Method for removing antibiotics in water body by using modified material

Abstract

The invention discloses a method for removing antibiotics in a water body by using a modified material, the method is characterized in that the modified material is used as a Fenton-like reaction catalyst to degrade the antibiotics in the water body, and the modified material is prepared by washing an internal solid waste material of a warmer with water and modifying with salicylic acid. According to the method, the modified material is a Fenton-like reaction catalyst which is large in specific surface area, multiple in active site, high in catalytic activity, stable in performance and environmentally friendly, the antibiotics in the water can be efficiently and thoroughly removed through Fenton-like reaction of the activating oxidizing agent, meanwhile, the pH value of a reaction system can be adjusted through the modified material, the pH value of a treated solution is close to neutral, and the treatment effect is good. The method has the advantages of being simple in process, convenient to operate, low in cost, high in treatment efficiency, good in treatment effect, small in dosage of added chemical agents, green, environmentally friendly and the like, antibiotics in water can be effectively removed, and reutilization of warmer waste can be achieved.

Description

Technical Field

[0001] The invention belongs to the field of environmental pollutant treatment and relates to a method for removing antibiotics in water by using modified materials. Background Art

[0002] Antibiotics have attracted widespread attention as emerging pollutants around the world. In particular, a large number of antibiotics used are not absorbed by humans and animals. They enter surface water and groundwater in the form of original drugs or metabolites with excrement, and eventually accumulate in soil and sediment, causing serious pollution. At the same time, the concentration of antibiotics in soil and sediment increases with the occurrence of pollution, thereby inducing the production of resistance genes and producing potential toxic effects on humans and animals. Therefore, how to effectively remove antibiotics in the environment is an urgent problem to be solved at this stage.

[0003] Advanced oxidation processes are a type of chemical oxidation method that has been widely studied and applied. Among them, the Fenton-like reaction method can effectively, quickly and thoroughly remove organic pollutants from polluted wastewater. At the same time, it can degrade organic pollutants into harmless substances such as inorganic salts, water and carbon dioxide. It is an environmentally friendly method for treating wastewater containing organic pollutants with application prospects. At the same time, obtaining a catalyst with low cost and good activation effect on oxidants is the key to effectively remove organic pollution from wastewater using the Fenton-like reaction method at this stage.

[0004] Warm baby, also known as warm patch, is a tool for heating, which is favored by the market. At the same time, with the sharp increase in market demand, such as the demand for warm baby reaches 1.614 billion pieces / year, and the mass of a piece of warm baby is usually 50g, so a large amount of warm baby solid waste is formed, wherein the internal solid waste material of the warm baby contains a high content of iron, which can provide iron ions for Fenton-like reaction, and is a potential Fenton-like reaction catalyst. However, in the actual research of the inventor of the present application, it is also found that if the internal solid waste material of the warm baby is directly used as a catalyst for Fenton-like reaction, due to the defects of easy agglomeration, small specific surface area, and few active sites in the internal solid waste material of the warm baby, it is difficult to quickly activate the oxidant, which leads to difficulty in achieving rapid and efficient degradation of organic pollutants in wastewater. In addition, since the internal solid waste materials of the warm baby also contain a large amount of alkaline components such as CaO, if they are directly added to the wastewater, the pH of the wastewater will rise sharply due to the hydrolysis of the alkaline components, which also makes it difficult for the internal solid waste materials of the warm baby to effectively activate the oxidant. In particular, in order to ensure the continuous progress of the Fenton-like reaction, it is necessary to continuously add acid solution to control the pH of the reaction system, which increases the difficulty of operation and processing costs. Therefore, how to prepare the internal solid waste materials of the warm baby into a catalyst material with a large specific surface area, many active sites, high catalytic activity, and stable performance is of great significance for the safe disposal of discarded warm babies and the effective treatment of antibiotic wastewater. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for removing antibiotics in water using modified materials, which has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good treatment effect and green environmental protection.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A method for removing antibiotics from water using modified materials, wherein the method uses the modified materials as Fenton-like reaction catalysts to degrade the antibiotics in the water; the modified materials are prepared from internal solid waste materials of a warm baby as raw materials after being washed with water and modified with salicylic acid.

[0008] The above method is further improved, and the preparation method of the modified material comprises the following steps:

[0009] S1. Take out the solid waste materials inside the warm pack;

[0010] S2, washing the internal solid waste material obtained in step S1;

[0011] S3, mixing the internal solid waste material obtained after the water washing treatment in step S2 with the salicylic acid solution to react to obtain a modified material.

[0012] The above method is further improved, in step S3, the mass volume ratio of the internal solid waste material obtained after the water washing treatment to the salicylic acid solution is 100g-150g:1L.

[0013] The above method is further improved in that the salicylic acid solution is prepared by dissolving salicylic acid in a methanol / acetone composite solvent.

[0014] The above method is further improved in that the mass volume ratio of the salicylic acid to the methanol / acetone composite solvent is 50g-60g:1L; the volume ratio of methanol to acetone in the methanol / acetone composite solvent is 2-3:2-3.

[0015] The above method is further improved, in step S3, the reaction time is 2h to 4h.

[0016] The above method is further improved, in step S3, after the reaction is completed, the following treatment is also included: washing the product obtained after the reaction with water, drying, to obtain a modified material; the washing time is 15min to 30min.

[0017] The above method is further improved, in step S1, the internal solid waste material includes the following components: 80wt% to 85wt% of Fe3O4, and 15wt% to 20wt% of C4H6MnO4·4H2O.

[0018] The above method is further improved, and step S3 further includes the following processing: crushing the modified material into particles with a diameter of 0.3 mm, and placing them in a porous flexible container for packaging.

[0019] The above method is further improved in that the wall of the porous flexible container is in a porous mesh shape; a plurality of holes are provided on the wall of the porous flexible container; and the pore diameter of the holes is 100 μm to 300 μm.

[0020] The above method is further improved in that the material of the porous flexible container is at least one of nylon material, gauze, non-woven fabric, and degradable packaging material.

[0021] The above method is further improved, wherein the specific surface area of ​​the modified material is 41.018 m 2 / g; the pore volume of the modified material is 0.153cc / g.

[0022] The above method is further improved, using the modified material as a Fenton-like reaction catalyst to degrade antibiotics in water, comprising the following steps: mixing the modified material with antibiotic wastewater, adding an oxidant to carry out a Fenton-like reaction, and completing the degradation of the antibiotics in the wastewater; the mass volume ratio of the modified material to the antibiotic wastewater is 1g~4g:1L.

[0023] The above method is further improved in that the mass volume ratio of the modified material to the antibiotic wastewater is 1.8g-3g:1L.

[0024] The above method is further improved, wherein the oxidant is a persulfate solution; the volume ratio of the persulfate solution to the antibiotic wastewater is 0.02-0.04:1; the mass concentration of persulfate in the persulfate solution is 2 g / L; and the persulfate is Na2S2O8.

[0025] The above method is further improved, wherein the antibiotic in the antibiotic wastewater is tetracycline; and the concentration of the antibiotic in the antibiotic wastewater is ≤20 mg / L.

[0026] The above method is further improved, wherein the time of the Fenton-like reaction is 4h to 6h; and the initial pH value of the Fenton-like reaction system is 4 to 9.

[0027] Compared with the prior art, the advantages of the present invention are:

[0028] (1) Aiming at the shortcomings of the internal solid waste materials of the warm baby, such as easy agglomeration, small specific surface area, few active sites, and containing a large amount of alkaline components, as well as the resulting low efficiency of antibiotic wastewater treatment, poor treatment effect, and the risk of secondary pollution, the present invention provides a method for removing antibiotics from water using a modified material, wherein the modified material is used as a Fenton-like reaction catalyst to degrade the antibiotics in the water, wherein the modified material is prepared by washing the internal solid waste materials of the warm baby as raw materials and modifying them with salicylic acid. In the present invention, the internal solid waste materials of the warm baby are used as raw materials, and through washing and salicylic acid modification, a modified material with a large specific surface area, many active sites, high catalytic activity, stable performance, and green environmental protection can be prepared. As a new type of Fenton-like reaction catalyst with excellent performance, it can achieve efficient and thorough removal of antibiotics in water by activating an oxidant to produce a Fenton-like reaction, and can convert antibiotics into small molecule non-polluting substances. In particular, in the present invention, after modification with salicylic acid, the alkaline substances on the surface of the modified material are effectively removed, which is conducive to the progress of the Fenton-like reaction. At the same time, the modified material also contains certain alkaline components. These alkaline components can adjust the pH value of the reaction system in the later stage of the Fenton-like reaction, so that the pH value of the treated solution is close to neutral. After testing, the pH value of the solution treated by the present invention is 7-8, so the treated solution can be directly discharged without further treatment, the operation is simple, and the treatment cost is low. The method of removing antibiotics from water bodies using modified materials of the present invention has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good treatment effect, small amount of chemical agents added, green and environmental protection, etc., which not only realizes the effective degradation of antibiotics, but also realizes the waste recycling of the "warm baby" after use.

[0029] Taking the activation of Na2S2O8 as an example, the modified material of the present invention and Na2S2O8 undergo a Fenton-like reaction, and the corresponding reaction equations are shown in Formula (1)-Formula (2). It can be seen from Formula (1)-Formula (2) that a sulfate radical (SO4 - ·), the SO4 - Free radicals with high redox potential can degrade most organic pollutants in nature, including antibiotics, and convert them into small molecules of non-polluting substances such as water and CO2.

[0030] Fe 3+ + S2O8 2- → Fe 2+ + S2O8 - (1)

[0031] Fe 2+ + S2O8 2-→ Fe 3+ + SO4 - + SO4 2 (2).

[0032] (2) In the present invention, the modified material used is prepared by washing the internal solid waste material of the warm baby as raw material and modifying it with salicylic acid. The internal solid waste material of the warm baby is used as raw material, and the internal solid waste material is first washed with water to wet the internal solid waste material, which is beneficial to the contact between the internal solid waste material and salicylic acid in the subsequent reaction process, and can accelerate the modification efficiency. At the same time, the soluble components on the surface of the internal solid waste material can also be removed by washing with water. On this basis, the internal solid waste material after wetting is modified with salicylic acid solution. On the one hand, the salicylic acid solution can be used to remove the original alkaline substances on the surface of the internal solid waste material, which can prevent the pH of the solution from rising sharply, and is beneficial to the Fenton-like reaction. However, the modified material obtained after modification with salicylic acid still contains certain alkaline components. These alkaline components The pH value of the reaction system can be adjusted in the later stage of the Fenton-like reaction, which is conducive to making the pH value of the effluent of the Fenton-like reaction meet the emission standard; on the other hand, the salicylic acid solution can fully expose more Fe2O3 and FeO components in the internal solid waste material, increase the contact area between the iron-containing components in the internal solid waste material and the solution, and can also increase the specific surface area and active sites of the original activated carbon component, which is conducive to improving the catalytic activity and catalytic efficiency of the modified material. Therefore, when the modified material is used as a Fenton-like reaction catalyst for activating the oxidant, more active substances can be quickly formed, and then the treatment efficiency and treatment effect of the reactant can be effectively improved, thereby preparing a modified material with a large specific surface area, many active sites, high catalytic activity, stable performance, and green environmental protection. At the same time, the modification method of the present invention also has the advantages of a wide source of raw materials, low preparation cost, simple operation, non-toxic and harmless products, and environmental friendliness, and is suitable for large-scale production and application, and can also realize the resource utilization of warm baby waste.

[0033] (3) In the present invention, the mass volume ratio of the internal solid waste material obtained after the water washing treatment to the salicylic acid solution is optimized to 100g to 150g: 1L, which can ensure that salicylic acid fully reacts with the internal solid waste material, improve the modification effect, and at the same time reduce the cost of the material modification process and reduce environmental impact. For example, when the amount of salicylic acid is too low, the modification of the internal solid waste material by salicylic acid is incomplete, the modification effect is not good, the expected performance improvement effect cannot be achieved, and it is difficult to improve the catalytic performance of the modified material. If the amount of salicylic acid is too high, it may lead to excessive modification of the internal solid waste material, thereby destroying the material structure, and is not conducive to improving the catalytic performance of the modified material. At the same time, it will also greatly increase the raw material cost of the modification process.

[0034] (4) In the present invention, by crushing the modified material into particles with a diameter of 0.3 mm and placing them in a porous flexible container for packaging, on the one hand, the specific surface area and active sites of the modified material can be increased, which is convenient for the modified material to effectively contact the target object. On the other hand, it can also effectively prevent the modified material from entering the external system and causing secondary pollution to the external environment. More importantly, it can also achieve the recycling of the modified material, which is conducive to reducing the cost of use. At the same time, the porous flexible container used is made of nylon material, gauze, non-woven fabric or degradable packaging material, which are non-toxic, bacteria-free, tough and environmentally friendly materials that have passed national safety inspections and have good water permeability. Therefore, by loading the modified material with a porous flexible container, it is not only convenient to recycle the modified material, but also does not affect the catalytic performance of the modified material, and does not cause any impact on the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0036] Figure 1 This is an X-ray photoelectron spectroscopy scanning energy spectrum analysis diagram of the unwashed internal solid waste material (A) and the washed internal solid waste material (B) in Example 1 of the present invention.

[0037] Figure 2a to 2c The electron scanning microscope images are of the unwashed internal solid waste material (A), the washed internal solid waste material (B), and the internal solid waste material (C) modified with salicylic acid in Example 1 of the present invention.

[0038] Figure 3 This is a scanning electron microscope energy spectrum component analysis diagram of the unwashed internal solid waste material (A) and the internal solid waste material (B) modified with salicylic acid in Example 1 of the present invention.

[0039] Figure 4 This is a diagram showing the removal effect of tetracycline in wastewater by the internal solid waste materials before and after modification at different reaction times in Example 1 of the present invention.

[0040] Figure 5 This is a diagram showing the effect of the modified material in Example 2 of the present invention on the cyclic removal of tetracycline in water.

[0041] Figure 6 This is a diagram showing the removal effect of tetracycline in water by the modified material before and after encapsulation in Example 3 of the present invention.

[0042] Figure 7 This is a diagram showing the removal effect of tetracycline in wastewater with different dosages of the modified material in Example 4 of the present invention.

[0043] Figure 8 This is a diagram showing the removal effect of tetracycline in wastewater by the modified material in Example 5 of the present invention under different pH conditions. DETAILED DESCRIPTION

[0044] The present invention is further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

[0045] In the following examples of the present invention, unless otherwise specified, the materials and instruments used are commercially available, the equipment used is conventional equipment, and the data obtained are the average values ​​of more than three repeated experiments.

[0046] Example 1

[0047] A method for removing antibiotics from water using modified materials, specifically using the modified materials as Fenton-like reaction catalysts to degrade antibiotics in water, comprising the following steps:

[0048] Take a 1L tetracycline solution with a mass concentration of 20mg / L (the initial pH value of the solution is 6.93), add 2g of unencapsulated modified material (numbered SAM-WP), and after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L. After mixing, carry out a Fenton-like reaction for 4h to complete the degradation of tetracycline.

[0049] Control group: unmodified internal solid waste materials (WP) were used instead of modified materials, and other conditions were the same.

[0050] In this embodiment, the modified material used is prepared by washing the internal solid waste material of the warm baby with water and modifying it with salicylic acid, and the steps include:

[0051] S1. Take out the internal solid waste materials in the discarded hot packs, wherein the main components of the collected internal solid waste materials (WP) are: 83.2wt% Fe3O4 and 16.8wt% C4H6MnO4·4H2O.

[0052] S2. Washing the internal solid waste material obtained in step S1 with water to moisten the internal solid waste material and remove soluble components on the surface of the internal solid waste material.

[0053] S3. Mix 150 g of the internal solid waste material obtained after water washing in step S2 with 1 L of salicylic acid solution, react under oscillation conditions for 2 hours, filter, wash with ultrapure water for 20 minutes, and dry to obtain a modified material, that is, an unencapsulated modified material.

[0054] In this embodiment, the specific surface area of ​​the prepared modified material is 41.018 m 2 / g, and the pore volume of the modified material is 0.153cc / g.

[0055] In step S3, the salicylic acid solution is prepared by the following method: 50 g of salicylic acid is dissolved in 1 L of methanol / acetone composite solvent to obtain a salicylic acid solution. The volume ratio of methanol to acetone in the methanol / acetone composite solvent is 1:1.

[0056] The modification method of this embodiment further includes the following treatment: crushing the modified material obtained in step S3 into particles with a diameter of 0.3 mm, placing the particles in a porous flexible container for packaging, and obtaining a packaged modified material.

[0057] In step S4, the wall of the porous flexible container is in the shape of a porous mesh, and the material of the porous flexible container is nylon material. Optionally, the material of the porous flexible container can also be at least one of gauze, non-woven fabric, and degradable packaging material.

[0058] The specific surface area and pore volume of the unwashed internal solid waste material (A), the washed internal solid waste material (B) and the internal solid waste material modified with salicylic acid (C) obtained in Example 1 were measured. The results are shown in Table 1:

[0059] Table 1 shows the specific surface area and pore volume of the unwashed internal solid waste material (A), the washed internal solid waste material (B) and the internal solid waste material modified with salicylic acid (C) in Example 1 of the present invention. It can be seen from Table 1 that the specific surface area of ​​the unwashed internal solid waste material (A) is relatively small, which is 24.413 m 2 / g, after washing, the specific surface area of ​​the internal solid waste material (B) increased to 28.764m 2 / g, which may be due to the formation of some cracks on the surface of the internal solid waste material due to the water washing treatment. Furthermore, after being treated with salicylic acid solution, the specific surface area of ​​the internal solid waste material (C) further increased to 41.018m 2 / g. At the same time, it can be seen from the test results in Table 1 that after water washing and salicylic acid modification, the pore volume of the internal solid waste material (C) increased significantly from 0.099cc / g to 0.153cc / g. This may be because salicylic acid removes the alkaline components on the surface of the internal solid waste material, leaving components such as Fe2O3, forming more pit structures.

[0060] Table 1 Specific surface area and pore volume values ​​of different internal solid waste materials

[0061] sample A B C <![CDATA[Specific surface area (m 2 / g)]]> 24.413 28.764 41.018 Pore ​​volume (cc / g) 0.099 0.105 0.153

[0062] X-ray photoelectron spectroscopy scanning was performed on the unwashed internal solid waste material (A) and the washed internal solid waste material (B):

[0063] Figure 1 This is an X-ray photoelectron spectroscopy scanning energy spectrum analysis diagram of the unwashed internal solid waste material (A) and the washed internal solid waste material (B) in Example 1 of the present invention. Figure 1 In the table, before refers to the test results of the unwashed internal solid waste material (A), and after use refers to the test results of the washed internal solid waste material (B). Figure 1 It can be seen that the peak values ​​and contents of various elements in the internal solid waste materials before and after ultrapure water treatment have not changed much, which means that when the materials are placed in a liquid environment, the various elements will still retain their respective structures and compositions, and have a high degree of stability.

[0064] Electron microscope scanning was performed on the unwashed internal solid waste material (A), the washed internal solid waste material (B), and the internal solid waste material modified with salicylic acid (C):

[0065] Figure 2a to 2c The electron scanning microscope images are of the unwashed internal solid waste material (A), the washed internal solid waste material (B), and the internal solid waste material (C) modified with salicylic acid in Example 1 of the present invention. Figure 2a It is unwashed internal solid waste material (A); Figure 2b It is the internal solid waste material after washing (B); Figure 2c The internal solid waste material (C) modified with salicylic acid. As shown in Figure 2, the surface of the unmodified internal solid waste material is relatively flat, but due to mechanical crushing, there are some pits; after being modified with salicylic acid, the surface morphology of the internal solid waste material has changed significantly, and the surface of the internal solid waste material has become uneven, forming many concave and convex structures. These changes increase the contact area between the internal solid waste material and the target, which is conducive to the subsequent Fenton reaction.

[0066] The unwashed internal solid waste materials and the internal solid waste materials modified with salicylic acid were subjected to scanning electron microscope energy spectrum component analysis:

[0067] Figure 3 The scanning electron microscope energy spectrum component analysis diagram of the unwashed internal solid waste material (A) and the internal solid waste material modified with salicylic acid (B) in Example 1 of the present invention. The scanning electron microscope energy spectrum component analysis further verifies that the modification treatment removes the CaO component on the surface of the internal solid waste material. Figure 3 It can be seen that after the internal solid waste materials were modified by salicylic acid, the proportion of Ca element decreased, and the mass fraction of Ca element decreased from 1.24% to 0.26%.

[0068] Samples were taken from the reaction system at 20 min, 40 min, 80 min, 120 min and 240 min of the Fenton-like reaction, and the content of tetracycline in the solution was detected by high performance liquid chromatography. The test results are shown in Figure 4 .

[0069] Figure 4 The figure is a diagram showing the removal effect of tetracycline in wastewater by the internal solid waste material before and after modification at different reaction times in Example 1 of the present invention. Under the same other conditions, the removal effect of tetracycline in wastewater by the modified material prepared by the present invention is significantly better than that of the unmodified internal solid waste material, wherein the modified internal solid waste material (SAM-WP) can adsorb 74% of tetracycline in 60 minutes, which is 15% higher than that of the unmodified internal solid waste material (WP). After adding Na2S2O8, the two materials can reach degradation equilibrium within 240 minutes, and the removal rates of tetracycline by SAM-WP and WP are 86.6% and 74.1%, respectively. It can be seen that the modified material of the present invention has good catalytic performance.

[0070] Example 2

[0071] A method for removing antibiotics from water using modified materials, specifically: using the modified materials to perform cyclic degradation treatment on tetracycline in water, comprising the following steps:

[0072] (1) Take a 1L tetracycline solution with a concentration of 20 mg / L (the initial pH value of the solution is 6.93), add 2g of the unencapsulated modified material prepared in Example 1 (numbered SAM-WP), after 60 minutes of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L, mix well, and perform a Fenton-like reaction for 4 hours to complete the degradation of tetracycline.

[0073] (2) Recovering the modified material, after washing and drying, and continuing to use it to degrade tetracycline in water in the manner of step (1).

[0074] (3) Repeat steps (1) and (2) to carry out cyclic degradation treatment of tetracycline in the water body for a total of three times.

[0075] After each reaction, samples were taken and the content of tetracycline in the solution was tested by high performance liquid chromatography. The test results are shown in Figure 5 .

[0076] Figure 5 This is a diagram showing the effect of the modified material in Example 2 of the present invention on the cyclic removal of tetracycline in water. Figure 5It can be seen that the removal rate of tetracycline by the modified material was 86.6% when it was used for the first time. When it was recycled for the third time, its removal rate of tetracycline was still as high as 64.8%, indicating that the modified material still has good degradation performance and good stability after being recycled for many times.

[0077] Example 3

[0078] A method for removing antibiotics from water using modified materials, specifically: using the modified materials before and after encapsulation to degrade tetracycline in the water, comprising the following steps:

[0079] Take a tetracycline solution with a volume of 1L and a concentration of 20mg / L (the initial pH value of the solution is 6.93), add 2g of the unencapsulated modified material (numbered SAM-WP) prepared in step S3 of Example 1, and after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L. After mixing evenly, perform a Fenton-like reaction for 4h to complete the degradation of tetracycline.

[0080] Control group: The encapsulated modified material prepared in step S4 of Example 1 was used instead of the unencapsulated modified material prepared in step S3, and tetracycline in water was degraded under the same conditions.

[0081] Samples were taken from the reaction system at 20 min, 40 min, 80 min, 120 min and 240 min of the Fenton-like reaction, and the content of tetracycline in the solution was detected by high performance liquid chromatography. The test results are shown in Figure 6 .

[0082] Figure 6 The figure is a diagram showing the removal effect of tetracycline in water by the modified material before and after encapsulation in Example 3 of the present invention. Figure 6 It can be seen that when the degradation equilibrium is reached, the removal rate of tetracycline by the modified material without flexible container packaging is 86.6%, and the removal rate of tetracycline by the modified material with flexible container packaging is 85.9%, which is not much different from each other. Figure 6 It can be seen that the degradation efficiency of tetracycline by the modified material is not much different regardless of whether it is packaged in a flexible container or not, which means that the effect of flexible container packaging on the degradation performance of the modified material is negligible.

[0083] Example 4

[0084] A method for removing antibiotics from water using modified materials, specifically using the modified materials as Fenton-like reaction catalysts to degrade antibiotics in water, comprising the following steps:

[0085] Take 5 portions of tetracycline solution with a volume of 1L and a mass concentration of 20 mg / L (the initial pH value of the solution is 6.93), add 0g, 0.8g, 1.2g, 1.6g, and 2g of the unencapsulated modified material (SAM-WP) prepared in Example 1, respectively. After 60 minutes of adsorption saturation, 20mL of Na2S2O8 solution with a mass concentration of 2g / L are added respectively. After mixing, a Fenton-like reaction is carried out for 4 hours to complete the degradation of tetracycline.

[0086] After the Fenton-like reaction was completed, samples were taken from the reaction system and the content of tetracycline in the solution was detected by high performance liquid chromatography. The test results are shown in Figure 7 .

[0087] Figure 7 The figure is a diagram showing the removal effect of tetracycline in wastewater by different dosages of the modified material in Example 4 of the present invention. Figure 7 It can be seen that with the increase in the amount of modified materials added, the degradation rate of tetracycline increases. When the amount of modified warm baby solid waste material added is 0.8g / L, the removal rate of tetracycline is 53.6%, and when the amount of modified warm baby solid waste material added is 2g / L, the removal rate of tetracycline is 86.6%. The reason may be that more modified materials can provide more catalytic sites.

[0088] Example 5

[0089] A method for removing antibiotics from water using modified materials, specifically using the modified materials as Fenton-like reaction catalysts to degrade antibiotics in water, comprising the following steps:

[0090] Take 5 portions of tetracycline solution with a volume of 1L and a mass concentration of 20 mg / L, adjust the initial pH values ​​of the tetracycline solutions to 2.12, 4.02, 6.15, 8.14 and 11.03, respectively, add 2g of the modified material (SAM-WP) prepared in Example 1 to each, and after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L to each, mix and carry out Fenton-like reaction for 4h to complete the degradation of tetracycline.

[0091] After the Fenton-like reaction was completed, samples were taken from the reaction system and the content of tetracycline in the solution was detected by high performance liquid chromatography. The test results are shown in Figure 8 .

[0092] Figure 8 The figure is a diagram showing the removal effect of tetracycline in wastewater by the modified material in Example 5 of the present invention under different pH conditions. Figure 8It can be seen that the removal rates of tetracycline by the modified material under the conditions of pH values ​​of 2.12, 4.02, 6.15, 8.14 and 11.03 are 52.2%, 76.4%, 79.3%, 74.0% and 20.0% respectively. It can be seen that the system has a good tetracycline removal effect in the initial pH range of 4-9, and when the pH value is 11.03, the degradation effect is greatly reduced, which is mainly related to the decrease in the adsorption capacity of the material for tetracycline under alkaline conditions. It can be seen that the modified material of the present invention exhibits excellent catalytic performance in the initial pH range of 4-9 and can effectively degrade tetracycline in water.

[0093] From the above results, it can be seen that the method of removing antibiotics in water by using modified materials in the present invention has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good treatment effect, small amount of chemical agents added, and green environmental protection. It not only realizes the effective degradation of antibiotics, but also realizes the waste reuse of the "warm baby" after use.

[0094] The above embodiments are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A method for removing antibiotics from water using modified materials, characterized in that: The method uses a modified material as a Fenton-like reaction catalyst to degrade antibiotics in water; the modified material is prepared by using internal solid waste materials of a warm baby as raw materials and then washing with water and modifying with salicylic acid.

2. The method according to claim 1, characterized in that The preparation method of the modified material comprises the following steps: S1. Take out the solid waste materials inside the warm pack; S2, washing the internal solid waste material obtained in step S1; S3, mixing the internal solid waste material obtained after the water washing treatment in step S2 with the salicylic acid solution to react to obtain a modified material.

3. The method according to claim 2, characterized in that In step S3, the mass volume ratio of the internal solid waste material obtained after water washing to the salicylic acid solution is 100g-150g:1L; the salicylic acid solution is prepared by dissolving salicylic acid in a methanol / acetone composite solvent; the mass volume ratio of the salicylic acid to the methanol / acetone composite solvent is 50g-60g:1L; the volume ratio of methanol to acetone in the methanol / acetone composite solvent is 2-3:2-3.

4. The method according to claim 2, characterized in that: In step S3, the reaction time is 2 h to 4 h.

5. The method according to claim 4, characterized in that In step S3, after the reaction is completed, the following treatment is further included: washing the product obtained after the reaction with water, drying, and obtaining a modified material; the washing time is 15 minutes to 30 minutes.

6. The method according to claim 5, characterized in that In step S1, the internal solid waste material includes the following components: 80wt% to 85wt% of Fe3O4, 15wt% to 20wt% of C4H6MnO4·4H2O; Step S3 also includes the following processing: crushing the modified material into particles with a diameter of 0.3 mm, placing them in a porous flexible container for packaging; the wall of the porous flexible container is a porous mesh; a plurality of holes are provided on the wall of the porous flexible container; the pore size of the holes is 100 μm to 300 μm; the material of the porous flexible container is at least one of nylon material, gauze, non-woven fabric, and degradable packaging material; the specific surface area of ​​the modified material is 41.018 m 2 / g; the pore volume of the modified material is 0.153cc / g.

7. The method according to any one of claims 1 to 6, characterized in that: The method uses a modified material as a Fenton-like reaction catalyst to degrade antibiotics in water, comprising the following steps: mixing the modified material with antibiotic wastewater, adding an oxidant to carry out a Fenton-like reaction, and completing the degradation of the antibiotics in the wastewater; the mass volume ratio of the modified material to the antibiotic wastewater is 1g-4g:1L.

8. The method according to claim 7, characterized in that The mass volume ratio of the modified material to the antibiotic wastewater is 1.8g-3g:1L.

9. The method according to claim 8, characterized in that The oxidant is a persulfate solution; the volume ratio of the persulfate solution to the antibiotic wastewater is 0.02-0.04:1; the mass concentration of persulfate in the persulfate solution is 2 g / L; the persulfate is Na2S2O8; the antibiotic in the antibiotic wastewater is tetracycline; the concentration of the antibiotic in the antibiotic wastewater is ≤20 mg / L.

10. The method according to claim 9, characterized in that The time of the Fenton-like reaction is 4 hours to 6 hours; the initial pH value of the Fenton-like reaction system is 4 to 9.

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