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

Abstract

The invention discloses a wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process and device, and belongs 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 the antibiotic wastewater, firstly, inhibiting factors of anaerobic organisms in the wastewater are selectively eliminated through pretreatment, then the pretreated wastewater is introduced into the anaerobic membrane bioreactor system to be mixed with specific inoculation sludge, and treated effluent is obtained after the wastewater is treated through the membrane module. The process and the device provided by the invention can realize efficient cooperative control of conventional pollutants, antibiotics and drug-resistant genes in the wastewater, have higher operation load and organic matter removal rate compared with a conventional anaerobic treatment process, have higher methane yield, realize efficient biological energy recovery and wastewater recycling, and are suitable for industrial production. Good industrial application prospects and social and economic benefits are realized.

Description

Technical Field

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

[0002] Fermentation antibiotic wastewater is a type of high-concentration organic wastewater with high pollutant load, high toxicity and strong antibacterial properties. It mainly comes from the waste fermentation liquid or synthetic waste liquid after the raw material extraction during the antibiotic production process. This type of wastewater has water quality characteristics such as large water volume, high antibiotic residual titer, high chemical oxygen demand (COD), high suspended solids content, and high complex salt ion concentration. Compared with physical and chemical technology, wastewater treatment technology with anaerobic biological treatment as the main process has the characteristics of small chemical reagent addition, low operating cost, and low secondary pollution. It is the first choice for treating fermentation antibiotic wastewater.

[0003] Antibiotics and other substances in wastewater have strong inhibitory effects and toxicity on the activity of anaerobic microorganisms, which limits the effect of anaerobic biological treatment and makes it difficult to meet the effluent quality requirements. In addition, the presence of high concentrations of residual antibiotics will also cause a large number of resistant bacteria and resistant genes to be produced during the anaerobic biological treatment process. These resistant bacteria, resistant genes and undegraded antibiotics enter the environment with the treated wastewater and residual sludge, which may pose a safety hazard. Therefore, before the wastewater enters the anaerobic biological treatment, it is necessary to use pretreatment technology to reduce the biological inhibition of antibiotics and other substances in the wastewater.

[0004] However, the pretreated fermentation antibiotic wastewater still has problems such as complex water quality composition and excessively high concentrations of conventional pollutants. In particular, a large amount of fermentation medium components or organic raw materials remain in the fermentation antibiotic wastewater, and high-concentration protein particles will wrap on the surface of granular sludge, limiting mass transfer and gas production processes, causing granular sludge to disintegrate, and limiting the application of anaerobic treatment processes that rely on granular sludge, such as upflow anaerobic sludge bed and anaerobic granular sludge expanded bed. The anaerobic membrane bioreactor (AnMBR) couples the anaerobic process with membrane separation, and uses the interception effect of the membrane to enrich more anaerobic functional microorganisms to prevent sludge loss. Therefore, the anaerobic membrane bioreactor does not rely on granular sludge and can withstand higher organic loads. It is suitable for treating high-concentration organic matter and high-solid wastewater such as fermentation antibiotic wastewater. In summary, the coupling of the biological inhibition reduction pretreatment system and the anaerobic membrane bioreactor system to treat fermentation antibiotic wastewater has great potential. 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 yield, thereby achieving efficient bioenergy recovery and wastewater resource utilization.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned purpose is: The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process includes: S1. performing biological inhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater; S2, mixing the pretreated wastewater with the anaerobic sludge, and treating the wastewater 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 component is a polyvinylidene fluoride hollow fiber ultrafiltration membrane, and the membrane pore size of the membrane component is 0.1-2 μm.

[0007] There are substances in fermentation antibiotic wastewater that may have inhibitory effects on anaerobic microorganisms. The inhibitory effects include direct toxicity to anaerobic microorganisms, competitive inhibition of competing with anaerobic bacteria for substrates, inhibition caused by affecting the living environment conditions of microorganisms such as osmotic pressure, and inhibition caused by the accumulation of related metabolites. For example, high concentrations of erythromycin residues, thiocyanate and sulfate may exist in thioerythromycin wastewater; high concentrations of penicillin residues, sulfates, and organic extractants may exist in penicillin wastewater; high concentrations of tetracycline residues and chloride ions may exist in tetracycline wastewater; high concentrations of cephalosporin residues, sulfides, etc. may exist in cephalosporin antibiotic wastewater. Biological inhibition reduction pretreatment refers to the degradation or separation of inhibitory pollutants in wastewater through pretreatment methods such as oxidation-reduction, hydrolysis, electrodialysis, coagulation and precipitation, and membrane separation, so as to achieve the purpose of reducing concentration or reducing toxic effects, improve the biodegradability of wastewater, and create good conditions for subsequent biological treatment. In the pretreatment for biological inhibition reduction, when the electrodialysis process is adopted, the anion exchange membrane and the cation exchange membrane are used for treatment to achieve highly selective separation of ions and reduce the substances that inhibit anaerobic microorganisms in the antibiotic wastewater. The present invention first eliminates the inhibition of fermentation antibiotic wastewater on anaerobic organisms through pretreatment, and then introduces the pretreated wastewater 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 yield, and achieve efficient bioenergy recovery and wastewater resource utilization.

[0008] Preferably, the membrane component is a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane.

[0009] More preferably, 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 polyanisole sulfonate.

[0010] 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 stirring reactor.

[0011] 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.

[0012] Preferably, the membrane assembly comprises a polyvinylidene fluoride hollow fiber ultrafiltration membrane or a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane.

[0013] Preferably, the preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane is specifically, Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methylpyrrolidone, stir and react at 60-80°C for 4-8h, add modified polymer and stir for 4-8h. After the reaction is completed, stop stirring, adjust the temperature to 50-60°C and degas under vacuum for 4-8h. After the treatment, naturally lower the temperature to room temperature to obtain a casting solution; pour the casting solution into a hollow fiber membrane spinning machine to prepare a membrane component.

[0014] More preferably, the mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:10-20.

[0015] More preferably, the usage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1 g:50-150 mL.

[0016] Preferably, the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is specifically as follows: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methylpyrrolidone, stir and react at 60-80°C for 4-8h, add modified polymer and stir for 4-8h. After the reaction is completed, stop stirring, adjust the temperature to 50-60°C and degas under vacuum for 4-8h. After the treatment, naturally lower the temperature to room temperature to obtain a casting solution; pour the casting solution into a hollow fiber membrane spinning machine to prepare a membrane component.

[0017] More preferably, the mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:10-20.

[0018] More preferably, the usage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1 g:50-150 mL.

[0019] More preferably, the modified polymer includes polyphthalaldehyde and sodium polyanisyl sulfonate. Using polyphthalaldehyde and sodium polyanisyl sulfonate as modified polymers to react with polyvinylidene fluoride to prepare a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane helps to 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 component to treat antibiotic wastewater can not only effectively improve the COD removal rate of antibiotic wastewater treatment, but also has a higher methane yield.

[0020] More preferably, the modified polymer includes polyphthalaldehyde, sodium polyanisole sulfonate and poly(1-vinylnaphthalene). In the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, further using poly(1-vinylnaphthalene) as the modified polymer can further improve the COD removal rate and methane production of antibiotic wastewater treatment, and achieve efficient bioenergy recovery and wastewater resource utilization.

[0021] More preferably, the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.1-0.2.

[0022] More preferably, the mass ratio of polyvinylidene fluoride powder to sodium polyanisole sulfonate is 1:0.05-0.1.

[0023] More preferably, the mass ratio of polyvinylidene fluoride powder to poly(1-vinylnaphthalene) is 1:0.05-0.1.

[0024] Preferably, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process is specifically, S1. performing biological inhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater; 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; and then treating the mud-water mixture through a membrane assembly to obtain treated effluent.

[0025] 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.

[0026] More preferably, the redox treatment is specifically to react the antibiotic wastewater with a redox agent, and stir the reaction at 100-300 rpm for 100-140 minutes at 60-70°C to obtain pretreated wastewater. The redox agent is an oxidant or a reductant, the oxidant includes at least one of hydrogen peroxide, persulfate, ferrate and peracetic acid, and the reductant 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.

[0027] More preferably, the hydrolysis treatment is to hydrolyze the antibiotic wastewater at 80-100° C. for 2-6 hours.

[0028] 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 stirring reactor.

[0029] More preferably, the trace metal elements include ferrous chloride, nickel chloride and cobalt chloride.

[0030] 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.

[0031] 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.

[0032] 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, and the temperature control range is -20-200°C.

[0033] Preferably, in the biological inhibition reduction system, the reactor includes a dosing tank, a stirring paddle, a condenser, a feed inlet, 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.

[0034] More preferably, the insulation medium in the insulation interlayer of the reactor is at least one of water, hot oil and antifreeze liquid.

[0035] Preferably, the biological inhibition reduction system also 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 measuring probe and a temperature control device. The power supply includes a positive electrode and a negative electrode, and the electrode plate includes a negative electrode plate and a positive electrode plate. The positive electrode of the power supply is connected to the positive electrode plate, and the negative electrode of the 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 inlet 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 includes a dosing tank, a stirring paddle, a condenser, a feed inlet, a liquid outlet, a reactor insulation interlayer and a reactor body. The reactor is made of glass, and the effective reaction volume in the reactor body and the reactor insulation interlayer volume ratio is 1:0.1-5; the insulation medium in the reactor insulation interlayer 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, which is a high and low temperature cycler.

[0036] Preferably, in the biological inhibition reduction system, the reaction vessel is made of glass.

[0037] Preferably, in the biological inhibition reduction system, the power supply includes a positive power supply electrode and a negative power supply electrode, the air electrode is connected to the positive power supply electrode, and the metal electrode is connected to the negative power supply electrode; the feed storage tank is connected to the metal electrode, and the production agent storage tank is connected to the air electrode.

[0038] 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.

[0039] 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.

[0040] More preferably, the water inlet matrix tank comprises a water bath insulation interlayer, a stirring motor, a stirring paddle and a leakproof 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.

[0041] More preferably, the number of blades of the stirring paddle is 3-5 pairs.

[0042] More preferably, the stirring paddle is made of polytetrafluoroethylene.

[0043] 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.

[0044] 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.

[0045] More preferably, the configuration of the membrane tank is an upflow anaerobic sludge blanket reactor or an anaerobic sludge expanded bed reactor.

[0046] More preferably, a membrane assembly is placed in the center of the membrane pool, an overflow port is provided on the top, a biogas reflux outlet is provided on the top, and a biogas reflux inlet is provided on the bottom. The biogas is collected from the top of the membrane pool by a diaphragm aeration pump and then refluxed from the air inlet at the bottom of the membrane pool. An air filter is provided at the bottom of the membrane pool.

[0047] 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.

[0048] The invention adopts polyphthalaldehyde, sodium polyanisole sulfonate 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 through a wastewater biological inhibition reduction and anaerobic reactor composite process, thereby having the following beneficial effects: the wastewater biological inhibition reduction and anaerobic reactor composite process of the invention not only has a high COD removal rate of 73.3-91.7%; but also has a high methane yield of 17.3-35.4 L / d on average per day, thereby realizing efficient bioenergy recovery and wastewater resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 The invention relates to a process flow of a composite device of wastewater biological inhibition reduction and anaerobic membrane bioreactor.

[0050] Figure 2 This is a structural diagram of the oxidation-coupled hydrolysis biological inhibition and reduction system device of the reagent dosing type used in Example 1.

[0051] Figure 3 This is a structural diagram of the electrodialysis-coupled hydrolysis biological inhibition and reduction system used in Example 2.

[0052] Figure 4 This is the structural diagram of the anaerobic membrane bioreactor system.

[0053] Figure 5 This is the change of COD concentration of wastewater treated by anaerobic membrane bioreactor.

[0054] Figure 6 The abundance of drug resistance genes. DETAILED DESCRIPTION

[0055] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0056] The experimental methods in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.

[0057] Embodiment 1: Preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and after the treatment, 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 polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL.

[0058] Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device, including: Inlet system, biological inhibition and reduction system, anaerobic membrane bioreactor system and outlet system. The inlet system includes an inlet storage tank, and the outlet system includes an outlet storage tank. 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 probe and a temperature control device. The power supply includes a positive electrode and a negative electrode of the power supply, the air electrode is connected to the positive electrode of the power supply, and the metal electrode is connected to the negative electrode of the power supply. The feed storage tank is connected to the metal electrode, and the production agent storage tank is connected to the air electrode. 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 reactor is made of glass, and the effective reaction volume in the reactor body and the reactor insulation interlayer volume ratio is 1:1; the insulation medium in the reactor insulation interlayer is water. One end of the temperature probe is immersed in the insulation medium in the reactor insulation interlayer 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. The anaerobic membrane bioreactor system includes a low-temperature circulation machine, an 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. The inlet substrate tank includes 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 inlet substrate tank to the water bath insulation interlayer is 1:1. The material of the stirring paddle is polytetrafluoroethylene. The number of the paddle blades of the stirring paddle is 4 pairs. The length ratio of the paddle blade of the stirring paddle to the inner diameter of the inlet substrate tank is 1:0.2. The anaerobic reactor is configured as a continuous stirred tank reactor (CSTR). The anaerobic reactor is equipped with an insulation interlayer. The volume ratio of the effective water storage volume of the anaerobic reactor to the insulation layer of the anaerobic reactor is 1:1. The temperature inside the anaerobic reactor is 35°C. The membrane pool is configured as an upflow anaerobic sludge blanket reactor (UASB). The membrane assembly is placed in the center of the membrane pool, with an overflow port on the top, a biogas return outlet on the top, and a biogas return inlet on the bottom. The biogas is collected from the top of the membrane pool by a diaphragm aeration pump and then returned from the bottom air inlet of the membrane pool. An air filter is set at the bottom of the membrane pool; the membrane pool is equipped 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 insulation layer is 1:1. The temperature in the membrane pool is 35°C. The material of the membrane assembly is polyvinylidene fluoride hollow fiber ultrafiltration membrane, the number of membrane pairs is 50, the membrane pore size is 0.1μm, and the membrane area is 1m 2 .

[0059] 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: S1. The antibiotic wastewater is subjected to oxidation-reduction treatment. The antibiotic wastewater is first reacted with hydrogen peroxide, and the reaction is stirred at 300 rpm for 120 minutes at 65°C to obtain pretreated wastewater. The volume ratio of hydrogen peroxide to antibiotic wastewater is 1:50.

[0060] S2. Use 1 mol / L hydrochloric acid solution to adjust the pH of the pretreated wastewater to 7.3, add ferrous chloride, nickel chloride and cobalt chloride; then fully mix with municipal anaerobic digestion sludge to obtain a mud-water mixture; then treat the mud-water mixture with a polyvinylidene fluoride hollow fiber ultrafiltration membrane to obtain treated effluent. The mass ratio of nickel chloride to ferrous chloride is 1:4; the mass ratio of nickel chloride to cobalt chloride is 1:1.

[0061] Embodiment 2: The preparation of polyvinylidene fluoride hollow fiber ultrafiltration membrane is the same as in Example 1.

[0062] Compared with Example 1, the wastewater biological inhibition and reduction and anaerobic membrane bioreactor composite device has the same conditions as Example 1 except that the biological inhibition and reduction system is changed. The biological inhibition and reduction system of this embodiment includes an electrodialysis power supply, an electrode plate, an electrodialysis membrane stack, an anode liquid storage tank, a feed storage tank, a reactor, a temperature measuring 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 includes a dosing tank, a stirring paddle, a condenser, a feed port, a liquid outlet, a reactor insulation interlayer and a reactor body. The reactor is made of glass. The effective reaction volume in the reactor body and the volume ratio of the reactor insulation interlayer are 1:1. The insulation medium in the reactor insulation interlayer is water. One end of the temperature probe is immersed in the insulation medium in the reactor insulation interlayer 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.

[0063] 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: S1. The antibiotic wastewater is subjected to electrodialysis treatment, and then the antibiotic wastewater is subjected to hydrolysis reaction at 90° C. for 4 hours to obtain pretreated wastewater.

[0064] S2. Use 1 mol / L hydrochloric acid solution to adjust the pH of the pretreated wastewater to 7.3, add ferrous chloride, nickel chloride and cobalt chloride; then fully mix with municipal anaerobic digestion sludge to obtain a mud-water mixture; then treat the mud-water mixture with a polyvinylidene fluoride hollow fiber ultrafiltration membrane to obtain treated effluent. The mass ratio of nickel chloride to ferrous chloride is 1:4; the mass ratio of nickel chloride to cobalt chloride is 1:1.

[0065] Embodiment 3: Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, add polyphthalaldehyde and sodium polyanisyl sulfonate and stir for 4h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and after the treatment, let the temperature naturally drop to room temperature to obtain a casting liquid; pour the casting liquid 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 dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.2; the mass ratio of polyvinylidene fluoride powder to sodium polyanisyl sulfonate is 1:0.1.

[0066] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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 example.

[0067] 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.

[0068] Embodiment 4: Compared with Example 3, the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is the same as that of Example 3 except that the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is changed to 1:0.1. Other conditions are the same as those of Example 3.

[0069] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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 example.

[0070] 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.

[0071] Embodiment 5: Compared with Example 3, the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is the same as that of Example 3 except that the mass ratio of polyvinylidene fluoride powder to sodium polyanisole is changed to 1:0.05. Other conditions are the same as those of Example 3.

[0072] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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 example.

[0073] 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.

[0074] Embodiment 6: Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, add polyphthalaldehyde and sodium polyanisyl sulfonate and stir for 4h, then add poly(1-vinyl naphthalene) and stir for 4h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and naturally lower the temperature to room temperature to obtain a casting solution after the treatment is completed; pour the casting solution 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 dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.2; the mass ratio of polyvinylidene fluoride powder to sodium polyanisyl sulfonate is 1:0.1; the mass ratio of polyvinylidene fluoride powder to poly(1-vinyl naphthalene) is 1:0.1.

[0075] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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 example.

[0076] 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.

[0077] Embodiment 7: Compared with Example 7, the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is the same as that of Example 7 except that the mass ratio of polyvinylidene fluoride powder to poly(1-vinylnaphthalene) is changed to 1:0.05. Other conditions are the same as those of Example 7.

[0078] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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 example.

[0079] 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.

[0080] Comparative Example 1: Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, add polyphthalaldehyde and stir for 4h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and after the treatment, let the temperature naturally drop to room temperature to obtain a casting liquid; pour the casting liquid 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 dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to polyphthalaldehyde is 1:0.2.

[0081] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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.

[0082] 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.

[0083] Comparative Example 2: Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, add sodium polyanisyl sulfonate and stir for 4h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and after the treatment, let the temperature naturally drop to room temperature to obtain a casting liquid; pour the casting liquid 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 dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to sodium polyanisyl sulfonate is 1:0.1.

[0084] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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.

[0085] 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.

[0086] Comparative Example 3: Preparation of modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, comprising: Weigh polyvinylidene fluoride powder and polyvinyl pyrrolidone, add N-methyl pyrrolidone, stir and react at 70℃ for 8h, add poly(1-vinyl naphthalene) and stir for 4h, stop stirring after the reaction, adjust the temperature to 60℃ and vacuum degas for 4h, and after the treatment, 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 polyvinylidene fluoride hollow fiber ultrafiltration membrane. The mass ratio of polyvinyl pyrrolidone to polyvinylidene fluoride powder is 1:15; the dosage ratio of polyvinyl pyrrolidone to N-methyl pyrrolidone is 1g:100mL; the mass ratio of polyvinylidene fluoride powder to poly(1-vinyl naphthalene) is 1:0.1.

[0087] Compared with Example 1, the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device is the same as 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.

[0088] 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.

[0089] Experimental example: 1. Determination of Chemical Oxygen Demand (COD) Erythromycin production wastewater generated in the production process of the fermentation pharmaceutical industry was collected, and the erythromycin production wastewater was treated by using the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device 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, and the COD values ​​of the inlet and outlet water in the anaerobic membrane bioreactor were determined by the potassium dichromate method every day, and the COD removal rate was calculated, the COD value of the inlet water was recorded as X1, and the COD value of the outlet water was recorded as X2, and the COD removal rate = (X1-X2) / X1×100%.

[0090] Figure 1 The invention relates to a process flow of a composite device of wastewater biological inhibition reduction and anaerobic membrane bioreactor.

[0091] 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, wherein 1 is a power supply, 2 is an air electrode, 3 is a metal electrode, 4 is a feed storage tank, 5 is a production agent storage tank, 6 is a dosing tank, 7 is a stirring paddle, 8 is a condenser, 9 is a feed port, 10 is a reactor insulation interlayer, 11 is a reactor body, 12 is a liquid outlet, 13 is a temperature probe, and 14 is a temperature control device.

[0092] Figure 3 This is a structural diagram of the biological inhibition reduction system device for electrodialysis coupled hydrolysis used in Example 2, wherein 1 is an electrodialysis power supply, 2 is a negative electrode plate, 3 is an electrodialysis membrane stack, 4 is a power cord, 5 is a positive electrode plate, 6 is a cathode liquid storage tank, 7 is a feed storage tank, 8 is a water inlet or a dosing port, 9 is a stirring paddle, 10 is a condenser, 11 is a temperature probe, 12 is a feed port, 13 is a reactor insulation interlayer, 14 is a reactor body, 15 is a liquid outlet, and 16 is a temperature control device.

[0093] Figure 4 This is the structural diagram of the anaerobic membrane bioreactor system, where 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 sealing 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.

[0094] Figure 5 This is the change of COD concentration in wastewater treated by anaerobic membrane bioreactor. After 180 days of long-term continuous operation, the COD removal efficiency of the anaerobic membrane bioreactor is stabilized at 70-80%.

[0095] The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite devices of Examples 1-7 and Comparative Examples 1-3 were used to treat erythromycin production wastewater. 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 removal rate on the 180th day of treatment was calculated. The measurement results are shown in Table 1.

[0096] Table 1 COD removal rate (%)

[0097] 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, 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 modified polymer to obtain modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the modified polymer includes polyphthalaldehyde and sodium polyanisole sulfonate, and then the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is used as the membrane component of the anaerobic reactor to treat antibiotic wastewater; while Example 1-2 uses polyvinylidene fluoride powder to react with polyvinyl pyrrolidone to obtain polyvinylidene fluoride hollow fiber ultrafiltration membrane for wastewater treatment. This shows that the present invention uses modified polyvinylidene fluoride hollow fiber ultrafiltration membrane as a membrane component to treat antibiotic wastewater, which can improve the COD removal rate of antibiotic wastewater treatment.

[0098] The COD removal rate of Example 3 of the present invention is higher than that of Examples 4-5 because different amounts of polyphthalaldehyde and sodium polyanisole are used in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; 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 polyanisole as modified 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 modified polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and Comparative Example 2 only uses sodium polyanisole as a modified 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.

[0099] The COD removal rate 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-vinyl naphthalene) as a modified polymer to react with polyvinylidene fluoride powder to prepare the 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 the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the amount of poly (1-vinyl naphthalene) used is different; the COD removal rate 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-vinyl naphthalene) as a modified polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane. This shows that further using poly (1-vinyl naphthalene) as a modified polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane can further improve the COD removal rate of antibiotic wastewater treatment.

[0100] 2. Determination of methane production 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, the daily methane production during the treatment process is determined by gas chromatography, and the daily average methane production is calculated. The measurement results are shown in Table 2.

[0101] Table 2 Average daily methane production (L / d)

[0102] 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, 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 modified polymer to obtain modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, the modified polymer includes polyphthalaldehyde and sodium polyanisole sulfonate, and then the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane is used as the membrane component of the anaerobic reactor to treat antibiotic wastewater; while Example 1-2 uses polyvinylidene fluoride powder to react with polyvinyl pyrrolidone to obtain polyvinylidene fluoride hollow fiber ultrafiltration membrane for wastewater treatment. This shows that the present invention uses 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.

[0103] The average daily methane production of Example 3 of the present invention is higher than that of Examples 4-5 because different amounts of polyphthalaldehyde and sodium polyanisole sulfonate are used in the preparation of the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane; the average daily methane production 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 polyanisole sulfonate as modified 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 modified polymer to react with polyvinylidene fluoride powder to prepare the modified polyvinylidene fluoride hollow fiber ultrafiltration membrane, and Comparative Example 2 only uses sodium polyanisole sulfonate as a modified 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 production of methane produced during the treatment of antibiotic wastewater.

[0104] 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 modified 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 modified 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 modified 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.

[0105] 3. Determination of the abundance of drug resistance genes 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, posing potential health hazards.

[0106] The oxytetracycline production wastewater generated in the production process of the fermentation pharmaceutical industry was collected, and the oxytetracycline production wastewater was treated using the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite device in Example 1. The oxytetracycline 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 220 days. After the treatment, the abundance of drug-resistant genes in the sludge and effluent of the anaerobic membrane bioreactor was detected using the metagenome.

[0107] Figure 5 The abundance of drug-resistant genes. In the sludge in the anaerobic membrane bioreactor, the abundance of drug-resistant genes was lower than the detection limit of quantitative PCR, and no drug-resistant genes were detected in the effluent of the anaerobic membrane bioreactor. This shows that the bioinhibition reduction pretreatment can achieve efficient removal of antibiotics in wastewater. At the same time, the membrane components of the anaerobic membrane bioreactor can effectively control the biomass of the effluent, further preventing the spread of drug-resistant genes, thereby achieving effective control of drug-resistant genes in the wastewater treatment process of the pharmaceutical industry.

[0108] 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.

[0109] 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 protection scope of the present invention.

Claims

1. Wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process, including: S1. performing biological inhibition reduction pretreatment on the antibiotic wastewater to obtain pretreated wastewater; S2, mixing the pretreated wastewater with the anaerobic sludge, and treating the wastewater 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 component is a polyvinylidene fluoride hollow fiber ultrafiltration membrane, and the membrane pore size of the membrane component is 0.1-2 μm.

2. According to the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process described in claim 1, it is characterized in that: The membrane component is a modified polyvinylidene fluoride hollow fiber ultrafiltration membrane.

3. According to the wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process described in claim 2, it is characterized in that: 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 at least includes polyphthalaldehyde and sodium polyanisole sulfonate.

4. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 1, 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.

5. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 1 is characterized in that: 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 the municipal sewage treatment plant. 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 the municipal sewage treatment plant is 1:0.5-2.

6. The device used in the wastewater biological inhibition and reduction and anaerobic membrane bioreactor composite process as described in any one of claims 1-5 includes 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 cycle machine with a temperature control range of -20-200°C.

7. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 6, characterized in that: In the biological inhibition and reduction system, the reactor comprises a dosing tank, a stirring paddle, a condenser, a feed inlet, 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.

8. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 6, 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.

9. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 8, characterized in that: The water inlet matrix tank comprises a water bath insulation interlayer, a stirring motor, a stirring paddle and a leakproof 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.

10. The wastewater biological inhibition reduction and anaerobic membrane bioreactor composite process according to claim 8, 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.

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