CN116899419B - High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof - Google Patents
High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof Download PDFInfo
- Publication number
- CN116899419B CN116899419B CN202311004208.6A CN202311004208A CN116899419B CN 116899419 B CN116899419 B CN 116899419B CN 202311004208 A CN202311004208 A CN 202311004208A CN 116899419 B CN116899419 B CN 116899419B
- Authority
- CN
- China
- Prior art keywords
- nanofiltration membrane
- nanomaterial
- nano material
- intermediate layer
- high temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 118
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 95
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 74
- 239000000725 suspension Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011229 interlayer Substances 0.000 claims abstract description 24
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 18
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000108 ultra-filtration Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- 238000000926 separation method Methods 0.000 description 29
- 230000004907 flux Effects 0.000 description 21
- 239000002131 composite material Substances 0.000 description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 description 16
- 235000011152 sodium sulphate Nutrition 0.000 description 16
- 239000004952 Polyamide Substances 0.000 description 15
- 229920002647 polyamide Polymers 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010918 textile wastewater Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- 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
- B01D67/00791—Different components in separate layers
-
- 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
- B01D69/1214—Chemically bonded layers, e.g. cross-linking
-
- 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
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- 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
-
- 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 invention discloses a high temperature resistant nanofiltration membrane based on a nanomaterial interlayer, a preparation method and application thereof, belonging to the technical field of water treatment materials, wherein the preparation method of the high temperature resistant nanofiltration membrane comprises the following steps: (1) Dispersing the nano material with the surface containing hydroxyl and an aminosilane coupling agent in an organic solvent, and fully reacting to obtain a stable suspension; (2) Coating the suspension in the step (1) on the surface of a porous base film to form a nano material intermediate layer, then carrying out interfacial polymerization reaction on a water phase solution containing polyamine monomers and an oil phase solution containing acyl chloride monomers on the nano material intermediate layer, and curing and crosslinking to obtain the high-temperature-resistant nanofiltration membrane based on the nano material intermediate layer; the method is simple and convenient to operate, has low equipment requirement, and the prepared high-temperature-resistant nanofiltration membrane has excellent nanofiltration performance and high-temperature resistance, and can keep the stability of the structure and performance at a higher working temperature.
Description
Technical Field
The invention belongs to the technical field of water treatment materials, and particularly relates to a high-temperature-resistant nanofiltration membrane based on a nanomaterial interlayer, and a preparation method and application thereof.
Background
The current society faces the problem of energy and water resource shortage, and the membrane separation technology has the advantages of no phase change, low energy consumption, simple operation, small environmental pollution and the like, so that the membrane separation technology is widely and deeply studied. The polyamide thin layer composite nanofiltration membrane has the characteristics of mild preparation conditions, good selective permeability and the like, so that the polyamide thin layer composite nanofiltration membrane is widely applied to the fields of hard water softening, food processing, sewage recovery and the like, but the use temperature of most nanofiltration membrane materials is low, and in order to ensure the service life of the membrane, the working temperature is generally required to be lower than 45 ℃, one important reason is that the separation layer is tightly connected with the base membrane, and the change of the high Wen Xiaji membrane pores can pull the separation layer, so that defects are generated in the separation layer, and the rejection rate is reduced.
The development of the high temperature resistant nanofiltration membrane has important practical significance, and is specifically expressed in the following three aspects: (1) The high temperature resistant nanofiltration membrane can directly carry out membrane separation on high temperature feed liquid, and the high temperature feed liquid does not need to be cooled in advance, so that the energy consumption in the production process is reduced; (2) The thermal movement speed of molecules at high temperature is increased, the solution viscosity is reduced, and the improvement of flux and mass transfer efficiency is facilitated; (3) In the food and pharmaceutical fields, it is often necessary to heat the feed solution to a higher temperature to inhibit bacterial growth.
Some current work has been done to improve the thermal stability of nanofiltration membranes by using polymeric materials with temperature resistant structures, or introducing nanomaterials with good heat resistance. The Chinese patent document with publication number of CN114432902A discloses a high-temperature-resistant composite nanofiltration membrane, wherein a base membrane and a separation layer are respectively made of ceramic materials and sulfonated polyaryletherketone, and the nanofiltration membrane has excellent high-temperature resistance and separation effect; there is also work to add graphene oxide to polyamide separation layers to improve the thermal stability of nanofiltration membranes (P.Wen, Y.Chen, X.Hu, B.Cheng, D.Liu, Y.Zhang, S.Nair, polyamide thin film composite nanofiltration membrane modified with acyl chlorided graphene oxide. J membrane. Sci.2017,535, 208-220.); the Chinese patent document with publication number of CN103861468A discloses a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane takes a hollow fiber ultrafiltration membrane as a base membrane, and the surface of the composite nanofiltration membrane is coated with a polyvinyl alcohol/nano particle composite functional layer, so that the composite nanofiltration membrane has good pollution resistance and temperature resistance.
Although the above method can prepare nanofiltration membranes having a certain temperature resistance, there is still a lack of related research and improvement methods for the problem that the separation layer is affected by the change of porosity due to thermal deformation of the substrate under high temperature conditions.
Disclosure of Invention
The invention provides a preparation method of a high-temperature resistant nanofiltration membrane based on a nanomaterial interlayer, which is simple and convenient to operate and low in equipment requirement, and the prepared high-temperature resistant nanofiltration membrane has excellent nanofiltration performance and high-temperature resistance, and can maintain the stability of structure and performance at a higher working temperature.
The technical scheme adopted is as follows:
a preparation method of a high-temperature resistant nanofiltration membrane based on a nanomaterial interlayer comprises the following steps:
(1) Dispersing the nano material with the surface containing hydroxyl and an aminosilane coupling agent in an organic solvent, and fully reacting to obtain a stable suspension;
(2) Coating the suspension in the step (1) on the surface of a porous base film to form a nano material intermediate layer, then carrying out interfacial polymerization reaction on a water phase solution containing polyamine monomers and an oil phase solution containing acyl chloride monomers on the nano material intermediate layer, and curing and crosslinking to obtain the high-temperature-resistant nanofiltration membrane based on the nano material intermediate layer;
the nano material comprises at least one of titanium dioxide, silicon dioxide, zinc oxide, zirconium dioxide, calcium carbonate, boron nitride, carbon nitride, black phosphorus, graphene oxide and molybdenum disulfide.
The aminosilane coupling agent comprises at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-diethylenetriaminopropyl methyldimethoxysilane and 3-diethylenetriaminopropyl trimethoxysilane.
The aminosilane coupling agent has hydrolysable alkoxy and amino, after the alkoxy is hydrolyzed, the silane coupling agent becomes silanol, unstable silanol can react with hydroxyl on the nano material and be combined with the silanol, the nano material is modified, if the aminosilane coupling agent is not added, the nano material suspension is directly sprayed to cause poor bonding force, the nano material is easy to fall off, and if the suspension in the step (1) is directly added into an aqueous phase solution, the solution layering and uneven film forming can be caused due to poor compatibility among raw materials.
Preferably, the concentration of the nano material in the organic solvent is 1-20 g/L, and the concentration of the aminosilane coupling agent in the organic solvent is 1-30 g/L. If the concentration of the aminosilane coupling agent is low, it is difficult to uniformly modify the surface of the nanomaterial; the higher concentration of the aminosilane coupling agent will result in reduced nanofiltration properties.
Further preferably, the concentration of the nanomaterial in the organic solvent is 1-10 g/L, and the concentration of the aminosilane coupling agent in the organic solvent is 1-15 g/L.
Preferably, the nanomaterial and the aminosilane coupling agent react at room temperature for a reaction time of 0.2 to 12 hours, more preferably 0.2 to 2 hours.
Preferably, the organic solvent is at least one of methanol, ethanol, isopropanol, toluene, n-hexane, diethyl ether and ethyl acetate.
The porous base membrane comprises, but is not limited to, polyethersulfone ultrafiltration membrane, polysulfone ultrafiltration membrane, polyacrylonitrile ultrafiltration membrane, polyimide ultrafiltration membrane, poly (m-phenylene isophthalamide) ultrafiltration membrane and the like.
Preferably, the coating method is a spraying method, and the spraying method is easy for large-scale preparation, good in uniformity, universal in substrate, short in time consumption, small in pollution and the like.
Preferably, in the aqueous phase solution, the polyamine monomer is at least one of piperazine, m-phenylenediamine, hexamethylenediamine, polyethyleneimine and diethylenetriamine; in the oil phase solution, acyl chloride monomers are at least one of trimesoyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride and adipoyl chloride, and the solvent of the oil phase solution is at least one of n-hexane, cyclohexane, n-heptane, benzene, toluene, ethyl acetate and isoparaffin.
Preferably, the concentration of the polyamine monomer in the aqueous phase solution is 0.1-10 g/L; in the oil phase solution, the concentration of the acyl chloride monomer is 0.1-5 g/L.
Preferably, the aqueous phase solution is uniformly dispersed on the surface of the porous base film with the nano material intermediate layer, redundant solution on the surface is removed after full infiltration, and then the oil phase solution is uniformly dispersed for interfacial polymerization reaction.
Preferably, the temperature of interfacial polymerization reaction is 15-35 ℃ and the time is 0.3-5 min.
Preferably, the curing and crosslinking temperature is 50-80 ℃, and the curing and crosslinking time is 3-60 min.
After the suspension is coated on the surface of the porous base film to form a nano material intermediate layer, the nano material intermediate layer comprises an aminosilane coupling agent and a nano material modified by the aminosilane coupling agent, and in the interfacial polymerization process, amino in the aminosilane coupling agent can react with polybasic acyl chloride to form an amide bond, so that the polyamide separation layer is stably combined on the surface of the nano material intermediate layer through a covalent bond, namely, the binding force between the nano material intermediate layer and the polyamide separation layer is good. The silica bond of the nano material intermediate layer has higher bond energy, the bond breakage can not occur at high temperature, the temperature resistance of the nanofiltration membrane can be improved, and meanwhile, the nano material intermediate layer can isolate the porous substrate and the separation layer, so that the defect caused by deformation and pulling of the separation layer of the porous substrate membrane at high temperature is avoided.
The invention also provides the high-temperature resistant nanofiltration membrane based on the nano material intermediate layer, which is prepared by the preparation method of the high-temperature resistant nanofiltration membrane based on the nano material intermediate layer, and comprises a porous base membrane, the nano material intermediate layer and a polyamide separation layer.
The invention also provides application of the high-temperature resistant nanofiltration membrane based on the nanomaterial interlayer in the field of water treatment; the separation layer of the high temperature resistant nanofiltration membrane is compact, defect-free and negatively charged, can effectively realize the selective separation of monovalent/divalent anions in a water body and the interception of most organic matters, has excellent high temperature resistance, and can be directly used in the nanofiltration separation process of high temperature feed liquid.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the aminosilane coupling agent to modify the surface of the nano material, the method does not need to use a large-scale specific device, the equipment requirement is low, strong acid, strong alkali or high temperature condition is not needed in the experimental process, the reaction condition is mild, and the method is easy to implement.
(2) According to the invention, the amino silane coupling agent modified nano material intermediate layer is introduced between the polyamide separation layer and the porous base film, so that the polyamide separation layer and the porous base film are stably combined on one hand, and the separation layer and the base film can be isolated from each other by the intermediate layer, and the pulling effect of thermal deformation between layers is reduced.
(3) The high temperature resistant nanofiltration membrane prepared by the method has the advantages of uniform and compact separation layer, few defects, excellent nanofiltration performance and water flux up to 35 L.m -2 ·h -1 ·bar -1 The rejection rate of sodium sulfate is more than 98 percent.
(4) The high temperature resistant nanofiltration membrane prepared by the method can keep stable structure and nanofiltration performance under the high temperature condition (90 ℃), and the phenomenon that the nanofiltration performance is seriously reduced because the pore diameter of a separation layer becomes too large does not occur.
Drawings
FIG. 1 is a scanning electron micrograph of a polyethersulfone ultrafiltration membrane.
FIG. 2 is a scanning electron micrograph of the thin-layer composite nanofiltration membrane of comparative example 1.
FIG. 3 is a scanning electron micrograph of a high temperature nanofiltration membrane based on an intermediate layer of nanomaterial in example 11.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1 preparation of a suspension
60mL of absolute ethyl alcohol is taken, 240mg of titanium dioxide nano material with hydroxyl groups on the surface and 300mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1h at room temperature of 25 ℃.
EXAMPLE 2 preparation of suspension
60mL of absolute ethyl alcohol is taken, 360mg of titanium dioxide nano material with hydroxyl groups on the surface and 300mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1 h.
EXAMPLE 3 preparation of suspension
60mL of absolute ethyl alcohol is taken, 240mg of titanium dioxide nano material with hydroxyl groups on the surface and 480mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1 h.
Example 4 preparation of suspension
60mL of absolute ethyl alcohol is taken, 360mg of carbon nitride nano material with hydroxyl group on the surface and 300mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1 h.
EXAMPLE 5 preparation of suspension
And taking 60mL of absolute ethyl alcohol, adding 240mg of molybdenum disulfide nano material with hydroxyl groups on the surface and 480mg of 3-aminopropyl triethoxysilane, carrying out ultrasonic mixing uniformly, transferring to a three-neck flask, and stirring for 1h to obtain a stable suspension.
EXAMPLE 6 preparation of suspension
60mL of ethyl acetate is taken, 240mg of titanium dioxide nano material with hydroxyl groups on the surface and 480mg of 3-aminopropyl trimethoxy silane are added, the mixture is transferred to a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1 h.
EXAMPLE 7 preparation of suspension
60mL of toluene is taken, 360mg of carbon nitride nano material with hydroxyl groups on the surface and 300mg of 3-aminopropyl methyl dimethoxy silane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 1 h.
EXAMPLE 8 preparation of suspension
60mL of absolute ethyl alcohol is taken, 360mg of carbon nitride nano material with hydroxyl group on the surface and 300mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 5 hours.
EXAMPLE 9 preparation of suspension
60mL of ethyl acetate is taken, 240mg of titanium dioxide nano material with hydroxyl groups on the surface and 480mg of 3-aminopropyl trimethoxy silane are added, the mixture is transferred to a three-neck flask after being evenly mixed by ultrasound, and a stable suspension is obtained after stirring for 7 h.
Example 10 preparation of suspension
60mL of absolute ethyl alcohol is taken, 360mg of carbon nitride nano material with hydroxyl group on the surface and 300mg of 3-aminopropyl triethoxysilane are added, the mixture is transferred into a three-neck flask after being evenly mixed by ultrasound, and stable suspension is obtained after stirring for 12 hours.
Example 11 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
Uniformly spraying the suspension in the embodiment 1 on the surface of a polyethersulfone ultrafiltration membrane to serve as a nanomaterial intermediate layer, preparing a porous base membrane with the nanomaterial intermediate layer, taking 2mg/mL of piperazine as an aqueous phase solution and taking n-hexane solution of trimesic acid chloride with the concentration of 3mg/mL as an oil phase solution, uniformly dispersing the aqueous phase solution on the surface of the nanomaterial intermediate layer, removing superfluous aqueous solution on the surface after fully soaking for a period of time, immediately dripping the oil phase solution, reacting for 2min at 25 ℃, further curing for 3min in an oven at 80 ℃, and obtaining the high-temperature-resistant nanofiltration membrane based on the nanomaterial intermediate layer, and fully drying or placing the nanofiltration membrane in ultrapure water in a vacuum drying oven for subsequent characterization and testing.
Example 12 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 11 only in that the suspension of example 4 was used to prepare the nanomaterial intermediate layer.
Example 13 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 11 only in that the suspension of example 5 was used to prepare the nanomaterial intermediate layer.
Example 14 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 12 only in that piperazine at 0.5mg/mL was used as the aqueous solution.
Example 15 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 12 only in that piperazine at 5mg/mL was used as the aqueous solution.
Example 16 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 12 only in that 2mg/mL of polyethylenimine was used as the aqueous solution.
Example 17 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 12 only in that 2mg/mL of polyethylenimine was used as the aqueous phase solution and 5mg/mL of isophthaloyl chloride in n-hexane was used as the oil phase solution.
Example 18 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 12 only in that piperazine at 5mg/mL was used as the aqueous phase solution and that trimesoyl chloride in n-hexane at 0.5mg/mL was used as the oil phase solution.
Example 19 preparation of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
This example differs from example 11 only in that the interfacial polymerization reaction time was 3min.
Comparative example 1 preparation of thin-layer composite nanofiltration membrane
Taking 2mg/mL of piperazine aqueous solution as aqueous phase solution, taking n-hexane solution of trimesoyl chloride with the concentration of 3mg/mL as oil phase solution, firstly uniformly dispersing the aqueous phase solution on the surface of a polyethersulfone ultrafiltration membrane, removing superfluous aqueous solution on the surface after fully soaking for a period of time, immediately dripping the oil phase solution on the surface of the membrane, reacting for 2min at 25 ℃, further curing for 3min in an oven at 80 ℃ to obtain a thin layer composite membrane, and fully drying in a vacuum drying oven or placing in ultrapure water for subsequent characterization and test.
Sample analysis
(1) Topography analysis
The surface morphology of the polyethersulfone ultrafiltration membrane, the polyamide thin layer composite nanofiltration membrane in comparative example 1 and the high temperature resistant nanofiltration membrane based on the nanomaterial intermediate layer in example 11 were characterized by scanning electron microscopy, as shown in fig. 1-3, respectively, and as can be seen in fig. 1, holes of several tens of nanometers are uniformly dispersed on the surface of the polyethersulfone ultrafiltration membrane, a dense polyamide separation layer is formed on the surface of the membrane after interfacial polymerization by piperazine and trimesoyl chloride (fig. 2), and the membrane has more undulating raised structures on the surface of the separation layer while maintaining the dense separation layer structure after introducing the nanomaterial intermediate layer (fig. 3).
(2) High temperature nanofiltration performance of high temperature resistant nanofiltration membrane based on nanomaterial interlayer
Since the residual acyl chloride groups on the surface of the polyamide nanofiltration membrane are easy to hydrolyze into carboxyl groups, the polyamide nanofiltration membrane is usually negatively charged, can effectively intercept high-valence anions, and evaluate the nanofiltration performance of the nanofiltration membrane by water flux and interception rate, wherein the water flux represents the volume of solution passing through the unit membrane area in unit time under unit operating pressure, and the unit is L.m -2 ·h -1 ·bar -1 The retention rate represents the removal rate of the target substance in the feed solution; the calculations are each calculated by the following formula:
wherein F is water flux; v is the volume of the solution passing through the surface of the nanofiltration membrane, and the unit is L; a is the surface area of the film, and the unit is m 2 The method comprises the steps of carrying out a first treatment on the surface of the t is test time, and the unit is h; p is the test pressure in bar;
wherein R is the retention rate; c (C) p And C f The solute concentration of the filtrate and the feed liquid is g/L respectively.
The thin-layer composite nanofiltration membrane prepared in comparative example 1 was subjected to a high-temperature feed liquid cross-flow filtration experiment, the high-temperature nanofiltration performance was verified by testing the water flux and the rejection rate, in the test process, the feed liquid was stably heated to 85 ℃ from normal temperature (25 ℃) by a heating device, the water flux and the rejection rate were tested every 10 ℃ in the heating process, the solute was sodium sulfate of 1g/L, the test pressure was stabilized at 6bar, and the test results are shown in table 1.
Table 1 water flux and sodium sulfate rejection rate of nanofiltration membrane in comparative example 1 in high temperature feed liquid experiment
Temperature/. Degree.C | Water flux/L.m -2 ·h -1 ·bar -1 | Sodium sulfate rejection/% |
25 | 9.9 | 98.5 |
35 | 15.1 | 95.1 |
45 | 21.0 | 92.3 |
55 | 27.3 | 88.3 |
65 | 32.6 | 85.6 |
75 | 38.2 | 81.9 |
85 | 42.1 | 78.3 |
As can be seen from Table 1, the water flux of the polyamide thin layer composite nanofiltration membrane without the nano material intermediate layer gradually increases in the heating process, because the water molecules thermally move faster due to the rising of the temperature, the viscosity of the system is reduced, the diffusion speed of each molecule in the feed liquid to the membrane surface is increased, the diffusion coefficient is increased, the chain segment movement of the polymer is enhanced, the polymer network expands, the pore diameter of the membrane is enlarged, the free volume in the membrane is increased, and the rejection rate of sodium sulfate is obviously reduced by more than 20%.
The high temperature resistant nanofiltration membrane based on the nanomaterial interlayer prepared in example 11 was subjected to a cross-flow filtration experiment under the same test conditions as those of table 1, and the results are shown in table 2.
TABLE 2 Water flux and sodium sulfate rejection of nanofiltration membranes in high temperature feed experiments in example 11
Temperature/. Degree.C | Water flux/L.m -2 ·h -1 ·bar -1 | Sodium sulfate rejection/% |
25 | 10.3 | 98.9 |
35 | 12.5 | 99.0 |
45 | 14.4 | 98.8 |
55 | 16.7 | 98.9 |
65 | 18.4 | 98.8 |
75 | 20.1 | 98.7 |
85 | 22.3 | 99.0 |
75 | 20.4 | 99.1 |
65 | 18.9 | 99.2 |
55 | 17.0 | 98.9 |
45 | 14.8 | 98.9 |
35 | 12.6 | 99.0 |
25 | 10.7 | 99.1 |
As can be seen from Table 2, similar to the thin-layer composite nanofiltration membrane of comparative example 1, due to acceleration of movement of water molecules and reduction of water viscosity, water flux gradually increases with increase of feed liquid temperature, and rejection rate of sodium sulfate is maintained above 98.5% in the whole test process, because the inorganic nanomaterial has good temperature resistance and mechanical property and higher melting point, and the aminosilane coupling agent can modify the surface of the nanomaterial to improve compatibility of the nanomaterial in a polymer matrix, amino groups on the aminosilane coupling agent can react with polybasic acyl chloride, so that the nanomaterial is stably combined in a polyamide separation layer, and meanwhile, the intermediate layer can serve as a heat insulation layer material, defects of the separation layer caused by thermal deformation pulling of the separation layer at high temperature of the base membrane are avoided, and stability of rejection rate is maintained.
The high temperature resistant nanofiltration membranes based on the nanomaterial interlayers prepared in examples 12-19 were tested for water flux and rejection to 1g/L aqueous sodium sulfate solution at 85 deg.c at a pressure of 6bar and the results are shown in table 3.
TABLE 3 Water flux and sodium sulfate rejection in feed liquid experiments at 85℃for nanofiltration membranes in examples 12-19
Testing | Water flux/L.m -2 ·h -1 ·bar -1 | Sodium sulfate rejection/% |
Example 12 | 28.3 | 98.7 |
Example 13 | 25.1 | 98.2 |
Example 14 | 22.0 | 98.3 |
Example 15 | 29.1 | 98.9 |
Example 16 | 22.6 | 99.1 |
Example 17 | 25.3 | 99.0 |
Example 18 | 30.2 | 98.1 |
Example 19 | 35.1 | 98.2 |
As can be seen from the data in Table 3, the high temperature resistant nanofiltration membranes based on the intermediate layers of the nanomaterials prepared in examples 12 to 19 maintained a rejection rate of sodium sulfate of 98.0% or more at 85℃and a water flux of 22.0 L.m -2 ·h -1 ·bar -1 The method has good universality, and various nano materials modified by the aminosilane coupling agent can be used for preparing the thin-layer composite nanofiltration membrane with good high temperature resistance.
(3) Stability of high temperature resistant nanofiltration membranes based on nanomaterial interlayers
The high temperature resistant nanofiltration membrane based on the middle layer of nanomaterial prepared in example 18 was tested for the change of water flux and retention rate of 1g/L aqueous sodium sulfate solution with time at 85 deg.c, the test pressure was 6bar, and the results are shown in table 4.
TABLE 4 Water flux and sodium sulfate rejection for nanofiltration membrane of example 18 run continuously in feed liquid experiments at 85℃
Time/day | Water flux/L.m -2 ·h -1 ·bar -1 | Sodium sulfate rejection/% |
1 | 30.2 | 98.1 |
10 | 30.4 | 98.2 |
20 | 30.7 | 98.0 |
30 | 30.4 | 98.1 |
40 | 30.3 | 97.8 |
50 | 30.3 | 97.9 |
60 | 30.6 | 97.5 |
70 | 30.4 | 97.5 |
80 | 30.2 | 97.3 |
90 | 30.1 | 97.0 |
As can be seen from Table 4, the retention rate of the high temperature resistant nanofiltration membrane based on the nano material middle layer to 85 ℃ high temperature sodium sulfate aqueous solution under continuous 90-day operation is above 97.0%, the retention attenuation rate is less than 5%, and the nanofiltration membrane has higher water flux, which proves that the nanofiltration membrane containing the nano material middle layer has good high temperature resistant stability, and is expected to be applied to the fields of high temperature feed liquid treatment such as textile wastewater, food medicine and the like.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the high-temperature-resistant nanofiltration membrane based on the nanomaterial interlayer is characterized by comprising the following steps of:
(1) Dispersing the nano material with the surface containing hydroxyl and an aminosilane coupling agent in an organic solvent, and fully reacting to obtain a stable suspension;
(2) Coating the suspension in the step (1) on the surface of a porous base film to form a nano material intermediate layer, then carrying out interfacial polymerization reaction on a water phase solution containing polyamine monomers and an oil phase solution containing acyl chloride monomers on the nano material intermediate layer, and curing and crosslinking to obtain the high-temperature-resistant nanofiltration membrane based on the nano material intermediate layer;
the nano material comprises at least one of titanium dioxide, silicon dioxide, zinc oxide, zirconium dioxide, calcium carbonate, boron nitride, carbon nitride, black phosphorus, graphene oxide and molybdenum disulfide;
the porous base membrane comprises a polyethersulfone ultrafiltration membrane, a polysulfone ultrafiltration membrane, a polyacrylonitrile ultrafiltration membrane, a polyimide ultrafiltration membrane or a poly m-phenylene isophthalamide ultrafiltration membrane;
the concentration of the nano material in the organic solvent is 1-20 g/L, and the concentration of the aminosilane coupling agent in the organic solvent is 1-30 g/L; the reaction time of the nano material and the aminosilane coupling agent is 0.2-12 h;
in the aqueous phase solution, the polyamine monomer is at least one of piperazine, m-phenylenediamine, hexamethylenediamine, polyethyleneimine and diethylenetriamine; in the oil phase solution, the acyl chloride monomer is at least one of trimesoyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride and adipoyl chloride.
2. The method for preparing the high temperature resistant nanofiltration membrane based on the nanomaterial interlayer according to claim 1, wherein the aminosilane coupling agent comprises at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-diethylenetriaminopropyl methyldimethoxysilane and 3-diethylenetriaminopropyl trimethoxysilane.
3. The method for preparing the high temperature resistant nanofiltration membrane based on the nanomaterial interlayer according to claim 1, wherein the solvent of the oil phase solution is at least one of n-hexane, cyclohexane, n-heptane, benzene, toluene, ethyl acetate and isoparaffin.
4. The method for preparing a high temperature resistant nanofiltration membrane based on a nanomaterial interlayer according to claim 1, wherein the concentration of the polyamine monomer in the aqueous phase solution is 0.1-10 g/L; in the oil phase solution, the concentration of the acyl chloride monomer is 0.1-5 g/L.
5. The method for preparing the high temperature resistant nanofiltration membrane based on the nanomaterial interlayer according to claim 1, wherein the temperature during the interfacial polymerization reaction is 15-35 ℃ and the time is 0.3-5 min; the curing and crosslinking temperature is 50-80 ℃, and the curing and crosslinking time is 3-60 min.
6. The high temperature resistant nanofiltration membrane based on a nanomaterial intermediate layer prepared by the method for preparing the high temperature resistant nanofiltration membrane based on a nanomaterial intermediate layer according to any one of claims 1 to 5.
7. The use of a high temperature nanofiltration membrane based on a nanomaterial interlayer according to claim 6 in the field of water treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311004208.6A CN116899419B (en) | 2023-08-10 | 2023-08-10 | High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311004208.6A CN116899419B (en) | 2023-08-10 | 2023-08-10 | High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116899419A CN116899419A (en) | 2023-10-20 |
CN116899419B true CN116899419B (en) | 2024-03-05 |
Family
ID=88360199
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311004208.6A Active CN116899419B (en) | 2023-08-10 | 2023-08-10 | High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116899419B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113248755A (en) * | 2021-05-18 | 2021-08-13 | 长春工业大学 | Preparation method of nano-silica/hydroxyl silane coupling agent composite modified polyurethane super-hydrophobic film |
CN115090130A (en) * | 2021-09-13 | 2022-09-23 | 浙江美易膜科技有限公司 | Nanofiltration membrane containing silica gel nanoparticle intermediate layer and preparation method thereof |
-
2023
- 2023-08-10 CN CN202311004208.6A patent/CN116899419B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113248755A (en) * | 2021-05-18 | 2021-08-13 | 长春工业大学 | Preparation method of nano-silica/hydroxyl silane coupling agent composite modified polyurethane super-hydrophobic film |
CN115090130A (en) * | 2021-09-13 | 2022-09-23 | 浙江美易膜科技有限公司 | Nanofiltration membrane containing silica gel nanoparticle intermediate layer and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
硅烷偶联剂 AAPTS对TiO2 纳米颗粒进行氨基化改性;武艳娜;聚醚砜复合膜的改性及其分离性能研究;第62-64页 * |
Also Published As
Publication number | Publication date |
---|---|
CN116899419A (en) | 2023-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018201924A1 (en) | Composite reverse osmosis membrane, and manufacturing method thereof | |
CN111773928B (en) | Aerogel composite membrane and preparation method and application thereof | |
CN108993165B (en) | Layered inorganic material organic solvent nanofiltration composite membrane and preparation method thereof | |
CN110548415B (en) | Large-flux positively-charged polyamide hybrid forward osmosis membrane and preparation method thereof | |
CN112387134B (en) | Solvent-resistant nanofiltration membrane as well as preparation method and application thereof | |
CN114053888B (en) | Hydrophilic conductive distillation membrane and preparation method and application method thereof | |
CN112316752A (en) | Sulfonamide micromolecule surface modified polyamide composite membrane and preparation method thereof | |
CN111790274A (en) | Preparation method of anti-pollution polysulfone composite nanofiltration membrane for water body filtration | |
CN113509845B (en) | Graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation, preparation and application | |
CN116899419B (en) | High-temperature-resistant nanofiltration membrane based on nanomaterial intermediate layer and preparation method and application thereof | |
CN108004682A (en) | A kind of method that electrostatic spinning prepares lotus positive electricity hybridized fiber film | |
CN102500241B (en) | Preparation method for anti-pollution permeable vaporization film | |
CN113750820B (en) | Preparation method and application of mixed matrix composite membrane based on polyethyleneimine modified porous montmorillonite | |
CN113750821B (en) | g-C based on embedded porous few layers 3 N 4 Preparation method and application of/ZIF-8 mixed matrix membrane | |
CN112755814B (en) | Black talc nanoparticle modified polyamide composite nanofiltration membrane | |
CN114405291B (en) | Preparation method of nanofiber forward osmosis composite membrane | |
CN114016285B (en) | Preparation method of functional nanofiber membrane for sea water desalination | |
CN112933983B (en) | Graphene silicon dioxide core-shell structure filled PDMS hybrid membrane and preparation method thereof | |
CN113750818B (en) | High-permeability polyamide reverse osmosis composite membrane and preparation method thereof | |
CN108927020B (en) | Cellulose-based composite nanofiltration membrane containing mesoporous polymer and preparation method thereof | |
CN113209837A (en) | Polyvinyl alcohol/attapulgite composite membrane and preparation method and application thereof | |
CN110624276A (en) | Preparation method of flat composite ceramic membrane for treating oily wastewater | |
CN114538960B (en) | Polyacrylic acid modified ceramic membrane, preparation method and application | |
CN114682106B (en) | Preparation method of self-supporting composite nanofiltration membrane | |
CN217340841U (en) | Receive filter membrane, receive filter membrane subassembly and water treatment facilities |
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 |