WO2022199554A1 - Composite ultrafiltration membrane material and preparation method therefor - Google Patents
Composite ultrafiltration membrane material and preparation method therefor Download PDFInfo
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- 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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- zirconium phosphate
- ultrafiltration membrane
- powder
- membrane material
- modified
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 51
- 239000011858 nanopowder Substances 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000009830 intercalation Methods 0.000 claims description 17
- 230000002687 intercalation Effects 0.000 claims description 17
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 239000004695 Polyether sulfone Substances 0.000 claims description 10
- 229920002492 poly(sulfone) Polymers 0.000 claims description 10
- 229920006393 polyether sulfone Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- -1 iodine, inorganic acid Chemical class 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 16
- 230000004907 flux Effects 0.000 description 15
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
A composite ultrafiltration membrane material and a preparation process thereof. The ultrafiltration membrane material consists of an intercalation-modified α-zirconium phosphate nano-powder and a membrane material body. The chemical general formula of modified material in the intercalation-modified α-zirconium phosphate nano-powder is R4NX. In the chemical general formula R4NX, the four R groups are the same or different, and X in the chemical general formula is one or more among fluorine, chlorine, bromine, iodine, inorganic acid root and carboxylate.
Description
本申请要求于2021年03月22日提交中国专利局、申请号为202110304044.3、发明名称为“一种复合超滤膜材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on March 22, 2021 with the application number 202110304044.3 and the invention titled "A composite ultrafiltration membrane material and its preparation method", the entire contents of which are incorporated by reference in this application.
本发明涉及一种复合超滤膜材料及其制备方法。The invention relates to a composite ultrafiltration membrane material and a preparation method thereof.
超滤膜技术在各类水处理中得到了广泛的应用，例如在污水处理、中水回用、果蔬饮料浓缩等领域。以中空纤维超滤膜为例，已经成为目前市政污水核心技术膜生物反应器(MBR)的核心材料，其性能直接影响了工程的运行效果和装备的使用寿命。经典的超滤膜材料大都是聚合物基材料，常用的超滤膜材料本体有聚偏氟乙烯材料、聚砜、聚醚砜、纤维素等。上述材料在使用过程中仍然面临严重的问题，其一，膜材料表面生物污染，即微生物附着在膜材料表面并以材料本体为碳源形成菌落生长，最终造成膜材料不可逆的破坏。其二，聚合物本体材料在使用过程中的受压形变问题。由于超滤膜的运行是在一定压力下实现的，尤其是作为纳滤或者反渗透支撑体的超滤膜材料，其耐压性能要求更高。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. Taking the hollow fiber ultrafiltration membrane as an example, it has become the core material of the membrane bioreactor (MBR), the core technology of municipal sewage, and its performance directly affects the operation effect of the project and the service life of the equipment. 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. First, 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. Second, 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.
α-磷酸锆是近年来快速发展起来的一种具有层状结构的无机纳米材料，被广泛用于抗菌研究。公开号为CN1938072A的中国专利中记载，磷酸锆作为一种杀菌剂与纤维共混制备抗菌型纤维具有良好的效果。此外，α-磷酸锆作为添加剂添加至高分子中可以显著增强材料的机械强度，此类研究在专利报道中已经得到验证。α-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. In addition, the addition of α-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.
然而在研究过程中仅仅将α-磷酸锆加入到超滤膜制备液中，制备的超滤膜材料虽然也具有较好的杀菌抑菌效果，但当磷酸锆颗粒浓度提高时与常用高分子膜原料共混时的相容性较差，因此在制膜过程中容易造成磷酸锆在膜材料中分布不均，造成膜的过滤性能不稳定。However, in the research process, only α-zirconium phosphate was added to the ultrafiltration membrane preparation solution. Although 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. When the raw materials are blended, 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.
发明内容SUMMARY OF THE INVENTION
本发明提供一种复合超滤膜材料及其制备方法，解决技术问题是1)传统聚合物超滤膜抗菌性差的问题；2)磷酸锆加入到超滤膜中相容性差，易造成膜结构不均匀，最终导致制膜稳定性差的问题。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.
为了解决上述技术问题，本发明采用以下技术方案：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
一种复合超滤膜材料，由插层修饰后的α-磷酸锆纳米粉末和膜材料本体组成；A composite ultrafiltration membrane material, which is composed of α-zirconium phosphate nano-powder modified by intercalation and a membrane material body;
所述插层修饰后的α-磷酸锆纳米粉末中的修饰材料其化学通式为R
4NX；
The modified material in the intercalated α-zirconium phosphate nano-powder has a general chemical formula of R 4 NX;
所述通式R
4NX中R基可以相同，也可不同，通式中X是氟、氯、溴、碘、无机酸根和羧酸根中的一种或几种。
The 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.
所述通式R
4NX是季铵盐。
The general formula R 4 NX is a quaternary ammonium salt.
插层修饰后的α-磷酸锆纳米粉末按照以下步骤进行制备：The α-zirconium phosphate nanopowder after intercalation modification is prepared according to the following steps:
1)配置0.8～1.2g/L的季铵盐水溶液；1) Configure 0.8～1.2g/L quaternary ammonium salt aqueous solution;
2)将α-磷酸锆纳米粉末加入到步骤1)所配季铵盐水溶液中，搅拌1～2h，静置12～24h，经过滤、洗涤和干燥，即得插层修饰后的α-磷酸锆纳米粉末。其中，α-磷酸锆纳米粉末在所述季铵盐水溶液的质量浓度为0.1～5％。2) Add the α-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 α-phosphoric acid after intercalation modification Zirconium Nanopowder. Wherein, the mass concentration of the α-zirconium phosphate nano-powder in the quaternary ammonium salt aqueous solution is 0.1-5%.
步骤2)中搅拌转速是300～800rap/min。In step 2), the stirring speed is 300-800 rap/min.
所述洗涤是采用丙酮洗涤；所述干燥的温度是20～100℃。The washing is with acetone; the drying temperature is 20-100°C.
一种复合超滤膜材料的制备方法，复合超滤膜材料按照以下步骤进行：A preparation method of a composite ultrafiltration membrane material, the composite ultrafiltration membrane material is carried out according to the following steps:
a)将插层修饰后的α-磷酸锆纳米粉末加入到铸膜液中，在温度为60℃条件下，搅拌12h，静置脱泡，得初级铸膜液；a) Add the α-zirconium phosphate nano-powder modified by intercalation into the casting solution, stir for 12 hours at a temperature of 60°C, and let it stand for defoaming to obtain the primary casting solution;
b)初级铸膜液经制膜后，即得复合超滤膜材料。b) The composite ultrafiltration membrane material is obtained after the primary casting solution is made into a membrane.
步骤a)所述铸膜液是聚偏氟乙烯铸膜液、聚砜铸膜液、聚醚砜铸膜液、聚丙烯腈铸膜液、聚醚醚酮铸膜液和纤维素铸膜液中的一种或几种；插层修饰后的α-磷酸锆纳米粉末和铸膜液的质量比为0.05～20:80～99.95。In step a), 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. One or more of the following; the mass ratio of the α-zirconium phosphate nano-powder after intercalation modification and the casting liquid is 0.05-20:80-99.95.
步骤b)所述制膜包括刮制平板膜、纤维纺丝机挤出膜和相转化成膜 中的一种或几种。The film-making in step b) includes one or more of scraping flat film, fiber spinning machine extrusion film and phase inversion film formation.
所述静置脱泡为在温度为40～80℃条件下静置12h以上。The standing for defoaming is standing for more than 12 hours at a temperature of 40-80°C.
本发明具有以下有益技术效果：The present invention has the following beneficial technical effects:
本发明公开了将季铵盐插层修饰后的α-磷酸锆纳米材料与聚合物本体共混制备水处理用超滤膜材料方法。制备的超滤膜材料兼具有材料增强和较持久的抗菌性能，插层修饰后的α-磷酸锆纳米材料作为添加剂与纯无机磷酸锆添加相比可以显著提高纳米颗粒与聚合物结构的相容性和膜材料制备的稳定性。既保证较好的杀菌抑菌效果，又可保证复合超滤膜性能的持久稳定。The invention discloses a method for preparing an ultrafiltration membrane material for water treatment by blending α-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 α-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.
图1实施例4制备的聚砜超滤膜表面电镜照片；The surface electron microscope photo of the polysulfone ultrafiltration membrane prepared in Fig. 1 embodiment 4;
图2照实施例4步骤添加未插层修饰的磷酸锆粒子电镜对比照片。Fig. 2 is an electron microscope contrast photograph of adding unintercalated zirconium phosphate particles according to the steps of Example 4.
下面结合具体实例进一步说明本发明。The present invention is further described below in conjunction with specific examples.
实施例1Example 1
步骤1：配置1g/L的十二烷基二甲基苄基氯化铵水溶液，室温下搅拌1h备用。Step 1: Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
步骤2：将2.5gα-磷酸锆纳米粉末加入到100mL步骤1所配十二烷基二甲基苄基氯化铵水溶液中，并继续搅拌2h，放置24h后，经过滤和100mL丙酮洗涤，室温下干燥，得插层修饰后的α-磷酸锆纳米粉末。Step 2: Add 2.5g of α-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 α-zirconium phosphate nanopowder modified by intercalation.
步骤3：配置聚醚砜铸膜液：将步骤2所制备的插层修饰后的α-磷酸锆纳米粉末与聚醚砜、甘油、N-甲基甲酰胺按照1:15:2:82的比例混合，在60℃下搅拌溶解12h，然后静置保温脱泡12h后，室温下静置备用，得聚醚砜铸膜液。Step 3: Prepare polyethersulfone casting solution: mix the intercalated α-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.
步骤4：将步骤3所得聚醚砜铸膜液用刮刀在玻璃板上刮制平板膜，并在25℃去离子水中相转化成膜，得到耐压抗菌聚醚砜超滤平板膜。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.
实施例2Example 2
步骤1：配置1g/L的十二烷基二甲基苄基氯化铵水溶液，室温下搅拌1h备用。Step 1: Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
步骤2：将3gα-磷酸锆纳米粉末加入到100mL步骤1所配十二烷基二甲基苄基氯化铵水溶液中，并继续搅拌2h，放置24h后，经过滤和150mL丙酮洗涤，室温下干燥，得插层修饰后的α-磷酸锆纳米粉末。Step 2: Add 3g of α-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 α-zirconium phosphate nano-powder after intercalation modification.
步骤3：配置聚偏氟乙烯铸膜液：将步骤2所制备的得插层修饰后的α-磷酸锆纳米粉末与聚醚砜、甘油和N-甲基甲酰胺按照质量比2:18:2:78的比例混合，在60℃下搅拌溶解12h，然后静置保温脱泡12h后，室温下静置备用，得聚偏氟乙烯铸膜液。Step 3: configure polyvinylidene fluoride casting solution: mix the intercalated α-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.
步骤4：将步骤3所得聚偏氟乙烯铸膜液通过中空纤维纺丝机挤出管状液膜，并在25℃去离子水中相转化成膜，经水洗晾干后得到耐压抗菌聚偏氟乙烯中空纤维超滤膜。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.
实施例3Example 3
步骤1：配置1g/L的十六烷基二甲基苄基氯化铵水溶液，室温下搅拌1h备用。Step 1: Prepare 1 g/L aqueous solution of hexadecyldimethylbenzylammonium chloride, stir at room temperature for 1 h for use.
步骤2：将2gα-磷酸锆纳米粉末加入到300mL步骤1所配十六烷基二甲基苄基氯化铵水溶液中，并继续搅拌2h，放置36h后，经过滤和120mL丙酮洗涤，室温下干燥，得插层修饰后的α-磷酸锆纳米粉末。Step 2: Add 2g of α-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 α-zirconium phosphate nano-powder after intercalation modification.
步骤3：配置再生纤维素铸膜液：将纤维素(Mw≈10.1×10
4)20g溶解于180g氢氧化钠/尿素混合水溶液中，其中氢氧化钠/尿素混合水溶液中氢氧化钠、尿素和水的质量比为5:8:100。搅拌至完全溶解，离心脱气30min后，向透明的纤维素溶液中添加2g步骤2制备的插层修饰后的α-磷酸锆纳米粉末搅拌12h后，室温静置脱泡12h后备用，得纤维素铸膜液。
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 α-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.
步骤4：将步骤3所得纤维素铸膜液用刮刀在玻璃板上刮制平板膜，并在25℃去离子水中相转化成膜，得到耐压抗菌纤维素超滤平板膜。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.
实施例4Example 4
步骤1：配置1g/L的十二烷基二甲基苄基氯化铵水溶液，室温下搅拌1h备用。Step 1: Prepare 1g/L aqueous solution of dodecyldimethylbenzylammonium chloride, stir at room temperature for 1h for use.
步骤2：将4gα-磷酸锆纳米粉末加入到100mL步骤1所配十二烷基二甲基苄基氯化铵水溶液中，并继续搅拌2h，放置24h后，经过滤和300 mL丙酮洗涤，室温下干燥，得插层修饰后的α-磷酸锆纳米粉末。Step 2: Add 4g α-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 α-zirconium phosphate nanopowder modified by intercalation.
步骤3：配置聚砜铸膜液：步骤2所制备的得插层修饰后的α-磷酸锆纳米粉末与聚砜、甘油和N-甲基甲酰胺按照质量比1:18:2:79的比例混合，在60℃下搅拌溶解12h，然后静置保温脱泡12h后，室温下静置备用，得聚砜铸膜液。Step 3: configure polysulfone casting solution: the intercalated modified α-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.
步骤4：将步骤3所得聚砜铸膜液用刮刀在玻璃板上刮制平板膜，并在25℃去离子水中相转化成膜，得到耐压抗菌聚砜超滤平板膜。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.
下面结合实验数据进一步说明本发明的有益效果：The beneficial effects of the present invention are further described below in conjunction with experimental data:
实验一experiment one
供试材料Test material
1材料与方法：1 Materials and methods:
1.1试验地点：济宁滤源特种分离应用技术研究院。1.1 Test location: Jining Filter Source Special Separation Application Technology Research Institute.
1.2实验检测：对大肠杆菌的抗菌性％、牛血清蛋白截留率和测试并换算超滤膜纯水通量样本方差。1.2 Experimental detection: % of antibacterial activity against Escherichia coli, rejection rate of bovine serum albumin and test and conversion of ultrafiltration membrane pure water flux sample variance.
1.3供试材料：实施例1、实施例2、实施例3、实施例4、对比1(除添加的为未插层修饰的磷酸锆粒子外，其它制备方法均与实施例1一致)、对比2(除添加的为未插层修饰的磷酸锆粒子外，其它制备方法均与实施例2一致)、对比3(除添加的为未插层修饰的磷酸锆粒子外，其它制备方法均与实施例3一致)和对比4(除添加的为未插层修饰的磷酸锆粒子外，其它制备方法均与实施例4一致)。1.3 Materials to be tested: Example 1, Example 2, Example 3, Example 4, Comparative 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) and Comparative 4 (except for the addition of unintercalated zirconium phosphate particles, other preparation methods are the same as those in Example 4).
1.4检测方法：1.4 Detection method:
根据GB/T 23763-2009测定膜的抗菌性；According to GB/T 23763-2009, the antibacterial property of the film was determined;
按照GB T 32360-2015，超滤膜材料性能评价标准方法。According to GB T 32360-2015, standard method for performance evaluation of ultrafiltration membrane materials.
本发明从应用角度考察铸膜液添加磷酸锆共混重复制备复合超滤膜的分离性能，通过相同条件配置的铸膜液所制备的不同批次超滤膜纯水通量的样本方差来评估插层修饰的磷酸锆添加对超滤膜产品制备的稳定性。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.
具体方法如下：The specific method is as follows:
将制备的超滤膜裁切成200mm*200mm的正方形大小放入膜片性能测试***，测试溶液为纯水，测试温度25℃，运行30min后，用量筒量 取在一定时间内透过液的体积，测试超滤膜的纯水通量。用相同配比铸膜液10批次以上超滤膜纯水通量数据的样本方差来评估超滤膜纯水通量稳定性，即样本中各数据与样本平均数的差的平方和的平均数叫做样本方差。样本方差越大，说明制膜稳定性越差，样本方差越小，说明制膜稳定性越好。Cut the prepared ultrafiltration membrane into squares of 200mm*200mm and put it into the membrane performance test system. The test solution is pure water and the test temperature is 25℃. 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. Use the sample variance of the pure water flux data of the ultrafiltration membranes over 10 batches of the same ratio of casting solution to evaluate the pure water flux stability of the ultrafiltration membrane, that is, the average sum of the squares of the differences between the data in the sample and the sample mean The number is called the sample variance. The larger the sample variance, the worse the film-making stability, and the smaller the sample variance, the better the film-making stability.
纯水通量按照下列公式计算：The pure water flux is calculated according to the following formula:
纯水通量单位：L/m
2h，滤液体积单位：L，膜片面积：m
2，测试时间：h。
Pure water flux unit: L/m 2 h, filtrate volume unit: L, membrane area: m 2 , test time: h.
超滤膜纯水通量样本方差按照下列公式计算：The sample variance of ultrafiltration membrane pure water flux is calculated according to the following formula:
s
2＝<(X
1-M)
2+(X
2-M)
2+...+(X
n-M)
2>/n
s 2 =<(X 1 -M) 2 +(X 2 -M) 2 +...+(X n -M) 2 >/n
其中S
2为样本方差，M为超滤膜平均纯水通量，X为超滤膜样品纯水通量，n为样品数。
where 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, and n is the number of samples.
本实验除检测物不同外，其他操作均一致。Except for the different test substances, other operations are the same in this experiment.
2结果与分析2 Results and Analysis
大肠杆菌的抗菌性％、牛血清蛋白截留率和超滤膜纯水通量样本方差。见表1。% antimicrobial activity of Escherichia coli, bovine serum albumin rejection and sample variance of pure water flux of ultrafiltration membranes. See Table 1.
表1实施例制备复合超滤膜抗菌性能、纯水通量和纯水通量的样本方差。Table 1 Example preparation composite ultrafiltration membrane antibacterial performance, pure water flux and sample variance of pure water flux.
表1实施例制备复合超滤膜抗菌性能、纯水通量和纯水通量的样本方差Table 1 Example preparation of composite ultrafiltration membrane antibacterial performance, pure water flux and sample variance of pure water flux
由表1可以看出，本申请将插层修饰的磷酸锆粒子与超滤本体材料共混制备复合超滤膜，保留了较好的杀菌和抑菌效果，同时制膜的重复稳定性更好。As can be seen from Table 1, 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. .
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
Claims (14)
- 一种插层修饰后的α-磷酸锆纳米粉末，其特征在于，所述插层修饰后的α-磷酸锆纳米粉末中的修饰材料的化学通式为R 4NX； An intercalation-modified α-zirconium phosphate nano-powder, characterized in that the general chemical formula of the modified material in the intercalated-modified α-zirconium phosphate nano-powder is R 4 NX;所述化学通式R 4NX中4个R基相同或不同，化学通式中X是氟、氯、溴、碘、无机酸根和羧酸根中的一种或几种。 The four R groups in the general chemical formula R 4 NX are the same or different, and X in the general chemical formula is one or more of fluorine, chlorine, bromine, iodine, inorganic acid radicals and carboxylate radicals.
- 根据权利要求1所述的插层修饰后的α-磷酸锆纳米粉末，其特征在于，所述修饰材料是季铵盐。The α-zirconium phosphate nano-powder modified by intercalation according to claim 1, wherein the modification material is a quaternary ammonium salt.
- 权利要求2所述的插层修饰后的α-磷酸锆纳米粉末的制备方法，其特征在于，包括以下步骤：The preparation method of the α-zirconium phosphate nano-powder after intercalation modification described in claim 2, is characterized in that, comprises the following steps:1)配置0.8～1.2g/L的季铵盐水溶液；1) Configure 0.8～1.2g/L quaternary ammonium salt aqueous solution;2)将α-磷酸锆纳米粉末加入到所述步骤1)的季铵盐水溶液中，搅拌1～2h，静置12～24h，经过滤、洗涤和干燥，即得所述插层修饰后的α-磷酸锆纳米粉末；2) Add the α-zirconium phosphate nano-powder into the quaternary ammonium salt aqueous solution in the step 1), stir for 1-2 h, stand for 12-24 h, filter, wash and dry to obtain the intercalated modified Alpha-zirconium phosphate nanopowder;所述α-磷酸锆纳米粉末在所述季铵盐水溶液中的质量浓度为0.1～5％。The mass concentration of the α-zirconium phosphate nano-powder in the quaternary ammonium salt aqueous solution is 0.1-5%.
- 一种复合超滤膜材料，其特征在于，由插层修饰后的α-磷酸锆纳米粉末和膜材料本体组成；A composite ultrafiltration membrane material, characterized in that it is composed of α-zirconium phosphate nano-powder modified by intercalation and a membrane material body;所述插层修饰后的α-磷酸锆纳米粉末中的修饰材料的化学通式为R 4NX； The general chemical formula of the modified material in the intercalated modified α-zirconium phosphate nano-powder is R 4 NX;所述化学通式R 4NX中4个R基相同或不同，化学通式中X是氟、氯、溴、碘、无机酸根和羧酸根中的一种或几种。 The four R groups in the general chemical formula R 4 NX are the same or different, and X in the general chemical formula is one or more of fluorine, chlorine, bromine, iodine, inorganic acid radicals and carboxylate radicals.
- 如权利要求4所述的复合超滤膜材料，其特征在于：所述修饰材料是季铵盐。The composite ultrafiltration membrane material according to claim 4, wherein the modification material is a quaternary ammonium salt.
- 如权利要求5所述的复合超滤膜材料，其特征在于：所述季铵盐为十二烷基二甲基苄基氯化铵或十六烷基二甲基苄基氯化铵。The composite ultrafiltration membrane material according to claim 5, wherein the quaternary ammonium salt is dodecyldimethylbenzylammonium chloride or cetyldimethylbenzylammonium chloride.
- 如权利要求5或6所述的复合超滤膜材料，其特征在于：所述插层修饰后的α-磷酸锆纳米粉末按照以下步骤进行制备：The composite ultrafiltration membrane material according to claim 5 or 6, wherein the α-zirconium phosphate nano-powder after the intercalation modification is prepared according to the following steps:1)配置0.8～1.2g/L的季铵盐水溶液；1) Configure 0.8～1.2g/L quaternary ammonium salt aqueous solution;2)将α-磷酸锆纳米粉末加入到所述步骤1)的季铵盐水溶液中，搅 拌1～2h，静置12～24h，经过滤、洗涤和干燥，即得所述插层修饰后的α-磷酸锆纳米粉末；2) Add the α-zirconium phosphate nano-powder into the quaternary ammonium salt aqueous solution in the step 1), stir for 1-2 h, stand for 12-24 h, filter, wash and dry to obtain the intercalated modified Alpha-zirconium phosphate nanopowder;所述α-磷酸锆纳米粉末在所述季铵盐水溶液中的质量浓度为0.1～5％。The mass concentration of the α-zirconium phosphate nano-powder in the quaternary ammonium salt aqueous solution is 0.1-5%.
- 如权利要求7所述的复合超滤膜材料，其特征在于，步骤2)中搅拌的转速是300～800rap/min；The composite ultrafiltration membrane material according to claim 7, wherein the rotating speed of stirring in step 2) is 300～800 rap/min;所述洗涤为丙酮洗涤；所述干燥的温度是20～100℃。The washing is acetone washing; the drying temperature is 20-100°C.
- 如权利要求4所述的复合超滤膜材料，其特征在于：所述膜材料本体的材质包括聚偏氟乙烯、聚砜、聚醚砜、聚丙烯腈、聚醚醚酮和纤维素中的一种或几种。The composite ultrafiltration membrane material according to claim 4, wherein the material of the membrane material body comprises polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polyetheretherketone and cellulose. one or more.
- 一种复合超滤膜材料的制备方法，其特征在于，复合超滤膜材料按照以下步骤进行：A preparation method of a composite ultrafiltration membrane material, characterized in that, the composite ultrafiltration membrane material is carried out according to the following steps:a)将插层修饰后的α-磷酸锆纳米粉末加入到铸膜液中，在温度为60℃条件下，搅拌12h，静置脱泡，得初级铸膜液；a) Add the α-zirconium phosphate nano-powder modified by intercalation into the casting solution, stir for 12 hours at a temperature of 60°C, and let it stand for defoaming to obtain the primary casting solution;b)所述初级铸膜液经制膜后，即得所述复合超滤膜材料。b) The composite ultrafiltration membrane material is obtained after the primary casting solution is formed into a membrane.
- 如权利要求10所述的复合超滤膜材料的制备方法，其特征在于，步骤a)所述铸膜液是聚偏氟乙烯铸膜液、聚砜铸膜液、聚醚砜铸膜液、聚丙烯腈铸膜液、聚醚醚酮铸膜液和纤维素铸膜液中的一种或几种；所述插层修饰后的α-磷酸锆纳米粉末和铸膜液的质量比为0.05～20:80～99.95。The method for preparing a composite ultrafiltration membrane material according to claim 10, wherein the membrane casting solution in step a) is a polyvinylidene fluoride membrane casting solution, a polysulfone membrane casting solution, a polyethersulfone membrane casting solution, One or more of polyacrylonitrile casting liquid, polyether ether ketone casting liquid and cellulose casting liquid; the mass ratio of the intercalated modified α-zirconium phosphate nano-powder and the casting liquid is 0.05 ~20:80~99.95.
- 如权利要求10所述的复合超滤膜材料的制备方法，其特征在于，步骤b)所述制膜包括刮制平板膜、纤维纺丝机挤出膜和相转化成膜中的一种或几种。The method for preparing a composite ultrafiltration membrane material according to claim 10, wherein the film making in step b) comprises one of scraping flat film, fiber spinning machine extrusion film and phase inversion film forming or several.
- 根据权利要求12所述的复合超滤膜材料的制备方法，其特征在于，步骤b)所述制膜为：刮制平板膜或纤维纺丝机挤出膜后，进行相转化成膜；所述相转化成膜在相转化液中进行，所述相转化液为去离子水。The method for preparing a composite ultrafiltration membrane material according to claim 12, wherein the membrane forming in step b) is: after scraping a flat membrane or extruding a membrane from a fiber spinning machine, phase inversion is performed to form a membrane; The phase inversion film formation is carried out in a phase inversion liquid, which is deionized water.
- 如权利要求10所述的复合超滤膜材料的制备方法，所述静置脱泡为在温度为40～80℃条件下静置12h以上。The preparation method of the composite ultrafiltration membrane material according to claim 10, wherein the static defoaming is to stand at a temperature of 40-80° C. for more than 12 hours.
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