CN106268371A - A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof - Google Patents
A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof Download PDFInfo
- Publication number
- CN106268371A CN106268371A CN201610643146.7A CN201610643146A CN106268371A CN 106268371 A CN106268371 A CN 106268371A CN 201610643146 A CN201610643146 A CN 201610643146A CN 106268371 A CN106268371 A CN 106268371A
- Authority
- CN
- China
- Prior art keywords
- hollow fiber
- polyacrylonitrile
- modifying agent
- film
- polyethylene glycol
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 52
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- 230000000694 effects Effects 0.000 claims abstract description 14
- -1 polypropylene Polymers 0.000 claims abstract description 11
- 150000003384 small molecules Chemical class 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 37
- 238000009987 spinning Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 230000001112 coagulating effect Effects 0.000 claims description 26
- 238000000108 ultra-filtration Methods 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 235000012489 doughnuts Nutrition 0.000 claims description 12
- 239000011265 semifinished product Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- PVBLJPCMWKGTOH-UHFFFAOYSA-N 1-aminocyclohexan-1-ol Chemical compound NC1(O)CCCCC1 PVBLJPCMWKGTOH-UHFFFAOYSA-N 0.000 claims description 6
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 6
- 229920001661 Chitosan Chemical group 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 229960002442 glucosamine Drugs 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001503 Glucan Polymers 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 3
- 229920003081 Povidone K 30 Polymers 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims 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 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract 2
- 229920001155 polypropylene Polymers 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 235000011187 glycerol Nutrition 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical group 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to technical field of membrane, especially a kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof, by process that the solution of polypropylene hollow fiber ultrafilter membrane employing modifying agent a is hydrolyzed, make its surface can form the hydrophilic group of activity, and the material composition of modifying agent a is used sodium hydroxide, potassium hydroxide, Lithium hydrate, sulphuric acid, guarantee that the active hydrophilic group formed on film surface can be grafted with the hydrophilic small molecules in modifying agent b, making can be by being chemically bonded on film surface, improve the hydrophilicity of polypropylene hollow fiber ultrafilter membrane, in particular so that the hydrophilic layer of film will not run off during re-using, improve the stability of the hydrophilicity of film.
Description
Technical field
The present invention relates to technical field of membrane, especially a kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof.
Background technology
Water is human survival and the most precious and irreplaceable regenerated resources in evolution, is the indispensability of human survival
Condition, therefore countries in the world all at Efforts To Develop to the exploitation of this precious resources, utilize and protect work.Membrane technology conduct
" water technology of 21 century ", through semicentennial development, has been completed turning from laboratory to large-scale industrial application
Become, become an energy-efficient novel separation technology, and less with its floor space, operation energy consumption is low, easy and simple to handle, environment
The advantages such as close friend have been increasingly becoming the optimization technique of water treatment field.It is widely used in food processing, medicine separating-purifying, contains
Oily sewage disposal, and the application in fields such as solaode, space flight and aviation, artificial organs is the most prominent.
Hollow fiber ultrafiltration membrane is to develop than one of polymeric membrane for separation earlier, is widely used in electronics, chemical industry, doctor
The various isolation and purification processes of the industry such as medicine, food.But it is in use, the problem of fouling membrane seems that ratio is more prominent,
There is substantial amounts of researcher that the production of hollow fiber ultrafiltration membrane and modified aspect are made that substantial amounts of research, such as patent Shen for this
Please number be " polyacrylonitrile/nano-oxide spinning slurry and hollow fiber ultrafiltration membrane and the preparation method " poly-third of 201210185842.X
Alkene nitrile 11-16%, nano aluminium oxide 3-4%, the ratio of nitrate 4.7-8%, DMF75.3-78%, by nitrate in DMF
After dissolving, add nano aluminium oxide, polyacrylonitrile is 55-60 DEG C of stirring and dissolving and forms spinning slurry；Nanometer is obtained after spinning
Aluminium oxide 6%-20%, molecular weight cut off are in the asymmetric hollow fiber ultrafiltration membrane of intrinsic pressure single skin of 10-100KD so that infiltration
Flux is at 100-550L/m2h 0.1MPa；Film burst pressure is at 0.8-1MPa；With polyacrylonitrile-nitrate-DMF spinning liquid
It is that institute's masking is compared, improves the permeation flux of film, improve hydrophilic.For another example the 201210227473.6 of Patent No.
" wet-type polyacrylonitrile composite hollow fibre ultrafilter membrane and preparation method thereof " use polyacrylonitrile resin 10-25, additive 5-15,
Organic solvent 55-84.5 and nano grade inorganic little molecule hydrophilic substance 0.5-5；By dry polyacrylonitrile resin, additive and
Nano grade inorganic little molecule hydrophilic substance is dissolved in organic solvent, stirs under constant temperature, obtains quaternary casting film after insulation deaeration
Liquid；Above-mentioned quaternary casting solution and pore solution are prepared film silk by spinning, is then pressed in the first constant temperature coagulation bath, passes through
Spool drives and is immersed in the second constant temperature coagulation bath by film silk, then immerses in ultra-pure water successively by prepared film silk and glycerol
In, take out and seal preservation after drying unnecessary glycerol, obtain hollow fiber ultrafiltration membrane.Make there is high water flux and rejection, surely
Qualitative strong and anti-pollution ability is good.
As fully visible, the hydrophilically modified method for film mainly includes physical blending, surface-coated and surface grafting；Thing
Reason is blended and is mixed under certain conditions with other hydrophilic materials by hydrophobic polymer polymer mainly by mechanical means,
Form the macromolecule mixture that surface can be higher, to improve the hydrophilic of hydrophobic polymer；Surface-coated is the table in hydrophobic membrane
Topcoating last layer hydroaropic substance, then carries out heat treatment or chemical treatment (such as plating, vapour deposition) makes coating fix, this
The major defect of method is that coat is unstable, and easy to fall off, modified effect is difficult to persistently；Surface grafting is in certain condition
Under, introduce hydrophilic group, the chemical composition changing film surface with this on hydrophobic membrane surface by chemical reaction, improve hydrophilic
Property.
In the hydrophilically modified method of above-mentioned film, surface grafting can introduce hydrophilic group so that the change on film surface
Composition is changed so that by being chemically bonded between hydrophilic radical and membrane body, it is ensured that modified state is stable, can not
Inverse.
And in prior art, in the hydrophilically modified method of hollow fiber ultrafiltration membrane, itself and be provided without Lithium hydrate,
Sodium hydroxide, potassium hydroxide or sulphuric acid are as modifying agent a；Will be in triethylamine, chitosan, ethylenediamine, Polyethylene Glycol, second two
Alcohol, glucosan, glucose, triethanolamine, glycerol, polyvinyl alcohol, hexamethylene diamine, p-phenylenediamine, para-aminophenol, poly-second two
Alcohol, BDO, butantriol, tetramethylolmethane, glucosamine, aminopropanol, 2-amino n-butyl alcohol, amino butanol, amino
Any one in Hexalin is as modifying agent b；Again modifying agent a, modifying agent b are used for polyacrylonitrile hollow fiber ultrafilter membrane
The hydrophilic modifying of surface grafting processes.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of polyacrylonitrile hollow fiber to surpass
Filter membrane and preparation method thereof.
It is achieved particular by techniques below scheme:
A kind of polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, comprises the following steps:
(1) in dry-wet machine reactor, organic solvent, polyacrylonitrile and additive, wherein, polyacrylonitrile quality hundred are imported
Proportion by subtraction is 10-18%, and additive mass percent is 0.2-5%, organic solvent 77-89.8%, and each component sum is
100%；Mechanical agitation is sufficiently mixed, and stands vacuum defoamation and obtains clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen so that in reactor in reactor
Pressure be 0.2MPa, open spinning pump, control rotating speed is 20r/min, and core liquid pump rotating speed controls at 15 revs/min, spinning pump
Spinning head extruding spinning, and by silk after the coagulating bath of 25 DEG C, be wound on wind-up roll, rolling speed is 25r/min, waits to spin
After silk completes, take off from wind-up roll, obtain doughnut just film；Above-mentioned coagulating bath uses water coagulating bath, it is possible to adopt
Use saline solution coagulating bath, it is also possible to use other coagulating baths enabling to silk solidification to process.
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then to be placed on mass percentage concentration be 50%
Glycerine water solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that
There is hydrolysis in film surface so that Surface Creation active hydrophilic group, then soaks in modifying agent b, by hydrophilic small molecules
It is grafted to film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
Described organic solvent is N-Methyl pyrrolidone (NMP), DMF (DMF), N, N-dimethyl
Any one in acetamide (DMAC), dimethyl sulfoxide (DMSO), acetone, oxolane, dichloromethane.
Described additive is polyethylene glycol 200, PEG400, Macrogol 600, polyethylene glycol-800, poly-second two
Alcohol 1000, Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, PEG 8000, PEG20000, poly-second
Glycol 20000, polyoxyethylene 50000, polyvinylpyrrolidone K13, PVP K30, polyvinylpyrrolidone
K40, polyvinylpyrrolidone K60, nano silicon, nano aluminium oxide, nano titanium oxide, CNT, Graphene, bromine
Change one or both any mass ratio combination of lithium, nano zine oxide.
Described modifying agent a is Lithium hydrate (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), concentrated sulphuric acid
(H2SO4Any one in).
Described modifying agent b be triethylamine, chitosan, ethylenediamine, Polyethylene Glycol, ethylene glycol, glucosan, glucose, three
Ethanolamine, glycerol, polyvinyl alcohol, hexamethylene diamine, p-phenylenediamine, para-aminophenol, Polyethylene Glycol, BDO, butantriol,
Any one in tetramethylolmethane, glucosamine, aminopropanol, 2-amino n-butyl alcohol, amino butanol, aminocyclohexanol.
The invention additionally provides polyacrylonitrile hollow fiber ultrafilter membrane prepared by said method, during it uses
Film properties is stable, and hydrophilic layer will not be occurred to run off, and flux still may remain in the 90% of initial flux after cleaning repeatedly
Above；This film is more excellent with the contact angle effect in the contact process of water.
The invention also provides for a kind of hydrophilically modified method of polyacrylonitrile hollow fiber ultrafilter membrane, by polyacrylonitrile
The solution of fibre ultrafiltration film employing Lithium hydrate, sodium hydroxide, potassium hydroxide or sulphuric acid soaks so that film surface occurs
Hydrolysis, and generate active hydrophilic group；It is placed on triethylamine, chitosan, ethylenediamine, Polyethylene Glycol, ethylene glycol, Portugal again
Polysaccharide, glucose, triethanolamine, glycerol, polyvinyl alcohol, hexamethylene diamine, p-phenylenediamine, para-aminophenol, Polyethylene Glycol, Isosorbide-5-Nitrae-
In butanediol, butantriol, tetramethylolmethane, glucosamine, aminopropanol, 2-amino n-butyl alcohol, amino butanol, aminocyclohexanol
Any one solution in soak so that hydrophilic small molecules is grafted to film surface,.
The technique scheme of the invention carries out the solution with modifying agent a and carries out mixing the condition of the hydrolysis soaked
Condition required for hydrolyzing according to traditional film surface mass for those skilled in the art is carried out；And it is hydrophilic in grafting
Condition during the little molecule of property, is carried out according to the mode of traditional film surface grafting modification.
In the invention, modifying agent a be configured to, with water, the solution that mass percentage concentration is about 3% after locate
Reason, i.e. the modifying agent a in the invention is during being configured to solution, and its mass percentage concentration is for fluctuate about 3%
The scope of 10-50%, all disclosure satisfy that the requirement of the invention, in this fluctuation range, does not brings any unforeseeable
Technique effect, those skilled in the art are all to do the replacement and adjustment being equal to.
In use, when its material composition is solid, it is configured to solution according to any mass ratio and water to modifying agent b
?；When it is liquid component, it can not be configured to solution with water, it is also possible to is configured to molten with water according to any mass ratio
After liquid, it is used further to process.
Compared with prior art, the technique effect of the present invention is embodied in:
By process that the solution of polyacrylonitrile hollow fiber ultrafilter membrane employing modifying agent a is hydrolyzed so that its surface
The hydrophilic group of activity can be formed, and the material composition of modifying agent a is used sodium hydroxide, potassium hydroxide, Lithium hydrate, sulfur
Acid, it is ensured that the active hydrophilic group formed on film surface can be grafted with the hydrophilic small molecules in modifying agent b so that at film table
Face can improve the hydrophilicity of polyacrylonitrile hollow fiber ultrafilter membrane by being chemically bonded, in particular so that the parent of film
Water layer will not run off during re-using, and improves the stability of the hydrophilicity of film.
Modifying agent b is especially selected by the present invention, and combines the main component in modifying agent a so that modifying agent a
After film surface action, it is possible to effectively have an effect with modifying agent b, effective raising is chemically bonded, and strengthens hydrophilic layer
Stability, reduces hydrophilic layer turnover rate, improves film stability in use.
The preparation technology of the invention is simple, it is thus achieved that the excellent quality of hollow fiber ultrafiltration membrane, optimize tradition work
Skill to the organic solvent in material composition, additive choose and the proportioning of consumption and polyacrylonitrile is carried out reasonably
Adjust so that being prepared as polyacrylonitrile hollow fiber ultrafilter membrane in spinning can be with modifying agent a, and modifying agent b is carried out accurately, surely
Fixed effect, it is ensured that the stay in grade of the product of acquisition, improves the quality of product.
The researcher of the invention also product to the invention have passed through substantial amounts of experimental study, and it is carried out with water
During hydrophilic contact, its contact angle is the most excellent；And carry out using tracking to process to product mechanical energy, and send out during using
After raw pollution, more repeatedly cleaning, its result shows, flux is maintained at more than the 90% of initial flux,
And rejection is higher, antifouling property is stronger.
The raw material of the invention is easy to get, and cost is relatively low, easy and simple to handle, it is easy to accomplish industrialized production.
Accompanying drawing explanation
Fig. 1 is polyacrylonitrile hollow fiber ultrafilter membrane sectional view.
Fig. 2 is polyacrylonitrile hollow fiber ultrafilter membrane AFM figure.
Fig. 3 is the hydrophilic contact angle test result of polyacrylonitrile hollow fiber ultrafilter membrane and water.
Detailed description of the invention
With specific embodiment, technical scheme is further limited below in conjunction with the accompanying drawings, but requirement
The scope of protection is not only limited to description.
Embodiment 1
A kind of polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, comprises the following steps:
(1) in dry-wet machine reactor, organic solvent, polyacrylonitrile and additive, wherein, polyacrylonitrile quality hundred are imported
Proportion by subtraction is 10%, and additive mass percent is 3%, organic solvent 87%；Mechanical agitation is sufficiently mixed, and stands vacuum defoamation and obtains
To clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen so that in reactor in reactor
Pressure be 0.2MPa, open spinning pump, control rotating speed is 20r/min, and core liquid pump rotating speed controls at 15 revs/min, spinning pump
Spinning head extruding spinning, and by silk after the coagulating bath of 25 DEG C, be wound on wind-up roll, rolling speed is 25r/min, waits to spin
After silk completes, take off from wind-up roll, obtain doughnut just film；Above-mentioned coagulating bath uses water coagulating bath, it is possible to adopt
Use saline solution coagulating bath, it is also possible to use other coagulating baths enabling to silk solidification to process.
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then to be placed on mass percentage concentration be 50%
Glycerine water solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that
There is hydrolysis in film surface so that Surface Creation active hydrophilic group, then soaks in modifying agent b, by hydrophilic small molecules
It is grafted to film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
Described organic solvent is N-Methyl pyrrolidone (NMP).
Described additive is polyethylene glycol 200.
Described modifying agent a is Lithium hydrate (LiOH).
Described modifying agent b is triethylamine.
Embodiment 2
A kind of polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, comprises the following steps:
(1) in dry-wet machine reactor, organic solvent, polyacrylonitrile and additive, wherein, polyacrylonitrile quality hundred are imported
Proportion by subtraction is 18%, and additive mass percent is 5%, organic solvent 77%；Mechanical agitation is sufficiently mixed, and stands vacuum defoamation and obtains
To clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen so that in reactor in reactor
Pressure be 0.2MPa, open spinning pump, control rotating speed is 20r/min, and core liquid pump rotating speed controls at 15 revs/min, spinning pump
Spinning head extruding spinning, and by silk after the coagulating bath of 25 DEG C, be wound on wind-up roll, rolling speed is 25r/min, waits to spin
After silk completes, take off from wind-up roll, obtain doughnut just film；Above-mentioned coagulating bath uses water coagulating bath, it is possible to adopt
Use saline solution coagulating bath, it is also possible to use other coagulating baths enabling to silk solidification to process.
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then to be placed on mass percentage concentration be 50%
Glycerine water solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that
There is hydrolysis in film surface so that Surface Creation active hydrophilic group, then soaks in modifying agent b, by hydrophilic small molecules
It is grafted to film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
Described organic solvent is DMF (DMF).
Described additive is nano zine oxide.
Described modifying agent a is sodium hydroxide (NaOH).
Described modifying agent b is aminocyclohexanol.
Embodiment 3
A kind of polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, comprises the following steps:
(1) in dry-wet machine reactor, organic solvent, polyacrylonitrile and additive, wherein, polyacrylonitrile quality hundred are imported
Proportion by subtraction is 15%, and additive mass percent is 0.2%, organic solvent 84.8%；Mechanical agitation is sufficiently mixed, and stands vacuum and takes off
Bubble obtains clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen so that in reactor in reactor
Pressure be 0.2MPa, open spinning pump, control rotating speed is 20r/min, and core liquid pump rotating speed controls at 15 revs/min, spinning pump
Spinning head extruding spinning, and by silk after the coagulating bath of 25 DEG C, be wound on wind-up roll, rolling speed is 25r/min, waits to spin
After silk completes, take off from wind-up roll, obtain doughnut just film；Above-mentioned coagulating bath uses water coagulating bath, it is possible to adopt
Use saline solution coagulating bath, it is also possible to use other coagulating baths enabling to silk solidification to process.
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then to be placed on mass percentage concentration be 50%
Glycerine water solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that
There is hydrolysis in film surface so that Surface Creation active hydrophilic group, then soaks in modifying agent b, by hydrophilic small molecules
It is grafted to film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
Described organic solvent is dichloromethane.
Described additive is any mass ratio combination of nano silicon, nano aluminium oxide.
Described modifying agent a is potassium hydroxide (KOH).
Described modifying agent b is butantriol.
Embodiment 4
A kind of polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, comprises the following steps:
(1) in dry-wet machine reactor, organic solvent, polyacrylonitrile and additive, wherein, polyacrylonitrile quality hundred are imported
Proportion by subtraction is 10%, and additive mass percent is 0.2%, organic solvent 89.8%；Mechanical agitation is sufficiently mixed, and stands vacuum and takes off
Bubble obtains clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen so that in reactor in reactor
Pressure be 0.2MPa, open spinning pump, control rotating speed is 20r/min, and core liquid pump rotating speed controls at 15 revs/min, spinning pump
Spinning head extruding spinning, and by silk after the coagulating bath of 25 DEG C, be wound on wind-up roll, rolling speed is 25r/min, waits to spin
After silk completes, take off from wind-up roll, obtain doughnut just film；Above-mentioned coagulating bath uses water coagulating bath, it is possible to adopt
Use saline solution coagulating bath, it is also possible to use other coagulating baths enabling to silk solidification to process.
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then to be placed on mass percentage concentration be 50%
Glycerine water solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that
There is hydrolysis in film surface so that Surface Creation active hydrophilic group, then soaks in modifying agent b, by hydrophilic small molecules
It is grafted to film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
Described organic solvent is oxolane.
Described additive is any mass ratio combination of PVP K30, nano zine oxide.
Described modifying agent a is concentrated sulphuric acid (H2SO4)。
Described modifying agent b is 2-amino n-butyl alcohol.
Embodiment 5
A kind of hydrophilically modified method of polyacrylonitrile hollow fiber ultrafilter membrane, uses polyacrylonitrile hollow fiber ultrafilter membrane
Soaking in the solution of Lithium hydrate, sodium hydroxide, potassium hydroxide or sulphuric acid, the mass percent of the effective ingredient in solution is
3%, it is possible to be 1.5%, 4.5%.Make film surface that hydrolysis occur, and generate active hydrophilic group；It is placed on three again
Ethamine, chitosan, ethylenediamine, Polyethylene Glycol, ethylene glycol, glucosan, glucose, triethanolamine, glycerol, polyvinyl alcohol, oneself
Diamidogen, p-phenylenediamine, para-aminophenol, Polyethylene Glycol, BDO, butantriol, tetramethylolmethane, glucosamine, amino
Any one solution in propanol, 2-amino n-butyl alcohol, amino butanol, aminocyclohexanol soaks, effective in this solution
The mass ratio of composition and water be arbitrarily than so that hydrophilic small molecules is grafted to film surface,.
Above-described embodiment is only limitted to make the present invention further explanation and explanation, is not the skill to the invention
The further restriction of art scheme, non-protruding essential characteristics that those skilled in the art make on this basis and non-significant progress
Improvement, belong to the protection category of the present invention.
Claims (7)
1. a polyacrylonitrile hollow fiber ultrafiltration membrane preparation method, it is characterised in that comprise the following steps:
(1) pouring organic solvent, polyacrylonitrile and additive in reactor into, wherein, polyacrylonitrile mass percent is 10-
18%, additive mass percent is 0.2-5%, organic solvent 77-89.8%, and each component sum is 100%；Machinery stirs
Mix and be sufficiently mixed, stand vacuum defoamation and obtain clear transparent solutions；
(2) controlling temperature is 25 DEG C, opens the outlet valve of reactor, is passed through nitrogen in reactor so that the pressure in reactor
Power is 0.2MPa, opens spinning pump, and control rotating speed is 20r/min, spinning head extruding spinning, and by silk through the coagulating bath of 25 DEG C
After, it being wound on wind-up roll, rolling speed is 25r/min, after spinning completes, takes off from wind-up roll, obtains doughnut
Just film；
(3) doughnut just film is placed in reverse osmosis water immersion 2 days, then is placed on the glycerol that mass percentage concentration is 50%
Aqueous solution soaks 2 days, obtains semi-finished product hollow fiber ultrafiltration membrane；
(4) by semi-finished product hollow fiber ultrafiltration membrane under the effect of the modifying agent a solution that mass percent is 3% so that film table
There is hydrolysis in face so that Surface Creation active hydrophilic group, then soaks in modifying agent b, hydrophilic small molecules is grafted
To film surface, it is thus achieved that polyacrylonitrile hollow fiber ultrafilter membrane.
2. preparation method as claimed in claim 1, it is characterised in that described organic solvent is N-Methyl pyrrolidone
(NMP), DMF (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), acetone, tetrahydrochysene
Any one in furan, dichloromethane.
3. preparation method as claimed in claim 1, it is characterised in that described additive is polyethylene glycol 200, Polyethylene Glycol
400, Macrogol 600, polyethylene glycol-800, cetomacrogol 1000, Macrogol 2000, Macrogol 4000, Polyethylene Glycol
6000, PEG 8000, PEG20000, PEG 20000, polyoxyethylene 50000, polyvinylpyrrolidone
K13, PVP K30, polyvinylpyrrolidone K40, polyvinylpyrrolidone K60, nano silicon, nano oxygen
Change aluminum, nano titanium oxide, CNT, Graphene, lithium bromide, one or both any mass ratio group of nano zine oxide
Close.
4. preparation method as claimed in claim 1, it is characterised in that described modifying agent a is Lithium hydrate (LiOH), hydrogen-oxygen
Change sodium (NaOH), potassium hydroxide (KOH), concentrated sulphuric acid (H2SO4Any one in).
5. preparation method as claimed in claim 1, it is characterised in that described modifying agent b is triethylamine, chitosan, second two
Amine, Polyethylene Glycol, ethylene glycol, glucosan, glucose, triethanolamine, glycerol, polyvinyl alcohol, hexamethylene diamine, p-phenylenediamine, right
Amino-phenol, Polyethylene Glycol, BDO, butantriol, tetramethylolmethane, glucosamine, aminopropanol, the positive fourth of 2-amino
Any one in alcohol, amino butanol, aminocyclohexanol.
6. the polyacrylonitrile hollow fiber ultrafilter membrane that prepared by the preparation method as described in any one of claim 1-5.
7. the hydrophilically modified method of polyacrylonitrile hollow fiber ultrafilter membrane, it is characterised in that by polyacrylonitrile hollow fiber
The solution of ultrafilter membrane employing Lithium hydrate, sodium hydroxide, potassium hydroxide or sulphuric acid soaks so that film surface occurs hydrolysis anti-
Should, and generate active hydrophilic group；Be placed on again triethylamine, chitosan, ethylenediamine, Polyethylene Glycol, ethylene glycol, glucosan,
Glucose, triethanolamine, glycerol, polyvinyl alcohol, hexamethylene diamine, p-phenylenediamine, para-aminophenol, Polyethylene Glycol, Isosorbide-5-Nitrae-fourth two
Appointing in alcohol, butantriol, tetramethylolmethane, glucosamine, aminopropanol, 2-amino n-butyl alcohol, amino butanol, aminocyclohexanol
Anticipate and a kind of solution soak so that hydrophilic small molecules is grafted to film surface,.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610643146.7A CN106268371A (en) | 2016-08-08 | 2016-08-08 | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610643146.7A CN106268371A (en) | 2016-08-08 | 2016-08-08 | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106268371A true CN106268371A (en) | 2017-01-04 |
Family
ID=57666514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610643146.7A Pending CN106268371A (en) | 2016-08-08 | 2016-08-08 | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268371A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179288A (en) * | 2017-07-03 | 2017-09-19 | 中国人民解放军第三军医大学 | The detection method of S-IgA in a kind of saliva |
| CN108744995A (en) * | 2018-06-06 | 2018-11-06 | 广州康盛生物科技有限公司 | A kind of antibacterial composite hollow fiber membrane and preparation method thereof |
| CN108771974A (en) * | 2018-06-11 | 2018-11-09 | 上海大学 | The preparation method of the polymeric membrane for organic molecule separation based on hydrogel insert structure |
| CN110075711A (en) * | 2019-05-06 | 2019-08-02 | 埃姆媞（无锡）分离技术有限公司 | A kind of big flux height retention specific complex nanofiltration membrane |
| CN110684233A (en) * | 2019-10-11 | 2020-01-14 | 海南大学 | Porous hydrogel film for extracting uranium from seawater and preparation method thereof |
| CN115945078A (en) * | 2023-02-22 | 2023-04-11 | 泰州南潇新材料科技有限公司 | Preparation method of hollow fiber polyamide membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507903A (en) * | 2009-02-27 | 2009-08-19 | 北京工业大学 | Polyacrylonitrile ultrafiltration membrane surface hydrolysis method |
| CN101733025A (en) * | 2010-01-21 | 2010-06-16 | 天津大学 | Polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution and preparation method thereof |
| CN101844041A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN104587852A (en) * | 2013-11-01 | 2015-05-06 | 贵阳时代沃顿科技有限公司 | A heavy metal ion adsorption type PS hollow fiber ultrafiltration membrane and a preparing method thereof |
| CN105457510A (en) * | 2014-09-09 | 2016-04-06 | 贵阳时代沃顿科技有限公司 | Hydrophilic polyether sulfone ultrafiltration membrane and preparation method thereof |
-
2016
- 2016-08-08 CN CN201610643146.7A patent/CN106268371A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507903A (en) * | 2009-02-27 | 2009-08-19 | 北京工业大学 | Polyacrylonitrile ultrafiltration membrane surface hydrolysis method |
| CN101733025A (en) * | 2010-01-21 | 2010-06-16 | 天津大学 | Polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution and preparation method thereof |
| CN101844041A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN104587852A (en) * | 2013-11-01 | 2015-05-06 | 贵阳时代沃顿科技有限公司 | A heavy metal ion adsorption type PS hollow fiber ultrafiltration membrane and a preparing method thereof |
| CN105457510A (en) * | 2014-09-09 | 2016-04-06 | 贵阳时代沃顿科技有限公司 | Hydrophilic polyether sulfone ultrafiltration membrane and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179288A (en) * | 2017-07-03 | 2017-09-19 | 中国人民解放军第三军医大学 | The detection method of S-IgA in a kind of saliva |
| CN108744995A (en) * | 2018-06-06 | 2018-11-06 | 广州康盛生物科技有限公司 | A kind of antibacterial composite hollow fiber membrane and preparation method thereof |
| CN108744995B (en) * | 2018-06-06 | 2019-04-23 | 广州康盛生物科技有限公司 | A kind of antibacterial composite hollow fiber membrane and preparation method thereof |
| CN108771974A (en) * | 2018-06-11 | 2018-11-09 | 上海大学 | The preparation method of the polymeric membrane for organic molecule separation based on hydrogel insert structure |
| CN110075711A (en) * | 2019-05-06 | 2019-08-02 | 埃姆媞（无锡）分离技术有限公司 | A kind of big flux height retention specific complex nanofiltration membrane |
| CN110075711B (en) * | 2019-05-06 | 2021-10-08 | 埃姆媞（无锡）分离技术有限公司 | Large-flux high-interception special composite nanofiltration membrane |
| CN110684233A (en) * | 2019-10-11 | 2020-01-14 | 海南大学 | Porous hydrogel film for extracting uranium from seawater and preparation method thereof |
| CN115945078A (en) * | 2023-02-22 | 2023-04-11 | 泰州南潇新材料科技有限公司 | Preparation method of hollow fiber polyamide membrane |
| CN115945078B (en) * | 2023-02-22 | 2023-09-12 | 泰州南潇新材料科技有限公司 | Preparation method of hollow fiber polyamide membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106268371A (en) | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof | |
| CN104607056B (en) | A kind of hollow fiber compound nanofiltration membrane and preparation method thereof | |
| CN102580560B (en) | Method for preparing nano-material-doped polymer film | |
| CN105617882B (en) | A kind of compound forward osmosis membrane of chitosan-modified stannic oxide/graphene nano and preparation method thereof | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN106731897B (en) | High-pollution-resistance polyvinylidene fluoride hollow fiber ultrafiltration membrane, and preparation method and device thereof | |
| CN104607064A (en) | Method for preparing polyvinylidene fluoride-graphene oxide composite hollow fiber membrane | |
| CN102397760A (en) | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof | |
| WO2021258701A1 (en) | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane | |
| CN206500037U (en) | A kind of preparation facilities of high pollution-resistant polyvinylidene fluoride hollow fiber ultrafiltration membrane | |
| CN105597552A (en) | Forward osmosis membrane with high water flux and high salt rejection rate and method for preparing forward osmosis membrane with one-step method | |
| CN107638813B (en) | Preparation method and application of hollow fiber solvent-resistant nanofiltration membrane | |
| CN101224392A (en) | Fabricating method of fiber powder modified polymer microporous film | |
| CN104524996A (en) | Polyvinylidene fluoride hollow fibrous membranes with pressure response characteristic and preparation method thereof | |
| KR20140046638A (en) | Method for manufacturing asymmetric hollow fiber membrane and asymmetric hollow fiber membrane manufactured using the same | |
| CN112516817A (en) | Polyvinylidene fluoride loose nanofiltration membrane and preparation method and application thereof | |
| CN103894079A (en) | Method for preparing polyurethane-based hollow fiber ultrafiltration membrane and product thereof | |
| CN113797763B (en) | Cellulose gel layer modified loose nanofiltration membrane for high-flux dye separation and preparation method and application thereof | |
| CN102512997B (en) | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof | |
| Su et al. | Preparation of thin-film composite membrane with Turing structure by PEO-assisted interfacial polymerization combined with choline chloride modification to improve permeability | |
| CN111974228B (en) | Nanoparticle-modified swelling-resistant sulfonated polyether sulfone nanofiltration membrane and preparation method thereof | |
| CN111013392B (en) | Hybrid ultrafiltration membrane and preparation method thereof | |
| CN112808019A (en) | Method for preparing polyaryletherketone tubular membrane by using green solvent thermal-induced phase method | |
| CN102512987B (en) | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane | |
| CN117018895A (en) | Preparation method of enhanced hollow fiber loose nanofiltration 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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 550000 1518 Li Yang Avenue, Guiyang national hi tech Industrial Development Zone, Guiyang, Guizhou Applicant after: Time Walton Technology Co., Ltd. Address before: 550018 206, 2 / F, office building, South Guizhou science and Technology Industrial Park, Guiyang hi tech Zone. Applicant before: Vontron Technology Co., Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |