CN105169974B - A kind of hollow fiber nanofiltration membrane and preparation method thereof - Google Patents
A kind of hollow fiber nanofiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN105169974B CN105169974B CN201510632621.6A CN201510632621A CN105169974B CN 105169974 B CN105169974 B CN 105169974B CN 201510632621 A CN201510632621 A CN 201510632621A CN 105169974 B CN105169974 B CN 105169974B
- Authority
- CN
- China
- Prior art keywords
- outer layer
- hollow fiber
- internal layer
- nanofiltration membrane
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 64
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000003085 diluting agent Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 60
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 43
- -1 polypropylene Polymers 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000010790 dilution Methods 0.000 claims description 25
- 239000012895 dilution Substances 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 23
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012965 benzophenone Substances 0.000 claims description 14
- 229920002492 poly(sulfone) Polymers 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229940081735 acetylcellulose Drugs 0.000 claims description 12
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 12
- 229920002301 cellulose acetate Polymers 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 12
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical group CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 claims description 6
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 6
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 6
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229940095102 methyl benzoate Drugs 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 239000001069 triethyl citrate Substances 0.000 claims description 6
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000013769 triethyl citrate Nutrition 0.000 claims description 6
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- UYWQUFXKFGHYNT-UHFFFAOYSA-N Benzylformate Chemical compound O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 claims 2
- WKLNPIPUIVGQIY-UHFFFAOYSA-N C1=CC=CC=C1.C(=O)OCC Chemical compound C1=CC=CC=C1.C(=O)OCC WKLNPIPUIVGQIY-UHFFFAOYSA-N 0.000 claims 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 132
- 229920000642 polymer Polymers 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 230000003321 amplification Effects 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 3
- 235000012489 doughnuts Nutrition 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- USEBIPUIVPERGC-UHFFFAOYSA-N Dibutylone Chemical compound CCC(N(C)C)C(=O)C1=CC=C2OCOC2=C1 USEBIPUIVPERGC-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical class COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of hollow fiber nanofiltration membrane and preparation method thereof, the NF membrane are made up of polymeric material internal layer, polymeric material outer layer and the intermediate layer that is mutually wound by the strand of internal layer and outer layer copolymer material.Its preparation method is that inner layer polymeric material and outer layer copolymer material are dissolved in high-temperature diluent, using two parallel dual-screw extruding machines and triple channel spinning head；The step of method one for causing to be separated by temperature or exchange of solvent obtains the internal layer and nano pore structure outer layer of co-continuous pore passage structure, that is, obtains hollow fiber nanofiltration membrane.The present invention possesses the features such as high intensity, resistance to backwash, high selection separating property.
Description
Technical field
The present invention relates to it is a kind of with resistance to backwash, oxidative resistance and high selection separation property hollow fiber nanofiltration membrane and its
Preparation method.
Background technology
The research and development of hollow fiber nanofiltration membrane are expected to lead the future of membrane technology.NF membrane is still predominantly compound at present
Rolled film, but in the patent reported at present, the inoxidizability and chlorine-resistant property of composite nanometer filtering film are very poor, in long-term use
There is the problem of performance degradation and life-span reduction.And hollow fiber nanofiltration membrane can realize the backwash of oxidisability cleaning agent, in
Empty fiber membrane can be made very thin, so make the hollow-fibre membrane loading density height after component, received in same units volume
The effective filtration area of filter membrane is bigger, but often flux is very low for the hollow-fibre membrane of high intensity, and practical operation energy consumption is higher.In
Hollow fiber NF membrane can realize that supporting layer and separating layer structure regulate and control respectively, and effective reduction prepares the polymeric material used in film
Cost, and decline operation energy consumption by improving flux, but adhesive property is poor between the internal layer of hollow-fibre membrane and outer layer,
Performance degradation occurs when long-term backwash and oxidizer treatment, therefore region be directly facing and controlled in the high-performance of sewage and drinking water treatment
Fiber nano filtering film is urgently developed.
It is currently known a kind of hollow fiber nanofiltration membrane (application number of cellulose acetate material：201410095592.X), tool
There is the co-continuous pore structure continuously reduced from inner surface (100nm) to outer surface (1nm), it is close that thermally induced phase separation obtains film wire
Proximity has nano pore structure, can realize nanofiltration performance under the conditions of the long-term backwash for the cleaning agent of resistance to oxidative,
But the thickness of nano pore structure is big (0.5~5 μm), the flux of hollow fiber nanofiltration membrane is reduced.
It is currently known a kind of double-layer hollow fiber NF membrane (application number：200910306839.7), by with nano pore structure
Outer layer and internal layer with finger-like pore structure form, obtain nascent duplicature, phase separation using coextrusion method
Method obtains perforated membrane.Because the internal layer aperture of finger-like pore structure and porosity are larger, and the outer layer thickness of nano pore structure can
0.1~1 μm is reduced to, therefore membrane flux is larger, but there is clear interface debonding between internal layer and outer layer, cause bonding interface
Performance deficiency, can not oxidative resistance cleaning agent backwash for a long time.
In summary, single layer hollow fiber nano filtering film has the co-continuous pore structure that continuously reduces, excellent in mechanical performance, but
It is big to be proximate to the nano pore structure thickness of proximity, causes the flux of film low；Double-layer hollow fiber NF membrane is received by reducing
The thickness of the outer layer of pore structure realizes that flux improves, but interfacial adhesion is insufficient；Therefore need to develop in internal layer and outer layer
Middle transition layer structure, under conditions of hollow fiber nanofiltration membrane high intensity is ensured, obtain the resistance to backwash of hollow-fibre membrane
The characteristics of energy is high, and oxidative resistance is strong, and water flux is big.
The content of the invention
The problem of purpose of the present invention is resistance to backwash property and poor oxidative resistance existing for existing NF membrane, carries
Go out a kind of hollow fiber nanofiltration membrane and preparation method thereof, prepared hollow fiber nanofiltration membrane possesses high intensity, resistance to backwash, resistance to
The features such as oxidisability and high selection separating property.
Technical scheme is as follows：
A kind of hollow fiber nanofiltration membrane, it is characterised in that the hollow fiber nanofiltration membrane is by polymeric material internal layer, polymerization
Thing material outer layer and intermediate layer composition, internal layer have co-continuous pore passage structure, and internal layer thickness is 99.9~400 μm；Outside
Layer has the nano pore structure continuously reduced from the inner surface to outer surface, and thickness is 0.1~10 μm；The intermediate layer is in internal layer
The mutual winding arrangement of the strand of polymeric material and outer layer copolymer material, transition region thickness are 0.1~1 μm.
In above-mentioned technical proposal, the bore dia of receiving of the inner surface of the polymeric material outer layer is 100~1000nm, polymerization
The bore dia of receiving of the outer surface of thing material outer layer is 0.5~10nm.
In above-mentioned technical proposal, the external diameter of the hollow fiber NF membrane is 0.6~2.0mm, and internal diameter is 0.4~1.4mm.It is poly-
Compound material inner layer uses one in polysulfones, polyether sulfone, acetyl cellulose, polyvinylidene fluoride, polypropylene and polyvinyl chloride
Kind or several combinations；Polymeric material outer layer is using polysulfones, polyether sulfone, SPSF, acetyl cellulose, polyamide and gathers
One or more of combinations in acid imide.
The preparation method of the hollow fiber nanofiltration membrane provided by the invention, it is characterised in that what methods described used sets
It is standby to be made up of the first parallel dual-screw extruding machine, the second parallel dual-screw extruding machine, triple channel spinning head and outer coagulating tank,
Its preparation method comprises the following steps：
1) polymeric material for preparing internal layer is added continuously to first parallel dual-screw extruding machine by hopper
In 1st section of bringing-up section, and the diluent of internal layer is preheated to after 100~210 DEG C and is added continuously to first double spiral shell in the same direction
In one or more bringing-up sections of bar extruder, the temperature of each bringing-up section forms internal layer casting solution at 100~210 DEG C；It is interior
The mass percent of polymeric material in layer casting solution for 20~40wt% between, diluent mass percent for 80~
60wt%；The diluent of internal layer includes master dilution agent and additive；The additive of internal layer is 1 with the mass ratio of master dilution agent：
16~1：1；
2) polymeric material for preparing outer layer is added continuously to second parallel dual-screw extruding machine by hopper
In 1st section of bringing-up section, after the diluent of outer layer is preheated into 100~210 DEG C, second in the same direction pair is added continuously to
In one or more bringing-up sections of screw extruder, then the temperature of each bringing-up section forms outer layer casting at 100~210 DEG C
The mass percent of the polymeric material of film liquid, wherein outer layer is between 20~40wt%；Diluent mass percent is 80
~60wt%；The diluent of outer layer includes master dilution agent and additive；The additive of outer layer and the mass ratio of master dilution agent
For 1：16~1：Between 1；
3) internal layer casting solution and outer layer casting solution are after Melt Pump, by inner gel medium, internal layer casting solution and outer layer casting film
Liquid is injected separately into the inner gel medium channel, internal layer casting solution passage and outer layer casting solution passage of triple channel spinning head, through spinneret
Mouth is emitted into tubulose bilayer liquid film, injects in outer gel media solidify afterwards, obtains nascent duplicature；Melt Pump bringing-up section, in
Hollow fiber spinneret exits temperature and the temperature of inner gel medium are 130~180 DEG C；The outer gel media temperature is 20~80
℃；
4) diluent of nascent duplicature is removed through extractant immersion, obtains described hollow fiber nanofiltration membrane.
In the method for the invention, it is characterised in that the master dilution agent of internal layer is triethyl phosphate, tributyl phosphate, phosphorus
Sour three monooctyl esters, benzophenone, gaultherolin, salethyl, methyl benzoate, ethyl benzoate, butyl benzoate, the last of the ten Heavenly stems two
One or more of groups in diethyl phthalate, dibutyl sebacate, di-n-octyl sebacate, triethyl citrate and Ergol
Close；The additive of internal layer be dimethyl sulfoxide (DMSO), dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, lauryl alcohol,
Hexadecanol, octadecyl alcolol, triethylene glycol, diethylene glycol, ethylene glycol, polyvinylpyrrolidone, polyethylene polypropylene polyethylene three are embedding
Section copolymer, sorbitan mono-oleic acid ester, Tween-80, stearic acid, diphenyl methane, eicosane,
One or more of combinations in tetradecanoic acid and oleic acid.The master dilution agent of outer layer be triethyl phosphate, tributyl phosphate,
Trioctyl phosphate, benzophenone, gaultherolin, salethyl, methyl benzoate, ethyl benzoate, butyl benzoate, the last of the ten Heavenly stems
It is one or more of in diethyl adipate, dibutyl sebacate, di-n-octyl sebacate, triethyl citrate and Ergol
Combination；At least a kind of master dilution agent with internal layer of master dilution agent of outer layer is identical；The additive of outer layer is lauryl alcohol, 16
Alcohol, octadecyl alcolol, diethylene glycol, triethylene glycol, diethylene glycol, ethylene glycol, neopelex, lauryl sodium sulfate,
Two citric acid monohydrate trisodiums, polyvinylpyrrolidone, cetyl trimethylammonium bromide, polyethylene polypropylene polyethylene three block
Copolymer, sorbitan mono-oleic acid ester, Tween-80, stearic acid, diphenyl methane, eicosane, ten
One or more of combinations in four alkanoic acids, oleic acid.
In the method for the present invention, the inner gel medium is in atoleine, glycerine or nitrogen, or the diluent of internal layer
One or more of combinations；Outer gel media is one in atoleine, glycerine, nitrogen or water, or the diluent of outer layer
Kind or several combinations.The extractant uses ethanol, water or acetone.
The present invention compared with prior art, has advantages below and high-lighting effect：Under 0.2~0.8MPa, to chlorination
The rejection of sodium salt solution<30%；To the rejection of divalence salt ion>95%；To molecular weight in 300~200,000 dalton
Pollutant cutoff performance>99%, mechanical stretch intensity>30MPa.The hollow fiber nanofiltration membrane possesses high intensity, resistance to recoil
Wash, high selection separating property the characteristics of.
Brief description of the drawings
Fig. 1 is the equipment schematic diagram for preparing hollow fiber nanofiltration membrane.
Fig. 2 a-2e are respectively hollow fiber nanofiltration membrane entirety cross-section morphology, outer layer outer surface pattern, outer layer inner surface shape
Looks, inner layer outer surface pattern and internal layer internal surface shape schematic diagram.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples.
Concretely, hollow fiber nanofiltration membrane provided by the invention is by polymeric material internal layer, polymeric material outer layer
And intermediate layer composition, internal layer have co-continuous pore passage structure, internal layer thickness is 99.9~400 μm；Outer layer has from interior
The nano pore structure that surface continuously reduces to outer surface, thickness are 0.1~10 μm；The intermediate layer is in inner layer polymeric material
With the mutual winding arrangement of strand of outer layer copolymer material, transition region thickness is 0.1~1 μm.Polymeric material outer layer it is interior
The bore dia of receiving on surface is 100~1000nm, and the bore dia of receiving of the outer surface of polymeric material outer layer is 0.5~10nm.It is hollow
The external diameter of fiber nano filtering film is 0.6~2.0mm, and internal diameter is 0.4~1.4mm.Shown in Fig. 2, (a) is that the entirety of hollow-fibre membrane is broken
Face pattern (80 times of amplification)；(b) it is outer layer outer surface pattern (3000 times of amplification)；(c) it is (the amplification 250 of outer layer internal surface shape
Times)；(d) it is inner layer outer surface pattern (3000 times of amplification)；(e) it is internal layer internal surface shape (3000 times of amplification).
In such scheme, polymeric material internal layer is using polysulfones, polyether sulfone, acetyl cellulose, polyvinylidene fluoride, poly-
One or more of combinations in propylene and polyvinyl chloride；Polymeric material outer layer is using polysulfones, polyether sulfone, SPSF, vinegar
One or more of combinations in acid cellulose ester, polyamide and polyimides.
Method provided by the invention, using equipment as shown in Figure 1, the equipment be by the first parallel dual-screw extruding machine 1,
Second parallel dual-screw extruding machine 2, triple channel spinning head 3 and outer coagulating tank 4 form, and it specifically comprises the following steps：
1) polymeric material for preparing internal layer is added continuously to first parallel dual-screw extruding machine by hopper
In 1st section of bringing-up section, and the diluent of internal layer is preheated to after 100~210 DEG C and is added continuously to first double spiral shell in the same direction
In one or more bringing-up sections of bar extruder, the temperature of each bringing-up section forms internal layer casting solution at 100~210 DEG C；It is interior
The mass percent of polymeric material in layer casting solution for 20~40wt% between, diluent mass percent for 80~
60wt%；The diluent of internal layer includes master dilution agent and additive；The additive of internal layer is 1 with the mass ratio of master dilution agent：
16~1：1；The master dilution agent of described internal layer is triethyl phosphate, tributyl phosphate, trioctyl phosphate, benzophenone, bigcatkin willow
Sour methyl esters, salethyl, methyl benzoate, ethyl benzoate, butyl benzoate, diethyl sebacate, dibutyl sebacate,
One or more of combinations in di-n-octyl sebacate, triethyl citrate and Ergol；The additive of internal layer is diformazan
Base sulfoxide, dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, lauryl alcohol, hexadecanol, octadecyl alcolol, three second two
Alcohol, diethylene glycol, ethylene glycol, polyvinylpyrrolidone, polyethylene polypropylene polyethylene triblock copolymer, sorbitol anhydride list oil
One in acid esters, Tween-80, stearic acid, diphenyl methane, eicosane, tetradecanoic acid and oleic acid
Kind or several combinations.
2) polymeric material for preparing outer layer is added continuously to second parallel dual-screw extruding machine by hopper
In 1st section of bringing-up section, after the diluent of outer layer is preheated into 100~210 DEG C, second in the same direction pair is added continuously to
In one or more bringing-up sections of screw extruder, then the temperature of each bringing-up section forms outer layer casting at 100~210 DEG C
The mass percent of the polymeric material of film liquid, wherein outer layer is between 20~40wt%；Diluent mass percent is 80
~60wt%；The diluent of outer layer includes master dilution agent and additive；The additive of outer layer and the mass ratio of master dilution agent
For 1：16~1：Between 1；The master dilution agent of described outer layer is triethyl phosphate, tributyl phosphate, trioctyl phosphate, hexichol
Ketone, gaultherolin, salethyl, methyl benzoate, ethyl benzoate, butyl benzoate, diethyl sebacate, the last of the ten Heavenly stems two
One or more of combinations in dibutyl phthalate, di-n-octyl sebacate, triethyl citrate and Ergol；The master of outer layer
At least a kind of master dilution agent with internal layer of diluent is identical；The additive of outer layer is lauryl alcohol, hexadecanol, octadecyl alcolol, diethyl
Glycol, triethylene glycol, diethylene glycol, ethylene glycol, neopelex, lauryl sodium sulfate, two citric acid monohydrates three
Sodium, polyvinylpyrrolidone, cetyl trimethylammonium bromide, polyethylene polypropylene polyethylene triblock copolymer, sorbierite
Acid anhydride monoleate, Tween-80, stearic acid, diphenyl methane, eicosane, tetradecanoic acid, oleic acid
In one or more of combinations.
3) internal layer casting solution and outer layer casting solution are after Melt Pump, by inner gel medium, internal layer casting solution and outer layer casting film
Liquid is injected separately into the inner gel medium channel, internal layer casting solution passage and outer layer casting solution passage of triple channel spinning head, through spinneret
Mouth is emitted into tubulose bilayer liquid film, injects in outer gel media solidify afterwards, obtains nascent duplicature；Melt Pump bringing-up section, in
Hollow fiber spinneret exits temperature and the temperature of inner gel medium are 130~180 DEG C；The outer gel media temperature is 20~80
℃；Inner gel medium is one or more of combinations in atoleine, glycerine or nitrogen, or the diluent of internal layer；It is outer solidifying
Glue medium is one or more of combinations in atoleine, glycerine, nitrogen or water, or the diluent of outer layer.
4) diluent of nascent duplicature is removed through extractant immersion, described extractant uses ethanol, water or acetone, obtained
To described hollow fiber nanofiltration membrane.
According to the present invention, monofilm is compared in the influence of the composition of ectonexine casting solution for the structure and performance of hollow-fibre membrane
Influence factor it is more complicated.On the one hand, the diluent of internal layer and the diluent of outer layer is used to include master dilution agent and add
Add agent；The diluent of outer layer is identical with one or more species of master dilution agent in the diluent of internal layer, and what is now obtained is hollow
Fiber nano filtering film has the transition zone of the mutual winding arrangement of strand.If master is dilute in the diluent of outer layer and the diluent of internal layer
Release agent species to differ completely, obtained hollow fiber nanofiltration membrane does not have a transition zone, and obtained hollow fiber nanofiltration membrane circle
Face adhesive property is very poor, and the pressure applied when easily being filtered in backwash process by nanofiltration is destroyed, and it is dirty to small molecule to influence it
Contaminate the cutoff performance of material.
On the other hand, the addition of additive is also indispensable to preparing high-performance hollow tunica fibrosa.Additive can be with
For adjusting casting film system rheological property so that ensure can spinnability.Meanwhile additive can be used for adjusting ectonexine casting solution
Chemical potential, both difference in chemical potential is matched to prevent ectonexine peeling off phenomenon.In this patent, gather used by internal layer
The surface energy of compound material is relatively low, if Kynoar, polyacrylic surface energy are respectively 25mN/m and 30mN/m, belongs to hydrophobic
Property polymer, and the surface energy of polymeric material is higher used by outer layer, such as acetyl cellulose, SPSF, polyamide
Deng polymeric material due to hydroxyl, amido link and sulfonic presence, belong to hydrophilic polymer, surface energy is larger.Outer layer is cast
Additive in film liquid can reduce the surface energy of casting solution, and the additive in internal layer casting solution can improve the surface energy of casting solution,
The thickness and bulk density of joint effect transition zone, prevent splitting phenomenon.
Therefore, it is of the invention by the high temperature casting solution for being formed inner layer polymeric material and diluent using coetrusion and outer
Polymeric material and the high temperature casting solution of diluent composition are molded, by simultaneous phase separation in internal layer and outer layer
Between formed with the mutual winding arrangement of strand transition zone.
Several specific embodiments are given below to be described further technical scheme, but described implementation
Mode is illustrated and is not construed as limiting the invention.
Embodiment 1
Using polysulfones, tributyl phosphate and hexadecanol as outer layer casting solution, its component is that polysulfones mass percent is
28wt.%, tributyl phosphate mass percent are 36wt.%, and hexadecanol mass percent is 36wt.%, by polypropylene, phosphoric acid
Tributyl and lauryl alcohol are as internal layer casting solution, and its component is that polypropylene mass percent is 32wt.%, tributyl phosphate quality
Percentage is 58wt.%, and hexadecanol mass percent is 10wt.%, is separately added into parallel dual-screw extruding machine and dissolves deaeration,
Obtain homogeneous casting solution.The homogeneous casting solution of polymer is injected by hollow fiber spinneret simultaneously through Melt Pump with inner gel medium
Solidification obtains spun filament in outer gel media.Diluent in spun filament is removed using extractant, obtains hollow fiber nanofiltration membrane.In detail
Thin preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Embodiment 2
Using polyether sulfone, gaultherolin and triethylene glycol as outer layer casting solution, its component is polyether sulfone mass percent
For 24wt.%, gaultherolin mass percent is 71wt.%, and triethylene glycol mass percent is 5wt.%, by polysulfones, water
Poplar acid methyl esters and ethylene glycol are as internal layer casting solution, and its component is that polysulfones mass percent is 28wt.%, gaultherolin quality
Percentage is 62wt.%, and quality of glycol percentage is 10wt.%, is separately added into parallel dual-screw extruding machine and dissolves deaeration,
Obtain homogeneous casting solution.The homogeneous casting solution of polymer is injected by hollow fiber spinneret simultaneously through Melt Pump with inner gel medium
Solidification obtains spun filament in outer gel media.Diluent in spun filament is removed using extractant, obtains hollow fiber nanofiltration membrane.In detail
Thin preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Embodiment 3
Using SPSF, trioctyl phosphate and triethylene glycol as outer layer casting solution, its component is SPSF quality hundred
It is 20wt.% to divide ratio, and trioctyl phosphate mass percent is 75wt.%, and triethylene glycol mass percent is 5wt.%, by polyethers
Sulfone, trioctyl phosphate and diethylene glycol are as internal layer casting solution, and its component is that polysulfones mass percent is 32wt.%, salicylic acid
Methyl esters mass percent is 64wt.%, and quality of glycol percentage is 4wt.%, is separately added into molten in parallel dual-screw extruding machine
Deaeration is solved, obtains homogeneous casting solution.The homogeneous casting solution of polymer is sprayed by doughnut simultaneously through Melt Pump with inner gel medium
Silk head injects solidification in outer gel media and obtains spun filament.Diluent in spun filament is removed using extractant, obtains doughnut
NF membrane.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Embodiment 4
Using cellulose acetate, benzophenone and stearic acid as outer layer casting solution, its component is cellulose acetate quality hundred
It is 40wt.% to divide ratio, and benzophenone mass percent is 55wt.%, and stearic acid mass percent is 5wt.%, by polyvinylidene fluoride
As internal layer casting solution, its component is that Kynoar mass percent is 40wt.% for alkene, benzophenone and dimethyl sulfoxide (DMSO),
Benzophenone mass percent is 30wt.%, and dimethyl sulfoxide (DMSO) mass percent is 30wt.%, is separately added into parallel dual-screw
Deaeration is dissolved in extruder, obtains homogeneous casting solution.The homogeneous casting solution of polymer passes through simultaneously through Melt Pump and inner gel medium
Hollow fiber spinneret injects solidification in outer gel media and obtains spun filament.Diluent in spun filament is removed using extractant, is obtained
To hollow fiber nanofiltration membrane.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Embodiment 5
Using polyamide, triethyl phosphate and octadecyl alcolol as outer layer casting solution, its component is that polyamide mass percent is
22wt.%, triethyl phosphate mass percent are 64wt.%, and octadecyl alcolol mass percent is 4wt.%, by cellulose acetate,
Triethyl phosphate and lauryl alcohol are as internal layer casting solution, and its component is that Kynoar mass percent is 20wt.%, hexichol first
Ketone mass percent is 75wt.%, and dimethyl sulfoxide (DMSO) mass percent is 5wt.%, is separately added into parallel dual-screw extruding machine
Deaeration is dissolved, obtains homogeneous casting solution.The homogeneous casting solution of polymer passes through doughnut simultaneously through Melt Pump and inner gel medium
Spinning head injects solidification in outer gel media and obtains spun filament.Diluent in spun filament is removed using extractant, obtains hollow fibre
Wiener filter membrane.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Embodiment 6
Using polyimides, diethyl sebacate and stearic acid as outer layer casting solution, its component is polyimides quality hundred
It is 30wt.% to divide ratio, and triethyl phosphate mass percent is 60wt.%, and octadecyl alcolol mass percent is 10wt.%, by poly- third
As internal layer casting solution, its component is that Kynoar mass percent is 35wt.% for alkene nitrile, diethyl sebacate and oleic acid,
Benzophenone mass percent is 50wt.%, and dimethyl sulfoxide (DMSO) mass percent is 15wt.%, is separately added into parallel dual-screw
Deaeration is dissolved in extruder, obtains homogeneous casting solution.The homogeneous casting solution of polymer passes through simultaneously through Melt Pump and inner gel medium
Hollow fiber spinneret injects solidification in outer gel media and obtains spun filament.Diluent in spun filament is removed using extractant, is obtained
To hollow fiber nanofiltration membrane.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
Comparative example 1
Using cellulose acetate, benzophenone as outer layer casting solution, its component is that cellulose acetate mass percent is
40wt.%, benzophenone mass percent are 60wt.%, using Kynoar, benzophenone as internal layer casting solution, its group
It is 40wt.% to be divided into Kynoar mass percent, and benzophenone mass percent is 60wt.%, is separately added into double in the same direction
Deaeration is dissolved in screw extruder, obtains homogeneous casting solution.The homogeneous casting solution of polymer through Melt Pump and inner gel medium simultaneously
Solidification in outer gel media is injected by hollow fiber spinneret and obtains spun filament.Removed in spun filament and diluted using extractant
Agent, obtain hollow fiber nanofiltration membrane.Obtained film wire does not observe the peeling between internal layer and outer layer under ESEM, so
And obvious peel off occurs between after separating experiment two layers.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and
Performance is listed in table 1.
Polysulfones, repefral are prepared single layer hollow fiber nano filtering film by comparative example 2 as casting solution, its component
It is 28wt.% for polysulfones mass percent, repefral mass percent is 72wt.%, adds parallel dual-screw
Deaeration is dissolved in extruder, obtains homogeneous casting solution.The homogeneous casting solution of polymer passes through simultaneously through Melt Pump and inner gel medium
Hollow fiber spinneret injects solidification in outer gel media and obtains spun filament.Diluent in spun filament is removed using extractant, is obtained
To hollow-fibre membrane.Detailed preparation parameter and gained hollow fiber nanofiltration membrane structure and performance are listed in table 1.
The preparation parameter and performance of the hollow fiber nanofiltration membrane of table 1
Claims (9)
1. a kind of hollow fiber nanofiltration membrane, it is characterised in that the hollow fiber nanofiltration membrane is by polymeric material internal layer, polymer
Material outer layer and intermediate layer composition, internal layer have co-continuous pore passage structure, and internal layer thickness is 99.9~400 μm；Outer layer
With the nano pore structure continuously reduced from the inner surface to outer surface, thickness is 0.1~10 μm；The intermediate layer is in interior strata
The mutual winding arrangement of the strand of compound material and outer layer copolymer material, transition region thickness are 0.1~1 μm.
A kind of 2. hollow fiber nanofiltration membrane according to claim 1, it is characterised in that the inner surface of polymeric material outer layer
Bore dia of receiving be 100~1000nm, the bore dia of receiving of the outer surface of polymeric material outer layer is 0.5~10nm.
3. a kind of hollow fiber nanofiltration membrane according to claim 1, it is characterised in that the external diameter of hollow fiber nanofiltration membrane is
0.6~2.0mm, internal diameter are 0.4~1.4mm.
4. according to a kind of hollow fiber nanofiltration membrane described in claim 1,2 or 3, it is characterised in that polymeric material internal layer is adopted
With one or more of combinations in polysulfones, polyether sulfone, acetyl cellulose, polyvinylidene fluoride, polypropylene and polyvinyl chloride；
Polymeric material outer layer uses one kind in polysulfones, polyether sulfone, SPSF, acetyl cellulose, polyamide and polyimides
Or several combination.
5. a kind of preparation method of hollow fiber nanofiltration membrane as claimed in claim 1, it is characterised in that what methods described used sets
Standby is by the first parallel dual-screw extruding machine (1), the second parallel dual-screw extruding machine (2), triple channel spinning head (3) and outer solidification
Bath (4) forms, and its preparation method comprises the following steps：
1) polymeric material for preparing internal layer is added continuously to the 1st section of first parallel dual-screw extruding machine by hopper
In bringing-up section, and the diluent of internal layer is preheated to after 100~210 DEG C and is added continuously to first Co rotating Twin Screw Extrusion
In one or more bringing-up sections of machine, the temperature of each bringing-up section forms internal layer casting solution at 100~210 DEG C；Internal layer casting film In liquidFor the mass percent of polymeric material between 20~40wt%, diluent mass percent is 80~60wt%；It is interior The internal layer of layerDiluent includes master dilution agent and additive；The additive of internal layer is 1 with the mass ratio of master dilution agent：16
~1：1；
2) polymeric material for preparing outer layer is added continuously to the 1st section of second parallel dual-screw extruding machine by hopper
In bringing-up section, after the diluent of outer layer is preheated into 100~210 DEG C, second parallel dual-screw is added continuously to
In one or more bringing-up sections of extruder, then the temperature of each bringing-up section forms outer layer casting solution at 100~210 DEG C,
Wherein the mass percent of the polymeric material of outer layer is between 20~40wt%；Diluent mass percent be 80~
60wt%；The diluent of outer layer includes master dilution agent and additive；The additive of outer layer and the mass ratio of master dilution agent are
1：16~1：Between 1；At least a kind of master dilution agent with internal layer of master dilution agent of outer layer is identical；
3) internal layer casting solution and outer layer casting solution are after Melt Pump, by inner gel medium, internal layer casting solution and outer layer casting solution point
Not Zhu Ru triple channel spinning head inner gel medium channel, internal layer casting solution passage and outer layer casting solution passage, sprayed through spinning nozzle
Go out into tubulose bilayer liquid film, inject in outer gel media solidify afterwards, obtain nascent duplicature；Melt Pump bringing-up section, hollow fibre
The temperature for tieing up spinneret exits temperature and inner gel medium is 130~180 DEG C；The outer gel media temperature is 20~80 DEG C；
4) diluent of nascent duplicature is removed through extractant immersion, obtains described hollow fiber nanofiltration membrane.
6. the preparation method of hollow fiber nanofiltration membrane according to claim 5, it is characterised in that the master dilution agent of internal layer is
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, benzophenone, gaultherolin, salethyl, methyl benzoate, benzene
Ethyl formate, butyl benzoate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, triethyl citrate and benzene first
One or more of combinations in acid benzyl ester；The additive of internal layer is dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide
Amine, 1-METHYLPYRROLIDONE, lauryl alcohol, hexadecanol, octadecyl alcolol, triethylene glycol, diethylene glycol, ethylene glycol, polyvinylpyrrolidine
Ketone, polyethylene polypropylene polyethylene triblock copolymer, sorbitan mono-oleic acid ester, Tween-80,
One or more of combinations in stearic acid, diphenyl methane, eicosane, tetradecanoic acid and oleic acid.
7. the preparation method of hollow fiber nanofiltration membrane according to claim 5, it is characterised in that the master dilution agent of outer layer
For triethyl phosphate, tributyl phosphate, trioctyl phosphate, benzophenone, gaultherolin, salethyl, methyl benzoate,
Ethyl benzoate, butyl benzoate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, triethyl citrate and benzene
One or more of combinations in benzyl formate；The additive of outer layer is lauryl alcohol, hexadecanol, octadecyl alcolol, diethylene glycol, three second
Glycol, diethylene glycol, ethylene glycol, neopelex, lauryl sodium sulfate, two citric acid monohydrate trisodiums, polyethylene
Pyrrolidones, cetyl trimethylammonium bromide, polyethylene polypropylene polyethylene triblock copolymer, sorbitol anhydride list oleic acid
One kind in ester, Tween-80, stearic acid, diphenyl methane, eicosane, tetradecanoic acid, oleic acid
Or several combination.
8. the preparation method of hollow fiber nanofiltration membrane according to claim 5, it is characterised in that interior in the step 3)
Gel media is one or more of combinations in atoleine, glycerine or nitrogen, or the diluent of internal layer；Outer gel media
For one or more of combinations in atoleine, glycerine, nitrogen or water, or the diluent of outer layer.
9. the preparation method of hollow fiber nanofiltration membrane according to claim 5, it is characterised in that extracted described in step 4)
Agent uses ethanol, water or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632621.6A CN105169974B (en) | 2015-09-29 | 2015-09-29 | A kind of hollow fiber nanofiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632621.6A CN105169974B (en) | 2015-09-29 | 2015-09-29 | A kind of hollow fiber nanofiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105169974A CN105169974A (en) | 2015-12-23 |
| CN105169974B true CN105169974B (en) | 2017-11-14 |
Family
ID=54892688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510632621.6A Active CN105169974B (en) | 2015-09-29 | 2015-09-29 | A kind of hollow fiber nanofiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105169974B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754609A (en) * | 2016-08-19 | 2018-03-06 | 上海键水科技发展有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN107475819A (en) * | 2017-09-21 | 2017-12-15 | 成都新柯力化工科技有限公司 | A kind of high imitative cotton spinning textured fiber and preparation method thereof |
| CN109758923A (en) * | 2019-01-22 | 2019-05-17 | 山东奥美环境股份有限公司 | A kind of high pressure resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN112442749B (en) * | 2019-08-27 | 2023-04-11 | 中国石油化工股份有限公司 | Preparation method and application of fiber material |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN110756064A (en) * | 2019-10-25 | 2020-02-07 | 中国乐凯集团有限公司 | Casting solution, ultrafiltration base membrane, preparation method and separation membrane |
| CN114618322B (en) * | 2022-02-24 | 2023-04-28 | 北京赛诺膜技术有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method and application thereof |
| CN117899800B (en) * | 2024-03-18 | 2024-06-11 | 天津工业大学 | Preparation method of metal hollow fiber catalytic membrane reactor, reactor and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101642683B (en) * | 2009-09-10 | 2012-05-02 | 苏州信望膜技术有限公司 | Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof |
| KR20140003086A (en) * | 2012-06-29 | 2014-01-09 | 웅진케미칼 주식회사 | Hollow fiber nano filtration membrane and manufacturing method thereof |
| CN103432915A (en) * | 2013-08-23 | 2013-12-11 | 长沙奕景环保科技有限公司 | Method for preparing polyvinylidene-fluoride bilayer hollow fiber membrane |
| CN103464003B (en) * | 2013-09-24 | 2016-08-10 | 清华大学 | A kind of method preparing polypropylene hollow fiber perforated membrane |
| KR20150069475A (en) * | 2013-12-13 | 2015-06-23 | 도레이케미칼 주식회사 | Hollow fiber type nanofiltration membrane and method for manufacturing thereof |
| CN103638822B (en) * | 2013-12-24 | 2015-08-19 | 深圳市诚德来实业有限公司 | A kind of hollow fiber nanofiltration membrane and preparation method thereof |
| CN103785310B (en) * | 2014-03-11 | 2016-01-27 | 中南大学 | The preparation method of a kind of polysiloxane acid imide-PEI composite double layer hollow-fibre membrane |
| CN103831023B (en) * | 2014-03-14 | 2016-08-17 | 清华大学 | A kind of preparation method of acetyl cellulose hollow fiber nano filter membrane |
| CN104474922A (en) * | 2014-11-14 | 2015-04-01 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane |
-
2015
- 2015-09-29 CN CN201510632621.6A patent/CN105169974B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105169974A (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105169974B (en) | A kind of hollow fiber nanofiltration membrane and preparation method thereof | |
| US8967391B2 (en) | Method for preparing composite multilayer porous hollow membrane and device and product thereof | |
| KR101462939B1 (en) | Hydrophilic Polyvinylidene Fluoride Based Hollow Fiber Membrane and Preparing Method Thereof | |
| JP5293959B2 (en) | Hollow fiber membrane and method for producing the same | |
| CN103831023B (en) | A kind of preparation method of acetyl cellulose hollow fiber nano filter membrane | |
| CN101642683A (en) | Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof | |
| JP2013510717A5 (en) | ||
| JP2013510717A (en) | Method for producing polyvinylidene fluoride composite reinforced liquid separation membrane | |
| CN107596925B (en) | Poly 4-methyl-1-pentene radial heterogeneous hollow fiber membrane and preparation method thereof | |
| KR20170139552A (en) | Composite hollow fiber membrane and manufacturing method thereof | |
| KR101758906B1 (en) | Dual-layer ultrafiltration hollow fiber membrane and manufacturing method thereof | |
| KR101394416B1 (en) | Method for Manufacturing Polyvinylidene fluoride Hollow fiber membrane and Hollow fiber membrane | |
| KR101269574B1 (en) | Acetylated alkyl cellulose membrane using thermal induced phase separation and preparing method thereof | |
| KR101514665B1 (en) | Multi-layer Hollow Fiber Membrane Having High Strength and Excellent Permeability and Preparing Method Thereof | |
| Hou et al. | Dual PVP roles for preparing PVDF hollow fiber membranes with bicontinuous structures via the complex thermally induced phase separation (c-TIPS) | |
| KR20130122451A (en) | Manufacturing method of pvdf hollow fiber membrane | |
| JP2011050881A (en) | Method of spinning hollow fiber membrane | |
| KR20100079630A (en) | Ultrafiltration membranes with improved water permeability and mechanical strength and manufacturing method thereof | |
| CN105214517B (en) | Heterogeneous in-situ fibrillation enhancing cellulose acetate hollow-fibre membrane and preparation method thereof | |
| KR102019466B1 (en) | Continuous Process of Preparing Hollow Fiber Membrane Wherein Uniform Bead Structures Are Evenly Formed Throughout the Membrane Using Extruder | |
| KR101434166B1 (en) | Manufacturing method of highly efficient hollow fiber membranes and poor solvent for manufacturing hollow fiber | |
| CN106807247B (en) | Polyamide imide/sulfonated polyether-ether-ketone and polyamide imide nanofiltration membrane and preparation process thereof | |
| KR101355017B1 (en) | Highly efficient hollow fiber membranes and manufacturing method thereof | |
| KR101284989B1 (en) | Manufacturing method of metallic hollow fiber having porosity | |
| KR20140026118A (en) | Manufacturing method of pvdf asymmetric porous hollow fiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |