A PANI / AZeo-nZVI material, its preparation method, and its application in treating high-salinity wastewater.

Abstract

A PANI / AZeo-nZVI material, its preparation, and its application in treating high-salinity wastewater are disclosed. The preparation method utilizes a polyaniline / zeolite (PANI / zeo) composite material as a carrier. This PANI / zeolite composite carrier enhances the selectivity for target pollutants. PANI encapsulates the zeolite to form a porous conductive network, retaining the adsorption properties of the zeolite while accelerating electron transfer through PANI's conductivity. This effectively solves the problems of nano-zero-valent iron and polyaniline agglomeration, addressing the selectivity issue in pollutant decomposition. It accelerates the migration of pollutants to the surface of the composite material, thereby accelerating the decomposition of antibiotics and improving the activity of anaerobic ammonia oxidation bacteria. This addresses the long-term performance suppression and slow recovery issues of anaerobic ammonia oxidation systems under high-salt environments and oxytetracycline pollution.

Description

Technical Field

[0001] This invention belongs to the field of high-salinity wastewater treatment technology, specifically relating to a PANI / AZeo-nZVI material and its preparation method, as well as its application in treating high-salinity wastewater containing antibiotics in an ammonia oxidation wastewater treatment system. Background Technology

[0002] Many industrial production processes generate large quantities of complex and difficult-to-degrade high-salt wastewater. Direct discharge can cause environmental problems such as soil salinization and eutrophication of water bodies. In particular, excessive discharge of nitrogen-containing wastewater can affect water quality and seriously threaten human health. Anaerobic ammonia oxidation (Anammox) is a process that utilizes anaerobic ammonia-oxidizing bacteria to degrade ammonia nitrogen (NH4+). + ) and nitrite (NO2) - Biological denitrification technology, which directly converts nitrogen into nitrogen (N2), is widely studied as an economical and sustainable biological denitrification technology due to its advantages of high denitrification performance, no need for organic carbon sources, and low energy consumption.

[0003] However, anaerobic ammonia oxidizing bacteria (AnAOB) grow slowly, and in actual wastewater, the presence of toxic antibiotics severely inhibits the stable denitrification performance of the process. For example, tetracycline antibiotics, due to their low cost and widespread use, and high solubility in water, have been detected in many regions; oxytetracycline (OTC) accounts for 82% of the tetracyclines detected in various locations. OTC accumulates in wastewater treatment plants through various pathways. Even when diluted to low levels, under long-term stress, it can damage cell structure, inhibit intracellular protein synthesis, reduce the secretion of extracellular polymeric substances (EPS), and significantly weaken the resistance of microorganisms to adverse factors. It has been reported that when the OTC concentration increases from 0 to 22 mg / L, anaerobic ammonia oxidation activity is severely inhibited, and NH4+... + -N removal efficiency dropped sharply to 25%. The relative abundance of the corresponding dominant bacterial genera decreased from 14.41% to 4.1%.

[0004] Polyaniline (PANI) possesses linear macromolecular chains with abundant amine and imine functional groups, exhibiting excellent adsorption and conductivity for various pollutants. It also demonstrates stability and some biocompatibility. Its ease of synthesis, tunable morphology, and chemical regeneration through doping / dedoping, along with its low-cost precursor / monomer profile and ability to be blended with various polymers and fillers through in-situ polymerization, have led to extensive research on its adsorption of pollutants. However, pure PANI is prone to aggregation, reducing its effective surface area. Natural zeolite, as an aluminosilicate mineral, is composed of two basic units: oxysilicon tetrahedra and oxyaluminum tetrahedra. Their framework structure contains interconnected voids filled with cations that can exchange with other cations (such as aniline cations). Using zeolite as a carrier, organic modifiers can change the surface properties of clay from hydrophilic to hydrophobic, significantly enhancing its affinity for organic pollutants. In recent years, nano-sized zero-valent iron (nZVI) has attracted widespread attention for its application in removing heavy metal ions and organic pollutants from wastewater. Its application in Anammox has also garnered significant interest. NZVI is used to lower the redox potential in the environment, creating a favorable anaerobic environment for the growth of anaerobic ammonium oxidation. However, in a high-salt, neutral environment, nZVI tends to aggregate, and salt ions compete with target pollutants for active sites on the surface of the nZVI. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a PANI / AZeo-nZVI material and its preparation method, as well as its application in treating high-salt wastewater containing antibiotics in an anaerobic ammonia oxidation wastewater treatment system. The concept lies in using a polyaniline / zeolite (PANI / zeo) composite material as a carrier. The PANI / zeolite composite carrier enhances the selectivity for target pollutants. PANI encapsulates the zeolite to form a porous conductive network, retaining the adsorption properties of the zeolite while accelerating electron transfer through PANI's conductivity. This effectively solves the problems of nano-zero-valent iron and polyaniline agglomeration, and addresses the selectivity issue in pollutant decomposition. It accelerates the migration of pollutants to the surface of the composite material, thereby accelerating the decomposition of antibiotics and improving the activity of anaerobic ammonia oxidation bacteria. This solves the problem of long-term performance inhibition and slow performance recovery in anaerobic ammonia oxidation systems under high-salt environments and oxytetracycline pollution.

[0006] In a first aspect, the present invention provides a method for preparing PANI / AZeo-nZVI material, comprising the following steps:

[0007] S1. Immerse natural zeolite powder with a size of less than 200 mesh in 1-5M hydrochloric acid solution A, stir vigorously at 50-80℃ for 6-24h, centrifuge the reaction solution, precipitate, wash until neutral, filter, take filter cake A, dry at 60-80℃, and obtain acidified natural zeolite powder.

[0008] S2. Add the acidified natural zeolite powder and aniline monomer obtained in step S1 to 0.5-2M hydrochloric acid solution B, wherein the mass ratio of the acidified natural zeolite powder to the aniline monomer is 0.5-3:1; treat the mixed solution with ultrasound for 30-60 min; at 0-4℃, add 0.5-2M HCl solution containing ammonium persulfate dropwise to the ultrasonically treated mixed solution, and continue the reaction for 2-6 h; centrifuge the reaction solution, precipitate, wash the precipitate until neutral, filter to obtain filter cake B, and dry at 60-80℃ (preferably dry for 4-8 hours) to obtain PANI / AZeo composite material, wherein the mass ratio of ammonium persulfate to aniline monomer in the 0.5-2M hydrochloric acid solution is 1.25-4.9:1;

[0009] S3. The PANI / AZeo composite material obtained in step S2 is added to a FeSO4·7H2O aqueous solution with a concentration of 0.054-0.107M and stirred to obtain a suspension; under N2 protection, a fresh NaBH4 aqueous solution with a concentration of 0.107-0.214M is added dropwise to the suspension and reacted for 30-90 minutes; the filter cake C is filtered, quickly washed several times with pure ethanol, and dried overnight in a vacuum oven at 60-80℃ to obtain PANI / AZeo-nZVI material.

[0010] The theoretical mass ratio of the PANI / AZeo composite material, FeSO4·7H2O in the FeSO4·7H2O aqueous solution, and NaBH4 in the fresh NaBH4 aqueous solution is 1:5~15:1.5~4.5.

[0011] Furthermore, the volume of hydrochloric acid solution B in step S2 is 100 mL / g based on the mass of aniline monomer;

[0012] Furthermore, the concentration of ammonium persulfate in the 0.5–2M HCl solution containing ammonium persulfate is 12.5–24.5 g / L.

[0013] Secondly, the present invention proposes the product of the above preparation method, namely PANI / AZeo-nZVI material.

[0014] Thirdly, this invention proposes the application of the above-mentioned PANI / AZeo-nZVI material in the treatment of high-salt wastewater containing antibiotics in an anaerobic ammonia oxidation wastewater treatment system.

[0015] Specifically, the PANI / AZeo-nZVI material is applied to an anaerobic ammonia oxidation wastewater treatment system to treat high-salt wastewater containing antibiotics, according to the following steps:

[0016] S1. Prepare simulated wastewater, the substrate of which includes 180 mg / L ammonia nitrogen, 216-234 mg / L nitrite nitrogen, 0-20 g / L inorganic salts and mineral media;

[0017] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0018] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0019] S2. Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the wastewater treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 20% to 40% of the effective solvent in the reactor, with an average diameter of 1 to 4 mm and a VSS of 4000 to 5000 mg / L.

[0020] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0021] Subsequently, NaCl was added to the reactor influent to control the influent salinity. The first addition was done at a NaCl concentration of 5 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 20 g / L, and the total nitrogen removal rate was maintained at 90%–98% for three days to complete sludge acclimatization.

[0022] S3. Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the antibiotic concentration at 0.01-1 mg / L, the pH at 6.0-8.0, and the salinity at 1-20 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0023] The PANI / Azeo-nZVI material is added at a ratio of 0.5–2.0 g / L of the effective reactor volume. The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent are measured daily. Nitrite nitrogen is added to the wastewater based on the measured ammonia nitrogen content, maintaining the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3. Preferably, the antibiotic is a tetracycline antibiotic. Further, the antibiotic includes one or more of oxytetracycline, tetracycline, and chlortetracycline. In particular, the antibiotic is oxytetracycline.

[0024] Preferably, the anaerobic ammonia oxidation wastewater treatment system is an upflow anaerobic reactor (UASB).

[0025] As a preferred option, in step S3, the ratio of the PANI / Azeo-nZVI material added to the effective volume of the reactor in the wastewater treatment system is 0–1.0 g / L; the VSS of the added anaerobic ammonia oxidation granular sludge is 4000–4600 mg / L, and the average particle size is 2–4 mm.

[0026] Furthermore, the antibiotic is a tetracycline antibiotic, specifically including one or more of oxytetracycline, tetracycline, and chlortetracycline.

[0027] The preferred anaerobic ammonia oxidation wastewater treatment system of this invention is an upflow anaerobic reactor (UASB). Furthermore, it is recommended that the ratio of PANI / Azeo-nZVI material dosage to the effective reactor volume in step S3 be within the range of 0.5–1.0 g / L; the MLVSS of the added anaerobic ammonia oxidation granular sludge should be 4200–5500 mg / L, with an average particle size of 2–4 mm. The beneficial effects of this invention are as follows:

[0028] (1) The preparation conditions of PANI / AZeo-nZVI material are mild, the process is simple, and it is easy to achieve large-scale production. (2) At the same time, adsorption and Fenton-like decomposition are used to remove some antibiotics in the anaerobic ammonia oxidation system that has been under long-term antibiotic pressure, and promote the improvement of anaerobic ammonia oxidation performance under high salt environment.

[0029] (3) The zeolite-polyaniline composite carrier is used to alleviate the defect of easy aggregation of polyaniline and nano-zero-valent iron. Polyaniline selectively adsorbs organic pollutants in water and accelerates electron migration, thereby achieving rapid degradation of pollutants in water without inhibiting anaerobic ammonia oxidation activity. At the same time, the introduction of polyaniline broadens the pH range of the material, and it also has a good antibiotic treatment effect in neutral and weakly alkaline water environments. Attached Figure Description

[0030] Figure 1 This is a diagram of the test setup for an ammonia oxidation wastewater treatment system.

[0031] Figure 2 The anaerobic ammonia oxidation apparatus of Embodiment 10 and Comparative Example 5 of this invention contains NH4. + -N processing performance comparison chart.

[0032] Figure 3 The anaerobic ammonia oxidation device of Embodiment 10 and Comparative Example 5 of this invention is NO2 - -N processing performance comparison chart.

[0033] Figure 4 The anaerobic ammonia oxidation device of Embodiment 10 and Comparative Example 5 of this invention contains NO3. - -N processing performance comparison chart.

[0034] Figure 5 The actual influent oxytetracycline OTC concentration and total nitrogen (TN) of the anaerobic ammonia oxidation unit in Examples 10 and 5 of this invention are... inf Total nitrogen (TN) in effluent eff Comparison chart of total nitrogen removal rate (TNRE) and anaerobic ammonia oxidation activity (SAA). Detailed Implementation

[0035] To better illustrate the technical solution of the invention, the following embodiments will be used for further description, but the scope of protection claimed by the present invention is not limited to the scope described in the specific embodiments. The concentration of oxytetracycline OTC was determined by spectrophotometry. Specific anammox activity (SAA) was calculated using Formula 1. Total nitrogen removal rate (TNRE, %) was calculated using Formula 2.

[0036]

[0037] C TNinf and C TNeff The values ​​represent the total nitrogen content (mg / L) of the inflow and outflow, respectively. HRT is the hydraulic retention time (D), and VSS is the concentration of anaerobic ammonia oxidation sludge biomass (g / L).

[0038] Example 1

[0039] (1) Take 5g of zeolite and add 50mL of 2mol / L hydrochloric acid. Stir vigorously at 80℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0040] (2) Take 0.5g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 0.5mol / L hydrochloric acid. Sonicate the mixture for 30min.

[0041] (3) At 0-4℃, 4.90g of ammonium persulfate dissolved in 200mL of 0.5mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0042] (4) The composite carrier was mixed with 0.054 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.107 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 60 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0043] Example 2

[0044] (1) Take 5g of zeolite and add 50mL of 1mol / L hydrochloric acid. Stir vigorously at 80℃ for 24h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0045] (2) Take 0.5g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 0.5mol / L hydrochloric acid. Sonicate the mixture for 60min.

[0046] (3) At 0-4℃, 4.90g of ammonium persulfate dissolved in 200mL of 0.5mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0047] (4) The composite carrier was mixed with 0.107 mol / L FeSO4·7H2O solution at a ratio of 1 g: 500 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.214 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 90 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 70 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0048] Example 3

[0049] (1) Take 5g of zeolite and add 50mL of 3mol / L hydrochloric acid. Stir vigorously at 70℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 70℃ to obtain acidified zeolite.

[0050] (2) Take 1g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 1.0mol / L hydrochloric acid. Sonicate the mixture for 40min.

[0051] (3) At 0-4℃, 4.90g of ammonium persulfate dissolved in 200mL of 0.5mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0052] (4) The composite carrier was mixed with 0.054 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.214 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 60 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0053] Example 4

[0054] (1) Take 5g of zeolite and add 50mL of 5mol / L hydrochloric acid. Stir vigorously at 50℃ for 6h. Take it out and wash it with deionized water until neutral. Dry it at 80℃ to obtain acidified zeolite.

[0055] (2) Take 3.0g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 2.0mol / L hydrochloric acid. Sonicate the mixture for 30min.

[0056] (3) At 0-4℃, 4.90g of ammonium persulfate dissolved in 200mL of 0.5mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0057] (4) The composite carrier was mixed with 0.054 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.214 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 60 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0058] Example 5

[0059] (1) Take 5g of zeolite and add 50mL of 2mol / L hydrochloric acid. Stir vigorously at 80℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0060] (2) Take 0.5g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 0.5mol / L hydrochloric acid. Sonicate the mixture for 30min.

[0061] (3) At 0-4℃, 4.90g of ammonium persulfate dissolved in 200mL of 0.5mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0062] (4) The composite carrier was mixed with 0.107 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.214 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 60 min, and the resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 80 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0063] Example 6

[0064] (1) Take 5g of zeolite and add 50mL of 2mol / L hydrochloric acid. Stir vigorously at 80℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0065] (2) Take 0.5g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 0.5mol / L hydrochloric acid. Sonicate the mixture for 30min.

[0066] (3) At 0-4℃, 1.25g of ammonium persulfate dissolved in 100mL of 1.0mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 6h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 70℃ to obtain polyaniline / acidified zeolite composite carrier.

[0067] (4) The composite carrier was mixed with 0.054 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.107 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 60 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0068] Example 7

[0069] (1) Take 5g of zeolite and add 50mL of 2mol / L hydrochloric acid. Stir vigorously at 80℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0070] (2) Take 0.5g of the acidified zeolite and 1g of aniline monomer and add them together to 100mL of 0.5mol / L hydrochloric acid. Sonicate the mixture for 30min.

[0071] (3) At 0-4℃, 2.45g of ammonium persulfate dissolved in 200mL of 2.0mol / L hydrochloric acid was added dropwise to the mixture and the reaction was continued for 2h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 80℃ to obtain polyaniline / acidified zeolite composite carrier.

[0072] (4) The composite carrier was mixed with 0.054 mol / L FeSO4·7H2O solution at a ratio of 1 g: 330 mL, and N2 was continuously introduced for 30 min to ensure that the air in the preparation environment was completely removed. While maintaining the N2 introduction, 0.107 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and dried under vacuum at 60 °C to obtain the polyaniline / acidified zeolite-nano zero-valent iron composite material.

[0073] Comparative Example 1

[0074] (1) Take 5g of zeolite and add 50mL of 2mol / L hydrochloric acid. Stir vigorously at 80℃ for 12h. Take it out and wash it with deionized water until neutral. Dry it at 60℃ to obtain acidified zeolite.

[0075] (2) The acidified zeolite prepared in step (1) was mixed with 0.108 mol / L FeSO4·7H2O solution at a ratio of 1 g: 160 mL. N2 was continuously purged for 30 min to ensure that air was completely removed from the preparation environment. While maintaining the N2 purging, 0.214 mol / L NaBH4 solution was added dropwise, and the volume ratio of FeSO4·7H2O solution to NaBH4 solution was controlled at 1:1. The reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and then vacuum dried at 60 °C to obtain the acidified zeolite-nano zero-valent iron composite material.

[0076] Comparative Example 2

[0077] (1) Add 1 mL of aniline monomer to a flask, add 100 mL of 0.5 mol / L hydrochloric acid, and sonicate the mixture for 30 min.

[0078] (2) At 0-4℃, 4.90g of ammonium persulfate dissolved in 100mL of 0.5mol / L hydrochloric acid was added dropwise and the reaction was continued for 4h. The black precipitate was washed repeatedly with deionized water and ethanol and dried at 60℃ to obtain polyaniline / acidified zeolite composite carrier.

[0079] (3) The composite carrier was mixed with 0.108 mol / L FeSO4·7H2O solution at a ratio of 1 g: 160 mL, and N2 was continuously purged for 30 min to ensure that air was completely removed from the preparation environment. While maintaining the N2 purging, 0.214 mol / L NaBH4 solution was added dropwise, controlling the volume ratio of FeSO4·7H2O solution to NaBH4 solution to 1:1, and the reaction was continued for 30 min. The resulting product was quickly washed with deionized water and ethanol, and then vacuum dried at 60 °C to obtain polyaniline-nano zero-valent iron composite material.

[0080] Table 1. Comparison of composite material properties in examples and comparative examples.

[0081]

[0082] The degradation performance of the composite materials prepared in Examples 1-7 was compared with that of oxytetracycline hydrochloride. The materials were added to a 200 mg / L OTC solution at a ratio of 0.5 g / L, and the mixture was shaken at 150 rpm in a shaker at 37 ± 2 °C. Samples were taken after 30 min of reaction, and the OTC concentration was determined spectrophotometrically. The results are shown in Table 1. Table 1 shows that the composite materials prepared in Examples 1-7 all showed good effects in removing oxytetracycline. The best effect was achieved by the polyaniline / acidified zeolite-nano zero-valent iron composite material of Example 1, with a degradation efficiency of 97.08%, far exceeding that of Comparative Examples 1 and 2. This confirms that the zeolite / polyaniline composite carrier accelerated the decomposition of oxytetracycline.

[0083] Example 8

[0084] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0085] (1) Prepare simulated wastewater. The substrate of the simulated wastewater includes 180 mg / L ammonia nitrogen, 220 mg / L nitrite nitrogen, 20 g / L inorganic salts and mineral media.

[0086] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0087] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0088] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 30% of the effective volume of the reactor, with an average diameter of 3-4 mm and a VSS of 4500-5000 mg / L.

[0089] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0090] Subsequently, NaCl was added to the reactor influent to control the influent salinity. The first addition was done at a NaCl concentration of 5 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 20 g / L, and the total nitrogen removal rate was maintained at 90%–98% for three days to complete sludge acclimatization.

[0091] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the concentration of antibiotics at 0.01 mg / L, the pH at 6.0-8.0, and the salinity at 10 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0092] PANI / Azeo-nZVI material was added at a ratio of 0.5 g / L of the effective reactor volume. The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily. Nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater was controlled at 1:1.2 to 1.3.

[0093] Example 9

[0094] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0095] (1) Prepare simulated wastewater. The substrate of the simulated wastewater includes 180 mg / L ammonia nitrogen, 234 mg / L nitrite nitrogen, 1 g / L inorganic salts and mineral media.

[0096] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0097] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0098] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 40% of the effective volume of the reactor, with an average diameter of 1-2 mm and a VSS of 5000-5500 mg / L.

[0099] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0100] Subsequently, NaCl was added to the reactor feedwater to control the feedwater salinity; the NaCl concentration was controlled at 5 g / L, and sludge acclimatization was completed when the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days.

[0101] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the antibiotic concentration at 0.5 mg / L, pH at 6.0-8.0, and salinity at 1 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0102] PANI / Azeo-nZVI material was added at a ratio of 1.0 g / L of the effective reactor volume. The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily. Nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater was controlled at 1:1.2 to 1.3.

[0103] Example 10

[0104] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0105] (1) Prepare simulated wastewater. The substrates of the simulated wastewater include 180 mg / L ammonia nitrogen, 216 mg / L nitrite nitrogen, 10 g / L inorganic salts and mineral media.

[0106] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0107] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0108] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 20% of the effective volume of the reactor, with an average diameter of 2-4 mm and a VSS of 4000-4500 mg / L.

[0109] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0110] Subsequently, NaCl was added to the reactor influent to control the influent salinity; the NaCl concentration was controlled at 5 g / L for the first addition. When the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days, the sludge acclimatization was completed.

[0111] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the concentration of antibiotics at 1.0 mg / L, the pH at 6.0-8.0, and the salinity at 10 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0112] PANI / Azeo-nZVI material was added at a ratio of 0.8 g / L of the effective reactor volume. The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily. Nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater was controlled at 1:1.2 to 1.3.

[0113] Comparative Example 3

[0114] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0115] (1) Prepare simulated wastewater. The substrate of the simulated wastewater includes 180 mg / L ammonia nitrogen, 220 mg / L nitrite nitrogen, 20 g / L inorganic salts and mineral media.

[0116] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0117] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0118] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 30% of the effective volume of the reactor, with an average diameter of 3-4 mm and a VSS of 4500-5000 mg / L.

[0119] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0120] Subsequently, NaCl was added to the reactor influent to control the influent salinity. The first addition was done at a NaCl concentration of 5 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90%–98% for more than three days, the NaCl concentration in the wastewater was increased to 20 g / L, and the total nitrogen removal rate was maintained at 90%–98% for three days to complete sludge acclimatization.

[0121] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the concentration of antibiotics at 0.01 mg / L, the pH at 6.0-8.0, and the salinity at 10 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0122] The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent are measured daily. Nitrite nitrogen is added to the wastewater based on the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater is controlled at 1:1.2 to 1.3.

[0123] Comparative Example 4

[0124] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0125] (1) Prepare simulated wastewater. The substrate of the simulated wastewater includes 180 mg / L ammonia nitrogen, 234 mg / L nitrite nitrogen, 1 g / L inorganic salts and mineral media.

[0126] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0127] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0128] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 40% of the effective volume of the reactor, with an average diameter of 1-2 mm and a VSS of 5000-5500 mg / L.

[0129] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0130] Subsequently, NaCl was added to the reactor feedwater to control the feedwater salinity; the NaCl concentration was controlled at 5 g / L, and sludge acclimatization was completed when the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days.

[0131] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the antibiotic concentration at 0.5 mg / L, pH at 6.0-8.0, and salinity at 1 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0132] The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent are measured daily. Nitrite nitrogen is added to the wastewater based on the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater is controlled at 1:1.2 to 1.3.

[0133] Comparative Example 5

[0134] The simulated nitrogen-containing wastewater described in the example contains NH4Cl and NaNO2 as pollutants in the influent, and NaCl as the inorganic salt. The reactor used for wastewater treatment in the example is as follows. Figure 3 The image shows an upflow anaerobic sludge blanket (UASB) reactor with a volume of 4.3L. It is a commercially available conventional water treatment device, and its application is not limited to UASB reactors.

[0135] (1) Prepare simulated wastewater. The substrates of the simulated wastewater include 180 mg / L ammonia nitrogen, 216 mg / L nitrite nitrogen, 10 g / L inorganic salts and mineral media.

[0136] The final composition of the mineral medium is (g / L): KH2PO4 0.01; CaCl2·2H2O 0.0056; MgSO4·7H2O 0.03; KHCO3 0.5;

[0137] Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O.

[0138] (2) Sludge acclimation: Anaerobic ammonia oxidation granular sludge is inoculated into the reactor of the sewage treatment system. The volume of the anaerobic ammonia oxidation granular sludge accounts for 20% of the effective volume of the reactor, with an average diameter of 2-4 mm and a VSS of 4000-4500 mg / L.

[0139] Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35–38°C using a water bath; the pH was maintained at 6.0–8.0, and the hydraulic retention time was 10–11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1:1.2–1.3; when the total nitrogen removal rate of the UASB remained at 90%–98% for more than three days, the reactor was considered to be operating stably.

[0140] Subsequently, NaCl was added to the reactor influent to control the influent salinity; the NaCl concentration was controlled at 5 g / L for the first addition. When the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90% to 98% for more than three days, the sludge acclimatization was completed.

[0141] (3) Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the concentration of antibiotics at 1.0 mg / L, the pH at 6.0-8.0, and the salinity at 10 g / L. The influent temperature is maintained at 35-38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14-15 h.

[0142] The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent are measured daily. Nitrite nitrogen is added to the wastewater based on the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater is controlled at 1:1.2 to 1.3.

[0143] The specific water output effects of Example 10 and Comparative Example 5 are shown in the figure. Figure 2 , Figure 3 , Figure 4 and Figure 5From day 1 to 25, during the nitrogen load increase phase, the influent to the anaerobic ammonia oxidation unit was maintained at 180±2 mg / L NH4+-N, 216±3 mg / L NO2-N, and 10 g / L salt, indicating that the anaerobic ammonia oxidizing bacteria gradually adapted to the new environment. Both Example 10 and Comparative Example 5 maintained a concentration of 111±3 mgN / gVSS / d. From day 26 onwards, actual wastewater containing oxytetracycline was introduced. Example 10 was treated with 0.8 g / L PANI@Azeo-nZVI material, while Comparative Example 5 was not treated. The performance of the units in Example 10 and Comparative Example 5 fluctuated significantly under oxytetracycline stress, with a significant increase in effluent NH4+-N and NO2-N (see...). Figure 2 , Figure 3 In Example 10, where the material was added, the amount of NO3-N reduced to NH4+-N, NO2-N, or N2 was significantly lower than in Comparative Example 5 due to the influence of nano-zero valent iron (see Comparative Example 5). Figure 4 The anaerobic ammonia oxidation performance was also significantly improved. Therefore, after the performance stabilized relatively between days 48 and 52, the TNRE of Comparative Example 5 was 68.59%, and that of Example 10 was 75.1%. The SAA of Comparative Example 5 was 103.42 mg N / g VSS / d, and that of Example 10 was 115.43 mg N / g VSS / d. This confirms that the addition of PANI@Azeo-nZVI improved the nitrogen removal efficiency of the reactors in these examples.

[0144] The effluent effluent effects of Examples 8-10 and Comparative Examples 3-5 are shown in Table 2. Table 2 shows that the effluent NH4 from Comparative Examples 3, 4, and 5... + -N, NO2 -After the -N concentration stabilized, the total nitrogen in the effluent remained stable at 87.87 mg / L, 112.82 mg / L, and 124.38 mg / L, with total nitrogen removal rates (TNRE) of 77.81%, 72.75%, and 68.59%, respectively. In Examples 8, 9, and 10, after effluent stabilization, the total nitrogen in the effluent was 79.08 mg / L, 91.49 mg / L, and 98.60 mg / L, with TNREs of 80.23%, 77.90%, and 75.1%, respectively. Meanwhile, the SAA levels in Examples 8, 9, and 10 were 103.44 mg N / g VSS / d, 96.22 mg N / g VSS / d, and 115.43 mg N / g VSS / d, respectively, significantly higher than those in Comparative Examples 3, 4, and 5 (100.57 mg N / g VSS / d, 89.87 mg N / g VSS / d, and 103.42 mg N / g VSS / d) by 2.77%, 6.60%, and 10.40%, respectively. The results indicate that the reactors in the examples with added PANI@Azeo-nZVI exhibited higher nitrogen removal efficiency. AnAOB's TNRE level slightly decreased due to long-term contact with OTC, but the introduction of PANI@Azeo-nZVI restored and enhanced the anaerobic ammonia oxidation activity.

[0145] Table 2 Performance of the device after stabilization

[0146]

[0147]

Claims

1. An application of a PANI / AZeo-nZVI material in the treatment of high-salinity wastewater containing antibiotics in an anaerobic ammonia oxidation wastewater treatment system, characterized in that, The preparation steps of the PANI / AZeo-nZVI material are as follows: S1. Natural zeolite powder with a size of less than 200 mesh is immersed in 1~5M hydrochloric acid solution A and stirred vigorously at 50~80℃ for 6~24h. The reaction solution is centrifuged, precipitated, washed until neutral, filtered, and the filter cake A is dried at 60~80℃ to obtain acidified natural zeolite powder. S2. Add the acidified natural zeolite powder and aniline monomer obtained in step S1 to 0.5-2M hydrochloric acid solution B, wherein the mass ratio of the acidified natural zeolite powder to the aniline monomer is 0.5-3:1; sonicate the mixed solution for 30-60 min; at 0-4℃, add dropwise a 0.5-2M hydrochloric acid solution containing ammonium persulfate to the sonicated mixture, and continue the reaction for 2-6 h; centrifuge the reaction solution, precipitate, wash the precipitate until neutral, filter to obtain filter cake B, and dry at 60-80℃ to obtain PANI / AZeo composite material, wherein the 0.5-2M hydrochloric acid solution containing ammonium persulfate... The mass ratio of ammonium persulfate to aniline monomer in the hydrochloric acid solution is 1.25~4.9:1; S3. The PANI / AZeo composite material obtained in step S2 is added to a FeSO4·7H2O aqueous solution with a concentration of 0.054~0.107M and stirred to obtain a suspension; under N2 protection, a fresh NaBH4 aqueous solution with a concentration of 0.107~0.214M is added dropwise to the stirred suspension and reacted for 30~90 minutes; filter and take filter cake C, quickly wash with pure ethanol, and dry overnight in a vacuum oven at 60~80℃ to obtain PANI / AZeo-nZVI material; The theoretical mass ratio of the PANI / AZeo composite material, FeSO4·7H2O in FeSO4·7H2O aqueous solution, and NaBH4 in fresh NaBH4 aqueous solution is 1:5.0~14.9:1.3~4.

1.

2. The application as described in claim 1, characterized in that: The volume of hydrochloric acid solution B in step S2 is 100 ml / g based on the mass of aniline monomer.

3. The application as described in claim 1, characterized in that: The concentration of ammonium persulfate in the 0.5-2M hydrochloric acid solution in step S2 is 12.5-24.5 g / L.

4. The application as described in claim 1, characterized in that: In step S2, after the precipitate is washed to neutral, it is dried at 60-80℃ for 4-8 hours.

5. The application as described in claim 1, characterized in that, The application of PANI / AZeo-nZVI material in anaerobic ammonia oxidation wastewater treatment systems for treating high-salt wastewater containing antibiotics is carried out according to the following steps: S10. Prepare simulated wastewater, the substrate of which includes 180 mg / L ammonia nitrogen, 216~234 mg / L nitrite nitrogen, 1~20 g / L inorganic salts and mineral media; The mineral medium composition concentrations (g / L) are: KH₂PO₄ 0.01; CaCl₂·2H₂O 0.0056; MgSO₄·7H₂O 0.03; KHCO₃ 0.5; Each liter of simulated wastewater was supplemented with 1.25 mL of trace element solution I and trace element solution II. The solute composition of trace element solution I was 5 g / L EDTA·2Na and 5 g / L FeSO4·7H2O, and the solute composition of trace element solution II was 15 g / L EDTA·2Na, 0.014 g / L H3BO4, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.43 g / L ZnSO4·7H2O, 0.21 g / L NiCl2·6H2O, 0.22 g / L NaMoO4·2H2O, and 0.24 g / L CoCl2·6H2O. S20. Sludge acclimation: Inoculate the reactor of the wastewater treatment system with anaerobic ammonia oxidation granular sludge, wherein the volume of the anaerobic ammonia oxidation granular sludge occupies 20% to 40% of the effective volume of the reactor, the average diameter is 1 to 4 mm, and the MLVSS is 4000 to 5500 mg / L. Simulated wastewater was pumped into the reactor using a peristaltic pump, and the temperature of the simulated wastewater in the reactor was maintained at 35-38℃ using a water bath; the pH was maintained at 6.0-8.0, and the hydraulic retention time was 10-11 hours; the concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily, and nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, controlling the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater at 1.2-1.3; when the total nitrogen removal rate of UASB remained at 90%-98% for more than three days, the reactor was considered to be operating stably. Subsequently, NaCl was added to the reactor influent to control the influent salinity. The first addition was done at a NaCl concentration of 5 g / L. When the total nitrogen removal rate of UASB remained at 90%~98% for more than three days, the NaCl concentration in the wastewater was increased to 10 g / L. When the total nitrogen removal rate of UASB remained at 90%~98% for more than three days, the NaCl concentration in the wastewater was increased to 20 g / L, and the total nitrogen removal rate was maintained at 90%~98% for three days to complete sludge acclimatization. S30. Actual wastewater treatment: After the reactor is running stably, actual wastewater containing antibiotics is pumped into the reactor as influent. Before pumping, the actual wastewater is diluted with water to maintain the antibiotic concentration at 0.01~1mg / L, pH at 6.0~8.0, and salinity at 1~20g / L; the influent temperature is maintained at 35~38℃, and the hydraulic retention time of the actual wastewater after entering the reactor is 14~15h. PANI / Azeo-nZVI material was added at a ratio of 0~1.0 g / L of the effective reactor volume. The concentrations of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen, and total nitrogen in the effluent were measured daily. Nitrite nitrogen was added to the wastewater according to the measured ammonia nitrogen content, and the mass ratio of ammonia nitrogen to nitrite nitrogen in the wastewater was controlled at 1:1.2~1.

3.

6. The application of the PANI / AZeo-nZVI material according to claim 1 in the treatment of high-salt wastewater containing antibiotics in an anaerobic ammonia oxidation wastewater treatment system, characterized in that: The antibiotic in question is a tetracycline antibiotic.

7. The application of the PANI / AZeo-nZVI material according to claim 5 in the treatment of high-salt wastewater containing antibiotics in an anaerobic ammonia oxidation wastewater treatment system, characterized in that: The anaerobic ammonia oxidation wastewater treatment system is an upflow anaerobic reactor (UASB).

8. The application according to claim 5, characterized in that: In step S30, the ratio of the PANI / Azeo-nZVI material added to the effective volume of the reactor in the wastewater treatment system is 0.5~1.0 g / L; the MLVSS of the added anaerobic ammonia oxidation granular sludge is 4200~5500 mg / L, and the average particle size is 2~4 mm.

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