Preparation and application method of catalyst for oxidative degradation of antibiotic wastewater by activated peroxyacetic acid

Abstract

The application discloses a preparation and application method of an activated peracetic acid oxidation degradation antibiotic wastewater catalyst, and the catalyst is a metal iron element doped carbon nitride catalyst modified by boron nitride quantum dots; the preparation method is as follows: melamine and anhydrous ferric chloride are dissolved in water, and then boron nitride quantum dots are added and stirred; the mixed solution is placed in a drying box, and the solvent is evaporated; the obtained solid is ground, and then transferred to a muffle furnace for calcination; finally, the product is washed with deionized water to remove impurities, and then dried, ground, and a composite catalyst is obtained. The catalyst prepared by the application has excellent oxidation degradation antibiotic wastewater capacity in an activated peracetic acid system, has strong environmental interference resistance, and has good reusability.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, and relates to catalysts for the degradation of antibiotic wastewater, particularly an activated peracetic acid oxidative degradation catalyst for antibiotic wastewater. This catalyst utilizes activated peracetic acid for the oxidative degradation of antibiotic wastewater. Furthermore, methods for preparing and applying the catalyst are provided. This technology can effectively mitigate the negative environmental impact of antibiotic wastewater and has significant environmental implications. Background Technology

[0002] The deep oxidation process of peracetic acid is an effective method for degrading emerging organic pollutants. It generates highly reactive oxides under various activation conditions, such as those induced by ultraviolet radiation and transition metals. This process offers advantages including high degradation efficiency, strong bactericidal ability, and the production of minimal toxic byproducts. Under ultraviolet activation conditions, energy breaks the O2O bonds in peracetic acid, generating hydroxyl radicals (·OH) and acetyl radicals (CH3C(O)O·). These radicals possess high oxidizing power and can degrade various organic pollutants. Furthermore, transition metal activation is also a major pathway promoting the activation of peracetic acid. Transition metal catalysts provide active sites, promoting the decomposition of peracetic acid and the generation of reactive oxides. Through these activation pathways, the deep oxidation process of peracetic acid can efficiently degrade organic pollutants, including emerging organic pollutants.

[0003] Carbon nitride (g-C3N4) is a nitrogen-rich nonmetallic layered material. It possesses advantages such as stable chemical structure, low cost, and simple preparation, making it widely used in advanced oxidation research. The nitrogen-rich environment of carbon nitride allows it to provide sufficient nitrogen atoms to form coordination structures with various metals. Iron is one of the most abundant metals in the Earth's crust, widely present in rocks, soil, and water bodies. By doping carbon nitride with iron, the unique redox properties of the central iron atom can be utilized. This doping gives carbon nitride better catalytic performance, improving its activity and stability in advanced oxidation processes. Furthermore, by controlling the morphology and structure of carbon nitride, such as by introducing carbon nitride quantum dots, its quantum confinement effect results in a higher surface-to-volume ratio, making the grain size of the quantum dots smaller than the volume-excited Bohr radius. This also generates more active sites for target molecules in the reaction. Currently, no research has been reported on the activation of peracetic acid by carbon nitride with a triazine structure. Authorized publication number CN 116002842 A describes a method for the degradation of carbamazepine by peracetic acid activated by a carbon nanotube-supported catalyst; however, this method uses cobalt, which is more toxic than iron. Furthermore, the degradation time of carbamazepine is long, limiting the practical application of advanced peracetic acid oxidation. Antibiotic wastewater pollution is a serious environmental problem. Due to the stable chemical properties of antibiotics and their difficulty in biodegradation, there is an urgent need to develop more efficient and environmentally friendly technologies for the treatment and comprehensive utilization of organic pollutants to mitigate their impact on the aquatic environment and organisms. Summary of the Invention

[0004] The first objective of this invention is to provide a catalyst for the oxidative degradation of antibiotic wastewater by peracetic acid.

[0005] The second objective of this invention is to provide a method for preparing an activated peracetic acid oxidative degradation catalyst for antibiotic wastewater.

[0006] The third objective of this invention is to provide a method for applying an activated peracetic acid catalyst for the oxidative degradation of antibiotic wastewater.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] (I) This invention provides a method for preparing an activated peracetic acid oxidative degradation catalyst for antibiotic wastewater, comprising the following steps: dissolving melamine and an iron precursor in water, then adding boron nitride quantum dots and stirring; placing the mixed solution in a drying oven to evaporate the solvent; grinding the solid obtained after evaporation, then transferring it to a muffle furnace for calcination to carry out the synthesis reaction; after the reaction is completed, washing, drying, and grinding the synthesized material in sequence to obtain a composite catalyst.

[0009] Furthermore, the iron precursor is anhydrous ferric chloride.

[0010] Furthermore, the ratio of melamine, iron precursor, and boron nitride quantum dots is 5g:0.811g:(2-10mL).

[0011] Furthermore, the melamine, iron precursor, and boron nitride quantum dots are mixed and stirred at a speed of 400 rpm for 24 hours.

[0012] Furthermore, the calcination time is 4 hours, the reaction temperature is 550°C, and the heating rate is 3°C / min.

[0013] Furthermore, the washing method is as follows: washing with deionized water 3 to 6 times; the drying temperature is 60°C.

[0014] (ii) The present invention also provides an activated peracetic acid oxidative degradation catalyst for antibiotic wastewater, wherein the catalyst is a boron nitride quantum dot modified metallic iron element doped carbon nitride composite catalyst, which is prepared by the preparation method described above.

[0015] (III) The present invention also provides an application method for activating the peracetic acid oxidative degradation catalyst for antibiotic wastewater, comprising: adding a peracetic acid solution to a beaker containing antibiotic wastewater to be degraded, stirring at 400 rpm, and then adding a boron nitride quantum dot modified iron element doped carbon nitride composite catalyst to initiate the degradation reaction.

[0016] Furthermore, the mass ratio of the added composite catalyst to the amount of added peracetic acid is (0.025-0.3g):(25-200μmol).

[0017] Furthermore, the degradation reaction temperature is room temperature (25±2℃), and the reaction time is 1-30 min.

[0018] The beneficial effects of this invention are as follows:

[0019] 1. This invention synthesizes a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst, wherein the boron nitride quantum dots enhance the electron transfer capability inside the catalyst and accelerate the advanced oxidation reaction; the substitution of iron introduces more active metals, which improves the oxidation capability of the system.

[0020] 2. The boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst prepared by this invention exhibits an iron ion leaching concentration lower than the national wastewater discharge standard in the cyclic experiment.

[0021] 3. The boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst prepared in this invention exhibits good catalytic oxidation ability in the activated peracetic acid system, and can realize the oxidative degradation of a variety of antibiotics.

[0022] 5. The boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst prepared by this invention has good stability and reusability. In the activated peracetic acid system, it still has high degradation performance for antibiotics after multiple cycles. Attached Figure Description

[0023] Figure 1 This is a SEM image of the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst in Example 1.

[0024] Figure 2 The image shows the FT-IR spectrum of the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst in Example 1.

[0025] Figure 3 EIS image of the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst in Example 1;

[0026] Figure 4 The graph shows the effect of boron nitride quantum dot modified iron-doped carbon nitride composite catalyst in Example 1 on the removal of tetracycline by activated peracetic acid oxidation degradation.

[0027] Figure 5 This is a graph showing the effect of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst in Example 9 on the degradation of tetracycline after 5 cycles.

[0028] Figure 6 This is a graph showing the effect of iron ion leaching concentration in five repeated experiments of the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst for the degradation of tetracycline in Example 9. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the reagents, methods, and equipment used are conventional reagents, methods, and equipment in this technical field.

[0030] Example 1

[0031] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, tetracycline is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0032] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0033] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 10mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0034] The boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was characterized, and the SEM, FT-IR, and EIS images are shown below. Figure 1-3 As shown.

[0035] (2) Oxidative degradation of antibiotics:

[0036] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM tetracycline wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0037] Samples were taken every 5 minutes, with the removal rate of tetracycline used as the evaluation index. The concentration of tetracycline was determined by HPLC, and the removal rate reached 91.70% after 30 minutes of reaction. The effect of the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst activating the peracetic acid oxidation and degradation of tetracycline is shown in the figure below. Figure 4 As shown.

[0038] Example 2

[0039] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, sulfadiazine is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0040] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0041] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 8mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0042] (2) Oxidative degradation of antibiotics:

[0043] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM sulfadiazine wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0044] Samples were taken every 5 minutes, with the removal rate of sulfadiazine used as the evaluation index. The concentration of sulfadiazine was determined by HPLC, and the removal rate of sulfadiazine reached 81.20% after 30 minutes of reaction.

[0045] Example 3

[0046] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, sulfamethoxazole is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0047] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0048] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 7mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0049] (2) Oxidative degradation of antibiotics:

[0050] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM sulfamethoxazole wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0051] Samples were taken every 5 minutes, with the removal rate of sulfamethoxazole used as the evaluation index. The concentration of sulfamethoxazole was determined by HPLC, and the removal rate of sulfamethoxazole reached 80.53% after 30 minutes of reaction.

[0052] Example 4

[0053] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, ciprofloxacin is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0054] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0055] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 9mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0056] (2) Oxidative degradation of antibiotics:

[0057] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM ciprofloxacin wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0058] Samples were taken every 5 minutes, with the removal rate of ciprofloxacin used as the evaluation index. The concentration of ciprofloxacin was determined by HPLC, and the removal rate of ciprofloxacin reached 71.38% after 30 minutes of reaction.

[0059] Example 5

[0060] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, norfloxacin is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0061] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0062] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 6mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0063] (2) Oxidative degradation of antibiotics:

[0064] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM norfloxacin wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0065] Samples were taken every 5 minutes, with the removal rate of norfloxacin used as the evaluation index. The concentration of norfloxacin was determined by HPLC, and the removal rate of norfloxacin reached 75.29% after 30 minutes of reaction.

[0066] Example 6

[0067] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, oxytetracycline is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0068] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0069] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 10mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0070] (2) Oxidative degradation of antibiotics:

[0071] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM oxytetracycline wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0072] Samples were taken every 5 minutes, with the removal rate of oxytetracycline used as the evaluation index. The concentration of oxytetracycline was determined by HPLC, and the removal rate of oxytetracycline reached 95.57% after 30 minutes of reaction.

[0073] Example 7

[0074] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, tetracycline is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0075] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0076] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 10mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0077] (2) Oxidative degradation of antibiotics:

[0078] A 50 μmol peracetic acid solution was added to a 100 mL beaker containing 10 μM tetracycline wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0079] Samples were taken every 5 minutes, with the removal rate of tetracycline used as the evaluation index. The concentration of tetracycline was determined by HPLC, and the removal rate of tetracycline reached 77.83% after 30 minutes of reaction.

[0080] Example 8

[0081] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, tetracycline is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0082] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0083] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 10mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0084] (2) Oxidative degradation of antibiotics:

[0085] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM tetracycline wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.1 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0086] Samples were taken every 5 minutes, with the removal rate of tetracycline used as the evaluation index. The concentration of tetracycline was determined by HPLC, and the removal rate of tetracycline reached 76.53% after 30 minutes of reaction.

[0087] Example 9

[0088] This embodiment prepares a catalyst for the oxidative degradation of antibiotic wastewater using activated peracetic acid. The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst. Using this catalyst in an activated peracetic acid system, tetracycline is selected as the target pollutant for the oxidative degradation of antibiotics. The specific technical solution is as follows:

[0089] (1) Synthesis of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst:

[0090] 5g of melamine and 0.811g of anhydrous ferric chloride were dissolved in 50mL of ultrapure water, followed by the addition of 10mL of boron nitride quantum dots. The mixture was stirred at 400rpm for 24h. The solution was then placed in a 60℃ drying oven to evaporate the solvent. The resulting solid was ground and then transferred to a muffle furnace for calcination at 550℃ for 4h at a heating rate of 3℃ / min. After the reaction was complete, the synthesized material was washed with deionized water to remove impurities (centrifugation conditions: 3000r / min, 3min), and then dried and ground at 60℃ to obtain a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst.

[0091] (2) Oxidative degradation of antibiotics:

[0092] A 100 μmol solution of peracetic acid was added to a 100 mL beaker containing 10 μM tetracycline wastewater to be treated. After stirring at 400 rpm until homogeneous, 0.2 g of boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction. The reaction temperature was 25 ± 2 °C and the reaction time was 30 min.

[0093] Samples were taken every 5 minutes, with the removal rate of tetracycline used as the evaluation index. The concentration of tetracycline was determined by HPLC, and the removal rate of tetracycline reached 91.70% after 30 minutes of reaction.

[0094] After the reaction, the boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was recycled for cyclic experiments. Even after five repetitions, the removal efficiency of tetracycline remained above 80%. Figure 5 As shown. Furthermore, by detecting the leaching concentration of metal elements after each cycle of the experiment, it was found that the leaching concentration of iron was lower than the national standard (GT 31962-2015), such as... Figure 6 As shown.

[0095] This invention selects carbon nitride with a nitrogen-rich environment and a triazine structure as the catalyst host. A boron nitride quantum dot-modified, iron-doped carbon nitride composite catalyst was prepared through boron nitride quantum dot modification and iron doping. Due to the enhanced charge transfer capability of boron nitride quantum dots and the unique redox properties of the central iron atom, the catalyst exhibits excellent oxidative degradation ability for antibiotic wastewater. In the degradation of various types of antibiotic wastewater, the boron nitride quantum dot-modified, iron-doped carbon nitride composite catalyst achieved a degradation performance of 71.38-95.57% in the activated peracetic acid system. Furthermore, in the tetracycline degradation cycling experiment, the catalyst itself also exhibits excellent reusability, and the leaching rate of iron during the cycling process is lower than the national standard limit.

[0096] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within the scope of its essence and protection. Such modifications or equivalent substitutions should also be considered to fall within the protection scope of the present invention.

Claims

1. A process for the preparation of an activated peroxoacetic acid oxidative degradation of antibiotic wastewater catalyst, characterized by, Includes the following steps: Melamine and iron precursor were dissolved in water, and then boron nitride quantum dots were added and stirred. Place the mixed solution in a drying oven to evaporate the solvent; The solid obtained after evaporation is ground and calcined to carry out a synthesis reaction; After the reaction was completed, the synthesized substances were washed, dried and ground in sequence to obtain the composite catalyst; The iron precursor is anhydrous ferric chloride; The ratio of melamine, iron precursor, and boron nitride quantum dots is 5g:0.811g: (2-10 mL).

2. The preparation method of the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 1, characterized in that, The melamine, iron precursor, and boron nitride quantum dots were mixed and stirred at 400 rpm for 24 hours.

3. The preparation method of the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 1, characterized in that, The calcination time was 4 hours, the reaction temperature was 550°C, and the heating rate was 3°C / min.

4. The preparation method of the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 1, characterized in that, The washing method is as follows: wash with deionized water 3 to 6 times; The drying temperature is 60°C.

5. A catalyst for the oxidative degradation of antibiotic wastewater by activated peracetic acid, characterized in that, The catalyst is a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst, prepared by the preparation method described in any one of claims 1 to 4.

6. The method for applying the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 5, characterized in that, include: A peracetic acid solution was added to a container containing antibiotic wastewater to be degraded. After stirring evenly, a boron nitride quantum dot-modified iron-doped carbon nitride composite catalyst was added to initiate the degradation reaction.

7. The method for applying the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 6, characterized in that, include: The ratio of the mass of the added composite catalyst to the mole of the added peracetic acid is: (0.025-0.3g): (25-200μmol).

8. The method for applying the activated peracetic acid oxidative degradation catalyst for antibiotic wastewater according to claim 6, characterized in that, include: The degradation reaction temperature is 25±2℃, and the reaction time is 1-30 min.

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