CN116637506A - Catalytic self-cleaning internal pressure type composite nanofiltration membrane and preparation method and application thereof - Google Patents
Catalytic self-cleaning internal pressure type composite nanofiltration membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN116637506A CN116637506A CN202310419251.2A CN202310419251A CN116637506A CN 116637506 A CN116637506 A CN 116637506A CN 202310419251 A CN202310419251 A CN 202310419251A CN 116637506 A CN116637506 A CN 116637506A
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- CN
- China
- Prior art keywords
- membrane
- mxene
- solution
- mofs
- internal pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 59
- 238000004140 cleaning Methods 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 239000004952 Polyamide Substances 0.000 claims abstract description 23
- 229920002647 polyamide Polymers 0.000 claims abstract description 23
- 230000004907 flux Effects 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 37
- 239000012510 hollow fiber Substances 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 30
- 238000001471 micro-filtration Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000108 ultra-filtration Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 9
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 65
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004098 Tetracycline Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229960002180 tetracycline Drugs 0.000 description 8
- 229930101283 tetracycline Natural products 0.000 description 8
- 235000019364 tetracycline Nutrition 0.000 description 8
- 150000003522 tetracyclines Chemical class 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 229920000053 polysorbate 80 Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 3
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The application discloses a catalytic self-cleaning internal pressure type composite nanofiltration membrane and a preparation method and application thereof. By compounding CuCo-MOFs/MXene with a polyamide membrane, the bi-metal MOFs macropore structure increases the permeability of the membrane, regulates and controls the performance of a nanofiltration separation layer, improves the compactness and the thickness, and realizes the improvement of the flux of the nanofiltration membrane. The CuCo-MOFs/MXene intermediate layer improves the fouling resistance of the nanofiltration membrane, and can entrap sulfate byproducts generated by persulfate oxidation. The flux recovery capability is improved, and the self-cleaning effect of the membrane is realized. The composite nanofiltration membrane is suitable for removing various organic pollutants and controlling the pollutants.
Description
Technical Field
The application belongs to the technical field of catalytic membrane separation and wastewater treatment, and particularly relates to a catalytic self-cleaning internal pressure type composite nanofiltration membrane, a preparation method and application thereof.
Background
Nanofiltration membrane technology plays an important role in modern membrane separation technology, and is widely applied to industrial wastewater, sea water desalination and material separation. However, the prior nanofiltration membrane technology has two main technical problems, namely, the asymmetric membrane desalination layer is compact and has difficult thickness control, the flux change is larger, and the desalination efficiency decay is obvious after long-term operation; secondly, the functional layer formed by surface coating, interfacial polymerization or self-assembly is unstable in structure, and the molecular weight cut-off is difficult to control accurately.
The hollow fiber nanofiltration membrane has a more stable component structure, good hydraulic impact resistance effect, high filling density and high water production efficiency, and has wider application space compared with the coiled nanofiltration membrane. As patent CN110152499a discloses a nanofiltration membrane and a preparation method of the nanofiltration membrane, which solves the stability problem of the functional layer of the nanofiltration membrane through the assembly of a tannic acid layer and a polyether amine layer. Patent CN111054219a proposes a preparation method of a hollow fiber nanofiltration membrane, which effectively suppresses defects in the growth process of an interfacial polymerization separation layer. Patent CN113578066a proposes a method for preparing a modified nanofiltration membrane based on MXene, wherein the thickness and the densification degree of a polyamide separation layer are regulated and controlled by an MXene intermediate layer, so as to optimize the balance and the selectivity function of the membrane separation layer. However, in the method, the surface of the nanofiltration membrane is covered with hydrophilic groups due to the crosslinking reaction, so that the pollution resistance and the hydrophilicity are reduced, and the flux recovery can be realized only through external chemical cleaning. Therefore, there is a need to develop a novel nanofiltration composite membrane with high fouling resistance.
MXene as a new two-dimensional material has excellent chemical property and rich functional groups, and can regulate and control the surface property of the polymer. In addition, the surface of MXene has active functional groups and coordination unsaturated points, and has excellent catalytic performance. The MXene composite bimetallic MOFs nano material can be used as a transition layer of a nanofiltration composite membrane, so that the hydrophilicity of the nanofiltration membrane is regulated, the catalytic performance is improved, and the separation functional layer and the self-cleaning capability of the membrane catalysis are improved.
Disclosure of Invention
In order to achieve the aim, the application provides a preparation method and application of a catalytic self-cleaning internal pressure type composite nanofiltration membrane, so as to achieve the anti-fouling and self-cleaning performances of the nanofiltration membrane.
The technical scheme of the application is as follows:
the first application aims to provide a catalytic self-cleaning internal pressure type composite nanofiltration membrane, which comprises a hollow fiber ultra-micro filtration base membrane, wherein a CuCo-MOFs/MXene composite material layer is compounded on the outer surface of the hollow fiber ultra-micro filtration base membrane, and a polyamide separation layer is polymerized on the outer surface of the CuCo-MOFs/MXene composite material layer.
Further, the CuCo-MOFs/MXene composite material layer is formed by growing CuCo-MOFs nano particles on the surface of the MXene material.
Preferably, the thickness of the MXene material is 20-100 mu m; the thickness of the polyamide separation layer is 40-80nm.
The second application aims to provide a preparation method of a catalytic self-cleaning internal pressure type composite nanofiltration membrane, which comprises the following steps:
s1, firstly, placing a hollow fiber ultra-micro filtration base membrane in a catalyst solution for ultrasonic treatment to obtain a composite ultra-filtration membrane; the catalyst is CuCo-MOFs/MXene;
s2, performing interfacial polymerization reaction on the composite ultrafiltration membrane and the polyamide solution, and generating a polyamide separation layer on the outer surface of the composite ultrafiltration membrane to obtain the catalytic self-cleaning internal pressure type hollow fiber nanofiltration membrane.
Further, the preparation method of the CuCo-MOFs/MXene comprises the following steps:
s11, dispersing a plurality of layers of MXene materials in a solution, and then adding a copper source and a cobalt source to mix to form a mixed solution A;
s12, preparing an organic ligand into a mixed solution B;
s13, mixing the mixed solution A and the mixed solution B, and then stirring to react to obtain the CuCo-MOFs/MXene.
Preferably, the thickness of the multi-layer MXene material in the step S11 is 20-100 μm;
the multi-layer MXene material is prepared by etching MAX phase, wherein the etching time is 24-48 h, and the temperature is 60-80 ℃.
Specifically, the MAX phase is Ti 3 AlC 2 ；
The etching is realized by adopting an etching solvent, wherein the etching solvent is hydrofluoric acid, a mixed solution of hydrochloric acid and sodium fluoride, a mixed solution of hydrochloric acid and lithium fluoride or a mixed solution of hydrochloric acid and ammonium fluoride.
Further, in the step S11, the molar ratio of the copper source to the cobalt source is 0.5-1.0; the copper source is at least one of copper acetylacetonate, copper chloride and copper sulfate, and the cobalt source is cobalt nitrate hexahydrate;
the mass concentration of the copper source in the mixed solution A is 1.2-1.8 g/L, the mass concentration of MXene is 100mg/L, and the mass ratio of DMF to isopropanol is 1: 1.
In a further scheme, in the step S12, the organic ligand is 2,3,6,7,10, 11-hexahydroxy triphenyl or dimethyl imidazole or terephthalic acid, the mass concentration of the mixed solution B is 1-1.5 g/L, and the mass ratio of DMF to isopropanol is 1: 1;
in the step S13, the stirring reaction is carried out for 6 to 8 hours under the condition of water solubility at 150 ℃.
Further, the mass concentration of the catalyst solution in the step S1 is 0.5-5%, the temperature of the ultrasonic treatment is 60-90 ℃ and the time is 2-4 h. The hollow fiber ultra-micro filtration base membrane is treated by alkali liquor, namely, is soaked in the alkali liquor.
Further, in the step S2, the interfacial polymerization reaction means that the composite ultrafiltration membrane is immersed in a water-phase polyamine solution and then immersed in an oil-phase polyacyl chloride solution, and a polyamide separation layer is formed through interfacial polymerization, wherein the thickness of the polyamide separation layer is 40-80nm.
The preferential scheme is that the solvent in the aqueous phase polyamine solution is anhydrous piperazine, the mass fraction of the aqueous phase polyamine solution is 0.5-0.8wt%, and the time for immersing the composite ultrafiltration membrane in the aqueous phase polyamine solution is 2-10 min;
the oil phase polybasic acyl chloride solution is formed by dissolving trimesoyl chloride in normal hexane solution, the concentration of the trimesoyl chloride is 0.2-0.5 wt%, and the time for immersing the composite ultrafiltration membrane in the oil phase polybasic acyl chloride solution is 1-3 min.
The third application aims to provide the application of the catalytic self-cleaning internal pressure type composite nanofiltration membrane, which is used as an internal pressure membrane for salt separation or pollutant removal under an oxidation system.
An oxidation system such as a persulfate oxidation system, a heterogeneous Fenton system, or a photoelectrocatalytic oxidation system.
Further, the pollutants comprise novel pollutants such as antibiotics, tetrabromobisphenol A flame retardant and the like or a mixture of conventional pollutants such as rhodamine B, bisphenol A and the like and sulfate;
the pure water flux of the internal pressure membrane reaches 40-60 LMH bar ～1 The flux recovery rate in the running period is more than 95%, the retention rate of sulfate reaches 95% -99.2%, and the removal rate of pollutants reaches 92% -95%.
The application provides a novel preparation method of an organic-inorganic catalytic self-cleaning internal pressure type composite nanofiltration membrane, which comprises the steps of firstly preparing a hollow fiber ultrafiltration membrane base membrane by a phase inversion method, secondly growing copper-cobalt MOFs nano particles on the surface of an MXene material, immersing the copper-cobalt MOFs nano particles on the surface of the base membrane, and preparing the composite nanofiltration membrane by an interfacial polymerization mode. The CuCo-MOFs/MXene composite material layer exists between the base membrane and the separation layer of the composite nanofiltration membrane, so that the permeation interception capacity of the separation layer can be regulated and selected, and the aim of stabilizing the structure of the composite nanofiltration membrane is fulfilled. Through internal pressure operation, under a persulfate oxidation system, a heterogeneous Fenton system or a photoelectrocatalysis oxidation system, firstly, the mixture passes through an inner base film and an intermediate composite material layer, finally, a separation layer is selected, copper-cobalt bimetallic MOFs (CuCo-MOFs) activate persulfate or hydrogen peroxide, active oxygen species-sulfate radicals, hydroxyl radicals and the like can be generated, organic pollutants on the surface and in holes of the film are degraded, film pollution is relieved, and film hydrophilicity is improved, so that self-cleaning performance of the composite nanofiltration film is achieved. In addition, sulfate radical generated by catalysis of the persulfate oxidation system can be intercepted by the selective separation layer, so that the rear-end treatment of sulfate is reduced, and the load of the selective separation layer is reduced.
The application has the following beneficial effects:
(1) According to the preparation method of the catalytic self-cleaning internal pressure type composite nanofiltration membrane, provided by the application, through the introduction of the bimetallic CuCo-MOFs intermediate layer, the double electron transmission capacity is enhanced and the catalytic efficiency is improved by utilizing the lamellar structure of the MXene material.
(2) Through organic-inorganic hybridization of CuCo-MOFs/MXene, the permeability of the membrane is increased by the bimetallic MOFs macropore structure, the performance of the separation layer can be regulated and controlled, the compactness of the separation layer is improved, and the flux is improved and the monovalent salt permeability is realized.
(3) Under the persulfate oxidation system, the CuCo-MOFs/MXene composite material layer at the middle position improves the fouling resistance of the nanofiltration membrane, and can entrap sulfate byproducts generated by persulfate oxidation.
(4) The composite nanofiltration membrane is suitable for removing various organic pollutants and controlling the pollutants.
Drawings
FIG. 1 is a schematic structural diagram of an internal pressure type composite nanofiltration membrane in the present application.
Detailed Description
The present application will be further illustrated with reference to the following examples, but the essential aspects of the present application are not limited to the following examples. Such methods are conventional, and such materials are commercially available from the open commercial sources unless specifically indicated, and those skilled in the art will recognize that any simple modification or substitution based on the teachings of the present application falls within the scope of the claimed application.
Example 1:
the structure schematic diagram of the catalytic self-cleaning internal pressure type composite nanofiltration membrane is shown in fig. 1, and the catalytic self-cleaning internal pressure type composite nanofiltration membrane comprises a hollow fiber ultra-micro filtration base membrane 1, wherein a CuCo-MOFs/MXene composite material layer 2 is compounded on the outer surface of the hollow fiber ultra-micro filtration base membrane, a polyamide separation layer 3 is polymerized on the outer surface of the CuCo-MOFs/MXene composite material layer 2, and the thickness of the polyamide separation layer 3 is 40-80nm.
Wherein the CuCo-MOFs/MXene composite material layer 2 is formed by growing CuCo-MOFs nano particles on the surface of the MXene material. The thickness of the MXene material in this example is 20-100 μm.
The hollow fiber ultra-micro filtration base membrane is existing and can be prepared by the following preparation method:
mixing cellulose acetate, polymer C (polyethersulfone or polyvinylidene fluoride or polytetrafluoroethylene) and polyvinylpyrrolidone in a mass ratio of 1:3-5:0.5-1, and adding a surfactant Tween 80; then dissolving in DMAC (dimethylacetamide) or NMP (N-methylpyrrolidone), stirring the polymer, defoaming, and preparing the spinning solution into the asymmetric hollow fiber ultra-micro filtration membrane with the aperture of 0.05-0.1 mu m through phase inversion.
Example 2:
1. 15g of cellulose acetate, 63g of polyvinylidene fluoride and 15g of polyvinylpyrrolidone are mixed, and 7g of Tween 80 is taken. Dissolved in 100ml of LDMAC. Stirring the spinning solution after polymer deaeration, preparing a hollow fiber ultra-micro filtration base film through phase inversion, wherein the aperture is 0.05 mu m, and soaking the base film in 50% pure water glycerol mixed solution for later use.
2. Weighing Ti 3 AlC 2 In total, 1g was placed in 50mL of a 9M mixed solution (HCl and LiF), sonicated for 30min, and reacted at 70℃for 24h at a rate of 500 revolutions per minute. The precipitate was washed with absolute ethanol until the impurities were removed. The thickness of the prepared multilayer MXene is about 80 μm.
3. The multilayer MXene0.01g prepared above is fully dispersed in a mixed solution of 100mL of DMF and isopropanol (the mass ratio is 1:1), then 0.15g of cupric acetylacetonate and 0.2g of cobalt nitrate hexahydrate are weighed and dissolved in the above dispersion, and mixed into a mixed solution A;
adding 2,3,6,7,10, 11-hexahydroxy triphenyl into DMF and isopropanol according to the mass ratio of 1:1, preparing a mixed solution B0.15g;
and uniformly mixing the mixed solution A and the mixed solution B, transferring the mixture into a reaction kettle, and stirring the mixture in a water bath kettle at 150 ℃ for reaction for 6 hours. And cleaning and drying to obtain the CuCo-MOFs/MXene catalyst.
4. Before use, the hollow fiber ultra-micro filtration base film is dried and then is placed in 1M sodium hydroxide solution to be soaked for 7 hours under the heating condition, so as to obtain the alkali treatment.
5. Weighing 0.5g of the prepared CuCo-MOFs/MXene catalyst, dissolving in 100mL of deionized water, placing the hollow fiber ultra-micro filtration base membrane subjected to alkali liquor treatment in the deionized water, carrying out ultrasonic treatment for 1h, and forming an intermediate transition layer (CuCo-MOFs/MXene composite material layer) with the thickness of 0.5-1 mm on the outer surface of the hollow fiber ultra-micro filtration base membrane to obtain the CuCo-MOFs/MXene composite ultrafiltration membrane.
Then the obtained composite ultrafiltration membrane is soaked in 0.5wt% of anhydrous piperazine aqueous phase solution for 2min, and is soaked in 0.3wt% of trimesoyl chloride solution for 2min after surface impurities are cleaned. A polyamide separation layer was formed by interfacial polymerization, wherein the thickness of the separation layer was 50nm. The catalytic self-cleaning internal pressure type composite nanofiltration membrane is prepared, and has a three-layer structure from inside to outside, namely an inner layer base membrane, an intermediate composite material layer and an outer layer polyamide separation layer.
The catalytic self-cleaning internal pressure type composite nanofiltration membrane prepared in the embodiment is an internal pressure membrane, organic pollutants are treated under a persulfate oxidation system, the concentration of persulfate in the system is 20mg/L, and the pure water flux of the composite nanofiltration membrane reaches 50LMH bar to ultra-high 1 The method comprises the steps of carrying out a first treatment on the surface of the The initial concentration of the tetracycline in the organic pollutant is 20mg/L, the concentration of the tetracycline in the effluent after the filtration treatment is 1.2mg/L, and the removal rate of the tetracycline is 94%.
Comparative example:
the conventional hollow fiber composite nanofiltration membrane, which was composed of a base membrane and a polyamide separation layer, was used as a comparative example, and compared with example 1, there was no intermediate CuCo-MOFs/MXene composite material layer.
Under the same conditions as in example 1, the initial concentration of tetracycline is 20mg/L, the concentration of tetracycline in the effluent after filtration treatment is 13.5mg/L, and the flux recovery rate of the hollow fiber composite nanofiltration membrane is only about 75%.
Therefore, the catalytic self-cleaning internal pressure type hollow fiber nanofiltration membrane prepared in the embodiment 1 of the application has the CuCo-MOFs/MXene composite material layer, so that the flux recovery rate of the membrane in the running period is rapidly increased to 95%, and the rejection rate of sulfate after catalytic oxidation reaches 98%.
The method for measuring the pure water flux is as follows:
the pure water flux of the membrane is measured by a cross-flow filtration device, the membrane is poured into a columnar component, and the inner surface area of the membrane is 0.15m 2 The pure water flux was measured at a membrane feed pressure of 2 bar. Jw1=v/(a×t), where V: through the liquid volume, a: area of film, t: filtration time.
Determination of flux recovery rate: after the membrane was taken out, immersed in ultrapure water and rinsed for 60 minutes, and irradiated under a 300W ultraviolet lamp for 30 minutes after one cycle of operation, the pure water flux Jw2 and the flux recovery rate were measured:
the pollutant retention rate was measured, and the concentration of the inlet water pollutant and the concentration of persulfate were set to 20mg/L at a membrane inlet pressure of 2 bar. The concentration and the rejection rate after the interception are measured,cf: inlet water contaminant concentration, cp: effluent contaminant concentration.
Example 3:
mixing 18g of cellulose acetate, 60g of polyether sulfone and 12g of polyvinylpyrrolidone and 5g of Tween 80. Dissolved in 100mL NMP (N-methylpyrrolidone). Heating and stirring the polymer, defoaming the polymer, preparing the hollow fiber microfiltration membrane through phase inversion, placing the hollow fiber microfiltration membrane in pure water glycerol mixed solution for soaking for later use, wherein the pore diameter is 0.1 mu m. Before use, the base film is dried and then soaked in 1M sodium hydroxide solution under heating for 6 hours.
Weighing Ti 3 AlC 2 A total of 1g was placed in 50mL of 50% ammonium fluoride solution, sonicated for 30min, and reacted at 70℃for 36h at a rate of 500 revolutions per minute. The precipitate was washed with absolute ethanol until the surface impurities were completely removed. Precipitation yields a multilayer MXene. The thickness is about 60 μm.
0.01g of the multilayer MXene prepared above was sufficiently dispersed in 100mL of a mixed solution of DMF and isopropanol (mass ratio: 1:1), then 0.18g of copper acetylacetonate and 0.24g of cobalt nitrate hexahydrate were weighed and dissolved in the above dispersion, and mixed to obtain a mixed solution A; adding 2,3,6,7,10, 11-hexahydroxytriphenyl into DMF and isopropanol according to the mass ratio of 1:1, preparing 0.12g of mixed solution B; and finally, uniformly mixing the mixed solution A and the mixed solution B, transferring the mixture into a reaction kettle, and stirring the mixture in a water bath kettle at 150 ℃ for reaction for 8 hours. And cleaning and drying to obtain the CuCo-MOFs/MXene catalyst.
And weighing 0.2g of the prepared CuCo-MOFs/MXene catalyst, dissolving in 100mL of deionized water, placing the hollow fiber ultra-micro filtration base membrane subjected to alkali liquor treatment in the deionized water, and carrying out ultrasonic treatment for 1h, wherein the thickness of an intermediate transition layer (CuCo-MOFs/MXene composite material layer) formed on the outer surface of the hollow fiber ultra-micro filtration base membrane is 0.2-0.5 mm, so as to obtain the CuCo-MOFs/MXene composite micro filtration membrane.
And then the obtained composite ultrafiltration membranes are respectively soaked in 0.5wt% of anhydrous piperazine aqueous phase solution for 2min, and are soaked in 0.3wt% of trimesoyl chloride solution for 2min after surface impurities are cleaned. A polyamide separation layer was formed by interfacial polymerization, wherein the thickness of the separation layer was 50nm. The catalytic self-cleaning internal pressure type composite nanofiltration membrane is prepared, and has a three-layer structure from inside to outside, specifically an inner base membrane, an intermediate composite material layer and an outer polyamide separation layer.
The composite nanofiltration membrane prepared in this example is an internal pressure membrane, and organic pollutants are treated under an oxidation system (persulfate oxidation system, persulfate concentration is 20 mg/L), and the detection is carried out by the detection method in example 1, wherein the pure water flux of the composite nanofiltration membrane reaches 40LMH bar -1 The initial concentration of rhodamine B in the organic pollutant is 20mg/L, and the concentration of rhodamine B in the effluent after filtering treatment is 1.5The removal rate of rhodamine B reaches 92.5 percent in mg/L.
Compared with a simple hollow fiber composite nanofiltration membrane without an intermediate transition layer, the membrane of the embodiment has the advantages that the flux recovery rate of the operation cycle is improved to 95%, the sulfate concentration after catalytic oxidation is 15mg/L, the sulfate concentration after filtration is 0.12mg/L, and the retention rate reaches 99.2%. Meanwhile, the anti-pollution performance of the membrane is improved, and the catalytic self-cleaning function of the membrane is realized.
Example 4:
mixing 15g of cellulose acetate, 70g of polyether sulfone and 10g of polyvinylpyrrolidone and 5g of Tween 80. Dissolved in 100mL NMP (N-methylpyrrolidone). Heating and stirring the polymer, defoaming the polymer, preparing the hollow fiber microfiltration membrane through phase inversion, placing the hollow fiber microfiltration membrane in pure water glycerol mixed solution for soaking for later use, wherein the pore diameter is 0.1 mu m. When in use, the base film is dried and then is soaked in 1M sodium hydroxide solution under heating condition for 6 hours.
Weighing Ti 3 AlC 2 A total of 1g was placed in 40mL of hydrofluoric acid solution, dispersed by ultrasonic for 30min, and reacted at 60℃for 24 hours at a rate of 500 rpm. The precipitate was washed with absolute ethanol until the surface impurities were completely removed. The precipitation gives a multilayer MXene with a thickness of about 80. Mu.m.
0.01g of the multilayer MXene prepared above was sufficiently dispersed in 100mL of a mixed solution of DMF and isopropanol (mass ratio: 1:1), then 0.15g of copper acetylacetonate and 0.2g of cobalt nitrate hexahydrate were weighed and dissolved in the above dispersion, and mixed to obtain a mixed solution A; adding 2,3,6,7,10, 11-hexahydroxytriphenyl into DMF and isopropanol according to the mass ratio of 1:1, preparing 0.15g of mixed solution B; and finally, uniformly mixing the mixed solution A and the mixed solution B, transferring the mixture into a reaction kettle, and stirring the mixture in a water bath kettle at 150 ℃ for reaction for 7 hours. And cleaning and drying to obtain the CuCo-MOFs/MXene catalyst.
And weighing 0.2g of the prepared CuCo-MOFs/MXene catalyst, dissolving in 100mL of deionized water, placing the base film treated by alkali liquor in the solution, carrying out ultrasonic treatment for 1h, and forming an intermediate transition layer (a CuCo-MOFs/MXene composite material layer) with the thickness of 0.2-0.5 mm on the outer surface of the hollow fiber ultra-micro filtration base film to obtain the CuCo-MOFs/MXene composite micro-filtration film. And then respectively soaking the obtained composite ultrafiltration membrane in 0.8wt% of anhydrous piperazine aqueous solution for 8min, cleaning surface impurities, and then soaking the obtained composite ultrafiltration membrane in 0.5wt% of trimesoyl chloride solution for 3min. A polyamide separation layer was formed by interfacial polymerization, wherein the thickness of the separation layer was 80nm. The catalytic self-cleaning internal pressure type composite nanofiltration membrane is prepared, and has a three-layer structure from inside to outside, namely an inner layer base membrane, an intermediate composite material layer and an outer layer polyamide separation layer.
The composite nanofiltration membrane prepared in the embodiment is an internal pressure membrane, and organic pollutants are treated under an oxidation system (persulfate oxidation system, wherein the concentration of persulfate is 20 mg/L), and the pure water flux of the composite nanofiltration membrane reaches 50LMH bar -1 The initial concentration of the tetracycline in the organic pollutants is 20mg/L, the concentration of the tetracycline in the effluent after the filtration treatment is 1.0mg/L, and the removal rate of the tetracycline is 95%.
Compared with a simple hollow fiber composite nanofiltration membrane without an intermediate transition layer, the composite nanofiltration membrane prepared by the embodiment has the advantages that the flux recovery rate of the operation period is improved to 96%, the sulfate concentration after catalytic oxidation in a system is 18mg/L, the sulfate concentration after filtration is 0.15mg/L, and the retention rate reaches 99.16%. Meanwhile, the anti-pollution performance of the membrane is improved, and the catalytic self-cleaning function of the membrane is realized.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present application. It will be apparent to those having ordinary skill in the art that various modifications can be readily made to the embodiments and the generic principles described herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present application is not limited to the embodiments described herein, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present application.
Claims (13)
1. The utility model provides a catalysis self-cleaning internal pressure formula compound nanofiltration membrane which characterized in that: the hollow fiber ultra-micro filtration membrane comprises a hollow fiber ultra-micro filtration base membrane, wherein a CuCo-MOFs/MXene composite material layer is compounded on the outer surface of the hollow fiber ultra-micro filtration base membrane, and a polyamide separation layer is polymerized on the outer surface of the CuCo-MOFs/MXene composite material layer.
2. The catalytic self-cleaning internal pressure type composite nanofiltration membrane as defined in claim 1, wherein: the CuCo-MOFs/MXene composite material layer is formed by growing CuCo-MOFs nano particles on the surface of the MXene material.
3. The catalytic self-cleaning internal pressure type composite nanofiltration membrane as defined in claim 2, wherein: the thickness of the MXene material is 20-100 mu m; the thickness of the polyamide separation layer is 40-80nm.
4. A preparation method of a catalytic self-cleaning internal pressure type composite nanofiltration membrane is characterized by comprising the following steps of: the method comprises the following steps:
s1, firstly, placing a hollow fiber ultra-micro filtration base membrane in a catalyst solution for ultrasonic treatment to obtain a composite ultra-filtration membrane; the catalyst is CuCo-MOFs/MXene;
s2, performing interfacial polymerization reaction on the composite ultrafiltration membrane and the polyamide solution, and generating a polyamide separation layer on the outer surface of the composite ultrafiltration membrane to obtain the catalytic self-cleaning internal pressure type hollow fiber nanofiltration membrane.
5. The method of manufacturing according to claim 4, wherein: the preparation method of the CuCo-MOFs/MXene comprises the following steps:
s11, dispersing a plurality of layers of MXene materials in a solution, and then adding a copper source and a cobalt source to mix to form a mixed solution A;
s12, preparing an organic ligand into a mixed solution B;
s13, mixing the mixed solution A and the mixed solution B, and then stirring to react to obtain the CuCo-MOFs/MXene.
6. The method of manufacturing according to claim 5, wherein: the thickness of the multi-layer MXene material in the step S11 is 20-100 mu m;
the multi-layer MXene material is prepared by etching MAX phase, wherein the etching time is 24-48 h, and the temperature is 60-80 ℃;
the MAX phase is Ti 3 AlC 2 ；
The etching is realized by adopting an etching solvent, wherein the etching solvent is hydrofluoric acid, a mixed solution of hydrochloric acid and sodium fluoride, a mixed solution of hydrochloric acid and lithium fluoride or a mixed solution of hydrochloric acid and ammonium fluoride.
7. The method of manufacturing according to claim 5, wherein: the molar ratio of the copper source to the cobalt source in the step S11 is 0.5-1.0; the copper source is at least one of copper acetylacetonate, copper chloride and copper sulfate, and the cobalt source is cobalt nitrate hexahydrate;
the mass concentration of the copper source in the mixed solution A is 1.2-1.8 g/L, the mass concentration of MXene is 100mg/L, and the mass ratio of DMF to isopropanol is 1: 1.
8. The method of manufacturing according to claim 5, wherein: in the step S12, the organic ligand is 2,3,6,7,10, 11-hexahydroxy triphenyl or dimethyl imidazole or terephthalic acid, the mass concentration of the mixed solution B is 1-1.5 g/L, and the mass ratio of DMF to isopropanol is 1: 1;
in the step S13, the stirring reaction is carried out for 6 to 8 hours under the condition of water solubility at 150 ℃.
9. The method of manufacturing according to claim 4, wherein: the mass concentration of the catalyst solution in the step S1 is 0.5-5%, the temperature of the ultrasonic treatment is 60-90 ℃ and the time is 2-4 h;
the hollow fiber ultra-micro filtration base membrane is treated by alkali liquor.
10. The method of manufacturing according to claim 4, wherein: in the step S2, the interfacial polymerization reaction is to immerse the composite ultrafiltration membrane in aqueous phase polyamine solution and then immerse the composite ultrafiltration membrane in oil phase polyacyl chloride solution, and generate a polyamide separation layer through interfacial polymerization, wherein the thickness of the polyamide separation layer is 40-80nm.
11. The method of manufacturing according to claim 10, wherein: the solvent in the aqueous phase polyamine solution is anhydrous piperazine, the mass fraction of the aqueous phase polyamine solution is 0.5-0.8 wt%, and the time for immersing the composite ultrafiltration membrane in the aqueous phase polyamine solution is 2-10 min;
the oil phase polybasic acyl chloride solution is formed by dissolving trimesoyl chloride in normal hexane solution, the concentration of the trimesoyl chloride is 0.2-0.5 wt%, and the time for immersing the composite ultrafiltration membrane in the oil phase polybasic acyl chloride solution is 1-3 min.
12. Use of a catalytic self-cleaning internal pressure type composite nanofiltration membrane as defined in any one of claims 1 to 3, wherein: used as an internal pressure membrane for salt separation or contaminant removal under an oxidizing system.
13. Use according to claim 12, characterized in that: the pollutants comprise antibiotics, tetrabromobisphenol A flame retardant or a mixture of rhodamine B and sulfate, bisphenol A and sulfate;
the pure water flux of the internal pressure membrane reaches 40-60 LMH bar ～1 The flux recovery rate in the running period is more than 95%, the retention rate of sulfate reaches 95% -99.2%, and the removal rate of pollutants reaches 92% -95%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117643806A (en) * | 2024-01-30 | 2024-03-05 | 中国科学院合肥物质科学研究院 | Double-channel composite membrane and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117643806A (en) * | 2024-01-30 | 2024-03-05 | 中国科学院合肥物质科学研究院 | Double-channel composite membrane and preparation method and application thereof |
| CN117643806B (en) * | 2024-01-30 | 2024-04-19 | 中国科学院合肥物质科学研究院 | Double-channel composite membrane and preparation method and application thereof |
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