-11 | Oxyle Ag | Assemblies and methods for treating polluted water |
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Cited By (17)
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| CN103977798A (en) * | 2014-06-04 | 2014-08-13 | 山东大学 | Silver oxide/barium titanate ultrasonic photo-catalyst and preparation method thereof |
| CN105000626A (en) * | 2015-06-26 | 2015-10-28 | 中山大学 | Method for reinforcing piezoelectric effect to improve organic pollutant degradation efficiency and application thereof |
| CN108479748A (en) * | 2018-02-09 | 2018-09-04 | 南方科技大学 | Organic pollutant degradation piezoelectricity photoelectron material and biodegrading process |
| CN108545805A (en) * | 2018-04-09 | 2018-09-18 | 沈阳化工大学 | A kind of method of efficient degradation methyl orange |
| CN108855073B (en) * | 2018-06-29 | 2021-01-01 | 上海交通大学 | Preparation method of niobium-lead co-doped palladium-loaded titanium dioxide/barium titanate nano heterojunction photocatalyst |
| CN108855073A (en) * | 2018-06-29 | 2018-11-23 | 上海交通大学 | A kind of niobium lead codope, the preparation method of the titanium dioxide/titanium acid barium nano heterojunction photocatalysis agent of palladium load |
| CN109607739A (en) * | 2018-12-13 | 2019-04-12 | 中山大学 | A kind of application of piezoelectric material barium titanate Ultrasound-activated persulfate in processing waste water |
| CN109607739B (en) * | 2018-12-13 | 2021-11-02 | 中山大学 | Application of piezoelectric material barium titanate ultrasonic activation persulfate in wastewater treatment |
| CN109529807A (en) * | 2018-12-23 | 2019-03-29 | 上海师范大学 | Enhance the piezoelectricity-photochemical catalyst and its preparation method and application that photocatalytic degradation reacts |
| CN110002574B (en) * | 2019-04-25 | 2021-09-10 | 淮海工学院 | System for removing pollutants by applying catalyst and aeration under dark condition |
| CN110002574A (en) * | 2019-04-25 | 2019-07-12 | 淮海工学院 | Applications catalyst and aeration removal pollutant system under a kind of dark condition |
| CN110510701A (en) * | 2019-08-16 | 2019-11-29 | 南京理工大学 | The method for bending Electrocatalysis Degradation waste water containing dye |
| CN110614102A (en) * | 2019-10-25 | 2019-12-27 | 福州大学 | Preparation and application of chlorine-doped zinc oxide nano-rod |
| CN112209476A (en) * | 2020-10-21 | 2021-01-12 | 新疆大学 | Method for degrading organic dye by applying low-dimensional zinc oxide nano material through piezoelectric catalysis |
| WO2022167915A1 (en) * | 2021-02-02 | 2022-08-11 | Oxyle Ag | Assemblies and methods for treating polluted water |
| CN113877516A (en) * | 2021-11-08 | 2022-01-04 | 佛山(华南)新材料研究院 | Preparation method of germanium selenide nano material and application of germanium selenide nano material |
| CN114538504A (en) * | 2022-02-28 | 2022-05-27 | 江苏科技大学 | PbTiO 23Flower-like particles, their preparation and use |
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Application publication date: 20130123 |