CN103058446B - Method for removing pesticide residues in water body by using magnetic titanium oxide micellar system - Google Patents

Abstract

The invention discloses a method for removing pesticide residues in water by using a magnetic titanium oxide micelle system, which relates to a method for removing pesticide residues in water. The object of the invention is to solve the problems of cumbersome process, high treatment cost and low removal efficiency in the removal technology of pesticide residues in water bodies. Methods: 1. Preparation of Fe ₃ O ₄ magnetic fluid; 2. Preparation of magnetic titanium oxide nanoparticles; 3. Removal of pesticide residues, that is, the removal of pesticide residues in the water to be treated is completed, and the treated water is obtained. The invention is mainly used for removing pesticide residues in water bodies.

Description

A method for removing pesticide residues in water using a magnetic titanium oxide micellar system

technical field

The invention relates to a method for removing pesticide residues in water bodies.

Background technique

With the development of modern agriculture, more and more types of pesticides are used in the world, and the dosage is increasing. Pesticide residues lead to environmental pollution and damage to the structure and function of the ecosystem, which has long been widely concerned at home and abroad. According to relevant reports, only about 20% of chemical pesticides remain directly on crops during the application process, and the rest enters soil and groundwater through natural sedimentation and precipitation, and a considerable part enters lakes and rivers with surface runoff. After long-term and large-scale use of various pesticides entered the water environment, it caused a series of problems such as water environment pollution, ecosystem damage, and food safety. Therefore, it is very necessary to study simple, convenient and quick methods of removing pesticides in the water environment for the protection of the ecological environment and human health and survival. At present, the removal methods of pesticide pollutants mainly include activated carbon adsorption, biodegradation and oxidation. However, most of these methods have disadvantages such as cumbersome treatment process, high treatment cost and low removal efficiency.

In recent years, the self-assembly behavior of ionic surfactants adsorbed on the surface of metal oxides has attracted the attention of physical chemists. Ionic surfactants can form mixed micelles on the surface of metal oxides such as alumina, silica, and iron oxide. Self-assembly system, related studies have shown that the solid-phase extraction method based on this single-molecule/bimolecular mixed micelle adsorption system generally has a strong adsorption capacity for hydrophobic, amphiphilic and ionic organic compounds.

To sum up, the existing pesticide residue removal technologies in environmental water samples have the problems of cumbersome process, high processing cost and low removal efficiency.

Contents of the invention

The purpose of the present invention is to solve the problems of cumbersome process, high processing cost and low removal efficiency in the removal technology of pesticide residues in water, and provide a method for removing pesticide residues in water using a magnetic titanium oxide micelle system.

A method for removing pesticide residues in water by using a magnetic titanium oxide micelle system, which is specifically completed by the following steps: 1. Preparation of Fe ₃ O ₄ magnetic fluid: first, FeCl ₂ 4H ₂ O and FeCl ₃ 6H ₂ O Completely dissolve in distilled water, and heat up from room temperature to 80°C-90°C at a stirring speed of 400rmp-600rmp, then add NH ₃ ·H ₂ O, and stir at a temperature of 80°C-90°C and a stirring speed of 400rmp-600rmp React under the conditions for 0.5h to 1.5h, and then use a magnet for magnetic separation to obtain a black solid product, wash the black solid product with distilled water until the pH of the washed wastewater is neutral, and then obtain Fe ₃ O ₄ magnetic fluid; steps The molar ratio of FeCl ₂ .4H ₂ O to FeCl _{3 .6H 2} O described in step 1 is 1:( _1.9 ～ ₂ ) _; The molar ratio is 1:(8～9);

2. Preparation of magnetic titanium oxide nanoparticles: firstly add Fe ₃ O ₄ magnetic fluid into distilled water, then add TiCl ₄ , and stir at a stirring speed of 400rmp-600rmp for 10min-20min, then add aqueous sodium hydroxide solution to adjust the pH value Adjust to 8.5~9.5, continue to stir at a stirring speed of 400rmp~600rmp for 5min~15min, then react at a temperature of 140°C~160°C for 5h~8h to obtain a brown solid product, wash the brown solid product with distilled water, and wash until The pH of the washed wastewater is neutral until the washed brown solid product is obtained, and then the washed brown solid product is dried at a temperature of 80 ° C to 100 ° C, and the magnetic titanium oxide nanoparticles are obtained after drying to constant weight ; The Fe ₃ O ₄ magnetic fluid described in step 2 has a volume ratio of 1g to distilled water: (30mL～80mL); the Fe ₃ O ₄ magnetic fluid described in step 2 has a mass and _TiCl volume ratio of 1g: (1mL～2mL);

3. Removal of pesticide residues: First, add magnetic titanium oxide nanoparticles and surfactants to the water body to be treated, then stir for 1min to 40min at a stirring speed of 300rmp to 600rmp, then use a magnet for magnetic separation, absorb the supernatant, Adopt 0.2 μm filter membrane to filter the supernatant, finish the removal of pesticide residues in the water body to be treated after filtration, obtain the water body after treatment; The mass ratio of described magnetic titanium oxide nanoparticles and surfactant is 1:(0.5～ 1.5); the volume ratio of the mass of the magnetic titanium oxide nanoparticles to the water body to be treated is 1g:(2L-10L).

Advantages of the present invention: 1. The method for preparing magnetic titanium oxide nanoparticles in the present invention is simple and the conditions are easy to control. The magnetic titanium oxide nanoparticles prepared in the present invention have good superparamagnetism, and its saturation magnetization can reach 20emu·g ^-1 ~35emu·g ^-1 ; 2. The magnetic titanium oxide nanoparticles prepared by the present invention are combined with surfactants to form a magnetic titanium oxide micelle system, which is a novel remover, and the remover It has both the large specific surface area of nanomaterials, the superparamagnetism of magnetic materials, the good stability of TiO ₂ and the strong removal ability of mixed micelles. When it is used to remove pesticide residues in water, the removal rate is It can reach more than 95%, and the method is simple to operate and low in processing cost, and can be used for the removal of different types of pesticide residues by optimizing the selection of conditions such as the concentration of the surfactant and the pH of the solution.

Description of drawings

Fig. 1 is the SEM picture of the magnetic titanium oxide nanoparticle prepared in test one step two; Fig. 2 is the Fourier transform infrared spectrogram of the magnetic titanium oxide nanoparticle prepared in test one step two; Fig. 3 is the magnetic titanium oxide nanoparticle prepared in test one step two Hysteresis loop; Fig. 4 is a liquid chromatogram, among the figure A represents the liquid chromatogram of the water body to be treated described in test ten, among the figure B represents the liquid chromatogram of water body after the treatment described in test ten, Among the figure, a represents the absorption peak of kaufthrin; Fig. 5 is the kinetic adsorption curve of the magnetic titanium oxide mixed micelle system formed by test six to eleven to the pesticide kaufthrin; Fig. 6 is the magnetic adsorption curve formed by test six to eleven The first-order kinetic fitting curve of the adsorption of kaufthrin by the titanium oxide micellar system; Figure 7 is the second-order kinetic fitting curve of the adsorption of kaufthrin by the magnetic titanium oxide micellar system formed in Experiments 6 to 11.

Detailed ways

Specific embodiment 1: This embodiment is a method for removing pesticide residues in water using a magnetic titanium oxide micelle system, specifically as follows: 1. Preparation of Fe ₃ O ₄ magnetic fluid: first FeCl ₂ 4H ₂ O and FeCl ₃ ·6H ₂ O are completely dissolved in distilled water, and the temperature is raised from room temperature to 80°C-90°C at a stirring speed of 400rmp-600rmp, then NH ₃ ·H ₂ O is added, and the temperature is 80°C- React at 90°C and a stirring speed of 400rmp to 600rmp for 0.5h to 1.5h, then use a magnet for magnetic separation to obtain a black solid product, wash the black solid product with distilled water until the pH of the washed wastewater is neutral, that is Obtain Fe ₃ O ₄ magnetic fluid;

2. Preparation of magnetic titanium oxide nanoparticles: firstly add Fe ₃ O ₄ magnetic fluid into distilled water, then add TiCl ₄ , and stir at a stirring speed of 400rmp-600rmp for 10min-20min, then add aqueous sodium hydroxide solution to adjust the pH value Adjust to 8.5~9.5, continue to stir at a stirring speed of 400rmp~600rmp for 5min~15min, then react at a temperature of 140°C~160°C for 5h~8h to obtain a brown solid product, wash the brown solid product with distilled water, and wash until The pH of the washed wastewater is neutral until the washed brown solid product is obtained, and then the washed brown solid product is dried at a temperature of 80 ° C to 100 ° C, and the magnetic titanium oxide nanoparticles are obtained after drying to constant weight ;

3. Removal of pesticide residues: First, add magnetic titanium oxide nanoparticles and surfactants to the water body to be treated, then stir for 1min to 40min at a stirring speed of 300rmp to 600rmp, then use a magnet for magnetic separation, absorb the supernatant, The supernatant is filtered with a 0.2 μm filter membrane, and after filtration, the removal of pesticide residues in the water to be treated is completed, and the treated water is obtained.

The molar ratio of FeCl ₂ .4H ₂ O to FeCl ₃ .6H ₂ O in Step 1 of this embodiment is 1:(1.9~2); the FeCl ₂ .4H ₂ O and The molar ratio of NH ₃ ·H ₂ O is 1:(8-9).

The volume ratio of the mass of Fe ₃ O ₄ magnetic fluid described in Step 2 of this embodiment to distilled water is 1g:(30mL～80mL); the mass of Fe ₃ O ₄ magnetic fluid described in Step 2 of this embodiment and TiCl The volume ratio of ₄ is 1g:(1mL~2mL).

The mass ratio of the magnetic titanium oxide nanoparticles described in step 3 of the present embodiment to the surfactant is 1:(0.5～1.5); The volume ratio is 1g:(2L～10L).

The method for preparing magnetic titanium oxide nanoparticles in this embodiment is simple, and the conditions are easy to control. The magnetic titanium oxide nanoparticles prepared in this embodiment have very good superparamagnetism, and their saturation magnetization can reach 20emu·g ^-1 ~ 35emu·g ^-1 .

Embodiment 2: The difference between this embodiment and Embodiment 1 is that in Step 1, the temperature is raised from room temperature to 80° C. to 88° C. at a stirring speed of 450 rpm to 550 rpm. Others are the same as the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in step 1, the temperature is 80°C-88°C and the stirring speed is 450rmp-550rmp for 0.8h-1.2h. Others are the same as those in Embodiment 1 or 2.

Embodiment 4: The difference between this embodiment and Embodiments 1 to 3 is: in step 2, add Fe ₃ O ₄ magnetic fluid to distilled water, then add TiCl ₄ , and stir at a stirring speed of 450rmp-550rmp 12min～18min. Others are the same as the specific embodiments 1 to 3.

Embodiment 5: The difference between this embodiment and Embodiment 1 to 4 is: in step 2, add sodium hydroxide aqueous solution to adjust the pH value to 8.6～9.4, and continue to stir at a stirring speed of 450rmp～550rmp for 8min～12min , and then react at a temperature of 145°C to 155°C for 5.5h to 7.5h to obtain a brown solid product. Others are the same as the specific embodiments 1 to 4.

Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the mass ratio of the magnetic titanium oxide nanoparticles to the surfactant described in Step 3 is 1:(0.8-1.2). Others are the same as the specific embodiments 1 to 5.

Specific embodiment seven: the difference between this embodiment and specific embodiment one to six is: the surfactant described in step 3 is cetyltrimethylammonium bromide, sodium lauryl sulfate or octadecyl Alkyltrimethylammonium bromide. Others are the same as the specific embodiments 1 to 6.

Adopt following test to verify effect of the present invention:

Experiment 1: A method for removing pesticide residues in water using a magnetic titanium oxide micelle system, specifically as follows: 1. Preparation of Fe ₃ O ₄ magnetic fluid: first, 10 mmol of FeCl ₂ 4H ₂ O and 20 mmol FeCl ₃ 6H ₂ O was completely dissolved in distilled water, and the temperature was raised from room temperature to 80°C at a stirring speed of 500rmp, then 80mmol of NH ₃ ·H ₂ O was added, and the temperature was 80°C and the stirring speed was 500rmp. React for 1 hour, and then use a magnet for magnetic separation to obtain a black solid product, wash the black solid product with distilled water, and wash until the pH of the washed wastewater is neutral, that is, Fe ₃ O ₄ magnetic fluid is obtained;

2. Preparation of magnetic titanium oxide nanoparticles: First, 1g of Fe ₃ O ₄ magnetic fluid was added to 50mL of distilled water, then 1mL of TiCl ₄ was added, and stirred at a stirring speed of 500rmp for 10min, and then sodium hydroxide aqueous solution was added to dissolve Adjust the pH value to 9±0.1, continue to stir at a stirring speed of 500rmp for 10 minutes, and then react at a temperature of 150°C for 6 hours to obtain a brown solid product. Wash the brown solid product with distilled water until the pH of the washed wastewater is neutral. To obtain a brown solid product after washing, and then dry the brown solid product after washing at a temperature of 100 ° C, and obtain magnetic titanium oxide nanoparticles after drying to constant weight;

3. Removal of pesticide residues: First, add 100mg of magnetic titanium oxide nanoparticles and 100mg of cetyltrimethylammonium bromide into 500mL of water to be treated, then stir for 30min at a stirring speed of 500rmp, using a magnet Magnetic separation, absorb the supernatant, and filter the supernatant with a 0.2μm filter membrane. After filtration, the removal of pesticide residues in the water to be treated is completed, and the treated water is obtained.

The water body to be treated in the third step of this test is a water sample with a concentration of 0.1 mg·L ^-1 of kaufthrin.

The magnetic titanium oxide nanoparticles described in step three of this test are combined with cetyltrimethylammonium bromide to form a magnetic titanium oxide micelle system, which is a new type of remover. The remover has both the large specific surface area of nanomaterials, the superparamagnetism of magnetic materials, the good stability of _TiO2 and the strong removal ability of mixed micelles.

Using a scanning electron microscope to observe the magnetic titanium oxide nanoparticles prepared in the first step two of the test, the detection results are shown in Figure 1, and Figure 1 is the SEM image of the magnetic titanium oxide nanoparticles prepared in the second step of the test one step, and it can be known from Figure 1 that the first step two of the test The prepared magnetic titanium oxide nanoparticles are nanoscale, so they have a large specific surface area, and the adsorption capacity will also be enhanced accordingly.

The magnetic titanium oxide nanoparticles prepared by Fourier transform infrared spectrometer detection test one step two, the test results are as shown in Figure 2, and Figure 2 is the Fourier infrared spectrogram of the magnetic titanium oxide nanoparticles prepared by test one step two, through Figure 2 It can be seen that there is an absorption peak of Fe-O at 580cm ^-1 , an absorption peak of Ti-O bond at 1390cm ^-1 , and an absorption peak of OH at 3430cm ^-1 , so it can be seen that the magnetic titanium oxide prepared in step 2 of test 1 _TiO2 in _{nanoparticles} has been successfully combined with _Fe3O4 .

Vibrating sample magnetometer is used to detect the magnetic titanium oxide nanoparticles prepared in the first step two of the test, and the test results are as shown in Figure 3, and the hysteresis loop of the magnetic titanium oxide nanoparticles prepared in the second step of the test in Figure 3 is shown by Figure 3. The saturation magnetic field strength of the magnetic titanium oxide nanoparticles prepared in the second step of the first test is 28.6 emu·g ^-1 , so the magnetic titanium oxide nanoparticles prepared by the second step of the first test can realize rapid separation under the action of an external magnetic field.

High performance liquid chromatography was used to detect the treated water body. It can be seen that the concentration of kaufenthrin in the treated water body is almost 0 mg·L ^-1 , and the removal rate of kaufthrin is 100% through calculation.

Test 2: The difference between this test and Test 1 is that the water body to be treated in Step 3 is a water sample with a concentration of 0.5 mg·L ^-1 of kaufenthrin. Others are the same as Experiment 1.

High performance liquid chromatography was used to detect the treated water body. It can be seen that the concentration of kaufenthrin in the treated water body is almost 0 mg·L ^-1 , and the removal rate of kaufthrin is 100% through calculation.

Test 3: The difference between this test and Test 1 is that the water body to be treated in Step 3 is a water sample with a concentration of 1.0 mg·L ^-1 of kaufenthrin. Others are the same as Experiment 1.

High performance liquid chromatography was used to detect the treated water body. It can be seen that the concentration of kaufthrin in the treated water body is 0.007mg·L ^-1 , and the removal rate of kaufrin is 99.3% through calculation.

Test 4: The difference between this test and Test 1 is that the water body to be treated in Step 3 is a water sample with a concentration of 5.0 mg·L ^-1 of kaufenthrin. Others are the same as Experiment 1.

High performance liquid chromatography was used to detect the treated water body. It can be seen that the concentration of kaufthrin in the treated water body is 0.145mg·L ^-1 , and the removal rate of kaufrin is 97.1% through calculation.

Test 5: The difference between this test and Test 1 is that the water body to be treated in Step 3 is a water sample with a concentration of 10.0 mg·L ^-1 of koflavin. Others are the same as Experiment 1.

High performance liquid chromatography was used to detect the treated water body. It can be seen that the concentration of kaufthrin in the treated water body is 0.460mg·L ^-1 , and the removal rate of kaufrin is 95.4% through calculation.

Experiment 6: A method for removing pesticide residues in water by using a magnetic titanium oxide micelle system, which is specifically completed in the following steps: 1. Preparation of Fe ₃ O ₄ magnetic fluid: the prime minister mixes 10 mmol of FeCl ₂ 4H ₂ O and 20 mmol of FeCl 2 . FeCl ₃ 6H ₂ O was completely dissolved in distilled water, and the temperature was raised from room temperature to 80°C at a stirring speed of 500rmp, then 80mmol of NH ₃ ·H ₂ O was added, and the temperature was 80°C and the stirring speed was 500rmp. React for 1 hour, and then use a magnet for magnetic separation to obtain a black solid product, wash the black solid product with distilled water, and wash until the pH of the washed wastewater is neutral, that is, Fe ₃ O ₄ magnetic fluid is obtained;

2. Preparation of magnetic titanium oxide nanoparticles: First, 1g of Fe ₃ O ₄ magnetic fluid was added to 50mL of distilled water, then 1mL of TiCl ₄ was added, and stirred at a stirring speed of 500rmp for 10min, and then sodium hydroxide aqueous solution was added to dissolve Adjust the pH value to 9±0.1, continue to stir at a stirring speed of 500rmp for 10 minutes, and then react at a temperature of 150°C for 6 hours to obtain a brown solid product. Wash the brown solid product with distilled water until the pH of the washed wastewater is neutral. To obtain a brown solid product after washing, and then dry the brown solid product after washing at a temperature of 100 ° C, and obtain magnetic titanium oxide nanoparticles after drying to constant weight;

3. Removal of pesticide residues: First, add 100mg of magnetic titanium oxide nanoparticles and 100mg of cetyltrimethylammonium bromide into 500mL of water to be treated, then stir for 1min at a stirring speed of 500rmp, and use a magnet to Magnetic separation, absorb the supernatant, and filter the supernatant with a 0.2μm filter membrane. After filtration, the removal of pesticide residues in the water to be treated is completed, and the treated water is obtained.

The water body to be treated in the third step of this test is a water sample with a concentration of 2.0 mg·L ^-1 of kaufenthrin.

The magnetic titanium oxide nanoparticles described in step three of this test are combined with cetyltrimethylammonium bromide to form a magnetic titanium oxide micelle system, which is a new type of remover. The remover has both the large specific surface area of nanomaterials, the superparamagnetism of magnetic materials, the good stability of _TiO2 and the strong removal ability of mixed micelles.

Experiment 7: The difference between this experiment and Experiment 6 is: stirring for 5 minutes at a stirring speed of 500 rpm. Others are the same as experiment six.

Experiment 8: The difference between this experiment and Experiment 6 is: stirring for 10 minutes at a stirring speed of 500 rpm. Others are the same as experiment six.

Test 9: The difference between this test and Test 6 is: stirring for 20 minutes at a stirring speed of 500 rpm. Others are the same as experiment six.

Experiment 10: The difference between this experiment and Experiment 6 is: stirring for 30 minutes at a stirring speed of 500 rpm. Others are the same as experiment six.

Use high-performance liquid chromatography to detect the water to be treated described in Test 10 and the treated water obtained in Test 10. The mobile phase is 85% acetonitrile aqueous solution, the flow rate is 1.0mL·min ^-1 , the detection wavelength is 243nm, and the temperature is room temperature. Detect, test result as shown in Figure 4, Fig. 4 is a liquid phase chromatogram, among the figure A represents the liquid phase chromatogram of the water body to be treated described in test ten, among the figure B represents the water body after the treatment described in test ten In the liquid chromatogram, a in the figure represents the absorption peak of kaufenthrin; as can be seen from Figure 4, the method of removing pesticide residues in the water body by using the magnetic titanium oxide micellar system in the test ten has a good removal effect.

Experiment 11: The difference between this experiment and Experiment 6 is: stirring for 40 minutes at a stirring speed of 500 rpm. Others are the same as experiment six.

The treated water body obtained by liquid chromatography detection test six to eleven, according to the formula Calculation of Q _t (the adsorption amount of stilthrin in the magnetic titanium oxide micellar system at different times), where C ₀ is the initial concentration of stilthrin, C _e is the equilibrium concentration of slavin, and V is the volume of the sample solution, m is the mass of magnetic titanium oxide nanoparticles, and the Q _t of experiments 6 to 11 are calculated to be 1.67mg·g ^-1 , 8.23mg·g ^-1 , 8.65mg·g ^-1 , 9.61mg·g ^{-1 respectively 1} , 9.73 mg·g ^-1 and 9.96 mg·g ^-1 . Taking Q _t as the ordinate and time as the abscissa to draw a kinetic adsorption curve, the results are shown in Figure 5, and Figure 5 shows the effect of the magnetic titanium oxide mixed micelles system formed in tests 6 to 11 on the pesticide kaufenthrin Kinetic adsorption curve. From Figure 5, it can be seen that the adsorption kinetics of the polymer synthesized in this experiment to kaufenthrin is relatively fast, and the adsorption equilibrium can be reached within 20 minutes.

对图5中的吸附动力学曲线进行拟合，其中，Q_e表示磁性氧化钛胶束体系对功夫菊酯的平衡吸附量，Q_t表示磁性氧化钛胶束体系在不同时间的吸附量，Q_1cal表示动力学一级反应方程的理论吸附量，k₁表示动力学一级反应速率常数，t表示时间。以ln（Q_e-Q_t）为纵坐标、以时间为横坐标进行拟合，结果如图6所示，图6是试验六至十一形成的磁性氧化钛胶束体系吸附功夫菊酯的一级动力学拟合曲线，通过Origin7.5作图软件进行拟合，得到一级动力学拟合曲线的线性方程的相关系数R²为0.9224。According to the kinetic equation

Fitting the adsorption kinetics curve in Fig. 5, wherein, Q _e represents the equilibrium adsorption capacity of the magnetic titania micelles system to kaufthrin, Q _t represents the adsorption capacity of the magnetic titania micelles system at different times, Q _1cal represents the theoretical adsorption amount of the kinetic first-order reaction equation, k ₁ represents the kinetic first-order reaction rate constant, and t represents time. Taking ln(Q _e -Q _t ) as the ordinate and time as the abscissa for fitting, the results are shown in Figure 6. Figure 6 shows the absorption of kaufrin by the magnetic titanium oxide micellar system formed in Experiments 6 to 11. The first-order kinetic fitting curve was fitted by Origin7.5 drawing software, and the correlation coefficient ^R2 of the linear equation of the first-order kinetic fitting curve was obtained as 0.9224.

对图5中的吸附动力学曲线图进行拟合，其中，Q_t表示磁性氧化钛胶束体系在不同时间的吸附量，Q_2cal表示动力学二级反应方程的理论吸附量，k₂表示动力学一级反应速率常数，t表示时间。以t/Q_t为纵坐标、以时间为横坐标进行拟合，结果如图7所示，图7是试验六至十一形成的磁性氧化钛胶束体系吸附功夫菊酯的二级动力学拟合曲线，通过Origin7.5作图软件进行拟合，得到二级动力学拟合曲线的线性方程的相关系数R²为0.9902，因此可知本发明利用磁性氧化钛胶束体系去除水体中农药残留功夫菊酯的方法符合二级动力学拟合结果。According to the second order equation of kinetics

Fit the adsorption kinetics curve in Figure 5, where _Qt represents the adsorption amount of the magnetic titanium oxide micellar system at different times, _Q2cal represents the theoretical adsorption amount of the kinetic second-order reaction equation, and _k2 represents the kinetic energy First order reaction rate constant, t is time. Taking t/Q _t as the ordinate and time as the abscissa for fitting, the results are shown in Figure 7, and Figure 7 is the second-order kinetics of the adsorption of kaufrin by the magnetic titanium oxide micelles system formed in experiments 6 to 11 Fitting curve is fitted by Origin7.5 mapping software, and the correlation coefficient R of the linear equation that obtains the second-order kinetic fitting curve is ^0.9902 , so it can be seen that the present invention utilizes the magnetic titanium oxide micelle system to remove pesticide residues in the water body The method of kaufenthrin was consistent with the second-order kinetic fitting results.

Claims (7)

1. method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues is characterized in that the method for utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues finishes according to the following steps:

One, preparation Fe ₃O ₄Magnetic fluid: at first with FeCl ₂4H ₂O and FeCl ₃6H ₂O is dissolved in the distilled water fully, and low whipping speed is to be warming up to 80 ℃～90 ℃ from room temperature under 400rmp～600rmp, then adds NH ₃H ₂O, and be that 80 ℃～90 ℃ and mixing speed are to react 0.5h～1.5h under 400rmp～600rmp condition in temperature, then utilize magnet to carry out Magnetic Isolation, obtain the black solid product, adopt distilled water washing black solid product, the wastewater pH after washing is extremely washed is till the neutrality, namely obtains Fe ₃O ₄Magnetic fluid; FeCl described in the step 1 ₂4H ₂O and FeCl ₃6H ₂The mol ratio of O is 1:(1.9～2); FeCl described in the step 1 ₂4H ₂O and NH ₃H ₂The mol ratio of O is 1:(8～9);

Two, the magnetic oxygenated titanium nano particle of preparation: at first with Fe ₃O ₄Magnetic fluid joins in the distilled water, then adds TiCl ₄And low whipping speed is to stir 10min～20min under 400rmp～600rmp, add again sodium hydrate aqueous solution the pH value is adjusted to 8.5～9.5, continuing low whipping speed is to stir 5min～15min under 400rmp～600rmp, then be 140 ℃～160 ℃ lower reaction 5h～8h in temperature, namely obtain the brown solid product, adopt distilled water washing brown solid product, wastewater pH after washing is extremely washed is till the neutrality, obtain washing rear brown solid product, then be under 80 ℃～100 ℃ brown solid product after washing to be dried in temperature, dry to constant weight and namely obtain magnetic oxygenated titanium nano particle; Fe described in the step 2 ₃O ₄The quality of magnetic fluid and the volume ratio of distilled water are 1g:(30mL～80mL); Fe described in the step 2 ₃O ₄The quality of magnetic fluid and TiCl ₄Volume ratio be 1g:(1mL～2mL);

Three, remove residues of pesticides: at first magnetic oxygenated titanium nano particle and surfactant are joined in the staying water, then low whipping speed is to stir 1min～40min under 300rmp～600rmp, then utilize magnet to carry out Magnetic Isolation, draw supernatant, adopt 0.2 μ m filter membrane that supernatant is filtered, namely finish the removal of staying water Pesticide Residues after the filtration, obtain processing rear water body; Described magnetic oxygenated titanium nano particle and surfactant mass ratio are 1:(0.5～1.5); The quality of described magnetic oxygenated titanium nano particle and the volume ratio of staying water are 1g:(2L～10L).

2. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1 is characterized in that low whipping speed is to be warming up to 80 ℃～88 ℃ from room temperature under 450rmp～550rmp in the step 1.

3. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1 is characterized in that being 80 ℃～88 ℃ in temperature in the step 1 is to react 0.8h～1.2h under 450rmp～550rmp condition with mixing speed.

4. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1 is characterized in that in the step 2 Fe ₃O ₄Magnetic fluid joins in the distilled water, then adds TiCl ₄, and low whipping speed is to stir 12min～18min under 450rmp～550rmp.

5. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1, it is characterized in that adding in the step 2 sodium hydrate aqueous solution pH value is adjusted to 8.6～9.4, continuing low whipping speed is to stir 8min～12min under 450rmp～550rmp, then be 145 ℃～155 ℃ lower reaction 5.5h～7.5h in temperature, namely obtain the brown solid product.

6. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1 is characterized in that the magnetic oxygenated titanium nano particle described in the step 3 and surfactant mass ratio are 1:(0.8～1.2).

7. a kind of method of utilizing magnetic oxygenated titanium micelle volume to remove the water body Pesticide Residues according to claim 1 is characterized in that the surfactant described in the step 3 is softex kw, lauryl sodium sulfate or Cetyltrimethylammonium bromide.

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