Preparation method of heterogeneous Fenton-like catalytic system and dye wastewater treatment method

Abstract

The invention discloses a preparation method of a heterogeneous Fenton-like catalytic system and a dye wastewater treatment method, the preparation method comprises the following steps: placing a fiber aggregate in a container, adding a Fe (SO4) 2 solution, then adding a CeO2-containing solution, and stirring in a constant temperature environment; and adding a K3Fe (CN) 6 solution, oscillating, taking out, washing and drying. The method comprises the following steps: adding a heterogeneous Fenton-like catalytic system into a container containing dye wastewater, and taking out the heterogeneous Fenton-like catalytic system after the heterogeneous Fenton-like catalytic system is treated for a certain time in a constant-temperature oscillator under the conditions of set frequency and set temperature; and then adding an H2O2 solution, and reacting under ultraviolet irradiation. The heterogeneous Fenton-like catalytic system is prepared by combining a Fenton-like catalyst with a fiber aggregate through an in-situ precipitation method. The heterogeneous Fenton-like catalytic system is placed in the dye wastewater, has a remarkable effect in the aspect of adsorbing the dye wastewater, can catalytically degrade the dye, and provides a new thought and technical means for wastewater treatment in the printing and dyeing industry.

Description

Technical Field

[0001] The present invention relates to a preparation method of a heterogeneous Fenton-like catalytic system and a method for treating dye wastewater, belonging to the technical field of dye wastewater treatment. Background Art

[0002] Dye wastewater usually refers to the wastewater containing pollutants such as dye residues, auxiliaries, salts, and organic matters generated in fabric dyeing. These dye wastewaters have some intractable characteristics, such as being difficult to degrade naturally, having a strong color, being somewhat polluting, and being likely to have an adverse impact on human health and the environment. In addition, they usually contain a large number of salt molecules and have a high pH value, etc., which makes the treatment more difficult. Therefore, it is particularly important to adopt effective treatment methods to protect the environment and human health. However, traditional physical, chemical, and biological treatment means often cannot completely decompose such colored pollutants, and in recent years, a series of methods such as Fenton oxidation have been widely used and have good effects in degrading pollutants in dye wastewater. How to prepare a Fenton-like catalytic system for treating dye wastewater has become a problem to be solved. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a heterogeneous Fenton-like catalytic system, which attaches the Fenton-like catalyst to the surface of a fiber aggregate.

[0004] The present invention also relates to a method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system, which can absorb and degrade dyes in the dye wastewater.

[0005] To solve the above technical problems, the purpose of the present invention is achieved as follows:

[0006] In the preparation method of the heterogeneous Fenton-like catalytic system involved in the present invention, a fiber aggregate is placed in a container, an Fe(SO4)2 solution is added, and then a solution containing CeO2 is added. The container is placed in a constant temperature environment and stirred for a set time; then a K3Fe(CN)6 solution is added and oscillated at a set oscillation frequency. The fiber aggregate is taken out, washed, and dried.

[0007] The solution containing CeO2 is glass grinding wastewater.

[0008] On the basis of the above scheme and as a preferred scheme of the above scheme: the dosage of Fe(SO4)2 is 0.5 - 100 g / L.

[0009] On the basis of the above scheme and as a preferred scheme of the above scheme: the dosage of CeO2 is 0.5 - 100 g / L.

[0010] Based on the above solution and as a preferred solution of the above solution: the dosage of K3Fe(CN)6 is 0.5 - 100 g / L.

[0011] Based on the above solution and as a preferred solution of the above solution: the temperature of the constant temperature environment is 25 °C, and the oscillation frequency is 90 r / min.

[0012] The present invention also relates to a method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system. Add the heterogeneous Fenton-like catalytic system to a container containing dye wastewater, wait for it to be treated for a certain period of time in a constant temperature oscillator under set frequency and set temperature conditions, and then take it out; then add H2O2 solution and react under ultraviolet light irradiation.

[0013] Based on the above solution and as a preferred solution of the above solution: the taken-out heterogeneous Fenton-like catalytic system is washed with pure water and dried.

[0014] Based on the above solution and as a preferred solution of the above solution: the heterogeneous Fenton-like catalytic system is taken out after being fully adsorbed for 60 min at 50 °C and 90 r / min in a constant temperature oscillator to reach adsorption-desorption equilibrium.

[0015] Based on the above solution and as a preferred solution of the above solution: the concentration of the H2O2 solution is 6%.

[0016] The beneficial effects of the present invention are: the preparation method of the heterogeneous Fenton-like catalytic system and the method for treating dye wastewater involved in the present invention combine the Fenton-like catalyst with the fiber aggregate through the in-situ precipitation method to prepare a heterogeneous Fenton-like catalytic system. Placing the heterogeneous Fenton-like catalytic system in dye wastewater has a significant effect on adsorbing dye wastewater and can also catalytically degrade dyes, providing new ideas and technical means for the treatment of wastewater in the printing and dyeing industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 are the color depth and levelness of the heterogeneous Fenton-like catalytic system cotton fabrics prepared in Examples 1 to 4;

[0018] Figure 2 are the color depth and levelness of the heterogeneous Fenton-like catalytic system polyamide fabrics prepared in Examples 5 to 8;

[0019] Figure 3 are the color depth and levelness of the heterogeneous Fenton-like catalytic system wool fiber masses prepared in Examples 9 to 12;

[0020] Figure 4are the color depth and levelness of the heterogeneous Fenton-like catalytic system cotton fabrics prepared in Examples 13 to 16;

[0021] Figure 5 are the color depth and levelness of the heterogeneous Fenton-like catalytic system polyamide fabrics prepared in Examples 17 to 20; Figure 6 are the color depth and levelness of the heterogeneous Fenton-like catalytic system wool fiber clusters prepared in Examples 21 to 24;

[0022] Figure 7 are the color depth and levelness of the heterogeneous Fenton-like catalytic system cotton fabrics prepared in Examples 25 to 28;

[0023] Figure 8 are the color depth and levelness of the heterogeneous Fenton-like catalytic system polyamide fabrics prepared in Examples 29 to 32; Figure 9 are the color depth and levelness of the heterogeneous Fenton-like catalytic system wool fiber clusters prepared in Examples 33 to 36;

[0024] Figure 10 is the line graph of the absorbance of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system cotton fabrics prepared in Examples 1 to 4 within 0 - 6 h;

[0025] Figure 11 is the line graph of the degradation rate of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system cotton fabrics prepared in Examples 1 to 4 within 0 - 6 h;

[0026] Figure 12 is the line graph of the absorbance of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system polyamide fabrics prepared in Examples 5 to 8 within 0 - 6 h;

[0027] Figure 13 is the line graph of the degradation rate of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system polyamide fabrics prepared in Examples 5 to 8 within 0 - 6 h;

[0028] Figure 14 is the line graph of the absorbance of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system wool fiber clusters prepared in Examples 9 to 12 within 0 - 6 h;

[0029] Figure 15 is the line graph of the degradation rate of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system wool fiber clusters prepared in Examples 9 to 12 within 0 - 6 h;

[0030] Figure 16Pictures of cotton fabrics after experiments in heterogeneous Fenton catalytic systems with unprocessed and CeO₂ wastewater contents of 0 mL, 10 mL, 20 mL, and 30 mL respectively;

[0031] Figure 17 Pictures of polyamide fabrics after experiments in heterogeneous Fenton catalytic systems with unprocessed and CeO₂ wastewater contents of 0 mL, 10 mL, 20 mL, and 30 mL respectively;

[0032] Figure 18 Pictures of wool fiber balls after experiments in heterogeneous Fenton catalytic systems with unprocessed and CeO₂ wastewater contents of 0 mL, 10 mL, 20 mL, and 30 mL respectively;

[0033] Figure 19 Pictures of cotton after experiments in heterogeneous Fenton catalytic systems with untreated and dosages of Fe(SO₄)₂ and K₃Fe(CN)₆ of 10 mL, 20 mL, 30 mL, and 40 mL respectively;

[0034] Figure 20 Pictures of polyamide after experiments in heterogeneous Fenton catalytic systems with untreated and dosages of Fe(SO₄)₂ and K₃Fe(CN)₆ of 10 mL, 20 mL, 30 mL, and 40 mL respectively;

[0035] Figure 21 Pictures of wool fiber balls after experiments in heterogeneous Fenton catalytic systems with untreated and dosages of Fe(SO₄)₂ and K₃Fe(CN)₆ of 10 mL, 20 mL, 30 mL, and 40 mL respectively;

[0036] Figure 22 Line charts of the absorbance of simulated dye wastewater of cotton fabrics in heterogeneous Fenton catalytic systems prepared in Examples 13 to 16 within 0 - 6 h;

[0037] Figure 23 Line charts of the degradation rate of simulated dye wastewater of cotton fabrics in heterogeneous Fenton catalytic systems prepared in Examples 13 to 16 within 0 - 6 h;

[0038] Figure 24 Line charts of the absorbance of simulated dye wastewater of polyamide fabrics in heterogeneous Fenton catalytic systems prepared in Examples 17 to 20 within 0 - 6 h;

[0039] Figure 25 Line charts of the degradation rate of simulated dye wastewater of polyamide fabrics in heterogeneous Fenton catalytic systems prepared in Examples 17 to 20 within 0 - 6 h;

[0040] Figure 26It is a line graph of the absorbance of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system wool fiber mass prepared in Examples 21 to 24 within 0-6 hours;

[0041] Figure 27 It is a line graph of the degradation rate of the simulated dye wastewater of the heterogeneous Fenton-like catalytic system wool fiber mass prepared in Examples 21 to 24 within 0-6 hours;

[0042] Figure 28 Pictures of the untreated cotton fabric and the heterogeneous Fenton-like catalytic system cotton fabric prepared in Examples 25 to 28 after the experiment;

[0043] Figure 29 Pictures of the untreated cotton fabric and the heterogeneous Fenton-like catalytic system polyamide fabric prepared in Examples 29 to 32 after the experiment;

[0044] Figure 30 Pictures of the untreated cotton fabric and the heterogeneous Fenton-like catalytic system wool fiber mass prepared in Examples 33 to 36 after the experiment. Detailed implementation manners

[0045] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0046] The preparation method of the heterogeneous Fenton-like catalytic system involved in the present invention is to place the fiber aggregate in a container, add Fe(SO4)2 solution, then add the solution containing CeO2, place the container in a constant temperature environment and stir for a set time; then add K3Fe(CN)6 solution and oscillate at the set oscillation frequency, take out the fiber aggregate, wash it and dry it. The fiber aggregate used is a fiber mass, a woven fabric, a knitted fabric or a non-woven fabric. The materials used can be cotton, polyamide, wool, or other fibers. The polyamide is specifically polyamide 6.

[0047] The solution containing CeO2 used is the CeO2 glass grinding wastewater collected from the factory, including glass rare earth abrasive, glass powder, pH regulator, surfactant and a small amount of other rare earth oxides; the other rare earth oxides are La2O3, Pr6O 11 、Nd2O3. Specifically, the glass grinding wastewater includes 0.318% of glass rare earth abrasive, 0.129% of glass powder, 0.005% of the pH regulator, 0.001% of the surfactant, and the total content of other rare earth oxides is 0.002%. The glass rare earth abrasive is CeO2. The glass grinding wastewater is formed after the abrasive is ground with glass. After grinding with glass, the particle size of the abrasive can be made smaller to reach the nanometer level, and the dispersion of the abrasive is better, so that the adhesion effect with the fiber is better and the adsorption effect is better.

[0048] Prussian blue (PB) is a coordination compound with a long history and is a typical metal-organic framework compound (MOFs). Due to the good catalytic activity of PB towards H2O2, it is called "artificial catalase" and has been used for the Fenton-like catalytic degradation of organic pollutants. Moreover, it has a unique chemical composition and a structure similar to that of Metal-Organic Frameworks (MOFs), making it an ideal choice for constructing heterogeneous Fenton-like systems compared with traditional catalysts. In Prussian blue, [Fe(CN)6] 3- is a complex ion, and Fe 3+ and CN - ions are located inside this ion and are stable in nature. The reaction equation with Fe 3+ ions is as shown in Equation (1-1). This substance can also react with Fe 2+ as shown in Equation (1-2).

[0049] [Fe(CN)6] 3- +Fe 3+ ===Fe[Fe(CN)] (1-1)

[0050] [Fe(CN)6] 3- +Fe 2+ ===Fe[Fe(CN)] - (1-2)

[0051] Furthermore, the dosage of Fe(SO4)2 is 0.5 - 100 g / L. The dosage of CeO2 is 0.5 - 100 g / L. The dosage of K3Fe(CN)6 is 0.5 - 100 g / L. The CeO2 wastewater is concentrated to a set concentration and then used to obtain the CeO2-containing solution described above.

[0052] The specific method is to place a certain amount of fiber aggregate in a 500 mL beaker. First, add 50 mL of Fe(SO4)2 solution, and then use a pipette to disperse different concentrations of the concentrated CeO2-containing solution in the mixed solution. Place the beaker in a 25 °C constant-temperature shaking water bath and stir gently for 1 h to make it evenly mixed. Then add 50 mL of K3Fe(CN)6 solution, adjust the stable oscillation frequency to 90 r / min and oscillate for 4 h. Subsequently, take out the fabric, wash it with pure water, put it in an 80 °C oven to dry, take it out after 15 min and store it in a sealed bag for preparing the test experiment.

[0053] Prepare an Fe(SO4)2 solution with C = 30×10 -3 mol / L and an Fe(SO4)2 solution with C = 20×10 -3K3Fe(CN)6 solution with a concentration of mol / L. Specifically, 4168 mg of Fe(SO4)2·6H2O and 3280 mg of K3Fe(CN)6 were weighed separately using an electronic balance, and each was added to 200 mL of deionized water and dissolved in a 500 mL beaker. Then, it was made up to the mark using a 500 mL volumetric flask. The concentration of the solution containing CeO2 was 3 g / L, and of course, its concentration can also be adjusted according to actual needs.

[0054] By changing the solution volume of the cerium oxide-containing solution, the dosages of Fe(SO4)2 and K3Fe(CN)6, and the ratio of Fe(SO4)2 to K3Fe(CN)6, gradient experiments with different fibers and different groups were prepared. Table 1 shows the gradient groups with the solution volume of the cerium oxide-containing solution changed; Table 2 shows the gradient groups with the dosages of Fe(SO4)2 and K3Fe(CN)6 changed; Table 3 shows the gradient groups with the ratio of Fe(SO4)2 to K3Fe(CN)6 changed.

[0055] Cotton fabrics were used in Examples 1 to 4, Examples 13 to 16, and Examples 25 to 28. The gram weight of the cotton fabric used was 160 grams per square meter. The specific size of the cotton fabric used was 10 cm * 10 cm.

[0056] Nylon fabrics were used in Examples 5 to 8, Examples 17 to 20, and Examples 29 to 32. The gram weight of the nylon fabric used was 160 grams per square meter. The specific size of the nylon fabric used was 10 cm * 10 cm.

[0057] Wool fiber balls were used in Examples 9 to 12, Examples 21 to 24, and Examples 33 to 36. The specific dosage was 5 grams.

[0058] Table 1 Gradient groups with the solution volume of the cerium oxide-containing solution changed

[0059]

[0060]

[0061] Table 2 Gradient groups with the solution volume of the cerium oxide-containing solution changed

[0062]

[0063] Table 3 Gradient groups with the ratio of Fe(SO4)2 to K3Fe(CN)6 changed

[0064]

[0065]

[0066] Such asFigure 1 , Figure 2 and Figure 3 The shades of color and level dyeing effects of the heterogeneous Fenton-like catalytic systems of Examples 1 to 12 shown in Figure 1 , Figure 2 , and Figure 3 . From left to right are the shades of color and level dyeing properties of cotton fabrics, nylon fabrics, and wool fiber masses with the dosages of the CeO2 solution being 0 mL, 10 mL, 20 mL, and 30 mL. Table 4 shows the Lab values of the heterogeneous Fenton-like catalytic systems prepared in Examples 1 to 12.

[0067] Table 4 Lab values of the heterogeneous Fenton-like catalytic systems prepared in Examples 1 to 12

[0068]

[0069]

[0070] Figure 4 , Figure 5 and Figure 6 Shown in Figure 5 , Figure 6 , and are the shades of color and level dyeing effects of the heterogeneous Fenton-like catalytic systems of Examples 13 to 24. From left to right are the shades of color and level dyeing properties of cotton fabrics, nylon fabrics, and wool fiber masses with the dosages of Fe(SO4)2 and K3Fe(CN)6 being 10 mL, 20 mL, 30 mL, and 40 mL respectively.

[0071] Figure 7 , Figure 8 and Figure 9 Shown in Figure 8 , Figure 9 , and are the shades of color and level dyeing effects of the heterogeneous Fenton-like catalytic systems of Examples 13 to 24. From left to right are the shades of color and level dyeing properties of cotton fabrics, nylon fabrics, and wool fiber masses with the ratios of Fe(SO4)2 to K3Fe(CN)6 being 5:1, 5:2, 5:3, and 5:4 respectively.

[0072] The present invention also relates to a method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system. Add the heterogeneous Fenton-like catalytic system to a container containing dye wastewater, and let it be treated for a certain period of time in a constant temperature oscillator under set frequency and set temperature conditions, then take it out; then add an H2O2 solution and react under ultraviolet light irradiation.

[0073] Specifically, clothing dye (purple) was used for simulation. The simulated concentration was 4g / L. 40mL of simulated dye wastewater was taken into a 100mL small beaker, and the heterogeneous Fenton-like catalytic system of each group of gradient experiments was added to each beaker. After it was fully adsorbed for 60min in a constant temperature oscillator at 50℃ and 90r / min to reach adsorption-desorption equilibrium, it was taken out, and then 5mL of 6% H2O2 solution was added to each small beaker for reaction. The reaction process was irradiated and catalyzed by LED ultraviolet UV lamp, and fully stirred every 5min. Within the set time, 3mL of the reaction suspension was transferred to the beaker using a pipette, and 50μL of NaOH solution (C=1mol / L) was quickly added, and the beaker was shaken to quench the reaction. Then they were placed in a UV-visible spectrophotometer one by one for detection. The simulated waste liquid spectrum was tested by UV spectrophotometer, and the maximum absorption wavelength of the simulated dye wastewater was measured to be 550mm. The wavelength was tested for the wastewater of each gradient experiment at 0h, 1h, 2h, 3h, 4h, 5h, and 6h. After the reaction was completed, all fibers were washed with pure water and dried in an electric constant temperature blast drying oven at 80°C for 10min. The heterogeneous Fenton-like catalytic system prepared by alternating the dosage of CeO2-containing solution, Fe(SO4)2 and K3Fe(CN)6 solution, and the ratio of Fe(SO4)2 and K3Fe(CN)6 was measured.

[0074] The test method for the degradation rate is to use the hourly data measured by the UV-Vis spectrophotometer, subtract the absorbance of the previous hour from the next hour as the numerator, and use the absorbance measured at 1 hour as the denominator to calculate the degradation rate at 1 hour, 2 hours, 3 hours, 4 hours, 5 hours and 6 hours. The UV-Vis spectrophotometer is an analytical instrument designed based on the principle of selective absorption of radiation in the UV-Vis spectrum by material molecules. When certain groups in the molecules absorb the light energy of this band, the transition of the electronic energy level will occur, resulting in a characteristic absorption spectrum. Since the molecular structure and atomic arrangement of different substances are different, their absorption of light energy is also different. Therefore, each substance has its own unique absorption spectrum curve characteristics. By measuring the absorbance at a specific wavelength, the type and content of the measured substance can be qualitatively or quantitatively analyzed.

[0075] The color test is to use a colorimeter with a D65 light source at an angle of 10° to measure the Lab value and maximum K / S value of the following fabrics. Since the fabric dyeing is not completely uniform, each fabric is measured three times during the test and the average value is taken.

[0076] The increase in the content of CeO2 has a better effect on improving the degradation of simulated dye wastewater by the integrated fibers. Generally speaking, increasing the content of CeO2 can enhance the degradation effect and reduce the reaction time. In the field of photocatalytic degradation, CeO2 can not only directly participate in the catalytic reaction as an active component, but also further improve its photocatalytic performance through means such as loading, doping, and semiconductor compounding. For example, by regulating the morphology, such as preparing multi-shell hollow structures, the visible light absorption ability and photocatalytic degradation efficiency can be significantly improved. In addition, doping quantum dots and constructing heterojunction structures are also effective ways to enhance photocatalytic performance, such as the degradation of organic pollutants, photocatalytic carbon dioxide reduction, water splitting for hydrogen production, and photocatalytic nitrogen fixation. Especially in the degradation of organic pollutants, the composite material can efficiently degrade organic pollutants in water under visible light irradiation, showing high degradation efficiency and good stability. These characteristics make it have great application potential in the fields of environmental protection and water treatment.

[0077] The influence of the dosage of CeO2 content on the degradation of simulated dye wastewater. The initial reaction conditions are that the concentration of hydrogen peroxide is 6% and the usage amount is 3 mL; the concentration of simulated dye wastewater is 4 g / L. Before the simulation experiment, the integrated fibers are first soaked and stirred in the simulated dye wastewater for 1 h to reach the maximum adsorption value of the fibers, excluding the absorption factor of the fibers themselves for the simulated dye wastewater. Subsequently, the absorbance is measured and used as the data at 0 h.

[0078] Through an ultraviolet spectrophotometer, Figure 10 that is, the absorbance of the simulated wastewater of cotton (CeO2 content gradient group), and based on the test data, Figure 11 is made for the degradation rate of the simulated wastewater of cotton (CeO2 content gradient group). According to the figure, as the content of CeO2 increases from 0 mL to 30 mL, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase in the content of CeO2. For example, in the cotton gradient experimental group, when the reaction proceeds to 3 h, the degradation rate of cotton 4 has reached 93.63%, while the degradation rate of pure cotton only reaches 89.87% at 6 h. In Figure 10 and Figure 11 cotton 1, cotton 2, cotton 3, and cotton 4 respectively refer to the heterogeneous Fenton catalytic system cotton fabrics prepared in Example 1, Example 2, Example 3, and Example 4.

[0079] Through an ultraviolet spectrophotometer, Figure 12 that is, the absorbance of the simulated wastewater of nylon (CeO2 content gradient group), and based on the test data, Figure 13, i.e., the degradation rate of the simulated wastewater of polyamide fiber (CeO₂ content gradient group). It can be seen from the figure that as the content of CeO₂ increases from 0 mL to 30 mL, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase of the CeO₂ content. In this gradient experimental group, when the reaction proceeds to 4 h, the degradation rate of polyamide fiber 4 has reached 97.09%, while that of ordinary polyamide fiber reaches 95.53% at 6 h, showing a large difference. Moreover, the time for polyamide fiber 1, polyamide fiber 2, and polyamide fiber 3 to reach 97% also shows a gradient. In Figure 12 and Figure 13 , polyamide fiber 1, polyamide fiber 2, polyamide fiber 3, and polyamide fiber 4 respectively refer to the heterogeneous Fenton catalytic system polyamide fabrics prepared in Example 5, Example 6, Example 7, and Example 8.

[0080] Through the ultraviolet spectrophotometer, the following Figure 14 is obtained, i.e., the absorbance of the simulated wastewater of wool (CeO₂ content gradient group), and based on the test data, Figure 15 is obtained, i.e., the degradation rate of the simulated wastewater of wool (CeO₂ content gradient group). It can be seen from the figure that as the dosage of CeO₂ increases from 0 mL to 30 mL, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase of the CeO₂ content. In this gradient experimental group, the degradation rate and degradation effect of the simulated dye wastewater show an obvious gradient increase and improvement with the increase of the CeO₂ content. However, the degradation rate of wool 3 at 6 h is slightly lower than that of wool 2. The possible reason for the analysis is that there is a certain error due to improper measurement during the experiment. The huge difference in the degradation rate indicates that the increase in the CeO₂ content can greatly improve the rate of the simulated dye wastewater. In Figure 14 and Figure 15 , wool 1, wool 2, wool 3, and wool 4 respectively refer to the heterogeneous Fenton catalytic system polyamide fabrics prepared in Example 9, Example 10, Example 11, and Example 12.

[0081] Generally speaking, the initial absorbances of cotton 4, wool 4, and polyamide fiber 4 are slightly higher than those of other groups, and the data approximately show an inverse gradient. The possible reason is that after the fibers are finished, due to the attachment of Prussian blue and cerium dioxide, a catalytic system is formed on the fabric. Therefore, under normal conditions, the adsorption capacity of the fibers decreases, resulting in too high initial absorbances of cotton 4, wool 4, and polyamide fiber 4.

[0082] Nylon fibers and wool fibers themselves have absorbency towards the selected simulated dye wastewater. During the experiment, after finishing, while the nylon and wool fibers catalyze the simulated dye wastewater, the fibers themselves also have a certain absorbency towards the simulated dye wastewater, and this absorbency decreases as the CeO2 content increases, and this absorbency is the strongest in pure nylon and pure wool. From this, it can be concluded that although nylon fibers and wool fibers themselves have absorbency towards the simulated dye wastewater and decrease with the increase of CeO2 content, the degradation rate of the integrated fibers towards the simulated dye wastewater still increases with the increase of CeO2 content, which is sufficient to show that the heterogeneous Fenton-like fibers do have a great effect on improving the degradation effect of dye wastewater.

[0083] As Figures 16 to 18 shown, and the Lab values and maximum K / S values of the above fabrics were measured for the heterogeneous Fenton-like catalytic system after the above experiment by a colorimeter, and Table 5 was obtained. Since the fabric dyeing is not completely uniform, each fabric was measured three times and the average value was taken during the test.

[0084] Table 5 Lab values and maximum K / S values after the simulation experiment of cotton, nylon and wool groups

[0085]

[0086]

[0087] Regarding the improvement of the specific better effect of the integrated heterogeneous Fenton-like catalytic system on the degradation of simulated dye wastewater with the increase of the dosage of Fe(SO4)2 and K3Fe(CN)6, generally speaking, increasing the dosage of Fe(SO4)2 and K3Fe(CN)6 can improve the degradation effect and reduce the reaction duration. The influence of the dosage of Fe(SO4)2 and K3Fe(CN)6 on the degradation of simulated dye wastewater, the initial reaction conditions are that the concentration of hydrogen peroxide is 6% and the usage amount is 3 mL; the concentration of simulated dye wastewater is 4 g / L. Before the simulation experiment, the integrated heterogeneous Fenton-like catalytic system was first soaked and stirred in the simulated dye wastewater for 1 h to reach the adsorption maximum value of the fiber, excluding the absorption factor of the fiber itself towards the simulated dye wastewater, and then the absorbance was measured and used as the data at 0 h. The fibers after the experiment are as Figures 19 to 21 shown. Figures 19 to 21 Pictures after the experiment of cotton fabrics of the heterogeneous Fenton-like catalytic system, nylon fabrics of the heterogeneous Fenton-like catalytic system and wool fiber clusters of the heterogeneous Fenton-like catalytic system with the dosage of Fe(SO4)2 and K3Fe(CN)6 being 10 mL, 20 mL, 30 mL and 40 mL respectively, which are untreated.

[0088] Obtained 3.22 through an ultraviolet spectrophotometer, and made Figure 23It can be obtained from the figure that on cotton, as the dosage of Fe(SO4)2 and K3Fe(CN)6 increases from 10 mL each to 40 mL each, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase in the dosage of Fe(SO4)2 and K3Fe(CN)6. Figure 22 and Figure 23 Cotton 1, Cotton 2, Cotton 3, and Cotton 4 in Figure 23 respectively refer to the cotton fabrics of the heterogeneous Fenton-like catalytic systems prepared in Example 13, Example 14, Example 15, and Example 16.

[0089] The following is obtained by an ultraviolet spectrophotometer Figure 24 , and the following is made based on the test data Figure 25 It can be obtained from the figure that on polyamide, as the dosage of Fe(SO4)2 and K3Fe(CN)6 increases from 10 mL each to 40 mL each, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase in the dosage of Fe(SO4)2 and K3Fe(CN)6. Figure 24 and Figure 25 Polyamide 1, Polyamide 2, Polyamide 3, and Polyamide 4 in Figure 25 respectively refer to the cotton fabrics of the heterogeneous Fenton-like catalytic systems prepared in Example 17, Example 18, Example 19, and Example 20.

[0090] The following is obtained by an ultraviolet spectrophotometer Figure 26 , and the following is made based on the test data Figure 27 It can be obtained from the figure that on wool, as the dosage of Fe(SO4)2 and K3Fe(CN)6 increases from 10 mL each to 400 mL each, the reduction rate of the absorbance of the simulated dye wastewater continuously accelerates, and the degradation rate of the simulated dye wastewater also accelerates with the increase in the dosage of Fe(SO4)2 and K3Fe(CN)6. Figure 26 and Figure 27 Wool 1, Wool 2, Wool 3, and Wool 4 in Figure 27 respectively refer to the wool fiber masses of the heterogeneous Fenton-like catalytic systems prepared in Example 21, Example 22, Example 23, and Example 24.

[0091] The increase in the ratio of Fe(SO4)2 and K3Fe(CN)6 has a specific improvement effect on the degradation of the simulated dye wastewater by the integrated fiber. Generally speaking, increasing the ratio of Fe(SO4)2 and K3Fe(CN)6 can improve the degradation effect and reduce the reaction duration. As Figures 28 - 30 shown.

[0092] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative efforts. Therefore, all technical solutions that can be obtained by those skilled in the art in this technical field based on the concept of the present invention through logical analysis, reasoning, or limited experiments on the basis of the prior art shall fall within the protection scope determined by the claims.

Claims

1. A method for preparing a heterogeneous Fenton-like catalytic system, characterized in that: Place the fiber assembly in a container, add Fe(SO4)2 solution, then add CeO2 solution, place the container in a constant temperature environment and stir for a set time; then add K3Fe(CN)6 solution, oscillate at a set oscillation frequency, take out the fiber assembly, wash it and dry it; The CeO2-containing solution is glass grinding wastewater.

2. The method for preparing heterogeneous Fenton-like catalyst fibers according to claim 1, characterized in that: The dosage of Fe(SO4)2 is 0.5-100g / L.

3. The method for preparing heterogeneous Fenton-like catalyst fibers according to claim 1, characterized in that: The dosage of CeO2 is 0.5-100g / L.

4. The method for preparing heterogeneous Fenton-like catalyst fibers according to claim 1, characterized in that: The dosage of K3Fe(CN)6 is 0.5-100g / L.

5. The method for preparing heterogeneous Fenton-like catalyst fibers according to claim 1, characterized in that: The temperature of the constant temperature environment is 25° C., and the oscillation frequency is 90 r / min.

6. A method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system, characterized in that: A heterogeneous Fenton-like catalytic system is added to a container containing dye wastewater, and after being treated for a certain period of time at a set frequency and set temperature in a constant temperature oscillator, it is taken out; then H2O2 solution is added and reacted under ultraviolet light.

7. A method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system according to claim 6, characterized in that: The taken out heterogeneous Fenton-like catalytic system is washed with pure water and dried.

8. The method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system according to claim 6, characterized in that: The heterogeneous Fenton-like catalytic system was fully adsorbed for 60 minutes in a constant temperature oscillator at 50° C. and 90 r / min to reach adsorption-desorption equilibrium and then taken out.

9. The method for treating dye wastewater based on a heterogeneous Fenton-like catalytic system according to claim 6, characterized in that: The concentration of the H2O2 solution is 6%.

Images