CN106830179B - Method for degrading azo dye in wastewater - Google Patents

Method for degrading azo dye in wastewater Download PDF

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CN106830179B
CN106830179B CN201710123353.4A CN201710123353A CN106830179B CN 106830179 B CN106830179 B CN 106830179B CN 201710123353 A CN201710123353 A CN 201710123353A CN 106830179 B CN106830179 B CN 106830179B
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wastewater
concentration
azo dyes
ultrasonic
degrading
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CN106830179A (en
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赵同谦
李鹏
邰超
佘加平
冯磊
齐永安
张国成
武俐
肖春艳
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Henan University of Technology
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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
    • C02F1/34—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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention relates to a method for degrading azo dyes in wastewater, wherein the method is carried out under Na2CO3And H2O2The degradation of the azo dye wastewater is promoted by generating carbonate free radicals through ultrasound in the presence of the organic acid. At ultrasound and H2O2In the presence of (B), by addition of Na2CO3Greatly improving the degradation efficiency of the azo dye. Measuring the maximum absorbance with UV-visible spectrophotometer, adding Na2CO3Then, the degradation rate of the Acid orange 8(Acid orange 8) azo dye wastewater in 2h is improved from 6 percent to more than 90 percent.

Description

Method for degrading azo dye in wastewater
Technical Field
The invention relates to a method for degrading azo dyes in wastewater, belonging to the technical field of dye wastewater treatment.
Background
Azo dyes are dyes which contain azo groups (-N ═ N-) in the molecule. Azo dyes are the most widely used synthetic dyes in the textile, paper, leather, printing and other industries, and account for 80% of the total amount of organic dye products. At least 10-15% of the dye can enter the water body, and the dye can stably exist in the water body due to the light resistance and oxidation resistance, so that the water body ecological system is damaged; in addition, azo dyes also have carcinogenic, teratogenic, mutagenic and biologically recalcitrant properties and are easily accumulated in the environment to further cause harm to the health of living beings and human beings. Therefore, the method has very important theoretical value and engineering practical significance for economically and efficiently treating the azo dye-containing wastewater. At present, physical methods such as activated carbon, organic bentonite and other adsorbents are used for only simply transferring pollutants, so that secondary pollution is easily caused and complete degradation cannot be realized. The efficiency of the conventional biodegradation technology is also not ideal due to the particularly high chroma, COD and BOD values of the printing and dyeing wastewater. The hydroxyl free radical generated by Fenton reaction can effectively and thoroughly degrade azo dyes, but a large amount of iron mud which is difficult to separate is easily formed.
The ultrasonic treatment of industrial waste water is a novel water treatment technology, but the azo dye has stable structure and poor ultrasonic treatment effect when being used alone. The ultrasonic wave and hydrogen peroxide react to produce hydroxyl radical OH with strong oxidizing capacity, which can produce oxidizing reaction on organic matter, but OH has short stay time and slow degradation rate. Researches find that the degradation effect of azo dyes is improved by using the synergistic effect of ultrasonic and other methods. In the existing patents for treating organic wastewater by utilizing synergistic effect, for example, CN200610085548.6 has high energy consumption when treating azo dye wastewater by utilizing ultrasonic waves and light radiation, and has low light utilization efficiency when the wastewater is low in transparency, so that the treatment time is long, the treatment effect is poor, and the method is not suitable for large-scale industrial application. CN201110324834.4 utilizes the active carbon loaded iron-cobalt bimetallic oxide as a catalyst to combine with persulfate and ultrasonic waves to treat organic matters in wastewater; CN201210252042.5 utilizes activated carbon loaded zinc oxide as a catalyst to combine with ultrasonic waves and peroxydisulfate to treat organic wastewater; both of them have the problems of complicated catalyst preparation process and high production cost, and use of metal oxideThe catalyst has a problem of elution of metal ions, and has secondary pollution when used in a large amount, and the catalyst efficiency of the former catalyst is lowered when recovered and recycled. In CN201410552018.2, TeO2Doped TiO 22The azo dye wastewater is degraded by catalysis and ultrasonic treatment, HCl is needed to be adjusted to a strong acid environment before treatment, continuous stirring is needed during treatment, and standing is needed after treatment to separate solid from liquid, so that the process is complex. In summary, the existing synergy has the following disadvantages:
(1) when the ultrasonic wave and the light radiation act independently, the treatment time is long, and the treatment effect is poor. (e.g. CN200610085548.6)
(2) When the catalyst is used to act together with the ultrasound and the oxidant, the preparation process of the catalyst is complex and the preparation cost is high. (e.g., CN201110324834.4 and CN201210252042.5)
Poplar et al (Yang et al, 2010) used different anions in conjunction with oxidant H2O2Degradation of acid orange 7 dye by persulfates and peroxymonosulfates was found to be with CO3 2-The synergistic effect of the peroxymonosulfate is the best. However, when persulfate or the like is used as the oxidizing agent, a large amount of SO is generated by decomposition of persulfate4 2-And the water is stable after entering the water body, and causes pollution to surface water, underground water and the like. And CO3 2-CO after entering the water body and in the atmosphere2The exchange is carried out without any influence on the water body.
Disclosure of Invention
To solve the problems as described above, the present invention provides a method for degrading azo dyes in wastewater using ultrasound and H2O2And Na2CO3To promote the degradation of the azo dye wastewater. As shown in fig. 1, at ultrasound and H2O2Due to Na2CO3The synergistic effect of the components greatly improves the degradation efficiency of the azo dye. The maximum absorbance was measured using UV-visible spectrophotometer by adding Na2CO3The degradation rate of the Acid orange 8(Acid orange 8) azo dye wastewater in 2h is improved from 6% to more than 90%.
In one aspect, the method for degrading azo dyes in wastewater of the present invention controls the reaction temperature using microwaves, uses ultrasound and H2O2And sodium carbonate, said method comprising the steps of:
(1) placing the azo dye wastewater into a reaction kettle, and adding Na2CO3Solid or Na2CO3Solution, adjusting Na2CO3The concentration of (a) is in the range of 2-200 mmol/L;
(2) adding hydrogen peroxide into the wastewater to adjust H2O2The concentration range in the wastewater is 1-100 mmol/L;
(3) stirring or diffusing Na2CO3Uniformly mixing the wastewater with hydrogen peroxide, and controlling the reaction temperature by microwave;
(4) and (3) extending an ultrasonic transducer probe into the dye wastewater, adjusting the ultrasonic power, setting an ultrasonic working mode, and turning on a switch of an ultrasonic generator for treatment.
In a preferred embodiment, the azo dye is selected from one or more of acid orange 8, gold orange II and acid red 9; preferably, the concentration of the azo dye in the wastewater is 30. mu. mol/L to 3 mmol/L.
In a preferred embodiment, the hydrogen peroxide concentration used is 30 wt%.
In a preferred embodiment, Na2CO3The concentration is 10 to 100mmol/L, preferably 25 to 80mmol/L, and more preferably 40 to 60 mmol/L.
In a preferred embodiment, H2O2The concentration is 5 to 80mmol/L, preferably 10 to 60mmol/L, and more preferably 15 to 40 mmol/L.
In a preferred embodiment, Na2CO3The concentration is 50 mmol/L; and H2O2The concentration was 20 mmol/L.
In a preferred embodiment, the temperature in step (3) is 30 to 80 ℃, preferably 40 to 60 ℃, and more preferably 45 to 55 ℃.
In a preferred embodiment, the frequency of the ultrasonic generator in the step (4) is 25 KHz; the ultrasonic power is 0-800 w, preferably 100-600 w, and more preferably 200-400 w.
In a preferred embodiment, the ultrasonic operation mode in the step (4) is 2s of operation and 2s of interval.
In a preferred embodiment, the sonication time in step (4) is between 60min and 180min, preferably between 90min and 150min, most preferably 120 min.
In a preferred embodiment, the method is carried out in an alkaline environment, and the pH value is preferably 9.5-12, more preferably 10-11.5, still more preferably 10.5-11, and most preferably 10.9.
Taking the azo dye wastewater Acid orange 8 as an example, the azo dye wastewater Acid orange 8 is treated by the method of the invention, so that the degradation of the azo dye is successfully realized. The chroma of the dye wastewater is changed from deep to light in a short time by the treatment of the method, and the dye wastewater becomes nearly transparent after a period of treatment. As shown in FIG. 2, the absorbance of the Acid orange 8 azo dye wastewater at the peak value becomes lower with the increase of the treatment time, and the absorption spectrum tends to be flat after two hours of treatment. And no other characteristic peak appears in the treatment process, which indicates that no other substances are generated.
Drawings
FIG. 1 shows the addition and non-addition of Na2CO3The concentration of Acid orange 8 azo dye in wastewater varies with time;
FIG. 2 is a graph of absorbance versus time for Acid orange 8 azo dye wastewater;
FIGS. 3(a) - (b) are graphs showing the concentration of Acid orange 8 azo dye wastewater with time at different concentrations in the first example;
FIGS. 4(a) - (d) are different H in example II2O2The concentration versus time curve of Acid orange 8 azo dye in wastewater at concentration, sodium carbonate concentration, pH and temperature;
FIG. 5 is a graph of the concentration of Acid orange 8 azo dye in wastewater as a function of time for the third example;
FIGS. 6(a) - (b) are graphs showing the concentration of gold orange II and acid red 9 azo dyes in wastewater as a function of time for example four.
Detailed Description
The invention utilizes ultrasound/H2O2/Na2CO3The synergistic effect of the two components degrades azo dyes in the wastewater. The ultrasonic frequency is fixed at 25KHz, the power is 400W, and the reaction temperature is controlled at 30 ℃ by using microwaves. Preparing azo dye wastewater with a certain concentration, and adding a certain amount of H according to a proportion2O2And Na2CO3Controlling the total volume to be 150 mL; and then, extending an ultrasonic probe into the dye wastewater, and setting an ultrasonic working mode to operate for 2s and interval for 2 s. And turning on a switch of the ultrasonic generator, and processing for 2 h. The change in absorbance over 2h was recorded using a UV-Vis spectrophotometer ( sampling time points 0, 20, 40, 60, 90, 120 min).
The first embodiment is as follows: degrading Acid orange 8 azo dye with different concentrations. Preparing 0.03mmol/L Acidorgange 8 solution, adding H2O2And Na2CO3To make H in solution2O2The concentration is 50mmol/L, Na2CO3The concentration was 5mmol/L and the total volume was 150 mL. An ultrasonic probe is extended into the dye wastewater, and the ultrasonic working mode is set to operate for 2s and interval for 2 s. And turning on a switch of the ultrasonic generator, wherein the processing time is 2 h. The change value of absorbance within 2h is recorded, and the degradation rate within 2h reaches 90% as shown in fig. 3 (a). The dye concentration was increased by 50-fold. A0.15 mmol/L solution of azo dye Acid orange 8 was prepared, and as shown in FIG. 3(b), an effect similar to that of FIG. 3(a) was obtained.
Example two: the azo dye concentration was fixed, and the optimum conditions were searched for. Preparing 0.1mmol/L azo dye Acidorgange 8 solution, adding H2O2And Na2CO3The total volume was 150mL, and the treatment was carried out at 30 ℃ for 2 hours. By separately varying H in the system2O2The concentration, the sodium carbonate concentration, the pH value and the temperature, and the degradation effect of the azo dye under different conditions. As shown in FIG. 4(a), the fixed sodium carbonate concentration was 50mmol/L with H2O2Increase of concentration, degradation efficiency of dye within 2hThe fruit is lifted accordingly. In FIG. 4(b), H is fixed2O2The concentration is 20mmol/L, the degradation effect of the dye is gradually improved within 2h along with the increase of the concentration of the sodium carbonate, but when the concentration of the sodium carbonate exceeds 50mmol/L, the benefit ratio is reduced. In FIG. 4(c), the degradation effect of the system on azo dyes is good in alkaline environment, and the effect is best when the pH is 10.9. In fig. 4(d), the temperature has a significant effect on the degradation effect of the azo dye, and the higher the temperature is, the better the degradation effect is, and the shorter the time required for achieving the same effect is. In summary, in H2O2The concentration is 20mmol/L, and the concentration of sodium carbonate is 50mmol/L, the degradation effect is good, and the benefit is better.
Example three: the azo dye Acid orange 8 is degraded in the optimal proportion. Preparing 0.1mmol/L azo dye Acid orange 8 solution, adding H2O2And Na2CO3To make H in solution2O2The concentration is 20mmol/L, Na2CO3The concentration was 50mmol/L and the total volume was 150 mL. An ultrasonic probe is extended into the dye wastewater, and the ultrasonic working mode is set to operate for 2s and interval for 2 s. And turning on a switch of the ultrasonic generator, and processing for 2 h. The change in absorbance within 2h was recorded, and the degradation rate within 2h was 92% as shown in FIG. 5.
Example four: the optimal proportion degrades other azo dyes. The azo dye Acid orange 8 in example three was replaced by the azo dyes gold orange II and Acid red 9. Respectively preparing 0.1mmol/L of golden orange II and acid red 9 solution, adding H2O2And Na2CO3To make H in solution2O2The concentration is 20mmol/L, Na2CO3The concentration was 50mmol/L and the total volume was 150 mL. An ultrasonic probe is extended into the dye wastewater, and the ultrasonic working mode is set to operate for 2s and interval for 2 s. And turning on a switch of the ultrasonic generator, and processing for 2 h. The change in absorbance within 2h was recorded, and the degradation rates within 2h were 96% and 82%, respectively, as shown in FIGS. 6(a) and (b).

Claims (10)

1. A method for degrading azo dyes in wastewater is characterized by comprising the following steps:
(1) placing the azo dye wastewater into a reaction kettle, and addingNa2CO3Solid or Na2CO3Solution, adjusting Na2CO3The concentration of (a) is in the range of 2-200 mmol/L;
(2) adding hydrogen peroxide into the wastewater to adjust H2O2The concentration range in the wastewater is 1-100 mmol/L;
(3) making Na by diffusion2CO3And H2O2Uniformly mixing the mixture in the wastewater, and controlling the reaction temperature by microwaves;
(4) and (3) extending an ultrasonic transducer probe into the dye wastewater, adjusting the ultrasonic power, setting an ultrasonic working mode, and turning on a switch of an ultrasonic generator for treatment.
2. The method for degrading azo dyes in wastewater according to claim 1, characterized in that: the azo dye is selected from one or more of acid orange 8, golden orange II and acid red 9; the concentration of the azo dye in the wastewater is 30 mu mol/L-3 mmol/L.
3. The method for degrading azo dyes in wastewater according to claim 1 or 2, wherein: the concentration of the hydrogen peroxide used is 30 wt%.
4. The method for degrading azo dyes in wastewater according to claim 3, wherein: na (Na)2CO3The concentration range is 10-100 mmol/L; h2O2The concentration range is 5-80 mmol/L.
5. The method for degrading azo dyes in wastewater according to claim 4, wherein: na (Na)2CO3The concentration is 50 mmol/L; h2O2The concentration was 20 mmol/L.
6. The method for degrading azo dyes in wastewater according to claim 5, wherein: the temperature in the step (3) is 30-80 ℃.
7. The method for degrading azo dyes in wastewater according to claim 6, wherein: the frequency of the ultrasonic generator in the step (4) is 25 KHz; the ultrasonic power is 0-800 w.
8. The method for degrading azo dyes in wastewater according to claim 7, wherein: and (4) working in an ultrasonic working mode of 2s at an interval of 2 s.
9. The method for degrading azo dyes in wastewater according to claim 8, wherein: the ultrasonic treatment time in the step (4) is 60-180 min.
10. The method for degrading azo dyes in wastewater according to claim 9, characterized in that: the method is implemented in an alkaline environment, and the pH value is 9.5-12.
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CN110702624A (en) * 2019-09-20 2020-01-17 家食安(青岛)健康科技有限公司 Device and method for rapidly evaluating degradation capability of colored organic matter
CN116062938A (en) * 2023-02-09 2023-05-05 华东师范大学 Advanced oxidation method for treating dye organic wastewater by alkali-activated hydrogen peroxide

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CN103159314A (en) * 2013-03-28 2013-06-19 中国科学院城市环境研究所 Method for eliminating antibiotics resistance gene pollution in water by hydrogen peroxide coupled ultrasonic method

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CN103159314A (en) * 2013-03-28 2013-06-19 中国科学院城市环境研究所 Method for eliminating antibiotics resistance gene pollution in water by hydrogen peroxide coupled ultrasonic method

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