CN117619155A - Method for preparing nanofiltration membrane by adopting novel oil phase system - Google Patents
Method for preparing nanofiltration membrane by adopting novel oil phase system Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 126
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 153
- 239000000463 material Substances 0.000 claims description 38
- 239000008346 aqueous phase Substances 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 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 27
- 229920002873 Polyethylenimine Polymers 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000004952 Polyamide Substances 0.000 claims description 17
- 229920002647 polyamide Polymers 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 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 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229940082004 sodium laurate Drugs 0.000 claims description 2
- AWMAOFAHBPCBHJ-UHFFFAOYSA-M sodium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound [Na+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C AWMAOFAHBPCBHJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005507 spraying Methods 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 2
- 230000002745 absorbent Effects 0.000 claims 2
- 150000003457 sulfones Chemical class 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 13
- 150000001298 alcohols Chemical class 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 3
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 96
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 229920002492 poly(sulfone) Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 159000000011 group IA salts Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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Classifications
-
- 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
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method for preparing nanofiltration membrane by adopting a novel oil phase system is prepared by adopting interfacial polymerization reaction. Adding alcohols which are insoluble in alkane solvents into an oil phase solution, wherein the oil phase monomer is a polybasic acyl chloride monomer, and obtaining the oil phase solution for interfacial polymerization reaction after ultrasonic dispersion. On one hand, the invention utilizes the hydroxyl groups and acyl chloride groups in alcohols to generate ester groups, thereby reducing the number of effective reactive groups of TMC to achieve the purposes of reducing the crosslinking degree and retaining more amino groups. On the other hand, as alcohols are insoluble in alkane solvents, a unique existence state of water-oil mixing micro turbidity can be formed in an oil phase after ultrasonic dissolution, the oil phase can have a nano structure, the reaction state of acyl chloride groups and amino groups can be regulated and controlled during interfacial polymerization reaction, the aim of regulating the structure of a functional separation layer can be achieved by regulating the concentration of alcohols in the oil phase solution and the dosage of oil phase monomers, the nano filter membrane can generate a nano structure favorable for separation performance, and the nano filter membrane can obtain high separation performance and water flux.
Description
Technical Field
The invention relates to the technical field of water treatment and salt recovery, in particular to a method for preparing a nanofiltration membrane by using a novel oil phase system.
Background
Population growth and economic development exacerbate the water resource crisis, water resource shortage and water environment pollution are increasingly serious, social health and sustainable development are seriously affected, and the water resource crisis becomes one of the most main problems facing the 21 st century. The nanofiltration technology accords with the development concept of energy conservation and high efficiency of the water treatment technology, and has great application potential in the field of water treatment. Nanofiltration can realize high-efficiency interception of multivalent salt and organic pollutants in water, has the characteristic of selective separation of a monovalent and multivalent salt mixed system, has the advantage of low energy consumption, and has been widely applied to sea water desalination, drinking water treatment, water reuse, industrial wastewater treatment and the like. NF mostly uses a membrane composite membrane (TFC) structure consisting of a Polyamide (PA) functional separation layer, an ultrafiltration membrane (UF) layer (commonly used polysulfone or polyethersulfone UF membrane) and a non-woven support layer. The key to achieving the sieving action of the material is the polyamide functional separation layer with a compact structure. The polyamide dense functional separation layer is generally prepared by interfacial polymerization of a polyamine monomer (dissolved in an aqueous phase) and a polyacyl chloride monomer (dissolved in an oil phase) via an aqueous-oil interface.
Through the development of over 40 years, the nanofiltration technology has significantly advanced and succeeded in the aspects of separation mechanism, membrane material, preparation method, process integration, design and the like, so that the nanofiltration technology enters the stage of vigorous development. However, most commercial nanofiltration membranes are electronegative and have a weak trapping capacity for multivalent positive ions, so positively charged nanofiltration membranes are a research hotspot in recent years.
The polyethylenimine is also called polyazacyclopropane, is a water-soluble high molecular polymer, has a uniform dendritic network structure, and contains a large number of amine groups on the surface. The polyethyleneimine has strong hydrophilicity and higher reactivity, and is suitable for preparing positively charged nanofiltration membranes. Positively charged nanofiltration membranes generally have high crosslink density and low permeability. Thus, the trade-off optimization of high throughput and high separation performance remains a challenge for positively charged nanofiltration membranes.
Disclosure of Invention
In view of the above-mentioned shortcomings and disadvantages of the prior art, the present invention provides a method for preparing nanofiltration membranes using a novel oil phase system. By adjusting the composition of the oil phase solution, the purpose of constructing a compact functional separation layer structure with a controllable structure is achieved, and the nanofiltration membrane is favorable for obtaining high separation performance and water flux.
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
a method for preparing nanofiltration membrane by adopting a novel oil phase system comprises the steps of adding an alcohol-containing hydroxyl reagent into an oil phase solution, performing ultrasonic dispersion, taking a turbid water-oil solution obtained after ultrasonic dispersion as an oil phase (the oil phase can have a nano structure) of interfacial polymerization reaction, taking the aqueous phase solution dissolved with polyamine as an aqueous phase of the interfacial polymerization reaction, and preparing a polyamide functional separation layer of the nanofiltration membrane through the interfacial polymerization reaction; the oil phase monomer in the oil phase solution is a polybasic acyl chloride monomer; the aqueous phase also includes an anionic surfactant or a cationic surfactant.
Furthermore, nanometer microdroplets with different sizes and numbers are obtained by adjusting the dosage proportion of the alcohol hydroxyl-containing reagent and the polybasic acyl chloride monomer in the oil phase solution, so that the aim of adjusting the structure of the polyamide functional separation layer is fulfilled.
Further, the alcohol hydroxyl-containing reagent is one or more than two of isopropanol, glycerol, polyethylene glycol, 1, 4-butanediol, ethylene glycol methyl ether and water; the mass percentage of the alcohol hydroxyl-containing reagent in the oil phase solution is 0.2% -1%.
Further, the polybasic acyl chloride monomer is one or more than two of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; preferably, the polyacyl chloride monomer is trimesoyl chloride (TMC). The mass percentage of the polybasic acyl chloride monomer in the oil phase solution is 0.02-1%; more preferably, the mass percentage of trimesic chloride (TMC) in the oil phase solution is 0.02-0.8%. The solvent in the oil phase solution is one or more of Isopar L, n-hexane, cyclohexane, toluene and benzene.
More preferably: the dosage ratio of the alcohol hydroxyl-containing reagent to the polybasic acyl chloride monomer in the oil phase solution is 4:1-20:1.
Further, the polyamine is one or more than two of polyethyleneimine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, diaminotoluene and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine in the water phase is 0.2-2%.
Further, the preparation method of the oil phase comprises the following steps: dissolving a polybasic acyl chloride monomer in a solvent of an oil phase, adding an alcohol-containing hydroxyl reagent which is insoluble in an alkane solvent into the oil phase solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction;
further, the interfacial polymerization reaction is realized by one of the following three ways:
firstly, coating a water phase on a permeable membrane base membrane material, standing, removing (e.g. pouring) a water phase flowing on the permeable membrane base membrane material, coating an oil phase on the permeable membrane base membrane material covered with the water phase, and performing heat treatment (the heat treatment promotes the polymerization reaction of a polyamine monomer and a polybasic acyl chloride monomer to generate polyamide) to obtain a polyamide functional separation layer on the permeable membrane base membrane material;
soaking the permeable membrane base membrane material in a water phase, standing, taking out the permeable membrane base membrane material, coating an oil phase on the permeable membrane base membrane material covered with the water phase, and performing heat treatment to obtain a polyamide functional separation layer on the permeable membrane base membrane material;
and thirdly, soaking the permeable membrane bottom membrane material in the water phase, standing, taking out the permeable membrane bottom membrane material, soaking the permeable membrane bottom membrane material covered with the water phase in the oil phase for a period of time, taking out, and performing heat treatment to obtain the polyamide functional separation layer on the permeable membrane bottom membrane material.
Further, the coating mode is spraying, coating, dipping or soaking; the temperature of the heat treatment is 30-130 ℃, preferably 50-90 ℃; heat treatment is carried out until no oil phase liquid remains on the surface of the membrane.
Further, the permeable membrane base membrane material comprises a non-woven fabric base material and a supporting layer, and the supporting layer is superposed on the surface of the non-woven fabric base material; the water phase and the oil phase are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is immersed in the water phase and the oil phase respectively in an upward way; wherein the material of the supporting layer is one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
Further, the water phase also comprises an acid absorber (acid binding agent), and the mass percentage of the acid absorber in the water phase is 0.1-1.5%. The acid absorber is alkaline salt, the alkaline salt is preferably sodium carbonate, the sodium carbonate can react with hydrogen ions generated in interfacial polymerization to promote the interfacial polymerization reaction, carbon dioxide can be generated in the reaction, and the pore-forming effect is achieved.
Further, the mass percentage concentration of the anionic surfactant or the cationic surfactant is 0.1-5%; the anionic surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium laurate, sodium camphorsulfonate and sodium citrate; the mass percentage concentration of the water phase solution is 0.1% -5%.
The cationic surfactant is one or a mixture of more of sodium dodecyl sulfate, dodecyl trimethyl ammonium chloride and dodecyl dimethyl benzyl ammonium chloride; the mass percentage concentration of the water phase solution is 0.1% -5%.
The invention has the beneficial effects that: in the reaction process, on one hand, hydroxyl in alcohol reacts with acyl chloride groups to generate ester groups, and consumption of the acyl chloride groups reduces the consumption of polyamine monomers in aqueous phase solution, so that uniform polyamide functional separation layers and nanofiltration membranes with stable membrane performance are obtained; on the other hand, as alcohols can not be dissolved in the oil phase, after ultrasonic dispersion, the oil phase can form emulsion, and nano-structure appears on the surface of the membrane when amidation reaction occurs in interfacial polymerization, the aim of adjusting the structure of the functional separation layer can be achieved by adjusting the respective concentration of the multi-acyl chloride monomer and the alcohols in the oil phase solution and the dosage proportion of the multi-acyl chloride monomer and the alcohols, and the nano-filtration membrane can obtain high separation capacity and water flux. Experiments prove that the method has the advantages of simple operation process, easily controlled technical parameters, better repeatability and low preparation cost, can greatly improve the performance of the nanofiltration membrane, and has ideal commercial application prospect.
In the invention, the permeable membrane base membrane material can be base membranes provided by any manufacturer, and the property difference and the type of the base membranes have no direct influence on the result of the invention, so that the commercially purchased polysulfone base membrane (or polyether sulfone, polyvinylidene fluoride or polytetrafluoroethylene base membrane) or the self-made base membrane can be selected. In the preparation method of the invention, raw materials of each component are easy to obtain, the preparation process is very simple, and any production link and process of the existing production line are not changed at all in the production process for production enterprises. Therefore, the preparation method provided by the invention has universal adaptability and is favorable for commercial popularization and application.
Drawings
FIG. 1 is an SEM image of the surface morphology and cross-section morphology of an alcohol modified composite nanofiltration membrane sample 1 prepared in example 2; wherein, (a) is 4 μm; (b) is 1 μm; (c) is 5 μm;
FIG. 2 is an SEM image of the surface morphology and cross-sectional morphology of the alcohol modified composite nanofiltration membrane sample 2 prepared in comparative example 2; wherein, (a) is 4 μm; (b) is 1 μm; (c) is 5 μm;
FIG. 3 is an infrared spectrum of polysulfone base film, oil phase and modified oil phase;
FIG. 4 is a graph showing the long-term stability test results of the alcohol-modified composite nanofiltration membrane sample 1 prepared in example 2.
Detailed Description
The invention is described in detail below in connection with specific embodiments for better understanding of the invention.
The embodiment of the invention provides a method for preparing a nanofiltration membrane by adopting a novel oil phase system, wherein a polyamide functional separation layer of the nanofiltration membrane is prepared by adopting an interfacial polymerization reaction, and an oil solution participating in the interfacial polymerization reaction is prepared according to the following method: the preparation of the oil phase raw solution is to fully dissolve the multi-component acyl chloride monomer in the oil phase solvent, respectively add alcohols into the dissolved oil phase raw solution to prepare the oil phase solution, and obtain the oil phase solution for interfacial polymerization after ultrasonic dispersion.
The preparation method of the invention has the design principle that: when the invention is used for preparing the oil phase solution, alcohols are added into the oil phase solution, and the alcohol hydroxyl can generate ester groups with acyl chloride groups, so that the polymerization reaction of the acyl chloride groups and amino groups is reduced, more amino groups are reserved on the surface of the membrane, and the charge of the surface of the membrane is enhanced. On the other hand, alcohols can not be dissolved in the oil phase, and after ultrasonic dispersion, the oil phase can be in a slightly turbid state (water-in-oil) and the contact area of water and oil is increased during interfacial polymerization reaction, so that the surface of the membrane can generate a nano structure.
The alcohol compound is affected by hydroxyl groups, intermolecular hydrogen bonds exist, and the physical properties of the alcohol are greatly different from those of corresponding hydrocarbons. According to the invention, the reagent containing the alcoholic hydroxyl group is added into the oil phase solution for the first time as the oil phase of the interfacial polymerization reaction, so that the number of acyl chloride groups can be reduced, and the oil phase is in a nano structure because alcohols are insoluble in alkane solvents, therefore, the aim of adjusting the structure of the functional separation layer can be achieved by adjusting the concentration of the reagent containing the alcoholic hydroxyl group and the dosage proportion of the acyl chloride monomer in the oil phase solution (nanometer microdroplets with different sizes and numbers are obtained), the compact functional separation layer with a controllable structure is formed, and the water flux of the nanofiltration membrane is improved while the high separation performance is obtained.
In order that the above-described aspects may be better understood, exemplary embodiments of the invention will be described in more detail below in connection with specific embodiments. The support layer of the permeable membrane backing material used in the following examples was polysulfone backing and polyethersulfone backing, the aqueous monomer used in the following examples was polyethyleneimine, the surfactant was sodium dodecyl sulfate, the oil solvent in the oil phase solution of the following examples was n-hexane, and the oil phase monomer was trimesoyl chloride.
Example 1
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of 1, 4-butanediol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. And then preparing a mixed aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven to obtain the nanofiltration film with a rough surface.
Example 2
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of 1, 4-butanediol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. And then preparing a mixed aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polyethersulfone bottom film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven to obtain the nanofiltration film with a rough surface.
Example 3
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of glycerol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. And then preparing a mixed aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Example 4
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of isopropanol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Example 5
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of polyethylene glycol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Example 6
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of water into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Example 7
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.4% of 1, 4-butanediol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven to obtain the nanofiltration film with a rough surface.
Example 8
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.6% of 1, 4-butanediol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate and 0.4% of PEI (polyethyleneimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Example 9
Preparing an oil phase solution containing 0.04% of trimesoyl chloride (TMC), adding 0.7% of 1, 4-butanediol into the dissolved oil phase raw solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction. Then preparing an aqueous phase solution containing 0.15% of sodium dodecyl sulfate, 0.2% of sodium carbonate and 0.4% of PEI (polyethylenimine). Firstly, coating an aqueous phase solution on a polysulfone base film, pouring out excessive aqueous phase solution after 180s, drying in the shade, coating an oil phase solution on the dried film, pouring out excessive oil phase solution after 90s, and performing heat treatment for 3min in a 70 ℃ oven.
Comparative example 1
In this comparative example, an oil phase solution was prepared without adding an alcohol modifier on the basis of example 1, and the other conditions and steps were the same as in example 1, thereby preparing a composite nanofiltration membrane. Through experimental tests, the retention rate of the prepared nanofiltration membrane to 2000PPm magnesium chloride is 96.9% at the highest, and the water flux is 27LMH at the highest, so that the nanofiltration membrane which is compact and has a smoother surface is obtained.
Comparative example 2
In this comparative example, an oil phase solution was prepared without adding an alcohol modifier on the basis of example 2, and the other conditions and steps were the same as in example 1, thereby preparing a composite nanofiltration membrane. Through experimental tests, the retention rate of the prepared nanofiltration membrane to 2000PPm magnesium chloride is 96.9% at the highest, and the water flux is 27LMH at the highest, so that the nanofiltration membrane which is compact and has a smoother surface is obtained.
Comparative example 3
In this comparative example, 1, 3-propane sultone was added to prepare an oil phase solution based on example 1, and other conditions and steps were the same as in example 1 to prepare a composite nanofiltration membrane. Through experimental tests, the retention rate of the prepared nanofiltration membrane to 2000PPm magnesium chloride is up to 99.2%, and the water flux is up to 32LMH. The 1, 3-propane sultone does not react with any substance, but can form a micro-nano structure, so that compared with the micro-nano structure, the effect of the alcohol hydroxyl reagent is not generated.
Comparative example 4
In this comparative example, on the basis of example 1, TMC (trimesic acid chloride) concentration was reduced to 0.01%, an oil phase solution was prepared, and the other conditions and steps were the same as in example 1, thereby preparing a composite nanofiltration membrane. Through experimental tests, the retention rate of the prepared nanofiltration membrane to 2000PPm magnesium chloride is up to 95.7%, and the water flux is up to 27LMH.
The membrane performance of the nanofiltration membranes prepared in the above examples and comparative examples was evaluated in terms of both "magnesium chloride desalination rate and water flux". In performance evaluation, except for example 2 and comparative example 2, the test pressure=0.5 MPa, the concentrate flow rate=1.0 GPM, the ambient temperature=25 ℃, and the concentrate refers to 2000ppm magnesium chloride aqueous solution. The test conditions used in example 2 and comparative example 2 were: test pressure = 0.5MPa, concentrate = 40L/h, ambient temperature = 25 ℃, and concentrate refers to 2000ppm magnesium chloride in water. In addition, for example 2, a long-term stability test was performed at a test pressure=0.5 MPa, a concentrate flow rate=40L/h, an ambient temperature=25 ℃, a feed solution was a mixed solution of magnesium chloride and lithium chloride having a content of 3000ppm, wherein the mass ratio of magnesium chloride to lithium chloride was 50:1, and a test time was 21 days.
In various embodiments, the desalination rate (rejection) is defined as the difference between the concentration of the concentrate and the produced water divided by the concentrate concentration; the water flux is defined as the water volume which penetrates through the composite separation membrane with unit area in unit time in the test process, and the unit is L/m 2 H (LMH). Each data point above was averaged from 9 samples.
The test results were as follows:
| maximum retention rate of magnesium chloride | Maximum water flux | |
| Example 1 | 96.5％ | 72LMH |
| Example 2 | 96.4％ | 56LMH |
| Example 3 | 96.4％ | 38LMH |
| Example 4 | 94.2％ | 36LMH |
| Example 5 | 97.1％ | 33LMH |
| Example 6 | 96.4％ | 44LMH |
| Example 7 | 97.9％ | 41LMH |
| Example 8 | 96.8％ | 61LMH |
| Example 9 | 95.2％ | 76LMH |
| Comparative example1 | 96.9％ | 27LMH |
| Comparative example 2 | 95.7％ | 20LMH |
| Comparative example 3 | 99.2％ | 32LMH |
| Comparative example 4 | 95.7％ | 27LMH |
It can be demonstrated by the above examples and comparative examples: the preparation method provided by the invention can ensure that the nanofiltration membrane maintains high retention rate and high water flux, and improves the uniformity and stability of the permeation performance of the nanofiltration membrane, and the method has good repeatability. From the above experimental results, in preparing the oil phase solution, the mass percentage concentration of the alcohol reagent in the oil phase solution is preferably 0.3% -0.8%, more preferably 0.5% -0.7%, respectively; the highest value of the water flux obtained at this time is the largest, and the highest rejection rate is also close to the largest value.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method for preparing a nanofiltration membrane by adopting a novel oil phase system is characterized in that an alcohol-containing hydroxyl reagent is added into an oil phase solution and subjected to ultrasonic dispersion, a turbid water-oil solution obtained after ultrasonic dispersion is used as an oil phase of interfacial polymerization reaction, a water phase solution dissolved with polyamine is used as a water phase of the interfacial polymerization reaction, and a polyamide functional separation layer of the nanofiltration membrane is prepared through the interfacial polymerization reaction; the oil phase monomer in the oil phase solution is a polybasic acyl chloride monomer; the aqueous phase also includes an anionic surfactant or a cationic surfactant.
2. The method for preparing the nanofiltration membrane by adopting the novel oil phase system as claimed in claim 1, wherein the purpose of adjusting the structure of the polyamide functional separation layer is achieved by adjusting the dosage proportion of the alcohol hydroxyl-containing reagent and the polybasic acyl chloride monomer in the oil phase solution to obtain nanometer microdroplets with different sizes and numbers.
3. The method for preparing nanofiltration membranes by adopting a novel oil phase system according to claim 1, wherein the alcohol hydroxyl group-containing reagent is one or more of isopropanol, glycerol, polyethylene glycol, 1, 4-butanediol, ethylene glycol methyl ether and water; the mass percentage of the alcohol hydroxyl-containing reagent in the oil phase solution is 0.2% -1%.
4. The method for preparing nanofiltration membranes by adopting a novel oil phase system according to claim 1, wherein the polybasic acyl chloride monomer is one or more of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; the mass percentage of the polybasic acyl chloride monomer in the oil phase solution is 0.02-1%; the solvent in the oil phase solution is one or more of Isopar L, n-hexane, cyclohexane, toluene and benzene.
5. The method for preparing nanofiltration membranes by adopting a novel oil phase system according to claim 1, wherein the ratio of the alcohol hydroxyl-containing reagent to the polybasic acyl chloride monomer in the oil phase solution is 4:1-20:1.
6. The method for preparing the nanofiltration membrane by adopting the novel oil phase system as claimed in claim 1, wherein the polyamine is one or more than two of polyethyleneimine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, diaminotoluene and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine in the water phase is 0.2-2%.
7. The method for preparing nanofiltration membranes by adopting a novel oil phase system as claimed in claim 1, wherein the preparation method of the oil phase is as follows: dissolving a polybasic acyl chloride monomer in a solvent of an oil phase, adding an alcohol-containing hydroxyl reagent which is insoluble in an alkane solvent into the oil phase solution, and performing ultrasonic dispersion to obtain an oil phase for interfacial polymerization reaction;
the interfacial polymerization reaction is realized in one of the following three ways:
firstly, coating an aqueous phase on a permeable membrane base membrane material, standing, removing an aqueous phase flowing on the permeable membrane base membrane material, coating an oil phase on the permeable membrane base membrane material coated with the aqueous phase, and obtaining a polyamide functional separation layer on the permeable membrane base membrane material after heat treatment;
soaking the permeable membrane base membrane material in a water phase, standing, taking out the permeable membrane base membrane material, coating an oil phase on the permeable membrane base membrane material covered with the water phase, and performing heat treatment to obtain a polyamide functional separation layer on the permeable membrane base membrane material;
and thirdly, soaking the permeable membrane bottom membrane material in the water phase, standing, taking out the permeable membrane bottom membrane material, soaking the permeable membrane bottom membrane material covered with the water phase in the oil phase for a period of time, taking out, and performing heat treatment to obtain the polyamide functional separation layer on the permeable membrane bottom membrane material.
8. The method for preparing nanofiltration membranes by adopting a novel oil phase system according to claim 7, wherein the coating mode is spraying, coating, dipping or soaking; the temperature of the heat treatment is 30-130 ℃, and the heat treatment is carried out until no oil phase liquid remains on the surface of the membrane.
9. The method for preparing a nanofiltration membrane by adopting a novel oil phase system according to claim 1, wherein the permeable membrane base membrane material comprises a non-woven fabric base material and a supporting layer, and the supporting layer is superposed on the surface of the non-woven fabric base material; the water phase and the oil phase are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is immersed in the water phase and the oil phase respectively in an upward way; wherein the material of the supporting layer is one of sulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
10. The method for preparing the nanofiltration membrane by adopting the novel oil phase system as claimed in claim 1, wherein the water phase further comprises an acid absorbent, and the mass percentage of the acid absorbent in the water phase is 0.1-1.5%; the mass percentage concentration of the anionic surfactant or the cationic surfactant is 0.1% -5%; the anionic surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium laurate, sodium camphorsulfonate and sodium citrate; the cationic surfactant is one or more of sodium dodecyl sulfate, dodecyl trimethyl ammonium chloride and dodecyl dimethyl benzyl ammonium chloride.
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