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CN-121972021-A - High-oxygen-permeability hollow fiber membrane material and preparation method thereof

CN121972021ACN 121972021 ACN121972021 ACN 121972021ACN-121972021-A

Abstract

The invention discloses a high oxygen permeability hollow fiber membrane material and a preparation method thereof, comprising the following steps of S1, adding a matrix material into an internal mixer to enable the matrix material to be fully plasticized and form a uniform continuous phase, S2, adding reinforcing filler into a uniform system obtained in the step S1 to enable the reinforcing filler to be uniformly distributed in the matrix material to form a nano reinforcing structure, S3, cooling the system, adding a functional material into a dispersion obtained in the step S2 to enable the functional material to be uniformly distributed in the matrix material, S4, placing a sizing material obtained in the step S3 into an open mill to carry out roll wrapping treatment, adding crosslinking to enable a crosslinking agent to be uniformly dispersed, then calendaring into sheets, S5, placing the sheets obtained in the step S4 into a hot press to carry out primary vulcanization, controlling the thickness of the film, and then carrying out secondary vulcanization to obtain a film product. The membrane material prepared by the preparation method provided by the invention can improve oxygen transfer efficiency, mechanical strength and biocompatibility.

Inventors

  • LU MEIJIE
  • ZENG HAIBING
  • LU MINMING

Assignees

  • 苏州科特环保股份有限公司

Dates

Publication Date
20260505
Application Date
20260402

Claims (11)

  1. 1. The preparation method of the high oxygen permeability hollow fiber membrane material is characterized by comprising the following steps: Step S1, adding a matrix material into an internal mixer, controlling the temperature to be 80-120 ℃, and mixing for a period of time to enable the matrix material to be fully plasticized and form a uniform continuous phase, wherein the matrix material is methyl vinyl silicone rubber raw rubber and vinyl polydimethylsiloxane, and the mass ratio of the raw rubber to the vinyl polydimethylsiloxane is (60-80): (10-30); s2, adding reinforcing filler into the uniform system obtained in the step S1, and mixing for a period of time at 80-120 ℃ to uniformly distribute the reinforcing filler in the matrix material to form a nano reinforcing structure; Step S3, cooling the system to 40-60 ℃, adding functional filler into the dispersion obtained in the step S2, mixing for a period of time to uniformly distribute the functional filler in a matrix material, and then discharging the sizing material from an internal mixer; s4, placing the sizing material obtained in the step S3 into an open mill for roll wrapping treatment, adding a cross-linking agent to mix for a period of time at 20-25 ℃ to enable the cross-linking agent to be uniformly dispersed, and then calendaring into sheets; And S5, placing the sheet obtained in the step S4 in a hot press, hot-pressing for 5-15 minutes at 120-150 ℃ and under 15-20 MPa for primary vulcanization, controlling the thickness of the film to be 100-200 mu m, and then performing secondary vulcanization for 1-3 hours at 120-140 ℃ to form a stable three-dimensional crosslinked network structure, so as to obtain the film product with high oxygen permeability.
  2. 2. The method for preparing a high oxygen permeability hollow fiber membrane material according to claim 1, wherein the number average molecular weight of the raw methyl vinyl silicone rubber is 10-65 ten thousand, the vinyl content is 0.10-0.30wt%, the vinyl polydimethylsiloxane is of a terminal vinyl structure, the viscosity is 500-1500 mPa.s, and the vinyl content is 0.10-0.35wt%.
  3. 3. The method for preparing the high-oxygen-permeability hollow fiber membrane material according to claim 1, wherein the reinforcing filler in the step S2 is gas-phase nano silicon dioxide, and the mass ratio of the reinforcing filler to the matrix material is (30-60) (70-90).
  4. 4. The method of producing a highly oxygen permeable hollow fiber membrane material according to claim 3, wherein the fumed silica is a hydrophobic fumed silica surface-modified with hexamethyldisilazane, dimethyldichlorosilane or dimethylsiloxane.
  5. 5. The method for preparing a high oxygen permeability hollow fiber membrane material according to claim 4, wherein the specific surface area of the reinforcing filler is 150-300 m2/g, and the surface carbon content is 0.5-3%.
  6. 6. The method for preparing the high-oxygen-permeability hollow fiber membrane material according to claim 1, wherein the functional filler in the step S3 is one or more of polysilsesquioxane, silicone resin and diatomite, and the mass ratio of the functional filler to the matrix material is (5-15) (70-90).
  7. 7. The method of claim 6, wherein the polysilsesquioxane has the formula (RSiO 1.5 ） n , wherein R is selected from the group consisting of methyl, vinyl and phenyl.
  8. 8. The preparation method of the high oxygen permeability hollow fiber membrane material according to claim 6, wherein the silicon resin is MQ or T-shaped silicon resin, the M/Q molar ratio is 0.7-1.0, and the diatomite median particle size is 5-20 μm.
  9. 9. The method for preparing a high oxygen permeability hollow fiber membrane material according to claim 1, wherein the cross-linking agent in the step S4 is platinum water and hydrogen-containing silicone oil, the amount of the platinum water is 0.02-0.5% of the mass of the matrix, and the amount of the hydrogen-containing silicone oil is 0.5-4% of the mass of the matrix.
  10. 10. The preparation method of the high-oxygen-permeability hollow fiber membrane material according to claim 9, wherein the platinum water is a catalyst solution formed by dispersing chloroplatinic acid in a polysiloxane system, the platinum content is 8000-18000 ppm, the hydrogen-containing silicone oil is a terminal side group hydrogen-containing structure, and the hydrogen content is 0.1-0.5%.
  11. 11. A high oxygen permeability hollow fiber membrane material made according to the method of any one of claims 1 to 10.

Description

High-oxygen-permeability hollow fiber membrane material and preparation method thereof Technical Field The invention relates to the technical field of membrane materials, in particular to a high-oxygen-permeability hollow fiber membrane material and a preparation method thereof. Background The membrane aeration biological membrane reactor (MABR) technology is a novel sewage treatment and water body restoration technology combining membrane aeration and biological membrane methods. The technology is suitable for the fields of standard improvement engineering of sewage treatment plants, advanced denitrification treatment systems of industrial wastewater (including high ammonia nitrogen or high organic load wastewater such as food processing wastewater, pharmaceutical wastewater, chemical wastewater and the like), in-situ restoration systems of river and lake polluted water bodies, cultivation tail water circulation treatment systems, landfill leachate biological denitrification systems, distributed integrated sewage treatment equipment and the like, and is particularly suitable for sewage treatment scenes needing to realize in-situ capacity expansion, enhanced denitrification and reduced aeration energy consumption under the condition of the existing structures. The MABR technology takes an oxygen permeable hollow fiber membrane as a carrier to realize bubble-free oxygen supply, oxygen is transmitted to water outside the membrane in a dissolution-diffusion mode through the membrane wall under the action of certain pressure (usually 10-50 kPa), and bubbles are not formed in the whole process, so that the bubble-free oxygen supply is realized. Microorganisms are attached to the outer surface of the hollow fiber membrane and form a biological membrane structure, oxygen diffuses outwards from the inside of the membrane, organic pollutants and ammonia nitrogen in the water body diffuse reversely to the surface of the membrane, and a counter mass transfer structure is formed at the interface of the biological membrane, so that synchronous nitrification and denitrification reactions are realized, and high-efficiency removal of pollutants such as nitrogen, phosphorus and the like is achieved. The technology has been applied to the standard improvement of municipal sewage treatment plants, the deep denitrification of industrial wastewater and the ecological restoration of polluted water bodies, and has obvious advantages in the aspects of high ammonia nitrogen wastewater enhanced denitrification, energy conservation and consumption reduction. The MABR system can be directly arranged in the aerobic zone of the traditional activated sludge process to replace microporous aeration devices such as aeration discs, aeration pipes and the like, and can realize high-efficiency oxygen supply under the condition of not changing the original tank body structure. Because oxygen diffuses into the water body through the membrane wall in a molecular state, the loss of bubble dissipation is avoided, the oxygen utilization rate is obviously improved, and the whole energy consumption of the system is obviously reduced. Therefore, the MABR technology is particularly suitable for in-situ capacity expansion and upgrading and reconstruction engineering of semi-buried, fully-buried and partially-submerged sewage treatment plants. The key of MABR technology is structural design and performance control of oxygen permeable hollow fiber membrane material, and the hollow fiber membrane material is required to meet the following requirements as a core functional material, and has high oxygen permeability coefficient and oxygen transfer rate so as to ensure sufficient oxygen supply of an inner layer of the biological membrane, good mechanical strength and pressure resistance so as to bear long-term continuous aeration operation, good biocompatibility so as to promote rapid attachment and stable growth of microorganisms, and long-term operation stability so as to avoid material aging and performance attenuation. Currently, hollow fiber membrane materials commonly used in the MABR field mainly include polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polydimethylsiloxane (PDMS), and the like. The PVDF hollow fiber membrane is generally prepared by adopting a phase inversion method, the membrane body is of a microporous structure, the pore diameter is generally 0.05-0.5 mu m, the wall thickness of the membrane is about 100-300 mu m, and the oxygen supply mechanism is that gas forms microbubbles through the membrane pores to enter a water body, and the microporous aeration mode is adopted. Although the membrane material has better mechanical strength, the membrane material has the problems of bubble dissipation, low oxygen utilization rate, easiness in pollution of pore channels and the like, and the foamless oxygen supply in the real sense is difficult to realize. PEO materials have certain hydrophilicity, but have lower oxygen permeability co