A method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) materials

Abstract

The present invention relates to the technical field of water body antibiotic degradation, and specifically relates to a method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) materials, comprising the following steps: S1, preparation of a gel solution; S2, preparation of Fe-C-N(M); S3, detection of wastewater; S4, determination of wastewater treatment system parameters: S4-1, primary correction of wastewater treatment system parameters; S4-2, secondary correction of wastewater treatment system parameters; S4-3, tertiary correction of wastewater treatment system parameters; S5, wastewater treatment. The method of the present invention prepares a gel solution by the gel method and pyrolyzes with melamine as a nitrogen source to prepare a nitrogen-doped derivative carbon material Fe-C-N(M), which has CNTs on its surface, has pores on the surface and the pore sizes are relatively concentrated, facilitating electron transfer, and has the best catalytic activity. It has a 100% removal rate for 5 mg / L of sulfamethazine SMZ within 15 minutes, indicating that N doping can improve the catalytic activity of the carbon material and can achieve a good removal effect on sulfamethazine SMZ after activating PMS.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and specifically relates to a method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) materials. Background Art

[0002] In recent years, with the development of medical standards and the breeding industry, the production and consumption of antibiotics or antibacterial agents have increased sharply, posing a threat to the environmental ecology and people's health. Most antibiotics are water-soluble and can be transferred to soil, surface water, and groundwater through various media in the environment. Since there are currently no specific requirements for the manure discharge of livestock, farmers often directly discharge breeding wastewater or animal manure into rivers and soil.

[0003] Antibiotics are relatively difficult to degrade under natural conditions, are continuously toxic to organisms in the environment, and pose a potential danger to the environmental ecosystem. When these sewage and manure containing antibiotics are discharged into the environment, they will have an adverse impact on the growth and development of animals and plants. Sulfamethazine (SMZ) is poorly soluble in water and is a sulfonamide antibiotic containing aromatic amine and sulfonamide functional groups, and sulfamethazine has been detected in different water environments.

[0004] In recent years, due to the advantages of economic efficiency, stability, and pollution-free in the activated persulfate oxidation technology, it has received more and more attention in the field of degrading organic macromolecular pollutants in environments such as water and soil. The literature "Study on the Preparation of Nitrogen-Doped Carbon Materials and Their Activation of Persulfate to Degrade Sulfamethoxazole" discloses that one or more of Fe(NO3)3·9H2O, dopamine hydrochloride, and melamine are ground as precursors to prepare 4 different catalysts for activating PMS to degrade sulfamethoxazole SMX, but no one has studied sulfamethazine (SMZ), and the literature also does not study the influence of coexisting ions in sewage. Summary of the Invention

[0005] To solve the above problems, the present invention provides a method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) materials, including the following steps:

[0006] S1. Preparation of gel solution: Mix Fe(NO3)3·9H2O powder and C3H6N6 powder and dissolve them in absolute ethanol, and ultrasonically disperse to obtain a first mixed solution. Dissolve H3BTC powder in absolute ethanol and ultrasonically disperse to obtain a second mixed solution. Pour the first mixed solution into the second mixed solution and stir to obtain a gel solution, where the molar ratio of Fe(NO3)3·9H2O, C3H6N6, and H3BTC is 6:1:4-5;

[0007] S2. Preparation of Fe-C-N(M): The gel solution in step S1 is air-dried and then calcined in an N2 atmosphere at 800 ± 5 °C for 2 - 3 h. After cooling, it is ground to obtain the Fe-C-N(M) crude powder. The Fe-C-N(M) crude powder is pickled with a sulfuric acid solution at 80 ± 3 °C for 10 - 12 h, and the solid particles are magnetically separated. The solid particles are washed with ultrapure water and dried to obtain Fe-C-N(M).

[0008] S3. Wastewater detection: The wastewater containing organic pollutants to be treated is detected to obtain the mass concentration of sulfamethazine SMZ in the wastewater, denoted as n mg / L.

[0009] S4. Determination of wastewater treatment system parameters: Take peroxymonosulfate PMS and the Fe-C-N(M) prepared in step S2 as the wastewater treatment system. According to the content of sulfamethazine SMZ in the wastewater, determine the content of each component in the wastewater treatment system, that is: after the wastewater treatment system is mixed with the wastewater, control the molar concentration of peroxymonosulfate PMS to be 0.1 - 0.12 nM, and the mass concentration of Fe-C-N(M) to be 10 - 13n mg / L.

[0010] S5. Wastewater treatment: Pour peroxymonosulfate PMS and the Fe-C-N(M) prepared in step S2 into the wastewater according to the amounts calculated in step S4, stir and react for 15 - 30 min to complete the wastewater treatment.

[0011] Further, in step S1, the solid-liquid weight ratio in the first mixed solution is 1:8 - 15, the ultrasonic dispersion time is 5 - 10 min, the solid-liquid weight ratio in the second mixed solution is 1:8 - 15, the ultrasonic dispersion time is 5 - 10 min, and the particle sizes of Fe(NO3)3·9H2O powder, C3H6N6 powder, and H3BTC powder are all less than 1 mm.

[0012] Note: By controlling the solid-liquid ratio and ultrasonic dispersion time of the first and second mixed solutions, ensure uniform dispersion. When the solid-liquid ratio in the first and second mixed solutions is larger, the ultrasonic dispersion time is correspondingly increased.

[0013] Further, in the step S1, when mixing Fe(NO3)3·9H2O powder and C3H6N6 powder, first place the Fe(NO3)3·9H2O powder in a vacuum container, evacuate to 0.2 MPa, then inject liquid nitrogen into the vacuum container to rapidly cool the Fe(NO3)3·9H2O powder, and start the external motor of the vacuum container to drive the vacuum container to rotate at a high speed so that the Fe(NO3)3·9H2O powder continuously impacts the inner wall of the vacuum container, with a rotation speed of 500 - 1000 rpm, for 10 - 15 min. Subsequently, inject C3H6N6 powder into the vacuum container and mix by rotation, with a rotation speed of 300 - 400 rpm, for 5 - 10 min.

[0014] Note: By rapidly cooling with liquid nitrogen in combination with high-speed collision under negative pressure, fine cracks are generated on the surface of the Fe(NO3)3·9H2O powder, and the liquid nitrogen passes through the fine cracks to generate extended micro-cracks under ultra-low temperature conditions, thereby promoting the mixing of the Fe(NO3)3·9H2O powder and the C3H6N6 powder, making the prepared first mixed liquid more uniform, and the obtained gel solution denser, and finally the synthesized Fe-C-N(M) has better catalytic effect.

[0015] Further, in the step S2, the heating rate of calcination is 5 - 6 °C / min, the cooling is natural cooling at room temperature, the molar concentration of the sulfuric acid solution is 0.5 M, wash with ultrapure water 4 - 5 times, and the drying temperature is 70 - 75 °C.

[0016] Note: By optimizing and adjusting the heating rate of the Fe-C-N(M) preparation, uneven heating caused by too fast heating is avoided. Adjusting the concentration of the sulfuric acid solution can save costs on the premise of ensuring the pickling effect, and finally ensure that an Fe-C-N(M) catalyst with a high specific surface area, uniform dispersion, small particle size, and concentrated pore size can be prepared.

[0017] Further, the persulfate PMS is potassium hydrogen sulfate complex salt 2KHSO5·KHSO4·K2SO4.

[0018] Note: The oxidation potential energy of the persulfate PMS comes from its high acid chemical properties. It is the first medium salt in peroxymonosulfuric acid H2SO5. The molecular structure of PMS is different from that of H2O2 and PDS. It is an asymmetric peroxide formed by replacing one SO 3- with H2O2. This unique structure makes PMS easily excited and activated by the catalyst. The PDS substance is neutral in water, while the PMS substance is acidic in water, and the cost of PMS is lower.

[0019] Further, in the step S3, it also includes detecting the pH value of the wastewater, the molar concentration of CO3 2- and HPO42- The molar concentration of the substance, and the wastewater treatment system parameters in step S4 are corrected according to the detection results. The correction method is as follows:

[0020] S4-1. Primary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected pH value of the wastewater. If the wastewater pH < 6, the wastewater treatment system parameters remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of Fe-C-N(M) increases by 0.5n mg / L. If the wastewater pH ≥ 10, the mass concentration of Fe-C-N(M) increases by 1n mg / L;

[0021] S4-2. Secondary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- < 1 mM, the wastewater treatment system parameters remain unchanged. If the molar concentration of CO3 2- in the wastewater is 1 ≤ < 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L. If the molar concentration of CO3 2- in the wastewater ≥ 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L, and the molar concentration of persulfate PMS increases by 0.03n mM;

[0022] S4-3. Tertiary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of HPO4 2- in the wastewater. If the molar concentration of HPO4 2- < 1 mM, the wastewater treatment system parameters remain unchanged. If the molar concentration of HPO4 2- in the wastewater is 1 ≤ < 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L. If the molar concentration of HPO4 2- in the wastewater ≥ 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L, and the molar concentration of persulfate PMS increases by 0.03n mM.

[0023] Note: By further optimizing and adjusting the addition amounts of Fe-C-N(M) and PMS according to the pH value of the wastewater and the influence of coexisting ions, the efficiency and treatment effect of the entire wastewater treatment process are ensured.

[0024] Furthermore, it further includes step S6,

[0025] S6. Primary reuse treatment: The solid materials in the wastewater after the treatment in step S5 are recovered by magnetic adsorption, and are washed twice alternately with absolute ethanol and deionized water to obtain primary reuse Fe-C-N(M). The primary reuse Fe-C-N(M) is reused for wastewater treatment again, and the operations of steps S3 - S5 are repeated. In step S4, after the wastewater treatment system is mixed with the wastewater, the molar concentration of persulfate PMS is controlled to be 0.12n mM, and the mass concentration of primary reuse Fe-C-N(M) is 13n mg / L.

[0026] Preferably, during the primary reuse treatment process, the parameters of the wastewater treatment system in step S4 are corrected, and the correction method is as follows:

[0027] S4-1. Primary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected pH value of the wastewater. If the wastewater pH < 6, the parameters of the wastewater treatment system remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of primary reuse Fe-C-N(M) increases by 0.6n mg / L. If the wastewater pH ≥ 10, the mass concentration of primary reuse Fe-C-N(M) increases by 1.2n mg / L.

[0028] S4-2. Secondary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- < 1 mM, the parameters of the wastewater treatment system remain unchanged. If the molar concentration of CO3 2- in the wastewater is 1 ≤ CO3 2- < 10, the mass concentration of primary reuse Fe-C-N(M) increases by 0.5n mg / L. If the molar concentration of CO3 2- in the wastewater ≥ 10, the mass concentration of primary reuse Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of persulfate PMS increases by 0.04n mM.

[0029] S4-3. Tertiary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected molar concentration of HPO4 2- in the wastewater. If the molar concentration of HPO4 2- < 1 mM, the parameters of the wastewater treatment system remain unchanged. If the molar concentration of HPO4 2- in the wastewater is 1 ≤ HPO4 2-If the molar concentration of the substance ≥ 10, the mass concentration of the recycled Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.04n mM.

[0030] Note: By recycling the Fe-C-N(M) after wastewater treatment, the cost can be further saved. The recycled Fe-C-N(M) is reused for antibiotic wastewater treatment and the parameters are corrected to ensure that the wastewater treatment process remains efficient and has good treatment effects.

[0031] Preferably, it further includes step S7.

[0032] S7. Secondary recycling treatment: The solid materials in the wastewater after the primary recycling treatment are recovered by magnetic adsorption, and are alternately washed twice with absolute ethanol and deionized water to obtain the secondary recycled Fe-C-N(M). The secondary recycled Fe-C-N(M) is reused for wastewater treatment, and the operations of steps S3 - S5 are repeated. In step S4, after the wastewater treatment system is mixed with the wastewater, the molar concentration of peroxymonosulfate PMS is controlled to be 0.13n mM, and the mass concentration of the secondary recycled Fe-C-N(M) is 15n mg / L.

[0033] Preferably, during the secondary recycling treatment, the parameters of the wastewater treatment system in step S4 are corrected. The correction method is as follows:

[0034] S4-1. Primary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected pH value of the wastewater. If the wastewater pH < 6, the parameters of the wastewater treatment system remain unchanged. If 6 ≤ wastewater pH < 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.8n mg / L. If the wastewater pH ≥ 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 1.6n mg / L.

[0035] S4-2. Secondary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- < 1 mM, the parameters of the wastewater treatment system remain unchanged. If 1 ≤ the molar concentration of CO3 2- in the wastewater < 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.7n mg / L. If the molar concentration of CO3 2- in the wastewater ≥ 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.7n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.05n mM.

[0036] S4-3, three corrections of wastewater treatment system parameters: according to the HPO4 detected in the wastewater 2- The concentration of the substance is used to modify the wastewater treatment system parameters. If HPO4 2- If the molar concentration of the substance is less than 1mM, the wastewater treatment system parameters remain unchanged. If 1≤HPO4 2- If the molar concentration of the substance is less than 10, the mass concentration of Fe-CN (M) in the secondary recycling increases by 0.8n mg / L. 2- If the molar concentration is ≥10, the mass concentration of secondary recycled Fe-CN(M) increases by 0.8n mg / L, and the molar concentration of permonosulfate PMS increases by 0.05n mM.

[0037] Description: The remaining Fe-CN(M) after the primary reuse Fe-CN(M) is used for wastewater treatment is recycled again, thereby further saving costs. The secondary reuse Fe-CN(M) is used again in antibiotic wastewater treatment and parameter correction is performed to ensure that the wastewater treatment process remains efficient and has good treatment effects.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] (1) The present invention adopts a gel method to prepare a gel solution, and uses melamine as a nitrogen source for pyrolysis to prepare a nitrogen-doped derived carbon material Fe-CN(M), so that CNTs appear on its surface. The surface has pores and the pore size is relatively concentrated, which is conducive to electron transfer. At the same time, it has the best catalytic activity. Within 15 minutes, it has a 100% removal rate for 5 mg / L sulfamethazine SMZ, indicating that N doping can improve the catalytic activity of carbon materials, and after activating PMS, it can have a good removal effect on sulfamethazine SMZ.

[0040] (2) The present invention produces micro cracks on the surface of Fe(NO3)3·9H2O powder by rapid cooling with liquid nitrogen combined with negative pressure high-speed collision, and generates extended micro cracks by allowing liquid nitrogen to pass through the micro cracks under the action of ultra-low temperature, thereby promoting the mixing of Fe(NO3)3·9H2O powder and C3H6N6 powder, making the prepared first mixed solution more uniform, and the obtained gel solution more dense, and the finally synthesized Fe-CN(M) has a better catalytic effect.

[0041] (3) The present invention has optimized the optimal dosages of PMS and Fe-C-N(M), and adjusted the dosages according to the influence of the pH value of the wastewater and coexisting ions, so as to ensure that the entire wastewater treatment process remains efficient and has good treatment effects. The mass concentration of sulfamethazine SMZ in the wastewater is designated as n, and thus the dosages and adjustment amounts of PMS and Fe-C-N(M) are adjusted based on n, enabling reasonable adjustments for different scales of wastewater volumes.

[0042] (4) The present invention recycles and utilizes the treated Fe-C-N(M), thereby further saving the consumption of raw materials, reducing costs, and adjusting the addition amount of its raw materials according to the number of recycling times and the influence of the pH value of the wastewater and coexisting ions, ensuring that the Fe-C-N(M) recovered at each stage can maintain efficient and good treatment effects. Description of the Drawings

[0043] Figure 1 It is a graph showing the relationship between the dosage of peroxymonosulfate PMS and the removal rate of sulfamethazine SMZ in Experimental Example 1 of the present invention;

[0044] Figure 2 It is a graph showing the relationship between the dosage of Fe-C-N(M) and the removal rate of sulfamethazine SMZ in Experimental Example 1 of the present invention;

[0045] Figure 3 It is a Zeta potential graph at different pH values in Experimental Example 2 of the present invention;

[0046] Figure 4 It is a graph showing the influence relationship of the concentration of CO3 2- on wastewater treatment in Experimental Example 3 of the present invention;

[0047] Figure 5 It is a graph showing the influence relationship of the concentration of HPO4 2- on wastewater treatment in Experimental Example 3 of the present invention;

[0048] Figure 6 It is a schematic diagram of the degradation effect of 4 recycling experiments in Experimental Example 5 of the present invention;

[0049] Figure 7 It is a schematic diagram of the metal ion dissolution amount of 4 recycling experiments in Experimental Example 5 of the present invention;

[0050] Figure 8 It is a degradation pathway diagram of sulfamethazine SMZ when treating sulfamethazine SMZ wastewater by the method of the present invention. Detailed Embodiments

[0051] To further elaborate on the methods adopted and the effects achieved by the present invention, the technical solutions of the present invention will be clearly and completely described below in combination with experiments.

[0052] Example 1: The content recorded in this example is a method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) materials, including the following steps:

[0053] S1. Preparation of gel solution: Mix Fe(NO3)3·9H2O powder and C3H6N6 powder and dissolve them in absolute ethanol, and ultrasonically disperse to obtain a first mixed solution. The solid-liquid weight ratio in the first mixed solution is 1:10, and the ultrasonic dispersion time is 8 min. Dissolve H3BTC powder in absolute ethanol and ultrasonically disperse to obtain a second mixed solution. Pour the first mixed solution into the second mixed solution and stir to obtain a gel solution. The solid-liquid weight ratio in the second mixed solution is 1:10, and the ultrasonic dispersion time is 8 min. Among them, the particle sizes of Fe(NO3)3·9H2O powder, C3H6N6 powder, and H3BTC powder are all less than 1 mm, and the molar ratio of Fe(NO3)3·9H2O, C3H6N6, and H3BTC is 6:1:4. When mixing Fe(NO3)3·9H2O powder and C3H6N6 powder, first place Fe(NO3)3·9H2O powder in a vacuum container, evacuate to 0.2 MPa, then inject liquid nitrogen into the vacuum container to rapidly cool Fe(NO3)3·9H2O powder, and turn on the external motor of the vacuum container to drive the vacuum container to rotate at a high speed so that Fe(NO3)3·9H2O powder continuously impacts the inner wall of the vacuum container. The rotation speed is 800 rpm, and it lasts for 12 min. Then inject C3H6N6 powder into the vacuum container and rotate and mix at a rotation speed of 350 rpm for 8 min;

[0054] S2. Preparation of Fe-C-N(M): Air-dry the gel solution in step S1 and calcine it at 800 °C for 3 h in an N2 atmosphere. After cooling, grind it to obtain Fe-C-N(M) coarse powder. The heating rate of calcination is 5 °C / min, and the cooling is natural cooling to 28 °C. Wash the Fe-C-N(M) coarse powder with a sulfuric acid solution at 80 °C for 10 h. The molar concentration of the sulfuric acid solution is 0.5 M. Magnetically separate the solid particles, and wash and dry the solid particles with ultrapure water to obtain Fe-C-N(M). Wash with ultrapure water 4 times, and the drying temperature is 70 °C;

[0055] S3. Wastewater detection: Detect the wastewater containing organic pollutants to be treated to obtain the mass concentration of sulfamethazine SMZ in the wastewater, denoted as n mg / L. At the same time, detect the pH value of the wastewater, the molar concentration of CO3 2- and the molar concentration of HPO4 2- ;

[0056] S4. Determination of wastewater treatment system parameters: Take persulfate PMS and Fe-C-N(M) prepared in step S2 as the wastewater treatment system. Persulfate PMS is potassium hydrogen sulfate complex salt 2KHSO5·KHSO4·K2SO4. According to the content of sulfamethazine SMZ in the wastewater, determine the content of each component in the wastewater treatment system, that is: after the wastewater treatment system is mixed with the wastewater, control the molar concentration of persulfate PMS to be 0.1n mM, and the mass concentration of Fe-C-N(M) to be 10n mg / L;

[0057] And correct the wastewater treatment system parameters in step S4 according to the test results. The correction method is:

[0058] S4-1. Primary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected pH value of the wastewater. If the wastewater pH < 6, the wastewater treatment system parameters remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of Fe-C-N(M) increases by 0.5n mg / L. If the wastewater pH ≥ 10, the mass concentration of Fe-C-N(M) increases by 1n mg / L;

[0059] S4-2. Secondary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- < 1 mM, the wastewater treatment system parameters remain unchanged. If the molar concentration of CO3 2- in the wastewater is 1 ≤ CO3 2- < 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L. If the molar concentration of CO3

[0060] in the wastewater ≥ 10, the mass concentration of Fe-C-N(M) increases by 0.4n mg / L, and the molar concentration of persulfate PMS increases by 0.03n mM; 2- S4-3. Tertiary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of HPO4 2- in the wastewater. If the molar concentration of HPO4 2- < 1 mM, the wastewater treatment system parameters remain unchanged. If the molar concentration of HPO4 2- in the wastewater is 1 ≤ HPO4

[0061] S5, Wastewater treatment: Pour the persulfate PMS and the Fe-C-N(M) prepared in step S2 into the wastewater according to the amount calculated in step S4, stir and react for 20 min to complete the wastewater treatment.

[0062] Example 2: The difference between this example and Example 1 is that it further includes step S6.

[0063] S6, Primary reuse treatment: Recover the solid materials in the wastewater after the treatment in step S5 by magnetic adsorption, wash twice alternately with absolute ethanol and deionized water to obtain the primary reuse Fe-C-N(M), and reuse the primary reuse Fe-C-N(M) for wastewater treatment again. Repeat the operations of steps S3 - S5. In step S4, after the wastewater treatment system is mixed with the wastewater, control the molar concentration of the persulfate PMS to be 0.12n mM and the mass concentration of the primary reuse Fe-C-N(M) to be 13n mg / L.

[0064] Meanwhile, correct the parameters of the wastewater treatment system in step S4. The correction method is as follows:

[0065] S4-1, Primary correction of wastewater treatment system parameters: Correct the parameters of the wastewater treatment system according to the detected pH value of the wastewater. If the wastewater pH < 6, the parameters of the wastewater treatment system remain unchanged. If 6 ≤ wastewater pH < 10, the mass concentration of the primary reuse Fe-C-N(M) increases by 0.6n mg / L. If the wastewater pH ≥ 10, the mass concentration of the primary reuse Fe-C-N(M) increases by 1.2n mg / L.

[0066] S4-2, Secondary correction of wastewater treatment system parameters: Correct the parameters of the wastewater treatment system according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- < 1 mM, the parameters of the wastewater treatment system remain unchanged. If 1 ≤ the molar concentration of CO3 2- in the wastewater < 10, the mass concentration of the primary reuse Fe-C-N(M) increases by 0.5n mg / L. If the molar concentration of CO3 2- in the wastewater ≥ 10, the mass concentration of the primary reuse Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of the persulfate PMS increases by 0.04n mM.

[0067] S4-3, Tertiary correction of wastewater treatment system parameters: Correct the parameters of the wastewater treatment system according to the detected molar concentration of HPO4 2- in the wastewater. If the molar concentration of HPO4 2- < 1 mM, the parameters of the wastewater treatment system remain unchanged. If 1 ≤ the molar concentration of HPO42- If the molar concentration of the substance is < 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L. If HPO4 2- in the wastewater has a molar concentration ≥ 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.04n mM.

[0068] Example 3: The difference between this example and Example 2 is that it further includes step S7.

[0069] S7. Secondary recycling treatment: The solid materials in the wastewater after the first recycling treatment are recovered by magnetic adsorption, and are alternately washed twice with absolute ethanol and deionized water to obtain the second recycled Fe-C-N(M). The second recycled Fe-C-N(M) is used for wastewater treatment again, and the operations of steps S3 - S5 are repeated. In step S4, after the wastewater treatment system is mixed with the wastewater, the molar concentration of peroxymonosulfate PMS is controlled to be 0.13n mM, and the mass concentration of the second recycled Fe-C-N(M) is 15n mg / L.

[0070] Meanwhile, the parameters of the wastewater treatment system in step S4 are corrected. The correction method is as follows:

[0071] S4-1. Primary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected pH value of the wastewater. If the wastewater pH < 10, the parameters of the wastewater treatment system remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of the second recycled Fe-C-N(M) increases by 0.8n mg / L. If the wastewater pH ≥ 10, the mass concentration of the second recycled Fe-C-N(M) increases by 1.6n mg / L.

[0072] S4-2. Secondary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- is < 1 mM, the parameters of the wastewater treatment system remain unchanged. If the molar concentration of CO3 2- in the wastewater is 1 ≤ < 10, the mass concentration of the second recycled Fe-C-N(M) increases by 0.7n mg / L. If the molar concentration of CO3 2- in the wastewater is ≥ 10, the mass concentration of the second recycled Fe-C-N(M) increases by 0.7n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.05n mM.

[0073] S4-3. Tertiary correction of wastewater treatment system parameters: The parameters of the wastewater treatment system are corrected according to the detected molar concentration of HPO4 2-The molar concentration of the substance is used to correct the parameters of the wastewater treatment system. If the molar concentration of HPO4 2- <1 mM, the parameters of the wastewater treatment system remain unchanged. If 1 ≤ the molar concentration of HPO4 2- <10 in the wastewater, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.8n mg / L. If the molar concentration of HPO4 2- ≥10 in the wastewater, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.8n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.05n mM.

[0074] Example 4: The difference between this example and Example 1 is that:

[0075] In step S1, the solid-liquid weight ratio in the first mixed solution is 1:8, and the ultrasonic dispersion time is 10 min. The solid-liquid weight ratio in the second mixed solution is 1:8, and the ultrasonic dispersion time is 10 min.

[0076] Example 5: The difference between this example and Example 1 is that:

[0077] In step S1, the solid-liquid weight ratio in the first mixed solution is 1:15, and the ultrasonic dispersion time is 5 min. The solid-liquid weight ratio in the second mixed solution is 1:15, and the ultrasonic dispersion time is 5 min.

[0078] Note: In Example 1, Example 4, and Example 5, when the solid-liquid ratio in the first mixed solution and the second mixed solution is larger, the ultrasonic dispersion time is correspondingly increased to ensure uniform dispersion of the first mixed solution and the second mixed solution.

[0079] Example 6: The difference between this example and Example 1 is that:

[0080] In step S1, the molar ratio of Fe(NO3)3·9H2O, C3H6N6, and H3BTC is 6:1:5;

[0081] In step S2, after air-drying the gel solution in step S1, it is calcined in an N2 atmosphere at 795 °C for 2 h, cooled and then ground to obtain Fe-C-N(M) crude powder. The heating rate of the calcination is 6 °C / min, and the cooling is natural cooling to 25 °C. The Fe-C-N(M) crude powder is pickled with a sulfuric acid solution at 77 °C for 12 h. The molar concentration of the sulfuric acid solution is 0.5 M. The solid particles are magnetically separated, and the solid particles are washed and dried with ultrapure water to obtain Fe-C-N(M). The ultrapure water is washed 5 times, and the drying temperature is 75 °C;

[0082] In step S4, the molar concentration of peroxymonosulfate PMS is controlled to be 0.11n mM, and the mass concentration of Fe-C-N(M) is 12n mg / L;

[0083] In step S5, pour the peroxymonosulfate PMS and the Fe-C-N(M) prepared in step S2 into the wastewater according to the amounts calculated in step S4, stir and react for 30 min to complete the wastewater treatment.

[0084] Example 7

[0085] The difference between this example and Example 1 is as follows:

[0086] In S2, after air-drying the gel solution in step S1, calcine it in an N2 atmosphere at 805 °C for 2 h, cool it and then grind it to obtain the Fe-C-N(M) crude powder. The heating rate of calcination is 6 °C / min, and the cooling is natural cooling at 22 °C. Wash the Fe-C-N(M) crude powder with a sulfuric acid solution at 83 °C for 12 h. The molar concentration of the sulfuric acid solution is 0.5 M. Magnetically separate the solid particles, and wash and dry the solid particles with ultrapure water to obtain Fe-C-N(M). Wash with ultrapure water 5 times, and the drying temperature is 75 °C;

[0087] In S4, control the molar concentration of peroxymonosulfate PMS to be 0.12n mM, and the mass concentration of Fe-C-N(M) to be 13n mg / L;

[0088] In S5, pour the peroxymonosulfate PMS and the Fe-C-N(M) prepared in step S2 into the wastewater according to the amounts calculated in step S4, stir and react for 15 min to complete the wastewater treatment.

[0089] Note: In Examples 1 and 6, the adjusted parameters are reasonable errors within the conventional range, and Fe-C-N(M) with good performance can be prepared within the numerical range given in the present invention.

[0090] Example 8: The difference between this example and Example 1 is that when mixing the Fe(NO3)3·9H2O powder and the C3H6N6 powder, first place the Fe(NO3)3·9H2O powder in a vacuum container, evacuate to 0.2 MPa, then inject liquid nitrogen into the vacuum container to rapidly cool the Fe(NO3)3·9H2O powder, and turn on the external motor of the vacuum container to drive the vacuum container to rotate at a high speed so that the Fe(NO3)3·9H2O powder continuously impacts the inner wall of the vacuum container. The rotation speed is 1000 rpm, and it lasts for 10 min. Then inject the C3H6N6 powder into the vacuum container and mix by rotation. The rotation speed is 400 rpm, and it lasts for 5 min.

[0091] Example 9: The difference between this example and Example 1 lies in that when mixing Fe(NO3)3·9H2O powder and C3H6N6 powder, first place the Fe(NO3)3·9H2O powder in a vacuum container, evacuate to 0.2 MPa, then inject liquid nitrogen into the vacuum container to rapidly cool the Fe(NO3)3·9H2O powder, and turn on the external motor of the vacuum container to drive the vacuum container to rotate at a high speed so that the Fe(NO3)3·9H2O powder continuously impacts the inner wall of the vacuum container. The rotation speed is 500 rpm and lasts for 15 min. Then inject C3H6N6 powder into the vacuum container and rotate and mix at a speed of 300 rpm for 10 min.

[0092] Note: Adjust the rotation speed during rotation to ensure that the Fe(NO3)3·9H2O powder can collide with sufficient impact force to generate microcracks. If the rotation speed is relatively high, an appropriate shortening of the rotation time can be considered to avoid fragmentation of the Fe(NO3)3·9H2O powder. When mixing, a relatively low rotation speed can be considered to ensure uniform mixing of the Fe(NO3)3·9H2O powder and C3H6N6 powder. At this time, a part of the C3H6N6 powder will enter the microcracks.

[0093] Experimental Example 1: To verify the optimal addition amounts of persulfate PMS and Fe-C-N(M), several comparative examples were set up. Comparative example 1 is without adding persulfate PMS, comparative example 2 is adding 0.05n mM persulfate PMS, comparative example 3 is adding 0.15n mM persulfate PMS, comparative example 4 is adding 0.2n mM persulfate PMS, comparative example 5 is without adding Fe-C-N(M), comparative example 6 is adding 5n mg / L Fe-C-N(M), comparative example 7 is adding 15n mg / L Fe-C-N(M), and comparative example 8 is adding 20n mg / L Fe-C-N(M). After step S3, the mass concentration of sulfamethazine SMZ in the wastewater was measured to be 5 mg / L. Therefore, n is taken as 5. The graphs showing the change of the removal rate of sulfamethazine SMZ over time in Example 1 and each comparative example are as Figure 1 and Figure 2As shown, without adding PMS and only adding Fe-C-N(M) material, SMZ reached the adsorption equilibrium in about 15 min, and the adsorption capacity was about 50%. As the PMS addition amount increased from 0 mM to 0.25 mM, the removal rate of SMZ increased from 50% to 100%. When the PMS addition amount increased to 0.5 mM, the reaction rate in the first 15 min was significantly accelerated. However, when the PMS addition amount increased from 0.5 mM to 1.0 mM, there was no obvious improvement in the removal rate and removal efficiency of SMZ, indicating that the PMS concentration had exceeded the maximum activation amount of the catalyst at this time, and there were no extra reaction sites on the catalyst surface to activate PMS. Therefore, 0.5 mM PSM was the optimal addition amount. When the catalytic addition amount was 0 mg / L, that is, only PMS was present, there was almost no degradation effect on SMZ. When the catalyst was added, the degradation of SMZ was rapidly improved. The catalyst with a concentration of 25 mg / L could remove 97.8% of SMZ within 30 min, while when 50 mg / L of the catalyst was added, SMZ was completely removed in about 15 min. This was because as the catalyst addition amount increased, the PMS activation sites increased, which promoted the generation of active substances and improved the degradation rate of SMZ. At the same time, the adsorption of SMZ by the catalyst Fe-C-N(M) also promoted the removal of SMZ. However, when the catalyst addition amount was increased to more than 50 mg / L, there was no obvious improvement in the removal rate of SMZ. Therefore, 50 mg / L of the catalyst was selected as the optimal addition amount.

[0094] Experimental Example 2: To verify the influence of pH value on the wastewater treatment effect, we divided the wastewater samples into 5 portions. The mass concentration of sulfamethazine (SMZ) in each portion of the wastewater was 5 mg / L, and the initial pH was 5.78. The initial pH value was adjusted by sodium hydroxide and sulfuric acid to obtain wastewater samples with pH values of 3, 7, 9, and 11. Subsequently, the wastewater treatment was carried out according to the method in Example 1 without parameter correction. We first analyzed the Zeta potential at different pH values. The catalyst activated PMS to generate SO4 2- which can be expressed by the following formula:

[0095]

[0096] Therefore, under alkaline conditions, the activation of PMS by the catalyst to generate SO4 will be inhibited 2- and the decomposition of PMS will proceed in the direction of generating SO5 with relatively weak oxidation ability - resulting in a decrease in the degradation ability of SMZ. From Figure 3It can be seen that the zero-point Zeta potential of the Fe-C-N(M) catalyst is around 6.1. The Zeta potential value of the Fe-C-N(M) catalyst is inversely proportional to the pH value. When the pH value in the solution is 11, the Zeta potential of the catalyst is -24.5 mV, while PMS exists in the solution in the form of anionic HSO 5- Due to the mutual repulsion of like charges, it hinders the adsorption of HSO5 - on the catalyst surface, affecting the generation of free radicals in the catalytic system. Therefore, it is necessary to correct the wastewater treatment system parameters according to the pH of the initial wastewater to ensure the treatment effect.

[0097] Experimental Example 3: To verify the influence of coexisting ions on wastewater treatment, an indoor simulation test was conducted. Four portions of wastewater with a sulfamethazine SMZ mass concentration of 5 mg / L were taken, and different CO3 2- concentrations were adjusted. Subsequently, another four portions of wastewater with a mass concentration of 5 mg / L were taken, and different HPO4 2- concentrations were adjusted. CO3 2- and HPO4 2- are both dibasic weak acids. Due to hydrolysis, the solution will be slightly alkaline. To eliminate the influence of pH value changes on this experiment, the initial pH value of the solution needs to be adjusted to neutral when adding different concentrations of CO3 2- and HPO4 2- . As shown in Figure 4 and Figure 5 , after adding 1 mM of CO3 2- and HPO4 2- , the degradation rate of SMZ decreased significantly. When the concentration of CO3 2- and HPO4 2- was increased to 10 mM, a more obvious inhibitory effect on the degradation effect was produced. The reasons are twofold. One is that CO3 2- and HPO4 2- may directly react with PMS, causing PMS to decompose. The other is that CO3 2- and HPO4 2- can act as radical quenchers, reacting with ·OH and SO4·- generated in the catalyst-activated PMS system to produce substances with lower activity. The reaction principle is shown in the following formula:

[0098]

[0099] Experimental Example 4: To verify the effectiveness of modifying the parameters of the wastewater treatment system, an indoor simulation test was conducted. Several comparative examples were set up. Comparative Example 9 was without any modification of the wastewater treatment system parameters. Comparative Example 10 was without modifying the wastewater treatment system in step S4-1. Comparative Example 11 was without modifying the wastewater treatment system in step S4-2. Comparative Example 12 was without modifying the wastewater treatment system in step S4-3. The other parameters were the same as those in Example 1. The mass concentration of sulfamethazine SMZ in the selected wastewater was 5 mg / L, the pH was 9, the molar concentration of CO3 2- was 5 mM, and the molar concentration of HPO4 2- was 5 mM. The removal rate of sulfamethazine SMZ in the water when the wastewater treatment reached 15 min is shown in Table 1:

[0100] Table 1 Removal rate of sulfamethazine SMZ in wastewater at 15 min of treatment in each group of cases

[0101] Case Removal rate % Example 1 99.9 Comparative Example 9 82.3 Comparative Example 10 97.5 Comparative Example 11 92.4 Comparative Example 12 86.6

[0102] It can be seen from the data in Table 1 that if the parameters of the wastewater treatment system are not modified, the removal rate at 15 min in Comparative Example 9 is significantly lower than that in Example 1, which also confirms the research conclusions in Experimental Examples 2 and 3. Furthermore, by comparing Comparative Examples 10-12, it can be seen that the pH has a relatively small impact on the removal rate of SMZ in the wastewater, while HPO4 2- has a greater impact on the removal rate of SMZ in the wastewater.

[0103] Experimental Example 5: To verify that the used Fe-C-N(M) can be recycled again, 4 recycling experiments were carried out. The degradation rates of activating PMS for SMZ in the first two times reached 100% within 30 min. The catalytic performance decreased slightly within 30 min during the third use, and the degradation rate was 90%. The degradation rate of the catalyst in the fourth time was 85%. The amounts of metal ion dissolution in the four experiments were 15.01 μg / L, 14.25 μg / L, 12.73 μg / L, and 10.1 μg / L respectively. After four cycles of use, the amount of iron ion dissolution decreased. Therefore, to recycle in this way, it is necessary to use the methods for modifying the parameters of the wastewater treatment system in Examples 2 and 3 to modify the parameters of the wastewater treatment system again, otherwise it will affect the use effect. At the same time, the fourth recycling is not recommended because at this time, the amount of iron ion dissolution of Fe-C-N(M) decreases significantly, and a large amount of raw materials need to be increased or Fe-C-N(M) needs to be added to maintain the treatment effect, resulting in an increase in cost.

Claims

1. A method for degrading antibiotics in wastewater by activating PMS with Fe-C-N(M) material, characterized in that, It includes the following steps: S1. Gel solution preparation: Mix Fe(NO3)3·9H2O powder and C3H6N6 powder and dissolve them in absolute ethanol, and obtain the first mixed solution by ultrasonic dispersion; dissolve H3BTC powder in absolute ethanol and obtain the second mixed solution by ultrasonic dispersion; pour the first mixed solution into the second mixed solution and stir to obtain the gel solution, where the molar ratio of Fe(NO3)3·9H2O, C3H6N6 and H3BTC is 6:1:4-5; S2. Preparation of Fe-C-N(M): Air-dry the gel solution in step S1 and calcine it in an N2 atmosphere at 800±5 °C for 2-3 h, cool and grind to obtain the Fe-C-N(M) crude powder; pickle the Fe-C-N(M) crude powder with sulfuric acid solution at 80±3 °C for 10-12 h, magnetically separate the solid particles, and wash and dry the solid particles with ultrapure water to obtain Fe-C-N(M); S3. Wastewater detection: Detect the wastewater containing organic pollutants to be treated to obtain the mass concentration of sulfamethazine SMZ in the wastewater, denoted as n mg / L; In the step S3, it also includes detecting the pH value of the wastewater, the molar concentration of CO3 2- and the molar concentration of HPO4 2- , and correcting the parameters of the wastewater treatment system in the step S4 according to the detection results. The correction method is as follows: S4-1. Primary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected pH value of the wastewater. If the wastewater pH < 6, the wastewater treatment system parameters remain unchanged; if the wastewater 6≤pH < 10, the mass concentration of Fe-C-N(M) increases by 0.5n mg / L; if the wastewater pH≥10, the mass concentration of Fe-C-N(M) increases by 1n mg / L; S4-2. Second correction of wastewater treatment system parameters: Based on the detected CO3 2- The concentration of the substance is used to modify the wastewater treatment system parameters. If CO3 2- If the molar concentration of the substance is less than 1mM, the wastewater treatment system parameters remain unchanged. If 1≤CO3 2- If the molar concentration of Fe-CN(M) is less than 10, the mass concentration of Fe-CN(M) increases by 0.4n mg / L. 2- If the molar concentration of the substance is ≥10, the mass concentration of Fe-CN(M) increases by 0.4n mg / L, and the molar concentration of peroxymonosulfate PMS increases by 0.03nmM; S4-3. Three - time correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of HPO4 in the wastewater. If the molar concentration of HPO4 2- 2- is < 1 mM, the wastewater treatment system parameters remain unchanged. If 1 ≤ the molar concentration of HPO4 2- in the wastewater < 10, the mass concentration of Fe - C - N(M) increases by 0.4n mg / L. If the molar concentration of HPO4 2- in the wastewater ≥ 10, the mass concentration of Fe - C - N(M) increases by 0.4n mg / L, and the molar concentration of persulfate PMS increases by 0.03n mM;​ S4. Determination of wastewater treatment system parameters: Take peroxymonosulfate PMS and Fe-C-N(M) prepared in step S2 as the wastewater treatment system, and determine the content of each component in the wastewater treatment system according to the content of sulfamethazine SMZ in the wastewater, that is: after the wastewater treatment system is mixed with the wastewater, control the molar concentration of peroxymonosulfate PMS to be 0.1-0.12n mM, and the mass concentration of Fe-C-N(M) to be 10-13n mg / L; S5. Wastewater treatment: Pour peroxymonosulfate PMS and Fe-C-N(M) prepared in step S2 into the wastewater according to the amount calculated in step S4, stir and react for 15-30 min to complete the wastewater treatment; S6. Primary reuse treatment: Recover the solid materials in the wastewater after treatment in step S5 by magnetic adsorption, wash them twice alternately with absolute ethanol and deionized water to obtain the primary reuse Fe-C-N(M), and reuse the primary reuse Fe-C-N(M) for wastewater treatment again. Repeat the operations in steps S3-S5. In step S4, after the wastewater treatment system is mixed with the wastewater, control the molar concentration of peroxymonosulfate PMS to be 0.12n mM, and the mass concentration of the primary reuse Fe-C-N(M) to be 13n mg / L; During the process of the primary reuse treatment, correct the wastewater treatment system parameters in step S4, and the correction method is: S4-1. Primary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected pH value of the wastewater. If the wastewater pH < 6, the wastewater treatment system parameters remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of the primary recycled Fe-C-N(M) increases by 0.6n mg / L. If the wastewater pH ≥ 10, the mass concentration of the primary recycled Fe-C-N(M) increases by 1.2n mg / L; S4-2. Secondary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of CO3 2- in the wastewater. If the molar concentration of CO3 2- is < 1 mM, the wastewater treatment system parameters remain unchanged. If 1 ≤ the molar concentration of CO3 2- in the wastewater < 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L. If the molar concentration of CO3 2- in the wastewater ≥ 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of persulfate PMS increases by 0.04n mM; S4-3. Three corrections to the wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected molar concentration of HPO4 2- in the wastewater. If the molar concentration of HPO4 2- is < 1 mM, the wastewater treatment system parameters remain unchanged. If 1 ≤ the molar concentration of HPO4 2- in the wastewater < 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L. If the molar concentration of HPO4 2- in the wastewater ≥ 10, the mass concentration of the first recycled Fe-C-N(M) increases by 0.5n mg / L, and the molar concentration of persulfate PMS increases by 0.04n mM.

2. The method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) material as claimed in claim 1, wherein In the step S1, the weight ratio of solid to liquid in the first mixed solution is 1:8 - 15, the ultrasonic dispersion time is 5 - 10 min, the weight ratio of solid to liquid in the second mixed solution is 1:8 - 15, the ultrasonic dispersion time is 5 - 10 min, and the particle sizes of the Fe(NO3)3·9H2O powder, C3H6N6 powder, and H3BTC powder are all less than 1 mm.

3. The method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) material according to claim 2, characterized in that, In the step S1, when mixing the Fe(NO3)3·9H2O powder and C3H6N6 powder, first place the Fe(NO3)3·9H2O powder in a vacuum container, evacuate to 0.2 MPa, then inject liquid nitrogen into the vacuum container to rapidly cool the Fe(NO3)3·9H2O powder, and turn on the external motor of the vacuum container to drive the vacuum container to rotate at a high speed so that the Fe(NO3)3·9H2O powder continuously impacts the inner wall of the vacuum container, with a rotation speed of 500 - 1000 rpm for 10 - 15 min. Then inject the C3H6N6 powder into the vacuum container and mix by rotation, with a rotation speed of 300 - 400 rpm for 5 - 10 min.

4. The method for degrading antibiotics in wastewater by activating PMS with Fe-C-N(M) material according to claim 1, characterized in that, In the step S2, the heating rate of calcination is 5 - 6 °C / min, the cooling is natural cooling at room temperature, the molar concentration of the sulfuric acid solution is 0.5 M, wash with ultrapure water 4 - 5 times, and the drying temperature is 70 - 75 °C.

5. The method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) material according to claim 1, characterized in that, The persulfate PMS is potassium hydrogen sulfate composite salt 2KHSO5·KHSO4·K2SO4.

6. The method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) material according to claim 1, characterized in that, It also includes the step S7. S7. Secondary recycling treatment: Recover the solid materials in the wastewater after the primary recycling treatment by magnetic adsorption, wash twice alternately with absolute ethanol and deionized water to obtain the secondary recycled Fe-C-N(M), and reuse the secondary recycled Fe-C-N(M) for wastewater treatment, repeating the operations of steps S3 - S5. In step S4, after the wastewater treatment system is mixed with the wastewater, control the molar concentration of the persulfate PMS to be 0.13n mM, and the mass concentration of the secondary recycled Fe-C-N(M) to be 15n mg / L.

7. A method for degrading antibiotics in wastewater by activating PMS using Fe-C-N(M) material as claimed in claim 6, characterized in that, During the secondary recycling treatment process, correct the wastewater treatment system parameters in step S4, and the correction method is: S4-1. Primary correction of wastewater treatment system parameters: Correct the wastewater treatment system parameters according to the detected pH value of the wastewater. If the wastewater pH < 6, the wastewater treatment system parameters remain unchanged. If the wastewater 6 ≤ pH < 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 0.8n mg / L. If the wastewater pH ≥ 10, the mass concentration of the secondary recycled Fe-C-N(M) increases by 1.6n mg / L; S4-2. Second correction of wastewater treatment system parameters: Based on the detected CO3 2- The concentration of the substance is used to modify the wastewater treatment system parameters. If CO3 2- If the molar concentration of the substance is less than 1mM, the wastewater treatment system parameters remain unchanged. If 1≤CO3 2- If the molar concentration of the substance is less than 10, the mass concentration of the secondary recycled Fe-CN (M) increases by 0.7n mg / L. 2- If the molar concentration of the substance is ≥10, the mass concentration of the secondary recycled Fe-CN(M) increases by 0.7n mg / L, and the molar concentration of the persulfate PMS increases by 0.05n mM; S4-3, three corrections of wastewater treatment system parameters: according to the HPO4 detected in the wastewater 2- The concentration of the substance is used to modify the wastewater treatment system parameters. If HPO4 2- If the molar concentration of the substance is less than 1mM, the wastewater treatment system parameters remain unchanged. If 1≤HPO4 2- If the molar concentration of the substance is less than 10, the mass concentration of Fe-CN (M) in the secondary recycling increases by 0.8n mg / L. 2- If the molar concentration is ≥10, the mass concentration of secondary recycled Fe-CN(M) increases by 0.8n mg / L, and the molar concentration of permonosulfate PMS increases by 0.05n mM.

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