WO2023116287A1 - 复合纳滤膜的制备方法和由此制备的复合纳滤膜 - Google Patents
复合纳滤膜的制备方法和由此制备的复合纳滤膜 Download PDFInfo
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- WO2023116287A1 WO2023116287A1 PCT/CN2022/132634 CN2022132634W WO2023116287A1 WO 2023116287 A1 WO2023116287 A1 WO 2023116287A1 CN 2022132634 W CN2022132634 W CN 2022132634W WO 2023116287 A1 WO2023116287 A1 WO 2023116287A1
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- preparation
- composite nanofiltration
- nanofiltration membrane
- solution
- membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000002346 layers by function Substances 0.000 claims abstract description 35
- 239000008346 aqueous phase Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- -1 amine compound Chemical class 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012779 reinforcing material Substances 0.000 claims abstract description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 6
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 50
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 37
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000000243 solution Substances 0.000 description 59
- 210000004379 membrane Anatomy 0.000 description 44
- 239000002585 base Substances 0.000 description 36
- 238000012546 transfer Methods 0.000 description 25
- 239000000178 monomer Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 15
- 210000002469 basement membrane Anatomy 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000004745 nonwoven fabric Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- UIMAOHVEKLXJDO-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triethylazanium Chemical compound CCN(CC)CC.C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C UIMAOHVEKLXJDO-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical class CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the size of the surface pore size of the base membrane will affect the mass transfer rate of the aqueous phase monomer during the interfacial polymerization reaction.
- the solvent environment in the interfacial polymerization miscibility zone on the surface of different base membranes is determined by This changes.
- other factors such as the mass transfer distribution of the monomer in the water phase also need to be included in the consideration of the impact of the interfacial polymerization reaction. This multi-factorial influence makes it difficult to form a simple rule for the law affected by the base membrane during the preparation of the composite nanofiltration membrane.
- the present disclosure aims to weaken the influencing factors of the different mass transfer rates of the aqueous phase monomers in the interfacial polymerization reaction due to the size of the surface pore size of the base membrane.
- a functional layer with an adjustable structure can be obtained, thereby obtaining a composite nanofiltration membrane with different maximum molecular weight cut-offs.
- the interfacial polymerization reaction under the same formulation conditions is coated on the base membrane with different surface average pore sizes.
- the functional layer structures of the corresponding nanofiltration membranes differ significantly only in the average pore size. That is, the surface average pore size of the functional layer of the composite nanofiltration membrane obtained by coating the base membrane surface with a larger average pore size is larger, while the composite nanofiltration membrane obtained by coating the base membrane surface with a smaller average pore size The surface average pore size of the functional layer is smaller.
- the amine compound is one or more selected from m-phenylenediamine, p-phenylenediamine, ethylenediamine, piperazine, preferably, the aqueous phase Based on the weight of the solution, the concentration of the amine compound is 3-5 wt%.
- the concentration of the silane coupling agent is 0.01-1 wt%.
- the concentration of the biomass acid is 0.1-10wt%.
- the biomass acid is at least one selected from tannic acid, tartaric acid, citric acid, and gluconic acid.
- the present disclosure relates to a preparation method of a composite nanofiltration membrane, which comprises the following steps:
- the polymer is at least one selected from bisphenol A polysulfone, polyarylsulfone, and polyethersulfone , based on the weight of the polymer solution, the concentration of the polymer is 10-20wt%;
- the base film obtained in the above steps is sequentially contacted with an aqueous phase solution comprising an amine compound, a silane coupling agent and a biomass acid, and an oil phase solution comprising polyacyl chlorides to form a functional layer;
- Composite nanofiltration membranes are obtained after post-treatment and drying.
- the technical idea of the preparation method of the present disclosure is to obtain basement membranes with different surface average pore sizes by adjusting the concentration of the polymer in the polymer solution, and then use the basement membrane as a support layer, by adding a silane coupling agent and Biomass acid is used to eliminate the influence of the mass transfer rate of the monomer in the water phase and other reaction variable factors such as the change of the interfacial polymerization reaction rate caused by the difference in the mass transfer distribution range of the monomer, so that the interfacial polymerization reaction is only affected by the surface average of the base film. Due to the influence of different pore sizes, functional layers with different surface average pore sizes are correspondingly obtained through interfacial polymerization, and the adjustable surface average pore size of the functional layer is realized in a simple way.
- the coating method is not particularly limited, and coating methods commonly used in the field of nanofiltration membrane preparation can be used, such as casting method, dip coating method, blade coating method, spin coating method, etc., and blade coating method is more preferred. After being coated on the non-woven fabric, it is then immersed in a coagulation bath to coagulate into a film.
- the coagulation bath is pure water, and the temperature of the coagulation bath is 10-15°C.
- the base film is soaked in an aqueous alkali metal hydroxide solution with a concentration of 1-10 wt%, washed with pure water, and dried before being used in subsequent steps.
- the purpose of immersion is to wash away the solvent in the casting solution remaining in the basement film.
- the alkali metal hydroxide may be, for example, sodium hydroxide, potassium hydroxide and the like.
- the bisphenol A polysulfone, polyarylsulfone, and polyethersulfone have structural units represented by the following general formulas (1) to (3):
- n is the number of structural units in a single molecular chain, and its value is between 5-50, preferably, the value of n is between 10-15.
- the concentration of the polymer is 10-20 wt%.
- the average pore diameter of the base film is in the range of 5-20 nm.
- the concentration of the silane coupling agent is 0.01-1 wt%.
- the amine compound used as the monomer of the water phase there is no special limitation on the amine compound used as the monomer of the water phase, and the amine compound commonly used in the interfacial polymerization reaction can be used.
- the amine compound is selected from m-phenylenediamine , p-phenylenediamine, ethylenediamine, and piperazine; more preferably, based on the weight of the aqueous phase solution, the concentration of the amine compound is 3-5 wt%.
- the solvent in the oil phase solution is at least one selected from dichloromethane, chloroform, dichloroethane, n-hexane, ethylcyclohexane, and propylene oxide.
- the polymer is selected from bisphenol A polysulfone, polyarylsulfone, at least one of polyethersulfone;
- the base film is soaked in an aqueous alkali metal hydroxide solution with a concentration of 1-5 wt%, then washed with pure water and dried for use;
- the base film obtained in the above steps is sequentially mixed with an aqueous phase solution containing an amine compound having a concentration of 3-5wt%, a silane coupling agent having a concentration of 0.01-1wt%, and a biomass acid having a concentration of 0.1-10wt%.
- the oil phase solution of polyacyl chlorides with a concentration of 0.10-0.50wt% is in contact to form a functional layer;
- the contact time with the water-phase solution and the oil-phase solution for example, it may be 5-300 seconds. Preferably, it is taken out after contact to remove excess solution on the surface.
- the present disclosure also relates to a composite nanofiltration membrane prepared by the preparation method according to the present disclosure.
- the composite nanofiltration membrane includes from bottom to top: a non-woven fabric layer, a polymer base film support layer, and a functional layer.
- the resulting nanofiltration membrane I can filter molecules with a molecular weight below 400 Da and retain molecules with a molecular weight above 400 Da.
- Preparation of polysulfone concentration is 20wt% casting solution, scraping film on non-woven fabric to prepare polysulfone-based membrane support layer I with surface average pore diameter of 5nm, soaking in 1wt% sodium hydroxide aqueous solution for 30mins, using Wash with ultrapure water and dry; then with 3.0wt% m-phenylenediamine, 0.2wt% 3-aminopropyltriethoxysilane, 2wt% gluconic acid, 4wt% camphorsulfonic acid, 2wt% triethyl Contact the aqueous phase solution of the amine for 20s, take it out and remove excess water droplets on the surface; contact it with an ethylcyclohexane solution containing 0.15wt% trimesoyl chloride for 20s, take it out, and heat-treat the above-mentioned membrane at 70°C 10mins.
- the resulting nanofiltration membrane IV can filter molecules with a mo
- basement membranes with different surface average pore sizes can be obtained as a support layer through the preparation method of the present disclosure, and then a silane coupling agent and biomass acid are added to the aqueous phase solution to eliminate the monomers in the aqueous phase, respectively.
- the influence of the mass transfer rate of the monomer and other reaction variable factors such as the change of the interfacial polymerization reaction rate caused by the difference in the mass transfer distribution range of the monomer can make the interfacial polymerization reaction only affected by the difference in the surface average pore size of the base membrane.
- the reaction is carried out on the base membrane to obtain functional layers with different surface average pore sizes.
- the resulting composite nanofiltration membrane not only maintains high water flux but also has different maximum molecular weight cut-offs, which can be used for high-selectivity filtration. Separation of substances with a molecular weight between 200Da and 400Da, between 400Da and 600Da, and between 600Da and 800Da.
- the preparation method of the present disclosure obtains basement membranes with different surface average pore sizes by adjusting the concentration of the polymer solution, and then eliminates the mass transfer rate of the aqueous phase monomer by adding silane coupling agent and biomass acid to the aqueous phase solution
- the impact of different mass transfer distribution ranges of monomers and other reaction variable factors such as changes in the interfacial polymerization reaction rate can make the interfacial polymerization reaction only affected by the difference in the surface average pore size of the base membrane, so that correspondingly different
- the functional layer with the surface average pore size can realize the adjustable surface average pore size of the functional layer in a simple way, and finally obtain a composite nanofiltration membrane with different maximum molecular weight cut-offs, which can be used for highly selective filtration and separation of molecular weights between 200Da and Substances between 400 Da, between 400 Da and 600 Da, and between 600 Da and 800 Da.
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Abstract
本公开涉及复合纳滤膜的制备方法和由此制备的复合纳滤膜。所述复合纳滤膜的制备方法包括以下步骤：制备聚合物溶液作为铸膜液，使所述铸膜液在增强材料上固化形成基膜；接着依次与包含胺类化合物、硅烷偶联剂和生物质酸的水相溶液、包含多元酰氯的油相溶液接触以形成功能层；经后处理、干燥后得到复合纳滤膜。在本公开的制备方法中，通过调节铸膜液中聚合物的浓度从而得到具有不同的表面平均孔径大小的基膜；通过在水相溶液中添加硅烷偶联剂和生物质酸以消除其他反应变量因素，使得界面聚合反应仅受基膜平均孔径大小的影响，相应地得到具有不同的表面平均孔径大小的功能层的复合纳滤膜，从而具有不同的最大截留分子量。
Description
本公开涉及复合纳滤膜的技术领域，特别涉及一种复合纳滤膜的制备方法和由此制得的复合纳滤膜。
复合纳滤膜分离技术是一种截留分子量介于反渗透和超滤膜之间的、对分子量在200-1000Da之间的物质进行分离的膜分离技术。市场已经发展出对于更细分的不同分子量的物质进行分离的复合纳滤膜技术的需求。譬如，部分药物主要成分的分离过程中采用的复合纳滤膜需要对分子量在200-400Da之间的物质进行分离，这就要求市场开发出对于分子量在200Da以下的物质能够滤过和对分子量在400Da以上的物质能够截留的复合纳滤膜。
这样更细分的组分分离要求使得复合纳滤膜必须具备孔径大小的分布范围较窄的特点。为此，制备得到具有高选择性的功能层的结构可调节的复合纳滤膜成为一种必需手段，而在功能层的结构可调节的基础上，才能获得具备孔径大小的分布范围较小的复合纳滤膜。现有技术中对于复合纳滤膜的孔径结构的调节，多是采用在界面聚合反应过程中的条件变化来实现所得复合纳滤膜的功能层的结构变化。
但是，在复合纳滤膜的制备过程中，基膜的结构和表面形貌对于界面聚合反应具有重要影响。因此，通过基膜的结构和表面形貌变化来实现功能层的结构的可调节可以作为一种直接且简单有效的手段。但是基膜的结构和表面形貌改变，所引起覆膜过程中的界面聚合反应条件的改变在常规覆膜方法中变化因素诸多。在此情况下，难以掌控其影响复合纳滤膜的功能层的孔径大小和分布的变化规律。
这需要考虑到以下两点情况：首先，功能层的制备是通过界面聚合反应，亦即以有机化学中经典的肖顿-鲍曼(Schotten-Bauman)反应为依据，采用逐步 增长机理制备具有分离作用的高分子量聚合物脱盐层。此过程将两种带有不同活性基团的单体或预聚物分别溶于两种互不相溶的溶剂中，当两种溶液互相接触时再在界面处反应。由于界面聚合反应速度极快且生成的功能层很薄，而且聚合反应中又涉及到单体传质和反应的同时进行、聚合物链增长、聚合物相分离等多个过程，所以难以对界面聚合反应过程监控从而实现对反应过程进行准确的动力学分析。其次，提供这种界面并且作为支撑材料的聚砜层，会直接地影响聚酰胺功能层的形成过程，进而影响复合纳滤膜的性能。
通常将提供界面聚合反应界面并且作为支撑材料的聚砜层称为基膜。一般地，基膜的断面结构主要决定复合膜的机械性能；而基膜的表面结构(表面孔径、孔分布)以及亲疏水性等，均能影响水相单体从基膜表面的膜孔传质到有机相中参与界面聚合反应的过程(传质速率、传质分布)，从而影响功能层的结构和复合膜的性能。此外，基膜和通过界面聚合反应形成的功能层初生膜的界面之间会存在共价键、氢键、静电吸引等相互作用，这些相互作用会影响聚合物链的组装，从而影响功能层的结构。
所以，仅就“基膜对功能层的结构和性能的影响”系列问题当中的“界面聚合膜表面粗糙结构的产生”而言，已有数种不同的理论和数学模型解释。当考虑采用通过基膜的结构和表面形貌变化来影响复合纳滤膜的功能层的结构时，需要做到弱化某些次要的相关因素，而只考虑主要的相关因素对界面聚合反应的影响。
基膜的表面孔径的大小会影响界面聚合反应过程中的水相单体传质速率，此时在相同的覆膜配方条件下，不同基膜的表面的界面聚合反应混溶区的溶剂环境由此发生变化。而除了水相单体传质速率改变以外，其他如水相单体传质分布的因素也需包含在界面聚合反应所受影响的考虑因素之中。这种多因素的影响使得复合纳滤膜制备过程中的受基膜影响的规律难以形成简单的规律。
发明内容
发明要解决的问题
为了解决现有技术中存在的上述问题，本公开旨在弱化由于基膜的表面孔径的大小导致在界面聚合反应中水相单体传质速率不同的影响因素，在受到较少因素影响的情况下得到结构可调节的功能层，从而得到具有不同的最大截留分子量的复合纳滤膜。
用于解决问题的方案
本公开的发明人通过深入研究发现，在基膜的制备过程中，通过调节铸膜液中聚合物的浓度可以得到具有不同的表面平均孔径大小的基膜；进一步地，通过在水相溶液中添加硅烷偶联剂和生物质酸以分别消除水相单体的传质速率的影响和因单体传质分布范围不同而引起的界面聚合反应速率变化等其他反应变量因素，可以使得界面聚合反应仅受基膜平均孔径大小不同的影响，在考虑相应的基膜引起复合纳滤膜的功能层的结构变化时，只需考虑基膜的表面平均孔径大小导致的水相单体传质分布的影响。
在相同的覆膜配方和界面聚合反应条件下，当基膜的表面平均孔径从大到小变化时，可以相应地得到功能层的表面平均孔径从大到小的复合纳滤膜，从而得到具有不同的最大截留分子量即具有选择性分离功能的复合纳滤膜。
综上，在传质速率与反应速率受基膜的表面平均孔径的影响均降低以后，在相同配方条件下的界面聚合反应分别在具有不同表面平均孔径大小的基膜上覆膜时，所得到的相应的纳滤膜的功能层结构只在平均孔径大小上存在明显区别。亦即，在具有较大平均孔径的基膜表面覆膜得到的复合纳滤膜的功能层的表面平均孔径更大，而在具有较小平均孔径的基膜表面覆膜得到的复合纳滤膜的功能层的表面平均孔径较小。
本公开提供一种复合纳滤膜的制备方法，所述方法包括以下步骤：
制备聚合物溶液作为铸膜液，使所述铸膜液在增强材料上固化形成基膜，所述聚合物为选自双酚A型聚砜、聚芳砜、聚醚砜中的至少一种，以所述聚合物溶液的重量计，所述聚合物的浓度为10-20wt％；
将以上步骤中得到的基膜依次与包含胺类化合物、硅烷偶联剂和生物质 酸的水相溶液、包含多元酰氯的油相溶液接触以形成功能层；
经后处理、干燥后得到复合纳滤膜。
根据本公开所述的制备方法，其中所述双酚A型聚砜、聚芳砜、聚醚砜分别具有由以下通式(1)至(3)表示的结构单元：
其中，n为单个分子链中的结构单元数，其值在5-50之间。
根据本公开所述的制备方法，其中所述胺类化合物为选自间苯二胺、对苯二胺、乙二胺、哌嗪中的一种或几种，优选地，以所述水相溶液的重量计，所述胺类化合物的浓度为3-5wt％。
根据本公开所述的制备方法，其中以所述水相溶液的重量计，所述硅烷偶联剂的浓度为0.01-1wt％。
根据本公开所述的制备方法，其中所述硅烷偶联剂为选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、3-氨丙基三乙氧基硅烷中的至少一种。
根据本公开所述的制备方法，其中以所述水相溶液的重量计，所述生物质酸的浓度为0.1-10wt％。
根据本公开所述的制备方法，其中所述生物质酸为选自鞣酸、酒石酸、柠檬酸、葡萄糖酸中的至少一种。
根据本公开所述的制备方法，其中所述多元酰氯为选自均苯三甲酰氯、对苯二甲酰氯、草酰氯中的至少一种。
根据本公开所述的制备方法，其中以所述油相溶液的重量计，所述多元酰氯的浓度为0.10-0.50wt％。
本公开还提供一种根据本公开所述的制备方法制得的复合纳滤膜。
发明的效果
通过本公开的制备方法可以得到具有不同的表面平均孔径的基膜作为支撑层，继而通过界面聚合反应在基膜上进行覆膜得到具有不同的表面平均孔径大小的功能层，所得的复合纳滤膜具有不同的最大截留分子量，可用于高选择性地过滤分离分子量在200Da至800Da之间的物质。
本公开涉及一种复合纳滤膜的制备方法，其包括以下步骤：
制备聚合物溶液作为铸膜液，使所述铸膜液在增强材料上固化形成基膜，所述聚合物为选自双酚A型聚砜、聚芳砜、聚醚砜中的至少一种，以所述聚合物溶液的重量计，所述聚合物的浓度为10-20wt％；
将以上步骤中得到的基膜依次与包含胺类化合物、硅烷偶联剂和生物质酸的水相溶液、包含多元酰氯的油相溶液接触以形成功能层；
经后处理、干燥后得到复合纳滤膜。
本公开制备方法的技术构思在于，通过调节聚合物溶液中聚合物的浓度得到具有不同的表面平均孔径的基膜，进而以基膜作为支撑层，通过在水相溶液中添加硅烷偶联剂和生物质酸以分别消除水相单体的传质速率的影响和因单体传质分布范围不同而引起的界面聚合反应速率变化等其他反应变量因素，使得界面聚合反应仅受基膜的表面平均孔径大小不同的影响，通过界面聚合反应相应地得到具有不同的表面平均孔径的功能层，以简单的方法实现功能层的表面平均孔径的可调节。
在相同的覆膜配方和界面聚合反应条件下，当基膜的表面平均孔径从大 到小变化时，可以相应地得到功能层的表面平均孔径从大到小的复合纳滤膜，从而得到具有不同的最大截留分子量即具有选择性分离功能的复合纳滤膜。
在本公开的制备方法中，将聚合物溶液作为铸膜液涂覆在增强材料上，优选地，所述增强材料为无纺布，例如PP无纺布、PET无纺布、PA无纺布。
对于涂覆方法没有特别限定，可以使用纳滤膜制备领域中通常使用的涂覆方法，例如流延法、浸涂法、刮涂法、旋转涂覆法等，更优选为刮涂法。涂覆在无纺布上之后接着浸在凝固浴中，凝固成膜。
在本公开的制备方法中，优选地，凝固浴为纯水，凝固浴温度为10-15℃。
在本公开的制备方法中，优选地，将基膜浸泡在浓度为1-10wt％的碱金属氢氧化物水溶液中，用纯水清洗、干燥后再用于后续步骤。浸泡的目的是洗去基膜中残留的铸膜液中的溶剂。所述碱金属氢氧化物例如可以是氢氧化钠、氢氧化钾等。
在本公开的制备方法中，优选地，所述双酚A型聚砜、聚芳砜、聚醚砜分别具有由以下通式(1)至(3)表示的结构单元：
其中，n为单个分子链中的结构单元数，其值在5-50之间，优选地，n值在10-15之间。
在本公开的制备方法中，优选地，以所述聚合物溶液的重量计，所述聚 合物的浓度为10-20wt％。
在本公开的制备方法中，优选地，通过对基膜表面进行扫描电子显微镜(SEM)分析，基膜(又称为支撑层)的表面平均孔径在5-20nm的范围内。
在本公开的制备方法中，硅烷偶联剂的加入使得作为水相单体的胺类化合物在基膜表面孔内铺展更均匀，并且大大加快了胺类化合物在界面聚合反应过程中的传质速率，弱化了胺类化合物的传质速率因基膜表面平均孔径大小不同而引起的变化，减少了因基膜的表面平均孔径大小不同而产生的传质速率的差异，从而使得在不同的表面平均孔径大小的基膜上覆膜时的胺类化合物的传质速率基本一致。因此，所得复合纳滤膜的功能层结构，只受胺类化合物的传质分布范围的影响而不受传质速率的影响。
在本公开的制备方法中，优选地，以所述水相溶液的重量计，所述硅烷偶联剂的浓度为0.01-1wt％。
在本公开的制备方法中，所述硅烷偶联剂为选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、3-氨丙基三乙氧基硅烷中的至少一种。
生物质酸的加入改变了界面聚合反应混溶区的酸碱度等。由勒夏特列原理可知，其改变了界面聚合反应形成聚酰胺的过程中释放HCl的速率，亦即降低了界面聚合反应速率。在具有不同的表面平均孔径大小的基膜上覆膜时，该作用使得界面聚合反应速率总是较慢的，因单体传质分布范围不同而引起的界面聚合反应速率变化趋于消失。
在本公开的制备方法中，优选地，以所述水相溶液的重量计，所述生物质酸的浓度为0.1-10wt％。
在本公开的制备方法中，优选地，所述生物质酸为选自鞣酸、酒石酸、柠檬酸、葡萄糖酸中的至少一种。
在本公开的制备方法中，对于作为水相单体的胺类化合物没有特别限定，可以使用界面聚合反应中通常使用的胺类化合物，优选地，所述胺类化合物为选自间苯二胺、对苯二胺、乙二胺、哌嗪中的一种或几种；更优选地，以 所述水相溶液的重量计，所述胺类化合物的浓度为3-5wt％。
在本公开的制备方法中，优选地，在水相溶液中还可以包含三乙胺、樟脑磺酸以形成水相缓冲体系三乙胺樟脑磺酸盐(TEA-CSA)，从而将水相溶液的pH值调节在8至10的范围内，以更有利于胺类化合物的扩散以及促进水相和油相两相的混溶以促进界面聚合反应的进行。
在本公开的制备方法中，对于作为油相单体的多元酰氯没有特别限定，可以使用界面聚合反应中通常使用的多元酰氯，优选地，所述多元酰氯为选自均苯三甲酰氯、对苯二甲酰氯、草酰氯中的至少一种；更优选地，以所述油相溶液的重量计，所述多元酰氯的浓度为0.10-0.50wt％。
在本公开的制备方法中，优选地，油相溶液中的溶剂为选自二氯甲烷、氯仿、二氯乙烷、正己烷、乙基环己烷、环氧丙烷中的至少一种。
作为一个非限制性实例，本公开的复合纳滤膜的制备方法包括以下步骤：
制备浓度为10-20wt％的聚合物溶液作为铸膜液，使所述铸膜液在无纺布上固化形成基膜，所述聚合物为选自双酚A型聚砜、聚芳砜、聚醚砜中的至少一种；
优选地，将基膜浸泡在浓度为1-5wt％的碱金属氢氧化物水溶液中，接着用纯水清洗并且干燥备用；
将以上步骤中得到的基膜依次与包含浓度为3-5wt％的胺类化合物、浓度为0.01-1wt％的硅烷偶联剂和浓度为0.1-10wt％的生物质酸的水相溶液、包含浓度为0.10-0.50wt％的多元酰氯的油相溶液接触以形成功能层；
经后处理、干燥后得到复合纳滤膜。
对于与水相溶液和油相溶液接触的时间没有特别限定，例如可以是5-300秒，优选地，在接触后取出，去除表面多余的溶液。
在本公开的制备方法中，所述后处理优选为去除表面多余的溶液，然后清洗，例如采用去离子水进行清洗。对于烘干温度没有特别限制，通常为50-70℃；对于烘干时间也没有特别限制，通常为1-30分钟。
本公开还涉及一种通过根据本公开的制备方法制备得到的复合纳滤膜， 优选地，所述复合纳滤膜从下至上依次包括：无纺布层、聚合物基膜支撑层、以及功能层。
实施例
下面结合具体的实施例进一步详细说明本公开，但本公开的技术方案绝不限于以下实施例。需要说明的是，实施例中采用的试剂、原料和设备除非特别说明，皆为商购可得的常规产品。
实施例1
配制聚砜浓度为20wt％的铸膜液，在无纺布上刮膜，在温度为12℃的水浴中进行凝固成膜，制备得到表面平均孔径为5nm的聚砜基膜支撑层I，在浓度为1wt％的氢氧化钠水溶液中浸泡30mins，用超纯水洗涤，晾干。接着与包含3.0wt％间苯二胺、0.1wt％的3-氨丙基三乙氧基硅烷、1wt％的鞣酸、4wt％樟脑磺酸、2wt％三乙胺的水相溶液接触20s，取出后去除表面多余的水滴；与包含0.15wt％均苯三甲酰氯的乙基环己烷溶液接触20s，取出，将上述制得膜片在70℃的条件下热处理10mins。得到的纳滤膜I可以使得分子量在400Da以下的分子被滤过并且使得分子量高于400Da的分子被截留。
实施例2
除了配制聚砜浓度为15wt％的铸膜液、在无纺布上刮膜制备得到表面平均孔径为10nm的聚砜基膜支撑层II以外，以与实施例1相同的方式进行，得到的纳滤膜II可以使得分子量在600Da以下的分子被滤过并且使得分子量高于600Da的分子被截留。
实施例3
除了配制聚砜浓度为10wt％的铸膜液、在无纺布上刮膜制备得到表面平均孔径为20nm的聚砜基膜支撑层III以外，以与实施例1相同的方式进行，得到的纳滤膜III可以使得分子量在800Da以下的分子被滤过并且使得分子量高于800Da的分子被截留。
实施例4
配制聚砜浓度为20wt％的铸膜液，在无纺布上刮膜制备得到表面平均孔径为5nm的聚砜基膜支撑层I，在浓度为1wt％的氢氧化钠水溶液中浸泡30mins，用超纯水洗涤，晾干；接着与包含3.0wt％间苯二胺、0.2wt％的3-氨丙基三乙氧基硅烷，2wt％的葡萄糖酸、4wt％樟脑磺酸、2wt％三乙胺的水相溶液接触20s，取出后去除表面多余的水滴；与包含0.15wt％均苯三甲酰氯的乙基环己烷溶液接触20s，取出，将上述制得膜片在70℃的条件下热处理10mins。得到的纳滤膜IV可以使得分子量在400Da以下的分子被滤过并且使得分子量高于400Da的分子被截留。
实施例5
除了配制聚砜浓度为15wt％的铸膜液、在无纺布上刮膜制备得到表面平均为10nm的聚砜基膜支撑层II以外，以与实施例4相同的方式进行，得到的纳滤膜V可以使得分子量在600Da以下的分子被滤过并且使得分子量高于600Da的分子被截留。
实施例6
除了配制聚砜浓度为10wt％的铸膜液、在无纺布上刮膜制备得到表面平均孔径为20nm的聚砜基膜支撑层III以外，以与实施例4相同的方式进行，得到的纳滤膜VI可以使得分子量在800Da以下的分子被滤过并且使得分子量高于800Da的分子被截留。
膜片性能检测：
选择四种不同分子量的标的物如下：PEG200(Da＝200)、结晶紫(Da＝407)、溴百里香酚蓝(Da＝624)、固绿(Da＝809)，分别溶解在水中得到各自浓度为1wt％的溶液作为浓水，然后使用以上实施例1-6中的复合纳滤膜在100psi压力条件下过滤得到产水，记录水通量和采用TOC检测法计算得出膜片的截留率，将实施例1-6中得到的各复合纳滤膜的截留率和水通量列于下表1中。
表1
从以上结果可以看出，通过本公开的制备方法可以得到具有不同的表面平均孔径的基膜作为支撑层，继而在水相溶液中添加硅烷偶联剂和生物质酸以分别消除水相单体的传质速率的影响和因单体传质分布范围不同而引起的界面聚合反应速率变化等其他反应变量因素，可以使得界面聚合反应仅受基膜的表面平均孔径大小不同的影响，通过界面聚合反应在基膜上进行覆膜得到具有不同的表面平均孔径大小的功能层，所得的复合纳滤膜不仅保持了较高的水通量而且具有不同的最大截留分子量，可用于高选择性地过滤分离分子量在200Da至400Da之间、400Da至600Da之间、600Da至800Da之间的物质。
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步的详细说明，应理解的是，以上所述仅为本公开的实施例而已，并不 用于限制本公开，凡在本公开的原则和精神之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
产业上的可利用性
本公开的制备方法通过调节聚合物溶液的浓度得到具有不同的表面平均孔径的基膜，进而通过在水相溶液中添加硅烷偶联剂和生物质酸以分别消除水相单体的传质速率的影响和因单体传质分布范围不同而引起的界面聚合反应速率变化等其他反应变量因素，可以使得界面聚合反应仅受基膜的表面平均孔径大小不同的影响，从而相应地得到具有不同的表面平均孔径大小的功能层，以简单的方法实现功能层的表面平均孔径大小的可调节，最终得到具有不同的最大截留分子量的复合纳滤膜，可用于高选择性地过滤分离分子量在200Da至400Da之间、400Da至600Da之间、600Da至800Da之间的物质。
Claims (10)
- 一种复合纳滤膜的制备方法，其特征在于，包括以下步骤：制备聚合物溶液作为铸膜液，使所述铸膜液在增强材料上固化形成基膜，所述聚合物为选自双酚A型聚砜、聚芳砜、聚醚砜中的至少一种，以所述聚合物溶液的重量计，所述聚合物的浓度为10-20wt％；将以上步骤中得到的基膜依次与包含胺类化合物、硅烷偶联剂和生物质酸的水相溶液、包含多元酰氯的油相溶液接触以形成功能层；经后处理、干燥后得到复合纳滤膜。
- 根据权利要求1所述的制备方法，其中所述双酚A型聚砜、聚芳砜、聚醚砜分别具有由以下通式(1)至(3)表示的结构单元：
其中，n为单个分子链中的结构单元数，其值在5-50之间。 - 根据权利要求1或2所述的制备方法，其中所述胺类化合物为选自间苯二胺、对苯二胺、乙二胺、哌嗪中的一种或几种，优选地，以所述水相溶液的重量计，所述胺类化合物的浓度为3-5wt％。
- 根据权利要求1或2所述的制备方法，其中以所述水相溶液的重量计，所述硅烷偶联剂的浓度为0.01-1wt％。
- 根据权利要求4所述的制备方法，其中所述硅烷偶联剂为选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、3-氨 丙基三乙氧基硅烷中的至少一种。
- 根据权利要求1或2所述的制备方法，其中以所述水相溶液的重量计，所述生物质酸的浓度为0.1-10wt％。
- 根据权利要求6所述的制备方法，其中所述生物质酸为选自鞣酸、酒石酸、柠檬酸、葡萄糖酸中的至少一种。
- 根据权利要求1或2所述的制备方法，其中所述多元酰氯为选自均苯三甲酰氯、对苯二甲酰氯、草酰氯中的至少一种。
- 根据权利要求1或2所述的制备方法，其中以所述油相溶液的重量计，所述多元酰氯的浓度为0.10-0.50wt％。
- 一种根据权利要求1-9中任一项所述的制备方法制备的复合纳滤膜。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101934201A (zh) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | 一种高选择性复合纳滤膜及其制备方法 |
| JP2014000568A (ja) * | 2012-05-22 | 2014-01-09 | Daicen Membrane Systems Ltd | 内圧式の中空糸型ｎｆ膜とその製造方法 |
| CN106215726A (zh) * | 2016-08-08 | 2016-12-14 | 贵阳时代沃顿科技有限公司 | 一种含硅耐溶剂纳滤膜及其制备方法 |
| CN111298660A (zh) * | 2020-02-27 | 2020-06-19 | 浙江理工大学 | 一种强稳定性抗污复合纳滤膜的制备方法 |
| CN113318598A (zh) * | 2021-05-17 | 2021-08-31 | 浙江工业大学 | 一种通过调节基膜孔径增强反渗透膜选择渗透性的方法 |
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| JP2014000568A (ja) * | 2012-05-22 | 2014-01-09 | Daicen Membrane Systems Ltd | 内圧式の中空糸型ｎｆ膜とその製造方法 |
| CN106215726A (zh) * | 2016-08-08 | 2016-12-14 | 贵阳时代沃顿科技有限公司 | 一种含硅耐溶剂纳滤膜及其制备方法 |
| CN111298660A (zh) * | 2020-02-27 | 2020-06-19 | 浙江理工大学 | 一种强稳定性抗污复合纳滤膜的制备方法 |
| CN113318598A (zh) * | 2021-05-17 | 2021-08-31 | 浙江工业大学 | 一种通过调节基膜孔径增强反渗透膜选择渗透性的方法 |
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| CN117138605B (zh) * | 2023-10-27 | 2024-01-23 | 湖南沁森高科新材料有限公司 | 一种超低压反渗透膜及其制备方法 |
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