CN113072162A - Method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis - Google Patents
Method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis Download PDFInfo
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis, which comprises the steps of firstly adjusting the pH value of the organic dye wastewater to 2-5, and simultaneously adjusting the dissolved oxygen concentration of the organic dye wastewater to 0-8.6 mg.L‑1Controlling the temperature of the wastewater to be 20-45 ℃ through a constant-temperature water bath box; introducing hydrogen peroxide into the organic dye wastewater, adding tungsten powder into the organic dye wastewater, and uniformly mixing; the ultrasonic degradation is carried out in an ultrasonic device. The invention utilizes organic dye wastewater and changes the ultrasonic work by ultrasonic wave/metal powder combined degradation technologyThe feasibility of the technology is explored by the aid of the rate, the initial pH value, the dissolved oxygen concentration, the hydrogen peroxide adding amount and the catalyst adding amount, and the technology can be applied to the aspect of degrading industrial dye wastewater.
Description
Technical Field
The invention relates to a water pollution control and water treatment technology, in particular to a method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis.
Background
Modern synthetic textile dyes, in particular azo dyes (such as methyl orange and methylene blue), account for about 50% of the global yield (70 ten thousand tons per year), and due to the characteristics of high chroma, high COD, stable chemical properties, difficulty in biodegradation and the like of dye wastewater, after the dye wastewater which does not reach the standard enters an ecosystem, organisms in water and soil can be influenced, harm is caused to the health of human beings, and ecological balance is damaged. However, about 15% of the dye is finally discharged into the waste water during the dyeing process, which has become a problem of increasing concern. In contrast, chemical, physical-chemical, biological and other methods are used at home and abroad for treatment, and various treatment methods have certain treatment efficiency on dye wastewater and have advantages and disadvantages.
Research shows that the zero-valent metal can be used for degrading chlorine-containing organic matters in water and reducing and removing heavy metal, pesticide, herbicide, azo dye, nitro aromatic compound, nitrate, perchlorate and other pollutants, so that the application of the metal reduction technology in the aspect of environmental pollution treatment is greatly promoted. The active zero-valent metal is easy to be oxidized in aqueous solution, and if the active zero-valent metal is in aerobic condition, the following reactions can be mainly carried out: 2M0+O2+nH2O→2Mn++2nOH-(ii) a If oxidized by water in the absence of oxygen: 2M0+nH2O→2Mn++nOH-+n/2H2. The utilization of zero-valent metals and their compounds to treat refractory pollutants is a popular research field at present.
In recent years, ultrasonic technology has received a great deal of attention in the treatment of harmful organic pollutants in wastewater and has achieved many excellent results on a laboratory scale. The ultrasonic wave has special physical effect, especially ultrasonic cavitation effect can generate high temperature and high pressure in cavitation bubbles, can promote some reactions which cannot be generated under conventional conditions, integrates the advantages of various water treatment technologies such as advanced oxidation, supercritical oxidation and the like, is simple and convenient to operate, has high degradation speed, is a novel effective water treatment means, and is especially used for treating organic matters which are difficult to degrade. Since the 90 s of the 20 th century, ultrasonic waves have been applied to water pollution control, particularly treatment for degrading toxic organic pollutants in wastewater, at home and abroad, and have made certain progress. However, the energy consumption for degrading organic matters by adopting a single ultrasonic cavitation technology is high, and the treatment effect is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis.
In order to achieve the purpose, the invention designs a method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis, which comprises the following steps:
1) adjusting the pH value of the organic dye wastewater to 2-5, and simultaneously adjusting the dissolved oxygen concentration of the organic dye wastewater to 0-8.6 mg.L-1Controlling the temperature of the wastewater to be 20-45 ℃ through a constant-temperature water bath box;
2) introducing hydrogen peroxide into the organic dye wastewater, then adding tungsten powder into the organic dye wastewater, and uniformly mixing; the ultrasonic degradation is carried out in an ultrasonic device.
Further, in the step 1), the organic dye wastewater is any one of methyl orange dye wastewater, Congo red dye wastewater and methylene blue dye wastewater.
The preparation method of the methyl orange dye wastewater comprises the following steps:
dissolving methyl orange powder in deionized water, diluting to a constant volume to obtain a methyl orange solution, taking a certain amount of the obtained methyl orange solution, and adding a proper amount of deionized water to dilute the methyl orange solution to obtain the methyl orange dye wastewater with the required initial concentration.
Further, in the step 1), the dissolved oxygen concentration of the organic dye wastewater is adjusted to be 8.6 mg.L-1。
Further, in the step 1), the temperature of the wastewater is controlled to 25 ℃ by the constant-temperature water bath box.
And further, in the step 2), the concentration of hydrogen peroxide in the organic dye wastewater is 2-15 mmol/L.
And further, the concentration of hydrogen peroxide in the organic dye wastewater is 5 mmol/L.
Still further, in the step 2), the addition amount of the tungsten powder is 1-10 g.L-1。
Still further, in the step 2), the addition amount of the tungsten powder is 10 g.L-1。
Still further, in the step 2), the working conditions of the ultrasonic device are as follows: the ultrasonic power is 100-500W, and the ultrasonic temperature is 10-80 ℃.
Still further, in the step 2), the working conditions of the ultrasonic device are as follows:
the ultrasonic power is 500W, and the ultrasonic temperature is 45 ℃.
The reaction mechanism of the invention (taking tungsten powder as an example):
1. from W to H2O system produced O2 -Oxidation by oxygen
2. From W to H2OH oxidation by O system
3. Direct electron transfer from metal surface
4. Strengthening degradation of zero-valent metal by ultrasonic wave
(1) By OH oxidation produced during sonication
(2) H generated by ultrasonic process2O2Further, OH generated by the reaction with the metal is oxidized.
The invention has the beneficial effects that:
1. the invention takes commercial metal powder (tungsten powder) as a catalyst, and has the advantages of cheap and easily obtained materials, stable physicochemical properties, excellent performance and simple treatment.
2. The ultrasonic wave has the main functions of cavitation, thermal effect and chemical effect, has the advantages of simple operation, high efficiency, wide application range and no secondary pollution, and has good application prospect.
3. The invention makes the dissolved oxygen concentration of the organic dye wastewater be 0-8.6 mg.L-1It is found through research that under different dissolved oxygen concentrationsThe degradation rate of the organic dye wastewater is not obviously changed, which shows that the sufficient dissolved oxygen of the system is ensured without blowing air in the process of degrading the organic dye by the commercial metal powder, and the method has the advantages of high efficiency and simple and convenient operation.
4. The method utilizes organic dye wastewater, changes the ultrasonic power, the initial pH, the dissolved oxygen concentration, the adding amount of hydrogen peroxide and the adding amount of a catalyst by an ultrasonic wave/metal powder combined degradation technology to explore the feasibility of the technology, and shows that the technology can be applied to the aspect of degrading industrial dye wastewater through research.
Drawings
FIG. 1 is a graph of the degradation profile of methyl orange dye wastewater at different initial pH values;
FIG. 2 is a graph showing the degradation curve of methyl orange dye wastewater at different hydrogen peroxide dosing amounts;
FIG. 3 is a graph showing the degradation profile of methyl orange dye wastewater in an aerobic environment and an anaerobic environment;
FIG. 4 is a graph showing the degradation profile of methyl orange dye wastewater at different ultrasonic powers;
FIG. 5 is a graph showing the degradation profile of methyl orange dye wastewater at different reaction temperatures;
FIG. 6 is a graph showing the degradation profile of methyl orange dye wastewater when different metals are used as catalysts;
FIG. 7 is a graph showing the degradation profile of dye wastewater with different types of dyes as target contaminants.
FIG. 8 shows X-ray diffraction (XRD) patterns of a catalyst (tungsten powder as an example) before and after the reaction;
FIG. 9 is a scanning electron micrograph of a catalyst (tungsten powder as an example) before and after a reaction;
in the drawings, FIG. 9 is a scanning electron microscope photograph of a commercial metal powder (taking tungsten powder as an example) of a catalyst before reaction (FIGS. 9A and 9B) and after reaction (FIGS. 9C and 9D);
FIG. 10 is a graph showing the experimental degradation of metal powder (tungsten powder for example) by wet cycling;
FIG. 11 is a graph showing the degradation rate of methyl orange dye wastewater treated in example 1 and comparative examples 1-5;
Detailed Description
The present invention is described in further detail below with reference to specific examples so as to be understood by those skilled in the art.
The method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis comprises the following steps:
1) adjusting the pH value of the organic dye wastewater to 2-5, adjusting the dissolved oxygen concentration of the organic dye wastewater, and controlling the temperature of the wastewater to 20-30 ℃ through a constant-temperature water bath box;
2) introducing an oxidant H into the organic dye wastewater2O2Then adding tungsten powder into the organic dye wastewater, and uniformly mixing; the ultrasonic degradation is carried out in an ultrasonic device.
The working parameter selection of the method comprises the following steps:
1. the preparation method of the methyl orange dye wastewater comprises the following steps:
dissolving methyl orange powder in deionized water, diluting to desired volume to obtain methyl orange solution, adding appropriate amount of deionized water to dilute to obtain 1 g.L-1The methyl orange dye wastewater;
2. preparation of 1 g.L-1Diluting the methyl orange dye wastewater to different concentrations after measuring the maximum absorption wavelength, and drawing a standard curve (so as to calculate the concentration by using the standard curve and then calculate the degradation rate);
3. taking out the solution with the concentration of 1 g.L-1The methyl orange dye wastewater solution is added into a jacket beaker, diluted to the concentration of 20mg/L by adding water, the pH value is adjusted to be 2, 3, 4, 5 and 6, and the dissolved oxygen concentration of the system is controlled to be 0-8.6 mg.L-1) Controlling the temperature of methyl orange dye wastewater to be constant (25 ℃, 30 ℃, 35 ℃, 40 ℃ and 45 ℃) by using a constant-temperature water bath box, adding hydrogen peroxide until the concentration of the hydrogen peroxide in the wastewater is 2-15mmol/L, adding accurately weighed catalysts (iron powder, copper powder and tungsten powder (1-5 mu m)), and performing ultrasonic degradation (100W, 200W, 300W, 400W and 500W).
The sample solution was obtained by filtration through a syringe filter (0.45 μm), and the solution was measured at its lambdamaxThe sample methyl orange concentration was calculated from the standard curve as absorbance at 464 nm. The degradation rate formula of methyl orange is as follows: descendSolution rate (%) - (C)0-Ct)/C0]×100％，C0Is the initial concentration of methyl orange dye wastewater, CtIs the concentration of the methyl orange dye wastewater under different experimental conditions.
4. Conclusion
4.1 Effect of initial pH of the solution on the degradation Effect of methyl orange dye wastewater
According to the method, under the condition that other conditions are not changed, the pH value is adjusted to 2, 3, 4 and 5 by hydrochloric acid, and the pH value is not adjusted in the reaction of a control group;
as shown in fig. 1: with the reduction of pH, the degradation rate of the methyl orange dye wastewater is increased and then decreased. When the initial pH value of the solution is gradually reduced to 3, the degradation rate of the methyl orange dye wastewater in 1h is up to 96.31 percent from 90.25 percent. When the initial pH value reaches 3, the pH value is continuously reduced, the degradation rate is also reduced, and the degradation rate of the methyl orange dye wastewater is 95.15 percent within 1 hour
4.2 Effect of hydrogen peroxide dosage on methyl orange dye wastewater degradation effect
Under the condition that other conditions are not changed, the adding amount of hydrogen peroxide of the reaction system is set to be 2.5, 5, 10 and 15mmol/L respectively, as shown in figure 2, when the adding amount is 5mmol/L, the degradation effect of the methyl orange dye wastewater is best, and after the reaction is carried out for 1 hour, the degradation rate reaches 93.34%.
4.3 Effect of aerobic and anaerobic Environment values on the degradation Effect of methyl orange dye wastewater
Under the condition that other conditions are kept unchanged, MO is degraded in an aerobic environment and an anaerobic environment respectively, as shown in figure 3, the MO and the MO are found to have obvious effects, and the degradation rate in the aerobic environment is slightly higher than that in the anaerobic environment.
4.4 Effect of ultrasonic conditions on the degradation Effect of methyl orange dye wastewater
a. Influence of ultrasonic power on degradation effect of methyl orange dye wastewater
Under the condition that other conditions are kept unchanged, the ultrasonic power is respectively set to be 100W, 200W, 300W, 400W and 500W. As shown in FIG. 4, as the ultrasonic power is increased from 100W to 500W, the degradation rate of the methyl orange dye wastewater after 21min reaction is also increased from 65.80% to 78.77%.
b. Influence of temperature on degradation effect of methyl orange dye wastewater
Under the condition that other conditions are kept unchanged, the temperatures of the reaction systems are respectively set to be 25 ℃, 30 ℃, 35 ℃, 40 ℃ and 45 ℃, and as shown in figure 5, the degradation rate of the methyl orange dye wastewater is accelerated along with the increase of the temperatures. When the temperature is 45 ℃, the degradation rate reaches 96.82 percent after 11min of reaction.
4.6 influence of different metal powders (iron, copper and tungsten) on wastewater degradation
Iron powder, copper powder and tungsten powder are selected as catalysts, and methylene blue, Congo red and rhodamine B are selected as target pollutants for degradation treatment, so that the degradation effect is obvious; the copper powder is not easy to disperse in the solution, so that the degradation effect is the worst (figures 6-7);
meanwhile, the solution was centrifuged, washed, and vacuum-dried to obtain reacted metal powders (iron powder, copper powder, and tungsten powder), as shown in fig. 8: the XRD peak of the tungsten powder before reaction is mainly classified into PDF #04-0806 type and has a body-centered cubic structure. After methyl orange is catalytically degraded in a reaction system for 4 hours, the residual tungsten powder and the original tungsten powder still have high similarity, which indicates that the reaction has little influence on the change of the main structure of the tungsten powder; as can be seen from FIG. 9, the tungsten powder is mainly spherical and has a large amount of flocs on the surface; many spherical particles were broken down into smaller particles and agglomeration could be observed.
Second, evaluate the performance of the tungsten powder (catalytic ability of the catalyst, stability and service life of the catalyst)
The tungsten powder is catalytically degraded by 20 mg.L according to the method-1And (3) reacting the methyl orange dye wastewater for 1 hour.
In order to evaluate the performance of the catalyst, not only the catalytic ability of the catalyst but also its stability and service life should be considered. In a 200mL circulating beaker at 25 ℃, 20 mg.L is catalyzed by 10g/L tungsten powder-1Degrading methyl orange dye wastewater, reacting for 1h, adding high-concentration methyl orange solution into the solution, and adjusting the concentration of methyl orange to 20 mg.L-1And repeating the above operations.
The results show that the final degradation rate of methyl orange after three degradation cycles is 99.26%, 96.62% and 96.15% respectively. The zero-valent tungsten powder can continuously and effectively degrade methyl orange through surface reaction, which shows that the zero-valent tungsten powder has better stability.
As shown in fig. 10, the tungsten powder has good cycle performance, and the catalytic performance is not significantly reduced after three cycles, which indicates that the tungsten powder has good stability.
Example 1
The method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis comprises the following steps:
1) adjusting the pH value of the organic dye wastewater to 3, and carrying out the reaction under the atmospheric environment to keep the dissolved oxygen concentration of the methyl orange dye wastewater at 8.6 mg.L-1Controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath box;
2) introducing hydrogen peroxide into the organic dye wastewater, wherein the concentration of the hydrogen peroxide is 5 mmol.L-1(ii) a Then adding tungsten powder into the organic dye wastewater, and uniformly mixing; ultrasonic degradation is carried out in an ultrasonic device with the ultrasonic power of 500W by controlling the temperature of the wastewater to be 45 ℃, and the addition amount of tungsten powder is 1 g.L-1。
Example 2
The method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis comprises the following steps:
1) adjusting the pH value of the organic dye wastewater to 5, and simultaneously adjusting the dissolved oxygen concentration of the methyl orange dye wastewater to 1.0 mg.L-1Controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath box;
2) introducing hydrogen peroxide into the organic dye wastewater, wherein the concentration of the hydrogen peroxide is 5mmol/L (5 mmol/L); then adding tungsten powder into the organic dye wastewater, and uniformly mixing; ultrasonic degradation is carried out in an ultrasonic device with the ultrasonic power of 100W and the ultrasonic temperature of 80 ℃, and the addition amount of tungsten powder is 10 g.L-1。
Example 3
The method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis comprises the following steps:
1) conditioning organic dye wasteThe pH value of the water is 2, and simultaneously, the dissolved oxygen concentration of the methyl orange dye wastewater is adjusted to 5.0 mg.L-1Controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath box;
2) introducing hydrogen peroxide into the organic dye wastewater, wherein the concentration of the hydrogen peroxide is 12mmol/L (5 mmol/L); then adding tungsten powder into the organic dye wastewater, and uniformly mixing; performing ultrasonic degradation in an ultrasonic device with ultrasonic power of 300W and ultrasonic temperature of 10 deg.C, wherein the addition amount of tungsten powder is 5 g.L-1。
Comparative example 1: adjusting the pH value of the organic dye wastewater to 2, and controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath tank.
Comparative example 2: adjusting the pH value of the organic dye wastewater to 2, and controlling the temperature of the wastewater to 20-30 ℃ through a constant-temperature water bath box; the ultrasonic degradation was carried out in an ultrasonic device with an ultrasonic power of 200W.
Comparative example 3: adjusting the pH value of the organic dye wastewater to 2, and controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath tank; then adding tungsten powder into the organic dye wastewater, and uniformly mixing, wherein the addition amount of the tungsten powder is 1 g.L-1。。
Comparative example 4: adjusting the pH value of the organic dye wastewater to 2, and controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath tank; introducing hydrogen peroxide into the organic dye wastewater, wherein the concentration of the hydrogen peroxide is 5 mmol.L-1(ii) a Then adding tungsten powder into the organic dye wastewater, and uniformly mixing, wherein the addition amount of the tungsten powder is 1 g.L-1。。
Comparative example 5: adjusting the pH value of the organic dye wastewater to 2, and controlling the temperature of the wastewater to 25 ℃ through a constant-temperature water bath tank; introducing hydrogen peroxide into the organic dye wastewater, wherein the concentration of the hydrogen peroxide is 5 mmol.L-1(ii) a Then adding tungsten powder into the organic dye wastewater, and uniformly mixing; performing ultrasonic degradation in an ultrasonic device with ultrasonic power of 200W, wherein the addition amount of tungsten powder is 1 g.L-1。
The comparison of the effect of treating methyl orange dye wastewater in example 1 and control groups 1-5 is shown in FIG. 11: the methyl orange dye wastewater is hardly degraded without ultrasound and catalyst; the degradation rate of the methyl orange dye wastewater is only improved slightly under the action of ultrasound, and although the cavitation effect of ultrasound is favorable for ultrasonic degradation theoretically, in practice, the power of an ultrasonic instrument is low, the cavitation effect generated by ultrasound is poor, and the degradation rate of the methyl orange dye wastewater is not improved greatly. The degradation rate of the methyl orange dye wastewater is obviously improved under the condition of not performing ultrasonic treatment but adding a catalyst, namely the catalyst has good catalytic action on the methyl orange dye wastewater, and hydrogen peroxide is added as an additional catalyst on the basis, so that the degradation rate is improved but is not obvious, and the proper addition of the additional oxidant has a certain promotion effect on the reaction. And when the ultrasonic wave is further introduced, the degradation rate of the methyl orange dye wastewater can reach 2.88 times that of the methyl orange dye wastewater without the ultrasonic wave, which shows that the tungsten powder and the ultrasonic wave are combined to catalyze and degrade the degradation effect of the methyl orange dye wastewater.
Other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method for degrading organic dye wastewater based on tungsten powder and ultrasonic catalysis is characterized by comprising the following steps: the method comprises the following steps:
1) adjusting the pH value of the organic dye wastewater to 2-5, and simultaneously adjusting the dissolved oxygen concentration of the organic dye wastewater to 0-8.6 mg.L-1Controlling the temperature of the wastewater to be 20-45 ℃ through a constant-temperature water bath box;
2) introducing hydrogen peroxide into the organic dye wastewater, then adding tungsten powder into the organic dye wastewater, and uniformly mixing; the ultrasonic degradation is carried out in an ultrasonic device.
2. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the organic dye wastewater is any one of methyl orange dye wastewater, Congo red dye wastewater and methylene blue dye wastewater.
3. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the dissolved oxygen concentration of the organic dye wastewater is adjusted to be 8.6 mg.L-1。
4. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the temperature of the wastewater is controlled to 25 ℃ by the constant-temperature water bath box.
5. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the concentration of hydrogen peroxide in the organic dye wastewater is 2-15 mmol/L.
6. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 5, wherein the method comprises the following steps: in the organic dye wastewater, the concentration of hydrogen peroxide is 5 mmol/L.
7. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the addition amount of the tungsten powder is 1-10 g.L-1。
8. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 7, wherein the method comprises the following steps: in the step 2), the addition amount of the tungsten powder is 10 g.L-1。
9. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the working conditions of the ultrasonic device are as follows: the ultrasonic power is 100-500W, and the ultrasonic temperature is 10-80 ℃.
10. The method for degrading organic dye wastewater based on tungsten powder synergistic ultrasonic catalysis as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the working conditions of the ultrasonic device are as follows: the ultrasonic power is 500W, and the ultrasonic temperature is 45 ℃.
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|---|---|---|---|---|
| CN115959757A (en) * | 2023-01-09 | 2023-04-14 | 武汉纺织大学 | Method for degrading organic pollutants by virtue of synergism of chloralkane and ultrasonic stirring |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673170A (en) * | 2016-12-21 | 2017-05-17 | 沈阳化工大学 | Method of catalytically and ultrasonically degrading organic dye gold orange II by using semiconductor material magnesium tungstate |
| CN106799200A (en) * | 2017-02-26 | 2017-06-06 | 河南师范大学 | A kind of WS2@MoS2Composite visible light catalyst and its preparation method and application |
| CN112174288A (en) * | 2020-10-09 | 2021-01-05 | 广东石油化工学院 | Method for degrading organic pollutants by iron salt-zero-valent iron concerted catalysis |
-
2021
- 2021-03-25 CN CN202110322306.9A patent/CN113072162A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673170A (en) * | 2016-12-21 | 2017-05-17 | 沈阳化工大学 | Method of catalytically and ultrasonically degrading organic dye gold orange II by using semiconductor material magnesium tungstate |
| CN106799200A (en) * | 2017-02-26 | 2017-06-06 | 河南师范大学 | A kind of WS2@MoS2Composite visible light catalyst and its preparation method and application |
| CN112174288A (en) * | 2020-10-09 | 2021-01-05 | 广东石油化工学院 | Method for degrading organic pollutants by iron salt-zero-valent iron concerted catalysis |
Non-Patent Citations (2)
| Title |
|---|
| PENG ZHOU 等: "Removal of Rhodamine B during the corrosion of zero valent tungsten via a tungsten species-catalyzed Fenton-like system", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS》 * |
| 汤茜 等: "超声-Fenton法降解模拟染料废水的实验研究", 《吉林师范大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959757A (en) * | 2023-01-09 | 2023-04-14 | 武汉纺织大学 | Method for degrading organic pollutants by virtue of synergism of chloralkane and ultrasonic stirring |
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