A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater

By using a two-stage system of wide-pH Fenton and anaerobic activated sludge microorganisms, the problems of incomplete mineralization and low removal efficiency in the treatment of sulfonamide antibiotic wastewater in existing technologies have been solved, achieving efficient and thorough wastewater treatment and reducing environmental pollution.

CN118239589BActive Publication Date: 2025-11-14TAIYUAN UNIVERSITY OF TECHNOLOGY
View PDF 2 Cites 0 Cited by

Patent Information

Application Number
CN202410628987.5
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-05-21
Publication Date
2025-11-14
Estimated Expiration
2044-05-21

AI Technical Summary

Technical Problem

Existing technologies for treating wastewater containing various sulfonamide antibiotics suffer from incomplete mineralization, severe secondary pollution, and limitations imposed by low pH values ​​in the Fenton oxidation system. Biological removal methods, on the other hand, have low efficiency and cannot meet wastewater treatment requirements.

Method used

A two-stage system using a wide-pH Fenton system and anaerobic activated sludge microorganisms was adopted. The sulfonamide antibiotics in the wastewater were pre-oxidized in the wide-pH Fenton system, and then further mineralized in the anaerobic activated sludge system. The iron ions and polyphosphate complexes were used to activate molecular oxygen to generate active oxides, which were then combined with the degradation of undecomposed organic matter by microorganisms.

Benefits of technology

It achieves efficient and rapid oxidative decomposition of antibiotics under neutral conditions, with a removal rate of 96.79%. Furthermore, it significantly improves the removal efficiency of sulfonamide antibiotics in wastewater and reduces environmental pollution through microbial mineralization of byproducts.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure CN118239589B_ABST
    Figure CN118239589B_ABST
Patent Text Reader

Abstract

This invention discloses a method for the efficient degradation and deep mineralization of sulfonamide antibiotics in wastewater, relating to the field of wastewater treatment technology. The method includes the following steps: preparing a phosphate buffer solution and adding Na6TPP working solution, adding SAs working solution, adjusting the pH, adding iron filings and carbon fibers, injecting air, and reacting for 3 hours to obtain a reaction solution; taking sterilized nutrient solution containing SAs-containing anaerobic activated sludge; adding activated sludge to the sterile nutrient solution to prepare the reaction solution, sealing and shaking for incubation; allowing it to stand for seven days after degradation, repeating the preparation of sterile nutrient solution, continuing enrichment, and obtaining SAs-containing activated sludge; after removing iron from the reaction solution using anion exchange resin, adding trace elements and vitamins to prepare an anaerobic activated sludge nutrient solution; inoculating the acclimated SAs-containing activated sludge into the nutrient solution, shaking for incubation, and continuing to degrade the remaining organic matter after pre-oxidation. This invention deeply mineralizes SAs, thereby increasing the degradation rate of sulfonamide antibiotics and total organic carbon.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and particularly to the field of antibiotic treatment in wastewater, specifically a method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater. Background Technology

[0002] In recent years, antibiotics have been widely used in agriculture, animal husbandry, and the medical industry. However, improper disposal of antibiotics, such as the indiscriminate discharge of pharmaceutical wastewater, livestock wastewater, and agricultural wastewater, has led to their entry into the environment, inducing the development of large numbers of resistant bacteria (ARBs) and antibiotic resistance genes (ARGs), posing a significant threat to human health. The persistence and poor biodegradability of antibiotics in the environment have drawn widespread attention from researchers to degradation technologies.

[0003] Antibiotics are classified into quinolones, imidazoles, tetracyclines, sulfonamides, and lactones, among others. Sulfonamides inhibit the growth of various Gram-positive bacteria, Gram-negative bacteria, and Nocardia spp., and can treat diseases caused by a variety of bacterial infections. In actual wastewater, multiple sulfonamide antibiotics (SAs) may coexist. Compared to the degradation of a single antibiotic, this type of wastewater environment places higher demands on wastewater treatment processes.

[0004] Advanced oxidation technologies, exemplified by the Fenton reaction, can efficiently degrade various antibiotic-like recalcitrant pollutants, but they suffer from drawbacks such as incomplete mineralization and severe secondary pollution. Furthermore, in existing Fenton oxidation systems, when the pH value is above 2.5, Fe(III) precipitation reduces the concentration of Fe(II) produced in the solution, and the low pH operating requirement limits the practical application of the Fenton oxidation process. While biological methods do not cause secondary pollution, their removal efficiency for antibiotic-like pollutants is low, and incomplete removal is also a common problem. Summary of the Invention

[0005] To address the problems of incomplete mineralization, severe secondary pollution, and low pH operation in Fenton oxidation systems when treating wastewater containing multiple sulfonamide antibiotics, and the low removal efficiency and incomplete removal of biological methods, which cannot meet the requirements of existing wastewater treatment, this invention provides a method for the efficient degradation and deep mineralization of sulfonamide antibiotics in wastewater.

[0006] This invention is achieved using the following techniques:

[0007] This invention provides a method for the efficient degradation and deep mineralization of sulfonamide antibiotics in wastewater. The method employs a wide-pH Fenton system for the efficient removal of sulfonamide antibiotics (SAs), and specifically includes the following steps:

[0008] a. Preparation of electrolyte solution

[0009] aa, Preparation of supporting electrolytes

[0010] Take 2.6 g / L NH4Cl, 3 g / L K2HPO4, and 1 g / L KH2PO4, mix them to prepare a phosphate buffer, and add 1 mL of 50 mM Na6TPP working solution to every 100 mL of phosphate buffer to obtain a supporting electrolyte with an initial Na6TPP concentration of 0.5 mM.

[0011] ab, Preparation of electrolyte solution

[0012] Take 100 mL of the supporting electrolyte prepared in step aa into an Erlenmeyer flask, add SAs working solution with a concentration of 2 mg / mL, which includes 2 mg / mL sulfadiazine, 2 mg / mL sulfamethoxazole and 2 mg / mL sulfaquinoxaline, so that the final concentration of SAs in the system is 5 mg / L, adjust the pH to 6.5, and prepare the electrolyte solution.

[0013] b. Construct a wide-pH Fenton system

[0014] Add 0.5g of iron filings and 5cm of [unclear text] to every 100mL of the electrolyte solution prepared in step ab. 3 The carbon fiber, wherein the particle size of the iron filings is less than 0.55 mm, the iron filings act as precursors of active oxygen molecules in the Fenton system, and air is injected into the solution at a rate of 2 L / min under 30°C conditions, and the reaction is carried out for 3 hours to obtain the reaction solution after pre-oxidation.

[0015] This method uses a wide-pH Fenton system to remove sulfonamide antibiotics. Compared with the existing Fenton system, this method has a high removal rate and shows a significant degradation advantage.

[0016] This invention also employs the following techniques:

[0017] This invention provides a method for the efficient degradation and deep mineralization of sulfonamide antibiotics in wastewater. The method employs a wide-pH Fenton-microbial two-stage system for the deep mineralization of sulfonamide antibiotics, and includes the following steps:

[0018] a. Preparation of electrolyte solution

[0019] aa, Preparation of supporting electrolytes

[0020] Take 2.6 g / L NH4Cl, 3 g / L K2HPO4, and 1 g / L KH2PO4, mix them to prepare a phosphate buffer, and add 1 mL of 50 mM Na6TPP working solution to every 100 mL of phosphate buffer to obtain a supporting electrolyte with an initial Na6TPP concentration of 0.5 mM.

[0021] ab, Preparation of electrolyte solution

[0022] Take 100 mL of the supporting electrolyte prepared in step aa into an Erlenmeyer flask, add SAs working solution with a concentration of 2 mg / mL, which includes 2 mg / mL sulfadiazine, 2 mg / mL sulfamethoxazole and 2 mg / mL sulfaquinoxaline, so that the final concentration of SAs in the system is 5 mg / L, adjust the pH to 6.5, and prepare the electrolyte solution.

[0023] b. Construct a wide-pH Fenton system

[0024] Add 0.5g of iron filings and 5cm of [unclear text] to every 100mL of the electrolyte solution prepared in step ab. 3 The carbon fiber, wherein the particle size of the iron filings is less than 0.55 mm, the iron filings serve as precursors of active oxygen molecules in the Fenton system, and air is injected into the solution at a rate of 2 L / min at 30 °C, and the reaction is carried out for 3 hours to obtain the reaction solution after pre-oxidation.

[0025] c. Enrichment culture of SAs anaerobic microorganisms

[0026] ca, prepare sterile nutrient solution

[0027] Take 80 mL of anaerobic activated sludge nutrient solution and place it in a 100 mL anaerobic bottle. The anaerobic activated sludge nutrient solution includes 0.02 g / L K2HPO4, 0.02 g / L KH2PO4, 0.5 g / L NaCl, 10 mL / L trace elements, 0.01 mL / L vitamins, and 5 mg / L SAs; among which, SAs include 5 mg / mL sulfadiazine, 5 mg / mL sulfamethoxazole, and 5 mg / mL sulfaquinoxaline; start the reactor, continuously purge with nitrogen gas for 2 min, seal and sterilize at 121℃ for 20 min to prepare a sterile nutrient solution;

[0028] cb, shaking culture

[0029] Add 20 mL of activated sludge to the sterile nutrient solution to prepare the reaction solution, seal it, and incubate it at 35°C with shaking at 150 rpm / min.

[0030] cc, enrichment culture

[0031] After the three SAs (sulfadiazine, sulfamethoxazole, and sulfaquinoxaline) in the reaction solution have been degraded by microorganisms for seven days, step ca is repeated to prepare a sterile nutrient solution. The anaerobic bottle after step cb is left to stand for 1 hour, the supernatant is discarded, and the bottom activated sludge is placed in the sterile nutrient solution to continue enriching the SAs functional microorganisms.

[0032] In the second and third acclimatization cycles, 10 mL of activated sludge from the previous cycle was taken and an equal amount of fresh activated sludge was added as a source of functional microorganisms to ensure the rapid enrichment of functional microorganisms.

[0033] The microorganisms are continuously acclimatized for multiple cycles until they can stably degrade SAs in the wastewater, thus producing acclimatized SAs activated sludge.

[0034] d. Domestication of deep mineralization functional microorganisms

[0035] After removing iron from the reaction solution prepared in step b using anion exchange resin, 10 mL / L of trace elements and 0.01 mL / L of vitamins were added to prepare an anaerobic activated sludge nutrient solution.

[0036] Microorganisms in the anaerobic system were used to further mineralize the SAs effluent after pre-oxidation in the Fenton system. 20 mL of SAs activated sludge prepared in step cc was inoculated into every 80 mL of nutrient solution and cultured with shaking at 35 °C to continue degrading the remaining organic matter after pre-oxidation. The total organic carbon concentration and SAs concentration were monitored.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] In this invention, a method for deep mineralization of salicylates (SAs) in wastewater utilizes a wide-pH Fenton system. In this system, iron ions, in combination with suitable ligands, can activate molecular oxygen to generate H₂O₂ and •OH. Polyphosphate (TPP) is a superior ligand that can combine with Fe(II) to produce even more H₂O₂ and •OH. The addition of TPP prevents the precipitation of Fe(III) in neutral or even weakly alkaline pH ranges, thus broadening the application scope of Fenton oxidation. This wide-pH Fenton system can rapidly oxidize and decompose mixed SAs in wastewater within a short time.

[0039] Experiments have shown that, using this method, after reacting for 80 minutes under near-neutral pH conditions, the removal rate of SAs can reach 96.79%, which is significantly better than the existing Fenton system. This represents a significant breakthrough in the applicability of the Fenton system and a remarkable improvement in removal efficiency.

[0040] Furthermore, in the method for deep mineralization of SAs in wastewater designed in this invention, a wide-pH Fenton system with TPP buffer as the electrolyte base is combined with anaerobic activated sludge microorganisms to treat wastewater containing mixed SAs. After the target antibiotics in the wastewater are rapidly degraded by Fenton pre-oxidation, the byproducts in the pre-oxidized effluent are further removed in the anaerobic activated sludge system, thereby achieving more thorough removal of SAs in a short period of time. This method not only retains the advantage of the wide-pH Fenton system in rapidly oxidizing and decomposing mixed SAs in wastewater in a short time, but also achieves deeper removal of SAs in the pre-oxidized effluent under the action of microorganisms in the subsequent anaerobic activated sludge system. That is, the anaerobic microorganisms in the anaerobic activated sludge system can use the organic matter that has not been decomposed in the wide-pH Fenton pre-oxidation system to produce methane, carbon dioxide, etc., which promotes the mineralization of pollutants and achieves deeper mineralization of SAs in wastewater, thereby reducing the pollution of SAs and their byproducts to the ecological environment.

[0041] Experiments show that the coupling of a wide-pH Fenton system and an anaerobic activated sludge microbial system has a better removal effect than the wide-pH Fenton system and the pure anaerobic activated sludge system. Moreover, the removal effect of this two-stage process on SAs and TOC remains basically stable after three coupling cycles. Attached Figure Description

[0042] Figure 1 Example 1 and Comparative Examples 1 and 2: Degradation rate of SAs.

[0043] Figure 2 Examples 1, 2 and Comparative Example 3 show the TOC removal rate after degradation and the reaction end time point, which are all the time points when the SAs mineralization effect is optimal during the current reaction process. Detailed Implementation

[0044] The specific embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Example 1

[0045] A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, comprising a wide-pH Fenton system in this embodiment, includes the following steps:

[0046] a. Preparation of electrolyte solution

[0047] aa, Preparation of supporting electrolytes

[0048] Take 2.6 g / L NH4Cl, 3 g / L K2HPO4, and 1 g / L KH2PO4, mix them to prepare a phosphate buffer, and add 1 mL of 50 mM Na6TPP working solution to every 100 mL of phosphate buffer to obtain a supporting electrolyte with an initial Na6TPP concentration of 0.5 mM.

[0049] ab, Preparation of electrolyte solution

[0050] Take 100 mL of the supporting electrolyte prepared in step aa into an Erlenmeyer flask, add SAs working solution with a concentration of 2 mg / mL, which includes 2 mg / mL sulfadiazine, 2 mg / mL sulfamethoxazole and 2 mg / mL sulfaquinoxaline, so that the final concentration of SAs in the system is 5 mg / L, adjust the pH to 6.5, and prepare the electrolyte solution.

[0051] b. Construct a wide-pH Fenton system

[0052] Add 0.5g of iron filings and 5cm of [unclear text] to every 100mL of the electrolyte solution prepared in step ab. 3 The carbon fiber, wherein the particle size of the iron filings is less than 0.55 mm, the iron filings are used as precursors of active oxygen molecules in the Fenton system, and air is injected into the solution at a rate of 2 L / min using an air pump in a constant temperature water bath at 30 °C, and the reaction is carried out for 3 hours to obtain the reaction solution after pre-oxidation.

[0053] The degradation effect of the wide pH Fenton system on SAs was observed and the degradation rate was calculated. After the degradation was completed, the total organic carbon concentration in the system was calculated and the degradation rate was calculated. Comparative Example 1

[0054] A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, wherein the comparative example constitutes a Fe-containing Fenton system, includes the following steps:

[0055] In Example 1, the 0.5 mM Na6TPP in step a of preparing the electrolyte solution was replaced with a 0.5 mM sodium sulfate solution, and the addition of 5 cm in step b was omitted. 3 The carbon fiber is used, and the rest of the operation is exactly the same.

[0056] The degradation effect of the ordinary Fenton system on SAs was observed, and the degradation rate was calculated. Comparative Example 2

[0057] A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, wherein the comparative example comprises a Fenton system containing only Fe and polyphosphate electrolyte, includes the following steps:

[0058] In step b of Example 1, omit the addition of 5cm. 3 The carbon fiber was used, and all other operations were exactly the same as those in Comparative Example 1.

[0059] The degradation effects of Fe and polyphosphate electrolyte solutions on SAs in a wide pH Fenton system were observed. The concentration changes of different groups of sulfonamide antibiotics were detected by high performance liquid chromatography, and the degradation rate was calculated.

[0060] Combining Example 1 with Comparative Examples 1 and 2, the effects of three factors—Fe, carbon fiber, and polyphosphate electrolyte solution—on the degradation rate of SAs in the wide pH Fenton system can be determined. Figure 1 As shown, after 80 min of reaction, the removal rate of SAs in the Fe-containing Fenton system (Comparative Example 1) was 46.72%, the removal rate of SAs in the Fe-containing Fenton system (Comparative Example 2) was 89.66%, and the removal rate of SAs in the wide pH Fenton system (Example 1) reached 96.79%, demonstrating a significant degradation advantage. Example 2

[0061] A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, in this embodiment, constitutes a wide-pH Fenton-microbe two-stage system, including the following steps:

[0062] a. Preparation of electrolyte solution

[0063] aa, Preparation of supporting electrolytes

[0064] Take 2.6 g / L NH4Cl, 3 g / L K2HPO4, and 1 g / L KH2PO4, mix them to prepare a phosphate buffer, and add 1 mL of 50 mM Na6TPP working solution to every 100 mL of phosphate buffer to obtain a supporting electrolyte with an initial Na6TPP concentration of 0.5 mM.

[0065] ab, Preparation of electrolyte solution

[0066] Take 100 mL of the supporting electrolyte prepared in step aa into an Erlenmeyer flask, add SAs working solution with a concentration of 2 mg / mL, which includes 2 mg / mL sulfadiazine, 2 mg / mL sulfamethoxazole and 2 mg / mL sulfaquinoxaline, so that the final concentration of SAs in the system is 5 mg / L, adjust the pH to 6.5, and prepare the electrolyte solution.

[0067] b. Construct a wide-pH Fenton system

[0068] Add 0.5g of iron filings and 5cm of [unclear text] to every 100mL of the electrolyte solution prepared in step ab. 3 The carbon fiber, wherein the particle size of the iron filings is less than 0.55 mm, the iron filings are used as precursors of active oxygen molecules in the Fenton system, and air is injected into the solution at a rate of 2 L / min using an air pump in a constant temperature water bath at 30 °C, and the reaction is carried out for 3 hours to obtain the reaction solution after pre-oxidation.

[0069] c. Enrichment culture of SAs anaerobic microorganisms

[0070] ca, to prepare sterile nutrient solution

[0071] Take 80 mL of anaerobic activated sludge nutrient solution and place it in a 100 mL anaerobic bottle. The anaerobic activated sludge nutrient solution includes 0.02 g / L K2HPO4, 0.02 g / L KH2PO4, 0.5 g / L NaCl, 10 mL / L trace elements, 0.01 mL / L vitamins, and 5 mg / L SAs; among which, SAs include 5 mg / mL sulfadiazine, 5 mg / mL sulfamethoxazole, and 5 mg / mL sulfaquinoxaline; start the reactor, continuously purge with nitrogen gas for 2 min, seal and sterilize at 121℃ for 20 min using a high-pressure steam sterilizer to prepare a sterile nutrient solution;

[0072] cb, shaking culture

[0073] Add 20 mL of activated sludge to the sterilized nutrient solution to prepare a reaction solution. Seal the solution with a high-temperature resistant T-type rubber stopper and culture it in a constant temperature shaking incubator at 35°C and a shaking speed of 150 rpm / min.

[0074] cc, enrichment culture

[0075] After the three SAs in the reaction solution have been degraded by microorganisms for seven days, repeat step ca to prepare sterilized nutrient solution. Let the anaerobic bottle cultured in step cb stand for 1 hour, discard the supernatant, and take the bottom activated sludge and place it in the sterilized nutrient solution to continue enriching SAs functional microorganisms.

[0076] In the second and third acclimatization cycles, 10 mL of activated sludge from the previous cycle was taken and an equal amount of fresh activated sludge was added as a source of functional microorganisms to ensure the rapid enrichment of functional microorganisms.

[0077] The microorganisms are continuously acclimatized for multiple cycles until they can stably degrade SAs in the wastewater, thus producing acclimatized SAs activated sludge.

[0078] d. Domestication of deep mineralization functional microorganisms

[0079] After removing iron from the reaction solution prepared in step b using anion exchange resin, 10 mL / L of trace elements and 0.01 mL / L of vitamins were added to prepare an anaerobic activated sludge nutrient solution.

[0080] Microorganisms in an anaerobic system were used to further mineralize the SAs effluent after pre-oxidation in the Fenton system. 20 mL of SAs activated sludge prepared in step cc was inoculated into every 80 mL of nutrient solution and cultured with shaking at 35 °C to continue degrading the remaining organic matter after pre-oxidation. The TOC (total organic carbon) and SAs concentration were monitored to observe the degradation effect of the wide pH Fenton system and the two-stage system of deep mineralization functional microorganisms on SAs. After the SAs degradation was completed, the total organic carbon concentration in the system was calculated. Comparative Example 3

[0081] A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, wherein the sulfonamides in the wastewater in this comparative example are treated only by microorganisms, includes the following steps:

[0082] a. Prepare a sterile nutrient solution

[0083] Take 80 mL of anaerobic activated sludge nutrient solution and place it in a 100 mL anaerobic bottle. The anaerobic activated sludge nutrient solution includes 0.02 g / L K2HPO4, 0.02 g / L KH2PO4, 0.5 g / L NaCl, 10 mL / L trace elements, 0.01 mL / L vitamins, and 5 mg / L SAs; among which, SAs include 5 mg / mL sulfadiazine, 5 mg / mL sulfamethoxazole, and 5 mg / mL sulfaquinoxaline; start the reactor, continuously purge with nitrogen gas for 2 min, seal and sterilize at 121℃ for 20 min using a high-pressure steam sterilizer to prepare a sterile nutrient solution;

[0084] b. Shaking culture

[0085] Add 20 mL of activated sludge to the sterilized nutrient solution to prepare a reaction solution. Seal the solution with a high-temperature resistant T-type rubber stopper and incubate it in a constant temperature shaking incubator at 35°C and a shaking speed of 150 rpm / min.

[0086] c, enrichment culture

[0087] After the three SAs in the reaction solution have been degraded by microorganisms for seven days, the sterile nutrient solution prepared in step a is repeated. The anaerobic bottle after step b culture is left to stand for 1 hour, the supernatant is discarded, and the bottom activated sludge is placed in the sterile nutrient solution to continue enriching the SAs functional microorganisms.

[0088] Continuous domestication for multiple cycles until the microorganisms can stably degrade SAs in wastewater;

[0089] The degradation effects of acclimated SAs activated sludge on SAs and TOC were observed, and the degradation rate was calculated.

[0090] After the degradation of Example 1 (wide pH Fenton system), Example 2 (wide pH Fenton-microbial two-stage system), and Comparative Example 3 (SAs anaerobic activated sludge system) was completed, the total organic carbon content in the wastewater was measured using a TOC analyzer, and the TOC removal rate was calculated as follows: Figure 2As shown: Example 1 used a wide-pH Fenton system, Comparative Example 3 used a pure anaerobic activated sludge system, while Example 2 used a coupling of a wide-pH Fenton system and an anaerobic activated sludge microbial system, which enabled the TOC removal rate to reach 83.12% within 3 days, an increase of 67.46% and 45.69% compared to Example 1 and Comparative Example 3, respectively. Meanwhile, the removal efficiency of this two-stage process for SAs and TOC remained basically stable after three coupling cycles.

[0091] The scope of protection claimed by this invention is not limited to the specific embodiments described above. Moreover, for those skilled in the art, this invention can have various modifications and alterations. Any modifications, improvements, and equivalent substitutions made within the concept and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater, characterized in that: Includes the following steps: a. Preparation of electrolyte solution Take 2.6 g / L NH4Cl, 3 g / L K2HPO4, and 1 g / L KH2PO4, mix them to prepare a phosphate buffer, and add 50 mM Na6TPP working solution to the phosphate buffer to obtain a supporting electrolyte with an initial Na6TPP concentration of 0.5 mM. Add the supporting electrolyte to the SAs working solution with a concentration of 2 mg / mL to make the final concentration of SAs in the system 5 mg / L, adjust the pH to 6.5, and prepare the electrolyte solution; b. Construct a wide-pH Fenton system Add 0.5g of iron filings and 5cm of [unclear text] to every 100mL of the electrolyte solution prepared in step a. 3 Carbon fibers were subjected to air injection into a solution at a rate of 2 L / min at 30 °C, and the reaction was carried out for 3 hours to obtain a reaction solution after pre-oxidation. c. Enrichment culture of SAs anaerobic microorganisms Take the anaerobic activated sludge nutrient solution and put it into an anaerobic bottle with an SA concentration of 5 mg / L. Start the reactor, continuously introduce nitrogen gas for 2 min, seal and sterilize at 121℃ for 20 min to prepare a sterile nutrient solution. Add 20 mL of activated sludge to the sterile nutrient solution to prepare the reaction solution, seal it, and incubate it at 35°C with shaking at 150 rpm / min. After the SAs in the reaction solution are degraded by microorganisms for seven days, the sterile nutrient solution is prepared again. The shaken anaerobic bottle is left to stand for 1 hour. The bottom activated sludge is placed in the sterile nutrient solution to continue enriching the SAs functional microorganisms. The process is repeated for multiple cycles until the microorganisms can stably degrade the SAs in the wastewater, and the acclimated SAs activated sludge is obtained. d. Domestication of deep mineralization functional microorganisms After removing iron from the reaction solution prepared in step b using anion exchange resin, 10 mL / L of trace elements and 0.01 mL / L of vitamins were added to prepare an anaerobic activated sludge nutrient solution. The SAs activated sludge prepared in step c was inoculated into the nutrient solution and cultured with shaking at 35°C to continue degrading the remaining organic matter after pre-oxidation. The concentrations of TOC (total organic carbon) and SAs were monitored.

2. The method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater according to claim 1, characterized in that: In step c, during the second and third acclimatization cycles, 10 mL of activated sludge from the previous cycle is taken, and an equal amount of fresh activated sludge is added as a source of functional microorganisms.

3. The method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater according to claim 1, characterized in that: In step d, 20 mL of SAs activated sludge prepared in step c is inoculated into every 80 mL of nutrient solution.

4. The method for efficiently degrading and deeply mineralizing sulfonamide antibiotics in wastewater according to claim 1, characterized in that: In step b, the particle size of the iron filings is less than 0.55 mm.

Citation Information

Patent Citations

  • Molecular oxygen activation-coupled water treatment method employing high-efficiency neutral electro-fenton oxidation

    CN103864183A

  • Novel electro-Fenton system

    CN106517443A