Modification method of solid waste material in warmer pad and modified material

Abstract

The invention discloses a modification method of an internal solid waste material of a warmer pad and a modified material, and the modification method comprises the following steps: taking out the internal solid waste material of the warmer pad, carrying out water washing treatment, mixing the internal solid waste material with a salicylic acid solution, and carrying out a reaction to obtain the modified material. According to the modification method, the internal solid waste material of the warmer pad is used as a raw material, the modified material which is large in specific surface area, multiple in active site, high in catalytic activity, stable in performance and environmentally friendly can be prepared through water washing and salicylic acid modification, and the modified material serves as a novel Fenton-like reaction catalyst with excellent performance and is widely used for activating an oxidizing agent; and meanwhile, resource utilization of the warmer pad waste can be achieved, the use value is high, and the application prospect is good. Meanwhile, the modification method disclosed by the invention also has the advantages of wide raw material source, low preparation cost, simplicity and convenience in operation, non-toxic and harmless product, environment friendliness and the like, and is suitable for large-scale production and application.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of new environmental materials, and relates to a method for modifying solid waste materials inside a warm baby and a modified material. Background Art

[0002] A warm baby, also known as a heating patch, is a tool for keeping warm, including a cloth bag and the heating material inside the bag. When air enters the bag through the bag, the oxygen in the air reacts chemically with the heating material inside the bag to generate heat. Therefore, warm babies are widely used as a heat preservation measure for people in cold winters and as a refuge commodity during disasters. With the sharp increase in market demand, such as the demand for warm babies reaching 1.614 billion pieces per year, and the mass of a piece of warm baby product is usually 50g, the mass of the internal solid waste materials brought by discarded warm babies is measured in tens of thousands of tons. In addition, the internal solid waste materials of warm babies are mainly composed of iron powder, activated carbon, vermiculite, water and salt, and have certain resource utilization value. Therefore, how to effectively treat discarded warm babies and realize the resource utilization of the internal solid waste materials of warm babies is of great significance.

[0003] At present, the treatment and disposal methods of the internal solid waste materials of the warm baby are mainly used as flower fertilizer or odor remover. At the same time, some factories also recycle the metal resources therein, but the economic benefits are poor. In addition, since the internal solid waste materials of the warm baby contain a high content of iron, they can provide iron ions for the Fenton-like reaction. However, in actual research, it is also found that if the internal solid waste materials of the warm baby are directly used as catalysts for the Fenton-like reaction, due to the defects of the internal solid waste materials of the warm baby such as easy agglomeration, small specific surface area, and few active sites, it is difficult to quickly activate the oxidant, which makes it difficult to achieve rapid and efficient degradation of organic pollutants in the 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. This is another important reason why the internal solid waste materials of the warm baby are difficult 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 cost. 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 baby and the resource utilization of the internal solid waste materials of the warm baby. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a method for modifying the solid waste materials inside a hot pack, which has a simple process, convenient operation, low cost and is green and environmentally friendly, and a modified material prepared thereby. The modified material has the advantages of large specific surface area, multiple active sites, high catalytic activity and stable performance.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A method for modifying solid waste materials inside a warm baby comprises the following steps:

[0007] S1. Take out the solid waste materials inside the warm pack;

[0008] S2, washing the internal solid waste material obtained in step S1;

[0009] 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.

[0010] The above modification 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.

[0011] The above modification method is further improved, in step S3, 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.

[0012] The above modification method is further improved, in step S3, the reaction time is 2h to 4h.

[0013] The above modification 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.

[0014] The above modification method is further improved, in step S1, the internal solid waste material includes a relative content of 8.09wt% of C element, a relative content of 55.83wt% of O element, and a relative content of 31.91wt% of Fe element.

[0015] The above modification 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.

[0016] The above-mentioned modification method is further improved, wherein 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 diameter of the holes is 100μm to 300μm; the material of the porous flexible container is at least one of nylon material, gauze, non-woven fabric, and degradable packaging material.

[0017] As a general technical concept, the present invention also provides a modified material, which is prepared by the above-mentioned modification method.

[0018] The modified material is further improved, and the specific surface area of ​​the modified material is 41.018m 2 / g; the pore volume of the modified material is 0.153cc / g.

[0019] Compared with the prior art, the advantages of the present invention are:

[0020] (1) In view of 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 defects such as poor catalytic activity and easy to bring about secondary pollution risks, the present invention provides a method for modifying the internal solid waste materials of the warm baby. The internal solid waste materials of the warm baby are used as raw materials. The internal solid waste materials are first washed with water to wet the internal solid waste materials, which is beneficial to the contact between the internal solid waste materials and salicylic acid in the subsequent reaction process, which can accelerate the modification efficiency. At the same time, the soluble components on the surface of the internal solid waste materials can also be removed by washing with water. On this basis, the internal solid waste materials after wetting are modified using a salicylic acid solution. On the one hand, 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 due to the continuous hydrolysis of the alkaline components on the surface of the internal solid waste material in the aqueous solution. Therefore, when the modified material is used as a Fenton-like reaction catalyst to activate the oxidant, the oxidant can be effectively prevented from failing, which is conducive to the progress of the Fenton-like reaction; in particular, the modified material obtained after salicylic acid modification also contains certain alkaline components, which can adjust the pH value of the reaction system in the later stage of the Fenton-like reaction, which is conducive to making the pH value of the water discharged from the Fenton-like reaction meet the emission standards. On the other hand, 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 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 to activate the oxidant, more active substances can be quickly formed, thereby effectively improving the treatment efficiency and treatment effect of the reactants. In the modification method of the present invention, the internal solid waste material of the warm baby is used as the raw material, and through water washing and salicylic acid modification, a modified material with large specific surface area, multiple active sites, high catalytic activity, stable performance and green environmental protection can be prepared. It can be used as a new type of Fenton reaction catalyst with excellent performance, widely used for activating oxidants, and can achieve rapid activation of oxidants. At the same time, it can also realize the resource utilization of the waste of the warm baby, with high use value and good application prospects. At the same time, the modification method of the present invention also has the advantages of 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.

[0021] (2) In the modification method of 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 and the internal solid waste material fully react and improve the modification effect. At the same time, it can reduce the cost of the material modification process and reduce the 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 cause 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.

[0022] (3) In the modification method of 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 with 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 use cost. 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

[0023] 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 drawings in the embodiments of the present invention.

[0024] Figure 1 This is a process flow chart for modifying the solid waste materials inside the warm baby in Example 1 of the present invention.

[0025] Figure 2 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.

[0026] Figure 3a to 3c 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.

[0027] Figure 4This 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.

[0028] Figure 5 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 2 of the present invention.

[0029] Figure 6 This is a diagram showing the effect of the modified material in Example 3 of the present invention on the cyclic removal of tetracycline in water.

[0030] Figure 7 This is a diagram showing the removal effect of tetracycline in water by the modified material before and after encapsulation in Example 4 of the present invention.

[0031] Figure 8 This is a diagram showing the removal effect of tetracycline in wastewater with different dosages of the modified material in Example 5 of the present invention.

[0032] Fig. 9 This is a diagram showing the removal effect of tetracycline in wastewater by the modified material in Example 6 of the present invention under different pH conditions. DETAILED DESCRIPTION

[0033] 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.

[0034] 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.

[0035] Example 1

[0036] A method for modifying solid waste materials inside a warm baby, the process flow chart of which is as follows: Figure 1 As shown, the following steps are included:

[0037] S1. Take out the internal solid waste materials from the waste of the hot pack, wherein the collected internal solid waste materials include a relative content of 8.09wt% of C element, a relative content of 55.83wt% of O element, and a relative content of 31.91wt% of Fe element.

[0038] S2. Washing the internal solid waste material obtained in step S1 with water to moisten the internal solid waste material and remove soluble components in the internal solid waste material.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] In step S4, the wall of the porous flexible container is a porous mesh, and a plurality of holes are provided on the wall of the porous flexible container. The pore diameter of the holes is 100 μm to 300 μm. 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.

[0043] 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.

[0044] 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:

[0045] 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.

[0046] Table 1 Specific surface area and pore volume values ​​of different internal solid waste materials

[0047] 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

[0048] X-ray photoelectron spectroscopy scanning was performed on the unwashed internal solid waste material (A) and the washed internal solid waste material (B):

[0049] Figure 2 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 2 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 2 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.

[0050] 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):

[0051] Figure 3a to 3c 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 3a It is unwashed internal solid waste material (A); Figure 3b It is the internal solid waste material after washing (B); Figure 3c The internal solid waste material (C) after being modified with salicylic acid. As shown in Figure 3, the surface of the unmodified internal solid waste material is relatively flat, but due to mechanical crushing, there are some potholes; 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.

[0052] 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:

[0053] Figure 4 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 4 It can be seen that after the internal solid waste materials were washed with water and modified with salicylic acid, the proportion of Ca element decreased, and the mass fraction of Ca element decreased from 1.24% to 0.26%.

[0054] Example 2

[0055] The removal effect of the modified material on tetracycline in water is investigated, specifically: the modified material is used to activate Na2S2O8 to degrade tetracycline in water, including the following steps:

[0056] 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 Example 1, and after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L. After mixing evenly, a Fenton-like reaction is carried out to complete the degradation of tetracycline.

[0057] Control group: Take a 1L tetracycline solution with a concentration of 20mg / L, add 2g of unmodified internal solid waste material (numbered WP), after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L, mix well, and carry out a Fenton-like reaction to complete the degradation of tetracycline.

[0058] 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 5 .

[0059] Figure 5 The figure 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 2 of the present invention. Figure 5It can be seen that under the same other conditions, the modified material prepared by the present invention has a significantly better removal effect on tetracycline in wastewater than 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 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.

[0060] Example 3

[0061] The stability of the modified material is investigated, specifically: the modified material is used to perform a cyclic degradation treatment on tetracycline in water, including the following steps:

[0062] (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 (numbered SAM-WP) prepared in Example 1, and after 60 minutes of adsorption saturation, add 20mL of a Na2S2O8 solution with a mass concentration of 2g / L, mix well, and perform a Fenton-like reaction to complete the degradation of tetracycline.

[0063] (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).

[0064] (3) Repeat steps (1) and (2) to carry out cyclic degradation treatment of tetracycline in the water body for a total of three times.

[0065] 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 6 .

[0066] Figure 6 This is a diagram showing the effect of the modified material in Example 3 of the present invention on the cyclic removal of tetracycline in water. Figure 6 It 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.

[0067] Example 4

[0068] The removal effect of the modified material on tetracycline in water before and after encapsulation is investigated. Specifically, the tetracycline in water is degraded using the modified material before and after encapsulation, including the following steps:

[0069] 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 Example 1, and after 60min of adsorption saturation, add 20mL of Na2S2O8 solution with a mass concentration of 2g / L. After mixing evenly, a Fenton-like reaction is carried out to complete the degradation of tetracycline.

[0070] Control group: The encapsulated modified material prepared in Example 1 was used instead of the unencapsulated modified material, and tetracycline in water was degraded under the same conditions.

[0071] 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 7 .

[0072] Figure 7 The figure is a diagram showing the removal effect of tetracycline in water by the modified material before and after encapsulation in Example 4 of the present invention. Figure 7 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 7 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.

[0073] Example 5

[0074] The degradation effect of modified materials with different addition amounts on antibiotics in water was investigated. Specifically, the modified materials were used as Fenton-like reaction catalysts to degrade antibiotics in water, including the following steps:

[0075] 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.

[0076] 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 .

[0077] Figure 8 The figure is a diagram showing the removal effect of tetracycline in wastewater by different dosages of the modified material in Example 5 of the present invention. Figure 8 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.

[0078] Example 6

[0079] The removal effect of modified materials on antibiotics in water under different pH conditions was investigated. Specifically, the modified materials were used as Fenton-like reaction catalysts to degrade antibiotics in water, including the following steps:

[0080] 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.

[0081] 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 Fig. 9 .

[0082] Fig. 9 The figure is a diagram showing the removal effect of tetracycline in wastewater by the modified material in Example 6 of the present invention under different pH conditions. Fig. 9 It 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.

[0083] It can be seen from the above results that in the modification method of the present invention, the internal solid waste material of the warm baby is used as the raw material, and through water washing and salicylic acid modification, a modified material with a large specific surface area, multiple active sites, high catalytic activity, stable performance, and green environmental protection can be prepared. As a new type of Fenton reaction catalyst with excellent performance, it is widely used in activating oxidants, and can achieve rapid activation of oxidants. At the same time, it can also realize the resource utilization of the waste of the warm baby, with high use value and good application prospects. 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.

[0084] 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 modifying solid waste materials inside a warm baby, characterized in that: The following steps are involved: 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.

2. The modification method according to claim 1, characterized in that: 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.

3. The modification method according to claim 2, characterized in that: In step S3, 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 modification method according to claim 1, characterized in that: In step S3, the reaction time is 2 h to 4 h.

5. The modification 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 modification method according to any one of claims 1 to 5, characterized in that: In step S1, the internal solid waste material includes a relative content of 8.09wt% of C element, a relative content of 55.83wt% of O element, and a relative content of 31.91wt% of Fe element.

7. The modification method according to any one of claims 1 to 5, characterized in that: Step S3 also 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.

8. The modification method according to claim 7, characterized in that: The wall of the porous flexible container is in the shape of a porous mesh; a plurality of holes are arranged on the wall of the porous flexible container; the pore diameter 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.

9. A modified material, characterized in that: The modified material is obtained by the modification method according to any one of claims 1 to 8.

10. The modified material according to claim 9, characterized in that 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.

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