Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process and device

Abstract

The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process and device belong to the technical field of industrial wastewater treatment. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device comprises a water inlet system, a biological inhibition reduction system, an anaerobic membrane bioreactor system and a water outlet system. The device is used for treating antibiotic wastewater. The device selectively eliminates the inhibition factors of anaerobic organisms in wastewater through pretreatment, introduces the pretreated wastewater into the anaerobic membrane bioreactor system, mixes the wastewater with specific inoculated sludge, and obtains treated effluent after treatment through a membrane assembly. The process and device can realize efficient and synergistic control of conventional pollutants, antibiotics and drug-resistant genes in wastewater. Compared with the conventional anaerobic treatment process, the process and device have higher operation load and organic matter removal rate, and have higher methane production, realize efficient biological energy recovery and wastewater resource utilization, and have good industrial application prospect and social and economic benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial wastewater treatment, in particular to a composite process and device for wastewater biological inhibition and reduction and anaerobic membrane bioreactor. Background Art

[0002] Fermentation antibiotic wastewater is a high-concentration organic wastewater characterized by high pollutant loads, high toxicity, and strong antibacterial properties. It primarily originates from spent fermentation broth or synthetic wastewater from the extraction of raw materials during antibiotic production. This type of wastewater is characterized by high water volume, high antibiotic residual potency, high chemical oxygen demand (COD), high suspended solids content, and high concentrations of complex salt ions. Compared to physical and chemical technologies, wastewater treatment technologies based on anaerobic biological treatment offer advantages such as low chemical reagent dosage, low operating costs, and reduced risk of secondary pollution. Therefore, they are the preferred treatment option for fermentation antibiotic wastewater.

[0003] Antibiotics and other substances present in wastewater have a strong inhibitory effect and toxicity on anaerobic microbial activity, limiting the effectiveness of anaerobic biological treatment and making it difficult to meet effluent quality requirements. Furthermore, the presence of high concentrations of residual antibiotics can lead to the generation of large numbers of drug-resistant bacteria and resistance genes during anaerobic biological treatment. These resistant bacteria, resistance genes, and undegraded antibiotics enter the environment with treated wastewater and residual sludge, potentially posing a safety hazard. Therefore, before wastewater enters anaerobic biological treatment, it is necessary to employ pretreatment technologies to reduce the bioinhibitory effects of substances such as antibiotics in the wastewater.

[0004] However, pretreated fermentation antibiotic wastewater still presents challenges such as complex water quality and excessively high concentrations of conventional pollutants. In particular, large amounts of fermentation medium components or organic raw materials remain in fermentation antibiotic wastewater. High concentrations of protein particles can coat the surface of granular sludge, restricting mass transfer and gas production, leading to granular sludge disintegration and limiting the application of anaerobic treatment processes that rely on granular sludge, such as upflow anaerobic sludge blankets and expanded anaerobic granular sludge beds. The anaerobic membrane bioreactor (AnMBR) couples anaerobic processes with membrane separation, leveraging the interception effect of the membrane to enrich more anaerobic microorganisms and prevent sludge loss. This makes the AnMBR independent of granular sludge and capable of withstanding higher organic loads, making it suitable for treating wastewaters with high organic and solid content, such as fermentation antibiotic wastewater. In summary, the coupling of a bioinhibition reduction pretreatment system with an anaerobic membrane bioreactor system holds great potential for treating fermentation antibiotic wastewater. Summary of the Invention

[0005] The purpose of the present invention is to provide a composite process and device for wastewater biological inhibition reduction and anaerobic membrane bioreactor. First, the inhibition of fermentation antibiotic wastewater on anaerobic organisms is eliminated through pretreatment, and then the pretreated wastewater is introduced into the anaerobic membrane bioreactor system to achieve efficient anaerobic treatment of fermentation antibiotic wastewater, improve the COD removal rate of antibiotic wastewater treatment, and at the same time have a higher methane production, thereby realizing efficient bioenergy recovery and wastewater resource utilization.

[0006] The technical solutions adopted by the present invention to achieve the above-mentioned purpose are:

[0007] Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process, including:

[0008] S1. performing a bioinhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater;

[0009] S2, mixing the pretreated wastewater with anaerobic sludge, and treating the mixture with a membrane module to obtain treated effluent;

[0010] The biological inhibition reduction includes at least one treatment method selected from oxidation-reduction, hydrolysis, electrodialysis, coagulation precipitation and membrane separation; the membrane component is a polyvinylidene fluoride hollow fiber ultrafiltration membrane, and the membrane pore size of the membrane component is 0.1-2 μm.

[0011] Fermentation antibiotic wastewater contains substances that may inhibit anaerobic microorganisms. The inhibitory effects include direct toxicity to anaerobic microorganisms, competitive inhibition due to competition with anaerobic bacteria for substrates, inhibition caused by affecting the osmotic pressure and other microbial living environment conditions, and inhibition caused by the accumulation of related metabolites. For example, erythromycin wastewater may contain high concentrations of erythromycin residues, thiocyanate, and sulfate; penicillin wastewater may contain high concentrations of penicillin residues, sulfate, and organic extractants; tetracycline wastewater may contain high concentrations of tetracycline residues and chloride ions; cephalosporin antibiotic wastewater may contain high concentrations of cephalosporin residues and sulfides. Bioinhibition reduction pretreatment refers to the degradation or separation of inhibitory pollutants in wastewater through pretreatment methods such as redox, hydrolysis, electrodialysis, coagulation and sedimentation, and membrane separation, in order to reduce concentrations or toxic effects, improve the biodegradability of the wastewater, and create good conditions for subsequent biological treatment. In the pretreatment process for reducing biological inhibition, electrodialysis is used, using anion exchange membranes and cation exchange membranes to achieve highly selective ion separation, thereby reducing substances that inhibit anaerobic microorganisms in antibiotic wastewater. This method first eliminates the inhibition of fermentation antibiotic wastewater on anaerobic organisms through pretreatment, and then introduces the pretreated wastewater into an anaerobic membrane bioreactor system, achieving efficient anaerobic treatment of fermentation antibiotic wastewater, improving the COD removal rate of the antibiotic wastewater treatment, and simultaneously achieving higher methane production, realizing efficient bioenergy recovery and wastewater resource utilization.

[0012] Preferably, the membrane component is a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane.

[0013] More preferably, in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, polyvinylidene fluoride powder is first reacted with polyvinyl pyrrolidone and then reacted with a modified polymer to obtain the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; the modified polymer includes at least polyphthalaldehyde and sodium polyanisyl sulfonate.

[0014] Preferably, the configuration of the anaerobic reactor is any one of an upflow anaerobic sludge blanket reactor, an anaerobic sludge expanded bed reactor and a continuous stirred reactor.

[0015] Preferably, the anaerobic sludge is at least one of the anaerobic acclimation sludge in the anaerobic treatment system for fermentation antibiotic production wastewater and the sludge discharged from the anaerobic digestion workshop of the municipal sewage treatment plant, and the mass ratio of the anaerobic acclimation sludge in the anaerobic treatment system for fermentation antibiotic production wastewater and the sludge discharged from the anaerobic digestion workshop of the municipal sewage treatment plant is 1:0.5-2.

[0016] Preferably, the membrane assembly comprises a polyvinylidene fluoride hollow fiber ultrafiltration membrane or a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane.

[0017] Preferably, the preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane is specifically as follows:

[0018] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 60-80°C for 4-8 hours, add modified polymer and stir for 4-8 hours. After the reaction is completed, stop stirring, adjust the temperature to 50-60°C and degas under vacuum for 4-8 hours. After the treatment is completed, let the temperature naturally drop to room temperature to obtain a casting solution; pour the casting solution into a hollow fiber membrane spinning machine to prepare a membrane assembly.

[0019] More preferably, the mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:10-20.

[0020] More preferably, the usage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1 g:50-150 mL.

[0021] Preferably, the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is specifically as follows:

[0022] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 60-80°C for 4-8 hours, add modified polymer and stir for 4-8 hours. After the reaction is completed, stop stirring, adjust the temperature to 50-60°C and degas under vacuum for 4-8 hours. After the treatment is completed, let the temperature naturally drop to room temperature to obtain a casting solution; pour the casting solution into a hollow fiber membrane spinning machine to prepare a membrane assembly.

[0023] More preferably, the mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:10-20.

[0024] More preferably, the usage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1 g:50-150 mL.

[0025] More preferably, the modified polymer includes polyphthalaldehyde and sodium polyanisylsulfonate. Using polyphthalaldehyde and sodium polyanisylsulfonate as the modified polymers to react with polyvinylidene fluoride to prepare a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane helps increase the presence of polar groups in the polyvinylidene fluoride hollow fiber ultrafiltration membrane, thereby increasing the hydrophilicity of the polyvinylidene fluoride hollow fiber ultrafiltration membrane. Using the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane module to treat antibiotic wastewater can not only effectively improve the COD removal rate of the antibiotic wastewater treatment, but also achieve higher methane production.

[0026] More preferably, the modified polymer includes polyphthalaldehyde, sodium polyanisylsulfonate, and poly(1-vinylnaphthalene). Further using poly(1-vinylnaphthalene) as a modified polymer in the preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membranes can further improve the COD removal rate and methane production in antibiotic wastewater treatment, achieving efficient bioenergy recovery and wastewater resource utilization.

[0027] More preferably, the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.1-0.2.

[0028] More preferably, the mass ratio of the polyvinylidene fluoride powder to the sodium polyanisole is 1:0.05-0.1.

[0029] More preferably, the mass ratio of polyvinylidene fluoride powder to poly(1-vinylnaphthalene) is 1:0.05-0.1.

[0030] Preferably, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is specifically,

[0031] S1. performing a bioinhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater;

[0032] S2. Using a hydrochloric acid solution with a concentration of 0.1-1 mol / L to adjust the pH of the pretreated wastewater to 7-7.3, adding trace metal elements and anaerobic sludge to obtain a mud-water mixture; then treating the mud-water mixture through a membrane assembly to obtain treated effluent.

[0033] More preferably, the bioinhibition reduction comprises at least one treatment method selected from the group consisting of oxidation-reduction, hydrolysis, electrodialysis, coagulation precipitation and membrane separation.

[0034] More preferably, the redox treatment comprises reacting the antibiotic wastewater with a redox agent at 60-70°C with stirring at 100-300 rpm for 100-140 minutes to obtain pretreated wastewater. The redox agent is an oxidizing agent or a reducing agent, wherein the oxidizing agent includes at least one of hydrogen peroxide, persulfate, ferrate, and peracetic acid, and the reducing agent includes at least one of sodium sulfite and sodium thiosulfate. The volume ratio of the redox agent to the antibiotic wastewater is 1:20-100.

[0035] More preferably, the hydrolysis treatment is to hydrolyze the antibiotic wastewater at 80-100° C. for 2-6 hours.

[0036] More preferably, the configuration of the anaerobic reactor is any one of an upflow anaerobic sludge blanket reactor, an anaerobic sludge expanded bed reactor and a continuous stirred reactor.

[0037] More preferably, the trace metal elements include ferrous chloride, nickel chloride and cobalt chloride.

[0038] More preferably, the mass ratio of nickel chloride to ferrous chloride is 1:3-5; the mass ratio of nickel chloride to cobalt chloride is 1:1-2.

[0039] More preferably, the anaerobic sludge is at least one of the anaerobic acclimation sludge in the anaerobic treatment system for wastewater produced by fermentation antibiotics and the sludge discharged from the anaerobic digestion workshop of a municipal sewage treatment plant, and the mass ratio of the anaerobic acclimation sludge in the anaerobic treatment system for wastewater produced by fermentation antibiotics and the sludge discharged from the anaerobic digestion workshop of a municipal sewage treatment plant is 1:0.5-2.

[0040] The present invention also discloses a device used in the composite process of wastewater biological inhibition and reduction and anaerobic membrane bioreactor, including an inlet system, a biological inhibition and reduction system, an anaerobic membrane bioreactor system and an outlet system; the biological inhibition and reduction system includes a power supply, an air electrode, a metal electrode, a feed storage tank, a production agent storage tank, a reactor, a temperature measuring probe and a temperature control device; the temperature control device is a high and low temperature circulation machine with a temperature control range of -20-200°C.

[0041] Preferably, in the biological inhibition reduction system, the reactor includes a dosing tank, a stirring paddle, a condenser, a feed port, a liquid outlet, a reactor insulation interlayer and a reactor body, and the ratio of the effective reaction volume of the reactor body to the volume of the reactor insulation interlayer is 1:0.1-5.

[0042] More preferably, the insulation medium in the insulation interlayer of the reactor is at least one of water, hot oil and antifreeze.

[0043] Preferably, the bioinhibition reduction system also includes an electrodialysis power supply, electrode plates, an electrodialysis membrane stack, an electrolytic solution storage tank, a feed storage tank, a reactor, a temperature probe, and a temperature control device. The power supply includes a positive and negative electrode, and the electrode plates include a negative and positive electrode plates. The positive electrode is connected to the positive electrode plate, and the negative electrode is connected to the negative electrode plate. The electrolytic solution storage tank is connected to the electrolytic solution inlet on the electrode plate, and the feed storage tank is connected to the feed inlet on the electrode plate. The effluent from electrodialysis treatment is connected to the reactor inlet via a conduit. The electrodialysis membrane stack is an ED membrane stack. The reactor includes a dosing tank, a stirring paddle, a condenser, a feed inlet, a liquid outlet, a reactor insulation jacket, and a reactor body. The reactor is made of glass, and the ratio of the effective reaction volume in the reactor body to the reactor insulation jacket volume is 1:0.1-5. The insulation medium in the reactor insulation jacket is water. One end of the temperature probe is immersed in the insulation medium in the insulation layer of the reactor and connected to the reactor, and the other end is connected to the temperature control device. The temperature control device is a high and low temperature cycler.

[0044] Preferably, in the biological inhibition and reduction system, the reactor is made of glass.

[0045] Preferably, in the biological inhibition reduction system, the power supply includes a positive electrode and a negative electrode, the air electrode is connected to the positive electrode, and the metal electrode is connected to the negative electrode; the feed storage tank is connected to the metal electrode, and the production agent storage tank is connected to the air electrode.

[0046] Preferably, in the biological inhibition reduction system, one end of the temperature probe is immersed in the insulation medium in the insulation interlayer of the reactor and connected to the reactor, and the other end is connected to the temperature control device.

[0047] Preferably, the anaerobic membrane bioreactor system includes a low-temperature circulation machine, a water inlet substrate tank, an anaerobic reactor, a membrane tank, a peristaltic pump, a wet gas flow meter, a biogas buffer device, a diaphragm aeration pump, a transmembrane pressure difference sensor and a data transmission device.

[0048] More preferably, the water inlet matrix tank includes a water bath insulation interlayer, a stirring motor, a stirring paddle and a leak-proof seven-leaf sealing tube, and the volume ratio of the effective water storage volume of the water inlet matrix tank to the water bath insulation interlayer is 1:0.1-5.

[0049] More preferably, the number of blades of the stirring paddle is 3-5 pairs.

[0050] More preferably, the stirring paddle is made of polytetrafluoroethylene.

[0051] More preferably, the length ratio of the blade extension of the stirring paddle to the inner diameter of the water inlet substrate tank is 1:0.2-0.45.

[0052] More preferably, the anaerobic reactor is provided with a thermal insulation interlayer, and the ratio of the effective water storage volume of the anaerobic reactor to the volume of the thermal insulation layer of the anaerobic reactor is 1:0.1-5.

[0053] More preferably, the configuration of the membrane tank is an upflow anaerobic sludge blanket reactor or an anaerobic sludge expanded bed reactor.

[0054] More preferably, a membrane assembly is placed in the center of the membrane pool, an overflow port is provided on the top, a biogas return outlet is provided on the top, and a biogas return inlet is provided at the bottom. The biogas is collected from the top of the membrane pool by a diaphragm aeration pump and then returned from the air inlet at the bottom of the membrane pool. An air filter is provided at the bottom of the membrane pool.

[0055] More preferably, the membrane pool is provided with a thermal insulation interlayer, and the ratio of the effective water storage volume of the membrane pool to the volume of the membrane pool thermal insulation layer is 1:0.1-5.

[0056] The present invention adopts polyphthalaldehyde, sodium polyanisylsulfonate and poly(1-vinylnaphthalene) as modified polymers to react with polyvinylidene fluoride to prepare a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and uses the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane component for treating antibiotic wastewater in a wastewater biological inhibition and reduction and anaerobic reactor composite process. Therefore, the present invention has the following beneficial effects: the wastewater biological inhibition and reduction and anaerobic reactor composite process not only has a high COD removal rate of 73.3-91.7%; but also has a high methane production, with an average daily methane production of 17.3-35.4 L / d, thereby realizing efficient bioenergy recovery and wastewater resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The invention relates to a process flow of a composite device of wastewater biological inhibition reduction and anaerobic membrane bioreactor.

[0058] Figure 2 This is a structural diagram of the oxidation-coupled hydrolysis bioinhibition reduction system device used in Example 1.

[0059] Figure 3 This is a structural diagram of the electrodialysis-coupled hydrolysis biological inhibition and reduction system used in Example 2.

[0060] Figure 4 This is the structural diagram of the anaerobic membrane bioreactor system.

[0061] Figure 5 This is the change of COD concentration in wastewater treated by anaerobic membrane bioreactor.

[0062] Figure 6 is the abundance of drug-resistant genes. DETAILED DESCRIPTION

[0063] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those skilled in the art and are not intended to limit the present invention in any way.

[0064] The experimental methods in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are commercially available unless otherwise specified.

[0065] Example 1:

[0066] Preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0067] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, and react at 70°C with stirring for 8 hours. After the reaction, stop stirring and adjust the temperature to 60°C for 4 hours under vacuum degassing. After the treatment, let the temperature naturally cool to room temperature to obtain a casting solution. The casting solution is poured into a hollow fiber membrane spinning machine to prepare a polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15, and the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL.

[0068] Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device, including:

[0069] The inlet system, the bioreduction system, the anaerobic membrane bioreactor system, and the outlet system are described as follows. The inlet system includes an inlet storage tank, and the outlet system includes an outlet storage tank. The bioreduction system consists of a power supply, an air electrode, a metal electrode, a feed storage tank, a production chemical storage tank, a reactor, a temperature probe, and a temperature control device. The power supply consists of a positive and a negative terminal. The air electrode is connected to the positive terminal, and the metal electrode is connected to the negative terminal. The feed storage tank is connected to the metal electrode, and the production chemical storage tank is connected to the air electrode. The reactor consists of a dosing tank, a stirring paddle, a condenser, a feed inlet, a liquid outlet, a reactor insulation jacket, and a reactor body. The reactor is made of glass, with a 1:1 ratio between the effective reaction volume and the reactor insulation jacket volume. The insulation medium in the reactor insulation jacket is water. One end of the temperature probe is immersed in the insulation jacket and connected to the reactor, while the other end is connected to the temperature control device, which is a high-low temperature cycler. The anaerobic membrane bioreactor system consists of a low-temperature circulation unit, an inlet substrate tank, an anaerobic reactor, a membrane tank, a peristaltic pump, a wet gas flow meter, a biogas buffer, a diaphragm aeration pump, a transmembrane pressure sensor, and data transmission equipment. The inlet substrate tank includes a water bath insulation jacket, a stirring motor, a stirring paddle, and a leak-proof seven-blade seal. The effective water storage volume of the inlet substrate tank is 1:1 with the water bath insulation jacket. The stirring paddle is made of polytetrafluoroethylene and has four pairs of blades. The blade length to the inlet substrate tank inner diameter ratio is 1:0.2. The anaerobic reactor is a continuously stirred tank reactor (CSTR) with an insulation jacket. The effective water storage volume to insulation jacket ratio is 1:1. The internal temperature of the anaerobic reactor is maintained at 35°C. The membrane tank is configured as an upflow anaerobic sludge blanket (UASB) reactor. A membrane assembly is placed in the center of the membrane tank, with an overflow port at the top, a biogas return outlet at the top, and a biogas return inlet at the bottom. Biogas is collected from the top of the membrane tank by a diaphragm aeration pump and then returned from the bottom inlet of the membrane tank. An air filter is installed at the bottom of the membrane tank. The membrane tank is equipped with an insulation interlayer. The ratio of the effective water storage volume of the membrane tank to the insulation layer volume of the membrane tank is 1:1. The temperature in the membrane tank is 35°C. The membrane assembly is made of polyvinylidene fluoride hollow fiber ultrafiltration membrane, with 50 membrane pairs, a membrane pore size of 0.1μm, and a membrane area of ​​1m 2 .

[0070] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process uses a wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device to treat antibiotic wastewater, including:

[0071] S1. Performing redox treatment on the antibiotic wastewater by reacting the antibiotic wastewater with hydrogen peroxide at 65°C and 300 rpm for 120 minutes to obtain pretreated wastewater. The volume ratio of hydrogen peroxide to antibiotic wastewater is 1:50.

[0072] S2. The pH of the pretreated wastewater was adjusted to 7.3 using a 1 mol / L hydrochloric acid solution. Ferrous chloride, nickel chloride, and cobalt chloride were then added. The wastewater was then thoroughly mixed with municipal anaerobic digestion sludge to obtain a sludge-water mixture. The sludge-water mixture was then treated through a polyvinylidene fluoride hollow fiber ultrafiltration membrane to obtain treated effluent. The mass ratio of nickel chloride to ferrous chloride was 1:4; the mass ratio of nickel chloride to cobalt chloride was 1:1.

[0073] Example 2:

[0074] The preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane is the same as that in Example 1.

[0075] The wastewater biological inhibition and reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the biological inhibition and reduction system is changed, other conditions are the same as Example 1. The biological inhibition and reduction system of this embodiment includes an electrodialysis power supply, an electrode plate, an electrodialysis membrane stack, a cathode liquid storage tank, a feed storage tank, a reactor, a temperature probe and a temperature control device. The power supply includes a positive power supply and a negative power supply, and the electrode plate includes a negative electrode plate and a positive electrode plate. The positive power supply is connected to the positive electrode plate, and the negative power supply is connected to the negative electrode plate. The cathode liquid storage tank is connected to the cathode liquid inlet on the electrode plate, the feed storage tank is connected to the feed port on the electrode plate, and the effluent after electrodialysis treatment is connected to the reactor inlet through a conduit. The electrodialysis membrane stack is an ED membrane stack. The reactor consists of a dosing tank, a stirring paddle, a condenser, a feed port, a liquid outlet, a reactor insulation jacket, and a reactor body. The reactor is made of glass, with a 1:1 ratio between the effective reaction volume of the reactor body and the volume of the insulation jacket. The insulation in the jacket is water. One end of the temperature probe is immersed in the insulation jacket and connected to the reactor. The other end is connected to a temperature control device, which is a high-low temperature cycler.

[0076] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process uses a wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device to treat antibiotic wastewater, including:

[0077] S1. The antibiotic wastewater is subjected to electrodialysis treatment, and then the antibiotic wastewater is hydrolyzed at 90° C. for 4 hours to obtain pretreated wastewater.

[0078] S2. The pH of the pretreated wastewater was adjusted to 7.3 using a 1 mol / L hydrochloric acid solution. Ferrous chloride, nickel chloride, and cobalt chloride were then added. The wastewater was then thoroughly mixed with municipal anaerobic digestion sludge to obtain a sludge-water mixture. The sludge-water mixture was then treated through a polyvinylidene fluoride hollow fiber ultrafiltration membrane to obtain treated effluent. The mass ratio of nickel chloride to ferrous chloride was 1:4; the mass ratio of nickel chloride to cobalt chloride was 1:1.

[0079] Example 3:

[0080] Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0081] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, and react at 70°C with stirring for 8 hours. Then add polyphthalaldehyde and sodium polyanisyl sulfonate and stir for 4 hours. After the reaction, stirrer is stopped and the temperature is adjusted to 60°C for 4 hours under vacuum degassing. After the treatment, the temperature is naturally lowered to room temperature to obtain a casting solution. The casting solution is poured into a hollow fiber membrane spinning machine to prepare a polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.2; and the mass ratio of polyvinylidene fluoride powder to sodium polyanisyl sulfonate is 1:0.1.

[0082] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced with the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example, and other conditions are the same as Example 1.

[0083] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example.

[0084] Example 4:

[0085] The preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane was performed in the same manner as in Example 3 except that the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde was changed to 1:0.1.

[0086] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced with the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example, and other conditions are the same as Example 1.

[0087] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example.

[0088] Example 5:

[0089] The preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane was performed in the same manner as in Example 3 except that the mass ratio of polyvinylidene fluoride powder to sodium polyanisylsulfonate was changed to 1:0.05. Other conditions were the same as in Example 3.

[0090] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced with the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example, and other conditions are the same as Example 1.

[0091] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example.

[0092] Example 6:

[0093] Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0094] PVDF powder and polyvinyl pyrrolidone were weighed, N-methyl pyrrolidone was added, and the mixture was stirred at 70°C for 8 hours. Polyphthalaldehyde and sodium polyanisylsulfonate were added and stirred for 4 hours. Poly(1-vinyl naphthalene) was then added and stirred for 4 hours. After the reaction, stirring was stopped and the temperature was adjusted to 60°C for 4 hours under vacuum degassing. After the treatment, the temperature was naturally lowered to room temperature to obtain a casting solution. The casting solution was poured into a hollow fiber membrane spinning machine to prepare a PVDF hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to PVDF powder was 1:15; the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone was 1g:100mL; the mass ratio of PVDF powder to polyphthalaldehyde was 1:0.2; the mass ratio of PVDF powder to sodium polyanisylsulfonate was 1:0.1; and the mass ratio of PVDF powder to poly(1-vinyl naphthalene) was 1:0.1.

[0095] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced with the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example, and other conditions are the same as Example 1.

[0096] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example.

[0097] Example 7:

[0098] The preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane was performed in the same manner as in Example 7 except that the mass ratio of polyvinylidene fluoride powder to poly(1-vinylnaphthalene) was changed to 1:0.05. Other conditions were the same as in Example 7.

[0099] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced with the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example, and other conditions are the same as Example 1.

[0100] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this example.

[0101] Comparative Example 1:

[0102] Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0103] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, and react at 70°C with stirring for 8 hours. Then add polyphthalaldehyde and stir for 4 hours. After the reaction, stop stirring and adjust the temperature to 60°C for 4 hours under vacuum degassing. After the treatment, let the temperature naturally cool to room temperature to obtain a casting solution. The casting solution is poured into a hollow fiber membrane spinning machine to prepare a polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; and the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.2.

[0104] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example, and other conditions are the same as Example 1.

[0105] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example.

[0106] Comparative Example 2:

[0107] Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0108] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, and react at 70°C with stirring for 8 hours. Then add sodium polyanisyl sulfonate and stir for 4 hours. After the reaction, stop stirring and adjust the temperature to 60°C for 4 hours under vacuum degassing. After the treatment, let the temperature naturally cool to room temperature to obtain a casting solution. The casting solution is poured into a hollow fiber membrane spinning machine to prepare a polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; and the mass ratio of polyvinylidene fluoride powder to sodium polyanisyl sulfonate is 1:0.1.

[0109] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example, and other conditions are the same as Example 1.

[0110] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example.

[0111] Comparative Example 3:

[0112] Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising:

[0113] Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, and react at 70°C with stirring for 8 hours. Then add poly(1-vinyl naphthalene) and stir for 4 hours. After the reaction, stop stirring and adjust the temperature to 60°C for 4 hours under vacuum degassing. After the treatment, let the temperature naturally cool to room temperature to obtain a casting solution. The casting solution is poured into a hollow fiber membrane spinning machine to prepare a polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the amount ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; and the mass ratio of polyvinylidene fluoride powder to poly(1-vinyl naphthalene) is 1:0.1.

[0114] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is compared with Example 1, except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane of the membrane assembly in the center of the membrane pool in the anaerobic membrane bioreactor system is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example, and other conditions are the same as Example 1.

[0115] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is the same as Example 1 except that the polyvinylidene fluoride hollow fiber ultrafiltration membrane is replaced by the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared in this comparative example.

[0116] Experimental example:

[0117] 1. Determination of chemical oxygen demand (COD)

[0118] Erythromycin production wastewater generated in the production process of the fermentation pharmaceutical industry was collected and treated using the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device described in Example 1. The erythromycin production wastewater was first pretreated by the biological inhibition reduction system to obtain pretreated wastewater. The pretreated wastewater was then passed into the anaerobic membrane bioreactor for continuous treatment for 180 days. The COD values ​​of the influent and effluent of the anaerobic membrane bioreactor were measured daily by the potassium dichromate method, and the COD removal rate was calculated. The COD value of the influent was recorded as X1, and the COD value of the effluent was recorded as X2. The COD removal rate = (X1-X2) / X1×100%.

[0119] Figure 1 The invention relates to a process flow of a composite device of wastewater biological inhibition reduction and anaerobic membrane bioreactor.

[0120] Figure 2 This is a structural diagram of the oxidative coupled hydrolysis biological inhibition and reduction system device for the agent dosing type used in Example 1, where 1 is the power supply, 2 is the air electrode, 3 is the metal electrode, 4 is the feed storage tank, 5 is the production agent storage tank, 6 is the dosing tank, 7 is the stirring paddle, 8 is the condenser, 9 is the feed port, 10 is the reactor insulation interlayer, 11 is the reactor body, 12 is the liquid outlet, 13 is the temperature probe, and 14 is the temperature control device.

[0121] Figure 3 This is a structural diagram of the biological inhibition reduction system device for electrodialysis coupled hydrolysis used in Example 2, where 1 is the electrodialysis power supply, 2 is the negative electrode plate, 3 is the electrodialysis membrane stack, 4 is the power cord, 5 is the positive electrode plate, 6 is the cathode liquid storage tank, 7 is the feed storage tank, 8 is the water inlet or dosing port, 9 is the stirring paddle, 10 is the condenser, 11 is the temperature probe, 12 is the feed port, 13 is the reactor insulation interlayer, 14 is the reactor body, 15 is the liquid outlet, and 16 is the temperature control device.

[0122] Figure 4 This is the structural diagram of the anaerobic membrane bioreactor system. 1 is a low-temperature circulation machine, 2 is a water bath insulation interlayer, 3 is a stirring motor, 4 is a stirring paddle, 5 is a leak-proof seven-leaf seal tube, 6 is a peristaltic pump, 7 is a wet gas flow meter, 8 is a biogas buffer device, 9 is a membrane assembly, 10 is a diaphragm aeration pump, 11 is a transmembrane pressure difference sensor, and 12 is a data transmission device.

[0123] Figure 5 This is the COD concentration change of wastewater treated by the anaerobic membrane bioreactor. After 180 days of long-term continuous operation, the COD removal efficiency of the anaerobic membrane bioreactor is stable at 70-80%.

[0124] Erythromycin production wastewater was treated using the combined wastewater bioinhibition and reduction and anaerobic membrane bioreactor devices of Examples 1-7 and Comparative Examples 1-3. The erythromycin production wastewater was first pretreated by the bioinhibition and reduction system to obtain pretreated wastewater. This pretreated wastewater was then passed through the anaerobic membrane bioreactor for continuous treatment for 180 days. The COD removal rate on treatment day 180 was calculated. The results are shown in Table 1.

[0125] Table 1 COD removal rate (%)

[0126]

[0127] As can be seen from Table 1, the COD removal rate of Example 3-5 of the present invention is higher than that of Example 1-2. This is because in the composite process of wastewater biological inhibition reduction and anaerobic membrane bioreactor, Example 3-5 first uses polyvinylidene fluoride powder to react with polyvinyl pyrrolidone and a modified polymer to obtain a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the modified polymer including polyphthalaldehyde and sodium polyanisylsulfonate, and then the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is used as a membrane assembly of an anaerobic reactor to treat antibiotic wastewater; while Example 1-2 uses polyvinylidene fluoride powder to react with polyvinyl pyrrolidone to obtain a polyvinylidene fluoride hollow fiber ultrafiltration membrane for wastewater treatment. This shows that the present invention uses the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane assembly to treat antibiotic wastewater, which can improve the COD removal rate of antibiotic wastewater treatment.

[0128] The COD removal rate of Example 3 of the present invention is higher than that of Examples 4-5 because the amounts of polyphthalaldehyde and sodium polyanisene sulfonate used in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane are different; the COD removal rate of Example 3 is higher than that of Comparative Examples 1-2 because in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Example 3 synergistically uses polyphthalaldehyde and sodium polyanisene sulfonate as modifying polymers to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, while Comparative Example 1 only uses polyphthalaldehyde as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and Comparative Example 2 only uses sodium polyanisene sulfonate as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. This shows that compared with the synergistic use of polyphthalaldehyde and sodium polyanisole as modified polymers to react with polyvinylidene fluoride powder to prepare modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the effect of improving the COD removal rate of antibiotic wastewater treatment is better.

[0129] The COD removal rate of Examples 6-7 of the present invention is higher than that of Example 3, because in the preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Examples 6-7 further use poly (1-vinyl naphthalene) as a modified polymer to react with polyvinylidene fluoride powder to prepare modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; The COD removal rate of Example 6 is higher than that of Example 7, because in the preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the usage amount of poly (1-vinyl naphthalene) is different; The COD removal rate of Example 6 is higher than that of Comparative Example 3, because in the preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Comparative Example 3 only uses poly (1-vinyl naphthalene) alone as a modified polymer to react with polyvinylidene fluoride powder to prepare modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. This illustrates that further using poly (1-vinyl naphthalene) as a modified polymer to react with polyvinylidene fluoride powder to prepare modified polyvinylidene fluoride hollow fiber ultrafiltration membrane can further improve the COD removal rate for antibiotic wastewater treatment.

[0130] 2. Determination of methane production

[0131] The oxytetracycline production wastewater generated in the production process of the fermentation pharmaceutical industry was collected and treated with the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device in Examples 1-7 and Comparative Examples 1-3, respectively. The organic load of the anaerobic membrane bioreactor was stabilized to 10 kg / m 3 / d, the treatment time is 220 days, and the daily methane production during the treatment process is measured by gas chromatography, and the average daily methane production is calculated. The measurement results are shown in Table 2.

[0132] Table 2 Average daily methane production (L / d)

[0133]

[0134] As can be seen from Table 2, the average daily methane production of Examples 3-5 of the present invention is higher than that of Examples 1-2. This is because in the composite process of wastewater biological inhibition reduction and anaerobic membrane bioreactor, Examples 3-5 first use polyvinylidene fluoride powder to react with polyvinyl pyrrolidone and a modified polymer to obtain a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the modified polymer including polyphthalaldehyde and sodium polyanisylsulfonate, and then use the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane component of an anaerobic reactor to treat antibiotic wastewater; while Example 1-2 uses polyvinylidene fluoride powder to react with polyvinyl pyrrolidone to obtain a polyvinylidene fluoride hollow fiber ultrafiltration membrane for wastewater treatment. This shows that the present invention uses the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane component to treat antibiotic wastewater, which can increase the average daily methane production and realize the resource utilization of antibiotic wastewater.

[0135] The average daily methane production in Example 3 of the present invention is higher than that in Examples 4-5 because different amounts of polyphthalaldehyde and sodium polyanisene sulfonate are used in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. The average daily methane production in Example 3 is higher than that in Comparative Examples 1-2 because, in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Example 3 synergistically uses polyphthalaldehyde and sodium polyanisene sulfonate as modifying polymers to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, while Comparative Example 1 only uses polyphthalaldehyde as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and Comparative Example 2 only uses sodium polyanisene sulfonate as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. This shows that compared with the synergistic use of polyphthalaldehyde and sodium polyanisole as modified polymers to react with polyvinylidene fluoride powder to prepare modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, it is more effective in increasing the average daily methane production generated during the treatment of antibiotic wastewater.

[0136] The average daily methane production of Examples 6-7 of the present invention is higher than that of Example 3 because, in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Examples 6-7 further use poly(1-vinylnaphthalene) as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; the average daily methane production of Example 6 is higher than that of Example 7 because the amount of poly(1-vinylnaphthalene) used in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is different; the average daily methane production of Example 6 is higher than that of Comparative Example 3 because, in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, Comparative Example 3 only uses poly(1-vinylnaphthalene) as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. This shows that further using poly(1-vinylnaphthalene) as a modifying polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane can further increase the average daily methane production.

[0137] 3. Determination of drug resistance gene abundance

[0138] Antibiotic selection pressure in antibiotic wastewater can promote the enrichment and spread of antibiotic-resistant bacteria and antibiotic resistance genes in wastewater biological treatment bacterial communities, causing potential health hazards.

[0139] Oxytetracycline production wastewater, generated during the fermentation pharmaceutical industry, was collected and treated using the combined wastewater bioinhibition reduction and anaerobic membrane bioreactor system described in Example 1. The oxytetracycline production wastewater was first pretreated by the bioinhibition reduction system to produce pretreated wastewater. This pretreated wastewater was then passed through the anaerobic membrane bioreactor for continuous treatment for 220 days. Following treatment, metagenomic analysis was used to determine the abundance of drug-resistance genes in the sludge and effluent from the anaerobic membrane bioreactor.

[0140] Figure 5 The abundance of drug-resistant genes is shown in Figure 2. In the sludge within the anaerobic membrane bioreactor, the abundance of drug-resistant genes was below the detection limit of quantitative PCR, and no drug-resistant genes were detected in the effluent from the anaerobic membrane bioreactor. This demonstrates that bioinhibition reduction pretreatment can effectively remove antibiotics from wastewater. Furthermore, the membrane components of the anaerobic membrane bioreactor effectively control the biomass in the effluent, further preventing the spread of drug-resistant genes and thus achieving effective control of drug-resistant genes in wastewater treatment for the pharmaceutical industry.

[0141] The conventional operations in the operating steps of the present invention are well known to those skilled in the art and will not be described in detail here.

[0142] The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process, including: S1. performing a bioinhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater; S2, mixing the pretreated wastewater with anaerobic sludge, and treating the mixture with a membrane module to obtain treated effluent; The biological inhibition reduction includes at least one treatment method selected from oxidation-reduction, hydrolysis, electrodialysis, coagulation precipitation and membrane separation; the membrane assembly is a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and the membrane pore size of the membrane assembly is 0.1-2 μm; in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the polyvinylidene fluoride powder is first reacted with polyvinyl pyrrolidone, and then reacted with a modified polymer to obtain the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; the modified polymer includes at least polyphthalaldehyde and sodium polyanisyl sulfonate.

2. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 1, characterized in that: The anaerobic sludge is at least one of the anaerobic acclimation sludge in the anaerobic treatment system for fermentation antibiotic production wastewater and the sludge discharged from the anaerobic digestion workshop of the municipal sewage treatment plant. The mass ratio of the anaerobic acclimation sludge in the anaerobic treatment system for fermentation antibiotic production wastewater and the sludge discharged from the anaerobic digestion workshop of the municipal sewage treatment plant is 1:0.5-2.

3. An apparatus adopting the wastewater biological inhibition and reduction and anaerobic membrane bioreactor composite process according to claim 1 or 2 comprises an inlet system, a biological inhibition and reduction system, an anaerobic membrane bioreactor system and an outlet system; the biological inhibition and reduction system comprises a power supply, an air electrode, a metal electrode, a feed storage tank, a production agent storage tank, a reactor, a temperature probe and a temperature control device; the temperature control device is a high and low temperature cycler with a temperature control range of -20-200°C.

4. The device according to claim 3, characterized in that In the biological inhibition and reduction system, the reactor includes a dosing tank, a stirring paddle, a condenser, a feed port, a liquid outlet, a reactor insulation interlayer and a reactor body. The ratio of the effective reaction volume of the reactor body to the volume of the reactor insulation interlayer is 1:0.1-5.

5. The device according to claim 3, characterized in that The anaerobic membrane bioreactor system comprises a low-temperature circulation machine, a water inlet substrate tank, an anaerobic reactor, a membrane tank, a peristaltic pump, a wet gas flow meter, a biogas buffer device, a diaphragm aeration pump, a transmembrane pressure difference sensor and a data transmission device.

6. The device according to claim 5, characterized in that The water inlet matrix tank comprises a water bath insulation interlayer, a stirring motor, a stirring paddle and a leak-proof seven-leaf sealing pipe. The volume ratio of the effective water storage volume of the water inlet matrix tank to the water bath insulation interlayer is 1:0.1-5.

7. The device according to claim 5, characterized in that The anaerobic reactor is provided with a heat-insulating interlayer, and the ratio of the effective water storage volume of the anaerobic reactor to the volume of the heat-insulating layer of the anaerobic reactor is 1:0.1-5.

8. The device according to claim 5, characterized in that The configuration of the anaerobic reactor is any one of an upflow anaerobic sludge blanket reactor, an anaerobic sludge expanded bed reactor and a continuous stirring reactor.

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