CN112058099A - 一种改性的pvdf膜及制备方法 - Google Patents
一种改性的pvdf膜及制备方法 Download PDFInfo
- Publication number
- CN112058099A CN112058099A CN202011009726.3A CN202011009726A CN112058099A CN 112058099 A CN112058099 A CN 112058099A CN 202011009726 A CN202011009726 A CN 202011009726A CN 112058099 A CN112058099 A CN 112058099A
- Authority
- CN
- China
- Prior art keywords
- mil
- solution
- membrane
- preparing
- glass fiber
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000004098 Tetracycline Substances 0.000 claims abstract description 29
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 29
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 10
- 238000005580 one pot reaction Methods 0.000 claims abstract description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 37
- 239000003365 glass fiber Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229940040944 tetracyclines Drugs 0.000 claims 1
- 229960002180 tetracycline Drugs 0.000 abstract description 28
- 229930101283 tetracycline Natural products 0.000 abstract description 28
- 239000000839 emulsion Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 32
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 230000004907 flux Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229960001701 chloroform Drugs 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000007281 self degradation Effects 0.000 description 4
- 229940063650 terramycin Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000004100 Oxytetracycline Substances 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 3
- 229960000625 oxytetracycline Drugs 0.000 description 3
- 235000019366 oxytetracycline Nutrition 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- -1 tetracycline compounds Chemical class 0.000 description 1
- 238000011287 therapeutic dose Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Images
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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
本发明公开了一种改性的PVDF膜及制备方法,属于膜分离技术领域,该膜以玻璃纤维为骨架,PVDF为主体,GO@MIL‑101‑NH2为核心,所述方法为首先制备氧化石墨烯,然后采用一锅法制备GO@MIL‑101‑NH2(Fe),再制备复合膜。本发明制备的膜既能进行油水分离,同时又能对乳状液中四环素类有机物进行光催化降解,与现在的技术相比,制备过程简单,原料易得,能够大规模制备,而且材料能够多次重复利用。
Description
技术领域
本发明涉及膜分离技术和光催化技术领域,特别是涉及一种改性的PVDF膜及制备方法。
背景技术
膜分离技术因具有结构简单、操作方便、能分离水中各类物质、且能在常温下进行操作,具有环保节能、低能耗、低成本等优势,在国内外受到了广泛的青睐。膜材料是膜分离技术的基础,是膜技术能否实现工业化的关键因素。然而,在膜分离过程中容易产生严重的膜污染(有机物污染、无机物污染、生物污染),导致膜阻力增大及膜通量下降进而导致出水水质恶化。需要加大曝气量、频繁清洗,这造成能耗的提高、膜寿命的下降,提高了水处理的成本。因此,膜污染现象,尤其是膜生物污染,是膜分离技术在饮用水及污、废水处理中广泛应用的主要障碍。
目前,膜处理技术中常用的膜材料为聚合物膜材料,聚偏氟乙烯(PVDF)因具有优良的化学稳定性、耐辐射性、耐热性和易成膜等特性,被制成超滤膜产品广泛应用于水处理领域。但由于其表面能低,制得的膜亲水性差,在水处理过程中易被水中的杂质污染,使膜水通量减小且不能恢复,导致在水处理运行过程中,聚偏氟乙烯超滤膜存在易污染、反冲洗、耐磨性差和停机清洗时间较多等问题,极大的限制了其在水厂的推广和使用。而且目前的分离膜只能进行油水分离,不能降解其中的有机物,亦限制了其应用。
随着社会的发展,抗生素越来越被大量使用,导致我国主要的河流都受到抗生素不同程度的污染,黄河、淮河、长江流域的抗生素含量也较高,其抗生素的浓度都在毫克每升的级别。在环境中的抗生素对环境存在潜在风险。残留抗生素使细菌产生耐药性和耐药基因,不但对人和动物的健康造成威胁,还会扰乱环境中的微生物种群关系,同时植物的生长发育也会受到影响,从而使生态系统平衡被扰乱。四环素类抗生素是一类广谱抗生素,主要使用方式为在动物饲料中添加亚治疗剂量的该药剂。并由于其价格低廉,四环素作为兽药被广泛使用于动物治疗方面。四环素类抗生素大量使用造成环境污染,对其生物降解机理和降解方法研究日益增多且逐渐深入,光催化是目前比较有效的简单的降解方法,但是研究中注重催化剂光催化效果,往往会忽略对催化剂的回收和循环利用。
发明内容
本发明的目的是提供一种GO@MIL-101-NH2和玻璃纤维混合改性的PVDF膜及其制备方法,所述膜既能进行油水分离,同时能对乳状液中四环素类有机物进行光催化降解。
为实现上述目的,本发明提供了如下方案:本发明提供一种改性的PVDF膜,该膜以玻璃纤维为骨架,PVDF为主体,GO@MIL-101-NH2(Fe)为核心。
作为本发明的进一步改进,所述PVDF和GO@MIL-101-NH2的(Fe)、PVDF和DMA的质量比为0.1:4:20,其中DMA是作为PVDF的溶剂,使得PVDF溶解为粘稠状液体,当PVDF:DMA的质量比为1:5时,粘稠度比较合适。
本发明还提供一种所述的GO@MIL-101-NH2(Fe)和玻璃纤维混合改性的PVDF膜的制备方法,包括以下步骤:
(1)制备氧化石墨烯:使用改良的Hummers法制备氧化石墨烯;
(2)制备GO@MIL-101-NH2(Fe)复合材料:采用一锅法制备GO@MIL-101-NH2(Fe);
(3)制备复合膜:将GO@MIL-101-NH2(Fe)分散到二甲基乙酰胺(DMA)中,超声处理,加入聚偏氟乙烯(PVDF),搅拌,直至溶液变的均匀和粘稠,得到粘性液体,将粘性液体均匀涂在玻璃纤维布上,喷洒去离子水使其凝结成膜,干燥,然后在玻璃纤维布另一侧均匀涂抹粘性液体,干燥,即得。
作为本发明的进一步改进,步骤(1)所述改良的Hummers法,包括以下步骤:
低温阶段:将石墨粉和硝酸钠溶解在混合酸溶液中,在20℃以下搅拌0.5h,保持20℃以下的温度然后缓慢加入7g高锰酸钾,搅拌1h;
中温阶段:将温度升至35℃,搅拌2h,然后将溶液缓慢加入150ml冰水中;
高温阶段:将温度升至90℃,连续加热20min后,溶液呈棕黄色并产生红色烟雾,停止加热并在不断搅拌下逐滴加入5ml质量分数为30%的H2O2,直到溶液变成金黄色;
使所得溶液静置过夜,倾析上清液,将下部混浊的液体离心,并用质量分数为30%HCl洗涤所得固体,直到上清液和氯化钡溶液混合后未出现白色沉淀,接下来,用去离子水将固体洗至中性,然后将所得固体真空干燥。
作为本发明的进一步改进,所述混合酸溶液为浓H2SO4和浓H3PO4的混合酸,浓H2SO4和浓H3PO4的体积比为9:1,步骤(1)中的离心条件为12000rpm、10min。
作为本发明的进一步改进,步骤(2)采用一锅法制备GO@MIL-101-NH2(Fe),包括以下步骤:向N-N-二甲基甲酰胺(DMF)中添加FeCl3·6H2O,然后添加2-氨基对苯二甲酸,超声处理使其溶解,加入氧化石墨烯粉末,每2.48mmol FeCl3·6H2O加入0.1g氧化石墨烯,将该溶液转移至250ml圆底烧瓶中,并在100-130℃油浴锅中加热18-22h,反应后,将其自然冷却至室温,并通过离心获得粗产物,将粗产物洗涤并用乙醇和DMF离心,将最终产物干燥,并进行8h的纯化处理,纯化后的深棕色产品为GO@MIL-101-NH2(Fe),最后将其完全研磨并用玛瑙研钵收集。所述纯化处理为用乙醇溶液在60℃回流。
作为本发明的进一步改进,步骤(2)中的离心条件为8000rpm、3min。
作为本发明的进一步改进,步骤(3)中GO@MIL-101-NH2(Fe)、二甲基乙酰胺和聚偏氟乙烯的质量比为0.1:20:4,粘性液体均匀涂在玻璃纤维布上,干燥后每平方厘米玻璃纤维布上含有粘性液体为20-30mg。
本发明还提供所述的GO@MIL-101-NH2和玻璃纤维混合改性的PVDF膜的应用,所述膜用于同时进行油水分离和四环素类有机物的光催化降解。
本发明公开了以下技术效果:
本发明提供一种既能进行油水分离,同时又能对乳状液中四环素类有机物进行光催化降解的复合膜的制备及应用。本发明以油水混合物以及水相中四环素类有机污染物为目标,对其进行分离和降解,通过紫外-可见分光光度计检测四环素类有机物的浓度。本发明以玻璃纤维为骨架,PVDF为主体,GO@MIL-101-NH2(Fe)为核心的复合材料,在油水分离方面有一定的效果,另外在对四环素类激素光催化降解方面具有优异的效果。本发明将PVDF和玻璃纤维结合,可有效解决现在油水分离膜耐磨性差的缺点,制备的膜具备良好的耐磨性、耐腐蚀性,与现在的技术相比,制备过程简单,原料易得,能够大规模制备,而且材料能够多次重复利用。在油水分离、及水相中四环素类化合物的降解具有良好的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为本发明复合膜的合成步骤示意图;
图2为实施例1制备的复合膜的接触角示意图,其中左侧为纯PVDF膜接触角,右侧为GO@MOF复合膜的接触角;
图3为实施例1制备的GO@MIL-101-NH2(Fe)和复合膜在不同倍数下的SEM图,其中a为25000倍数下GO@MIL-101-NH2(Fe)的SEM图,b为2000倍数下GO@MIL-101-NH2(Fe)的SEM图,c为15000倍数下复合膜的SEM图,d为1000倍数下复合膜的SEM图;
图4为实施例1制备的复合膜的EDS图;
图5为实施例1制备的复合膜和空白膜对污染物的分离过程装置图;
图6为实施例1空白膜和复合膜对污染物分离油通量效果对比图;
图7为实施例1制备的复合膜对三氯甲烷的油通量的重复测试;
图8为复合膜对四环素降解率、空白膜对四环素降解率和四环素自降解率;
图9为复合膜对土霉素降解率、土霉素自降解率;
图10为三乙醇胺空穴(h+ VB)捕获剂,异丙醇羟基自由基(·OH)捕获剂,对苯醌超氧自由基(·O2 -)捕获剂,对四环素光催化降解的影响;
图11为GO@MOF粉末、空白膜、0.1g GO@MOF复合膜、0.4g GO@MOF复合膜的XRD图;
图12为复合膜的红外光谱图;
图13图a、b、c、d分别对应为复合材料的XPS总谱、N 1s分图谱、O 1s分图谱、Fe 2p分图谱;
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立的包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
实施例1
用改良的Hummers方法制备氧化石墨烯,分为三个阶段:
低温阶段:将1.2g石墨粉和0.5g硝酸钠溶解在150ml混合酸溶液(135ml浓H2SO4+15ml浓H3PO4)中,在20℃以下搅拌0.5h,保持20℃以下的温度然后缓慢加入7g高锰酸钾,搅拌1h;
中温阶段:将温度升至35℃,搅拌2h,然后将溶液缓慢加入150ml冰水中;
高温阶段:将温度升至90℃,连续加热20min后,溶液呈棕黄色并产生红色烟雾,停止加热并在不断搅拌下逐滴加入5ml H2O2(浓度为30%),直到溶液变成金黄色;
使所得溶液静置过夜,倾析上清液,将下部混浊的液体离心(12000rpm、10min),并用30%HCl洗涤所得固体,直到上清液和氯化钡溶液混合后未出现白色沉淀。接下来,用去离子水将固体洗至中性,然后将所得固体在50℃下真空干燥12h。
GO@MIL-101-NH2(Fe)复合材料的制备
以上述合成的氧化石墨烯为原料,采用一锅法热合成GO@MIL-101(Fe)复合材料:向72ml DMF中添加1.62g FeCl3·6H2O,然后添加0.494g 2-氨基对苯二甲酸,超声处理20分钟使其溶解。将该溶液转移至250ml圆底烧瓶中,并加入0.1g的氧化石墨烯。随后在110℃油浴锅中加热20小时。反应后,将其自然冷却至室温,并通过离心(8000rpm、3min)获得粗产物,将粗产物用乙醇和DMF洗涤并离心,将最终产物置于150℃鼓风干燥炉中,并进行8h的纯化处理。纯化后的深棕色产品为GO@MIL-101-NH2(Fe),最后将其完全研磨并用玛瑙研钵收集。
复合膜的制备
将研碎的0.5g GO@MIL-101-NH2(Fe)分散到20ml DMA中,在60℃超声处理10分钟,均匀分散,将4g PVDF聚偏氟乙烯加入分散液中,并用玻璃棒搅拌,直至溶液变得均匀和粘稠。取出切好的8cm*8cm玻璃纤维布,将准备好的粘性液体均匀地涂在玻璃纤维布上。用去离子水喷洒使其凝结成膜,然后将其放入60℃的鼓风干燥箱中放置1小时。随后在另一侧涂抹并喷涂,将其放入60℃干燥箱中24h,得到复合膜。本发明膜的合成步骤见图1,实施例1制备的空白膜和复合膜的接触角示意图见图2,接触角相差不大,证明少量的GO@MIL-101-NH2(Fe)对其接触角没有太大影响。
实施例1制备的GO@MIL-101-NH2(Fe)和复合膜SEM图见图3,复合膜的EDS图见图4。
实施例2
乳化液的制备
水包油乳化液的制备:取0.5g汽油,0.05g的十二烷基磺酸钠,1L去离子水搅拌混合,将混合液放入超声装置中,室温下超声2h,得到乳化均匀的油水乳化液,制的乳状液呈现乳白色,为水包油型,放置24h,乳液无明显变化,表明乳化结构具有稳定性。
实施例3
油水分离实验
重油:硝基苯、二氯甲烷、三氯甲烷、苯甲醇;轻油:甲苯、环己烷、对二甲苯、汽油。取5ml各种有机相,40ml水(被亚甲基蓝染色)混合后加入到特制装置中,见图5,计算各类有机物的油通量,并使空白膜和复合膜进行对比,添加催化剂的复合膜相比空白膜油水分离的效果明显提高,对于硝基苯和三氯甲烷油通量分别约为1.2×105和1.37×105mg·m-2·h-1。为检验材料的重复利用效果,以三氯甲烷为分离对象进行重复测试。
实施例4
光催化实验
配置浓度为100mg/L的四环素溶液,取出100ml的溶液放入烧杯中,加入相应的光催化剂,加入两滴过氧化氢作为引发剂,置于光化学反应器中,并使烧杯保持在黑暗与密闭的环境下吸附1h后打开紫外灯。每隔30min取出反应液,反应时间为3h。反应液离心分离,取部分上清液,使用紫外-分光光度计测定吸光度,得到反应后四环素的浓度并计算四环素的去除率。测得复合膜有效的提高了四环素降解效率,降解率可以达到90%;复合膜对土霉素的降解率可达93%。
实施例5
对膜的张力进行测试
分别对复合膜、MOF复合膜、空白膜及无纤维复合膜进行了五次张力测试,结果见表1,复合膜的平均张力为740cN、空白膜平均张力725cN、无纤维复合膜平均张力374.84cN。
表1
实施例6
光催化捕获剂实验
配置浓度为100mg/L的四环素溶液,取出100ml的溶液放入烧杯中,加入相应的光催化剂,加入两滴过氧化氢作为引发剂,置于光化学反应器中,并使烧杯保持在黑暗与密闭的环境下吸附1h后打开紫外灯。随后分别加入捕获剂空穴(h+ VB)捕获剂三乙醇胺,羟基自由基(·OH)捕获剂异丙醇,超氧自由基(·O2 -)捕获剂对苯醌。每隔30min取出反应液,反应时间为3h。反应液离心分离,取部分上清液,使用紫外-分光光度计测定吸光度,得到反应后四环素的浓度并计算四环素的去除率。
对比例1
未加入玻璃纤维的膜,其余步骤同实施例1,其拉伸强度不足。无玻璃纤维的拉伸强度为374.84cN,且制备出的膜不平滑。
对比例2
未加入GO@MIL-101-NH2(Fe)直接铺膜的材料,其余步骤同实施例1,膜在油水分离过程,油通量不及复合膜。在光催化方面没有明显的效果。
测试实施例和对比例制备的膜的油水分离性能,油通量对比情况,见图6,测试过程及结果如下:
计算油通量:F=V/(A*T),
过滤效率:μ=(m1/m0)*100%
V为过滤后油相的体积,A为膜的面积,T为过滤时间,m1过滤后质量,m0过滤前的质量。
复合膜对三氯甲烷的油通量的重复测试,经过10次循环,结果见图7,油通量稳定在15万g·m-2·h-1,分离效率在90%左右。
复合膜对四环素降解率、空白膜(未经改性的PVDF膜)对四环素降解率和四环素自降解率结果见图,由图8可知,复合膜对四环素的降解率在90%左右。
复合膜对土霉素降解率、土霉素自降解率结果见图9,由图9可知,复合膜对土霉素的降解率可达93%。
捕获剂对四环素光催化降解的影响,见图10;图10显示三乙醇胺、异丙醇对四环素的降解有比较明显的影响。对苯醌对其无太大影响,可以证明光催化降解的主要成分为空穴(h+ VB)和羟基自由基(·OH)。
材料的XRD分析
通过X射线衍射(XRD)对GO@MOF粉末、空白膜、和0.1g GO@MOF复合膜(即GO@MIL-101-NH2、PVDF和DMA的比例为0.1:4:20)分析,见图11,由图11可看出0.1g GO@MOF复合膜的特征峰比较低,那是因为GO@MIL-101-NH2量过少导致的,加大其量并测量0.4g GO@MOF复合膜,在纯GO@MOF膜和0.1g GO@MOF复合膜都出现MIL-101-NH2的特征峰,表明MIL-101-NH2负载成功。
材料的红外分析
通过红外测试见图12,由图12可以看出GO@MIL-101-NH2(Fe)的红外与已报道的MIL-101-NH2(Fe)的红外基本一致,这是由于GO的含量较少,其峰被MIL-101-NH2(Fe)覆盖,另外氧化石墨烯的加入对MIL-101-NH2(Fe)晶体的生长无太大影响。
材料的XPS分析
XPS进一步分析了GO@MIL-101-NH2(Fe)复合膜的化学环境。见图13。与已知的PVDF空白膜相比,GO@MIL-101-NH2(Fe)复合膜显示出一些新的N1s,O 1s和Fe 2p三种信号,GO@MIL-101-NH2(Fe)复合膜的N1s光谱在399、399.8和400.5eV处出现峰分别对应于Fe–N,C–N和–NH2键。在O1s谱中,在532.25和533.25eV处的两个峰分别归因于Fe–O和C–O键。然而,相对于EDS(Fe元素含量较少),XPS探测到的Fe 2p信号非常弱,结合以上分析结果,我们确认已成功制备GO@MIL-101-NH2(Fe)复合膜。
本发明的复合膜在油水分离方面具有良好的效果,其中对硝基苯、二氯甲烷、三氯甲烷、苯甲醇、甲苯、环己烷、对二甲苯等有机物的油水混合物都有良好的分离效果,其中对三氯甲烷的油通量达到16万g·m-2·h-1,其分离效率达到92%。经过十次重复实验,其油通量和分离效率只有稍微的减小。对于光催化降解方面,对油水分离过程中水相中的四环素、土霉素具有良好的催化降解的效果,对于两种激素的降解率达到90%。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (9)
1.一种改性的PVDF膜,其特征在于:该膜以玻璃纤维为骨架,PVDF为主体,GO@MIL-101-NH2为核心,PVDF和GO@MIL-101-NH2(Fe)均匀分布在玻璃纤维的骨架中。
2.根据权利要求1所述的改性的PVDF膜,其特征在于,所述GO@MIL-101-NH2(Fe)和PVDF的质量比为0.1:4。
3.一种如权利要求1-2任一项所述的改性的PVDF膜的制备方法,其特征在于,包括以下步骤:
(1)制备氧化石墨烯:使用改良的Hummers法制备氧化石墨烯;
(2)制备GO@MIL-101-NH2(Fe)复合材料:以步骤(1)制备的氧化石墨烯为原料,采用一锅法制备GO@MIL-101-NH2(Fe);
(3)制备复合膜:将GO@MIL-101-NH2(Fe)分散到二甲基乙酰胺中,超声处理,加入聚偏氟乙烯,搅拌,直至溶液变的均匀且粘稠,得到粘性液体,将粘性液体均匀涂在玻璃纤维布上,喷洒去离子水使其凝结成膜,干燥,然后在玻璃纤维布另一侧均匀涂抹粘性液体,干燥,即得。
4.根据权利要求3所述的改性的PVDF膜的制备方法,其特征在于,步骤(1)所述改良的Hummers法,包括以下步骤:
低温阶段:将石墨粉和硝酸钠溶解在混合酸溶液中,在20℃以下搅拌0.5h,保持20℃以下的温度然后缓慢加入7g高锰酸钾,搅拌1h;
中温阶段:将温度升至35℃,搅拌2h,然后将溶液缓慢加入到150ml冰水中;
高温阶段:将温度升至90℃,连续加热20min后,溶液呈棕黄色并产生红色烟雾,停止加热,而后在不断搅拌下逐滴加入5ml质量分数为30%的H2O2,直到溶液变成金黄色;
使所得溶液静置过夜,倾析上清液,将下部混浊的液体离心,并用质量分数为30%HCl洗涤所得固体,直到上清液和氯化钡溶液混合后未出现白色沉淀,接下来,用去离子水将固体洗至中性,最后将所得固体真空干燥。
5.根据权利要求4所述的改性的PVDF膜的制备方法,其特征在于,所述混合酸溶液为浓H2SO4和浓H3PO4的混合酸,浓H2SO4和浓H3PO4的体积比为9:1,步骤(1)中的离心条件为12000rpm、10min。
6.根据权利要求3所述的改性的PVDF膜的制备方法,其特征在于,步骤(2)采用一锅法制备GO@MIL-101-NH2(Fe),包括以下步骤:向二甲基甲酰胺中添加FeCl3·6H2O,然后添加2-氨基对苯二甲酸,超声处理使其溶解,加入氧化石墨烯粉末,将该溶液转移至250ml圆底烧瓶中,并在100-130℃油浴锅中加热18-22h,反应后,使其自然冷却至室温,并通过离心获得粗产物,将粗产物用乙醇和DMF洗涤并离心,将所得产物干燥,并进行8h的纯化处理,纯化后的深棕色产品即为GO@MIL-101-NH2(Fe),最后将其完全研磨并用玛瑙研钵收集。
7.根据权利要求6所述的改性的PVDF膜的制备方法,其特征在于,步骤(2)中的离心条件为8000rpm、3min。
8.根据权利要求3所述的改性的PVDF膜的制备方法,其特征在于,步骤(3)中GO@MIL-101-NH2(Fe)、二甲基乙酰胺和聚偏氟乙烯的质量比为0.1:20:4,粘性液体均匀涂在玻璃纤维布上,干燥后每平方厘米为20-30mg。
9.一种如权利要求1-2任一项所述的改性的PVDF膜的应用,其特征在于,所述膜用于同时进行油水分离和四环素类有机物的光催化降解。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011009726.3A CN112058099B (zh) | 2020-09-23 | 2020-09-23 | 一种改性的pvdf膜及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011009726.3A CN112058099B (zh) | 2020-09-23 | 2020-09-23 | 一种改性的pvdf膜及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112058099A true CN112058099A (zh) | 2020-12-11 |
CN112058099B CN112058099B (zh) | 2021-08-31 |
Family
ID=73681612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011009726.3A Active CN112058099B (zh) | 2020-09-23 | 2020-09-23 | 一种改性的pvdf膜及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112058099B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112791601A (zh) * | 2020-12-24 | 2021-05-14 | 成都恒固新材料科技有限公司 | 一种基于协同分离和光芬顿自清洁的复合膜 |
CN114849495A (zh) * | 2022-04-15 | 2022-08-05 | 西华大学 | 基于铁基mof材料的可见光驱动自清洁复合膜及制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105597577A (zh) * | 2016-02-24 | 2016-05-25 | 复旦大学 | 基于金属有机骨架/氧化石墨烯复合物的荷正电纳滤膜及其制备方法 |
CN106582317A (zh) * | 2016-12-12 | 2017-04-26 | 北京工业大学 | 一种用于有机溶剂纳滤的金属有机骨架修饰氧化石墨烯片层结构复合膜的制备方法 |
CN107803119A (zh) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | 一种复合膜层的制备方法以及利用其去除制药废水中残留四环素的方法 |
CN108176254A (zh) * | 2017-12-29 | 2018-06-19 | 山东大学 | 一种金属有机骨架/氧化石墨烯油水分离膜及其制备方法 |
-
2020
- 2020-09-23 CN CN202011009726.3A patent/CN112058099B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105597577A (zh) * | 2016-02-24 | 2016-05-25 | 复旦大学 | 基于金属有机骨架/氧化石墨烯复合物的荷正电纳滤膜及其制备方法 |
CN106582317A (zh) * | 2016-12-12 | 2017-04-26 | 北京工业大学 | 一种用于有机溶剂纳滤的金属有机骨架修饰氧化石墨烯片层结构复合膜的制备方法 |
CN107803119A (zh) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | 一种复合膜层的制备方法以及利用其去除制药废水中残留四环素的方法 |
CN108176254A (zh) * | 2017-12-29 | 2018-06-19 | 山东大学 | 一种金属有机骨架/氧化石墨烯油水分离膜及其制备方法 |
Non-Patent Citations (1)
Title |
---|
YANAN DONG ET AL.: "Inflence of microwave-assisted synthesis on the structural and textural properties of mesoporous MIL-101(Fe) and NH2-MIL-101(Fe) for enhanced tetracycline adsorption", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112791601A (zh) * | 2020-12-24 | 2021-05-14 | 成都恒固新材料科技有限公司 | 一种基于协同分离和光芬顿自清洁的复合膜 |
CN114849495A (zh) * | 2022-04-15 | 2022-08-05 | 西华大学 | 基于铁基mof材料的可见光驱动自清洁复合膜及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN112058099B (zh) | 2021-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jia et al. | The BiOCl/diatomite composites for rapid photocatalytic degradation of ciprofloxacin: Efficiency, toxicity evaluation, mechanisms and pathways | |
Elleuch et al. | A new insight into highly contaminated landfill leachate treatment using Kefir grains pre-treatment combined with Ag-doped TiO2 photocatalytic process | |
Rao et al. | Novel titanium dioxide/iron (III) oxide/graphene oxide photocatalytic membrane for enhanced humic acid removal from water | |
Su et al. | Combination and hybridisation of treatments in dye wastewater treatment: a review | |
CN112058099B (zh) | 一种改性的pvdf膜及制备方法 | |
CN104016511B (zh) | 用于废水深度处理的臭氧/光催化氧化‑膜分离集成方法及集成装置 | |
Samuel et al. | Treatment of oily wastewater using photocatalytic membrane reactors: a critical review | |
Pandey et al. | Recent advancement in visible‐light‐responsive photocatalysts in heterogeneous photocatalytic water treatment technology | |
JP2003524520A (ja) | 水溶性ポリマーを含有する廃棄物流の処理方法およびシステム | |
Lv et al. | Introduction of cluster-to-metal charge transfer in UiO-66-NH2 for enhancing photocatalytic degradation of bisphenol a in the existence of peroxymonosulfate | |
CN106946407A (zh) | 一种碎煤加压气化废水生化出水的回用处理方法 | |
Li et al. | Highly efficient sunlight-driven self-cleaning electrospun nanofiber membrane NM88B@ HPAN for water treatment | |
Feng et al. | Novel dual-heterojunction photocatalytic membrane reactor based on Ag2S/NH2-MIL-88B (Fe)/poly (aryl ether nitrile) composite with enhanced photocatalytic performance for wastewater purification | |
Gao et al. | Effect of carbon nitride synthesized by different modification strategies on the performance of carbon nitride/PVDF photocatalytic composite membranes | |
Al-Musawi et al. | The application of a new recyclable photocatalyst γ-Fe2O3@ SiO2@ ZIF8-Ag in the photocatalytic degradation of amoxicillin in aqueous solutions | |
CN105749981B (zh) | 一种碳纳米管/氧化锌ptfe膜及其制备方法 | |
CN102527396A (zh) | 高效共掺杂复合光催化剂的制备及应用方法 | |
Kim et al. | Comparison study of dyestuff wastewater treatment by the coupled photocatalytic oxidation and biofilm process | |
CN110302780B (zh) | 一种双金属团簇负载型光催化剂及制备方法和应用 | |
CN108212181A (zh) | 一种用于污水处理的中空微球光催化剂及制备方法 | |
CN110152494A (zh) | 基于氧化石墨烯定向分离膜的膜污染控制方法 | |
Liu et al. | Removal of antibiotics from black water by a membrane filtration-visible light photocatalytic system | |
Yang et al. | Well-designed MOF-derived hollow octahedral structure TiO2 coupled with ultra-thin porous g-C3N4 to enhance the degradation of real liquor brewing wastewater | |
CN110665545A (zh) | 一种可回收型磁性有机二茂铁-TiO2光催化剂及其制法 | |
Ahmadi et al. | Photocatalytic degradation of dye (Reactive Red 198) and pharmaceutical (tetracycline) using MIL-53 (Fe) and MIL-100 (Fe): catalyst synthesis and pollutant degradation |
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 |