CN117000061B - Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof - Google Patents
Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN117000061B CN117000061B CN202311018536.1A CN202311018536A CN117000061B CN 117000061 B CN117000061 B CN 117000061B CN 202311018536 A CN202311018536 A CN 202311018536A CN 117000061 B CN117000061 B CN 117000061B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- phase solution
- nanofiltration membrane
- layer composite
- thin layer
- 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 98
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 65
- 239000004952 Polyamide Substances 0.000 title claims abstract description 63
- 229920002647 polyamide Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 73
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000008346 aqueous phase Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 239000012071 phase Substances 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000010612 desalination reaction Methods 0.000 claims abstract description 4
- 239000008233 hard water Substances 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- 239000013535 sea water Substances 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims abstract description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- WMVOLWCNQIESCJ-UHFFFAOYSA-N 1-dodecyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCC[NH+]1CN(C)C=C1 WMVOLWCNQIESCJ-UHFFFAOYSA-N 0.000 claims description 4
- OLLYMAMAGXVXBS-UHFFFAOYSA-N 1-methyl-3-tetradecyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCN1C[NH+](C)C=C1 OLLYMAMAGXVXBS-UHFFFAOYSA-N 0.000 claims description 3
- HSBMPUYCFQSKRP-UHFFFAOYSA-N 1-bromoimidazole Chemical compound BrN1C=CN=C1 HSBMPUYCFQSKRP-UHFFFAOYSA-N 0.000 claims description 2
- MRBKRIWWRHEXIM-UHFFFAOYSA-N 1-decyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCC[NH+]1CN(C)C=C1 MRBKRIWWRHEXIM-UHFFFAOYSA-N 0.000 claims description 2
- ZDEPXVXEADUOAV-UHFFFAOYSA-N 1-decyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[NH+]1CN(C)C=C1 ZDEPXVXEADUOAV-UHFFFAOYSA-N 0.000 claims description 2
- WREWAMXVXPPKQU-UHFFFAOYSA-N 1-dodecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+]1CN(C)C=C1 WREWAMXVXPPKQU-UHFFFAOYSA-N 0.000 claims description 2
- FSXANJBLYFVXEU-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCCCCCCCN1CN(C)C=C1 FSXANJBLYFVXEU-UHFFFAOYSA-N 0.000 claims description 2
- WXJHMNWFWIJJMN-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCN1C[NH+](C)C=C1 WXJHMNWFWIJJMN-UHFFFAOYSA-N 0.000 claims description 2
- BPGYFPOMDKAMBJ-UHFFFAOYSA-N 1-methyl-3-tetradecyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCN1C[NH+](C)C=C1 BPGYFPOMDKAMBJ-UHFFFAOYSA-N 0.000 claims description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 238000000108 ultra-filtration Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000004695 Polyether sulfone Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000693 micelle Substances 0.000 description 6
- 229920006393 polyether sulfone Polymers 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- -1 salt ions Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002891 organic anions Chemical class 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- QWLSTCVUGYAKLE-UHFFFAOYSA-M 1-dodecyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+]=1C=CN(C)C=1 QWLSTCVUGYAKLE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- TUNNRCBQRMKLOO-UHFFFAOYSA-N [Br].C(CCCCCCCCCCC)N1CN(C=C1)C Chemical compound [Br].C(CCCCCCCCCCC)N1CN(C=C1)C TUNNRCBQRMKLOO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polyamides (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyamide thin layer composite nanofiltration membrane and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Adding an ionic liquid with amphipathy into an aqueous phase solution containing polyamine to prepare an aqueous phase solution containing the ionic liquid; (2) Dissolving polybasic acyl chloride in an organic solvent to prepare an oil phase solution containing the polybasic acyl chloride; (3) And carrying out interfacial polymerization reaction on the aqueous phase solution containing the ionic liquid and the oil phase solution to obtain the polyamide thin layer composite nanofiltration membrane. The polyamide thin layer composite nanofiltration membrane has the characteristics of high crosslinking degree, narrow pore diameter distribution, ultra-thin performance and the like, has higher water flux and higher interception performance on divalent ions, can be applied to the fields of sea water desalination, hard water softening, sewage purification and the like, has extremely high surface electronegativity, extremely high interception of divalent anions and low interception rate of monovalent anions, and can realize separation of divalent/monovalent mixed anions.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a polyamide thin layer composite nanofiltration membrane, a preparation method and application thereof.
Background
With the development of industry, water resource shortage is still an important problem faced by human beings at present, so that advanced water treatment technology is needed to alleviate the water resource shortage problem faced by human beings, and membrane separation technology is widely applied to the fields of sea water desalination, hard water softening, brackish water purification, sewage treatment and the like due to high efficiency, low energy consumption and simple and convenient operation. The separation membrane is a core component of membrane separation technology, and can be divided into a microfiltration membrane (10 4 -50 nm), an ultrafiltration membrane (50-2 nm), a nanofiltration membrane (2-0.5 nm) and a reverse osmosis membrane (below 0.5 nm) according to the pore size of the separation membrane.
Among these separation membranes, nanofiltration membranes, which are novel membrane separation materials, originate from the 80 th century at the earliest, are novel separation membranes which appear after ultrafiltration membranes and reverse osmosis membranes, and are widely and intensively studied because of small permeation resistance, low operation energy consumption and excellent separation performance, and can effectively intercept divalent salt ions and most of organic matters in water. At present, a thin layer composite nanofiltration membrane consisting of a porous substrate membrane and an ultrathin separation layer becomes a research hot spot because the materials of the substrate and the separation layer have wide selection range and the structure and the property of the separation layer are easy to accurately regulate and control.
At present, the interfacial polymerization method is the most commonly used method for preparing the polyamide nanofiltration membrane because of simple and convenient operation process, mild reaction conditions and higher synthesis efficiency. The interfacial polymerization method adopts two monomers with higher reactivity to generate polycondensation reaction at mutually incompatible two-phase interfaces to generate the polymer film. Polyamide thin-layer composite nanofiltration membranes are the most widely used type of thin-layer composite nanofiltration membranes. The polyamide separating layer is obtained by interfacial polymerization of water phase monomer (amine) and oil phase monomer (aromatic acyl chloride). Along with the increasingly popularization of the industrial application of the polyamide thin layer composite nanofiltration membrane, the control preparation of the polyamide skin layer is found to still face a plurality of challenges, and is a key problem for restricting the improvement of the membrane performance. The active layer of the traditional polyamide nanofiltration membrane is obtained by interfacial polymerization reaction between an amine monomer (piperazine) and an aromatic acyl chloride monomer (trimesoyl chloride). However, the traditional interfacial polymerization reaction rate is extremely fast, and the polyamide separation layer with the thickness of tens or even hundreds of nanometers can be formed in a few seconds. Therefore, in the interfacial polycondensation reaction system, the structure and the property of the generated crosslinked polyamide skin layer are extremely uncontrollable, thereby restricting the effective regulation and control of the separation layer structure and the random cutting of the performance of the thin-layer composite membrane, causing the permeation flux and the selectivity of the obtained thin-layer composite nanofiltration membrane to still have a 'game' effect which eliminates each other, and being difficult to synchronously promote.
The key point for solving the problem is how to regulate the interfacial polymerization reaction rate, thereby realizing slow and uniform interfacial polycondensation. In recent years, researchers have prepared a series of ultra-thin nanofiltration membranes with few defects and high crosslinking degree from the viewpoints of monomer design, surface modification of a base membrane, construction of an intermediate layer/a sacrificial layer, and the like.
Ionic Liquids (ILs) are a class of liquid salts consisting of organic cations, inorganic or organic anions, with melting points generally below 100 ℃. The ionic liquid has the advantages of difficult volatilization and stable and adjustable structural property.
In a plurality of reports at present, the preparation of the polyamide thin layer composite nanofiltration membrane by adopting the surface active ionic liquid to regulate and control the interfacial polymerization reaction is still blank in the technical field range, and has important research value and application prospect.
Disclosure of Invention
The invention provides an application of ionic liquid in preparing a polyamide thin layer composite nanofiltration membrane by regulating and controlling interfacial polymerization reaction, and solves the problems of extremely high interfacial polymerization reaction rate, poor controllability and the like in the prior art by regulating and controlling the ionic liquid.
The technical scheme of the invention is as follows:
The application of the ionic liquid in preparing the polyamide thin layer composite nanofiltration membrane by regulating and controlling the interfacial polymerization reaction comprises the following steps:
(1) Adding an ionic liquid with amphipathy into an aqueous phase solution containing polyamine to prepare an aqueous phase solution containing the ionic liquid;
(2) Dissolving polybasic acyl chloride in an organic solvent to prepare an oil phase solution containing the polybasic acyl chloride;
(3) And carrying out interfacial polymerization reaction on the aqueous phase solution containing the ionic liquid and the oil phase solution to obtain the polyamide thin layer composite nanofiltration membrane.
The ionic liquid organic cation or organic anion is provided with an alkyl chain with adjustable length, and the ionic liquid organic cation or organic anion can play a role in surface activity by adjusting the length of the alkyl chain. The surface active ionic liquid tends to be distributed at the organic solvent/water phase interface, reducing interfacial tension. If the ionic liquid with the surface activity is used as the water phase additive, the ionic liquid can be more rapidly dispersed and distributed to the organic solvent/water interface than the polyamine, so that a smoother, uniform and stable interface place is provided for the interfacial polymerization reaction, and the interfacial polymerization reaction can be stably and orderly carried out. And simultaneously, the chain length of the alkyl chain on the ionic liquid cation can be regulated and controlled, so that interface layers with different thicknesses are formed. In addition, ionic liquid in the aqueous phase can generate electrostatic attraction, hydrogen bond and pi-pi interaction with the polyamine, and can reduce the diffusion rate of the polyamine to an organic solvent/water interface, thereby reducing the interfacial polymerization reaction rate. Therefore, the interfacial polymerization reaction is regulated and controlled by the ionic liquid, the prepared polyamide active layer is thinner, the surface is smooth, the pore size distribution is narrow, and finally the thin-layer composite nanofiltration membrane with high flux, high salt interception and high fouling resistance is obtained.
Preferably, the ionic liquid is imidazole chloride ionic liquid and/or imidazole bromide ionic liquid.
Further preferably, the ionic liquid is one of 1-octyl-3-methylimidazole bromide, 1-decyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-octyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole chloride, 1-dodecyl-3-methylimidazole chloride and 1-tetradecyl-3-methylimidazole chloride.
The critical micelle concentration of the 1-dodecyl-3-methylimidazole bromine salt is 10.8mmol/L, and the critical micelle concentration of other ionic liquids can be slightly reduced along with the growth of alkyl chains on imidazole rings or slightly increased along with the reduction of the length of the alkyl chains.
Preferably, in the aqueous phase solution containing the ionic liquid, the concentration of the ionic liquid is the critical micelle concentration.
Preferably, the polyamine is piperazine; in the aqueous phase solution, the concentration of the polyamine is 0.5-2g/L.
Preferably, the polybasic acyl chloride is trimesoyl chloride; in the oil phase solution, the concentration of the polybasic acyl chloride is 0.5-2g/L.
Preferably, the interfacial polymerization reaction time is 30s-2min.
A preferable technical scheme is as follows:
The application of the ionic liquid in preparing the polyamide thin layer composite nanofiltration membrane by regulating and controlling the interfacial polymerization reaction comprises the following steps:
(1) Adding an ionic liquid with amphipathy into an aqueous phase solution containing polyamine to prepare an aqueous phase solution containing the ionic liquid;
(2) Dissolving polybasic acyl chloride in an organic solvent to prepare an oil phase solution containing the polybasic acyl chloride;
(3) Soaking a porous base film by adopting an aqueous phase solution containing ionic liquid, removing the redundant aqueous phase solution, and adding an oil phase solution on the porous base film soaked with the aqueous phase monomer solution to perform interfacial polymerization reaction; and removing redundant oil phase solution after the reaction is finished, drying and solidifying, soaking in deionized water, and taking out and drying to obtain the polyamide thin layer composite nanofiltration membrane.
Preferably, the porous base membrane is an ultrafiltration membrane or a microfiltration membrane of Polyethersulfone (PES), polypropylene (PP) and polyvinylidene fluoride (PVDF).
Preferably, the drying and curing temperature is 40-80 ℃; the drying and curing time is 5-10min.
Preferably, the deionized water soaking time is 1-3 days.
The invention also provides the polyamide thin layer composite nanofiltration membrane prepared by the method. The polyamide thin layer composite nanofiltration membrane has the characteristics of high crosslinking degree, narrow pore diameter distribution, ultra-thin performance and the like, has higher water flux, and has higher interception performance on divalent ions.
The invention also provides application of the polyamide thin-layer composite nanofiltration membrane in the fields of sea water desalination, hard water softening, sewage purification and the like.
The invention also provides application of the polyamide thin layer composite nanofiltration membrane in separation of divalent and monovalent mixed anions.
The polyamide thin-layer composite nanofiltration membrane prepared by the invention has high rejection rate for divalent anions, but has low rejection rate for monovalent anions, can realize separation of divalent and monovalent mixed anions, and is particularly suitable for separation of Na 2SO4 and NaCl and Na 2SiO3 and NaOH.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the ionic liquid with amphipathy is used as the water phase additive for the first time, and the ionic liquid with amphipathy tends to be distributed on the organic solvent/water phase interface, so that the interfacial tension is reduced. The ionic liquid provides a smoother, more uniform and stable interface place for the interfacial polymerization reaction, and compared with the traditional interfacial polymerization reaction, the ionic liquid enables the interfacial polymerization reaction to occur stably and orderly. Meanwhile, ionic liquid in the water phase can generate electrostatic attraction, hydrogen bond and pi-pi interaction with polyamine, so that the diffusion rate of the polyamine to an interface can be reduced, the polymerization reaction rate of the interface can be reduced, an ultrathin polyamide skin with narrow pore diameter distribution can be prepared, and a high-divalent anion-trapping and high-flux thin-layer composite nanofiltration membrane (the trapping rate of the polyamide thin-layer composite nanofiltration membrane prepared by the preferred embodiment to Na 2SO4 is 98.6%, the flux is 40.6 L.m -2·h-1·bar-1, and the trapping rate of the thin-layer composite nanofiltration membrane prepared by the traditional interfacial polymerization to Na 2SO4 is 97.3%, and the flux is 18.8 L.m -2·h-1·bar-1) can be obtained.
(2) The ionic liquid with amphipathy can help the polyamine to wet and spread on porous basal membranes (PP, PVDF, PES ultrafiltration membranes or microfiltration membranes) with different wettability to form a continuous and uniform aqueous monomer liquid layer, so that a complete, continuous and defect-free polyamide skin layer is formed through interfacial polymerization; the polyamine solution without the aqueous phase ionic liquid additive has poor wettability on hydrophobic substrates such as PP, PVDF ultrafiltration membranes or microfiltration membranes, so that the surface hydrophobic substrate membrane often needs hydrophilization modification.
(3) The amphiphilic ionic liquid can effectively regulate and control interfacial polymerization reaction with extremely low addition (about 10.8 mmol/L) to prepare the polyamide thin layer composite nanofiltration membrane with ultrathin cortex and narrow pore diameter distribution. The ionic liquid is low in addition amount, so that the method is suitable for large-scale industrial production.
(4) Compared with the nanofiltration membrane prepared by the traditional method, the nanofiltration membrane prepared by the invention has extremely high surface electronegativity and extremely high rejection rate for divalent anions, for example, the nanofiltration membrane prepared by the preferred embodiment can have the rejection rate of Na 2SO4 as high as 98.6 percent, but the rejection rate of NaCl as low as 7.1 percent, so that the separation of Na 2SO4/NaCl or Na 2SiO3/NaOH can be realized.
(5) The nanofiltration membrane prepared by the invention has small surface roughness and smoother surface, and has better anti-fouling property compared with the traditional nanofiltration membrane.
Drawings
FIG. 1 is an SEM image of the surface of a polyamide nanofiltration membrane separation layer prepared by interfacial polymerization without adding a surface active ionic liquid in comparative example 1;
FIG. 2 is an SEM image of the surface of a polyamide nanofiltration membrane separation layer obtained by interfacial polymerization reaction with the addition of a surface active ionic liquid (1-dodecyl-3-methylimidazolium bromide) in example 1;
FIG. 3 is an AFM characterization diagram of a polyamide nanofiltration membrane prepared by interfacial polymerization without adding a surfactant ionic liquid in comparative example 1; (a) is roughness and (b) is thickness;
FIG. 4 is an AFM characterization chart of a polyamide nanofiltration membrane obtained by interfacial polymerization reaction with addition of a surface active ionic liquid (1-dodecyl-3-methylimidazole bromide) in example 1; (a) is roughness and (b) is thickness.
Detailed Description
For better understanding of the technical solution of the present invention, the present invention will be described in further detail with reference to the following examples, but the content of the present invention is not limited to the following examples, and experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The following PES ultrafiltration membranes were purchased from sea salt New Oriental plasticizing technology Co., ltd; the aperture of the PES microfiltration membrane is 0.05-0.1 mu m.
Comparative example 1
A polyamide film prepared by free interfacial polymerization without surface active ionic liquid regulation comprising:
(1) 10mL of piperazine (aqueous solution A) with the concentration of 1g/L is taken in a culture dish, and then 10mL of trimesoyl chloride (organic phase solution B) with the concentration of 1.5g/L is added for interfacial polymerization reaction.
(2) After 30s of reaction, the polyamide film is fished out of absolute ethyl alcohol by a silicon wafer and washed.
(3) And (3) taking out the film after washing, and heating and curing the film in an oven at 60 ℃ for 10min to obtain the polyamide film prepared by interfacial polymerization of the traditional water phase monomer piperazine and the oil phase monomer trimesoyl chloride.
(4) And observing the surface morphology, roughness and thickness of the glass. The SEM characterization chart of the surface morphology is shown in figure 1; AFM testing is shown in fig. 3.
Example 1
The preparation of the polyamide film by adopting the surface active ionic liquid to regulate and control the interfacial polymerization reaction comprises the following steps:
(1) 10mL of 1g/L piperazine aqueous solution (aqueous solution A) added with amphiphilic surface active ionic liquid (1-dodecyl-3-methylimidazole bromide) with the concentration of critical micelle concentration (10.8 mmol/L) is taken in a culture dish, and then 10mL of trimesoyl chloride (organic phase solution B) with the concentration of 1.5g/L is added for interfacial polymerization reaction.
(2) After 30s of reaction, the membrane was fished out of absolute ethanol with a silicon wafer and washed.
(3) And (3) taking out the membrane after washing, and heating and curing the membrane in an oven at 60 ℃ for 5min to obtain the polyamide thin layer nanofiltration membrane prepared by adopting interfacial polymerization regulated and controlled by surface active ionic liquid.
(4) Observing the apparent changes of the surface morphology, roughness, thickness and the like of the polyamide nano-polyamide separation layer formed by not adding the surface active ionic liquid, wherein an SEM (scanning electron microscope) characterization chart of the surface morphology is shown in figure 2; AFM testing is shown in fig. 4. From the appearance (as shown in (a) of fig. 2 and 4), the appearance of the whole film is changed, and the particle feel on the surface of the film is obviously reduced; from the aspect of roughness, the whole film is smoother, and the surface roughness of the film is obviously reduced; the thickness of the polyamide nanofiltration membrane was significantly reduced by 40.+ -.5 nm, compared to the thickness of the polyamide nanofiltration membrane (FIG. 3 (b)) without the addition of the surface active ionic liquid, which was shown in FIG. 4 (b), when the thickness was seen to be 40.+ -.5 nm, indicating that the addition of the surface active ionic liquid (1-dodecyl-3-methylimidazolium bromide) to the aqueous phase significantly reduced the thickness of the polyamide nanofiltration membrane.
Comparative example 2
The polyamide thin layer composite nanofiltration membrane prepared by interfacial polymerization reaction without adopting surface active ionic liquid regulation comprises the following components:
(1) Fixing the PES ultrafiltration bottom film in a specific polymerization device, adding 5mL of aqueous phase solution A, standing for 30s, and then adopting a vacuum filtration method to pump out the aqueous phase.
(2) Then adding 5mL of organic phase solution B for polymerization reaction for 1min, pouring out the organic phase, putting into a 60 ℃ oven for curing for 5min, and taking out.
(3) Soaking in deionized water for 1 day, and drying to obtain the traditional polyamide thin layer composite nanofiltration membrane which is prepared by adopting no surface active ionic liquid to regulate interfacial polymerization reaction.
Example 2
The preparation of the polyamide thin layer composite nanofiltration membrane by adopting the surface active ionic liquid to regulate and control the interfacial polymerization reaction comprises the following steps:
(1) PES ultrafiltration bottom film is fixed in a specific polymerization device, 5mL of aqueous phase solution A (1 g/L piperazine aqueous solution) added with amphiphilic surface active ionic liquid (1-dodecyl-3-methylimidazole bromine salt) with critical micelle concentration (10.8 mmol/L) is added, and after standing for 30s, the aqueous phase is pumped out by adopting a vacuum filtration method.
(2) Then adding 5mL of organic phase solution B for polymerization reaction for 1min, pouring out the organic phase, putting into a 60 ℃ oven for curing for 5min, and taking out.
(3) Soaking in deionized water for 1 day, and drying to obtain the polyamide thin layer composite nanofiltration membrane prepared by adopting surface active ionic liquid to regulate interfacial polymerization reaction.
Example 3
The preparation of the polyamide thin layer composite nanofiltration membrane by adopting the surface active ionic liquid to regulate and control the interfacial polymerization reaction comprises the following steps:
(1) PES ultrafiltration membrane is fixed in a specific polymerization device, 5mL of aqueous phase solution A added with amphiphilic surface active ionic liquid (1-tetradecyl-3-methylimidazole bromide) with the concentration of critical micelle concentration (10.8 mmol/L) is added, and after standing for 30s, the aqueous phase is pumped out by adopting a vacuum pumping filtration method.
(2) Then adding 5mL of organic phase solution B for polymerization reaction for 1min, pouring out the organic phase, putting into a 60 ℃ oven for curing for 5min, and taking out.
(3) Soaking in deionized water for 1 day, and drying to obtain the polyamide thin layer composite nanofiltration membrane prepared by adopting surface active ionic liquid to regulate interfacial polymerization reaction.
Test example 1: interception performance test
The rejection rate can be used to express the rejection performance of a membrane on a certain solute, and is specifically shown as a formula (1):
R＝(1－CP/Cf)×100％ (1)
wherein R represents the rejection rate, C f (mg/L) represents the concentration of solute in the feed solution, and C p (mg/L) represents the concentration of solute in the permeate solution.
The polyamide thin-layer composite nanofiltration membranes prepared in example 2 and comparative example 2 were placed in a cross-flow device, respectively, na 2SO4 and NaCl salt solution (the concentration is 1.0 g/L) were added to the feed side, and the filtrate after nanofiltration membrane filtration was collected and the conductivity was measured by a conductivity meter.
The interception rate of the polyamide nanofiltration membrane prepared by adding the surface active ionic liquid in the example 2 and controlling the interfacial polymerization reaction is measured to be 98.6% for Na 2SO4 and 7.1% for NaCl.
The nanofiltration membrane of the polyamide skin layer of comparative example 2, to which no surface active ionic liquid was added, was subjected to the above test, and it was measured that the rejection rate for Na 2SO4 was 97.3% and the rejection rate for NaCl was 21%.
Test example 2: water flux test
The water flux represents the volume of flow per unit of membrane area per unit time at a certain pressure, calculated specifically according to formula (2):
J＝V/(A*T) (2)
Where V (L) represents the filtrate volume, A (m 2) represents the test area of the sample, and T (h) represents the time taken to collect filtrate of volume V.
Example 2 the nanofiltration membrane of polyamide skin layer prepared by adding surface active ionic liquid to regulate interfacial polymerization reaction has water flux in the range of 40-50 L.m -2·h-1·bar-1.
Comparative example 2 the nanofiltration membrane of polyamide skin layer, which was prepared without addition of surface active ionic liquid, was subjected to the above test, and the water flux was measured to be in the range of 18-20 l·m -2·h-1·bar-1.
The properties of the polyamide skin-layer nanofiltration membranes prepared in example 1 and example 3 were similar to those of the polyamide skin-layer nanofiltration membrane prepared in example 2.
The foregoing embodiments have described the technical solutions and advantages of the present invention in detail, and it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like that fall within the principles of the present invention should be included in the scope of the invention.
Claims (9)
1. The application of the ionic liquid in preparing the polyamide thin layer composite nanofiltration membrane by regulating and controlling the interfacial polymerization reaction is characterized by comprising the following steps:
(1) Adding an ionic liquid with amphipathy into an aqueous phase solution containing polyamine to prepare an aqueous phase solution containing the ionic liquid; the ionic liquid is imidazole chloride ionic liquid and/or imidazole bromide ionic liquid;
(2) Dissolving polybasic acyl chloride in an organic solvent to prepare an oil phase solution containing the polybasic acyl chloride;
(3) And carrying out interfacial polymerization reaction on the aqueous phase solution containing the ionic liquid and the oil phase solution to obtain the polyamide thin layer composite nanofiltration membrane.
2. The use according to claim 1, wherein the ionic liquid is one of 1-octyl-3-methylimidazole bromide, 1-decyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-octyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole chloride, 1-dodecyl-3-methylimidazole chloride and 1-tetradecyl-3-methylimidazole chloride.
3. The use according to claim 1, wherein the polyamine is piperazine; in the aqueous phase solution, the concentration of the polyamine is 0.5-2 g/L.
4. The use according to claim 1, wherein the polyacyl chloride is trimesoyl chloride; in the oil phase solution, the concentration of the polybasic acyl chloride is 0.5-2 g/L.
5. The use according to claim 1, wherein the interfacial polymerization reaction time is 30 s-2 min.
6. The use of claim 1, wherein step (3) comprises: soaking a porous base film by adopting an aqueous phase solution containing ionic liquid, removing the redundant aqueous phase solution, and adding an oil phase solution on the porous base film soaked with the aqueous phase monomer solution to perform interfacial polymerization reaction; and removing redundant oil phase solution after the reaction is finished, drying and solidifying, soaking in deionized water, and taking out and drying to obtain the polyamide thin layer composite nanofiltration membrane.
7. A polyamide thin layer composite nanofiltration membrane prepared according to the steps of any one of claims 1-6 for use.
8. Use of the polyamide thin layer composite nanofiltration membrane as defined in claim 7 in the fields of sea water desalination, hard water softening and sewage purification.
9. Use of the polyamide thin layer composite nanofiltration membrane as claimed in claim 7 for separation of divalent and monovalent mixed anions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311018536.1A CN117000061B (en) | 2023-08-14 | 2023-08-14 | Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311018536.1A CN117000061B (en) | 2023-08-14 | 2023-08-14 | Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117000061A CN117000061A (en) | 2023-11-07 |
| CN117000061B true CN117000061B (en) | 2024-08-30 |
Family
ID=88565271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311018536.1A Active CN117000061B (en) | 2023-08-14 | 2023-08-14 | Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117000061B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118558162A (en) * | 2024-05-20 | 2024-08-30 | 浙江大学 | High-performance polyamide composite membrane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294178A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Polyamide nano filter membrane containing zwitterions and preparation method thereof |
| AU2021105044A4 (en) * | 2020-12-31 | 2021-09-30 | Qilu University Of Technology | Cellulose/aramid nanofiber composite film and preparation method and application therof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654322B (en) * | 2018-05-22 | 2020-02-04 | 石河子大学 | Preparation method and application of alkaline functional ionic liquid-based blend membrane |
| CN110026091B (en) * | 2019-03-15 | 2021-02-23 | 清华大学 | Ionic liquid modified positively charged composite nanofiltration membrane and preparation method thereof |
| CN115518532A (en) * | 2022-10-12 | 2022-12-27 | 哈尔滨工业大学（深圳） | Nanofiltration membrane post-treatment method for heavy metal wastewater treatment |
| CN116078169A (en) * | 2022-11-11 | 2023-05-09 | 杭州师范大学 | Polyamide composite nanofiltration membrane modified by multi-reactive group ionic liquid and preparation method and application thereof |
-
2023
- 2023-08-14 CN CN202311018536.1A patent/CN117000061B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294178A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Polyamide nano filter membrane containing zwitterions and preparation method thereof |
| AU2021105044A4 (en) * | 2020-12-31 | 2021-09-30 | Qilu University Of Technology | Cellulose/aramid nanofiber composite film and preparation method and application therof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117000061A (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109550406B (en) | Preparation method of amphoteric particle in-situ constructed metal organic framework separation membrane | |
| Saren et al. | Synthesis and characterization of novel forward osmosis membranes based on layer-by-layer assembly | |
| CN103041713B (en) | A kind of preparation method of hollow fiber nanofiltration membrane | |
| JP2015231624A (en) | Reverse osmosis separation membrane excellent in salt removal rate and permeation flow characteristics and production method of the same | |
| CN105642129A (en) | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof | |
| CN111282447A (en) | Preparation method of desalination composite membrane with nanoscale ultrathin separation layer | |
| CN110801736B (en) | Preparation method of organic solvent-resistant and difficult-to-peel nanofiltration membrane | |
| CN113856501A (en) | Composite nanofiltration membrane and preparation method and application thereof | |
| CN114642967B (en) | Nanofiltration membrane based on reactive supporting layer, preparation method and application | |
| CN117000061B (en) | Polyamide thin layer composite nanofiltration membrane and preparation method and application thereof | |
| CN114713042B (en) | Nanofiltration membrane with high resolution and water flux and preparation method thereof | |
| CN112808021A (en) | Method for preparing reverse osmosis membrane by adopting novel water phase system | |
| CN111203104A (en) | Preparation method of reverse osmosis membrane with ultrathin asymmetric polyamide rejection layer | |
| JP2014521499A (en) | Polyamide-based reverse osmosis separation membrane excellent in initial permeate flow rate and method for producing the same | |
| US20130292325A1 (en) | Method for preparing reverse osmosis membrane, and reverse osmosis membrane prepared thereby | |
| CN113262644A (en) | Novel high-flux positively-charged nanofiltration membrane and preparation method thereof | |
| CN110585931A (en) | High-flux organic solvent-resistant composite nanofiltration membrane containing metal skeleton compound intermediate layer and preparation method thereof | |
| CN113491955A (en) | Composite membrane with heterostructure separation layer and preparation method thereof | |
| CN115845639A (en) | Nanofiltration membrane containing molecular sieve organic composite material intermediate layer and preparation method thereof | |
| CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
| CN116371221B (en) | Polyamide nanofiltration membrane and preparation method and application thereof | |
| CN114682103B (en) | Film composite nanofiltration membrane and preparation method and application thereof | |
| CN115055061A (en) | Preparation method of polyamide composite nanofiltration membrane with high osmotic selectivity | |
| CN111282453B (en) | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane | |
| CN111437740B (en) | Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane |
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 |