CN105148750B - A kind of method that polyamide composite film surface is modified - Google Patents
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- CN105148750B CN105148750B CN201510518201.5A CN201510518201A CN105148750B CN 105148750 B CN105148750 B CN 105148750B CN 201510518201 A CN201510518201 A CN 201510518201A CN 105148750 B CN105148750 B CN 105148750B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 229920002647 polyamide Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 4
- 150000005524 benzylchlorides Chemical class 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical class BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical class BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 5
- 238000011109 contamination Methods 0.000 abstract description 4
- 238000001728 nano-filtration Methods 0.000 abstract description 4
- 238000011033 desalting Methods 0.000 abstract description 2
- 238000001223 reverse osmosis Methods 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 150000002460 imidazoles Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 150000003222 pyridines Chemical class 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 12
- 230000004907 flux Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000012510 hollow fiber Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 241001044369 Amphion Species 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000768 polyamine Chemical group 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of method that polyamide composite film surface is modified.Comprise the following steps：（1）By the copolymer dissolving containing nitrogen heterocycle perssads such as imidazoles, pyridines in a solvent, it is made into coating liquid；（2）Polyamide composite film to be modified is immersed in coating liquid after a period of time, dried after taking-up, coat is formed on film surface；（3）Polyamide composite film after surface is coated carries out the quaternized crosslinking Treatment in surface, and azacyclo- amphoteric ion polymer gel layer is formed on film surface.The contamination resistance and anti-chlorine performance of the modified polyamide composite film in surface are significantly increased, and extend service life of the polyamide composite film in the application such as nanofiltration separation and reverse osmosis seawater desalting.Present invention process is simple, reaction condition is gentle, and the combination property to improvement polyamide composite film is significant.
Description
Technical field
The invention belongs to functional material and technical field of membrane separation, it is related to the side that a kind of polyamide composite film surface is modified
Method.
Background technology
UF membrane is that occur in early 20th century, the new technology emerged rapidly after 1960s.Membrane separation technique
Both separation, concentration, purifying and refined function had been had concurrently, have again efficiently, energy-saving and environmental protection, molecular level filtering and filter process it is simple,
The feature such as easily controllable.At present, membrane separation technique be widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy,
The field such as the energy, oil, water process, electronics, bionical, generates huge economic benefit and social benefit, as current separation
One of most important means in science.
The PA membrane generated based on interfacial polymerization is one of the most frequently used material of composite membrane selection layer, and it possesses height
Retention, the advantage such as high flux and relatively low operating pressure is had been used at drink water purifying, desalinization, environmental wastewater
Reason, catalyst separates the every field such as circulation.
However, the nanofiltration separation driven for relative high pressure, one needs the major issue solved to be fouling membrane.Film
Pollution refers to particle, colloid, macromolecular, the deposition on film surface or fenestra inwall such as salt.Pollutant is broadly divided into inorganic, has
Machine, biological three major types.In the process of running, the pollutant such as protein or colloidal particle passes through the hydrophobic phase interaction with film surface to film
With, be firmly adsorbed on inside film surface or fenestra, cause membrane flux temporary or it is permanent decay cause membrane lifetime to reduce.
In addition, before using nanofiltration membrane separation, due to containing more bacterial micro-organism in feeding liquid, it will usually using addition oxygen
The mode of agent such as sodium hypochlorite is pre-processed to feeding liquid.There is the work sensitive to Active Chlorine attack yet with polyamide
Property site, therefore its chlorine-resistant property is very poor, the Active Chlorine remained in material liquid can heavy damage composite membrane polyamide selection layer
The Orton of chlorination on the chlorination of structure, such as amido link, aromatic rings is reset, and causes the destruction of polyamide interchain hydrogen bond, strand structure
The transformation of elephant, the increase of film surface hydrophobic is eventually even the fracture of amido link, under making the separating property of composite membrane greatly
Drop, reduces its service life.Common business polyamide composite film requires that the active chlorine concentrations in material liquid are less than 0.1ppm, and
Further pretreatment to the removal chlorine residue of stoste then can additionally increase the operating cost of separation process.Therefore, while improving film
Antipollution and chlorine-resistant property it is imperative.
Generally improve film antifouling property be to be coated by surface, surface grafting, blending etc. physico-chemical process to
The hydrophily of film is improved, reduces the roughness and change film surface charge distribution of film to realize.As patent CN101462024 is carried
Go out and polyamide composite film coated into PVA solution, and form PVA anti-soils layer to the mode that it is crosslinked, with improve film water flux and
Contamination resistance.Recent study shows, introduces amphion, by itself and water formation water and ion, can improve the parent of film
Aqueous energy, and the absorption of protein is effectively hindered, substantially increase the antifouling property of film.Such as An using amphion as
A kind of aqueous phase monomers, by carrying out interfacial polymerization with oil phase monomer TMC, prepare the Nano filtering composite membrane of the high anti-soil of high flux.It is right
In the chlorine-resistant property for improving film, typically such as change monomeric species, grafting or painting to Active Chlorine sensitivity site by eliminating or protecting
The means for covering protection sacrifice layer are realized.Such as patent CN104023830A, using comprising with epoxy-terminated fluorine compounds and
Polyamine forms aqueous phase monomers layer, by making oil-phase solution and the aqueous phase monomers as aqueous phase solution on porous supporting body
Layer contact, forms the aramid layer for including fluorine compounds, has obtained the aramid layer of the high chlorine-resistant property of high flux.However, at present
Not yet occur by introducing azacyclo- amphion gel layer while improving the report of polyamide composite film antipollution and chlorine-resistant property
Road.
The content of the invention
There is provided a kind of method that polyamide composite film surface is modified for existing technical problem by the present invention.Skill of the present invention
Art plan explanation is as follows：
A kind of method that polyamide composite film surface is modified, comprises the following steps：
（1）Azepine cyclopolymer is dissolved in deionized water, the mass percentage concentration of azepine cyclopolymer for 0.01% ~
10%, it is configured to the coating liquid of stable homogeneous；
（2）By quaternizing agent dissolving in a solvent, the mass percentage concentration of quaternizing agent is 0.1% ~ 10%, is obtained
Quaterisation liquid；
（3）Polyamide composite film is soaked in coating liquid and taken out after 1 ~ 24 hour, deionized water thoroughly cleaning is used, in sky
Dried in gas；
（4）Polyamide composite film after surface is coated soaks in quaterisation liquid, carries out cross-linking reaction 1 ~ 48
Hour, reaction temperature be 30 ~ 70 C, film surface formed bisexual ion purification azacyclo- polymer gel, finally spend from
Polyamide composite film thoroughly cleaning is obtained the polyamide composite film of surface modification by sub- water.
Described polyamide composite film is shaped as Flat Membrane or hollow-fibre membrane.
Described azacyclo- copolymer is poly-（N- vinyl imidazoles-acrylic acid）, it is poly-（N- vinyl imidazole -2- acryloyls
Amine -2- methyl propane sulfonic acids）, it is poly-（2- vinylpyridines-acrylic acid）Or it is poly-（N- vinylpyridine -2- acrylamide -2- methyl-props
Sulfonic acid）；
Described quaternizing agent is for 1,3- dibromopropanes, 1,4- dibromobutanes or to two benzyl chlorides.
Described solvent is methanol, ethanol, n-hexane or normal heptane.
The contamination resistance and anti-chlorine performance of the modified polyamide composite film in surface are significantly increased, and are extended polyamide and are combined
Service life of the film in the application such as nanofiltration separation and reverse osmosis seawater desalting.Present invention process is simple, reaction condition is gentle, right
The combination property for improving polyamide composite film is significant.
Embodiment
Examples below will make more detailed description to the present invention, but the embodiment does not constitute the limit to the present invention
System.Associated from present disclosure or derived all deformations, be considered protection scope of the present invention.
Comparative example 1
Using former polyamide flat composite membrane as comparative example 1, the performances such as its flux retention are tested respectively.
Comparative example 2
Using the hollow composite membrane of former polyamide as comparative example 2, the performances such as its flux retention are tested respectively.
Embodiment 1
Will be poly-（N- vinyl imidazoles-acrylic acid）In deionized water, it is 0.01% to be configured to mass percentage concentration for dissolving
Stable homogeneous coating liquid.Polyamide flat composite membrane is soaked in coating liquid and taken out after 1 hour, it is thorough with deionized water
Cleaning, dries in atmosphere；
By the dissolving of 1,3- dibromopropanes in methyl alcohol, the quaterisation liquid that mass percentage concentration is 0.1% is obtained, will
Polyamide flat composite membrane after the coating of surface soaks in quaterisation liquid, carries out cross-linking reaction 1 hour, reaction temperature
For 30 C, the azacyclo- polymer gel of bisexual ion purification is formed on film surface, finally with deionized water by polyamide flat board
Composite membrane thoroughly cleaning, obtains the polyamide flat composite membrane of surface modification.
Embodiment 2
Will be poly-（N- vinyl imidazole -2- acrylamide-2-methyl propane sulfonics）Dissolving in deionized water, is configured to quality
Percentage concentration is the coating liquid of 1% stable homogeneous.Taken after polyamide hollow fiber composite membrane is soaked into 6 hours in coating liquid
Go out, use deionized water thoroughly cleaning, dry in atmosphere；
By Isosorbide-5-Nitrae-dibromobutane dissolving in ethanol, the quaterisation liquid that mass percentage concentration is 0.5% is obtained, will
Polyamide hollow fiber composite membrane after the coating of surface soaks in quaterisation liquid, carries out cross-linking reaction 12 hours, reaction
Temperature is 50 C, and the azacyclo- polymer gel of bisexual ion purification is formed on film surface, finally with deionized water by polyamide
Hollow fiber composite membrane thoroughly cleaning, obtains the polyamide hollow fiber composite membrane of surface modification.
Embodiment 3
Will be poly-（N- vinylpyridines-acrylic acid）Dissolving in deionized water, be configured to mass percentage concentration for 5% it is equal
One stable coating liquid.Polyamide flat composite membrane is soaked in coating liquid and taken out after 12 hours, it is thoroughly clear with deionized water
Wash, dry in atmosphere；
Two benzyl chlorides will be dissolved in n-hexane, and the quaterisation liquid that mass percentage concentration is 5% be obtained, by surface
Polyamide flat composite membrane after coating soaks in quaterisation liquid, carries out cross-linking reaction 24 hours, and reaction temperature is 40
C, the azacyclo- polymer gel of bisexual ion purification is formed on film surface, finally with deionized water by polyamide plate compounding
Film thoroughly cleaning, obtains the polyamide flat composite membrane of surface modification.
Embodiment 4
Will be poly-（N- vinylpyridine -2- acrylamide-2-methyl propane sulfonics）Dissolving in deionized water, is configured to quality
Percentage concentration is the coating liquid of 10% stable homogeneous.Polyamide hollow fiber composite membrane is soaked after 24 hours in coating liquid
Take out, use deionized water thoroughly cleaning, dry in atmosphere；
Two benzyl chlorides will be dissolved in normal heptane, and the quaterisation liquid that mass percentage concentration is 10% be obtained, by surface
Polyamide hollow fiber composite membrane after coating soaks in quaternary ammonium reaction liquid, carries out cross-linking reaction 48 hours, reaction temperature
For 70 C, the azacyclo- polymer gel of bisexual ion purification is formed on film surface, it is finally with deionized water that polyamide is hollow
Composite fiber membrane thoroughly cleaning, obtains the polyamide hollow fiber composite membrane of surface modification.
Film properties test：
Water flux and salt rejection rate：Film is tested by cross-flow devices, flux is the film of unit area in unit
The volume of the interior water passed through, unit L/m2H, salt rejection rate is penetrating fluid and the ratio of stoste electrical conductivity.Test condition：Charging
Liquid is water or 2000 ppm magnesium sulfate solutions, and operation temperature is 25 C, and operating pressure is 0.4 MPa, and pH value of solution is 7.0.
Antipollution is tested：The parameter of polyamide composite film antifouling property is evaluated by resistance to protein contamination.Filled with cross-flow
Test 100ppm BSA and 2000ppm magnesium sulfate mixed solutions, membrane flux after test run 12 hours are put, and is calculated under membrane flux
Drop rate.
Chlorine-resistant property is tested：With 2000ppm aqueous sodium hypochlorite solution, with the hydrochloric acid solution that molar fraction is 1 mol/L
Aqueous sodium hypochlorite solution pH is adjusted to 4.0, is taken out after composite membrane is soaked 40 hours, is used deionized water thoroughly cleaning, evaluate it
Water flux and salt rejection rate.
Table 1 lists antipollution chlorine-resistant polyamide prepared by the compound nanometer filtering membrane of polyamide and embodiment 1 ~ 4 of comparative example 1
The antipollution and chlorine-resistant property of Nano filtering composite membrane.
Table 1
。
Claims (5)
1. a kind of method that polyamide composite film surface is modified, it is characterised in that comprise the following steps：
（1）Azepine cyclopolymer is dissolved in deionized water, the mass percentage concentration of azepine cyclopolymer is 0.01% ~ 10%,
It is configured to the coating liquid of stable homogeneous；
（2）By quaternizing agent dissolving in a solvent, the mass percentage concentration of quaternizing agent is 0.1% ~ 10%, obtains quaternary ammonium
Change reaction solution；
（3）Polyamide composite film is soaked in coating liquid and taken out after 1 ~ 24 hour, deionized water thoroughly cleaning is used, in atmosphere
Dry；
（4）Polyamide composite film after surface is coated soaks in quaterisation liquid, carries out cross-linking reaction 1 ~ 48 hour,
Reaction temperature is 30 ~ 70 C, and the azacyclo- polymer gel of bisexual ion purification is formed on film surface, finally will with deionized water
Polyamide composite film thoroughly cleaning, obtains the polyamide composite film of surface modification.
2. the method that a kind of polyamide composite film surface according to claim 1 is modified, it is characterised in that described polyamides
Amine composite membrane is shaped as Flat Membrane or hollow-fibre membrane.
3. the method that a kind of polyamide composite film surface according to claim 1 is modified, it is characterised in that described azepine
Ring copolymer is poly-（N- vinyl imidazoles-acrylic acid）, it is poly-（N- vinyl imidazole -2- acrylamide-2-methyl propane sulfonics）, it is poly-
（2- vinylpyridines-acrylic acid）Or it is poly-（N- vinylpyridine -2- acrylamide-2-methyl propane sulfonics）.
4. the method that a kind of polyamide composite film surface according to claim 1 is modified, it is characterised in that described quaternary ammonium
Change reagent is for 1,3- dibromopropanes, 1,4- dibromobutanes or to two benzyl chlorides.
5. the method that a kind of polyamide composite film surface according to claim 1 is modified, it is characterised in that described solvent
For methanol, ethanol, n-hexane or normal heptane.
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| CN106268375B (en) * | 2016-08-14 | 2018-09-11 | 太原市晋华恒远科技有限公司 | A kind of preparation method of ion liquid functionalization polyphenylene sulfide porous film |
| CN108114612B (en) * | 2016-11-26 | 2021-04-20 | 中国科学院大连化学物理研究所 | Layered MOF nanosheet composite membrane |
| CN110354692B (en) * | 2018-04-10 | 2021-09-14 | 武汉大学深圳研究院 | Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer |
| CN113720761B (en) * | 2021-09-09 | 2023-07-14 | 东风汽车集团股份有限公司 | Method for testing chlorine resistance of polyamide automobile parts |
| CN114053886A (en) * | 2021-11-18 | 2022-02-18 | 万华化学集团股份有限公司 | Polyamide composite reverse osmosis membrane and preparation method thereof |
| CN115121126B (en) * | 2022-07-18 | 2023-07-25 | 中国科学院赣江创新研究院 | Structure for regulating and controlling interfacial polymerization nanofiltration membrane by using rare earth recovery hydrogel layer and preparation method of structure |
| CN115228291B (en) * | 2022-08-10 | 2024-06-25 | 万华化学集团股份有限公司 | Anti-pollution, antibacterial and high-flux reverse osmosis membrane and preparation method and application thereof |
| CN115414791B (en) * | 2022-08-15 | 2024-04-19 | 华中科技大学 | Surface quaternization modified nanofiltration membrane, preparation and application of surface quaternization modified nanofiltration membrane in separation of magnesium and lithium in salt lake |
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| CN101530748B (en) * | 2009-03-17 | 2012-07-11 | 郑州大学 | Method for preparing composite charged mosaic membrane via interfacial polymerization |
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