CN110496533A - A kind of high-performance Nano filtering composite membrane containing polymer coating - Google Patents
A kind of high-performance Nano filtering composite membrane containing polymer coating Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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Abstract
The present invention relates to one kind to have polymer coating nanofiltration membrane preparation method, introduces polymer coating in open support film surface；Then the volatilization of solvent is carried out；Then interface polymerization reaction is carried out on the backing material containing polymer coating, monomer used by interfacial polymerization is respectively polyamine and polynary acyl chlorides, after interface polymerization reaction, carries out thermal crosslinking treatment；The open support layer material used, using following high polymer materials, such as ceramic materials such as polysulfones, polyether sulfone, polyether-ether-ketone, polycarbonate, Kynoar, polyacrylonitrile, polyethylene, polypropylene or inorganic porous materials such as aluminum oxide, titanium dioxide；Or it introduces before the polymer coating and first carries out the interface polymerization reaction in the open support film surface.So as to overcome the See-saw effect of nanofiltration, reverse osmosis permeability of the membrane and cutoff performance, the nanofiltration membrane of high permeability, high rejection is obtained.This method has the advantages that low cost, implementation are simple, has great importance to the extensive use and circular economy of membrane material.
Description
Technical field
The present invention relates to technical field of membrane, in particular to the preparation method of the high-performance Nano filtering composite membrane containing polymer coating
And obtained membrane material.
Background technique
Membrane technology has been one of the mostly important technology of relative maturity in water process and environmental protection.Wherein the most
Typically nanofiltration membrane can retain multivalent state ion, to realize the Selective Separation of ion.Commercialization nanofiltration membrane choosing at present
In the preparation method of selecting property cortex, interfacial polymerization is most commonly seen.But the flux and separating property for improving nanofiltration membrane simultaneously are difficult
It is realized by existing interfacial polymerization method.In recent years, there is patent literature report, between interface polymerization reaction layer and supporting layer
A very thin composite layer is introduced, defect existing for interfacial polymerization process preparation nanofiltration membrane can be effectively made up.Journal of
Membrane Science,476,10,(2015),Environmental Science&Technology Letters,5,
243, (2018), ACS Applied Materials&interfaces, 8,32512, the document reports such as (2016) introducing carbon
Nanotube (CNTs), graphene oxide (GO), poly-dopamine (PD) etc. promote the results of compound film properties.In addition, CN
107789992 report the preparation method of the modified composite nanometer filtering film of pure COFs (organic covalent material) middle layer, CN
107638805 report the preparation method of the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol.CN 106731884 is mentioned
Inorganic, organic material binding force can be effectively increased by having arrived inter coat.CN 106215722 reports a kind of grafting oxidation stone
Black ene coatings high temperature resistant composite nanometer filtering film and preparation method thereof.
Due to the material expensive of above-mentioned polymer coating, introduce coating process complexity, it is difficult to meet the industrialization of nanofiltration membrane
Using.Therefore, suitable coating of high molecular polymer material is searched out, nanofiltration membrane is made up not by the advantage of material itself
Foot, it is crucial for obtaining high performance composite film material.The invention discloses a kind of novel middle layer high polymer materials, work as use
Simple coating process is introduced into composite membrane, significantly promotes the cutoff performance and flux of composite membrane.
Summary of the invention
It is an object of the present invention to provide a kind of low costs, separation membrane material easy to operate and preparation method thereof, especially
High-performance Nano filtering composite membrane and preparation containing polymer coating, it is poor mainly to solve nanofiltration membrane desalting performance in the prior art, flux
Low technical problem, and the nanofiltration membrane with high desalination performance is prepared using the technology.
Used technical solution is as follows to solve above-mentioned technical problem by the present invention: one kind having polymer coating nanofiltration membrane
Preparation method includes the following steps: to introduce polymer coating in open support film surface；Then the volatilization of solvent is carried out；Then
Interface polymerization reaction is carried out on the backing material containing polymer coating, monomer used by interfacial polymerization is respectively polynary
Amine and polynary acyl chlorides after interface polymerization reaction, carry out thermal crosslinking treatment；The open support layer material used uses
Following high polymer materials such as polysulfones, polyether sulfone, polyether-ether-ketone, polycarbonate, Kynoar, polyacrylonitrile, polyethylene, gather
The ceramic materials such as propylene or inorganic porous material such as aluminum oxide, titanium dioxide；Or it introduces before the polymer coating first
The interface polymerization reaction is carried out in the open support film surface.
The polymer coating materials be selected from sulfonated polysulfone, sulfonated polyether sulfone, sulfonated polyether-ether-ketone, sulfonation polyacrylonitrile,
In sulfonated polyethylene vinyl alcohol, sulfonated polystyrene etc. it is one or more.
The solvent of the polymer coating is selected from dimethylformamide, dimethyl acetamide, N-methyl pyrrolidones, first
One of alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-hexane are a variety of；Preferably according to proper ratio mixed solvent,
To increase the solubility of coated polymeric.
Further, the polymer coating or interfacial polymerization process incorporation way are LBL self-assembly, electrostatic spraying, brush
It applies, impregnate, rotary coating.
Further, the polynary acyl chlorides contains two or more COCl group or SO2Cl group and company
The isostructural monomer of fat-based, phenyl, xenyl, naphthalene is connect, wherein the concentration of acyl chlorides is 0.01%-10%；Described is polynary
Amine can be piperazine, ethylenediamine, pentanediamine, butanediamine, diethylenetriamines, trien, m-xylene diamine or above-mentioned
Mixture, polyamine monomer concentration are 0.01%-20%.
The technical solution includes porous support layer pre-treatment step；The pretreatment is water-soluble with 20-50% isopropanol
Liquid or 20-50% ethanol water wash porous support layer, finally completely stand-by with pure water rinsing；.
During preparing nanofiltration membrane, the solvent of the polynary amine aqueous solution is water or organic solvent or their mixture,
Organic solvent such as acetone, methanol, ethyl alcohol, isopropanol etc.；The solvent of the solution of acid chloride can for Isopar series, n-hexane,
Toluene, dimethylbenzene, ethyl acetate or said mixture.The nanoparticle that 0.001-5% is added in coating material adds range
Preferentially it is selected as 0.001-2%.The nanoparticle includes silica dioxide nano particle, MOFs, COFs；In the technical solution
Nanoparticle range includes existing known cyclic annular or non-annularity pattern, has hole or non-porous organic or inorganic nanoparticle.
During the present invention prepares nanofiltration membrane, the surfactant includes cationic surfactant, such as quaternized
Object；Anionic surfactant, such as dodecyl sodium sulfate；Zwitterionic surfactant, such as amino acid pattern；Non-ionic surface
Activating agent, such as polyoxyethylene-type.During the present invention prepares nanofiltration membrane, in the polynary amine aqueous solution or solution of acid chloride, contain
The surfactant of 0.001%-5%.
It include adding the nanoparticle of 0.001-5% in polymer coating in the technical solution, nanoparticle of the present invention
Son addition range is preferentially selected as 0.001-2%.In the technical solution nanoparticle range include it is existing known cyclic annular or
Non-annularity pattern has hole or non-porous organic or inorganic nanoparticle.The nanoparticle include silica dioxide nano particle,
MOFs、COFs。
During preparing nanofiltration membrane, in the polynary amine aqueous solution or solution of acid chloride, the flux containing 0.001%-5% changes
Into agent, the flux enhancing agent is C1-C8Single or multiple alcohol, C4-C10Diamines or C2-C10Hydramine.
Nanofiltration membrane prepared by the present invention containing polymer coating can pass through the number of plies of regulation polymer coating, preparation
Composite membrane with different rejections and different water flux performances.
The nanofiltration membrane thermal crosslinking treatment process can be hot bath immersion or oven, and treatment temperature is in 50-120
Between DEG C, the time is handled in 20min or more.
Porous support layer is first pre-processed, and step is, the pretreatment for 20-50% isopropanol water solution or
20-50% ethanol water washs porous support layer, finally completely stand-by with pure water rinsing.
The nanofiltration membrane containing polymer coating of preparation, by regulating and controlling the number of plies of polymer coating, preparation has different cut
Stay the composite membrane of rate and different water flux performances；Nanofiltration membrane containing polymer coating, to salt, such as sodium sulphate, magnesium sulfate, chlorination
The rejection of the organic matter of magnesium, calcium chloride and sodium chloride or molecular weight lower than 1000g/mol can reach 95% or more than.
The technical solution includes porous support layer pre-treatment step.The pretreatment is water-soluble with 20-50% isopropanol
Liquid or 20-50% ethanol water wash porous support layer, finally completely stand-by with pure water rinsing.
The technical solution polymer coating, the coating number of plies range are 1-100 layers.Preferential range of choice is 1-15
Layer, the water flux that the polymer-coated number of plies excessively will lead to film reduce.During the present invention prepares nanofiltration membrane, the polyamine is molten
In liquid or solution of acid chloride, the surfactant containing 0.001%-5%.
The polynary acyl chlorides of the raw material of the interfacial polymerization process be containing two or more COCl group or
SO2Cl group simultaneously connects the isostructural monomer of fat-based, phenyl, xenyl, naphthalene.Wherein the concentration of acyl chlorides is 0.01%-
10%；The polyamine is piperazine, ethylenediamine, pentanediamine, butanediamine, diethylenetriamines, trien, isophthalic two
Methylamine or said mixture, polyamine monomer concentration are 0.01%-20%.
The mode of the interfacial polymerization process can be LBL self-assembly, electrostatic spraying, brushing, immersion, rotary coating.It is quiet
Electrospray can control the quantity for participating in interfacial polymerization monomer, and then the thickness of control interface polymerization, become preferential selection mode.
The polyamine can be piperazine, ethylenediamine, pentanediamine, butanediamine, diethylenetriamines, triethylene four
Amine, m-xylene diamine or said mixture.During the present invention prepares nanofiltration membrane, the solvent of the polynary amine aqueous solution can be water
Or organic solvent or their mixture, organic solvent such as acetone, methanol, ethyl alcohol, isopropanol etc..The solution of acid chloride it is molten
Agent can be Isopar series, n-hexane, toluene, dimethylbenzene, ethyl acetate or said mixture.
During the present invention prepares nanofiltration membrane, the open support layer material used, using following high polymer materials, such as
Polysulfones, polyether sulfone, polyether-ether-ketone, polycarbonate, Kynoar, polyacrylonitrile, polyethylene, polypropylene etc., are also possible to nothing
The ceramic materials such as machine porous material such as aluminum oxide, titanium dioxide.
During the present invention prepares nanofiltration membrane, in the polynary amine aqueous solution or solution of acid chloride, contain 0.001%-5%'s
Flux enhancing agent.
During the present invention prepares nanofiltration membrane, the flux enhancing agent is C1-C8Single or multiple alcohol, C4-C10Diamines or
C2-C10Hydramine.
Nanofiltration membrane prepared by the present invention containing polymer coating can pass through the number of plies of regulation polymer coating, preparation
Composite membrane with different rejections and different water flux performances.
Nanofiltration membrane prepared by the present invention containing polymer coating, to salt, such as sodium sulphate, magnesium sulfate, magnesium chloride, calcium chloride
And the rejection highest of the organic matter of sodium chloride or molecular weight lower than 1000g/mol can achieve 95% or more than.
Rejection (R) in the present invention is defined as: under certain condition, concentration of raw material (Cf) and penetrating fluid concentration (Cp) poor,
Again divided by concentration of raw material (Cf), R=(Cf-Cp)/Cf.Nanofiltration membrane desalting performance prepared by the present invention containing polymer coating
Test condition be concentration of salt solution be 1000mg/L, test pressure is 1.0MPa, and system is controlled at 25 DEG C, cross-flow operation
Mode.
The utility model has the advantages that compared with prior art, i.e., with corresponding (similar thickness) the open support layer material used
Compare, open support layer material, that is, polysulfones, polyether sulfone, polyether-ether-ketone, polycarbonate, Kynoar, polyacrylonitrile, poly- second
Alkene, polypropylene etc. or the ceramic materials such as inorganic porous material such as aluminum oxide, titanium dioxide.The present invention is using simple
Coating process is introduced into composite membrane, significantly promotes the cutoff performance and flux of open support tunic.Composite film material is sulfonation
Class high molecular material has the advantages that material is easy to get, introduces coating process simplicity.Polymer coating of the invention introduces composite membrane
Technology can effectively make up defect existing for the nanofiltration membrane prepared in interfacial polymerization process, to realize higher desalting performance and logical
The promotion of amount.The technology of the present invention, which is applicable to make up a variety of lower activated monomers crosslinkings, leads to the active layer salt rejection rate difference of preparation
Problem.All technical staff having about interfacial polymerization film preparation basis are equal it is inferred that material and side using the type
Method can be improved reverse osmosis and nanofiltration membrane performance, be the ways and means that a type can be popularized.The present invention also has following
Feature: for the not perfect of current technology, polymer coating of the invention promotes the preparation method of Nano filtering composite membrane performance, passes through
Polymer coating changes and the separating property of control membrane material, promotes the extensive use of membrane material, with important economic and environment-friendly
Meaning.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph in the nanofiltration membrane section with sulfonated polyether-ether-ketone polymer coating that embodiment 2 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph in the nanofiltration membrane section with sulfonated polyether sulfone polymer coating that embodiment 5 obtains.
Fig. 3 is the scanning electron microscope (SEM) photograph in the nanofiltration membrane section for the non-polymer coating that embodiment 3 obtains.
Fig. 4 is the atomic force microscopy for the nanofiltration film surface with sulfonated polyether-ether-ketone polymer coating that embodiment 2 obtains
Mirror figure, Ra value represent the roughness of average surface value of film surface.
Fig. 5 is the atomic force microscopy diagram of the nanofiltration film surface for the non-polymer coating that embodiment 3 obtains, and Ra value represents
The roughness of average surface value of film surface.
Fig. 6 is the atomic force microscope that the non-polymer coating that embodiment 9 obtains has nanofiltration film surface existing for additive
Figure, Ra value represent the roughness of average surface value of film surface.
(A) is schemed in Fig. 7, figure (B) is respectively embodiment 2 and what example 3 obtained has sulfonated polyether-ether-ketone polymer coating
The resistance to compaction data of stability that nanofiltration membrane and the nanofiltration membrane of non-polymer coating test the metabisulfite solution of 1000mg/L.
Specific embodiment
Specific embodiments of the present invention are given below, are only used for the present invention is described in detail, does not constitute and right of the present invention is wanted
The limitation asked.Any person skilled in art can extend and open up on the basis of thinking provided by the invention and case
Any other similar system.
Embodiment 1
Film of the invention is prepared as follows.In porous support layer polyethylene film, (range of thickness is unlimited, such as common
100 microns, can use existing polyethylene film) to carry out oxygen plasma modified for upper surface, it can also be used
Its hydrophilic modifying, such as coating PVA；Trien, monoethanolamine and dimethylamino are gone up in supporting layer upper surface after taking-up
The aqueous solution of yl pyridines makes the solution and supporting layer be kept in contact 2min, is dried up film surface liquid with nitrogen after outwelling, so
The 0.15% Isopar G solution containing pyromellitic trimethylsilyl chloride is poured on supporting layer afterwards, the organic solution and supporting layer is made to keep connecing
1min is touched, is then outwelled.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.Sulphur is gone up in 20/20/60 ratio later
Change polyether sulfone/water/n,N-dimethylacetamide, so that the solution and porous support layer is kept 2s, then outwell, be placed on 50- later
2h in 55 DEG C of baking ovens.
The polymer coating materials be selected from sulfonated polysulfone, sulfonated polyether sulfone, sulfonated polyether-ether-ketone, sulfonation polyacrylonitrile,
In sulfonated polyethylene vinyl alcohol, sulfonated polystyrene etc. it is one or more；The solvent of the polymer coating is selected from dimethyl
One of formamide, dimethyl acetamide, N-methyl pyrrolidones, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-hexane are more
Kind；Preferably according to proper ratio mixed solvent, to increase the solubility of coated polymeric.The polynary acyl chlorides
Contain two or more COCl group or SO2Cl group and the knot such as connect fat-based, phenyl, xenyl, naphthalene
The monomer of structure, wherein the concentration of acyl chlorides is 0.01%-10%；The polyamine be piperazine, ethylenediamine, pentanediamine, butanediamine,
Diethylenetriamines, trien, m-xylene diamine or said mixture, polyamine monomer concentration are 0.01%-20%.
The test of membrane separating property is carried out with reverse osmosis unit.Material liquid uses concentration for the Na of 1000mg/L2SO4It is water-soluble
Liquid, test pressure are 10bar.It was found that the flux of the film is 19.6Lm-2·h-1, rejection 99.2%.Material liquid is using dense
Degree is the NaCl aqueous solution of 1000mg/L, and test pressure is 10bar.It was found that the flux of the film is 21.6Lm-2·h-1, retention
Rate is 96.3%.
Embodiment 2
Film of the invention is prepared as follows.Sulfonated polyether-ether-ketone/methanol is gone up in porous support layer polysulfones upper surface
Solution is made the solution and porous support layer keep 2s, is then outwelled, be placed on 2h in 30 DEG C of baking ovens later in 20/80 ratio.It takes
The aqueous solution for going up diethylenetriamines and dimethyl aminopyridine after out in supporting layer upper surface protects the solution and supporting layer
Contact 2min is held, is dried up film surface liquid with nitrogen after outwelling, 0.32% is then poured on supporting layer containing 1,3,6- naphthalenes
The Isopar G solution of three sulfonic acid chlorides, makes the organic solution and supporting layer be kept in contact 1min, then outwells.It is placed on 90 DEG C later
Make solvent volatilization 3min in baking oven.As a result see Fig. 1, Fig. 4 and Fig. 7 in Figure of description.Fig. 1 is compared to Fig. 3 interfacial polymerization layer
Thickness it is significantly thinner, the introducing meeting of polymer coating is so that interfacial polymerization thinner layer thickness.Fig. 4 is bright compared to Fig. 5 roughness
Aobvious to reduce, the introducing meeting of polymer coating is so that interfacial polymerization bed roughness declines.Fig. 7 illustrate the presence of polymer coating according to
Stablize film properties, there is good resistance to consolidation effect.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 17.4Lm-2·h-1, rejection 99.7%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 17.8Lm-2·h-1, rejection 82.3%.
Embodiment 3
Film of the invention is prepared as follows.Diethylenetriamines and diformazan are gone up in porous support layer polysulfones upper surface
The aqueous solution of base aminopyridine makes the solution and supporting layer be kept in contact 2min, is blown film surface liquid with nitrogen after outwelling
It is dry, the Isopar G solution of 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene is then poured on supporting layer, makes the organic solution and branch
Support layer is kept in contact 1min, then outwells.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.As a result see Figure of description
Middle Fig. 3, Fig. 5 and Fig. 7.The median surface Fig. 3 polymer layer is thicker compared to from the point of view of Fig. 1, Fig. 2, and Fig. 5 is compared to Fig. 4 film surface roughness
Larger, Fig. 7 illustrates not introduce the compound membrane stability of polymer coating, resistance to compactibility is not so good as the film of polymer coating.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 5.4Lm-2·h-1, rejection 91.8%.Material liquid uses concentration for 1000mg/L's
NaCl aqueous solution, test pressure are 10bar.It was found that the flux of the film is 4.6Lm-2·h-1, rejection 32.6%.
Embodiment 4
It is film-made according to the method for embodiment 2, this method by being changed polymer coating sequence by interfacial polymerization process before
For later, when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution tests pressure
For 10bar, discovery flux is 16.7Lm-2·h-1, rejection 99.4%.
Embodiment 5
It is film-made according to the method for embodiment 2, this method is by pressing 20/ for sulfonated polyether sulfone/water/n,N-dimethylacetamide
20/60 ratio is added, and when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution,
Test pressure is 10bar, and discovery flux is 14.5Lm-2·h-1, rejection 95.2%.As a result see in Figure of description and scheme
2.Fig. 2 is significantly thinner compared to the thickness of Fig. 3 interfacial polymerization layer, and the introducing meeting of polymer coating is so that interfacial polymerization thickness degree becomes
It is thin.
Embodiment 6
It is film-made according to the method for embodiment 4, this method by being changed polymer coating sequence by interfacial polymerization process before
For later, when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution tests pressure
For 10bar, discovery flux is 15.3Lm-2·h-1, rejection 95.6%.
Embodiment 7
It is film-made according to the method for embodiment 2, this method is by pressing sulfonated polyethylene vinyl alcohol/n,N-dimethylacetamide
20/80 ratio is added, and when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution,
Test pressure is 10bar, and discovery flux is 12.3Lm-2·h-1, rejection 94.6%.
Embodiment 8
It is film-made according to the method for embodiment 2, this method is by being changed to triethylene for aqueous phase monomers diethylenetriamines
Tetramine, when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar, discovery flux are 16.9Lm-2·h-1, rejection 99.2%.
Embodiment 9
It is film-made according to the method for embodiment 2, this method is improved by the way that monoethanolamine is added in water phase, in an oven
Heat cross-linking 10min, when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test
Pressure is 10bar, and discovery flux is 20.2Lm-2·h-1, rejection 99.4%.As a result see Fig. 6 in Figure of description.Fig. 6
Obviously become larger compared to Fig. 4, Fig. 5 film surface roughness, illustrates that the addition of alcamines additive will increase the thick of interfacial polymerization layer
Rugosity.
Embodiment 10
It being film-made according to the method for embodiment 2, this method is improved by the way that camphorsulfonic acid triethyl ammonium is added in water phase,
Heat cross-linking 10min in an oven, when testing the film in aforementioned manners, material liquid uses concentration for the Na of 1000mg/L2SO4Water
Solution, test pressure are 10bar, and discovery flux is 19.3Lm-2·h-1, rejection 98.3%.
Embodiment 11
Film of the invention is prepared as follows.Diethylenetriamines and diformazan are gone up in porous support layer polysulfones upper surface
The aqueous solution of base aminopyridine makes the solution and supporting layer be kept in contact 2min, is blown film surface liquid with nitrogen after outwelling
It is dry, the Isopar G solution of 0.03% three sulfonic acid chloride Han 1,3,6- naphthalene is then poured on supporting layer, makes the organic solution and branch
Support layer is kept in contact 1min, then outwells.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.Repeat the above steps ten
It is secondary, carry out LBL self-assembly interfacial polymerization.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 8.6Lm-2·h-1, rejection 93.6%.Material liquid uses concentration for 1000mg/L's
NaCl aqueous solution, test pressure are 10bar.It was found that the flux of the film is 9.6Lm-2·h-1, rejection 53.4%.
Embodiment 12
Film of the invention is prepared as follows.Sulfonated polyether-ether-ketone/methanol solution is used into brush in 20/80 ratio
The mode of brushing is coated uniformly on porous support layer polysulfones, so that the solution and porous support layer is kept 2s, is then outwelled, later
It is placed on 2h in 30 DEG C of baking ovens.In the water-soluble of supporting layer upper surface upper diethylenetriamines and dimethyl aminopyridine after taking-up
Liquid makes the solution and supporting layer be kept in contact 2min, is dried up film surface liquid with nitrogen after outwelling, then on supporting layer
The Isopar G solution for pouring into 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene, makes the organic solution and supporting layer be kept in contact 1min,
Then it outwells.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 20.4Lm-2·h-1, rejection 99.8%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 20.6Lm-2·h-1, rejection 92.3%.
Embodiment 13
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polyethylene film upper surface to change
Property, sulfonated polyether-ether-ketone/methanol solution is gone up in 20/80 ratio later, the solution and porous support layer is made to keep 2s, then
It outwells, is placed on 2h in 30 DEG C of baking ovens later.Diethylenetriamines and dimethylamino pyrrole are gone up in supporting layer upper surface after taking-up
The aqueous solution of pyridine makes the solution and supporting layer be kept in contact 2min, dries up film surface liquid with nitrogen after outwelling, then exist
The Isopar G solution that 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene is poured on supporting layer makes the organic solution and supporting layer keep connecing
1min is touched, is then outwelled.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 30.6Lm-2·h-1, rejection 98.6%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 32.5Lm-2·h-1, rejection 73.6%.
Embodiment 14
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polyethylene film upper surface to change
Property, sulfonated polyether sulfone/water/n,N-dimethylacetamide is gone up in 20/20/60 ratio later, makes the solution and open support
Layer keeps 2s, then outwells, is placed on 2h in 30 DEG C of baking ovens later.After taking-up supporting layer upper surface upper diethylenetriamines and
The aqueous solution of dimethyl aminopyridine, makes the solution and supporting layer is kept in contact 2min, with nitrogen by film surface liquid after outwelling
Body drying, the Isopar G solution of 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene is then poured on supporting layer, makes the organic solution
It is kept in contact 1min with supporting layer, is then outwelled.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 26.9Lm-2·h-1, rejection 93.2%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 21.3Lm-2·h-1, rejection 52.3%.
Embodiment 15
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polypropylene film upper surface to change
Property, the aqueous solution of trien and dimethyl aminopyridine is gone up after taking-up in supporting layer upper surface, makes the solution and branch
Support layer is kept in contact 2min, is dried up film surface liquid with nitrogen after outwelling, and 0.32% is then poured on supporting layer and contains 1,
The Isopar G solution of 3,6- naphthalene, three sulfonic acid chloride, makes the organic solution and supporting layer be kept in contact 1min, then outwells.It puts later
Make solvent volatilization 3min in 90 DEG C of baking ovens.Sulfonated polyether sulfone/water/N, N- dimethyl are gone up in 20/20/60 ratio later
Acetamide makes the solution and porous support layer keep 2s, then outwells, be placed on 2h in 30 DEG C of baking ovens later.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 29.3Lm-2·h-1, rejection 93.6%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 25.2Lm-2·h-1, rejection 64.3%.
Embodiment 16
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polypropylene film upper surface to change
Property, the aqueous solution of trien, monoethanolamine and dimethyl aminopyridine is gone up after taking-up in supporting layer upper surface, makes this
Solution and supporting layer are kept in contact 2min, dry up film surface liquid with nitrogen after outwelling, then pour on supporting layer
The Isopar G solution of 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene, makes the organic solution and supporting layer be kept in contact 1min, then
It outwells.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.Later in 20/20/60 ratio upper sulfonated polyether sulfone/
Water/n,N-dimethylacetamide makes the solution and porous support layer keep 2s, then outwells, be placed on 2h in 30 DEG C of baking ovens later.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 32.3Lm-2·h-1, rejection 91.6%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 31.6Lm-2·h-1, rejection 52.3%.
Embodiment 17
Film of the invention is prepared as follows.The aqueous solution that piperazine is gone up in porous support layer polyether sulfone upper surface, makes
The solution and supporting layer are kept in contact 2min, dry up film surface liquid with nitrogen after outwelling, then pour on supporting layer
The 0.15% Isopar G solution containing pyromellitic trimethylsilyl chloride, makes the organic solution and supporting layer be kept in contact 1min, then outwells.
It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.Sulfonated polyether sulfone/water/N, N- are gone up in 20/20/60 ratio later
Dimethyl acetamide makes the solution and porous support layer keep 2s, then outwells, be placed on 2h in 30 DEG C of baking ovens later.
The test of membrane separating property is carried out with reverse osmosis unit.Material liquid uses concentration for the Na of 1000mg/L2SO4It is water-soluble
Liquid, test pressure are 10bar.It was found that the flux of the film is 18.3Lm-2·h-1, rejection 99.6%.Material liquid is using dense
Degree is the NaCl aqueous solution of 1000mg/L, and test pressure is 10bar.It was found that the flux of the film is 22.5Lm-2·h-1, retention
Rate is 83.6%.
Embodiment 18
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polyethylene film upper surface to change
Property, sulfonated polyether sulfone/water/n,N-dimethylacetamide is gone up in 20/20/60 ratio later, makes the solution and open support
Layer keeps 2s, then outwells, is placed on 2h in 30 DEG C of baking ovens later.The aqueous solution of piperazine is gone up after taking-up in supporting layer upper surface,
So that the solution and supporting layer is kept in contact 2min, dried up film surface liquid with nitrogen after outwelling, is then fallen on supporting layer
Enter the 0.15% Isopar G solution containing pyromellitic trimethylsilyl chloride, so that the organic solution and supporting layer is kept in contact 1min, then fall
Fall.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
The test of membrane separating property is carried out with reverse osmosis unit.Material liquid uses concentration for the Na of 1000mg/L2SO4It is water-soluble
Liquid, test pressure are 10bar.It was found that the flux of the film is 19.6Lm-2·h-1, rejection 98.5%.Material liquid is using dense
Degree is the NaCl aqueous solution of 1000mg/L, and test pressure is 10bar.It was found that the flux of the film is 23.6Lm-2·h-1, retention
Rate is 89.2%.
Embodiment 19
Film of the invention is prepared as follows.Oxygen plasma is carried out in porous support layer polyethylene film upper surface to change
Property, sulfonated polyether sulfone/water/n,N-dimethylacetamide is sprayed on using Electrostatic Spray Technology in 20/20/60 ratio later more
On the supporting layer of hole, it is placed on 2h in 30 DEG C of baking ovens later.The aqueous solution for going up piperazine after taking-up in supporting layer upper surface, makes the solution
It is kept in contact 2min with supporting layer, film surface liquid is dried up with nitrogen after outwelling, 0.15% is then poured on supporting layer
Isopar G solution containing pyromellitic trimethylsilyl chloride, makes the organic solution and supporting layer be kept in contact 1min, then outwells.It puts later
Make solvent volatilization 3min in 90 DEG C of baking ovens.
The test of membrane separating property is carried out with reverse osmosis unit.Material liquid uses concentration for the Na of 1000mg/L2SO4It is water-soluble
Liquid, test pressure are 10bar.It was found that the flux of the film is 23.8Lm-2·h-1, rejection 96.5%.Material liquid is using dense
Degree is the NaCl aqueous solution of 1000mg/L, and test pressure is 10bar.It was found that the flux of the film is 29.6Lm-2·h-1, retention
Rate is 82.3%.
Embodiment 20
Film of the invention is prepared as follows.Use Electrostatic Spray Technology by piperazine in porous support layer polysulfones upper surface
Aqueous solution and the Isopar G solution spraying containing pyromellitic trimethylsilyl chloride in membrane surface.Be placed in 90 DEG C of baking ovens later make it is molten
Agent volatilization 3min.Later in 20/20/60 ratio upper sulfonated polyether sulfone/water/n,N-dimethylacetamide, make the solution with
Porous support layer keeps 2s, then outwells, is placed on 2h in 30 DEG C of baking ovens later.
The test of membrane separating property is carried out with reverse osmosis unit.Material liquid uses concentration for the Na of 1000mg/L2SO4It is water-soluble
Liquid, test pressure are 10bar.It was found that the flux of the film is 25.7Lm-2·h-1, rejection 95.3%.Material liquid is using dense
Degree is the NaCl aqueous solution of 1000mg/L, and test pressure is 10bar.It was found that the flux of the film is 29.5Lm-2·h-1, retention
Rate is 79.6%.
Embodiment 21
Film of the invention is prepared as follows.Carboxylated is carried out in porous support layer polyacrylonitrile upper surface to be modified, it
Sulfonated polyether sulfone/water/n,N-dimethylacetamide is gone up in 20/20/60 ratio afterwards, keeps the solution and porous support layer
Then 2s is outwelled, be placed on 2h in 30 DEG C of baking ovens later.Diethylenetriamines and dimethyl are gone up in supporting layer upper surface after taking-up
The aqueous solution of aminopyridine makes the solution and supporting layer be kept in contact 2min, is dried up film surface liquid with nitrogen after outwelling,
Then the Isopar G solution that 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene is poured on supporting layer, makes the organic solution and supporting layer
It is kept in contact 1min, is then outwelled.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 31.2Lm-2·h-1, rejection 91.6%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 26.5Lm-2·h-1, rejection 45.2%.
Embodiment 22
Film of the invention is prepared as follows.Carboxylated is carried out in porous support layer polyacrylonitrile upper surface to be modified, it
The aqueous solution for going up diethylenetriamines and dimethyl aminopyridine in supporting layer upper surface afterwards keeps the solution and supporting layer
2min is contacted, is dried up film surface liquid with nitrogen after outwelling, 0.32% is then poured on supporting layer containing 1,3,6- naphthalenes three
The Isopar G solution of sulfonic acid chloride, makes the organic solution and supporting layer be kept in contact 1min, then outwells.It is placed on 90 DEG C of bakings later
Make solvent volatilization 3min in case.Sulfonated polyether sulfone/water/N, N- dimethylacetamide are gone up in 20/20/60 ratio after taking-up
Amine makes the solution and porous support layer keep 2s, then outwells, be placed on 2h in 30 DEG C of baking ovens later.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 24.0Lm-2·h-1, rejection 96.4%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 19.8Lm-2·h-1, rejection 61.2%.
Embodiment 23
Film of the invention is prepared as follows.Triethylene is gone up in porous support layer polyether-ether-ketone supporting layer upper surface
The aqueous solution of tetramine and dimethyl aminopyridine, makes the solution and supporting layer is kept in contact 2min, with nitrogen by film after outwelling
Surface liquid drying, the Isopar G solution of 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene is then poured on supporting layer, there is this
Machine solution and supporting layer are kept in contact 1min, then outwell.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.It presses later
20/20/60 ratio goes up sulfonated polyether sulfone/water/n,N-dimethylacetamide, and the solution and porous support layer is made to keep 2s,
Then it outwells, is placed on 2h in 30 DEG C of baking ovens later.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 22.3Lm-2·h-1, rejection 94.9%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 19.4Lm-2·h-1, rejection 65.3%.
Embodiment 24
Film of the invention is prepared as follows.In porous support layer polyether-ether-ketone supporting layer upper surface by 20/20/60
Ratio goes up sulfonated polyether sulfone/water/n,N-dimethylacetamide, so that the solution and porous support layer is kept 2s, then outwells, it
After be placed on 2h in 30 DEG C of baking ovens.The aqueous solution that trien, monoethanolamine and dimethyl aminopyridine are gone up after taking-up, makes
The solution and supporting layer are kept in contact 2min, dry up film surface liquid with nitrogen after outwelling, then pour on supporting layer
The Isopar G solution of 0.32% three sulfonic acid chloride Han 1,3,6- naphthalene, makes the organic solution and supporting layer be kept in contact 1min, then
It outwells.It is placed in 90 DEG C of baking ovens later and makes solvent volatilization 3min.
Above-mentioned nanofiltration membrane is placed in 8% sulfuric acid solution and is impregnated for 24 hours, is rinsed film to neutrality with clear water after taking-up, with anti-
The test of permeability apparatus progress membrane separating property.Material liquid uses concentration for the Na of 1000mg/L2SO4Aqueous solution, test pressure are
10bar.It was found that the flux of the film is 35.3Lm-2·h-1, rejection 85.2%.Material liquid uses concentration for 1000mg/L
NaCl aqueous solution, test pressure be 10bar.It was found that the flux of the film is 34.2Lm-2·h-1, rejection 39.5%.
It above are only part preferred embodiment of the invention, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there are various change and change within the scope of the method for the present invention, made any variation and more
Change, within that scope of the present invention.
Claims (10)
1. one kind has polymer coating nanofiltration membrane preparation method, characterized in that include the following steps: in open support film surface
Introduce polymer coating；Then the volatilization of solvent is carried out；Then interface is carried out on the backing material containing polymer coating
Polymerization reaction, monomer used by interfacial polymerization are respectively polyamine and polynary acyl chlorides, after interface polymerization reaction, carry out heat
Crosslinking Treatment；The open support layer material used, using following high polymer materials, as polysulfones, polyether sulfone, polyether-ether-ketone,
Polycarbonate, Kynoar, polyacrylonitrile, polyethylene, polypropylene or inorganic porous material such as aluminum oxide, dioxy
Change the ceramic materials such as titanium；
Or it introduces before the polymer coating and first carries out the interface polymerization reaction in the open support film surface.
2. preparation method according to claim 1, characterized in that the polymer coating materials are selected from sulfonated polysulfone, sulphur
Change one of polyether sulfone, sulfonated polyether-ether-ketone, sulfonation polyacrylonitrile, sulfonated polyethylene vinyl alcohol, sulfonated polystyrene etc. or
It is a variety of；The solvent of the polymer coating is selected from dimethylformamide, dimethyl acetamide, N-methyl pyrrolidones, methanol, second
One of alcohol, normal propyl alcohol, isopropanol, n-hexane are a variety of；Preferably according to proper ratio mixed solvent, to increase
Add the solubility of coated polymeric.
3. preparation method according to claim 1 or 2, it is characterised in that: the polymer coating or interfacial polymerization process
Incorporation way is LBL self-assembly, electrostatic spraying, brushing, immersion, rotary coating.
4. preparation method according to claim 1 or 2, it is characterised in that: nanofiltration membrane heat treatment cross-linking process can be with
It is hot bath immersion or oven, treatment temperature is between 30-120 DEG C；It is described introduce polymeric layer number of plies range be
1-15 layers.
5. preparation method according to claim 1 or 2, it is characterised in that: the polynary acyl chlorides contain there are two or two
A above COCl group or SO2Cl group simultaneously connects the isostructural monomer of fat-based, phenyl, xenyl, naphthalene, wherein acyl
The concentration of chlorine is 0.01%-10%；The polyamine is piperazine, ethylenediamine, pentanediamine, butanediamine, diethylenetriamines, three
Ethylene tetra, m-xylene diamine or said mixture, polyamine monomer concentration are 0.01%-20%.
6. preparation method according to claim 1 or 2, it is characterised in that: porous support layer is first pre-processed, step
It is that the pretreatment is washs porous support layer with 20-50% isopropanol water solution or 20-50% ethanol water, finally
It is completely stand-by with pure water rinsing.
7. preparation method according to claim 5, it is characterised in that: during preparation nanofiltration membrane, the polynary amine aqueous solution
Solvent be water or organic solvent or their mixture, organic solvent such as acetone, methanol, ethyl alcohol, isopropanol；The acyl chlorides
The solvent of solution is Isopar series, n-hexane, toluene, dimethylbenzene, ethyl acetate or said mixture；Prepare nanofiltration membrane mistake
Cheng Zhong, in the polynary amine aqueous solution or solution of acid chloride, the surfactant containing 0.001%-5%；The surface-active
Agent includes cationic surfactant, such as quaternary ammonium compound；Anionic surfactant, such as dodecyl sodium sulfate；Amphoteric ion
Surfactant, such as amino acid pattern；Nonionic surfactant, such as polyoxyethylene-type.
8. preparation method according to claim 1 or 2, it is characterised in that: add the nanometer of 0.001-5% in coating material
Particle addition range is preferentially selected as 0.001-2%.Nanoparticle range includes existing known cyclic annular in the technical solution
Or non-annularity pattern, there are hole or non-porous organic or inorganic nanoparticle；The nanoparticle include silica dioxide nano particle,
MOFs、COFs。
9. preparation method according to claim 7, it is characterised in that: during preparation nanofiltration membrane, the polynary amine aqueous solution
Or in solution of acid chloride, the flux enhancing agent containing 0.001%-5%, the flux enhancing agent is C1-C8Single or multiple alcohol, C4-
C10Diamines or C2-C10Hydramine.
10. a kind of nanofiltration membrane that preparation method described in one of -9 obtains according to claim 1, it is characterised in that: contain polymerization
The nanofiltration membrane of object coating, it is compound with different rejections and different water flux performances by regulating and controlling the number of plies of polymer coating
Film；Nanofiltration membrane containing polymer coating, to salt, such as sodium sulphate, magnesium sulfate, magnesium chloride, calcium chloride and sodium chloride or point
Son amount lower than 1000g/mol organic matter rejection can reach 95% or more than.
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| CN111804151A (en) * | 2020-07-27 | 2020-10-23 | 上海恩捷新材料科技有限公司 | MBR (membrane bioreactor) flat filter membrane for domestic sewage treatment and preparation method thereof |
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| CN114432902B (en) * | 2020-11-05 | 2023-03-14 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method and application thereof |
| US11642632B2 (en) | 2020-11-13 | 2023-05-09 | New Micropore, Inc. | Nanofiltration composite membranes |
| WO2022109865A1 (en) * | 2020-11-25 | 2022-06-02 | 扬州实略信息科技有限公司 | Wastewater deep treater |
| CN113522058A (en) * | 2021-08-16 | 2021-10-22 | 中国科学院上海高等研究院 | High-performance composite forward osmosis membrane based on polyolefin microporous substrate and preparation method thereof |
| CN113856501A (en) * | 2021-09-29 | 2021-12-31 | 中国科学院过程工程研究所 | Composite nanofiltration membrane and preparation method and application thereof |
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