A method for synergistically degrading macrolide antibiotic production wastewater by using wave-absorbing solid acid catalyst and acid heat

Abstract

This invention discloses a method for the acid-thermal synergistic degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst. The method employs a sulfonated resin-based composite solid acid, which possesses abundant acidic sites and excellent microwave energy absorption characteristics, as a catalyst. The sulfonated resin-based composite solid acid is added to wastewater containing macrolide antibiotics. The -SO3H released by the solid acid catalyzes the hydrolysis of the glycosidic bonds of macrolide antibiotics, and under microwave radiation, it achieves acid-thermal synergistic hydrolysis of macrolide antibiotics. The degradation method for macrolide antibiotics in an aqueous system provided by this invention can treat high-concentration antibiotic pharmaceutical wastewater. The process is simple and the degradation effect is good. The sulfonated resin-based composite solid acid has low corrosivity, is environmentally friendly and safe, and can be recycled. This provides a new method for the degradation of macrolide antibiotics in high-concentration antibiotic wastewater, reduces the emergence of drug-resistant bacteria, and has broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of environmental protection, specifically relating to a method for the acid-thermal synergistic degradation of wastewater from the production of macrolide antibiotics using a microwave-absorbing solid acid catalyst. Background Technology

[0002] my country is a major global consumer and producer of antibiotics. However, the large-scale production and use of antibiotics pose significant environmental risks. Traditional physicochemical and biochemical methods for treatment are challenging, and antibiotics themselves are toxic to microorganisms and have poor biodegradability, making it difficult to consistently meet discharge standards for treated wastewater. Even at extremely low concentrations in natural water bodies, long-term exposure can lead to chronic toxicity, inducing antibiotic resistance genes in bacteria. This not only disrupts the natural balance of ecosystems but also causes serious pollution problems. Excessive discharge can also lead to the emergence of drug-resistant bacteria, affecting the diversity of microbial communities. The spread and transfer of drug-resistant bacteria in the environment, in turn, affects the efficacy of antibiotics, reducing the effectiveness of existing antibiotics. Therefore, there is an urgent need to develop more efficient and economical methods and processes for treating antibiotic production wastewater to effectively reduce the antibiotic activity and antibacterial properties in the wastewater.

[0003] Currently, acid hydrolysis is a better pretreatment technology for antibiotic wastewater. However, liquid acids pose risks such as equipment corrosion, high toxicity, and significant environmental hazards during transportation, storage, and use. Solid acids, on the other hand, are safer powdered acids, offering advantages such as no irritating odor, no corrosion, safe and convenient transportation, and low cost. Furthermore, solid acids are recyclable, cause less damage to equipment, and reduce wastewater disposal. Existing literature utilizes SiO2 / SO3H solid acids as catalysts to degrade spiramycin in wastewater. This process is simple, has low requirements for equipment corrosion resistance, and the catalyst has good reusability, but the catalytic time is long and the catalytic activity is not high. Common heteropolyacid solid acid catalysts have attracted widespread attention in the field of acid catalysis due to their strong Brønsted acidity, excellent thermal stability, and low corrosivity. However, their low specific surface area and easy solubility in polar solvents result in insufficient exposure of active sites, and they are difficult to recover and recycle in liquid-phase reactions. In recent years, microwaves have been widely used in fields such as organic synthesis, environmental remediation, and water treatment process optimization due to their superior heating properties. Currently, many researchers are applying magnetic metal absorbing materials to microwave treatment of organic pollutant wastewater. However, traditional magnetic metal absorbing materials often suffer from drawbacks such as impedance mismatch and weak microwave attenuation, which severely restricts their practical application in the field of electromagnetic absorption and thus affects their microwave absorption characteristics.

[0004] Therefore, there is an urgent need in the field of antibiotic wastewater treatment to find a green and efficient solid acid catalyst that can effectively perform acid hydrolysis and has good microwave energy absorption characteristics to solve the problem of reducing the antibacterial properties of high-concentration antibiotic production wastewater. Based on this, this invention differs from the traditional acid hydrolysis approach for treating antibiotic wastewater by proposing a solid acid-acid-thermal synergistic method. Utilizing polystyrene-divinylbenzene resin, a sulfonated resin-based solid acid catalyst with abundant acidic sites and good microwave energy absorption characteristics is developed. This catalyst achieves highly efficient synergistic catalytic hydrolysis of antibiotics under microwave-assisted conditions, showing promising application prospects in the field of water pollutant treatment technology. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies for treating high concentrations of macrolide antibiotics in wastewater by providing a sulfonated resin-based solid acid catalyst with abundant acidic sites and good microwave energy absorption characteristics for the degradation of macrolide antibiotics. This solves the problem of large amounts of macrolide antibiotics accumulating in the environment due to insufficient wastewater treatment capacity in wastewater treatment plants, which threatens the environment and human health.

[0006] To address the aforementioned technical problems, this invention provides a method for the acid-thermal synergistic degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst. The method utilizes a sulfonated resin-based composite solid acid, which possesses both abundant acidic sites and excellent microwave energy absorption characteristics, as a catalyst. The sulfonated resin-based composite solid acid is added to wastewater containing macrolide antibiotics to degrade the macrolide antibiotics in the wastewater.

[0007] The characteristic feature is that (a) the preparation method of the sulfonated resin-based composite solid acid is as follows: (1) Contact 3 g of polystyrene divinylbenzene resin with 30 mL of dichloroethane in a three-necked flask for 30 minutes to allow the polystyrene divinylbenzene resin to swell; (2) Add concentrated sulfuric acid (H2SO4, 98%) to the solution obtained in step (1) and stir to form a homogeneous solution; (3) Place the mixture obtained in step (2) in a water bath and maintain the temperature at 70°C. o C, the reaction time is 180 minutes, with continuous stirring during the process; (4) Wash the particles obtained in step (3) with large amounts of deionized water and ethanol alternately until neutral to remove excess sulfonating reagent and swelling agent; (5) Place the sulfonated product obtained in step (4) in a petri dish, and then dry it in a vacuum drying oven at 60°C for 12 hours until constant weight to obtain sulfonated polystyrene divinylbenzene resin. (6) Add 5 g of niobium pentachloride to 200 mL of deionized water and stir vigorously with a magnetic force for 10 min until the solution is transparent. Adjust the pH of the solution to 2.1 with concentrated ammonium hydroxide and stir the mixture for 3 h. (7) The solid obtained by centrifugation in step (6) is thoroughly washed with deionized water, and the precipitate is dried in a vacuum drying oven at 80°C for 12 hours to constant weight to obtain niobium pentoxide; (8) Take 1 g of niobium pentoxide obtained in step (7), disperse it in 200 mL of 1 M H3PO4 solution and stir at room temperature for 48 h. Separate the solid by centrifugation, wash it thoroughly with deionized water, and dry it in a vacuum drying oven at 80 °C for 12 hours to constant weight to obtain phosphorylated niobium pentoxide. (9) Dissolve 0.87 g FeCl3·6H2O and 0.48 g Zn(NO3)2·6H2O in 30 mL of deionized water, then add 0.4 g urea as a dispersant, stir until the solid is completely dissolved, pour the mixture into a 100 mL polytetrafluoroethylene-lined hydrothermal reactor, seal it firmly and keep it in an oven at 180℃ for 8 h; (10) Wash the sample obtained in step (9) continuously with deionized water and dry it in a vacuum drying oven at 60°C for 3 hours. Then place it in a muffle furnace and gradually heat it to 400°C at a rate of 5°C / min and calcine it for 2 hours to obtain ZnFe2O4. (11) Weigh 0.8 g of niobium pentoxide phosphorylated obtained in step (8) and 0.2 g of ZnFe2O4 obtained in step (10), place them in a ball milling jar containing 50 g of ball milling beads, and continuously ball mill at a speed of 500 r / min for 2 h; (12) Take 5 g of the sulfonated resin obtained in step (5) and dissolve it in a mixture containing 0.25 g of the solid particles obtained in step (11), 100 mL of distilled water and 13.5 mL of acetone, and stir at room temperature for 24 h; (13) The solid obtained in step (12) was separated by centrifugation, thoroughly washed with deionized water, and dried in a vacuum drying oven at 60°C for 12 hours to constant weight to obtain the final catalyst, named ZF@NbP / PS-S.

[0008] The sulfonated resin-based composite solid acid obtained in (ii) is characterized by having an acid density of 152.41 μmol / L, a maximum reflection loss of -21.17 dB at a thickness of 6.5 mm, an effective absorption band that can cover 4.85-7.13 GHz, and an effective absorption bandwidth of 2.28 GHz.

[0009] The method for the synergistic acid-thermal degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst, as described in (iii), is characterized by the following steps: (1) Dissolve 50 mg of macrolide standard in a small amount of deionized water in a 100 mL beaker, and then dilute to 1000 mL volumetric flask with deionized water to obtain a macrolide antibiotic solution with a concentration of 50 mg / L. (2) Take 50 mL of the antibiotic solution from step (1) into a three-necked flask, and then add 0.015 g of the prepared sulfonated resin-based composite solid acid catalyst. Perform two parallel tests for each group. (3) The reaction system obtained in step (2) was continuously stirred for 8 minutes in a microwave experimental reactor with a microwave power of 350 W and a stirring rate of 400 rpm. Every minute, a sample (about 1 mL) was collected using a syringe needle, filtered through a 0.22 μm aqueous membrane, and placed in a liquid chromatography vial for later use. (4) Use high performance liquid chromatography to measure the changes in the concentration of macrolide antibiotics in the samples collected in step (3); (5) Preferably, the macrolide antibiotic in step (1) is tylosin.

[0010] The method for degrading macrolide antibiotics in the wastewater system described in (iv) is characterized in that the macrolide antibiotics include one or more of erythromycin, roxithromycin, erythromycin, fluerythromycin, clarithromycin, pyruvicin, azithromycin, spiramycin, and tylosin.

[0011] The method for the acid-thermal synergistic degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst, as described in (v), is characterized in that the solid acid catalyst can provide -SO3H in the wastewater system, which can act on the glycosidic bonds connecting the lactone ring and the sugar group of macrolide antibiotics. Under microwave radiation, residual oxygen-containing groups such as sulfonic acid groups and structural defects on the surface and edge of ZF@NbP / PS-S induce dipole polarization and defect polarization, respectively, which together enhance the catalytic system, thereby achieving efficient degradation of antibiotics.

[0012] The method for the synergistic degradation of macrolide antibiotic production wastewater by the microwave-absorbing solid acid catalyst described in (vi) is characterized in that the solid acid catalyst acts on wastewater containing high concentrations of macrolide antibiotics, and the removal rate of macrolide antibiotics can reach 100%, thereby achieving the removal of recalcitrant organic pollutants.

[0013] The method described in (vii) is characterized in that it can be applied to the pretreatment stage of wastewater treatment projects for macrolide antibiotic production, and significantly reduces the antibacterial activity of antibiotic wastewater before it enters conventional biological treatment.

[0014] The microwave-absorbing solid acid catalyst-thermal synergistic degradation method described in this invention is a novel method for the degradation of macrocyclic lactone antibiotics, and has the following advantages: 1. The method of the present invention for the acid-thermal synergistic degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst can effectively decompose high concentrations of macrolide antibiotics in antibiotic production wastewater, leaving no antibiotic residues.

[0015] 2. The microwave-absorbing solid acid catalyst prepared by this invention is inexpensive, readily available, green, and environmentally friendly. After use, it can be easily separated from the product for recycling, reducing secondary pollution to the environment caused by the catalyst itself, and is environmentally friendly.

[0016] 3. The method of the present invention provides mild hydrolysis conditions, simple reaction operation, and easy control of operating conditions during the treatment of macrolide antibiotic wastewater.

[0017] 4. The method of this invention can selectively hydrolyze and degrade macrolide antibiotics without interference from other coexisting substances in the wastewater. Therefore, this invention has excellent application prospects in the treatment of wastewater containing high concentrations of macrolide antibiotics. Attached Figure Description

[0018] Figure 1 This is a reflection loss curve of the sulfonated resin-based composite solid acid in this embodiment. Figure 2 The diagram shows the efficiency of the sulfonated resin-based composite solid acid prepared in this invention in acid-thermal synergistic degradation of tylosin under different microwave powers. Figure 3 The diagram shows the efficiency of the sulfonated resin-based composite solid acid prepared in this invention in acid-thermal synergistic degradation of tylosin under different dosages. Figure 4 The efficiency of sulfonated resin-based composite solid acid-thermal synergistic degradation of tylosin under different concentrations of chemical oxygen demand (COD) interference is shown in the figure. Figure 5 The efficiency of sulfonated resin-based composite solid acid-thermal synergistic degradation of tylosin under different concentrations of total nitrogen (TN) interference is shown in the graph. Figure 6 The efficiency of sulfonated resin-based composite solid acid-thermal synergistic degradation of tylosin prepared under different concentrations of humic acid (HA) interference is shown in the graph. Figure 7 The graph shows the efficacy of the sulfonated resin-based composite solid acid prepared in this invention in reducing tylosin after 5 cycles. Detailed Implementation

[0019] The present invention will be described in further detail with reference to specific embodiments, but the present invention is not limited to the following embodiments.

[0020] Example 1: A method for preparing a sulfonated resin-based composite solid acid, comprising the following steps: (1) Contact 3 g of polystyrene divinylbenzene resin with 30 mL of dichloroethane in a three-necked flask for 30 minutes to allow the polystyrene divinylbenzene resin to swell; (2) Add concentrated sulfuric acid (H2SO4, 98%) to the solution obtained in step (1) and stir to form a homogeneous solution; (3) Place the mixture obtained in step (2) in a water bath and maintain the temperature at 70°C. oC, the reaction time is 180 minutes, during which stirring is continuous; (4) wash the particles obtained in step (3) with a large amount of deionized water and ethanol alternately until neutral, and remove excess sulfonating reagent and swelling agent; (5) place the sulfonated product obtained in step (4) in a petri dish, and then dry it in a vacuum drying oven at 60°C for 12 hours to constant weight to obtain sulfonated polystyrene divinylbenzene resin; (6) add 5 g of niobium pentachloride to 200 mL of deionized water, stir vigorously with a magnetic force for 10 min until the solution is transparent, adjust the pH of the solution to 2.1 with concentrated ammonium hydroxide, and stir the mixture for 3 h; (7) separate the solid obtained in step (6) by centrifugation, wash thoroughly with deionized water, and dry the precipitate in a vacuum drying oven at 80°C for 12 hours to constant weight to obtain niobium pentoxide; (8) take 1 g of niobium pentoxide obtained in step (7), disperse it in 200 mL of 1 M H3PO4 solution and stir at room temperature for 48 minutes. h, the solid obtained by centrifugation was thoroughly washed with deionized water and dried in a vacuum drying oven at 80°C for 12 hours to constant weight to obtain niobium pentoxide phosphorylation; (9) 0.87 g FeCl3·6H2O and 0.48 g Zn(NO3)2·6H2O were dissolved in 30 mL of deionized water, and 0.4 g urea was added as a dispersant. The mixture was stirred until the solid was completely dissolved. The mixture was poured into a 100 mL polytetrafluoroethylene-lined hydrothermal reactor, sealed firmly, and kept in an oven at 180°C for 8 h; (10) the sample obtained in step (9) was continuously washed with deionized water and dried in a vacuum drying oven at 60°C for 3 hours. Then it was placed in a muffle furnace and heated to 400°C at a rate of 5 °C / min and calcined for 2 h to obtain ZnFe2O4; (11) 0.8 g of niobium pentoxide phosphorylation obtained in step (8) and 0.2 g of ZnFe2O4 obtained in step (10) were weighed and placed in a container containing 50 (12) Take 5 g of sulfonated resin obtained in step (5) and dissolve it in a mixture containing 0.25 g of solid particles obtained in step (11), 100 mL of distilled water and 13.5 mL of acetone. Stir at room temperature for 24 h. (13) Separate the solid obtained in step (12) by centrifugation, wash thoroughly with deionized water, and dry in a vacuum drying oven at 60 °C for 12 hours to constant weight to obtain the final catalyst, named ZF@NbP / PS-S.

[0021] Figure 1It can be seen that the sulfonated resin-based composite solid acid catalyst prepared with concentrated sulfuric acid as the sulfonating agent has good microwave absorption capability. The maximum reflection loss of ZF@NbP / PS-S reaches -21.17 dB at a thickness of 6.5 mm, the effective absorption band can cover 4.85-7.13 GHz, and the effective absorption bandwidth (EAB) reaches 2.28 GHz. The effective ball milling doping of ZnFe2O4 and niobium pentoxide phosphorylation allows ZnFe2O4 to be uniformly mixed into the resin surface and interior, generating more microwave interfaces and promoting the improvement of the microwave absorption performance of the composite solid acid.

[0022] Example 2: The sulfonated resin-based composite solid acid prepared in this invention undergoes acid-thermal synergistic degradation of macrolide antibiotics under different microwave powers. Dissolve 50 mg of tylosin standard in a small amount of deionized water in a 100 mL beaker, then dilute to a volumetric flask with deionized water to obtain a 50 mg / L tylosin solution. Take 50 mL of the prepared tylosin solution into a three-necked flask, then add 0.015 g of the prepared sulfonated resin-based composite solid acid catalyst. Stir continuously for 8 minutes at preset microwave powers (150, 250, 350, 450 W) at a stirring rate of 400 rpm. Collect approximately 1 mL of sample every minute using a syringe, filter through a 0.22 μm aqueous membrane, and measure the tylosin degradation dynamics using high-performance liquid chromatography (HPLC).

[0023] Figure 2 The results showed that as the microwave power increased from 150 W to 450 W, the energy converted into molecular vibrational polarization increased, leading to an increase in temperature and consequently, an improvement in the removal efficiency of tylosin and a gradual increase in the hydrolysis reaction efficiency. At any power level, 50 mg / L of tylosin could be completely degraded to 0 mg / L within 8 minutes. This performance represents a significant cost advantage for practical antibiotic production wastewater treatment, indicating that the solid acid catalyst has a clear performance advantage.

[0024] Example 3: The sulfonated resin-based composite solid acid prepared in this invention undergoes acid-thermal synergistic degradation of macrolide antibiotics under different dosages. Dissolve 50 mg of tylosin standard in a small amount of deionized water in a 100 mL beaker, then dilute to a 1000 mL volumetric flask with deionized water to obtain a 50 mg / L tylosin solution. Take 50 mL of the prepared tylosin solution into a three-necked flask, and then add 0.1 g / L, 0.2 g / L, 0.3 g / L, and 0.4 g / L of the prepared sulfonated resin-based composite solid acid catalyst, respectively. Stir continuously for 8 minutes at a microwave power of 350 W and a stirring rate of 400 rpm. Collect samples (approximately 1 mL) every minute using a syringe, filter through a 0.22 μm aqueous membrane, and measure the tylosin degradation dynamics using high-performance liquid chromatography (HPLC).

[0025] Figure 3 The results showed that the hydrolysis efficiency of tylosin increased with increasing catalyst dosage, especially at a catalyst dosage of 0.4 g / L, where tylosin could be completely hydrolyzed within 3 minutes. However, when the catalyst dosage exceeded 0.3 g / L, the increase in hydrolysis rate began to slow down. Excessively high catalyst concentrations interfered with microwave transmission or absorption, indicating that the dosage of the sulfonated resin-based composite solid acid gradually reached saturation, and further increasing the dosage was meaningless.

[0026] Example 4: The sulfonated resin-based composite solid acid prepared in this invention undergoes acid-thermal synergistic degradation of macrolide antibiotics under the coexistence of high concentrations of organic matter (COD) and antibiotics. Mixed solutions with COD concentrations of 0 mg / L, 500 mg / L, 1000 mg / L, 5000 mg / L, and 20000 mg / L, and a tylosin concentration of 50 mg / L were prepared using glucose to simulate antibiotic production wastewater containing high concentrations of organic matrix. 0.3 g / L of sulfonated resin-based composite solid acid was added under microwave power of 350 W, and the mixture was continuously stirred for 8 minutes at a stirring rate of 400 rpm. Samples (approximately 1 mL) were collected every minute using a syringe, filtered through a 0.22 μm aqueous membrane, and the degradation dynamics of tylosin were measured using high-performance liquid chromatography (HPLC).

[0027] Figure 4 The results showed that the degradation efficiency of tylosin by sulfonated resin-based composite solid acid was almost unaffected by changes in COD concentration. Even when the coexisting COD concentration increased to 20,000 mg / L, tylosin could still be completely removed within 4 minutes.

[0028] Example 5: The sulfonated resin-based composite solid acid prepared in this invention undergoes acid-thermal synergistic degradation of macrolide antibiotics under the coexistence of high concentrations of ammonia nitrogen (TN) and antibiotics. Mixed solutions with TN concentrations of 0 mg / L, 500 mg / L, and 1000 mg / L, and a tylosin concentration of 50 mg / L were prepared using peptone to simulate antibiotic production wastewater containing high concentrations of ammonia nitrogen. 0.3 g / L of sulfonated resin-based composite solid acid was added under microwave power of 350 W, and the mixture was continuously stirred for 8 minutes at a stirring rate of 400 rpm. Samples (approximately 1 mL) were collected every minute using a syringe, filtered through a 0.22 μm aqueous membrane, and the degradation dynamics of tylosin were measured using high-performance liquid chromatography (HPLC).

[0029] Figure 5 The results showed that the addition of TN in the concentration range of 0-1000 mg / L significantly inhibited the hydrolysis of tylosin, since peptone can also be hydrolyzed by solid acid. When the TN concentration was 500 mg / L, the half-life increased to 27.2834 min, but tylosin could still be removed by increasing the contact time.

[0030] Example 6: The sulfonated resin-based composite solid acid prepared in this invention undergoes acid-thermal synergistic degradation of macrolide antibiotics under the coexistence of high-concentration humic acid (HA) and antibiotics. Mixed solutions of humic acid with HA concentrations of 0 mg / L, 200 mg / L, and 500 mg / L, and tylosin concentration of 50 mg / L were prepared to simulate antibiotic production wastewater containing high concentrations of humic acid. 0.3 g / L of sulfonated resin-based composite solid acid was added under microwave power of 350 W, and the mixture was continuously stirred for 8 minutes at a stirring rate of 400 rpm. Samples (approximately 1 mL) were collected every minute using a syringe, filtered through a 0.22 μm aqueous membrane, and the degradation dynamics of tylosin were measured using high-performance liquid chromatography (HPLC).

[0031] Figure 6 The results showed that HA had a relatively small inhibitory effect on the degradation of tylosin by the sulfonated resin-based composite solid acid. Even with a coexisting HA concentration as high as 200 mg / L, 100% of tylosin could still be degraded within 10 minutes. The solid acid prepared in this invention can effectively treat pharmaceutical wastewater with high HA concentrations.

[0032] Example 7: The sulfonated resin-based composite solid acid prepared in this invention degrades macrolide antibiotics in 5 cycles. Dissolve 50 mg of tylosin standard in a small amount of deionized water in a 100 mL beaker, then dilute to a volumetric flask with deionized water to obtain a 50 mg / L tylosin solution. Take 50 mL of the prepared tylosin solution into a three-necked flask, then add 0.3 g / L of the prepared sulfonated resin-based composite solid acid catalyst. Stir continuously for 8 minutes at a microwave power of 350 W and a stirring rate of 400 rpm. Collect approximately 1 mL of sample every minute using a syringe, filter through a 0.22 μm aqueous membrane, and measure the tylosin degradation dynamics using high-performance liquid chromatography (HPLC). The sulfonated resin-based composite solid acid material is subjected to strong magnetic adsorption and centrifugation, repeatedly washed with distilled water, dried in a 60°C oven, and the reaction is repeated. The reaction process is repeated 5 times.

[0033] Figure 7 The results showed that the recycled sulfonated resin-based composite solid acid still achieved a 90% degradation rate of tylosin within 4 minutes in the third reaction. The degradation rate of tylosin decreased by only about 14% in the fifth reaction. The sulfonated resin-based composite solid acid prepared in this invention has good recyclability and is an economical, efficient, and environmentally friendly functional material.

[0034] The specific embodiments described above are merely preferred embodiments of the present invention. However, other aspects and embodiments will be obvious to those skilled in the art. Without departing from the principle of the present invention, several modifications and improvements can be made, all of which fall within the protection scope of this application.

Claims

1. A method for synergistically degrading macrolide antibiotic production wastewater by acid-thermal with wave-absorbing solid acid catalyst, characterized in that Using sulfonated resin-based composite solid acid, which has both abundant acidic sites and good microwave energy absorption characteristics, as a catalyst, the sulfonated resin-based composite solid acid is added to wastewater containing macrolide antibiotics to achieve acid-thermal synergistic hydrolysis and degradation of macrolide antibiotics.

2. The method of claim 1, wherein the wave-absorbing solid acid catalyst acid-thermal synergistically degrades the macrolide antibiotic production wastewater, characterized in that It can treat high-concentration antibiotic pharmaceutical wastewater. The process is simple and has a good degradation effect. The solid acid catalyst has low corrosivity, is green and safe, and can be recycled.

3. The sulfonated resin-based composite solid acid of claim 1, characterized in that The material preparation method is as follows: (1) Contact 3 g of polystyrene divinylbenzene resin with 30 mL of dichloroethane in a three-necked flask for 30 minutes to allow the polystyrene divinylbenzene resin to swell; (2) Add concentrated sulfuric acid to the solution obtained in step (1) and stir to form a homogeneous solution; (3) The mixture obtained in step (2) was placed in a water bath, and the temperature was kept at 70 o C, and the reaction time was 180 minutes, during which continuous stirring was performed. (4) Wash the particles obtained in step (3) with large amounts of deionized water and ethanol alternately until neutral to remove excess sulfonating reagent and swelling agent; (5) Place the sulfonated product obtained in step (4) in a petri dish, and then dry it in a vacuum drying oven at 60°C for 12 hours until constant weight to obtain sulfonated polystyrene divinylbenzene resin. (6) Add 5 g of niobium pentachloride to 200 mL of deionized water and stir vigorously with a magnetic force for 10 min until the solution is transparent. Adjust the pH of the solution to 2.1 with concentrated ammonium hydroxide and stir the mixture for 3 h. (7) The solid obtained by centrifugation in step (6) is thoroughly washed with deionized water, and the precipitate is dried in a vacuum drying oven at 80°C for 12 hours to constant weight to obtain niobium pentoxide; (8) Take 1 g of niobium pentoxide obtained in step (7), disperse it in 200 mL of 1 M H3PO4 solution and stir at room temperature for 48 h. Separate the solid by centrifugation, wash it thoroughly with deionized water, and dry it in a vacuum drying oven at 80 °C for 12 hours to constant weight to obtain phosphorylated niobium pentoxide. (9) Dissolve 0.87 g FeCl3·6H2O and 0.48 g Zn(NO3)2·6H2O in 30 mL of deionized water, then add 0.4 g urea as a dispersant, stir until the solid is completely dissolved, pour the mixture into a 100 mL polytetrafluoroethylene-lined hydrothermal reactor, seal it firmly and keep it in an oven at 180℃ for 8 h; (10) Wash the sample obtained in step (9) continuously with deionized water and dry it in a vacuum drying oven at 60°C for 3 hours. Then place it in a muffle furnace and gradually heat it to 400°C at a rate of 5°C / min and calcine it for 2 hours to obtain ZnFe2O4. (11) Weigh 0.8 g of niobium pentoxide phosphorylated obtained in step (8) and 0.2 g of ZnFe2O4 obtained in step (10), place them in a ball milling jar containing 50 g of ball milling beads, and continuously ball mill at a speed of 500 r / min for 2 h; (12) Take 5 g of the sulfonated resin obtained in step (5) and dissolve it in a mixture containing 0.25 g of the solid particles obtained in step (11), 100 mL of distilled water and 13.5 mL of acetone, and stir at room temperature for 24 h; (13) The solid obtained in step (12) was separated by centrifugation, thoroughly washed with deionized water, and dried in a vacuum drying oven at 60°C for 12 hours to constant weight to obtain the final catalyst, named ZF@NbP / PS-S.

4. The sulfonated resin-based composite solid acid obtained in claim 3, characterized in that Its acid density reaches 152.41 μmol / L, and the maximum reflection loss can reach -21.17 dB with a thickness of 6.5 mm. The effective absorption band can cover 4.85-7.13 GHz, and the effective absorption bandwidth (EAB) reaches 2.28 GHz.

5. The method for the synergistic acid-thermal degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst as described in claim 1, characterized in that... The application can be completed by following these steps: (1) Dissolve 50 mg of macrolide standard in a small amount of deionized water in a 100 mL beaker, and then dilute to 1000 mL volumetric flask with deionized water to obtain a macrolide antibiotic solution with a concentration of 50 mg / L. (2) Take 50 mL of the antibiotic solution from step (1) into a three-necked flask, and then add 0.015 g of the prepared sulfonated resin-based composite solid acid catalyst. Perform two parallel tests for each group. (3) The reaction system obtained in step (2) was continuously stirred for 8 minutes in a microwave experimental reactor with a microwave power of 350 W and a stirring rate of 400 rpm. Every minute, a sample (about 1 mL) was collected using a syringe needle, filtered through a 0.22 μm aqueous membrane, and placed in a liquid chromatography vial for later use. (4) Use high performance liquid chromatography to measure the changes in the concentration of macrolide antibiotics in the samples collected in step (3); (5) Preferably, the macrolide antibiotic in step (1) is tylosin.

6. The method for degrading macrolide antibiotics in the wastewater system according to claim 5, characterized in that... The macrolide antibiotics include one or more of the following: erythromycin, roxithromycin, erythromycin, fluerythromycin, clarithromycin, tylosin, azithromycin, spiramycin, and tylosin.

7. The method for the synergistic acid-thermal degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst as described in claim 1, characterized in that... Solid acid catalysts can provide -SO3H in wastewater systems, which can act on the glycosidic bonds connecting the lactone ring and sugar group of macrocyclic lactone antibiotics. Under microwave irradiation, residual oxygen-containing groups such as sulfonic acid groups and structural defects on the surface and edge of ZF@NbP / PS-S induce dipole polarization and defect polarization, respectively, which together enhance the catalytic system and thus achieve efficient degradation of antibiotics.

8. The method for the synergistic acid-thermal degradation of macrolide antibiotic production wastewater using a microwave-absorbing solid acid catalyst as described in claim 1, characterized in that the solid acid catalyst, when acting on wastewater containing high concentrations of macrolide antibiotics, can achieve a 100% removal rate of macrolide antibiotics, thereby removing recalcitrant organic pollutants.

9. The method according to claim 1, characterized in that... This method can be applied to the pretreatment stage of wastewater treatment projects for macrolide antibiotic production, significantly reducing its antibacterial activity before the antibiotic wastewater enters conventional biological treatment.

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