A method for removing antibiotics from water using metal-organic framework / wood aerogel composites

Abstract

The present invention discloses a method for removing antibiotics from water using a metal-organic framework (MOF) / wood aerogel composite material. The method comprises the following steps: mixing the MOF / wood aerogel composite material, persulfate, and antibiotic wastewater to perform an oscillating reaction to degrade and remove the antibiotics in the wastewater; the MOF / wood aerogel composite material comprises MIL-100(Fe) and wood aerogel, with the MIL-100(Fe) anchored within the pores of the wood aerogel. The MOF / wood aerogel composite material can achieve efficient degradation and removal of antibiotic wastewater. The treatment method has simple processes and equipment, is easy to operate, has low processing costs, and exhibits excellent antibiotic degradation and removal performance. Furthermore, the composite material has good recyclability. As a widely used method for effectively degrading and removing antibiotics, it has high potential and prospects for practical applications.

Description

Technical Field

[0001] The present invention belongs to the field of antibiotic wastewater treatment, relates to a method for treating antibiotics in water, and specifically relates to a method for removing antibiotics in water by utilizing a metal organic framework / wood aerogel composite material. Background Art

[0002] The ecological hazards and health risks caused by the widespread use of antibiotics have received increasing attention. The large-scale use of antibiotics leads to their residues in environmental media. The residual antibiotics can induce and accelerate the generation of drug-resistant strains and the spread of resistance genes. The water environment is one of the important accumulation terminals of antibiotics. Due to the increasingly serious antibiotic pollution, traditional sewage treatment methods are unable to effectively remove antibiotics. Therefore, effective technologies are needed to remove antibiotics from the water environment. At present, in the treatment of antibiotic pollution in water bodies, advanced oxidation processes based on persulfate activation to produce highly reactive oxygen species to achieve antibiotic degradation and removal are receiving increasing attention due to their simple operation, controllable cost and high treatment efficiency.

[0003] In persulfate advanced oxidation processes, emerging metal-organic frameworks (MOFs) are widely used in the treatment of organic pollutants in water due to their high density of unsaturated metal centers, high specific surface area, and ease of functionalization. However, MOF powders face challenges such as spontaneous aggregation and stacking during use, resulting in performance degradation, and significant material losses during use and recycling, limiting their further application in water treatment. The strategy of anchoring MOFs on supports to enhance their performance has attracted widespread attention. However, the preparation of many MOF / support composites is relatively complex, and the support has poor compatibility, resulting in the easy detachment of the supported MOFs, which not only reduces performance but also easily causes secondary pollution. Therefore, selecting compatible and suitable supports to further improve the performance of MOFs, obtain recyclable MOF / support composites with excellent catalytic performance, and develop methods for preparing MOF / support composites with advantages such as simple synthesis, convenient operation, and environmental friendliness are of great significance for enhancing the application of MOF-based materials in antibiotic wastewater treatment. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the existing technology and provide a method for treating antibiotics in water bodies using a metal organic framework / wood aerogel composite material. The method has simple treatment process and equipment, convenient operation, low treatment cost, high treatment efficiency and good reusability.

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

[0006] A method for treating antibiotics in water using a metal-organic framework / wood aerogel composite material is characterized by comprising the following steps: mixing the metal-organic framework / wood aerogel composite material, persulfate, and antibiotic wastewater to carry out a contact reaction, thereby completing the treatment of the antibiotic wastewater; the metal-organic framework / wood aerogel composite material comprises MIL-100(Fe) and wood aerogel, and the MIL-100(Fe) is anchored in the pores of the wood aerogel.

[0007] The above method is further improved, and the preparation method of the metal organic framework / wood aerogel composite material comprises the following steps:

[0008] S1. Place balsa wood blocks in a mixed solution of sodium sulfite and sodium hydroxide and react at 100°C for 4 hours. Then transfer the wood blocks to a hydrogen peroxide solution and react at 100°C for 2 hours. After the reaction, wash and freeze-dry to obtain wood aerogel.

[0009] S2, placing the wood aerogel prepared in step S1 in a solution of ferric chloride in N,N-dimethylformamide and subjecting it to vacuum impregnation treatment;

[0010] S3, adding trimesic acid to the ferric chloride solution containing the wood aerogel in step S2, dissolving the solution with ultrasonic waves, and then performing a solvothermal reaction. After the reaction, washing and drying are performed to obtain a MIL-100(Fe) / wood aerogel composite material;

[0011] The above preparation method is further improved, in step S1, the density of the balsa wood block is 120kg / m 3 The concentrations of sodium sulfite and sodium hydroxide in the mixed solution are 0.5 mol / L and 2 mol / L, respectively.

[0012] The above preparation method is further improved in that in step S1, the concentration of the hydrogen peroxide solution is 2.5 mol / L.

[0013] The above preparation method is further improved in that, in step S2, the vacuum impregnation treatment time is 2 hours.

[0014] The above preparation method is further improved, in step S3, the amount of trimesic acid used is 0.315 g.

[0015] The above preparation method is further improved in that, in step S3, the solvent thermal reaction temperature is 150°C and the reaction time is 24 hours; the product obtained after the reaction is washed and dried. The washing is performed using N,N-dimethylformamide and ultrapure water; the number of washes is 3 to 5; the drying is performed under freeze-drying conditions; and the drying time is 12 to 24 hours.

[0016] The above method is further improved, wherein the mass-to-volume ratio of the metal organic framework / wood aerogel composite material to the antibiotic wastewater is 1.3g:0.3g:1L; the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotic in the antibiotic wastewater is 20mg / L~50mg / L; and the pH of the antibiotic wastewater is 2~10.

[0017] The above method is further improved in that the rotation speed of the oscillation reaction is 150 r / min to 200 r / min; and the time of the oscillation reaction is 80 minutes.

[0018] Compared with the prior art, the advantages of the present invention are:

[0019] (1) In the present invention, cheap renewable wood material is used as a precursor, and MIL-100 (Fe) is grown in situ in the pores of porous wood aerogel. MIL-100 (Fe) is evenly distributed in the internal pores of the wood aerogel, which reduces the spontaneous agglomeration and stacking effect of the powdered MIL-100 (Fe), exposes more catalytic active sites, and enhances the catalytic performance. At the same time, the anchoring of MIL-100 (Fe) on the wood aerogel achieves low material loss during use and recycling, and enhances the material's recycling performance. In addition, the porous structure of the wood aerogel helps to reduce the mass transfer resistance during the catalytic process and improve the material performance. Compared with the existing technology, the porous metal organic framework / wood aerogel composite material of the present invention has the advantages of high catalytic performance and good recyclability, can achieve efficient removal of antibiotics, and has potential practical application prospects.

[0020] (2) In the present invention, the pore structure properties of wood materials are improved. Considering the low porosity formed by the dense cell structure of wood materials themselves, low-density balsa wood is selected as the raw material. Sodium sulfite and sodium hydroxide are combined with a hydrogen peroxide system to achieve the selective removal of lignin and hemicellulose inside the balsa wood, effectively increasing the specific surface area and porosity of the material. Compared with the original wood, the specific surface area and porosity of the wood aerogel are increased by 25%. The larger specific surface area and porosity increase the contact frequency between the catalytic active center and the pollutant. Accordingly, the MIL-100(Fe) / wood aerogel material exhibits a faster degradation rate of antibiotics, achieving efficient degradation of antibiotics.

[0021] (3) In the present invention, the in-situ loading process of MOFs is improved. Before the solvent thermal reaction, the wood aerogel is added to the solution of metal salts. Through vacuum impregnation, the metal ions are tightly and evenly combined with the oxygen functional groups on the inner surface of the pores of the wood aerogel, thereby making the MOFs loading more uniform and stable, and the prepared composite material has better performance.

[0022] (4) The present invention provides a method for treating antibiotics in water using a metal-organic framework / wood aerogel composite material to activate persulfate. The metal-organic framework / wood aerogel, persulfate, and antibiotic wastewater are mixed and oscillated to react, effectively removing antibiotics from water. The preparation process of the metal-organic framework / wood aerogel composite material of the present invention has the advantages of convenient operation and simple synthesis, and is suitable for large-scale preparation. The treatment process and equipment of the present invention are simple and low-cost, and the composite material has good catalytic performance and high reusability. It is a method that can be widely adopted and can effectively remove antibiotics from water. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0024] Figure 1 These are scanning electron microscope images of different samples prepared in Example 1 of the present invention, where (a) and (b) are vertical and cross-sectional structural images of the original wood, (c) and (d) are vertical and cross-sectional structural images of the wood aerogel, (e) and (f) are vertical and cross-sectional structural images of MIL-100(Fe) / WA, (g) is an enlarged image of (f), (h) is the morphology of MIL-100(Fe), and (i) is a real shot of wood, wood aerogel, and MIL-100(Fe) / WA.

[0025] Figure 2 X-ray diffraction patterns of the metal organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA), wood, and MIL-100(Fe) prepared in Example 1 of the present invention.

[0026] Figure 3 These are nitrogen adsorption and desorption curves of the metal organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA), and wood prepared in Example 1 of the present invention, where the mosaic is a pore size distribution diagram.

[0027] Figure 4 This is a diagram showing the effect of metal organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA), and metal organic framework / wood (MIL-100(Fe) / wood) prepared in Example 1 of the present invention on removing tetracycline hydrochloride.

[0028] Figure 5 This is a diagram showing the effect of the metal organic framework / wood aerogel (MIL-100(Fe) / WA) in Example 2 of the present invention in removing tetracycline hydrochloride under different pH conditions.

[0029] Figure 6 This is a diagram showing the removal effect of the metal organic framework / wood aerogel (MIL-100(Fe) / WA) on tetracycline hydrochloride at different concentrations in Example 3 of the present invention. DETAILED DESCRIPTION

[0030] The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the scope of protection of the present invention is not limited thereby.

[0031] The raw materials and instruments used in the following examples are all commercially available. In the following examples, unless otherwise specified, the data obtained are the average values ​​of more than three repeated experiments.

[0032] Example 1

[0033] A method for treating antibiotics in water using a metal organic framework / wood aerogel composite material, specifically using the metal organic framework / wood aerogel composite material to activate persulfate to remove tetracycline hydrochloride in water, comprising the following steps:

[0034] Take 1 part of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA, 20×10×5mm), add it to 50mL of a 30mg / L tetracycline hydrochloride solution, oscillate at a speed of 150r / min, and adsorb for 20 minutes to complete the adsorption treatment of tetracycline hydrochloride. Then, 15mg of sodium persulfate is added, oscillate at a speed of 150r / min, and catalyze the reaction for 60 minutes to complete the degradation treatment of tetracycline hydrochloride.

[0035] After the reaction was completed, 4 mL of sample was taken and filtered with a 0.45 μm nylon filter. The absorbance of the filtrate was measured by UV-visible spectrophotometer to determine the concentration of the remaining antibiotic after the reaction. The removal effect of MIL-100(Fe) / WA on tetracycline hydrochloride was obtained. The results are shown in Figure 2. Figure 4 shown.

[0036] In this embodiment, the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA) comprises MIL-100(Fe) and a wood aerogel substrate, and MIL-100(Fe) is in situ grown on the surface of the internal pores of the wood aerogel.

[0037] In this embodiment, the preparation method of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA) is to delignify and hemicellulose-treat balsa wood blocks, and then in situ grow MIL-100(Fe) within the wood aerogel pores by a solvothermal method, including the following steps:

[0038] (1) Balsa wood blocks were placed in a mixed solution of sodium sulfite (0.5 mol / L) and sodium hydroxide (2 mol / L) and reacted at 100°C for 4 hours. The blocks were then transferred to a hydrogen peroxide solution (2.5 mol / L) and reacted at 100°C for 2 hours. After the reaction, the blocks were washed with ultrapure water and freeze-dried to obtain wood aerogels.

[0039] (2) The wood aerogel obtained in step (1) was placed in a 30 mL solution of ferric chloride in N,N-dimethylformamide (1.5 mmol / L) and vacuum impregnated for 2 hours.

[0040] (3) Add 0.315 g of trimesic acid to the mixed solution after vacuum impregnation in step (2) and dissolve it by ultrasonication.

[0041] (4) The mixed solution in step (3) was transferred to a polytetrafluoroethylene liner and subjected to solvent thermal reaction at 150° C. for 24 hours. The obtained material was washed with N,N-dimethylformamide and ultrapure water, and freeze-dried to obtain MIL-100(Fe) / WA.

[0042] In this example, the preparation method of the metal organic framework / wood composite material (MIL-100(Fe) / wood) used for comparison is basically the same as the preparation method of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA), with the only difference being that the wood used has not been subjected to the delignification and hemicellulose treatment described in step (1).

[0043] In this example, the preparation method of MIL-100(Fe) used for comparison is different from the preparation method of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA). Specifically, 0.315 g of trimesic acid and 0.405 g of ferric chloride hexahydrate are added to an N,N-dimethylformamide solution (30 mL), ultrasonically dissolved, and then transferred to a polytetrafluoroethylene liner. The reaction is solvent-thermally reacted at 150° C. for 24 hours. The resulting material is washed with ethanol and vacuum-dried to obtain MIL-100(Fe).

[0044] In this embodiment, the preparation method of the wood aerogel (WA) used for comparison is different from the preparation method of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA). Specifically, the balsa wood block is placed in a mixed solution of sodium sulfite (0.5 mol / L) and sodium hydroxide (2 mol / L), and reacted at 100°C for 4 hours. Then, the wood block is transferred to a hydrogen peroxide solution (2.5 mol / L) and reacted at 100°C for 2 hours. After completion, the wood aerogel is washed with ultrapure water and freeze-dried to obtain the wood aerogel.

[0045] Figure 1 Scanning electron micrographs of the metal-organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA), wood, and MIL-100(Fe) prepared in Example 1 of the present invention. (a) and (b) show the vertical and cross-sectional structures of the original wood, (c) and (d) show the vertical and cross-sectional structures of the wood aerogel, and (e) and (f) show the vertical and cross-sectional structures of MIL-100(Fe) / WA. Comparison of the three reveals that after delignification and hemicellulose removal, followed by in-situ loading of MIL-100(Fe), the microstructure of the wood aerogel, derived from its own pores, remains unchanged, and its porous structure is retained. Figure (g) is a further magnification of (f), showing relatively uniform loading of MIL-100(Fe) on the inner walls of the wood aerogel pores. Figure (h) shows the microscopic morphology of MIL-100(Fe). (i) is a photograph of wood, WA, and MIL-100(Fe) / WA.

[0046] Figure 2 The X-ray diffraction patterns of the metal organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA), wood and MIL-100(Fe) prepared in Example 1 of the present invention are shown in FIG. Figure 2 As shown, wood and wood aerogel exhibit similar peaks, both of which are cellulose peaks. The wood aerogel has a sharper peak, indicating that the NaOH / Na2SO3 and H2O2 systems effectively remove hemicellulose and lignin, thereby increasing the crystallinity of cellulose in WA. MIL-100(Fe) / WA displays a peak at 2θ = 11°, which is characteristic of MIL-100(Fe), demonstrating effective loading of MIL-100(Fe) on WA.

[0047] Figure 3 The nitrogen adsorption and desorption curves of the metal organic framework / wood aerogel (MIL-100(Fe) / WA), wood aerogel (WA) and wood prepared in Example 1 of the present invention are shown in FIG. Figure 3 As can be seen, the adsorption and desorption curves of all three materials are type IV isotherms, indicating that the mesopores dominate the interior of the materials. WA has a higher nitrogen adsorption capacity than wood, indicating that delignification and hemicellulose effectively increase the pore volume of WA. MIL-100(Fe) / WA has a higher nitrogen adsorption capacity than WA, which is due to the high pore volume of MIL-100(Fe) loading, which increases the nitrogen adsorption capacity of the composite material.

[0048] Figure 4The figure shows a comparison of the effects of metal organic framework / wood aerogel (MIL-100(Fe) / WA), metal organic framework / wood (MIL-100(Fe) / wood), WA and persulfate alone in removing tetracycline hydrochloride in Example 1. As can be seen from the figure, the performance of persulfate alone or WA-activated persulfate in removing tetracycline hydrochloride is weak. After MIL-100(Fe) loading, the material removal performance is significantly improved. Compared with MIL-100(Fe) / wood, MIL-100(Fe) / WA-activated persulfate shows a faster degradation rate and higher removal performance in degrading antibiotics. This is because the removal of lignin and hemicellulose effectively increases the pore volume and specific surface area of ​​the composite material, strengthens the contact between pollutants and active sites, and enhances the pollutant removal performance.

[0049] Example 2

[0050] A method for treating antibiotics in water using a metal organic framework / wood aerogel composite material, specifically using the metal organic framework / wood aerogel composite material to activate persulfate to remove tetracycline hydrochloride in water, comprising the following steps:

[0051] Five portions of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA, 20×10×5 mm) in Example 1 were added to tetracycline hydrochloride solutions with initial pH values ​​of 2, 4, 6, 8, and 10, respectively, wherein the volume of the tetracycline hydrochloride solution was 50 mL and the concentration was 30 mg / L. The mixture was oscillated and adsorbed at a speed of 150 r / min for 20 minutes. 15 mg of sodium persulfate was added and the catalytic reaction was carried out for 60 minutes to complete the degradation of tetracycline hydrochloride.

[0052] After the reaction, 4 mL of sample was taken and filtered with a 0.45 μm nylon filter. The absorbance of the filtrate was measured by UV-visible spectrophotometer to determine the concentration of tetracycline hydrochloride after the reaction. The removal effect of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA) on tetracycline hydrochloride solutions with different pH values ​​was obtained. The results are shown in Figure 2. Figure 5 shown.

[0053] Figure 5 The figure shows the effect of removing tetracycline hydrochloride by activating persulfate under different pH conditions in the metal organic framework / wood aerogel composite material (MIL-100 (Fe) / WA) in Example 2 of the present invention. Figure 5It can be seen that the MIL-100(Fe) / WA activated persulfate system still exhibits good tetracycline hydrochloride removal performance between pH 2 and 8. At pH 10, degradation performance decreases slightly, which is due to the weakening of the active center under alkaline conditions. The results of the pH effect experiment show that MIL-100(Fe) / WA has good tetracycline removal performance between pH 4 and 10, demonstrating that MIL-100(Fe) / WA has a wide pH adaptability and high practical application value.

[0054] Example 3

[0055] A method for treating antibiotics in water using a metal organic framework / wood aerogel composite material, specifically using the metal organic framework / wood aerogel composite material to activate persulfate to remove tetracycline hydrochloride in water, comprising the following steps:

[0056] Four portions of the metal organic framework / wood aerogel composite material (MIL-100(Fe) / WA, 20×10×5 mm) from Example 1 were added to tetracycline hydrochloride solutions having concentrations of 10 mg / L, 20 mg / L, 30 mg / L, and 50 mg / L, respectively, where the volume of the tetracycline hydrochloride solution was 50 mL. The mixture was oscillated and adsorbed at a speed of 150 r / min for 20 minutes. 15 mg of sodium persulfate was added, and the catalytic reaction was carried out for 60 minutes to complete the degradation of tetracycline hydrochloride.

[0057] After the reaction, 4 mL of sample was taken and filtered with a 0.45 μm nylon filter. The absorbance of the filtrate was measured by UV-visible spectrophotometer to determine the concentration of tetracycline hydrochloride after the reaction. The treatment effect of metal organic framework / wood aerogel on tetracycline hydrochloride of different concentrations was obtained. The results are shown in Figure 2. Figure 6 shown.

[0058] Figure 6 The figure shows the removal effect of the metal organic framework / aerogel composite material (MIL-100(Fe) / WA) on tetracycline hydrochloride solutions of different concentrations in Example 3 of the present invention. Figure 6 As can be seen, the MIL-100(Fe) / WA activated persulfate system effectively degraded and removed tetracycline hydrochloride at tetracycline hydrochloride solution concentrations of 10 mg / L, 20 mg / L, and 30 mg / L, respectively. However, removal performance decreased at a high concentration of 50 mg / L. This demonstrates that the metal-organic framework / wood aerogel composite (MIL-100(Fe) / WA) of the present invention exhibits excellent removal efficiency for tetracycline hydrochloride solutions of varying concentrations.

[0059] As can be seen from the above, the present invention utilizes a metal-organic framework / wood aerogel composite material (MIL-100(Fe) / WA) to remove antibiotics from water. By mixing MIL-100(Fe) / WA with persulfate and tetracycline hydrochloride wastewater for a contact reaction, the method can efficiently degrade and remove antibiotics from water. This method not only has a simple treatment process, convenient operation, and low equipment requirements, but also exhibits excellent catalytic and recyclable properties, and is environmentally friendly. This method is a widely applicable and highly effective method for removing antibiotics from water, with potential application value and commercial prospects.

[0060] The above embodiments are merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited to the above embodiments. All technical solutions that fall within the scope of protection of the present invention are within the scope of protection of the present invention. It should be noted that improvements and modifications that can be made by a person skilled in the art without departing from the principles of the present invention are also considered to be within the scope of protection of the present invention.

Claims

1. A method for removing antibiotics from water using a metal organic framework / wood aerogel composite material, characterized in that: The following steps are involved: The metal organic framework / wood aerogel composite material, persulfate and antibiotic wastewater are mixed and oscillated to complete the treatment of antibiotic wastewater; the metal organic framework / wood aerogel composite material contains MIL-100(Fe) and wood aerogel, and MIL-100(Fe) is anchored in the pores of the wood aerogel.

2. The method according to claim 1, characterized in that The method for preparing the metal organic framework / wood aerogel composite material comprises the following steps: S1. Place balsa wood blocks in a mixed solution of sodium sulfite and sodium hydroxide and react at 100°C for 4 hours. Then transfer the wood blocks to a hydrogen peroxide solution and react at 100°C for 2 hours. Wash and freeze-dry to obtain wood aerogel. S2, placing the wood aerogel prepared in step S1 in a solution of ferric chloride in N,N-dimethylformamide and subjecting it to vacuum impregnation treatment; S3. Adding trimesic acid to the ferric chloride solution containing the wood aerogel in step S2, dissolving the solution by ultrasonication and then performing a solvothermal reaction. After the reaction is completed, washing and drying are performed to obtain a MIL-100(Fe) / wood aerogel composite material.

3. The method according to claim 2, characterized in that In step S1, the density of the balsa wood block is 120 kg / m 3 The concentrations of sodium sulfite and sodium hydroxide in the mixed solution are 0.5 mol / L and 2 mol / L respectively, and the concentration of the hydrogen peroxide solution is 2.5 mol / L.

4. The method according to claim 2, characterized in that In step S2, the concentration of ferric chloride is 1.5 mmol / L, and the volume of the solution is 30 mL.

5. The method according to claim 2, characterized in that In step S2, the vacuum impregnation treatment time is 2 hours.

6. The method according to claim 2, characterized in that In step S3, the amount of trimesic acid used is 0.315 g.

7. The method according to claim 2, characterized in that In step S3, the solvent thermal reaction temperature is 150° C. and the reaction time is 24 hours; the product obtained after the reaction is completed is washed and dried; the washing uses N,N-dimethylformamide and ultrapure water; the number of washes is 3 to 5 times; the drying treatment is carried out under freeze-drying conditions; and the drying time is 12 to 24 hours.

8. The method according to any one of claims 1 to 7, characterized in that The mass-to-volume ratio of the metal organic framework / wood aerogel composite material, persulfate and antibiotic wastewater is 1.3g:0.3g:1L; the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotic in the antibiotic wastewater is 20mg / L-50mg / L; and the pH of the antibiotic wastewater is 2-10.

9. The method according to any one of claims 1 to 7, characterized in that The rotation speed of the oscillating reaction is 150 r / min to 200 r / min; and the time of the oscillating reaction is 80 minutes.

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