CN108585111B

CN108585111B - Method for degrading meloxicam by catalyzing and ultrasonically degrading zinc tungstate serving as semiconductor material

Info

Publication number: CN108585111B
Application number: CN201810451859.2A
Authority: CN
Inventors: 王新; 许明玲; 郝俊旭; 周玲玲; 王晓芳; 刘彬
Original assignee: Liaoning University
Current assignee: Liaoning University
Priority date: 2018-05-12
Filing date: 2018-05-12
Publication date: 2021-04-30
Anticipated expiration: 2038-05-12
Also published as: CN108585111A

Abstract

The invention discloses a semiconductor material zinc tungstate (ZnWO)₄) A method for catalyzing ultrasonic degradation of meloxicam comprises the step of mixing a semiconductor nano material ZnWO₄Mixing with meloxicam, putting into a container, and performing ultrasonic degradation in an ultrasonic device; and centrifuging the sample, taking the supernatant clear solution, and performing ultraviolet-visible (UV-vis) absorption spectrum measurement. The method judges ZnWO by degrading meloxicam by ultrasound₄Acoustic catalytic activity, and ultraviolet spectrum to determine the change in absorbance of meloxicam₄The acoustic catalytic activity of (a). ZnWO₄Safe and nontoxic, stable in physicochemical property, high-efficiency and recyclable, and has no secondary pollution. Verification shows that ZnWO₄Has considerable prospect in the aspect of catalyzing and ultrasonically degrading pharmaceutical wastewater.

Description

Method for degrading meloxicam by catalyzing and ultrasonically degrading zinc tungstate serving as semiconductor material

Technical Field

The invention relates to the technical field of ultrasonic degradation of pharmaceutical wastewater, in particular to a semiconductor material ZnWO₄A method for catalyzing ultrasonic degradation of meloxicam.

Background

The raw materials of the medicine are complex in components, the production process is various, the product types are various, the content of wastewater pollutants is high, the biodegradability is poor, the water quality and the water quantity change are large, the pollutants which are difficult to degrade are remained in the water body for a long time after being discharged into the water body, most of the pollutants have stronger toxicity and three-cause effects, are accumulated and enriched through a food chain, finally enter a human body to generate toxicity, and are one of the wastewater which is recognized in the world and is difficult to treat.

ZnWO₄Is a monoclinic crystal, has stable physical and chemical properties, and has the capability of resisting radiation and strong light because of having a special junctionThe structure and properties, generally considered as an effective material for dealing with the problem of water pollution, have been extensively studied in recent years. In recent years, the advanced oxidation method draws more and more attention with its unique advantages, and ultrasonic irradiation is an advanced oxidation process and an emerging technology for treating wastewater. The ultrasonic degradation mainly comprises three ways of free radical oxidation, high-temperature pyrolysis and supercritical water oxidation, and the cavitation effect of the three ways breaks the molecular valence bond and forms hydroxyl free radical, so that organic matters are degraded; the high temperature and high pressure generated when the cavitation bubbles collapse can enable the acoustic catalyst to play a catalytic role. The ultrasonic energy is concentrated, the propagation distance is long, and the nano catalyst can be assisted to degrade organic matters due to the unique property of the ultrasonic energy, so that the ultrasonic energy-concentrated nano catalyst has a good research prospect.

Disclosure of Invention

The invention aims to provide a semiconductor material ZnWO₄Method for catalytic ultrasonic degradation of meloxicam, which uses ZnWO₄As a semiconductor acoustic catalyst, the catalytic ultrasonic degradation of meloxicam is carried out in an ultrasonic device by changing ZnWO₄The pH value, the addition amount, the initial concentration of the meloxicam, the time and the power of ultrasound and the like are investigated, the feasibility of the technology is further explored, and the research shows that the technology can be applied to the field of treating pharmaceutical wastewater.

The purpose of the invention is realized by the following technical scheme:

semiconductor material ZnWO₄A method for catalyzing ultrasonic degradation of meloxicam comprises the step of mixing a semiconductor nano material ZnWO₄Mixing with meloxicam, putting into a container, and performing ultrasonic degradation in an ultrasonic device; centrifuging the sample, taking the supernatant clear solution, and performing UV-vis spectrometry.

The method, the ZnWO₄The pH value of (A) is 5-9.

The method, the ZnWO₄The addition amount of (B) is 0.50-1.50 g.L^-1。

The method is characterized in that the initial concentration of the meloxicam is 6-18 mg.L^-1。

In the method, the ultrasonic time is 0-150 min.

The ultrasonic power of the method is 100-200W.

The invention has the advantages and effects that:

1. the invention uses ZnWO₄As a semiconductor catalyst, the catalyst has the advantages of safety, no toxicity, stable physicochemical property, high efficiency, recoverability and no secondary pollution. Verification shows that ZnWO₄Has considerable prospect in the aspect of catalyzing and ultrasonically degrading waste water.

2. The main functions of the ultrasonic waves in the present invention are cavitation, thermal effect and chemical effect. ZnWO₄As an acoustic catalyst, the meloxicam has good catalytic degradation effect on meloxicam. The process of the invention takes the ultrasonic method as a novel pharmaceutical wastewater treatment technology, and has the advantages of simple and convenient operation, high efficiency, wide application range and no secondary pollution.

Drawings

FIG. 1(a) shows the product ZnWO prepared in example 1₄X-ray diffraction (XRD) spectrum of (a);

FIGS. 1(b) and (c) are scanning electron micrographs of the product prepared in example 1;

FIG. 2 is a diagram of the structure of meloxicam;

FIG. 3 is a scheme showing the use of ZnWO in example 3₄The influence of the addition amount of the catalyst when the catalyst is used as an acoustic catalyst on the effect of catalyzing ultrasonic degradation of the meloxicam solution;

FIG. 4 is a scheme showing the use of ZnWO in example 4₄When the catalyst is used as a sound catalyst for catalyzing ultrasonic degradation of meloxicam, the influence of different ultrasonic time on the catalytic ultrasonic degradation effect is avoided.

Detailed Description

The present invention will be described in detail with reference to examples.

Tungstate semiconductor material ZnWO₄Has good effect of catalyzing ultrasonic degradation of meloxicam, and the initial raw material of the preparation method is ZnWO which is cheap and easy to obtain₄The purpose of degrading meloxicam is achieved by ultrasound without any auxiliary agent. ZnWO prepared by hydrothermal method₄Is a nano-scale semiconductor material. ZnWO₄Has granular structure, monoclinic crystal, stable physical and chemical properties, and good soundCatalytic performance.

Example 1ZnWO₄Preparation method

The method comprises the following steps:

the method comprises the following steps: according to a certain ratio, mixing 0.17 mol.L^-1Na of (2)₂WO₄·2H₂Adding the O solution into a beaker, and adding 0.17 mol.L under the stirring condition^-1Zn(NO₃)₂·6H₂And O, adjusting the pH value to about 6 by using NaOH or HCl solution, magnetically stirring for 30min at room temperature, and carrying out ultrasonic treatment for 30 min.

Step two: and (3) putting the solution prepared in the step one into a high-pressure reaction kettle with a polytetrafluoroethylene lining for reaction at 180 ℃, and naturally cooling to room temperature after the reaction is finished.

Step three: the product is filtered, washed, dried and ground to prepare ZnWO₄And (3) powder.

FIG. 1(a) shows the product ZnWO prepared in example 1₄X-ray diffraction (XRD) spectrum of (a); FIGS. 1(b) and (c) are scanning electron micrographs of the product prepared in example 1; as can be seen from the figure, the product synthesized in example 1 is ZnWO₄The form of the compound is granular.

Figure 2 is a diagram of the structure of meloxicam.

Example 2 method for degrading meloxicam by zinc tungstate catalysis and ultrasound

The method comprises the following steps:

the method comprises the following steps: taking 20mL of meloxicam solution with the concentration of 10mg/L into a conical flask, and adding accurately weighed 10mg of nano ZnWO₄And (3) performing ultrasonic degradation on the powder.

Step two: the suspension was sampled and centrifuged to obtain the supernatant.

Step three: measuring the UV-vis spectrum within 200-450 nm. The rate of degradation of meloxicam can be measured by using a solution of meloxicam at the lambda of the meloxicam_maxCalculated as absorbance at 360nm, the formula is: percent degradation rate (%) [ (A)₀-A_t)/A₀]×100％，A₀Is the initial absorbance of the meloxicam solution, A_tIs the absorbance of meloxicam solution under different experimental conditions.

Example 3 method for ultrasonic degradation of meloxicam under catalysis of semiconductor material zinc tungstate

ZnWO₄The degradation experiment of meloxicam is performed in ZnWO₄The addition of ZnWO is carried out in an amount of 0.50 to 1.50g/L₄The pH value of the ultrasonic wave is 6, the concentration of the meloxicam is 10mg/L, the ultrasonic power is 200W, and the ultrasonic time is 120 min.

Taking 20mL of 10mg/L meloxicam solution, and adding 0.50g/L of nano ZnWO at one time₄The powder was sonicated for 120 min. And sampling the suspension, centrifuging, taking the supernatant, and measuring the UV-vis spectrum of the supernatant within 200-450 nm.

ZnWO₄The above experiment was repeated while changing the amounts of addition of (A) to (B) in the order of 0.75, 1.00, 1.25 and 1.50 g/L.

FIG. 3 is a scheme showing the use of ZnWO in example 3₄When the compound is used as an acoustic catalyst, the addition amount of the compound has an influence on the effect of catalyzing ultrasonic degradation of the meloxicam solution; as can be seen from FIG. 3, when ZnWO is used₄When the addition amount of (A) is 1.00g/L, the degradation effect is best, and the degradation rate can reach 75.67%.

Example 4 method for ultrasonic degradation of meloxicam under catalysis of semiconductor material zinc tungstate

ZnWO₄The degradation experiment of meloxicam is performed in ZnWO₄Is added in an amount of 1.00g/L, ZnWO₄The pH value of the ultrasonic wave is 6, the concentration of the meloxicam is 10mg/L, the ultrasonic power is 200W, and the ultrasonic time is 0, 30, 60, 90, 120 and 150min in sequence.

20mL of 10mg/L meloxicam solution is taken, and 1.00g/L of nano ZnWO is added in one time₄Pulverizing, and ultrasonic treating for 30 min. And sampling the suspension, centrifuging, taking the supernatant, and measuring the UV-vis spectrum of the supernatant within 200-450 nm.

FIG. 4 is a scheme showing the use of ZnWO in example 4₄When the acoustic catalyst is used for catalyzing and ultrasonically degrading meloxicam, the influence of different ultrasonic time on the catalytic ultrasonic degradation effect is shown in figure 4, and as the ultrasonic time is prolonged, ZnWO₄The effect of catalytic ultrasonic degradation is gradually enhanced, and the ultrasonic effect reaches the best after 120 min.

Claims

1. Semiconductor material ZnWO₄Catalytic ultrasonic degradationThe method for preparing meloxicam is characterized by comprising the step of mixing semiconductor nano material ZnWO₄Mixing with meloxicam, putting into a container, and performing ultrasonic degradation in an ultrasonic device; centrifuging a sample, taking an upper clear solution, and performing UV-vis spectrometry;

the ZnWO₄The addition amount of (5) was 0.50-1.50g^-1；

The ultrasonic time is 120-150 min.

2. The method of claim 1, wherein the initial concentration of meloxicam is 6-18mg L^-1。

3. The method of claim 1, wherein the ultrasonic power is 100-.