A composite catalytic material and its preparation method and application

Abstract

The invention discloses a composite catalytic material, a preparation method and an application thereof, and belongs to the technical field of wastewater treatment. The composite catalytic material comprises halloysite nanotubes and / or steel slag, and the mass fractions of the components in the composite catalytic material are CaO: 0.97% to 52.54%, Fe2O3: 0.57% to 16.65%, SiO2: 2.47% to 11.24%, Al2O3: 3.54% to 11.24%, MgO: 0 to 3.24%, CuO: 0 to 2.64%, and the remainder are impurities. The composite catalytic material of the invention has a good removal effect on chloramphenicol, is simple to operate, effectively improves the removal rate of chloramphenicol, and can completely remove chloramphenicol at room temperature. The preparation method is simple in steps, and the raw materials are cheap and readily available, making the composite catalytic material suitable for large-scale mass production in industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a composite catalytic material and a preparation method and application thereof. Background Art

[0002] Halloysite nanotubes (HNTs) are a new type of nanomaterial; they are silicate minerals with a hollow tubular structure. Due to their favorable aspect ratio and strong adsorption properties, they are often used as catalyst supports. Steel slag (GZ) is a major solid waste generated during the steelmaking process. Its main components include various active metal oxides such as Fe2O3, FeO, MnO, and CuO, making it advantageous in activating persulfate to degrade organic pollutants. Effective utilization of GZ can both recycle steel slag and achieve advanced treatment of organic wastewater, achieving a "waste-to-waste" strategy.

[0003] Tolidine, generally refers to tilidine, the chemical formula is C 17 H 23 NO2 is a synthetic opioid narcotic analgesic with an analgesic intensity comparable to pethidine. It is primarily used to relieve traumatic, postoperative, and visceral colic pain. It can also be administered before surgical anesthesia. It is a type of pharmaceutical and personal care product (PPCP), a new type of micropollutant that has emerged in aquatic environments in recent years. With the improvement of people's living standards, the use of PPCPs has also increased, and large quantities of PPCPs enter natural water bodies through various pathways each year. Because PPCPs are often difficult to degrade, bioaccumulate, and have long-term harmful effects, they have attracted widespread attention from researchers.

[0004] Currently, there are few methods for degrading chloramphenicol in wastewater in my country, and most rely on microbial degradation, which has drawbacks such as incomplete degradation, prolonged degradation time, and high costs. When groundwater is used as a drinking water source, chloramphenicol cannot be reduced to acceptable concentrations. This can ultimately lead to chloramphenicol exposure to the environment and contamination of drinking water through discharge from municipal wastewater treatment plants or indirect backflow, polluting the environment and endangering human health.

[0005] Therefore, it is very important and necessary to study an efficient and effective method for treating chlorhexidine wastewater. Summary of the Invention

[0006] In view of the above situation, the present invention provides a composite catalytic material, a preparation method and application thereof. By using the composite catalytic material made of halloysite nanotubes and / or steel slag, the steel slag is recycled and the pollutant sulfide in wastewater is efficiently removed.

[0007] In order to solve the above technical problems, the first aspect of the present invention provides a composite catalytic material, the raw materials of the composite catalytic material include halloysite nanotubes and / or steel slag, and the mass fractions of each component in the composite catalytic material are CaO: 0.97%~52.54%, Fe2O3: 0.57%~16.65%, SiO2: 4.57%~42.47%, Al2O3: 5.48%~36.54%, MgO: 0~3.24%, CuO: 0~2.64%, and the rest are impurities.

[0008] According to some embodiments of the present invention, the inner diameter of the halloysite nanotube is 10nm-20nm, the outer diameter is 50nm-70nm, and the length is 200nm-2000nm. Preferably, the inner diameter of the halloysite nanotube is 15nm, the outer diameter is 60nm, and the length is 1000nm.

[0009] According to some embodiments of the present invention, the mass fractions of the components in the steel slag are CaO: 50% to 53%, Fe2O3: 15% to 17%, SiO2: 4% to 6%, Al2O3: 3% to 6%, MgO: 3% to 5%, CuO: 0 to 4%, and the rest are impurities, preferably CaO: 52.43%, Fe2O3: 16.54%, SiO2: 4.57%, Al2O3: 5.48%, MgO: 3.24%, CuO: 2.64%, and the rest are impurities.

[0010] According to some embodiments of the present invention, the raw materials of the composite catalytic material include halloysite nanotubes and steel slag, and the mass ratio of the halloysite nanotubes to steel slag is 1:(0.01~1), preferably 1:(0.2~1), for example 1:1, 1:0.2, 1:0.4, 1:0.6, 1:0.8.

[0011] The second aspect of the present invention provides a method for preparing the composite catalytic material, comprising ball milling the raw materials and then calcining them under an inert gas atmosphere to obtain the composite catalytic material.

[0012] According to some embodiments of the present invention, the present invention converts steel slag into a powder with uniform particle size by ball milling, and uniformly mixes the steel slag and halloysite nanotubes, wherein the particle size of the steel slag after ball milling is 10 nm to 15 nm, preferably 12.42 nm;

[0013] And / or, the inner diameter of the halloysite nanotube after ball milling is 2 nm to 5 nm, preferably 3.64 nm, the outer diameter is 10 nm to 20 nm, preferably 16.32 nm, and the length is 100 nm to 200 nm, preferably 140 nm.

[0014] According to some embodiments of the present invention, the ball milling is carried out in a ball mill; preferably, the rotation speed of the ball mill is 900 r / min to 1000 r / min, preferably 1000 r / min, and the ball milling time is 70 min to 90 min, preferably 80 min.

[0015] According to some embodiments of the present invention, the calcination is carried out in a tube furnace; preferably, the heating rate of the tube furnace is 5°C / min to 10°C / min, preferably 5°C / min;

[0016] And / or, the inert gas is at least one of nitrogen, argon, and helium;

[0017] And / or, the calcination conditions include a calcination temperature of 500° C. to 600° C., preferably 500° C., and a calcination time of 4 h to 5 h, preferably 4 h.

[0018] The third aspect of the present invention provides the use of the above-mentioned composite catalytic material or the composite catalytic material prepared by the above-mentioned preparation method in degrading wastewater, preferably, the wastewater contains analgesic drugs, and more preferably, the analgesic drugs are at least one of tolidine, aspirin, and paracetamol.

[0019] According to some embodiments of the present invention, the initial concentration of the analgesic drug to be degraded in the wastewater is 1 ppm to 2 ppm, and the concentration after degradation is 0 ppm to 0.66 ppm;

[0020] And / or, the ratio of the wastewater to the composite catalytic material is (100-150) mL: (0.05-1) g, preferably 100 mL: 0.05 g;

[0021] And / or, the wastewater further comprises sodium persulfate; preferably, the ratio of the wastewater to sodium persulfate is (100-150) mL: (1-2) mL, preferably 100 mL: 1 mL.

[0022] Beneficial effects:

[0023] In the composite catalytic material of the present invention, steel slag and / or halloysite nanotubes can activate sodium persulfate to generate sulfate radicals (SO 4- ·), sulfate radicals have strong oxidizing properties, and the chlorpheniramine in the wastewater is converted into small molecular substances under the oxidation of sulfate radicals. Sodium persulfate can also produce hydroxyl radicals (HO·) after being activated by steel slag and / or halloysite nanotubes. Hydroxyl radicals can also degrade the chlorpheniramine in the wastewater. At the same time, sodium persulfate itself has oxidizing properties and can oxidize the chlorpheniramine in the wastewater, thereby degrading the chlorpheniramine in the wastewater;

[0024] In the composite catalytic material of the present invention, the halloysite nanotubes have strong adsorption properties and can adsorb the chloramphenicol in the wastewater onto the surface of the composite catalytic material, thereby accelerating the degradation of the chloramphenicol in the wastewater, shortening the degradation time, and improving the degradation efficiency;

[0025] The composite catalytic material prepared by the present invention has a good effect on removing chloramphenicol contained in wastewater, is simple to operate, effectively improves the removal rate of chloramphenicol, and can completely remove chloramphenicol at room temperature. In addition, the preparation method of the composite catalytic material is simple, the raw materials are cheap and easily available, and the composite catalytic material is suitable for large-scale mass production in industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a scanning electron microscope image of the composite catalytic material HNTs / GZ prepared in Example 1 of the present invention;

[0027] Figure 2 This is a scanning electron microscope image of the composite catalytic material GZ prepared in Example 2 of the present invention;

[0028] Figure 3 This is a scanning electron microscope image of the composite catalytic material HNTs prepared in Example 3 of the present invention;

[0029] Figure 4 The present invention provides examples 1-7, comparative examples 1-2 and control examples for the removal of chloramphenicol from wastewater. DETAILED DESCRIPTION

[0030] The present invention will be further described below with reference to the following examples, but the present invention is not limited to these examples.

[0031] The steel slag described in the present invention is provided by Maanshan Iron and Steel Group Co., Ltd., and its main contents are shown in the following table (mass fraction):

[0032] CaO <![CDATA[Fe2O3]]> <![CDATA[SiO2]]> <![CDATA[Al2O3]]> MgO CuO impurities 52.43％ 16.54％ 4.57％ 5.48％ 3.24％ 2.64％ 15.10％ ;

[0033] The halloysite nanotubes described in the present invention were purchased from Guangzhou Runwo Material Technology Co., Ltd., with a molecular formula of Al2Si2O5(OH)4·nH2O and analytical grade;

[0034] The ball mill described in the present invention was purchased from Beijing Xuxin Shengke Instrument Equipment Co., Ltd.; model number is JC-QM-4;

[0035] The tube furnace described in the present invention was purchased from Tianjin Zhonghuan Electric Furnace Co., Ltd.; the model is SX-G;

[0036] The water bath constant temperature oscillator described in the present invention was purchased from Shanghai Dibai Experimental Equipment Co., Ltd.; model number is DZKW;

[0037] The high performance liquid chromatograph described in the present invention was purchased from Waters, USA; model number is e2695;

[0038] The scanning electron microscope image of the composite catalytic material in the present invention was taken using a TESCAN MIRA4 scanning electron microscope.

[0039] Example 1

[0040] This embodiment provides a method for preparing a composite catalytic material

[0041] 1 g of halloysite nanotubes (HNTs, inner diameter of 15 nm, outer diameter of 60 nm, length of 1000 nm) and 1 g of steel slag (GZ) were weighed and placed in a ball mill. The ball mill was milled at a speed of 1000 r / min for 80 min to obtain a mixture of halloysite nanotubes and steel slag after ball milling, wherein the particle size of the steel slag after ball milling was 12.42 nm; the inner diameter of the halloysite nanotubes after ball milling was 3.64 nm, the outer diameter was 16.32 nm, and the length was 140 nm; the mixture of halloysite nanotubes and steel slag after ball milling was placed in a tube furnace, and the tube furnace was heated to 500 ° C at a heating rate of 5 ° C / min under N2 atmosphere and calcined at this temperature for 4 h to obtain the composite catalytic material HNTs / GZ; the mass fractions of the components in the composite catalytic material HNTs / GZ are shown in Table 1; the scanning electron microscope image of the composite catalytic material HNTs / GZ is shown in Figure 1 ,Depend on Figure 1 It can be seen that after loading GZ, the tubular morphology of the halloysite nanotubes did not change significantly, and the granular GZ was evenly adhered to the rod-shaped halloysite nanotubes.

[0042] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0043] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25°C and the speed was set at 160 rpm.

[0044] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0045] Example 2

[0046] This embodiment provides a method for preparing a composite catalytic material

[0047] The preparation method described in Example 1 was used, except that no halloysite nanotubes (HNTs) were added to obtain the composite catalytic material GZ. The mass fractions of the components in the composite catalytic material GZ are shown in Table 1. The scanning electron microscope image of the composite catalytic material GZ is shown in Figure 2 ,Depend on Figure 2 It can be seen that the surface of GZ after ball milling is rough; the particle size of the steel slag after ball milling is 12.42nm.

[0048] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0049] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of chloramphenicol in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the composite catalytic material GZ was added to the conical flask. After all the materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25° C. and the speed was set at 160 r / min.

[0050] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0051] Example 3

[0052] This embodiment provides a method for preparing a composite catalytic material

[0053] The preparation method described in Example 1 was used, except that no steel slag (GZ) was added to obtain the composite catalytic material HNTs. The mass fractions of the components in the composite catalytic material HNTs are shown in Table 1. The scanning electron microscope image of the composite catalytic material HNTs is shown in Figure 3 ,Depend on Figure 3 It can be seen that the HNTs after ball milling are hollow rod-like structures; the inner diameter of the halloysite nanotubes after ball milling is 3.64 nm, the outer diameter is 16.32 nm, and the length is 140 nm.

[0054] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0055] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material HNTs was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25°C and the speed was set at 160 r / min.

[0056] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0057] Comparative Example 1

[0058] This comparative example provides a method for preparing a composite catalytic material

[0059] The preparation method described in Example 1 is adopted, and the composite catalytic material is HNTs / GZ.

[0060] This comparative example continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0061] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of deionized water was added to the conical flask, and the concentration of deionized water was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25°C and the speed was set at 160 r / min.

[0062] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0063] Comparative Example 2

[0064] This comparative example provides a method for preparing a composite catalytic material

[0065] The composite catalytic material GZ was obtained by adopting the preparation method described in Example 1, except that halloysite nanotubes (HNTs) were not added.

[0066] This comparative example continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0067] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of chloramphenicol in the wastewater was 2 ppm. Then, 1 mL of deionized water was added to the conical flask, and the concentration of the deionized water was 7 mM. Then, 0.05 g of the composite catalytic material GZ was added to the conical flask. After all the materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25° C. and the speed was set at 160 r / min.

[0068] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0069] Comparative Example 3

[0070] This comparative example provides a method for preparing a composite catalytic material

[0071] The composite catalytic material HNTs was obtained by adopting the preparation method described in Example 1, except that steel slag (GZ) was not added.

[0072] This comparative example continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0073] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of deionized water was added to the conical flask, and the concentration of deionized water was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material HNTs was added to the conical flask. After all the materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25°C and the speed was set at 160 r / min.

[0074] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0075] Example 4

[0076] This embodiment provides a method for preparing a composite catalytic material

[0077] 1 g of halloysite nanotubes (HNTs, inner diameter 15 nm, outer diameter 60 nm, length 1000 nm) and 0.8 g of steel slag (GZ) were placed in a ball mill and milled at a speed of 1000 r / min for 80 min to obtain a mixture of halloysite nanotubes and steel slag. The steel slag particle size after ball milling was 12.42 nm; the inner diameter of the halloysite nanotubes after ball milling was 3.64 nm, the outer diameter was 16.32 nm, and the length was 1000 nm. 140nm; the ball-milled halloysite nanotube and steel slag mixture is placed in a tube furnace, and the tube furnace is heated to 500°C at a heating rate of 5°C / min under a N2 atmosphere and calcined at this temperature for 4h to obtain the composite catalytic material 80% HNTs / GZ (80% HNTs / GZ means that the mass of GZ is 80% of the mass of HNTs, the same below); the mass fractions of each component in the composite catalytic material 80% HNTs / GZ are shown in Table 1.

[0078] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0079] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material 80% HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The water bath constant temperature oscillator was set at 25°C and the speed was set at 160 rpm.

[0080] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0081] Example 5

[0082] This embodiment provides a method for preparing a composite catalytic material

[0083] 1 g of halloysite nanotubes (HNTs, inner diameter of 15 nm, outer diameter of 60 nm, and length of 1000 nm) and 0.6 g of steel slag (GZ) were weighed and placed in a ball mill. The ball mill was milled at a speed of 1000 r / min for 80 min to obtain a mixture of halloysite nanotubes and steel slag after ball milling, wherein the particle size of the steel slag after ball milling was 12.42 nm; the inner diameter of the halloysite nanotubes after ball milling was 3.64 nm, the outer diameter was 16.32 nm, and the length was 140 nm; the mixture of halloysite nanotubes and steel slag after ball milling was placed in a tube furnace, and the tube furnace was heated to 500° C. at a heating rate of 5° C. / min under a N2 atmosphere and calcined at this temperature for 4 h to obtain the composite catalytic material 60% HNTs / GZ; the mass fractions of each component in the composite catalytic material 60% HNTs / GZ are shown in Table 1.

[0084] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0085] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material 60% HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The water bath constant temperature oscillator was set at 25°C and the speed was set at 160 rpm.

[0086] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0087] Example 6

[0088] This embodiment provides a method for preparing a composite catalytic material

[0089] 1 g of halloysite nanotubes (HNTs, inner diameter of 15 nm, outer diameter of 60 nm, and length of 1000 nm) and 0.4 g of steel slag (GZ) were weighed and placed in a ball mill. The ball mill was milled at a speed of 1000 r / min for 80 min to obtain a mixture of halloysite nanotubes and steel slag after ball milling, wherein the particle size of the steel slag after ball milling was 12.42 nm; the inner diameter of the halloysite nanotubes after ball milling was 3.64 nm, the outer diameter was 16.32 nm, and the length was 140 nm; the halloysite nanotubes and steel slag mixture after ball milling was placed in a tube furnace, and the tube furnace was heated to 500° C. at a heating rate of 5° C. / min under a N2 atmosphere and calcined at this temperature for 4 h to obtain the composite catalytic material 40% HNTs / GZ; the mass fractions of each component in the composite catalytic material 40% HNTs / GZ are shown in Table 1.

[0090] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0091] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material 40% HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The water bath constant temperature oscillator was set at 25°C and the speed was set at 160 rpm.

[0092] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0093] Example 7

[0094] This embodiment provides a method for preparing a composite catalytic material

[0095] 1 g of halloysite nanotubes (HNTs, with an inner diameter of 15 nm, an outer diameter of 60 nm, and a length of 1000 nm) and 0.2 g of steel slag (GZ) were weighed and placed in a ball mill. The ball mill was milled at a speed of 1000 r / min for 80 min to obtain a mixture of halloysite nanotubes and steel slag after ball milling, wherein the particle size of the steel slag after ball milling was 12.42 nm; the inner diameter of the halloysite nanotubes after ball milling was 3.64 nm, the outer diameter was 16.32 nm, and the length was 140 nm; the mixture of halloysite nanotubes and steel slag after ball milling was placed in a tube furnace, and the tube furnace was heated to 500° C. at a heating rate of 5° C. / min under a N2 atmosphere and calcined at this temperature for 4 h to obtain the composite catalytic material 20% HNTs / GZ; the mass fractions of each component in the composite catalytic material 20% HNTs / GZ are shown in Table 1.

[0096] This embodiment continues to provide a method for degrading chloramphenicol in wastewater using a composite catalytic material prepared by the above method.

[0097] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of tadalafil in the wastewater was 2 ppm. Then, 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. Then, 0.05 g of the above-mentioned composite catalytic material 20% HNTs / GZ was added to the conical flask. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The water bath constant temperature oscillator was set at 25°C and the speed was set at 160 rpm.

[0098] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0099] Control Example

[0100] This comparative example provides a method for degrading chloramphenicol in wastewater.

[0101] 100 mL of wastewater was added to a conical flask, wherein the initial concentration of chloramphenicol in the wastewater was 2 ppm, and then 1 mL of sodium persulfate (PS) was added to the conical flask, and the concentration of sodium persulfate was 7 mM. After all materials were added to the conical flask, the timer was started, and the conical flask was placed in a water bath constant temperature oscillator for reciprocating oscillation. The temperature of the water bath constant temperature oscillator was set at 25°C and the speed was set at 160 r / min.

[0102] Finally, samples were taken from the conical flask with a syringe at 10 min, 20 min, 30 min, 60 min, 120 min, 240 min, 360 min, and 480 min, respectively. The samples were filtered through a 0.45 μm membrane and injected into a test tube containing 2.5 mL of anhydrous ethanol and the volume was adjusted to 5 mL. Then they were shaken evenly. After shaking evenly, the mixed solution in the test tube was poured into a sample injection bottle and its concentration was measured by high performance liquid chromatography. The statistical results are shown in Table 2. The removal rate (%) of chloramphenicol in each time period was calculated. The statistical results are shown in Table 3 and Figure 4 .

[0103] Table 1 Mass fraction of each component in the composite catalytic materials prepared in Examples 1-7 of the present invention

[0104] Example Composite catalytic materials CaO <![CDATA[Fe2O3]]> <![CDATA[SiO2]]> <![CDATA[Al2O3]]> MgO CuO other 1 HNTs / GZ 52.54％ 16.65％ 9.89％ 11.24％ 3.04％ 2.47％ 4.17％ 2 GZ 52.43％ 16.54％ 4.57％ 5.48％ 3.24％ 2.64％ 15.10％ 3 HNTs 0.97％ 0.57％ 42.47％ 36.54％ / / 19.45％ 4 80% HNTs / GZ 52.34％ 16.24％ 10.15％ 11.03％ 2.89％ 2.21％ 5.14％ 5 60% HNTs / GZ 52.04％ 15.67％ 10.48％ 10.48％ 2.48％ 1.98％ 6.87％ 6 40% HNTs / GZ 51.65％ 15.31％ 11.03％ 10.15％ 2.03％ 1.75％ 8.08％ 7 20% HNTs / GZ 50.24％ 15.13％ 11.24％ 9.89％ 1.97％ 1.48％ 10.05％

[0105] In Table 1, “ / ” indicates not detected.

[0106] Table 2 Concentration values ​​of the composite catalytic materials prepared in Examples 1-7 and Comparative Examples 1-3 in different time periods when they were immediately applied to the degradation wastewater

[0107]

[0108] Table 3 Removal rate of chloramphenicol in wastewater by the composite catalytic materials prepared in Examples 1-7 and Comparative Examples 1-3

[0109]

[0110] In Table 3, the removal rate of chloramphenicol is expressed as η, and the calculation formula is as follows:

[0111] η=(C o -C t ) / C o ×100%; where C o is the initial concentration of thiazolidinedione (ppm), C t is the concentration of pain relief after t min of reaction (ppm).

[0112] It can be seen from the records in Tables 1-3 that when the mass ratio of halloysite nanotubes to steel slag in the raw materials of the composite catalytic material of the present invention is 1:1 or the raw materials only include steel slag, the prepared composite catalytic material can effectively activate sodium persulfate to generate sulfate radicals (SO 4-·), sulfate radicals have strong oxidizing properties, and the chlorpheniramine in the wastewater is converted into small molecular substances under the oxidation of sulfate radicals. At the same time, sodium persulfate can be activated to produce hydroxyl radicals (HO·), which can also degrade the chlorpheniramine in the wastewater. In addition, sodium persulfate itself has oxidizing properties and can oxidize the chlorpheniramine in the wastewater, thereby degrading the chlorpheniramine in the wastewater, and the degradation rate can reach 100%;

[0113] When the mass ratio of halloysite nanotubes to steel slag in the raw materials of the composite catalytic material of the present invention is 1:(0.2~0.8), the degradation rate of chlorpyrifos decreases with the decrease of the proportion of steel slag in the composite catalytic material, and the degradation rate is 75%~93%; when the raw materials of the composite catalytic material of the present invention only contain halloysite nanotubes, the degradation rate of chlorpyrifos is significantly reduced, and the degradation rate is 67%; it can be seen that the activation effect of halloysite nanotubes on sodium persulfate is weak or can only partially activate sodium persulfate, but halloysite nanotubes have strong adsorption properties and can adsorb chlorpyrifos in wastewater to the surface of the composite catalytic material, thereby accelerating the degradation of chlorpyrifos in wastewater, shortening the degradation time, and improving the degradation efficiency.

[0114] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A composite catalytic material, characterized in that: The raw materials of the composite catalytic material include halloysite nanotubes and steel slag, and the mass fractions of the components in the composite catalytic material are CaO: 0.97% to 52.54%, Fe2O3: 0.57% to 16.65%, SiO2: 4.57% to 42.47%, Al2O3: 5.48% to 36.54%, MgO: 0 to 3.24%, CuO: 0 to 2.64%, and the rest are impurities; The preparation method of the composite catalytic material comprises ball milling the raw materials and then calcining them in an inert gas atmosphere to obtain the composite catalytic material; the particle size of the steel slag after ball milling is 10nm to 15nm; The composite catalytic material is used for degrading analgesic drugs contained in wastewater.

2. The composite catalytic material according to claim 1, characterized in that The halloysite nanotube has an inner diameter of 10 nm to 20 nm, an outer diameter of 50 nm to 70 nm, and a length of 200 nm to 2000 nm.

3. The composite catalytic material according to claim 2, characterized in that: The halloysite nanotube has an inner diameter of 15 nm, and / or an outer diameter of 60 nm, and / or a length of 1000 nm.

4. The composite catalytic material according to any one of claims 1 to 3, characterized in that The mass fractions of the components in the steel slag are CaO: 50% to 53%, Fe2O3: 15% to 17%, SiO2: 4% to 6%, Al2O3: 3% to 6%, MgO: 3% to 5%, CuO: 0 to 4%, and the rest are impurities.

5. The composite catalytic material according to claim 4, characterized in that: The mass fractions of the components in the steel slag are CaO: 52.43%, Fe2O3: 16.54%, SiO2: 4.57%, Al2O3: 5.48%, MgO: 3.24%, CuO: 2.64%, and the rest are impurities.

6. The composite catalytic material according to any one of claims 1 to 3, characterized in that: The raw materials of the composite catalytic material include halloysite nanotubes and steel slag, and the mass ratio of the halloysite nanotubes to the steel slag is 1:(0.01-1).

7. The composite catalytic material according to claim 6, characterized in that: The mass ratio of the halloysite nanotubes to the steel slag is 1:(0.2-1).

8. A method for preparing the composite catalytic material according to any one of claims 1 to 7, characterized in that: The process comprises ball milling the raw materials and then calcining them in an inactive gas atmosphere to obtain the composite catalytic material.

9. The preparation method according to claim 8, characterized in that The particle size of the steel slag after ball milling is 12.42 nm; and / or the inner diameter of the halloysite nanotubes after ball milling is 2 nm to 5 nm, the outer diameter is 10 nm to 20 nm, and the length is 100 nm to 200 nm.

10. The preparation method according to claim 9, characterized in that The inner diameter of the ball-milled halloysite nanotubes is 3.64 nm, and / or the outer diameter is 16.32 nm, and / or the length is 140 nm.

11. The preparation method according to any one of claims 8 to 10, characterized in that: The ball milling is carried out in a ball mill.

12. The preparation method according to claim 11, characterized in that The rotation speed of the ball mill is 900 r / min to 1000 r / min, and the ball milling time is 70 min to 90 min.

13. The preparation method according to claim 12, characterized in that The rotation speed of the ball mill is 1000 r / min, and / or the ball milling time is 80 min.

14. The preparation method according to any one of claims 8 to 10, characterized in that The calcination is carried out in a tube furnace; And / or, the inert gas is at least one of nitrogen, argon, and helium; And / or, the calcination conditions include a calcination temperature of 500° C. to 600° C. and a calcination time of 4 h to 5 h.

15. The preparation method according to claim 14, characterized in that The heating rate of the tubular furnace is 5°C / min to 10°C / min.

16. Use of the composite catalytic material according to any one of claims 1 to 7 or the composite catalytic material prepared by the preparation method according to any one of claims 8 to 15 in degrading wastewater.

17. The use according to claim 16, characterized in that The wastewater contains analgesic drugs.

18. The preparation method according to claim 17, characterized in that: The analgesic drug is at least one of tolidine, aspirin, and paracetamol.

19. The use according to claim 17 or 18, characterized in that The initial concentration of the analgesic drugs to be degraded in the wastewater is 1 ppm to 2 ppm, and the concentration after degradation is 0 to 0.66 ppm; and / or, the ratio of the wastewater to the composite catalytic material is (100-150) mL: (0.05-1) g; And / or, the wastewater also includes sodium persulfate.

20. The use according to claim 19, characterized in that The ratio of the wastewater to sodium persulfate is (100-150) mL: (1-2) mL.

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