CN112808021A - Method for preparing reverse osmosis membrane by adopting novel water phase system - Google Patents
Method for preparing reverse osmosis membrane by adopting novel water phase system Download PDFInfo
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- CN112808021A CN112808021A CN202110061022.9A CN202110061022A CN112808021A CN 112808021 A CN112808021 A CN 112808021A CN 202110061022 A CN202110061022 A CN 202110061022A CN 112808021 A CN112808021 A CN 112808021A
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- phase solution
- water phase
- oil phase
- membrane
- permeable membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 91
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 37
- 239000008346 aqueous phase Substances 0.000 claims abstract description 36
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 19
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 113
- 239000000463 material Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 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 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000004952 Polyamide Substances 0.000 claims description 19
- 229920002647 polyamide Polymers 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920002492 poly(sulfone) Polymers 0.000 claims description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims description 14
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 13
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 4
- 229940082004 sodium laurate Drugs 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 150000007519 polyprotic acids 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 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
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate 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
- 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
- 230000004907 flux Effects 0.000 abstract description 14
- 125000000129 anionic group Chemical group 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000005063 solubilization Methods 0.000 abstract description 2
- 230000007928 solubilization Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 75
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 210000002469 basement membrane Anatomy 0.000 description 16
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for preparing a reverse osmosis membrane by adopting a novel water phase system, wherein the reverse osmosis membrane is prepared by adopting interfacial polymerization, and a water phase solution participating in the interfacial polymerization is prepared according to the following method: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction. On one hand, the invention utilizes the synergistic solubilization of the anion and cation surfactant compound system to improve the solubility and dispersion uniformity of the polyamine in the water phase. On the other hand, due to the unique existence state of the anionic and cationic surfactant complexing system in the water phase, the water phase can generate a nano structure, the purpose of adjusting the structure of the functional separation layer can be achieved by adjusting the respective concentration of the anionic and cationic surfactant in the water phase solution and the dosage ratio of the anionic and cationic surfactant in the water phase solution, and the reverse osmosis membrane can obtain high rejection rate and water flux.
Description
Technical Field
The invention relates to the technical field of sea water desalination or sewage treatment, in particular to a method for preparing a reverse osmosis membrane by adopting a novel water phase system.
Background
One of the most serious problems facing the 21 st century is the growing water pollution and the shortage of global fresh water resources. Seawater desalination and sewage recycling based on reverse osmosis technology are effective ways for increasing fresh water resources. The reverse osmosis membrane is an artificial semipermeable membrane with certain characteristics and is made by simulating a biological semipermeable membrane, and is a core component of a reverse osmosis technology. Currently, polyamide reverse osmosis composite membranes are the most advanced, efficient and widely used reverse osmosis membrane type. The polyamide reverse osmosis composite membrane generally comprises a non-woven fabric substrate, a polysulfone support layer and a polyamide compact functional separation layer. Wherein, the key layer for realizing material screening is a polyamide compact functional separation layer. The polyamide compact functional separation layer is generally prepared by interfacial polymerization reaction of polyamine monomer (dissolved in water phase) and polyacyl chloride monomer (dissolved in oil phase) through a water-oil interface, and the performance of the polyamide compact functional separation layer mainly depends on the dissolution degree and the dispersion uniformity of the polyamine monomer in the water phase. Although the performance of the reverse osmosis composite membrane is greatly improved after more than 30 years of development, the research and development of the reverse osmosis composite membrane with high flux and high rejection is still one of the main research and development directions in the field.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a reverse osmosis membrane by using a novel aqueous phase system, wherein the composition of the aqueous phase solution is adjusted to adjust the dissolution degree and dispersion uniformity of polyamine monomers in the aqueous phase solution, so as to form a compact functional separation layer with a controllable structure, thereby achieving the purpose of improving the water flux and rejection rate of the reverse osmosis membrane.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a method for preparing a reverse osmosis membrane using a novel aqueous system, wherein a polyamide functional separation layer of the reverse osmosis membrane is prepared by interfacial polymerization, and an aqueous solution participating in the interfacial polymerization is prepared as follows: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction.
Wherein the agitation mixing and/or sonication comprises: only stirring and mixing, only ultrasonic treatment, firstly stirring and then ultrasonic treatment, or firstly ultrasonic and then stirring; preferably, only mixing with stirring is performed.
According to a preferred embodiment of the present invention, an acid scavenger (acid scavenger) is further added to the aqueous solution. The acid scavenger is a weak base.
According to a preferred embodiment of the invention, the method further comprises: coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing (e.g. pouring) the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; or,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, and carrying out heat treatment to obtain the polyamide compact functional separation layer on the permeable membrane bottom membrane material.
It should be noted that the present invention is not limited to the above-mentioned coating method, and any method can be used to uniformly transfer (e.g., spray coating, dipping, soaking, etc.) the aqueous phase solution and the oil phase solution onto the permeable membrane base material.
According to the preferred embodiment of the invention, the bottom membrane material of the permeable membrane comprises a non-woven fabric substrate and a supporting layer, wherein the supporting layer is superposed on the surface of the non-woven fabric substrate; and the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode. Wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
According to the preferred embodiment of the invention, the anionic surfactant is one or a mixture of several of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium laurate, sodium camphor sulfonate and sodium citrate; the mass percentage concentration of the water phase solution is 0.1-5%.
According to the preferred embodiment of the invention, the cationic surfactant is one or a mixture of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and benzyl triethyl ammonium chloride; the mass percentage concentration of the water phase solution is 0.1-5%.
According to the preferred embodiment of the invention, the polyamine monomer is one or a mixture of more of m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine monomer in the aqueous phase is 0.1-3%.
According to a preferred embodiment of the present invention, the acid scavenger (acid scavenger) in the aqueous solution is an organic base, and the mass percentage of the organic base in water is 0.1-1.5%. The organic base is preferably triethylamine or diisopropylethylamine, more preferably diisopropylethylamine, which makes the aqueous solution more stable. Triethylamine has a certain probability of acylation with acyl and removal of an ethyl group. Diisopropylethylamine is more stable.
According to a preferred embodiment of the present invention, in the oil phase solution, the poly-acyl chloride monomer is one or a mixture of several of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; and the mass percentage of the oil phase solution is 0.1-2.0%. Preferably, the polybasic acid chloride monomer is trimesoyl chloride (TMC). More preferably, the mass percentage of trimesoyl chloride (TMC) in the oil phase solution is 0.1-1.5%.
According to a preferred embodiment of the present invention, in the oil phase solution dissolved with the polybasic acid chloride monomer, the oil phase solvent is one or a mixture of Isopar L (1 isoparaffin solvent), n-hexane, cyclohexane, toluene and benzene.
According to the preferred embodiment of the present invention, the heat treatment condition is a temperature of 100 ℃ to 130 ℃; the preferred temperature is 110 ℃ to 130 ℃.
(III) advantageous effects
The invention has the technical effects that: by an interfacial polymerization method, in the reaction process, on one hand, the solubility and dispersion uniformity of the polyamine in the water phase are improved by utilizing the synergistic solubilization of a compound system of the anionic and cationic surfactants, the variety range of the polyamine which can be used is expanded, the consumption of the polyamine monomer in the water phase solution is reduced, and the uniform polyamide functional separation layer and the reverse osmosis membrane with stable membrane performance are obtained; on the other hand, due to the unique existence state of the complex system of the anionic and cationic surfactants in the water phase, the water phase can generate a nano structure (micelle, vesicle and the like), the structure of the functional separation layer can be adjusted by adjusting the respective concentration of the anionic and cationic surfactants in the water phase solution and the dosage ratio of the anionic and cationic surfactants, and the reverse osmosis membrane can obtain high rejection rate and water flux. Repeated experiments prove that the method has simple operation process, easily controlled technical parameters, better reproducibility and low preparation cost, and can greatly improve the performance of the reverse osmosis composite membrane, thereby having ideal commercial application prospect.
In the invention, the permeable membrane basement membrane material can be any basement membrane provided by manufacturers, and the performance difference of the basement membrane and the type of the basement membrane have no direct influence on the result of the invention, so that commercially purchased polysulfone basement membrane (or polyether sulfone, polyvinylidene fluoride or polytetrafluoroethylene basement membrane) or self-made basement membrane can be selected. In the preparation method, the raw materials of the components are easy to obtain, and the raw materials used in the aqueous phase solution are very easy to dissolve in water, so that the preparation process is very simple, and for production enterprises, any production link and process of the existing production line are not required to be changed completely in the production process. Therefore, the preparation method has universal adaptability and is beneficial to commercial popularization and application.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail below with reference to specific embodiments.
The embodiment of the invention provides a method for preparing a reverse osmosis membrane by adopting a novel water phase system, wherein a polyamide functional separation layer of the reverse osmosis membrane is prepared by adopting interfacial polymerization, and a water phase solution participating in the interfacial polymerization is prepared according to the following method: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction.
When the metal nanoparticle hybrid reverse osmosis membrane is prepared, the following steps can be designed according to the idea of the invention:
step 1: preparing an aqueous phase solution:
and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous solution containing the polyamine monomer and the acid absorbent together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous solution for the interfacial polymerization reaction.
Step 2: polymerizing to obtain polyamide functional separation layer
Coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing (such as pouring) the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment (the heat treatment promotes the polymerization reaction of the polybasic acyl chloride monomer and the polybasic acyl chloride monomer to generate polyamide) to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; or,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material, or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, carrying out heat treatment (promoting the polyreaction of the polyamine monomer and the polybasic acyl chloride monomer to generate polyamide), and then obtaining a polyamide compact functional separation layer on the permeable membrane bottom membrane material.
Wherein, the membrane material of the bottom of the permeable membrane can be purchased or self-made in the market. The permeable membrane base membrane material comprises a non-woven fabric base material and a supporting layer, wherein the supporting layer is superposed on the surface of the non-woven fabric base material; and the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode. Wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
The design principle of the preparation method of the invention is as follows: when the aqueous phase solution is prepared, a compound system of the anionic and cationic surfactants is added into the aqueous phase solution to solubilize the polyamine monomer together. The strong electrostatic action exists between the anionic surfactant and the cationic surfactant, so that the anionic surfactant and the cationic surfactant have high surface activity which is incomparable with a single surfactant, namely, the complex systems of the anionic surfactant and the cationic surfactant have good synergistic effect on the performance of reducing the surface tension of an aqueous solution.
The invention utilizes the aqueous phase solution with the anionic and cationic surfactant complex system as the aqueous phase of the interfacial polymerization reaction for the first time, not only can play a role in enhancing the dissolution of polyamine monomers, but also can enable the aqueous phase to have a nano structure (micelle, vesicle and the like) due to the existence of the complex system, so the structure of the functional separation layer can be adjusted by adjusting the respective concentration of the anionic and cationic surfactants in the aqueous phase solution and the dosage proportion of the anionic and cationic surfactants (obtaining nano micelles or vesicles with different sizes and quantities and the like), thereby being beneficial to forming the compact functional separation layer with a controllable structure, and improving the water flux of the reverse osmosis composite membrane while obtaining high rejection rate.
In order to better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below with reference to specific embodiments. The bottom membrane material of the permeable membrane used in the following examples is a polysulfone bottom membrane, which is a self-made bottom membrane, and the performance of the bottom membrane is consistent with that of a commercially available bottom membrane product. The film production date was less than 30 days to the experimental date, during which time it was stored in 2% aqueous sodium bisulfite. Before the interfacial reaction is carried out to prepare the composite membrane, the polysulfone base membrane is soaked in pure water 24 hours in advance. The oil solvent in the oil phase solution of each of the following examples was Isopar L.
Example 1
A mixed aqueous solution containing 0.5 mass% of sodium lauryl sulfate and 0.5 mass% of dodecyltrimethylammonium chloride (anionic surfactant: cationic surfactant =1: 1) was prepared, and 1 mass% of MPD (m-phenylenediamine) and 0.2 mass% of triethylamine were added and mixed uniformly. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 2
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium benzenesulfonate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 120 ℃ oven.
Example 3
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 4
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of hexadecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 5
Preparing a mixed aqueous solution containing 0.5 mass percent of sodium laurate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of triethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 6
A mixed aqueous solution containing 1.0 mass% of sodium dodecyl sulfate and 1.0 mass% of dodecyltrimethylammonium chloride (anionic surfactant: cationic surfactant =1: 1) was prepared, and then 1 mass% of MPD and 0.2 mass% of triethylamine were added and mixed uniformly. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 7
Preparing a mixed aqueous solution containing 1.0 mass percent of sodium benzenesulfonate and 1.0 mass percent of dodecyl dimethyl benzyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Example 8
Preparing a mixed aqueous solution containing 1.5 mass percent of sodium dodecyl sulfate and 0.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =3: 1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 120 ℃ oven.
Example 9
Preparing a mixed aqueous solution containing 1.5 mass percent of sodium laurate and 1.5 mass percent of dodecyl trimethyl ammonium chloride (anionic surfactant: cationic surfactant =1: 1), adding 1 mass percent of MPD and 0.2 mass percent of diisopropylethylamine, and uniformly mixing. Then preparing trimesoyl chloride (TMC) oil phase solution with the mass fraction of 0.2 percent. Firstly coating the polysulfone basement membrane with the aqueous phase solution, pouring off the redundant solution after 60s, drying in the shade, coating the oil phase solution on the dried membrane in the shade, pouring off the redundant oil phase solution after 30s, and carrying out heat treatment for 2min in a 130 ℃ oven.
Comparative example 1
In the comparative example, an aqueous solution was prepared without adding a complex system of an anionic surfactant and an anionic surfactant on the basis of example 1, and a reverse osmosis membrane was prepared under the same conditions and in the same steps as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.7% at most, and the water flux is 53LMH at most.
Comparative example 2
In this comparative example, an aqueous phase solution was prepared by adding 1% by mass of dodecyltrimethylammonium chloride (cationic surfactant) to an aqueous phase based on example 1, and a reverse osmosis membrane was prepared under the same conditions and in the same manner as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.5% at most, and the water flux is 51LMH at most.
Comparative example 3
In this comparative example, a reverse osmosis membrane was prepared in the same manner as in example 1 except that 1 mass% sodium lauryl sulfate (anionic surfactant) was added to the aqueous phase alone, the mass% of MPD was 1.5%, and the other conditions and steps were the same as in example 1. Through experimental tests, the rejection rate of the prepared reverse osmosis membrane to 500PPm sodium chloride is 98.9% at most, and the water flux is 55LMH at most.
The membrane performance of the nano hybrid reverse osmosis membrane prepared in each example and comparative example is evaluated from two aspects of sodium chloride desalination rate and water flux. When the performance is evaluated, the test pressure is =0.75MPa, the flow rate of concentrated water is =1.0 GPM, the environmental temperature is =25 ℃, the pH value of the concentrated water is =6.5-7.5, and the concentrated water refers to a 500ppm sodium chloride aqueous solution.
In each example, the rejection (rejection) is defined as the difference between the concentrations of concentrate and product water divided by the concentrate concentration; the water flux is defined as the volume of water per unit time that permeates the composite separation membrane per unit area in the above test procedure and is expressed in L/m2H (LMH). Each data point above was averaged from 9 samples.
The test results were as follows:
| maximum retention of sodium chloride | Maximum water flux | |
| Example 1 | 99.5% | 72LMH |
| Example 2 | 99.3% | 66LMH |
| Example 3 | 99.5% | 61LMH |
| Example 4 | 99.3% | 67LMH |
| Example 5 | 99.6% | 58LMH |
| Example 6 | 99.5% | 70LMH |
| Example 7 | 99.3% | 69LMH |
| Example 8 | 99.4% | 74LMH |
| Example 9 | 99.5% | 66LMH |
| Comparative example 1 | 98.7% | 53LMH |
| Comparative example 2 | 98.5% | 51LMH |
| Comparative example 3 | 98.9% | 55LMH |
The examples and comparative examples described above demonstrate that: the preparation method of the invention can ensure that the nano hybrid reverse osmosis membrane keeps high water flux while keeping high rejection rate, improves the uniformity and stability of the permeability of the reverse osmosis membrane and has good reproducibility. In addition, in the case of using only an anionic surfactant or only a cationic surfactant, the rejection rate and water flux of the prepared reverse osmosis membrane are significantly reduced even though the amount of the anionic/cationic surfactant is equal to the total amount of the two ionic surfactants used simultaneously. From the above experimental results, in the preparation of the aqueous solution, the mass percentage concentrations of the anionic and cationic surfactants in water are preferably 0.5% -2%, and more preferably 1-1.5%; in addition, the compounding ratio (mass ratio) of the anionic surfactant and the cationic surfactant is preferably 1:1-3:1, more preferably 3:1, the highest value of the obtained water flux is the largest, and the highest retention rate is close to the maximum value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a reverse osmosis membrane by using a novel aqueous phase system is characterized in that a polyamide functional separation layer of the reverse osmosis membrane is prepared by adopting interfacial polymerization reaction, and an aqueous phase solution participating in the interfacial polymerization reaction is prepared according to the following method: and (2) forming a compound system by the anionic surfactant and the cationic surfactant according to a proportion, adding the compound system into the aqueous phase solution containing the polyamine monomer together, and stirring, mixing and/or ultrasonically dispersing to obtain the aqueous phase solution for the interfacial polymerization reaction.
2. The method according to claim 1, wherein an acid scavenger is further added to the aqueous solution.
3. The method of claim 2, further comprising: coating the prepared water phase solution on a bottom membrane material of a permeable membrane, standing for a period of time, removing the water phase solution flowing on the bottom membrane material of the permeable membrane, coating an oil phase solution dissolved with a polybasic acyl chloride monomer on the bottom membrane material of the permeable membrane, and performing heat treatment to obtain a polyamide compact functional separation layer on the bottom membrane material of the permeable membrane; or,
soaking a permeable membrane bottom membrane material in a water phase solution, standing for a period of time, taking out the permeable membrane bottom membrane material, coating an oil phase solution in which a polybasic acyl chloride monomer is dissolved on the permeable membrane bottom membrane material or soaking the permeable membrane bottom membrane material in the oil phase solution in which the polybasic acyl chloride monomer is dissolved for a period of time, taking out, and carrying out heat treatment to obtain the polyamide compact functional separation layer on the permeable membrane bottom membrane material.
4. The method according to claim 3, wherein the bottom membrane material of the permeable membrane comprises a non-woven fabric substrate and a support layer, wherein the support layer is laminated on the surface of the non-woven fabric substrate; the water phase solution and the oil phase solution are coated on the supporting layer, or the supporting layer of the permeable membrane bottom membrane material is sequentially and respectively soaked in the water phase solution and the oil phase solution in an upward mode; wherein, the supporting layer is made of one of polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile.
5. The method of claim 1, wherein 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%.
6. The method according to claim 1 or 5, wherein the cationic surfactant is one or a mixture of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and benzyl triethyl ammonium chloride; the mass percentage concentration of the water phase solution is 0.1-5%.
7. The method according to claim 1, wherein the polyamine monomer is one or more of m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene, and 2, 5-dimethylpiperazine, and the mass percentage of the polyamine monomer in the aqueous phase is 0.1-3%.
8. The method according to claim 2, wherein the acid scavenger in the aqueous solution is an organic base, and the mass percentage of the acid scavenger in water is 0.1-1.5%.
9. The method according to claim 1, wherein in the oil phase solution, the polybasic acyl chloride monomer is one or a mixture of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride; and the mass percentage of the oil phase solution is 0.1-2.0%.
10. The method according to claim 9, wherein in the oil phase solution dissolved with the polybasic acid chloride monomer, the oil phase solvent is Isopar L (1 isoalkane solvent), n-hexane, cyclohexane, toluene and benzene, or a mixture of several of Isopar L (1 isoalkane solvent), n-hexane, cyclohexane, toluene and benzene;
the heat treatment condition is that the temperature is 100-130 ℃; the preferred temperature is 110 ℃ to 130 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973463A (en) * | 2021-05-20 | 2021-06-18 | 蓝星（杭州）膜工业有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN113786738A (en) * | 2021-08-26 | 2021-12-14 | 同济大学 | Method for recycling scrapped low-pressure membrane based on interface wettability regulation and control and polyamide nanofiltration membrane prepared by method |
| CN114669194A (en) * | 2021-12-27 | 2022-06-28 | 浙江易膜新材料科技有限公司 | Preparation method of single-multivalent ion high-resolution nanofiltration membrane |
| CN115770491A (en) * | 2022-12-13 | 2023-03-10 | 蓝星（杭州）膜工业有限公司 | High-flux composite membrane and preparation method thereof |
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| CN116943461A (en) * | 2023-06-21 | 2023-10-27 | 广东工业大学 | Nanofiltration membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569308A (en) * | 2018-11-16 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane |
| CN109647199A (en) * | 2018-12-20 | 2019-04-19 | 时代沃顿科技有限公司 | A kind of preparation method of reverse osmosis membrane and thus obtained reverse osmosis membrane |
| CN109999665A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | Lotus positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN109999666A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN111111475A (en) * | 2020-01-15 | 2020-05-08 | 南京工业大学 | Preparation method of graphene oxide modified triptycenyl polyamide separation membrane |
-
2021
- 2021-01-18 CN CN202110061022.9A patent/CN112808021B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569308A (en) * | 2018-11-16 | 2019-04-05 | 杭州水处理技术研究开发中心有限公司 | A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane |
| CN109647199A (en) * | 2018-12-20 | 2019-04-19 | 时代沃顿科技有限公司 | A kind of preparation method of reverse osmosis membrane and thus obtained reverse osmosis membrane |
| CN109999665A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | Lotus positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN109999666A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application |
| CN111111475A (en) * | 2020-01-15 | 2020-05-08 | 南京工业大学 | Preparation method of graphene oxide modified triptycenyl polyamide separation membrane |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973463A (en) * | 2021-05-20 | 2021-06-18 | 蓝星（杭州）膜工业有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN113786738A (en) * | 2021-08-26 | 2021-12-14 | 同济大学 | Method for recycling scrapped low-pressure membrane based on interface wettability regulation and control and polyamide nanofiltration membrane prepared by method |
| CN114669194A (en) * | 2021-12-27 | 2022-06-28 | 浙江易膜新材料科技有限公司 | Preparation method of single-multivalent ion high-resolution nanofiltration membrane |
| CN115814609A (en) * | 2022-12-05 | 2023-03-21 | 蓝星（杭州）膜工业有限公司 | High-yield decolorizing membrane for treating printing and dyeing wastewater and preparation method thereof |
| CN115814609B (en) * | 2022-12-05 | 2023-09-26 | 蓝星（杭州）膜工业有限公司 | High-water-yield decolorizing film for treating printing and dyeing wastewater and preparation method thereof |
| CN115770491A (en) * | 2022-12-13 | 2023-03-10 | 蓝星（杭州）膜工业有限公司 | High-flux composite membrane and preparation method thereof |
| CN115770491B (en) * | 2022-12-13 | 2024-07-23 | 蓝星（杭州）膜工业有限公司 | High-flux composite membrane and preparation method thereof |
| CN116943461A (en) * | 2023-06-21 | 2023-10-27 | 广东工业大学 | Nanofiltration membrane and preparation method and application thereof |
| CN116943461B (en) * | 2023-06-21 | 2024-01-09 | 广东工业大学 | Nanofiltration membrane and preparation method and application thereof |
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