An MBR reactor and its application

Abstract

This invention discloses an MBR reactor, belonging to the field of wastewater treatment technology. The MBR reactor of this invention includes an aerobic zone and a membrane module. Aerobic sludge is added to the aerobic zone, and the membrane module has a membrane. Functional mycelial balls are inoculated onto the aerobic sludge. The membrane contains inorganic particles. The method for preparing the functional mycelial balls includes: a) providing a mixed spore suspension of Aspergillus niger and Phanerochaete chrysosporium, adding biodegradable polymer particles, and culturing; b) adding a mixed bacterial suspension of Bacillus belye and Bacillus argentis to the mixed spore suspension, and culturing again. The main purpose of this invention is to reduce membrane fouling, improve the self-cleaning performance of the membrane, and increase the removal efficiency of pollutants such as residual antibiotics in wastewater.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and more specifically, to an MBR reactor and its application. Background Technology

[0002] MBR (Membrane Bio-Reactor) reactors are a novel wastewater treatment technology that organically combines membrane separation and biological treatment technologies. They offer advantages such as high pollutant removal rates, high sludge concentration, low residual sludge volume, and high effluent quality, leading to their widespread application in wastewater treatment. However, during operation, membrane fouling, caused by suspended solids, organic matter, and microbial adsorption and precipitation on the membrane surface, severely impacts membrane permeability, consequently affecting wastewater treatment efficiency and effluent quality. In particular, microbial adhesion to the membrane surface forms a biofilm, which further facilitates microbial adsorption and reduces membrane flux. Currently, to improve membrane antifouling capabilities and permeability, physical blending modification methods, such as inorganic nanoparticles and organic polymer blending, are used to modify the membrane bulk, thereby improving its hydrophilicity, pore structure, or imparting properties such as pressure resistance and catalytic oxidation.

[0003] Chinese patent CN106621862A discloses an antifouling PVDF membrane and its preparation method. This invention provides an antifouling PVDF membrane and its preparation method, comprising: 10-30 parts of polyvinylidene fluoride (PVDF), 60-90 parts of solvent, 5-15 parts of pore-forming agent, 1-10 parts of blending modifier, and 0.5-5 parts of nanomaterials. The blending modifier is one or more of sulfonated polyethersulfone, phenolphthalein-type polyethersulfone, polybutadiene anhydride, polyamide, and lithium chloride. The nanomaterials are one or more of nano-TiO2, nano-SiO2, nano-MgO, graphene oxide, graphene, nano-Al2O3, and nano-ZrO2. The PVDF membrane provided by this invention not only improves the uniformity of membrane pore size distribution and enhances the membrane's hydrophilicity and antifouling properties, but also reduces the number of membrane cleaning cycles, thereby extending the membrane's service life.

[0004] However, the above-mentioned solutions failed to achieve synergistic effects between the membrane and microorganisms in the application of PVDF membranes in membrane bioreactors, and also failed to solve the problem of increasing microbial content while reducing microbial adhesion on the membrane. Summary of the Invention

[0005] The technical problem that the invention aims to solve

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide an improved MBR reactor with a membrane loaded with inorganic particles and functional mycelial balls with synergistic interaction between fungi and bacteria, which improves the decomposition effect of pollutants such as organic matter and microorganisms in wastewater and attached to the membrane surface; while increasing the microbial content in the reactor, it reduces the adhesion of microorganisms to the membrane, thereby reducing the degree of membrane fouling and clogging, realizing membrane self-cleaning, and improving the removal capacity of COD, total nitrogen, and residual antibiotics.

[0007] Technical solution

[0008] To achieve the above objectives, the present invention provides an MBR reactor, comprising an aerobic zone and a membrane module, wherein aerobic sludge is added to the aerobic zone, characterized in that:

[0009] The membrane of the membrane module contains inorganic particles, including one or more of nano manganese dioxide powder, nano titanium dioxide powder, nano aluminum oxide powder, and nano ferric oxide powder.

[0010] The aerobic sludge is inoculated with functional mycelial balls, which include:

[0011] Aspergillus niger, Protozoa chrysospora, Bacillus belye, and Bacillus argentea.

[0012] As a further improvement of the present invention, the inorganic particles are one, two or more of the following: nano manganese dioxide powder, nano titanium dioxide powder, nano aluminum oxide powder, and nano ferric oxide powder.

[0013] As a further improvement of the present invention, the functional mycelial balls are prepared according to the following method:

[0014] a) Provide a spore suspension of Aspergillus niger and a spore suspension of Proteobacterium chrysosporum, mix them to obtain a blended spore suspension, and culture it; wherein, the blended spore suspension also contains biodegradable polymer particles;

[0015] The concentration of the Aspergillus niger spore suspension was 10. 6 ~10 7 spores / mL;

[0016] The spore suspension concentration of *Procambarus chrysospora* was 10. 5 ~10 6 spores / mL;

[0017] b) Provide a bacterial suspension containing Bacillus belyssioides and a bacterial suspension containing Bacillus argentissioides, and mix them to obtain a blended bacterial suspension.

[0018] The blended bacterial solution and the blended spore suspension are mixed and cultured.

[0019] The concentration of the bacterial solution containing Bacillus belyceae is 10. 8 ~10 9 CFU / mL;

[0020] The concentration of the bacterial solution containing Bacillus argentea is 10. 9 ~10 10 CFU / mL.

[0021] It's important to note that if the bacterial concentration is low, many mycelial balls will fail to colonize during the initial stages of mycelial ball formation, resulting in "empty" mycelial balls and a decrease in overall pollutant removal efficiency. Conversely, if the bacterial concentration is high, bacteria tend to exist in a free state in wastewater and attach extensively to the MBR membrane, exacerbating membrane fouling. On the other hand, excessively high fungal concentrations lead to massive mycelial proliferation, generating excessive foam during aeration and significantly reducing dissolved oxygen and mass transfer efficiency. Conversely, excessively low fungal concentrations result in a lower number of mycelial balls forming, leading to lower biomass per unit volume and decreased pollutant treatment efficiency. Additionally, spores / mL refers to the number of spores per unit volume.

[0022] As a further improvement of the present invention, the functional mycelial balls are prepared by the following method: a) a mixed spore suspension of Aspergillus niger and Phanerochaete chrysosporium is provided, biodegradable polymer particles are added, and culture is carried out; b) a mixed bacterial suspension of Bacillus belye and Bacillus argentis is added to the mixed spore suspension, and culture is carried out again;

[0023] An optional method for step a) is as follows: Aspergillus niger and P. chrysophagus are inoculated separately on the surface of PDA solid medium. After the spores mature, the spores are washed off with sterile PDA liquid medium to prepare spore suspensions of Aspergillus niger and P. chrysophagus. The spore suspensions of Aspergillus niger and P. chrysophagus are mixed to obtain a blended spore suspension, and biodegradable polymer particles are added for culturing.

[0024] An optional method for step b) is as follows: Bacillus belyssus and Bacillus argentis are inoculated separately into LB liquid medium and cultured to the logarithmic growth phase to obtain bacterial suspensions of Bacillus belyssus and Bacillus argentis; then the bacterial suspensions of Bacillus belyssus and Bacillus argentis are mixed to obtain a blended bacterial suspension, and the blended bacterial suspension is added to a blended spore suspension and cultured again.

[0025] As a further improvement of the present invention, in step a), the mixing volume ratio of the spore suspension of Aspergillus niger to the spore suspension of Proteobacterium chrysosporum is 1:1 to 1:1.5.

[0026] As a further improvement of the present invention, in step a), the biodegradable polymer particles are sterile polylactic acid particles, the particle size of the biodegradable polymer particles is 0.5~1mm, and the mass concentration of the biodegradable polymer particles is 0.1~0.2%.

[0027] and / or

[0028] In step b), the bacterial solution containing Bacillus belye and the bacterial solution containing Bacillus argentis are mixed at a volume ratio of 1:1 to 1:2 to obtain a blended bacterial solution;

[0029] The blended bacterial solution and the blended spore suspension are mixed at a volume ratio of 1:8 to 1:10.

[0030] As a further improvement of the present invention, the loading of the inorganic particles on the membrane is 5~10 mg / g.

[0031] As a further improvement of the present invention, the ratio of the amount of functional mycelial balls added to the filtration area of ​​the membrane is 500~700 mg / cm². 2 .

[0032] The membrane of the membrane module is prepared according to the following method:

[0033] S1) Prepare solution A containing polyvinylidene fluoride, polytetrafluoroethylene and polyvinylpyrrolidone;

[0034] The polyvinylidene fluoride has a mass concentration of 21.9% to 22.9%, the polytetrafluoroethylene and solvent have a mass concentration of 5.2% to 6.0%, and the polyvinylpyrrolidone has a mass concentration of 1% to 3%.

[0035] S2) Prepare a dispersion B containing inorganic particles;

[0036] The mass concentration of the inorganic particles is 1-2%.

[0037] S3) Mix the solution A and the dispersion B at a mass ratio of 1:1 to 1:1.5 to obtain a mixed solution C;

[0038] S4) Perform a film-forming treatment on the mixed solution C to obtain the membrane of the membrane module.

[0039] As a further improvement of the present invention, in step S2), the mass concentration of the inorganic particles is 1~2%.

[0040] Preferably, the membrane is prepared by the following method: S1) adding and dissolving polyvinylidene fluoride, polytetrafluoroethylene and polyvinylpyrrolidone in a solvent to obtain solution A; S2) adding inorganic nanoparticles to the solvent to disperse them in the solvent to obtain dispersion B; S3) mixing solution A and dispersion B at a mass ratio of 1:1 to 1:1.5 to obtain mixed solution C; S4) forming a membrane from mixed solution C.

[0041] As a further improvement of the present invention, the amount of aerobic mud added in the aerobic zone is 1~2g / L.

[0042] It should be noted that 1~2g / L refers to adding 1~2g of aerobic sludge per 1L of wastewater. Too much aerobic sludge will lead to a decrease in membrane flux; too little aerobic sludge will result in too low biomass and a decrease in reactor treatment efficiency.

[0043] It should be noted that adding functional mycelium balls to aerobic sludge can produce aerobic sludge inoculated with functional mycelium balls.

[0044] This invention also provides an application of an MBR reactor in the treatment of organic wastewater.

[0045] Preferably, the organic wastewater is antibiotic wastewater.

[0046] This invention also provides a method for treating organic wastewater using an MBR reactor:

[0047] At runtime:

[0048] Supply oxygen to the aerobic zone and aerate it at a rate of 1.5~2L / min;

[0049] Ozone is introduced into the MBR reactor at a rate of 0.3-0.5 L / min for 30-40 seconds, followed by a pause of 90-120 seconds, and the process is repeated in this sequence.

[0050] The hydraulic retention time of the MBR reactor is controlled at 40-45 h, and the pH of the organic wastewater in the MBR reactor is 7.5-8.0.

[0051] This invention also provides an application of an MBR reactor in the treatment of organic wastewater, including:

[0052] An MBR reactor is employed, comprising an aerobic zone and a membrane module, wherein aerobic sludge is added to the aerobic zone, characterized in that:

[0053] The membrane of the membrane module contains inorganic particles, including one, two or more of nano manganese dioxide powder, nano titanium dioxide powder, nano aluminum oxide powder, and nano ferric oxide powder.

[0054] The aerobic sludge is inoculated with functional mycelial balls, which include:

[0055] Aspergillus niger, Protozoa chrysospora, Bacillus belye, and Bacillus argentea.

[0056] The functional mycelial balls were prepared according to the following method:

[0057] a) Provide a spore suspension of Aspergillus niger and a spore suspension of Proteobacterium chrysosporum, mix them to obtain a blended spore suspension, and culture it; wherein, the blended spore suspension also contains biodegradable polymer particles;

[0058] The concentration of the Aspergillus niger spore suspension was 10. 6 ~10 7 spores / mL;

[0059] The spore suspension concentration of *Procambarus chrysospora* was 10. 5 ~10 6 spores / mL;

[0060] b) Provide a bacterial suspension containing Bacillus belyssioides and a bacterial suspension containing Bacillus argentissioides, and mix them to obtain a blended bacterial suspension.

[0061] The blended bacterial solution and the blended spore suspension are mixed and cultured.

[0062] The concentration of the bacterial solution containing Bacillus belyceae is 10. 8 ~10 9 CFU / mL;

[0063] The concentration of the bacterial solution containing Bacillus argentea is 10. 9 ~10 10 CFU / mL.

[0064] An optional method for step a) is as follows: Aspergillus niger and P. chrysophagus are inoculated separately on the surface of PDA solid medium. After the spores mature, the spores are washed off with sterile PDA liquid medium to prepare spore suspensions of Aspergillus niger and P. chrysophagus. The spore suspensions of Aspergillus niger and P. chrysophagus are mixed to obtain a blended spore suspension, and biodegradable polymer particles are added for culturing.

[0065] An optional method for step b) is as follows: Bacillus belyssus and Bacillus argentis are inoculated separately into LB liquid medium and cultured to the logarithmic growth phase to obtain bacterial suspensions of Bacillus belyssus and Bacillus argentis; then the bacterial suspensions of Bacillus belyssus and Bacillus argentis are mixed to obtain a blended bacterial suspension, and the blended bacterial suspension is added to a blended spore suspension and cultured again.

[0066] The ratio of the amount of functional mycelial balls added to the filtration area of ​​the membrane is 500~700 mg / cm². 2 .

[0067] As a further improvement of the present invention, in step a), the mixing volume ratio of the spore suspension of Aspergillus niger to the spore suspension of Proteobacterium chrysosporum is 1:1 to 1:1.5.

[0068] As a further improvement of the present invention, in step a), the biodegradable polymer particles are sterile polylactic acid particles, the particle size of the biodegradable polymer particles is 0.5~1mm, and the mass concentration of the biodegradable polymer particles is 0.1~0.2%.

[0069] and / or

[0070] In step b), the bacterial solution containing Bacillus belye and the bacterial solution containing Bacillus argentis are mixed at a volume ratio of 1:1 to 1:2 to obtain a blended bacterial solution;

[0071] The blended bacterial solution and the blended spore suspension are mixed at a volume ratio of 1:8 to 1:10.

[0072] The loading of inorganic particles on the membrane is 5~10 mg / g.

[0073] The membrane of the membrane module is prepared according to the following method:

[0074] S1) Prepare solution A containing polyvinylidene fluoride, polytetrafluoroethylene and polyvinylpyrrolidone;

[0075] The polyvinylidene fluoride has a mass concentration of 21.9% to 22.9%, the polytetrafluoroethylene and solvent have a mass concentration of 5.2% to 6.0%, and the polyvinylpyrrolidone has a mass concentration of 1% to 3%.

[0076] S2) Prepare a dispersion B containing inorganic particles;

[0077] S3) Mix the solution A and the dispersion B at a mass ratio of 1:1 to 1:1.5 to obtain a mixed solution C;

[0078] S4) Perform a film-forming treatment on the mixed solution C to obtain the membrane of the membrane module.

[0079] In step S2), the mass concentration of the inorganic particles is 1-2%.

[0080] In step S4), the mixed solution C can be coated using a coating device and a phase inversion method to form a film, thereby obtaining the membrane of the membrane module. This film formation method is simple to operate and has low preparation cost. Specifically, the coating device is adjusted to 200~250μm, the mixed solution C is spread evenly on a glass plate, and allowed to stand for 20~30s. The glass plate with the mixed solution C is then immersed in deionized water at 20~25℃ to complete the phase inversion process. The membrane is then slowly rinsed with flowing deionized water at a flow rate not exceeding 400~500mL / min for 40~60min to completely remove residual solvent from the membrane and obtain the membrane.

[0081] In step S2), the inorganic particles are one, two, or more of nano-manganese dioxide powder, nano-titanium dioxide powder, nano-aluminum oxide powder, and nano-ferric oxide powder; the solvents of solution A and dispersant B in steps S1) and S2) are one, two, or more of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and acetone.

[0082] The aerobic mud dosage in the aerobic zone is 1~2g / L.

[0083] During operation: oxygen is supplied to the MBR reactor at an aeration rate of 1.5~2L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.3~0.5L / min for 30~40s, followed by a pause of 90~120s, and this cycle is repeated. Ozone is also introduced into the MBR reactor at a rate of 0.3~0.5L / min for 30~40s, followed by a pause of 90~120s, and this cycle is repeated.

[0084] The hydraulic retention time of the MBR reactor is controlled at 40-45 h, and the pH of the organic wastewater in the MBR reactor is 7.5-8.0.

[0085] Beneficial effects

[0086] Compared with the prior art, the technical solution provided by this invention has the following advantages:

[0087] (1) The inorganic particles loaded on the membrane module in the MBR reactor of the present invention serve as catalysts. During use, they can catalyze the oxidant ozone to generate hydroxyl radicals with stronger oxidizing power, promote the oxidative decomposition of pollutants such as organic matter and microorganisms in wastewater and attached to the membrane surface by the oxidant, so as to improve the degradation of antibiotics and achieve membrane self-cleaning, and delay membrane fouling and clogging. Aspergillus niger and Protozoa flavus are fungi, Bacillus belyssus and Bacillus argentis are bacteria. The functional hyphae of fungi and bacteria work together to increase the microbial content in the reactor while reducing the attachment of microorganisms on the membrane, reducing the degree of fouling and clogging of the membrane by microbial attachment, and further improving the removal rate of COD, total nitrogen and residual antibiotics.

[0088] (2) There are various complex relationships among different microorganisms, such as competition, inhibition, and synergy. The four microorganisms selected in this invention have a synergistic effect, that is, they achieve a "1+1>2" effect in terms of function. The fungi in the functional mycelial balls of this invention are Aspergillus niger and P. chrysosporium flavonoids, which can enhance the removal of COD and residual antibiotics, while having a small amount of total nitrogen removal capacity, and providing the skeleton of the mycelial balls. The bacteria are Bacillus belyssus and Bacillus argentis, which can enhance the denitrification efficiency of the system, while having a certain effect on the removal of COD and residual antibiotics. Due to their small size, they can be wrapped and encased in the fungal mycelial balls. When a large number of functional bacteria are wrapped in the fungal mycelial balls, the functions of the two can complement each other, thereby improving the removal of COD, total nitrogen, and residual antibiotics by the functional mycelial balls. Moreover, the selected Aspergillus niger, P. chrysosporium flavonoids, Bacillus belyssus, and Bacillus argentis can tolerate ozone, avoiding the impact of ozone on the survival of microorganisms. There may be many other ozone-resistant fungi and bacteria, but simply mixing ozone-resistant bacteria together is not enough. Extensive research is needed to eliminate factors such as bacterial competition and inhibition. Constructing functional bacterial communities through random combinations of ozone-resistant bacteria to achieve synergistic effects is quite challenging.

[0089] (3) The sterile polylactic acid particles in the functional mycelial balls of the present invention can provide an attachment carrier for mycelia in the early stage, which is conducive to the attachment and growth of mycelial balls; moreover, the sterile polylactic acid particles have good biocompatibility and degradability, do not inhibit the growth of microorganisms, and can be used as a carbon source to provide nutrition for microorganisms after degradation. Attached Figure Description

[0090] Figure 1 This is a schematic diagram of a method for constructing an MBR reactor according to this application;

[0091] Figure 2 This is a schematic diagram of the structure of an MBR reactor according to this application.

[0092] Explanation of the labels in the diagram:

[0093] 10. Aerobic sludge; 101. Functional mycelial balls; 20. Membrane module; 30. Aeration pipe; 40. Pump. Detailed Implementation

[0094] The structures, proportions, and sizes illustrated in the accompanying drawings are merely for illustrative purposes and to aid those skilled in the art in understanding and reading the invention. They are not intended to limit the scope of the invention and therefore have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to size, without affecting the effectiveness and purpose of the invention, should still fall within the scope of the technical content disclosed herein. Furthermore, terms such as "upper," "lower," "left," "right," and "middle" used in this specification are merely for clarity and not intended to limit the scope of implementation. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention's implementation.

[0095] It should also be understood that, for clarity, certain features of this disclosure may be described herein in the context of individual embodiments, but may also be provided in combination with each other in individual embodiments. That is, unless obviously incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment, and such combination is considered to represent another different embodiment. Conversely, for brevity, various features of this disclosure described in the context of individual embodiments may also be provided individually or in any sub-combination. Finally, while a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure may also be considered an independent embodiment in itself.

[0096] Unless otherwise stated, it should be understood that each individual element in the list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments denoted as "A, B, or C" should be interpreted as including embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0097] In this disclosure, the singular forms of the articles “a,” “one,” and “the” also include the corresponding plural references, and references to a particular value include at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “substance” is a reference to at least one of such substance and its equivalents.

[0098] Ordinal terms such as “first” and “second” may be used to describe various components or fluids, but these components and fluids are not limited by these terms. Therefore, without departing from the teachings of this disclosure, these terms are used only to distinguish one component / fluid from another.

[0099] When an item is described using the combined terms “...and / or ...", the description should be understood to include any one of the listed items and all combinations thereof.

[0100] Concentration, amount, and other numerical data may be presented in range format herein. It should be understood that such range format is used solely for convenience and brevity and should be flexibly interpreted to include not only the values ​​explicitly stated as the limits of the range, but also all individual values ​​or subranges encompassed within the range, as if each value and subrange were explicitly stated. For example, a range of values ​​from about 1 to about 4.5 should be interpreted to include not only the explicitly stated limits of 1 to 4.5, but also individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that describe only a single value, such as “less than about 4.5,” which should be interpreted to include all the aforementioned values ​​and ranges. Furthermore, this interpretation should apply regardless of the breadth of the range or characteristic described.

[0101] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0102] in:

[0103] Aspergillus niger ( Aspergillus niger Purchased from the German Center for Microbial and Cell Culture Collection (DSMZ), accession number DSM 11167.

[0104] Phanerochaete chrysosporium ( Phanerochaete chrysosporium Burdsall The sample was purchased from the American Type Culture Collection (ATCC) with accession number ATCC 24725.

[0105] Bacillus belesiensis ( Bacillus velezensis Purchased from the China Industrial Microbial Culture Collection Center, accession number CICC 20025.

[0106] Bacillus argentea ( Bacillus aryabhattai Purchased from the China Industrial Microbial Culture Collection Center, accession number CICC 24574.

[0107] Combination Figure 2The working principle of an MBR reactor: An MBR reactor includes an aerobic zone and a membrane module 20. A membrane is installed on the membrane module 20 and located within the aerobic zone. Aerobic sludge 10 is added to the aerobic zone and distributed throughout. Functional mycelial balls 101 are inoculated onto the aerobic sludge 10. After the wastewater to be treated enters the aerobic zone of the reactor, oxygen is supplied to the aerobic zone through aeration pipes 30, typically from the bottom of the MBR reactor; ozone is also introduced into the aerobic zone. The membrane module 20 is submerged in the wastewater, and the aerobic sludge 10 inoculated with functional mycelial balls 101 is evenly distributed in the wastewater, removing antibiotics, organic matter, and other pollutants. Then, under the negative pressure generated by pump 40, the wastewater passes through the membrane in the membrane module 20 for filtration and is transferred outside the reactor.

[0108] The present invention will be further described below with reference to embodiments.

[0109] Example 1

[0110] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 70°C to obtain solution A, wherein the mass concentration of PVDF was 22.4%, the mass concentration of PTFE was 5.6%, and the mass concentration of PVP was 2%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 4 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 2%. Solution A and dispersion B were mixed at a mass ratio of 1:1 and ultrasonically and stirred for 20 hours to obtain mixed solution C. Adjust the coating device to 250 μm, spread the mixed solution C evenly on the glass plate, let it stand for 30 s, immerse the glass plate with mixed solution C in 20 °C deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 400 mL / min for 50 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 10 mg / g.

[0111] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 1×10⁻⁶. 7 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 6 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 9CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 10 CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.1% and a particle size of 1 mm were added. The mixture was cultured at 28°C and 180 rpm for 18 h with shaking. A blended bacterial solution was obtained by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1. This blended bacterial solution was then added to the system, with a volume ratio of 1:8 between the blended bacterial solution and the blended spore suspension. The mixture was then cultured at 32°C and 280 rpm for another 36 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment. These functional mycelial balls were then added to aerobic sludge to obtain the aerobic sludge used in this embodiment.

[0112] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls added to the membrane filtration area was 700 mg / cm². 2 Aeration is continuously supplied to the aerobic zone at a rate of 2 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.5 L / min, with a 40-second introduction followed by a 120-second pause, and this cycle is repeated. Antibiotic wastewater is introduced into the MBR reactor, and the hydraulic retention time (HRT) is controlled at 45 h. The pH of the antibiotic wastewater in the MBR reactor is controlled at 8.0.

[0113] The transmembrane pressure difference reflects the degree of membrane fouling; a larger transmembrane pressure difference indicates a higher degree of membrane fouling and clogging. After 30 days of continuous reactor operation, the transmembrane pressure difference was 12.7 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 32 mg / L, total nitrogen was 13 mg / L, and residual antibiotics were 9.7 mg / L. The removal rates for COD, total nitrogen, and residual antibiotics were 90.9%, 79.7%, and 75.9%, respectively.

[0114] Example 2

[0115] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 65°C to obtain solution A, wherein the mass concentration of PVDF was 21.9%, the mass concentration of PTFE was 5.2%, and the mass concentration of PVP was 1%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 3 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 1%. Solution A and dispersion B were mixed at a mass ratio of 1:1 and ultrasonically and stirred for 16 hours to obtain mixed solution C. Adjust the coating device to 200 μm, spread the mixed solution C evenly on the glass plate, let it stand for 20 s, immerse the glass plate with the mixed solution C in 20℃ deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 400 mL / min for 40 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 5 mg / g.

[0116] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 1×10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 9 CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.1% and a particle size of 0.5 mm were added. The mixture was cultured at 28°C and 180 rpm for 18 h with shaking. A blended bacterial solution was obtained by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1. This blended bacterial solution was then added to the system at a volume ratio of 1:8 to the blended spore suspension, and the mixture was cultured at 30°C and 250 rpm for another 20 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment. These functional mycelial balls were then added to aerobic sludge to obtain the aerobic sludge used in this embodiment.

[0117] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls added to the membrane filtration area was 500 mg / cm². 2 Aeration is continuously supplied to the aerobic zone at a rate of 1.5 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.3 L / min, with a 30-second introduction followed by a 90-second pause, and this cycle is repeated. Antibiotic wastewater is then introduced into the MBR reactor, with the HRT (Heat Retention Time) controlled at 40 h and the pH of the antibiotic wastewater within the MBR reactor controlled at 7.5.

[0118] The transmembrane pressure difference reflects the degree of membrane fouling; a larger transmembrane pressure difference indicates a higher degree of membrane fouling and clogging. After 30 days of continuous reactor operation, the transmembrane pressure difference was 15.5 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 26 mg / L, total nitrogen was 14 mg / L, and residual antibiotics were 7.3 mg / L. The removal rates for COD, total nitrogen, and residual antibiotics were 92.6%, 78.1%, and 81.9%, respectively.

[0119] Example 3

[0120] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 70°C to obtain solution A, wherein the mass concentration of PVDF was 22.9%, the mass concentration of PTFE was 6%, and the mass concentration of PVP was 3%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 4 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 2%. Solution A and dispersion B were mixed at a mass ratio of 1:1.5 and ultrasonically stirred for 20 hours to obtain mixed solution C. Adjust the coating device to 250 μm, spread the mixed solution C evenly on the glass plate, let it stand for 30 s, immerse the glass plate with mixed solution C in 25 °C deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 500 mL / min for 60 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 10 mg / g.

[0121] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 1×10⁻⁶. 7 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 6 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 9 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 10 CFU / mL. Spore suspensions of *Aspergillus niger* and *Phanerochaete chrysospora* were mixed at a volume ratio of 1:1.5, and sterile polylactic acid (PLA) particles (0.2% by mass, particle size controlled at 1 mm) were added. The mixture was cultured at 30℃ and 220 rpm for 20 h with shaking. Bacillus belye and *Bacillus argentea* were mixed at a volume ratio of 1:1 to obtain a blended bacterial solution. This blended bacterial solution was then added to the system at a volume ratio of 1:10 to the blended spore suspension, and the mixture was further cultured at 32℃ and 280 rpm for 36 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, obtaining the functional mycelial balls used in this embodiment. These functional mycelial balls were then added to aerobic mud to obtain the aerobic mud used in this embodiment.

[0122] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls added to the membrane filtration area was 700 mg / cm². 2 Continuous oxygen supply is provided to the aerobic zone at an aeration rate of 2 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.5 L / min, with a 40-second introduction followed by a 120-second pause, and this cycle is repeated. Antibiotic wastewater is then introduced into the MBR reactor, with the HRT (Heat Retention Time) controlled at 45 h and the pH of the antibiotic wastewater within the MBR reactor controlled at 8.0.

[0123] The transmembrane pressure difference reflects the degree of membrane fouling; a larger transmembrane pressure difference indicates a higher degree of membrane fouling and clogging. After 30 days of continuous reactor operation, the transmembrane pressure difference was 16.1 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 28 mg / L, total nitrogen was 15 mg / L, and residual antibiotics were 7.0 mg / L. The removal rates for COD, total nitrogen, and residual antibiotics were 92.1%, 76.6%, and 82.6%, respectively.

[0124] Example 4

[0125] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 65°C to obtain solution A, wherein the mass concentration of PVDF was 21.9%, the mass concentration of PTFE was 5.2%, and the mass concentration of PVP was 1%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 3 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 1%. Solution A and dispersion B were mixed at a mass ratio of 1:1 and ultrasonically and stirred for 16 hours to obtain mixed solution C. Adjust the coating device to 200 μm, spread the mixed solution C evenly on the glass plate, let it stand for 20 s, immerse the glass plate with the mixed solution C in 20℃ deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 400 mL / min for 40 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 5 mg / g.

[0126] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 1×10⁻⁶. 7 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 6 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 9 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 10CFU / mL. Spore suspensions of *Aspergillus niger* and *Phanerochaete chrysospora* were mixed at a volume ratio of 1:1.5, and sterile polylactic acid (PLA) particles (0.2% mass concentration, 1 mm particle size) were added. The mixture was cultured at 30°C and 220 rpm with shaking for 20 h. Bacillus belye and *Bacillus argentea* were mixed at a volume ratio of 1:1 to obtain a blended bacterial solution. This blended bacterial solution was then added to the system at a volume ratio of 1:10 to the blended spore suspension, and the mixture was further cultured at 32°C and 280 rpm with shaking for 36 h. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, obtaining the functional mycelial balls used in this embodiment. These functional mycelial balls were then poured into aerobic mud to obtain the aerobic mud used in this embodiment.

[0127] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls added to the membrane filtration area was 700 mg / cm². 2 Continuous oxygen supply is provided to the aerobic zone at an aeration rate of 2 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.5 L / min, with a 40-second introduction followed by a 120-second pause, and this cycle is repeated. Antibiotic wastewater is then introduced into the MBR reactor, with the HRT (Heat Retention Time) controlled at 45 h and the pH of the antibiotic wastewater within the MBR reactor controlled at 8.0.

[0128] The transmembrane pressure difference reflects the degree of membrane fouling; a larger transmembrane pressure difference indicates a higher degree of membrane fouling and clogging. After 30 days of continuous reactor operation, the transmembrane pressure difference was 16.9 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 30 mg / L, total nitrogen was 17 mg / L, and residual antibiotics were 9.2 mg / L. The removal rates for COD, total nitrogen, and residual antibiotics were 91.5%, 73.4%, and 77.2%, respectively.

[0129] Example 5

[0130] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 70°C to obtain solution A, wherein the mass concentration of PVDF was 22.9%, the mass concentration of PTFE was 6%, and the mass concentration of PVP was 3%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 4 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 2%. Solution A and dispersion B were mixed at a mass ratio of 1:1.5 and ultrasonically stirred for 20 hours to obtain mixed solution C. Adjust the coating device to 250 μm, spread the mixed solution C evenly on the glass plate, let it stand for 30 s, immerse the glass plate with mixed solution C in 25 °C deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 500 mL / min for 60 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 10 mg / g.

[0131] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 1×10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 9 CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.1% and a particle size of 0.5 mm were added. The mixture was cultured at 28°C and 180 rpm for 18 h with shaking. A blended bacterial solution was obtained by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1. This blended bacterial solution was then added to the system at a volume ratio of 1:8 to the blended spore suspension, and the mixture was cultured at 30°C and 250 rpm for another 20 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment. These functional mycelial balls were then poured into aerobic mud to obtain the aerobic mud used in this embodiment.

[0132] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls added to the membrane filtration area was 500 mg / cm². 2 Aeration is continuously supplied to the aerobic zone at a rate of 1.5 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.3 L / min, with a 30-second introduction followed by a 90-second pause, and this cycle is repeated. Antibiotic wastewater is then introduced into the MBR reactor, with the HRT (Heat Retention Time) controlled at 40 h and the pH of the antibiotic wastewater within the MBR reactor controlled at 7.5.

[0133] The transmembrane pressure difference reflects the degree of membrane fouling; a larger transmembrane pressure difference indicates a higher degree of membrane fouling and clogging. After 30 days of continuous reactor operation, the transmembrane pressure difference was 15.8 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 21 mg / L, total nitrogen was 19 mg / L, and residual antibiotics were 8.8 mg / L. The removal rates for COD, total nitrogen, and residual antibiotics were 94.1%, 70.3%, and 78.2%, respectively.

[0134] Examples 6-9

[0135] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 67°C to obtain solution A, wherein the mass concentration of PVDF was 22.4%, the mass concentration of PTFE was 5.6%, and the mass concentration of PVP was 2%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 3.5 h to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 1.5%. Solution A and dispersion B were mixed at a mass ratio of 1:1.3 and ultrasonically stirred for 16 h to obtain mixed solution C. Adjust the coating device to 200 μm, spread the mixed solution C evenly on the glass plate, let it stand for 20 s, immerse the glass plate with mixed solution C in deionized water at 23 °C to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 450 mL / min for 50 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 7.5 mg / g.

[0136] Aspergillus niger and Phanerochaete chrysosporium were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. Bacillus belye and Bacillus aureus were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the Aspergillus niger spore suspension was controlled at 5 × 10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 5 × 10⁻⁶ spores / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 5 × 10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 5×10⁻⁶. 9 CFU / mL. Spore suspensions of *Aspergillus niger* and *Phanerochaete chrysospora* were mixed at a volume ratio of 1:1.3. Sterile polylactic acid (PLA) particles with a mass concentration of 0.15% and a particle size of 0.7 mm were added. The mixture was incubated at 29°C and 200 rpm with shaking for 19 h. A mixed bacterial solution was obtained by thoroughly mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1. This mixed bacterial solution was then added to the system, with a volume ratio of 1:9 between the mixed bacterial solution and the mixed spore suspension. The mixture was then incubated at 31°C and 260 rpm with shaking for another 28 h. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the functional mycelial balls used in this embodiment. These functional mycelial balls were then poured into aerobic mud to obtain the aerobic mud used in this embodiment.

[0137] Four 4L MBR reactors were set up, labeled A0, A1, A2, and A3. The prepared membranes were installed on the MBR membrane modules, and membrane modules with a filtration area of ​​100 cm² were inserted into each MBR reactor. 2 Then, aerobic sludge was inoculated into MBR reactors A0, A1, A2, and A3, respectively, at a dosage of 1 g / L. The ratio of the amount of functional mycelial balls on the aerobic sludge to the filtration area of ​​the membrane in MBR reactors A0, A1, A2, and A3 was 0 mg / cm². 2 250mg / cm 2 500mg / cm 2 800mg / cm 2 In each MBR reactor, oxygen is continuously supplied to the aerobic zone at an aeration rate of 1.7 L / min. Ozone is uniformly introduced into the MBR reactor at a rate of 0.4 L / min, with a 35-second introduction followed by a 100-second pause, and this cycle is repeated. Antibiotic wastewater is introduced into the MBR reactor, and the HRT (Heat Retention Time) of the MBR reactor is controlled at 42 h, while the pH of the antibiotic wastewater in the MBR reactor is controlled at 7.8.

[0138] Four reactors were operated continuously under the same conditions for 30 days to treat antibiotic wastewater. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. After treatment, the transmembrane pressure difference and the removal rate of each pollutant are shown in Table 1.

[0139] Table 1. Effect of the ratio of functional mycelial ball dosage to membrane filtration area on antibiotic wastewater treatment

[0140]

[0141] As shown in Examples 6-8 of Table 1, the removal rates of COD, total nitrogen, and residual antibiotics continuously increased with the increase of the amount of mycelial balls added to the MBR reactor. In Example 6, the ratio of the amount of functional mycelial balls added to the membrane filtration area was 0 mg / cm². 2 In other words, no functional mycelial balls were added, resulting in poor removal of COD, total nitrogen, and residual antibiotics. As shown in Examples 8 and 9, the removal efficiency increased with the ratio of functional mycelial balls added to the membrane filtration area in the MBR reactor from 500 mg / cm². 2 Increased to 800 mg / cm 2 The removal rates of COD, total nitrogen, and residual antibiotics decreased, and the transmembrane pressure difference increased significantly. This was because the amount of functional mycelium balls added was too large, resulting in more free microorganisms, which led to more microorganisms adhering to the membrane, aggravating membrane fouling and increasing the transmembrane pressure difference. Moreover, the manganese dioxide on the membrane could not catalyze ozone to generate hydroxyl radicals in a timely and effective manner to remove residual antibiotics.

[0142] Example 10

[0143] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 68°C to obtain solution A, wherein the mass concentration of PVDF was 22%, the mass concentration of PTFE was 5.4%, and the mass concentration of PVP was 1.5%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 3.2 h to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 1.5%. Solution A and dispersion B were mixed at a mass ratio of 1:1.3 and ultrasonically stirred for 17 h to obtain mixed solution C. The coating device was adjusted to 210 μm, and the mixed solution C was spread evenly on the glass plate. After standing for 25 seconds, the glass plate with mixed solution C was immersed in deionized water at 22 °C to complete the phase inversion process. Then, the membrane was slowly rinsed with flowing deionized water at a flow rate of 420 mL / min for 45 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane was 7.5 mg / g.

[0144] Aspergillus niger and *Phanerochaete chrysosporium* were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. *Bacillus belye* and *Bacillus argentea* were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the *Aspergillus niger* spore suspension was controlled at 3 × 10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 6 × 10⁻⁶ / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 9 CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.15% and a particle size of 0.7 mm were added. The mixture was cultured at 29°C and 200 rpm for 19 h with shaking. A blended bacterial solution was obtained by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1.5. This blended bacterial solution was then added to the system, with a volume ratio of 1:8 between the blended bacterial solution and the blended spore suspension. The mixture was then cultured at 32°C and 280 rpm for another 36 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment. These functional mycelial balls were then poured into aerobic mud to obtain the aerobic mud used in this embodiment.

[0145] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 The ratio of functional mycelial balls added to the membrane filtration area was 500 mg / cm². 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 1.5 g / L. Aeration was continuously supplied to the aerobic zone at a rate of 2 L / min. Ozone was uniformly introduced into the MBR reactor at a rate of 0.5 L / min, with a 40-second induction followed by a 120-second pause, and this cycle was repeated. Antibiotic wastewater was then introduced into the MBR reactor, maintaining a hydraulic retention time (HRT) of 45 h and a pH of 8.0.

[0146] Example 11

[0147] Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) were added to N,N-dimethylacetamide (DMAC) and uniformly dissolved in DMAC at 70°C to obtain solution A, wherein the mass concentration of PVDF was 22.7%, the mass concentration of PTFE was 6%, and the mass concentration of PVP was 3%. Nano-MnO2 powder was added to DMAC and ultrasonically treated for 4 hours to uniformly disperse it in DMAC, obtaining dispersion B, with a nano-MnO2 mass concentration of 2%. Solution A and dispersion B were mixed at a mass ratio of 1:1.5 and ultrasonically stirred for 19 hours to obtain mixed solution C. Adjust the coating device to 250 μm, spread the mixed solution C evenly on the glass plate, let it stand for 30 s, immerse the glass plate with mixed solution C in 25 °C deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 480 mL / min for 60 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 7.5 mg / g.

[0148] Aspergillus niger and *Phanerochaete chrysosporium* were inoculated onto the surface of PDA solid medium. After the spores matured, they were washed off with sterile PDA liquid medium to prepare spore suspensions. *Bacillus belye* and *Bacillus argentea* were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the *Aspergillus niger* spore suspension was controlled at 6 × 10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 6 × 10⁻⁶ / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 2×10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 2×10⁻⁶. 9CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1.5 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.2% and a particle size of 1 mm were added. The mixture was cultured at 29°C and 200 rpm for 20 h with shaking. A blended bacterial solution was obtained by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:2. This blended bacterial solution was then added to the system, with a volume ratio of 1:8 between the blended bacterial solution and the blended spore suspension. The mixture was then cultured at 31°C and 260 rpm for another 30 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment. These functional mycelial balls were then poured into aerobic mud to obtain the aerobic mud used in this embodiment.

[0149] The prepared membrane is installed on the MBR membrane module, and the membrane module with a filtration area of ​​100 cm² is inserted into a 4L MBR reactor. 2 The ratio of functional mycelial balls added to the membrane filtration area was 600 mg / cm². 2 Aerobic sludge was inoculated into the MBR reactor at a dosage of 2 g / L. Aeration was continuously supplied to the aerobic zone at a rate of 2 L / min. Ozone was uniformly introduced into the MBR reactor at a rate of 0.4 L / min, with a 35-second induction followed by a 110-second pause, and this cycle was repeated. Antibiotic wastewater was then introduced into the MBR reactor, maintaining a hydraulic retention time (HRT) of 45 h and a pH of 7.8.

[0150] Comparative Example 1

[0151] Basically the same as Example 2, except that a commercially available PVDF membrane with a filtration area of ​​100 cm² is installed in a 4L MBR reactor. 2 .

[0152] After 30 days of continuous operation, the transmembrane pressure difference was 29.8 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 85 mg / L, total nitrogen was 38 mg / L, and residual antibiotics were 26.3 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 75.9%, 45.3%, and 34.7%, respectively.

[0153] Comparative Example 2

[0154] The process is essentially the same as in Example 2, except that polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyvinylpyrrolidone (PVP) are added to N,N-dimethylacetamide (DMAC), where the mass concentration of PVDF is 22.4%, PTFE is 5.6%, and PVP is 2%. The PVDF and PVP are uniformly dissolved in DMAC at 50°C to obtain solution A. Nano-MnO2 powder is added to DMAC and ultrasonically treated for 1 hour to uniformly disperse it, obtaining dispersion B with a nano-MnO2 mass concentration of 2%. Solution A and dispersion B are mixed at a mass ratio of 1:2 and ultrasonically and stirred for 10 hours to obtain mixed solution C. Adjust the coating device to 200 μm, spread the mixed solution C evenly on the glass plate, let it stand for 10 s, immerse the glass plate with the mixed solution C in 20 °C deionized water to complete the phase inversion process, and then slowly rinse the membrane with flowing deionized water at a flow rate of 800 mL / min for 20 min to completely remove the residual solvent on the membrane and obtain the membrane. The loading of inorganic particles on the membrane is 10 mg / g.

[0155] After 30 days of continuous operation, the transmembrane pressure difference was 26.7 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 101 mg / L, total nitrogen was 47 mg / L, and residual antibiotics were 31.4 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 71.4%, 26.6%, and 22.1%, respectively.

[0156] Comparative Example 3

[0157] The procedure was essentially the same as in Example 1, except that: *Aspergillus niger* and *Procambarus chrysospora* were inoculated onto the surface of PDA solid medium, and after the spores matured, they were washed off with sterile PDA liquid medium to prepare a spore suspension. *Bacillus belye* and *Bacillus argentea* were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the *Aspergillus niger* spore suspension was controlled at 1 × 10⁻⁶. 5 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 9 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 5 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 6CFU / mL. A spore suspension of *Aspergillus niger* and *Phanerochaete chrysospora* was mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles (0.05% by mass, particle size controlled at 0.2 mm) were added. The mixture was incubated at 33°C and 250 rpm for 12 h with shaking. A blended bacterial solution was also prepared by mixing *Bacillus belyssioides* and *Bacillus argentea* at a volume ratio of 1:1. This blended bacterial solution was then added to the system, with a volume ratio of 1:15 between the blended bacterial solution and the blended spore suspension. The mixture was incubated at 28°C and 220 rpm for another 15 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment.

[0158] After 30 days of continuous operation, the transmembrane pressure difference was 20.9 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 84 mg / L, total nitrogen was 30 mg / L, and residual antibiotics were 17.2 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 76.2%, 53.1%, and 57.3%, respectively.

[0159] Comparative Example 4

[0160] The process is basically the same as in Example 2, except that: *Aspergillus niger* and *Procambarus chrysospora* were inoculated onto the surface of PDA solid medium, and after the spores matured, they were washed off with sterile PDA liquid medium to prepare a spore suspension. *Bacillus belye* and *Bacillus aureus* were inoculated into LB liquid medium and cultured to the logarithmic growth phase. The concentration of the *Aspergillus niger* spore suspension was controlled at 1 × 10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 5 spores / mL; the bacterial concentration of Bacillus belyceae was controlled at 1×10⁻⁶. 8 CFU / mL, the bacterial concentration of Bacillus argentea is 1×10⁻⁶. 9 CFU / mL. A mixed spore suspension was prepared by mixing *Aspergillus niger* spore suspension and *Phanerochaete chrysosporium* spore suspension at a volume ratio of 1:1 and incubating at 28°C and 180 rpm for 18 h with shaking. A mixed bacterial solution was prepared by mixing *Bacillus belye* bacterial solution and *Bacillus argentea* bacterial solution at a volume ratio of 1:1. This mixed bacterial solution was then added to the system, with a volume ratio of the mixed bacterial solution to the mixed spore suspension of 1:8. The system was then incubated at 30°C and 250 rpm for another 20 h with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment.

[0161] After 30 days of continuous operation, the transmembrane pressure difference was 25.4 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 77 mg / L, total nitrogen was 36 mg / L, and residual antibiotics were 16.8 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 78.2%, 43.8%, and 58.3%, respectively.

[0162] Comparative Example 5

[0163] The procedure is basically the same as in Example 1, except that: aerobic sludge is inoculated into the MBR reactor at a dosage of 1 g / L. Aeration is continuously supplied to the aerobic zone at an aeration rate of 1.5 L / min. Antibiotic wastewater is introduced into the MBR reactor, and the HRT of the MBR reactor is controlled at 40 h, while the pH of the antibiotic wastewater in the MBR reactor is controlled at 7.5.

[0164] After 30 days of continuous operation, the transmembrane pressure difference was 28.7 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 168 mg / L, total nitrogen was 45 mg / L, and residual antibiotics were 34.3 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 52.4%, 29.7%, and 14.9%, respectively.

[0165] Comparative Example 6

[0166] The process is basically the same as in Example 2, except that: *Aspergillus niger* and *Procambarus chrysospora* were inoculated onto the surface of PDA solid culture medium, and after the spores matured, they were washed off with sterile PDA liquid culture medium to prepare a spore suspension. The concentration of the *Aspergillus niger* spore suspension was controlled at 1 × 10⁻⁶. 6 The spore concentration of *Phanerochaete chrysosporium* was 1 × 10⁻⁶ spores / mL. 5 The spores / mL of Aspergillus niger and Phanerochaete chrysospora were mixed at a volume ratio of 1:1 to obtain a blended spore suspension. Sterile polylactic acid (PLA) particles with a mass concentration of 0.1% and a particle size of 0.5 mm were added. The mixture was incubated at 28°C and 180 rpm for 18 hours with shaking. The resulting mycelial balls were filtered and washed with sterile physiological saline to complete the preparation of the mycelial balls, yielding the functional mycelial balls used in this embodiment.

[0167] After 30 days of continuous operation, the transmembrane pressure difference was 14.4 kPa. The influent COD was 353 mg / L, total nitrogen was 64 mg / L, and residual antibiotics were 40.3 mg / L. The treated effluent COD was 80 mg / L, total nitrogen was 39 mg / L, and residual antibiotics were 16.4 mg / L. The removal rates of COD, total nitrogen, and residual antibiotics were 77.3%, 39.1%, and 59.3%, respectively.

[0168] The present invention and its embodiments have been described above illustratively. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual method is not limited to this. Therefore, if those skilled in the art are inspired by this description and design similar structures and embodiments without departing from the spirit of the present invention, such designs should fall within the protection scope of the present invention.

Claims

1. An MBR reactor, comprising an aerobic zone and a membrane module, wherein aerobic sludge is added to the aerobic zone, characterized in that: The membrane of the membrane module contains inorganic particles, including one or more of nano manganese dioxide powder, nano titanium dioxide powder, nano aluminum oxide powder, and nano iron oxide powder. The aerobic sludge is inoculated with functional mycelial balls, which include: Aspergillus niger, Protozoa chrysospora, Bacillus belye, and Bacillus argentea.

2. The MBR reactor according to claim 1, characterized in that: The functional mycelial balls were prepared according to the following method: a) Provide a spore suspension of Aspergillus niger and a spore suspension of Proteobacterium chrysosporum to obtain a blended spore suspension, and culture it; wherein, the blended spore suspension also contains biodegradable polymer particles; The concentration of the Aspergillus niger spore suspension was 10. 6 ~10 7 spores / mL; The spore suspension concentration of *Procambarus chrysospora* was 10. 5 ~10 6 spores / mL; b) Provide a bacterial suspension containing Bacillus belyssioides and a bacterial suspension containing Bacillus argentissioides, and mix them to obtain a blended bacterial suspension. The blended bacterial solution and the blended spore suspension are mixed and cultured. The concentration of the bacterial solution containing Bacillus belyceae is 10. 8 ~10 9 CFU / mL; The concentration of the bacterial solution containing Bacillus argentea is 10. 9 ~10 10 CFU / mL.

3. The MBR reactor according to claim 2, characterized in that: In step a), the mixing volume ratio of the Aspergillus niger spore suspension to the Protozoa chrysophagus spore suspension is 1:1 to 1:1.

5.

4. The MBR reactor according to claim 3, characterized in that: In step a), the biodegradable polymer particles are sterile polylactic acid particles, the particle size of the biodegradable polymer particles is 0.5~1mm, and the mass concentration of the biodegradable polymer particles is 0.1~0.2%; And / or, In step b), the bacterial solution containing Bacillus belye and the bacterial solution containing Bacillus argentis are mixed at a volume ratio of 1:1 to 1:2 to obtain a blended bacterial solution; The blended bacterial solution and the blended spore suspension are mixed at a volume ratio of 1:8 to 1:

10.

5. An MBR reactor according to claim 1, characterized in that: The loading of inorganic particles on the membrane is 5~10 mg / g.

6. An MBR reactor according to any one of claims 1 to 5, characterized in that: The ratio of the amount of functional mycelial balls added to the filtration area of ​​the membrane is 500~700 mg / cm². 2 .

7. An MBR reactor according to any one of claims 1 to 5, characterized in that: The membrane of the membrane module is prepared according to the following method: S1) Prepare solution A containing polyvinylidene fluoride, polytetrafluoroethylene and polyvinylpyrrolidone; The polyvinylidene fluoride has a mass concentration of 21.9% to 22.9%, the polytetrafluoroethylene and solvent have a mass concentration of 5.2% to 6.0%, and the polyvinylpyrrolidone has a mass concentration of 1% to 3%. S2) Prepare a dispersion B containing inorganic particles; The mass concentration of the inorganic particles is 1-2%. S3) Mix the solution A and the dispersion B at a mass ratio of 1:1 to 1:1.5 to obtain a mixed solution C; S4) Perform a film-forming treatment on the mixed solution C to obtain the membrane of the membrane module.

8. An MBR reactor according to claim 7, characterized in that: The aerobic mud dosage in the aerobic zone is 1~2g / L.

9. The application of the MBR reactor according to any one of claims 1-8 in the treatment of organic wastewater.

10. A method for treating organic wastewater using the MBR reactor according to any one of claims 1-8, characterized in that: At runtime: Supply oxygen to the aerobic zone and aerate it; Ozone is introduced into the MBR reactor at a rate of 0.3-0.5 L / min for 30-40 seconds, followed by a pause of 90-120 seconds, and the process is repeated in this sequence. The hydraulic retention time of the MBR reactor is controlled at 40-45 h, and the pH of the organic wastewater in the MBR reactor is 7.5-8.0.

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