CN108380062A - Have big flux hydrophilic and oleophobic water-oil separationg film and its preparation and application of antibacterial functions - Google Patents
Have big flux hydrophilic and oleophobic water-oil separationg film and its preparation and application of antibacterial functions Download PDFInfo
- Publication number
- CN108380062A CN108380062A CN201810074091.1A CN201810074091A CN108380062A CN 108380062 A CN108380062 A CN 108380062A CN 201810074091 A CN201810074091 A CN 201810074091A CN 108380062 A CN108380062 A CN 108380062A
- Authority
- CN
- China
- Prior art keywords
- water
- oil
- porous silica
- hydrophilic
- oil separationg
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000004907 flux Effects 0.000 title abstract description 21
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 10
- 230000006870 function Effects 0.000 title abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 240
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910001868 water Inorganic materials 0.000 claims abstract description 78
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 4
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 112
- 229910001220 stainless steel Inorganic materials 0.000 claims description 40
- 239000010935 stainless steel Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 23
- 239000004744 fabric Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 37
- 239000012528 membrane Substances 0.000 abstract description 27
- 239000002351 wastewater Substances 0.000 abstract description 14
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 235000019198 oils Nutrition 0.000 description 35
- 239000002245 particle Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 15
- 229910000077 silane Inorganic materials 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000000944 linseed oil Substances 0.000 description 12
- 235000021388 linseed oil Nutrition 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 235000019476 oil-water mixture Nutrition 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 230000002207 retinal effect Effects 0.000 description 8
- 239000011856 silicon-based particle Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000012876 topography Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000001586 eradicative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 102100039397 Gap junction beta-3 protein Human genes 0.000 description 4
- 101100061841 Homo sapiens GJB3 gene Proteins 0.000 description 4
- 241000549556 Nanos Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- -1 silicon Alkane Chemical class 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- 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
- B01D61/38—Liquid-membrane separation
- B01D61/40—Liquid-membrane separation using emulsion-type membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—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
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of water-oil separationg film, the big flux hydrophilic and oleophobic water-oil separationg film for having antibacterial functions and its preparation and application are disclosed.Method is：(1) in protective gas, using organic solvent as reaction medium, silane coupling agent is reacted with porous silica, obtains modified porous silica；The silane coupling agent is the silane coupling agent containing quaternary ammonium salt group；(2) modified porous silica is made by suspension using water, obtains modified porous silica suspension；Modified porous silica suspension is mixed with polyvinyl alcohol water solution, obtains mixed liquor；(3) mixed liquor is formed a film on silk screen, obtaining hydrophilic and oleophobic water-oil separationg film.The water-oil separationg film membrane flux of the present invention is high, and sterilizing ability is strong；And the addition of modified porous silica, improve separation film strength；And the seperation film of the present invention is environmentally protective.The water-oil separationg film of the present invention is applied in oily waste water separation.
Description
Technical field
The invention belongs to the technical field of water-oil separationg film, it is related to that a kind of membrane flux is big, has the hydrophilic of antibacterial functions hates
Oily oil-water separation mesh film and the preparation method and application thereof.
Background technology
In recent years, oily waste water largely results from all trades and professions, can reach discharging standards after the cleaning of some waste water.And
Some sewage are directly discharged to environment without unqualified after oil removing or oil removing, destroy ecological environment.Water is raw on this celestial body
One of basic demand deposited, however, tellurian freshwater resources are limited, and over time, population in the world and water
Usage amount continue to increase.Protection and improvement water body environment, prevent oil pollution, are the environmental problem that the world is paid close attention to jointly, stone
The leakage of oil, not only makes us waste non-renewable petroleum resources, while being caused again to organism in water irreversible
Injury.For this problem of oil pollution, the first step will find suitable countermeasure to prevent to pollute from source, and second step is to grind
Quickly and effectively method clears up contaminated ocean to hair, water body is restored to the state of script, reduces prestige of the pollution to environment
The side of body.
The membrane separation process that recent decades grow up has huge potentiality for processing oily waste water.Membrane separation technique is gathered around
There is energy conservation and environmental protection, the advantages that separation process is easily controllable, and separation is high, and operation temperature is moderate.But technical field of membrane separation according to
So there are many problems to be solved, such as the decline of membrane flux, germ contamination, surface contamination.Oily waste water derives from a wealth of sources, industry
Production, sanitary wastewater, oil exploitation etc. are possible to generate oily waste water.In waste water not only contain oil, also contain various particles,
The impurity such as micelle, macromolecular substances, salt.In oil water separation process, above-mentioned impurity may be attached on film surface, to reduce film
Flux shortens membrane lifetime.
It proposes to carry out oleophobic to inorganic nano-particle using fluorine alkyl siloxanes solution in Chinese patent CN105148563A
It is modified, it is mixed with the hydrophilic coating being prepared then, hydrophilic and oleophobic water-oil separationg film is made.Its inorganic nano used
Particle is full particle, the coarse diadactic structure of micro-nano is constructed in water-oil separationg film, but can not improve membrane flux, and it makes
Fluorine alkyl siloxanes solution is fluorine material, will generate harm to environment and biology.
Invention content
To overcome the drawbacks described above of existing water-oil separationg film, the purpose of the present invention is to provide a kind of hydrophilic and oleophobic greases point
Preparation method from film.Porous inorganic particle porous silica is applied in film by the present invention, porous silica silicon particle
With internal gutter, the rate of nethike embrane oil-water separation is effectively increased so that membrane flux improves.In addition, by porous silica
After silane coupler modified, film has anti-microbial property.Also, since porous silica inorganic particulate is doped to
In organic hydrophilic polymer, the swellability of organic hydrophilic polymer is reduced, enhances the mechanical strength of nethike embrane.Furthermore institute
The raw material and reaction system of use are environmentally friendly, will not cause secondary pollution, will not generate wound to the body of operator
Evil.
Another object of the present invention is to provide obtain hydrophilic and oleophobic water-oil separationg film by above-mentioned preparation method.It is described hydrophilic
Hate oily water-oil separationg film, separative efficiency is high, membrane flux has both greatly antibacterial functions.
It is still another object of the present invention to provide the applications for having above-mentioned hydrophilic and oleophobic water-oil separationg film.The hydrophilic and oleophobic
Application of the water-oil separationg film in oily waste water separation.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of hydrophilic and oleophobic water-oil separationg film, includes the following steps：
(1) in protective gas, using organic solvent as reaction medium, silane coupling agent and porous silica are carried out
Reaction, obtains modified porous silica；The silane coupling agent is the silane coupling agent containing quaternary ammonium salt group；
(2) modified porous silica is made by suspension using water, obtains modified porous silica suspension；
Modified porous silica suspension is mixed with polyvinyl alcohol water solution, obtains mixed liquor；
(3) mixed liquor is formed a film on silk screen, obtaining hydrophilic and oleophobic water-oil separationg film.
Silane coupling agent described in step (1) is silane coupling agent OFS-6032；
Porous silica is prepared by the following method to obtain described in step (1)：Pore-foaming agent, catalyst are mixed with water
Uniformly, silicon source is then instilled, is kept the temperature after dripping off, is filtered, is washed, is dried, calcining obtains porous silica (SiO2)。
Aperture is 50~200nm in the porous silica.
The pore-foaming agent is that cetyl trimethylammonium bromide (CTAB), polyethylene glycol 2000 (PEG2000), three block are total
One or more of polymers P123；
The catalyst is sodium hydroxide (NaOH), ammonium hydroxide (NH3·H2O one kind in)；
The silicon source is tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), methyltrimethoxysilane
One or more of (TEMS)；
Silicon source/catalyst/pore-foaming agent the molar ratio is (1~3)/(0.2~1)/(0.1~0.5)；
Described be uniformly mixed refers to stirring to homogeneous system, and the speed of the stirring is 400~800r/min；Stirring when
Between be 0.5~4h；
The rate of addition of the silicon source be 2.5~5mL/h the times；
The temperature of the mixing and heat preservation is 30~90 DEG C；The time of the heat preservation is 1~5h；The drying time is 8
~15h；The temperature of drying is 60~80 DEG C.
The temperature of the calcining is 400~800 DEG C；The time of the calcining is 4~10h.
Organic solvent described in step (1) be N-Methyl pyrrolidone, acetone, absolute ethyl alcohol, methanol, methylisobutylketone,
More than one in isopropanol；
The mass ratio of silane coupling agent and porous silica described in step (1) is (0.1~3)：(0.1~1) g；Silicon
The dosage of alkane coupling agent is 1g/cm according to density3Carry out the conversion of quality and volume；
Reaction time described in step (1) is 12~48h；The protective gas is nitrogen.
The modified specific preparation process of porous silica described in step (1) is：(a) by porous silica ultrasound point
It dissipates in organic solvent, obtains the dispersion liquid of porous silica；(b) silane coupling agent is dissolved in organic solvent, obtains silicon
Alkane coupling agent solution；(c) silane coupler solution is added portionwise in the dispersion liquid of porous silica, is reacted, centrifuged, dried
It is dry, obtain modified porous silica.
The porous silica need to carry out vacuum drying treatment, and the condition of the drying is 100 DEG C~120 DEG C dryings 24
~48h.
In the dispersion liquid of the porous silica mass volume ratio of porous silica and organic solvent be (0.1~
1)g：(50~200) mL；
The dosage of silane coupling agent is the 1%~3% of consumption of organic solvent in the silane coupler solution.
The time of ultrasonic disperse is 0.5~2h；Ultrasonic power is 300~500W, and frequency is 20~40kHz；The reaction
It is carried out in protective gas, the protective gas is nitrogen.
The dosage of modified porous silica is water quality in modified porous silica suspension described in step (2)
The 2%~10% of amount；The mass concentration of the polyvinyl alcohol water solution is 2%~5%；
The degree of polymerization of polyvinyl alcohol described in step (2) is 1900~2400, and the alcoholysis degree of the polyvinyl alcohol is 95%
~99%.
The mass ratio of modified porous silica suspension and polyvinyl alcohol water solution described in step (2) is (5:1)
~(1:5).
Silk screen described in step (3) is stainless steel cloth, copper mesh or fabric webs；The mesh number of the silk screen is 100-
300 mesh；
Silk screen described in step (3) is the silk screen of cleaning, and the silk screen of the cleaning refers to using clear water, ethyl alcohol, distilled water
Silk screen is cleaned by ultrasonic successively, is dried.The supersonic frequency is 15~40KHz, and power is 100~200W.
Film forming described in step (3) refers to immersing silk screen in mixed liquor impregnate or mixed liquor is sprayed at silk screen
On；The time of the immersion is 3~6 minutes；Impregnate or spraying after, silk screen need to be dried processing, the temperature of processing for 90~
150 DEG C, the time of processing is 0.5~1.5h；The drying is vacuum drying.
Application in application of the hydrophilic and oleophobic water-oil separationg film in water-oil separating, especially oily waste water separation.
The present invention provides application of the hydrophilic and oleophobic oil-water separation mesh film in oiliness sewage treatment.It such as can be used for containing
There are the edible oils such as soybean oil, linseed oil, peanut oil, corn oil, olive oil, dodecane, the tetradecane, hexadecane, octadecane isometric
Alkane, the aromatic hydrocarbons such as benzene,toluene,xylene, mixed benzene, methyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid
The organic solvents such as butyl ester, ethyl acetate, butyl acetate, carbon tetrachloride, dichloromethane, chloroform, gasoline, kerosene, diesel oil and
The water-oil separating of all kinds of solvent naphthas.
The method that hydrophilic and oleophobic oil-water separation mesh film of the present invention uses organic inorganic hybridization, is polymerize by organic hydrophilic
Object polyvinyl alcohol is blended with modified inorganic nano-particle porous silica to be made.Organic hydrophilic polymer polyethylene alcohol has
There is hydrophilic performance, viscosity is good, is easy to be sprawled film forming, and do not dissolve in cold water with 95 DEG C or more hot water are dissolved in, and
The special performance that PVA will not be precipitated again after solution cooling.But individually formed a film with PVA, obtained film is easy to be swollen in water,
So addition nano inoganic particle porous silica builds binary micro-nano structure, to enhance the hydrophilicity and mechanicalness of film
Energy.
In addition, the porous silica being modified through the silane coupling agent OFS-6032 containing quaternary ammonium salt group makes film have
Standby anti-microbial property.
The contact angle of the oil-water separation mesh film of the present invention and water, linseed oil is respectively to be less than 20 °, be more than 120 °, membrane flux
More than 1000mLm-2·s-1, and the membrane flux for adulterating the water-oil separationg film of solid Nano particles of silicon dioxide is less than 500mL
m-2·s-1.The oil content of oil water mixture is 900-940mg/L before separation, and water sample oil content is less than 48mg/L after separation, reaches
Discharge standard (50mg/L) after national oily waste water treatment, and separative efficiency is higher than 90%.
With absorption quantity it is 1.0X10 by oil-water separation mesh film of the present invention5At the staphylococcus aureus of CFU/ml
After managing for 24 hours, eradicative rate is above 90%, shows superpower bactericidal property.
The porous, inorganic nano-particle of the present invention is addition pore template during synthesizing nano-particle, is wrapped
It is wrapped with the inorganic nano-particle of pore template, places it in high temperature and calcines, pore template is removed, to obtain.Have
Porous nano particle has certain hydrophily or oleophobic property with the polymer-doped hydridization nethike embrane surface layer of organic hydrophilic, works as oil
When aqueous mixtures touch surface, due to the hydrophilic and oleophobic of film surface, water can be under the action of gravity and capillary force in a steady stream
It is constantly past to flow down, and oily envelope barrier, to realize water-oil separating.In addition, since porous inorganic particle is applied to film
In, porous silica silicon particle has internal gutter, effectively increases the rate of nethike embrane oil-water separation so that membrane flux improves.
Compared with prior art, the present invention has the following advantages and beneficial effects：
The water-oil separationg film membrane flux of the present invention is high, and sterilizing ability is strong, preferably realizes water-oil separating；And modification is more
The addition of hole silica improves separation film strength；And the seperation film of the present invention is environmentally protective.
Description of the drawings
Fig. 1 is the infrared spectrogram of porous nano silica in embodiment 1；
Fig. 2 is the grain size distribution of porous nano silica in embodiment 1；
Fig. 3 is the transmission electron microscope picture of porous nano silica in embodiment 1；Wherein a, b are that the TEM of variable grain schemes；
Fig. 4 is the scanning electron microscope (SEM) photograph of porous nano silica in embodiment 1；
Fig. 5 is that water-oil separationg film carries out used schematic device when oil water mixture separation in embodiment 1；1- greases
Seperation film, 2- oil collection vessels, 3- water collecting containers；
Fig. 6 is the scanning electron microscope for the water-oil separationg film that in embodiment 1 prepared by 300 mesh stainless steel cloth of blank and embodiment
Figure；Wherein a is the SEM figures of 200 times of blank stainless steel cloths, and b is the SEM figures of 200 times of water-oil separationg films, and c is 500 times of greases point
SEM figures from film；
Fig. 7 is the surface contact angle of water and oil not in the water-oil separationg film of blank stainless steel cloth and embodiment 1
Optical picture；Wherein a is optical picture of the water in the surface contact angle of blank stainless steel cloth, and b is linseed oil in blank stainless steel wire
The optical picture of the surface contact angle of net, c are optical picture of the water in the surface contact angle of water-oil separationg film, and d is linseed oil in grease
The optical picture of the surface contact angle of seperation film.
Specific implementation mode
The present invention is described in further detail with reference to embodiment and attached drawing, but embodiments of the present invention are not
It is limited to this.
Embodiment 1
(1) synthesis of porous nano silica：
(1-1) 0.5g pore-foaming agent CTAB and 0.14g catalyst ns aOH is added in reaction vessel, and 240mL deionizations are added
Water after system becomes homogeneous in container, is slowly instilled with constant flow pump in 30min with 80 DEG C of constant temperature stirring (500r/min) 1h
2.5mL silicon source TEOS keep the temperature 2h after dripping off, generate white suspension；The molar ratio of each material is TEOS：NaOH：CTAB=1:
0.3:0.2；
(1-2) filters the white suspension of gained with pressure-reducing filter, then with deionized water by the solid water of gained
It washes, is put into therewith in 60 DEG C of baking ovens and dries 12h, then be put in calcining in Muffle furnace and (be warming up to 650 from room temperature with the speed of 2 DEG C/min
DEG C, 6h is kept at this temperature), porous SiO is thus made2(i.e. porous nano silica)；
(2) modification of porous nano silica
(2-1) dries porous nano silica for 24 hours in vacuum drying chamber in 100 DEG C；
Porous nano silica ultrasonic (ultrasonic power 300W, frequency 20kHz) dispersion that (2-2) dries 0.1g
In the N-Methyl pyrrolidone of 50mL, the time of ultrasonic disperse is 30min, obtains porous nano silica dispersion liquid；With
N-Methyl pyrrolidone diluted silane coupling agent OFS-6032 (Daukangnin GmbH, the cationic styrene amine function of 50mL
Silane), obtain silane coupler solution (dosage of silane coupling agent is 1%, 0.5mL of N-Methyl pyrrolidone)；Ultrasound
Under the conditions of, by silane coupler solution point, 3 batches are added in porous nano silica dispersion liquid, then in N2Atmosphere reaction 24 is small
When, centrifugation, 60 DEG C of drying obtain modified porous nano silica；
(3) by the 300 mesh stainless steel cloths of a diameter of 5cm successively with clear water, absolute ethyl alcohol, distilled water ultrasound (150W,
It 40KHz) cleans up, room temperature dries；
(4) modified porous nano silica is uniformly mixed (ultrasonic disperse) with water, obtains modified porous titanium dioxide
Silicon suspension (dosage of modified porous nano silica is the 5% of water quality)；
(5) by modified porous silica suspension and PVA aqueous solutions (mass concentration of PVA solution is 2%,
PVA1995, i.e. alcoholysis degree are 95%, the degree of polymerization 1900) it is 1 in mass ratio:2 mixing, ultrasonic disperse uniformly (15kHz,
200W；The time of dispersion is 0.5h), obtain mixed liquor；
(6) stainless steel cloth of step (3) is immersed in the mixed liquor of step (5), is impregnated its vertical lifting after five minutes
It rises, the silk screen after film is hung over and maintains the temperature at 120 DEG C of drying 30min in constant-temperature vacuum baking oven, obtains water-oil separationg film M1 (parents
Water hates oily water-oil separationg film).
The characterization test of porous nano silica in the present embodiment：
The structure of the porous nano silica of synthesis is tested using Fourier Transform Infrared Spectrometer (Tensor 21),
The results are shown in Figure 1 for it.By the infrared spectrogram of Fig. 1 as it can be seen that each absorption peak of synthesized porous nano silica and standard
Silica spectrogram is consistent, these are all SiO2·xH2The characteristic peak of O.3770-3200cm-1Peak be constitution water absorption peak
(antisymmetric OH stretching vibrations), and pore water and the absorption peak of surface adsorption water are in 1650-1600cm-1(bending of HOH is shaken
It is dynamic), 1060-1089cm-1、810cm-1And 460-470cm-1The peak at place is the antisymmetric stretching vibration, right by Si-O-Si respectively
Caused by claiming stretching vibration and bending vibration.Infrared spectrum analysis figure illustrates to have synthesized required structure.
The grain of porous nano silica is measured using laser particle size analyzer (MALVERN ZS NanoS, England)
Diameter is distributed, and test results are shown in figure 2.Fig. 2 is the grain size distribution of porous nano silica in embodiment 1.It can by Fig. 2
Know, porous nano silica particle diameter distribution is more concentrated, and illustrates that particle is more uniform, and diameter is about 500nm.
The particle size of porous silica and interior is observed using transmission electron microscope (HITACHI H7650, Japan)
Portion's structure, amplification factor are 30000 times, and test results are shown in figure 3.Fig. 3 is porous nano silica in embodiment 1
Transmission electron microscope picture；Wherein a, b are that the TEM of variable grain schemes.From the figure 3, it may be seen that sample particle diameter is in 500nm or so, surface is smooth, and
There is hollow hole in post-calcination sample surface and inside.
The surface topography and ruler of porous silica are observed using scanning electron microscope (HITACHI S3700, Japan)
Very little, amplification factor is 20000 times, and test results are shown in figure 4.Fig. 4 is the scanning of porous nano silica in embodiment 1
Electron microscope.Silica dioxide granule is uniform as seen from Figure 4.
The performance test of water-oil separationg film：
The water-oil separationg film (hydrophilic and oleophobic water-oil separationg film) of the present embodiment is mounted on oily-water seperating equipment, then will
Water by volume 1:1 mixes with linseed oil, and oil water mixture magnetic stirrer is uniform, from the upper of oily-water seperating equipment
Square tube mouth pours into 80mL oil water mixtures, and separator schematic diagram is as shown in Fig. 5.Fig. 5 be embodiment 1 in water-oil separationg film into
Row oil water mixture used schematic device when detaching；1- water-oil separationg films, 2- oil collection vessels, 3- water collecting containers.
For grease by water-oil separationg film, seperation film makes grease reach good separating effect, in order to further assess the separation of film
Effect obtains the membrane flux of film by testing the time used in the UF membrane 80mL oil water mixtures of certain effective separation area,
The oil content in the front and back water of separation is measured with Infrared Oil Determination Instrument, calculates the water-oil separating efficiency of membrane, membrane flux J and separative efficiency
The calculation formula of R is respectively such as formula 1,2.Test show that membrane separation efficiency is up to 95%, membrane flux 1300mLm-2·s-1, the oil content of oil water mixture before detaching is measured with Infrared Oil Determination Instrument as 931mg/L, the oil content of filtrate is 46mg/ after separation
L meets prescribed requirement less than the oil content (50mg/L) of oily wastewater after the processing of requirements of the national standard.
Formula 1：J=V/ (T*A), J- membrane fluxs, the volume for the grease that V- need to be detached, T- times, A- films efficiently separate
Area；Formula 2：R=[(C0-Cp)/C0] * 100%, R- separative efficiencies, CpOil content after separation in water, C0Water before separation
In oil content.
By 300 mesh stainless steel cloth of blank and water-oil separationg film manufactured in the present embodiment (hydrophilic and oleophobic nethike embrane) scanning electricity
Sub- microscope (HITACHI S3700, Japan) observes surface topography, shown in Fig. 6, wherein a be 200 times of blank not
The SEM figures of rust steel wire, b are the SEM figures of 200 times of water-oil separationg films, and c is that the SEM of 500 times of water-oil separationg films schemes.It can from Fig. 6
Know, for 300 mesh blank stainless steel cloth appearances without apparent coarse, screen diameter is about 50 μm.And hydrophilic and oleophobic retinal surface is recessed
Convex injustice, porous silica are blended together with PVA, are attached in the mesh of stainless steel wire nethike embrane, and each grid
In have the fenestra of micron-scale, about 30 μm of aperture, and be also all dispersed with around fenestra the protrusion of micro-nano structure.
Water and linseed oil are tested respectively in blank stainless steel cloth and the present embodiment with JC2000B type surface tension testers
Water-oil separationg film on surface contact angle, test results are shown in figure 7.Fig. 7 is water and oil not in blank stainless steel cloth
With the optical picture of the surface contact angle in the water-oil separationg film of the present embodiment, wherein a is water on the surface of blank stainless steel cloth
The optical picture of contact angle, b are optical picture of the linseed oil in the surface contact angle of blank stainless steel cloth, and c is water in water-oil separating
The optical picture of the surface contact angle of film, d are optical picture of the linseed oil in the surface contact angle of water-oil separationg film.Water is measured in blank
The contact angle for cleaning 300 mesh stainless steel cloths and the retinal surface of above-mentioned preparation is respectively 90.1 ° and 15.3 °, and linseed oil is in sky
300 mesh stainless steel cloths of white cleaning and the contact angle of film surface are respectively 56.1 ° and 139.5 °.This illustrates stainless steel cloth originally
It is hydrophobic oleophilic oil, and the film prepared is hydrophilic and oleophobic.
It selects staphylococcus aureus as antibacterial experiment bacterium colony, strain is cultivated for 24 hours in 37 DEG C of 5% meat soup, so
It centrifuges by 3000rpm, after discarding supernatant, lower layer's strain is rinsed with the PBS buffer solutions of PH7.4, through centrifugal elutriation 3 afterwards
It is secondary；Then it will be distributed in PBS buffer solutions by the strain rinsed, obtain concentration 1X105The species suspension of CFU/mL.It will
Seperation film M0 (preparation method of seperation film M0 and 1 phase of embodiment made from unmodified porous nano silica doping PVA
Together, the step of only preparation of seperation film M0 is without embodiment 1 (2)) it is prepared as reference and the present embodiment after ultraviolet light sterilization
Water-oil separationg film M1 after ultraviolet light sterilization, be respectively placed in suspension and cultivated for 24 hours at 37 DEG C, using Japanese Olympus
CX31 type biomicroscopes measure surviving colonies number, and eradicative rate is shown in Table 1 up to 90%.
Embodiment 2
(1) synthesis of porous silica silicon particle：
(1-1) is by 1.0g pore-foaming agent CTAB and 0.2g catalyst ns H3·H2O (mass concentration 25% in aqueous solution) is added anti-
It answers in container, 240mL deionized waters is added, with 85 DEG C of constant temperature stirring (480r/min) 1h, after system becomes homogeneous in container, with
Constant flow pump slowly instills 2.5mL silicon source TEOS in 30min, and 2h is kept the temperature after dripping off, and generates white suspension；The molar ratio of each material
For TEOS：NH3·H2O：CTAB=1:0.5:0.4；
(1-2) filters the white suspension of gained with pressure-reducing filter, then with deionized water by the solid water of gained
It washes, is put into therewith in 60 DEG C of baking ovens and dries 12h, then be put in calcining in Muffle furnace and (be warming up to 650 from room temperature with the speed of 2 DEG C/min
DEG C, 6h is kept at this temperature), porous SiO is thus made2(i.e. porous nano silica)；
(2) modification of porous nano silica
(2-1) dries porous nano silica for 24 hours in vacuum drying chamber in 100 DEG C；
Porous nano silica ultrasonic (ultrasonic power 300W, frequency 20kHz) dispersion that (2-2) dries 0.3g
In the N-Methyl pyrrolidone of 70mL, the time of ultrasonic disperse is 30min, obtains porous nano silica dispersion liquid；With
N-Methyl pyrrolidone diluted silane coupling agent OFS-6032 (Daukangnin GmbH, the cationic styrene amine function of 50mL
Silane), obtain silane coupler solution (dosage of silane coupling agent is 2%, 1mL of N-Methyl pyrrolidone)；The item of ultrasound
Under part, by silane coupler solution point, 3 batches are added in porous nano silica dispersion liquid, then in N2Atmosphere reaction 36 is small
When, centrifugation, 60 DEG C of drying obtain modified porous nano silica；
(3) by the 300 mesh stainless steel cloths of a diameter of 5cm successively with clear water, absolute ethyl alcohol, distilled water ultrasound (150W,
It 40KHz) cleans up, room temperature dries；
(4) modified porous nano silica is uniformly mixed (ultrasonic disperse) with water, obtains modified porous titanium dioxide
Silicon suspension (dosage of modified porous nano silica is the 7% of water quality)；
(5) by modified porous silica suspension and PVA aqueous solutions (mass concentration of PVA solution is 3%,
PVA1999, i.e. alcoholysis degree are 99%, the degree of polymerization 1900) it is 1 in mass ratio:2 mixing, ultrasonic disperse uniformly (15kHz,
200W；The time of dispersion is 0.5h), obtain mixed liquor；
(6) stainless steel cloth of step (3) is immersed in the mixed liquor of step (5), immersion after ten minutes vertically carries it
Silk screen after film is hung over and maintains the temperature at 120 DEG C of drying 30min in constant-temperature vacuum baking oven, obtains water-oil separationg film M2 by pull-up
(hydrophilic and oleophobic water-oil separationg film).
The structure of the porous nano silica of synthesis is tested using Fourier Transform Infrared Spectrometer (Tensor 21),
Structure is similar with attached drawing 1.Porous nano dioxy is measured using laser particle size analyzer (MALVERN ZS NanoS, England)
The particle diameter distribution of SiClx, porous nano silica particle diameter distribution are more concentrated, and particle is more uniform, and diameter is about 480nm, and attached
Fig. 2 is similar.The particle size of porous silica and interior is observed using transmission electron microscope (HITACHI H7650, Japan)
Portion's structure, for sample particle diameter in 505nm or so, surface is smooth, and hollow hole occur in post-calcination sample surface and inside.Make
The surface topography and size of porous silica, titanium dioxide are observed with scanning electron microscope (HITACHI S3700, Japan)
Silicon particle is uniform.
The water-oil separationg film (hydrophilic and oleophobic water-oil separationg film) of the present embodiment is subjected to water-oil separating test, test condition with
Embodiment 1 is identical.Test show that membrane separation efficiency is up to 95%, membrane flux 1500mLm-2·s-1, with Infrared Oil Determination Instrument
The oil content for measuring the preceding oil water mixture of separation is 933mg/L, and the oil content of filtrate is 48mg/L in beaker after separation, is less than state
The oil content (50mg/L) of oily wastewater, meets prescribed requirement after the processing that family's standard requires.
The water-oil separationg film (hydrophilic and oleophobic film) of 300 mesh stainless steel cloth of blank and the present embodiment is aobvious with scanning electron
Micro mirror (HITACHI S3700, Japan) observes surface topography, and result is similar with attached drawing 6.Outside 300 mesh blank stainless steel cloths
It sees without apparent coarse, screen diameter is about 50 μm.And hydrophilic and oleophobic retinal surface is uneven, porous silica and PVA
It is blended together, is attached in the mesh of stainless steel wire nethike embrane, and have the fenestra of micron-scale, aperture in each grid
About 33 μm, and also all it is dispersed with around fenestra the protrusion of micro-nano structure.It is measured with JC2000B type surface tension testers
The contact angle that water cleans 300 mesh stainless steel cloths and retinal surface manufactured in the present embodiment in blank be respectively 92.1 ° and
14.5 °, the contact angle that linseed oil cleans 300 mesh stainless steel cloths and film surface in blank is respectively 55.3 ° and 137.4 °.
It selects staphylococcus aureus as antibacterial experiment bacterium colony, tests the antibiotic property of the water-oil separationg film of the present embodiment,
Test condition is the same as embodiment 1.Surviving colonies number is measured using Japanese Olympus CX31 type biomicroscopes, eradicative rate reaches
95%, it is shown in Table 1.
Embodiment 3
(1) synthesis of porous silica silicon particle：
(1-1) is by 2.5g pore-foaming agent PEG2000 and 0.2g catalyst ns H3·H2Reaction vessel is added in O (mass concentration 25%)
In, 240mL deionized waters are added, with 85 DEG C of constant temperature stirring (500r/min) 1h, after system becomes homogeneous in container, with constant flow pump
2.5mL silicon source TEOS are slowly instilled in 60min, 1h is kept the temperature after dripping off, generate white suspension；The molar ratio of each material is
TEOS：NH3·H2O：PEG2000=1:0.5:0.1；
(1-2) filters the white suspension of gained with pressure-reducing filter, then with deionized water by the solid water of gained
It washes, is put into therewith in 60 DEG C of baking ovens and dries 12h, then be put in calcining in Muffle furnace and (be warming up to 650 from room temperature with the speed of 2 DEG C/min
DEG C, 6h is kept at this temperature), porous SiO is thus made2(i.e. porous nano silica)；
(2) modification of porous nano silica
(2-1) dries porous nano silica for 24 hours in vacuum drying chamber in 100 DEG C；
Porous nano silica ultrasonic (ultrasonic power 300W, frequency 20kHz) dispersion that (2-2) dries 0.2g
In the N-Methyl pyrrolidone of 60mL, the time of ultrasonic disperse is 30min, obtains porous nano silica dispersion liquid；With
N-Methyl pyrrolidone diluted silane coupling agent OFS-6032 (Daukangnin GmbH, the cationic styrene amine function of 150mL
Silane), obtain silane coupler solution (dosage of silane coupling agent is 1%, 1.5mL of N-Methyl pyrrolidone)；Ultrasound
Under the conditions of, by silane coupler solution point, 3 batches are added in porous nano silica dispersion liquid, then in N2Atmosphere reaction 36 is small
When, centrifugation, 60 DEG C of drying obtain modified porous nano silica；
(3) by the 200 mesh stainless steel cloths of a diameter of 5cm successively with clear water, absolute ethyl alcohol, distilled water ultrasound (150W,
It 40KHz) cleans up, room temperature dries；
(4) modified porous nano silica is uniformly mixed (ultrasonic disperse) with water, obtains modified porous titanium dioxide
Silicon suspension (dosage of modified porous nano silica is the 5% of water quality)；
(5) by modified porous silica suspension and PVA aqueous solutions (mass concentration of PVA solution is 5%,
PVA2495, i.e. alcoholysis degree are 95%, the degree of polymerization 2400) it is 1 in mass ratio:2 mixing, ultrasonic disperse uniformly (15kHz,
200W；The time of dispersion is 0.5h), obtain mixed liquor；
(6) stainless steel cloth of step (3) is immersed in the mixed liquor of step (5), is impregnated its vertical lifting after five minutes
It rises, the silk screen after film is hung over and maintains the temperature at 120 DEG C of drying 60min in constant-temperature vacuum baking oven, obtains water-oil separationg film M3 (parents
Water hates oily water-oil separationg film).
The structure of the porous nano silica of synthesis is tested using Fourier Transform Infrared Spectrometer (Tensor 21),
Structure is similar with attached drawing 1.Porous nano dioxy is measured using laser particle size analyzer (MALVERN ZS NanoS, England)
The particle diameter distribution of SiClx, porous nano silica particle diameter distribution are more concentrated, and particle is more uniform, and diameter is about 490nm, and attached
Fig. 2 is similar.The particle size of porous silica and interior is observed using transmission electron microscope (HITACHI H7650, Japan)
Portion's structure, for sample particle diameter in 505nm or so, surface is smooth, and hollow hole occur in post-calcination sample surface and inside.Make
The surface topography and size of porous silica, titanium dioxide are observed with scanning electron microscope (HITACHI S3700, Japan)
Silicon particle is uniform.
The water-oil separationg film (hydrophilic and oleophobic water-oil separationg film) of the present embodiment is subjected to water-oil separating test, test condition with
Embodiment 1 is identical.Test show that membrane separation efficiency is up to 96%, membrane flux 1380mLm-2·s-1, with Infrared Oil Determination Instrument
The oil content for measuring the preceding oil water mixture of separation is 925mg/L, and the oil content of filtrate is 40mg/L in beaker after separation, is less than state
The oil content (50mg/L) of oily wastewater, meets prescribed requirement after the processing that family's standard requires.
The water-oil separationg film (hydrophilic and oleophobic film) of 200 mesh stainless steel cloth of blank and the present embodiment is aobvious with scanning electron
Micro mirror (HITACHI S3700, Japan) observes surface topography, and result is similar with attached drawing 6.Outside 200 mesh blank stainless steel cloths
It sees without apparent coarse, screen diameter is about 60 μm.And hydrophilic and oleophobic retinal surface is uneven, porous silica and PVA
It is blended together, is attached in the mesh of stainless steel wire nethike embrane, and have the fenestra of micron-scale, aperture in each grid
About 40 μm, and also all it is dispersed with around fenestra the protrusion of micro-nano structure.It is measured with JC2000B type surface tension testers
The contact angle that water cleans 200 mesh stainless steel cloths and retinal surface manufactured in the present embodiment in blank be respectively 91.3 ° and
16.8 °, the contact angle that linseed oil cleans 200 mesh stainless steel cloths and film surface in blank is respectively 55.5 ° and 136.8 °.
It selects staphylococcus aureus as antibacterial experiment bacterium colony, tests the antibiotic property of the water-oil separationg film of the present embodiment,
Test condition is the same as embodiment 1.Surviving colonies number is measured using Japanese Olympus CX31 type biomicroscopes, eradicative rate reaches
98%, it is shown in Table 1.
Embodiment 4
(1) synthesis of porous silica silicon particle：
(1-1) 5g pore-foaming agent PEG2000 and 0.2g catalyst ns aOH is added in reaction vessel, and 240mL deionizations are added
Water after system becomes homogeneous in container, is slowly instilled with constant flow pump in 30min with 85 DEG C of constant temperature stirring (500r/min) 1h
2.5mL silicon source TEOS keep the temperature 2h after dripping off, generate white suspension；The molar ratio of each material is TEOS：NaOH：PEG2000=
1:0.45:0.21；
(1-2) filters the white suspension of gained with pressure-reducing filter, then with deionized water by the solid water of gained
It washes, is put into therewith in 60 DEG C of baking ovens and dries 12h, then be put in calcining in Muffle furnace and (be warming up to 650 from room temperature with the speed of 2 DEG C/min
DEG C, 6h is kept at this temperature), porous SiO is thus made2(i.e. porous nano silica)；
(2) modification of porous nano silica
(2-1) dries porous nano silica for 24 hours in vacuum drying chamber in 100 DEG C；
Porous nano silica ultrasonic (ultrasonic power 300W, frequency 20kHz) dispersion that (2-2) dries 0.5g
In the N-Methyl pyrrolidone of 100mL, the time of ultrasonic disperse is 30min, obtains porous nano silica dispersion liquid；With
N-Methyl pyrrolidone diluted silane coupling agent OFS-6032 (Daukangnin GmbH, the cationic styrene amine function of 150mL
Silane), obtain silane coupler solution (dosage of silane coupling agent is 1%, 1.5mL of N-Methyl pyrrolidone)；Ultrasound
Under the conditions of, by silane coupler solution point, 3 batches are added in porous nano silica dispersion liquid, then in N2Atmosphere reaction 48 is small
When, centrifugation, 60 DEG C of drying obtain modified porous nano silica；
(3) by the 300 mesh stainless steel cloths of a diameter of 5cm successively with clear water, absolute ethyl alcohol, distilled water ultrasound (150W,
It 40KHz) cleans up, room temperature dries；
(4) modified porous nano silica is uniformly mixed (ultrasonic disperse) with water, obtains modified porous titanium dioxide
Silicon suspension (dosage of modified porous nano silica is the 5% of water quality)；
(5) by modified porous silica suspension and PVA aqueous solutions (mass concentration of PVA solution is 5%,
PVA2499, i.e. alcoholysis degree are 99%, the degree of polymerization 2400) it is 1 in mass ratio:2 mixing, ultrasonic disperse uniformly (15kHz,
200W；The time of dispersion is 0.5h), obtain mixed liquor；
(6) stainless steel cloth of step (3) is immersed in the mixed liquor of step (5), vertically carries it after impregnating 15 minutes
Silk screen after film is hung over and maintains the temperature at 110 DEG C of drying 30min in constant-temperature vacuum baking oven, obtains water-oil separationg film M4 by pull-up
(hydrophilic and oleophobic water-oil separationg film).
The structure of the porous nano silica of synthesis is tested using Fourier Transform Infrared Spectrometer (Tensor 21),
Structure is similar with attached drawing 1.Porous nano dioxy is measured using laser particle size analyzer (MALVERN ZS NanoS, England)
The particle diameter distribution of SiClx, porous nano silica particle diameter distribution are more concentrated, and particle is more uniform, and diameter is about 480nm, and attached
Fig. 2 is similar.The particle size of porous silica and interior is observed using transmission electron microscope (HITACHI H7650, Japan)
Portion's structure, for sample particle diameter in 505nm or so, surface is smooth, and hollow hole occur in post-calcination sample surface and inside.Make
The surface topography and size of porous silica, titanium dioxide are observed with scanning electron microscope (HITACHI S3700, Japan)
Silicon particle is uniform.
The water-oil separationg film (hydrophilic and oleophobic water-oil separationg film) of the present embodiment is subjected to water-oil separating test, test condition with
Embodiment 1 is identical.Test show that membrane separation efficiency is up to 95%, membrane flux 1240mLm-2·s-1, with Infrared Oil Determination Instrument
The oil content for measuring the preceding oil water mixture of separation is 920mg/L, and the oil content of filtrate is 46mg/L in beaker after separation, is less than state
The oil content (50mg/L) of oily wastewater, meets prescribed requirement after the processing that family's standard requires.
The water-oil separationg film (hydrophilic and oleophobic film) of 300 mesh stainless steel cloth of blank and the present embodiment is aobvious with scanning electron
Micro mirror (HITACHI S3700, Japan) observes surface topography, and result is similar with attached drawing 6.Outside 300 mesh blank stainless steel cloths
It sees without apparent coarse, screen diameter is about 50 μm.And hydrophilic and oleophobic retinal surface is uneven, porous silica and PVA
It is blended together, is attached in the mesh of stainless steel wire nethike embrane, and have the fenestra of micron-scale, aperture in each grid
About 34 μm, and also all it is dispersed with around fenestra the protrusion of micro-nano structure.It is measured with JC2000B type surface tension testers
The contact angle that water cleans 200 mesh stainless steel cloths and retinal surface manufactured in the present embodiment in blank be respectively 91.4 ° and
15.5 °, the contact angle that linseed oil cleans 200 mesh stainless steel cloths and film surface in blank is respectively 54.3 ° and 128.8 °.
It selects staphylococcus aureus as antibacterial experiment bacterium colony, tests the antibiotic property of the water-oil separationg film of the present embodiment,
Test condition is the same as embodiment 1.Surviving colonies number is measured using Japanese Olympus CX31 type biomicroscopes, eradicative rate reaches
92%, it is shown in Table 1.
The anti-microbial property test result of 1 water-oil separationg film M0~M4 of table
The unmodified prepared water-oil separationg film of M0- porous nano silicas, M1~M4 is respectively Examples 1 to 4 institute
The water-oil separationg film of preparation.
Above several case study on implementation are the preferable several embodiments of the present invention, described in the above content to illustrate the invention
Basic principle, therefore the present invention is not limited to the above embodiments.Under the premise of the basic principle and range of the present invention, can also
There is various change and improve, these changes and improvements both fall within scope of the claimed invention.
Claims (10)
1. a kind of preparation method of hydrophilic and oleophobic water-oil separationg film, it is characterised in that：Include the following steps：
(1) in protective gas, using organic solvent as reaction medium, silane coupling agent and porous silica are carried out anti-
It answers, obtains modified porous silica；The silane coupling agent is the silane coupling agent containing quaternary ammonium salt group；
(2) modified porous silica is made by suspension using water, obtains modified porous silica suspension；It will change
The porous silica suspension of property is mixed with polyvinyl alcohol water solution, obtains mixed liquor；
(3) mixed liquor is formed a film on silk screen, obtaining hydrophilic and oleophobic water-oil separationg film.
2. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 1, it is characterised in that：Described in step (1)
Silane coupling agent is silane coupling agent OFS-6032.
3. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 1, it is characterised in that：Described in step (2)
The dosage of modified porous silica is the 2%~10% of water quality in modified porous silica suspension；It is described poly-
The mass concentration of vinyl alcohol aqueous solution is 2%~5%；Modified porous silica suspension described in step (2) and poly- second
The mass ratio of enol aqueous solution is (5:1)~(1:5).
4. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 1, it is characterised in that：Described in step (1)
The mass ratio of silane coupling agent and porous silica is (0.1~3)：(0.1~1)；The dosage of silane coupling agent is according to density
For 1g/cm3Carry out the conversion of quality and volume；
The degree of polymerization of polyvinyl alcohol described in step (2) is 1900~2400；The alcoholysis degree of the polyvinyl alcohol be 95%~
99%.
5. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 1, it is characterised in that：
Porous silica is prepared by the following method to obtain described in step (1)：Pore-foaming agent, catalyst are mixed with water
It is even, silicon source is then instilled, is kept the temperature after dripping off, is filtered, is washed, is dried, calcining obtains porous silica.
6. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 5, it is characterised in that：The pore-foaming agent is ten
One or more of six alkyl trimethyl ammonium bromides, polyethylene glycol 2000, triblock copolymer P123；
The catalyst is one kind in sodium hydroxide, ammonium hydroxide；
The silicon source is one or more of tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane；
Silicon source/catalyst/pore-foaming agent the molar ratio is (1~3)/(0.2~1)/(0.1~0.5).
7. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 5, it is characterised in that：It is described be uniformly mixed be
Refer to stirring to homogeneous system；
The rate of addition of the silicon source is 2.5~5mL/h；
The temperature of the mixing and heat preservation is 30~90 DEG C；The time of the heat preservation is 1~5h；
The temperature of the calcining is 400~800 DEG C；The time of the calcining is 4~10h.
8. the preparation method of hydrophilic and oleophobic water-oil separationg film according to claim 1, it is characterised in that：Described in step (1)
Organic solvent is more than one in N-Methyl pyrrolidone, acetone, absolute ethyl alcohol, methanol, methylisobutylketone, isopropanol；
Reaction time described in step (1) is 12~48h；The protective gas is nitrogen；
Silk screen described in step (3) is stainless steel cloth, copper mesh or fabric webs.
9. a kind of hydrophilic and oleophobic water-oil separationg film obtained by any one of claim 1~8 preparation method.
10. application of the hydrophilic and oleophobic water-oil separationg film in water-oil separating according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810074091.1A CN108380062B (en) | 2018-01-25 | 2018-01-25 | High-flux hydrophilic-oleophobic oil-water separation membrane with antibacterial function and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810074091.1A CN108380062B (en) | 2018-01-25 | 2018-01-25 | High-flux hydrophilic-oleophobic oil-water separation membrane with antibacterial function and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108380062A true CN108380062A (en) | 2018-08-10 |
| CN108380062B CN108380062B (en) | 2020-09-22 |
Family
ID=63077075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810074091.1A Expired - Fee Related CN108380062B (en) | 2018-01-25 | 2018-01-25 | High-flux hydrophilic-oleophobic oil-water separation membrane with antibacterial function and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108380062B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109966929A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | A kind of continuous water-oil separationg film and preparation method thereof |
| CN110270236A (en) * | 2019-06-26 | 2019-09-24 | 惠州学院 | A kind of preparation method and applications of grease proofing anti-swelling water-oil separationg film |
| CN114307696A (en) * | 2021-12-30 | 2022-04-12 | 浙江正益生物科技有限公司 | Oleophobic hybrid silica oil-water separation membrane and preparation method thereof |
| CN114470970A (en) * | 2020-11-12 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrophilic and oleophobic oil-water filtering material and preparation method thereof |
| CN115463453A (en) * | 2022-09-08 | 2022-12-13 | 同济大学 | Fluorine-free hydrophilic oleophobic particle for oily sewage and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383816A (en) * | 2014-11-10 | 2015-03-04 | 东华大学 | Polymer film with improved antifouling property and preparation method thereof |
| WO2015084052A1 (en) * | 2013-12-03 | 2015-06-11 | Samsung Electronics Co., Ltd. | Organic/inorganic hybrid membrane for fouling resistance, method of preparing membrane for fouling resistance, and water treatment device including said membrane |
| CN105107395A (en) * | 2015-09-30 | 2015-12-02 | 南京理工大学 | Preparation method of hollow mesoporous silica sphere/polyether sulfone composite ultrafiltration membrane |
| CN105435651A (en) * | 2015-12-22 | 2016-03-30 | 山东科技大学 | Method for preparing strong-hydrophilicity PET membrane |
| CN107149885A (en) * | 2017-06-23 | 2017-09-12 | 同济大学 | A kind of preparation method of antibacterial stable against biological contamination polymer separation film |
| CN107583470A (en) * | 2017-09-18 | 2018-01-16 | 上海大学 | Super hydrophilic and underwater superoleophobic water-oil separationg film and preparation method thereof |
-
2018
- 2018-01-25 CN CN201810074091.1A patent/CN108380062B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015084052A1 (en) * | 2013-12-03 | 2015-06-11 | Samsung Electronics Co., Ltd. | Organic/inorganic hybrid membrane for fouling resistance, method of preparing membrane for fouling resistance, and water treatment device including said membrane |
| CN104383816A (en) * | 2014-11-10 | 2015-03-04 | 东华大学 | Polymer film with improved antifouling property and preparation method thereof |
| CN105107395A (en) * | 2015-09-30 | 2015-12-02 | 南京理工大学 | Preparation method of hollow mesoporous silica sphere/polyether sulfone composite ultrafiltration membrane |
| CN105435651A (en) * | 2015-12-22 | 2016-03-30 | 山东科技大学 | Method for preparing strong-hydrophilicity PET membrane |
| CN107149885A (en) * | 2017-06-23 | 2017-09-12 | 同济大学 | A kind of preparation method of antibacterial stable against biological contamination polymer separation film |
| CN107583470A (en) * | 2017-09-18 | 2018-01-16 | 上海大学 | Super hydrophilic and underwater superoleophobic water-oil separationg film and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109966929A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | A kind of continuous water-oil separationg film and preparation method thereof |
| CN109966929B (en) * | 2019-03-20 | 2021-09-21 | 华南理工大学 | Continuous oil-water separation membrane and preparation method thereof |
| CN110270236A (en) * | 2019-06-26 | 2019-09-24 | 惠州学院 | A kind of preparation method and applications of grease proofing anti-swelling water-oil separationg film |
| CN110270236B (en) * | 2019-06-26 | 2021-10-01 | 惠州学院 | Preparation method and application of oil-proof swelling-resistant oil-water separation membrane |
| CN114470970A (en) * | 2020-11-12 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrophilic and oleophobic oil-water filtering material and preparation method thereof |
| CN114307696A (en) * | 2021-12-30 | 2022-04-12 | 浙江正益生物科技有限公司 | Oleophobic hybrid silica oil-water separation membrane and preparation method thereof |
| CN114307696B (en) * | 2021-12-30 | 2024-04-09 | 浙江正益生物科技有限公司 | Oleophobic hybrid silicon dioxide oil-water separation membrane and preparation method thereof |
| CN115463453A (en) * | 2022-09-08 | 2022-12-13 | 同济大学 | Fluorine-free hydrophilic oleophobic particle for oily sewage and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108380062B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108380062A (en) | Have big flux hydrophilic and oleophobic water-oil separationg film and its preparation and application of antibacterial functions | |
| CN105542221B (en) | A kind of wear-resisting super-hydrophobic super-oleophylic polyurethane sponge, preparation method and its application in grease continuously separates | |
| Rong et al. | A facile strategy toward 3D hydrophobic composite resin network decorated with biological ellipsoidal structure rapeseed flower carbon for enhanced oils and organic solvents selective absorption | |
| CN106632829B (en) | The material and preparation method that pH controls are changed by super-amphiphobic to super-hydrophobic/super-oleophilic | |
| CN103893999B (en) | A kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water and preparation method thereof | |
| CN109081331B (en) | Graphene-based aerogel with asymmetric wettability, preparation method and application thereof | |
| CN107904935B (en) | Hydrophobic silk fabric and preparation method and application thereof | |
| CN105038586B (en) | Super hydrophobic coating and preparation method and application | |
| CN107938319B (en) | Hydrophobic cotton fabric and preparation method and application thereof | |
| CN106693898B (en) | Doping-degree-controllable porous reduced graphene oxide oil absorption material and preparation method thereof | |
| CN113499760A (en) | High-flux super-hydrophobic wood, preparation method and application thereof | |
| CN110684233A (en) | Porous hydrogel film for extracting uranium from seawater and preparation method thereof | |
| CN103316507A (en) | Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof | |
| CN113426430B (en) | Intelligent oil-water separation material and preparation method and application thereof | |
| CN102863647B (en) | Preparation method of organic-inorganic hybrid ionic membrane | |
| CN108176255B (en) | Polyvinylidene fluoride-titanium dioxide hybrid membrane and preparation method and application thereof | |
| CN110721596A (en) | Preparation method of novel environment-friendly and efficient oil-water separation composite membrane | |
| CN113457474B (en) | Nanofiber membrane material, preparation method and application thereof | |
| CN107020071A (en) | A kind of super-hydrophobic compound carbon aerogels oil absorption material and preparation method thereof | |
| CN110237568A (en) | A kind of high-throughput switching mode oil-water separating net membrane preparation method based on natural bionic | |
| CN110331520A (en) | A kind of coated with silica barium titanate/polyetherimide composite material and the preparation method and application thereof | |
| CN110756179A (en) | Preparation method of super-hydrophobic super-oleophylic modified sponge material | |
| Zhang et al. | Polymer brush-grafted cotton with petal-like microstructure as superhydrophobic and self-cleaning adsorbents for oil/water separation | |
| CN105107235B (en) | Demulsifying agent for separation of oil-in-water emulsion system and preparation method and application thereof | |
| CN112108130A (en) | Intelligent super-hydrophobic material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200922 |