WO2022199554A1 - Matériau de membrane d'ultrafiltration composite et son procédé de préparation - Google Patents

Matériau de membrane d'ultrafiltration composite et son procédé de préparation Download PDF

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Publication number
WO2022199554A1
WO2022199554A1 PCT/CN2022/082128 CN2022082128W WO2022199554A1 WO 2022199554 A1 WO2022199554 A1 WO 2022199554A1 CN 2022082128 W CN2022082128 W CN 2022082128W WO 2022199554 A1 WO2022199554 A1 WO 2022199554A1
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Prior art keywords
zirconium phosphate
ultrafiltration membrane
powder
membrane material
modified
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PCT/CN2022/082128
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English (en)
Chinese (zh)
Inventor
袁涛
邓洪波
朱明月
谷峰
Original Assignee
山东格兰克环保新材料有限公司
济宁滤源特种分离应用技术研究院
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Publication of WO2022199554A1 publication Critical patent/WO2022199554A1/fr
Priority to ZA2022/12853A priority Critical patent/ZA202212853B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a composite ultrafiltration membrane material and a preparation method thereof.
  • Ultrafiltration membrane technology has been widely used in various water treatment, such as sewage treatment, reclaimed water reuse, fruit and vegetable beverage concentration and other fields.
  • sewage treatment such as sewage treatment, reclaimed water reuse, fruit and vegetable beverage concentration and other fields.
  • MLR membrane bioreactor
  • Most of the classic ultrafiltration membrane materials are polymer-based materials.
  • Commonly used ultrafiltration membrane materials include polyvinylidene fluoride, polysulfone, polyethersulfone, and cellulose. The above-mentioned materials still face serious problems in the use process.
  • the surface of the membrane material is biologically fouled, that is, microorganisms adhere to the surface of the membrane material and use the material body as a carbon source to form colonies to grow, eventually causing irreversible damage to the membrane material.
  • the problem of compression deformation of the polymer bulk material during use Since the operation of the ultrafiltration membrane is realized under a certain pressure, especially the ultrafiltration membrane material used as a nanofiltration or reverse osmosis support body, its pressure resistance performance is required to be higher.
  • ⁇ -Zirconium phosphate is an inorganic nanomaterial with a layered structure that has been rapidly developed in recent years, and is widely used in antibacterial research.
  • the Chinese Patent Publication No. CN1938072A records that zirconium phosphate as a bactericide is blended with fibers to prepare antibacterial fibers with good results.
  • the addition of ⁇ -zirconium phosphate as an additive to the polymer can significantly enhance the mechanical strength of the material, and such research has been verified in patent reports.
  • the prepared ultrafiltration membrane material also has a good bactericidal and bacteriostatic effect, when the concentration of zirconium phosphate particles increases, it is different from that of commonly used polymer membranes.
  • the compatibility is poor, so it is easy to cause uneven distribution of zirconium phosphate in the membrane material during the membrane production process, resulting in unstable filtration performance of the membrane.
  • the invention provides a composite ultrafiltration membrane material and a preparation method thereof, which solve the technical problems: 1) the problem of poor antibacterial properties of traditional polymer ultrafiltration membranes; 2) the poor compatibility of adding zirconium phosphate into the ultrafiltration membrane, which is easy to cause membrane structure Non-uniformity eventually leads to the problem of poor film formation stability.
  • the present invention adopts the following technical solutions:
  • a composite ultrafiltration membrane material which is composed of ⁇ -zirconium phosphate nano-powder modified by intercalation and a membrane material body;
  • the modified material in the intercalated ⁇ -zirconium phosphate nano-powder has a general chemical formula of R 4 NX;
  • R groups in the general formula R 4 NX may be the same or different, and X in the general formula is one or more of fluorine, chlorine, bromine, iodine, inorganic acid radicals and carboxylate radicals.
  • R 4 NX is a quaternary ammonium salt.
  • the ⁇ -zirconium phosphate nanopowder after intercalation modification is prepared according to the following steps:
  • step 2) Add the ⁇ -zirconium phosphate nano-powder into the quaternary ammonium salt aqueous solution prepared in step 1), stir for 1-2 hours, stand for 12-24 hours, filter, wash and dry to obtain the ⁇ -phosphoric acid after intercalation modification Zirconium Nanopowder.
  • the mass concentration of the ⁇ -zirconium phosphate nano-powder in the quaternary ammonium salt aqueous solution is 0.1-5%.
  • step 2) the stirring speed is 300-800 rap/min.
  • the washing is with acetone; the drying temperature is 20-100°C.
  • a preparation method of a composite ultrafiltration membrane material, the composite ultrafiltration membrane material is carried out according to the following steps:
  • the casting solution is polyvinylidene fluoride casting solution, polysulfone membrane casting solution, polyethersulfone membrane casting solution, polyacrylonitrile membrane casting solution, polyether ether ketone membrane casting solution and cellulose membrane casting solution.
  • the mass ratio of the ⁇ -zirconium phosphate nano-powder after intercalation modification and the casting liquid is 0.05-20:80-99.95.
  • the film-making in step b) includes one or more of scraping flat film, fiber spinning machine extrusion film and phase inversion film formation.
  • the standing for defoaming is standing for more than 12 hours at a temperature of 40-80°C.
  • the invention discloses a method for preparing an ultrafiltration membrane material for water treatment by blending ⁇ -zirconium phosphate nanomaterials modified by quaternary ammonium salt intercalation with a polymer body.
  • the prepared ultrafiltration membrane material has both material enhancement and long-lasting antibacterial properties.
  • the intercalation modified ⁇ -zirconium phosphate nanomaterial as an additive can significantly improve the phase between the nanoparticles and the polymer structure compared with the addition of pure inorganic zirconium phosphate. Capacitance and stability of membrane material preparation. It not only ensures good bactericidal and bacteriostatic effect, but also ensures the lasting stability of the composite ultrafiltration membrane performance.
  • Fig. 2 is an electron microscope contrast photograph of adding unintercalated zirconium phosphate particles according to the steps of Example 4.
  • Step 1 Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
  • Step 2 Add 2.5g of ⁇ -zirconium phosphate nano-powder into 100mL of dodecyldimethylbenzylammonium chloride aqueous solution prepared in step 1, and continue to stir for 2h. After standing for 24h, filter and wash with 100mL of acetone. and drying under low temperature to obtain ⁇ -zirconium phosphate nanopowder modified by intercalation.
  • Step 3 Prepare polyethersulfone casting solution: mix the intercalated ⁇ -zirconium phosphate nanopowder prepared in step 2 with polyethersulfone, glycerol, and N-methylformamide in a ratio of 1:15:2:82 Proportionally mixed, stirred and dissolved at 60° C. for 12 hours, then stood for 12 hours for thermal insulation and defoaming, and then stood at room temperature for later use to obtain a polyethersulfone film casting solution.
  • Step 4 Use a scraper to scrape the polyethersulfone film casting solution obtained in step 3 on a glass plate to form a flat film, and phase-convert it into a film in deionized water at 25° C. to obtain a pressure-resistant antibacterial polyethersulfone ultrafiltration flat film.
  • Step 1 Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
  • Step 2 Add 3g of ⁇ -zirconium phosphate nano-powder to 100mL of the aqueous solution of dodecyldimethylbenzylammonium chloride prepared in step 1, and continue to stir for 2h. After standing for 24h, filter and wash with 150mL of acetone. drying to obtain ⁇ -zirconium phosphate nano-powder after intercalation modification.
  • Step 3 configure polyvinylidene fluoride casting solution: mix the intercalated ⁇ -zirconium phosphate nano-powder prepared in step 2 with polyethersulfone, glycerol and N-methylformamide in a mass ratio of 2:18: Mix in a ratio of 2:78, stir and dissolve at 60°C for 12 hours, then stand for 12 hours for thermal insulation and defoaming, and then stand at room temperature for later use to obtain a polyvinylidene fluoride casting solution.
  • Step 4 The polyvinylidene fluoride casting solution obtained in step 3 is extruded through a hollow fiber spinning machine to extrude a tubular liquid membrane, and phase-converted into a membrane in deionized water at 25 ° C. After washing and drying, pressure-resistant antibacterial polyvinylidene fluoride is obtained. Ethylene hollow fiber ultrafiltration membrane.
  • Step 1 Prepare 1 g/L aqueous solution of hexadecyldimethylbenzylammonium chloride, stir at room temperature for 1 h for use.
  • Step 2 Add 2g of ⁇ -zirconium phosphate nanopowder to 300mL of the aqueous solution of cetyldimethylbenzylammonium chloride prepared in step 1, and continue to stir for 2h. After standing for 36h, filter and wash with 120mL of acetone. drying to obtain ⁇ -zirconium phosphate nano-powder after intercalation modification.
  • Step 3 configure regenerated cellulose casting solution: dissolve 20 g of cellulose (Mw ⁇ 10.1 ⁇ 10 4 ) in 180 g of sodium hydroxide/urea mixed aqueous solution, wherein sodium hydroxide, urea and urea in the sodium hydroxide/urea mixed aqueous solution The mass ratio of water is 5:8:100. Stir until completely dissolved, centrifuge and degas for 30 minutes, add 2 g of the intercalated ⁇ -zirconium phosphate nano-powder prepared in step 2 to the transparent cellulose solution, stir for 12 hours, stand at room temperature for deaeration for 12 hours, and then use to obtain fibers. Plain casting liquid.
  • Step 4 The cellulose casting solution obtained in Step 3 is scraped on a glass plate to form a flat film, and phase-converted into a film in deionized water at 25° C. to obtain a pressure-resistant antibacterial cellulose ultrafiltration flat film.
  • Step 1 Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
  • Step 2 Add 4g ⁇ -zirconium phosphate nano-powder into 100mL of the aqueous solution of dodecyldimethylbenzylammonium chloride prepared in step 1, and continue to stir for 2h. After standing for 24h, filter and wash with 300 mL of acetone. and drying under low temperature to obtain ⁇ -zirconium phosphate nanopowder modified by intercalation.
  • Step 3 configure polysulfone casting solution: the intercalated modified ⁇ -zirconium phosphate nano-powder prepared in step 2 is mixed with polysulfone, glycerol and N-methylformamide in a mass ratio of 1:18:2:79 Proportionally mixed, stirred and dissolved at 60° C. for 12 hours, then kept for 12 hours for thermal insulation and defoaming, and then stood at room temperature for later use to obtain a polysulfone film casting solution.
  • Step 4 Use a scraper to scrape the polysulfone film casting solution obtained in step 3 on a glass plate to form a flat film, and phase-convert it into a film in deionized water at 25° C. to obtain a pressure-resistant antibacterial polysulfone ultrafiltration flat film.
  • Example 1 except for the addition of unintercalated zirconium phosphate particles, other preparation methods are consistent with Example 1
  • Comparative 2 except for the added zirconium phosphate particles without intercalation modification, other preparation methods are consistent with Example 2
  • contrast 3 except for the addition of unintercalated modified zirconium phosphate particles, other preparation methods are the same as the implementation of Consistent with Example 3
  • Comparative 4 except for the addition of unintercalated zirconium phosphate particles, other preparation methods are the same as those in Example 4).
  • the present invention investigates the separation performance of the composite ultrafiltration membrane prepared by adding zirconium phosphate to the casting solution from the application point of view, and evaluates the sample variance of the pure water flux of different batches of ultrafiltration membranes prepared from the casting solution under the same conditions. Stability of intercalation-modified zirconium phosphate additions to the preparation of ultrafiltration membrane products.
  • the test solution is pure water and the test temperature is 25°C. After running for 30min, measure the amount of permeate in a measuring cylinder within a certain period of time. volume, to test the pure water flux of the ultrafiltration membrane.
  • the pure water flux is calculated according to the following formula:
  • Pure water flux unit L/m 2 h
  • filtrate volume unit L
  • membrane area m 2
  • test time h.
  • the sample variance of ultrafiltration membrane pure water flux is calculated according to the following formula:
  • S2 is the sample variance
  • M is the average pure water flux of the ultrafiltration membrane
  • X is the pure water flux of the ultrafiltration membrane sample
  • n is the number of samples.
  • Table 1 Example preparation composite ultrafiltration membrane antibacterial performance, pure water flux and sample variance of pure water flux.
  • the present application blends the intercalated modified zirconium phosphate particles with the ultrafiltration bulk material to prepare a composite ultrafiltration membrane, which retains better bactericidal and bacteriostatic effects, while the repetitive stability of the membrane is better. .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un matériau de membrane d'ultrafiltration composite et son procédé de préparation. Le matériau de membrane d'ultrafiltration est constitué d'une nano-poudre de phosphate d'α-zirconium modifiée par intercalage et d'un corps de matériau de membrane. La formule générale chimique de matériau modifié dans la nano-poudre de phosphate d'α-zirconium modifiée par intercalage est R4NX. Dans la formule chimique générale R4NX, les quatre groupes R sont identiques ou différents, et X dans la formule générale chimique est un ou plusieurs éléments parmi le fluor, le chlore, le brome, l'iode, la racine d'acide inorganique et le carboxylate.
PCT/CN2022/082128 2021-03-22 2022-03-22 Matériau de membrane d'ultrafiltration composite et son procédé de préparation WO2022199554A1 (fr)

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CN202110304044.3A CN113198326B (zh) 2021-03-22 2021-03-22 一种复合超滤膜材料及其制备方法

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CN113198326B (zh) * 2021-03-22 2022-08-12 山东格兰克环保新材料有限公司 一种复合超滤膜材料及其制备方法

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