CN105498549B - A kind of composite nanometer filtering film and its preparation method and application - Google Patents
A kind of composite nanometer filtering film and its preparation method and application Download PDFInfo
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- CN105498549B CN105498549B CN201410553383.5A CN201410553383A CN105498549B CN 105498549 B CN105498549 B CN 105498549B CN 201410553383 A CN201410553383 A CN 201410553383A CN 105498549 B CN105498549 B CN 105498549B
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Abstract
The invention discloses a kind of composite nanometer filtering films, the composite nanometer filtering film includes the supporting layer to stack together and separating layer, wherein, the separating layer be the polymer containing hydroxyl be dissolved in the silane coupling agent containing amino react by collosol and gel and heat cross-linking in solvent after form the initial composite NF membrane for the cross-linked network structure being located in the support layer surface, then the initial composite NF membrane is carried out in sultones post-processing being modified and is obtained.Composite nanometer filtering film of the present invention not only has higher salt rejection rate and water penetration (water flux), also has stronger acid resistance, and preparation method is simple, great prospects for commercial application.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering films and preparation method thereof and the composite nanometer filtering film in water treatment field
Using.
Background technology
Nanofiltration is a kind of pressure-driven membrane separating process between reverse osmosis between ultrafiltration, and the pore diameter range of NF membrane exists
Several rans, it is poor less than the removing of 200 organic matter to monovalention and molecular weight, and to divalent or multivalent ion and molecule
The organic matter measured between 200~500 has higher removal efficiency.It can be widely used in fresh water softening, seawater softening, drinking water
The chemical industry system such as purification, water correction, water-oil separating, wastewater treatment and recycling and dyestuff, antibiotic, polypeptide and polysaccharide
The fields such as classification, purifying and the concentration of product.
Currently, commercial nanofiltration membrane mostly using polysulfone ultrafiltration membrane as supporting layer, carries out polynary in situ in ultrafiltration membrane upper surface
The interfacial polymerization of aqueous amine phase and polynary acyl chlorides organic phase, final product are composite nanometer filtering film.Common aqueous phase monomers are piperazine
Or piperazine replace amine, organic phase be pyromellitic trimethylsilyl chloride or a kind of multifunctional carboxylic acid halides, such as patent No. US4769148 with
The content reported disclosed in US4859384, a large amount of unreacted acid chloride groups are hydrolyzed into carboxylic acid, keep nanofiltration film surface band negative
Electricity, using charge effect, polypiperazine-amide composite nanometer filtering film has higher rejection to high-valence anion, to monovalent anion
With adjustable rejection.In addition, the patent No. US4765897, US4812270 and US4824574 additionally provide a kind of how will
The method that polyamide composite reverse osmosis membrane is transformed into NF membrane.But due to the limitation of material self character, in extreme pH environments
Under, especially under basic conditions, traditional polyamide-based NF membrane can degrade, and pH models are used due to polyamide nanofiltration membrane
Generally 2~11 are enclosed, so being only used for neutral medium or the weak acid and weak base medium close to neutrality.
In recent years, researchers develop a variety of NF membranes, and the product of a variety of commercializations occur.In addition, many new
Material, such as sulfonated polyether ketone, sulfonated polyether sulfone etc. are also applied to nanofiltration field.
Document《Acid stable thin-film composite membrane for nanofiltration
Prepared from naphthalene-1,3,6-trisulfonylchloride (NTSC) and piperazine (PIP),
J.Membr.Sci.,415-416,122-131,2012》Middle report：Sulfonamide material has very strong acid resistance, utilization polynary
The composite nanometer filtering film that sulfonic acid chloride monomer is obtained with piperazine by interfacial polymerization can keep stable separation property in pH=0 environment
Energy.
Document《Sulfonated poly(etheretherketone)based composite membranes for
Nanofiltration of acidic and alkaline media, J.Membr.Sci., 381,81-89,2011》Middle report
Road：Sulfonated polyether-ether-ketone not only has acid resistance, but also has very strong alkali resistance, can more obtain that cutoff performance is excellent to be received by crosslinking
Filter membrane material, moreover, the polyetheretherketonematerials materials after crosslinking have very strong solvent resistance, it can be in isopropanol and acetone isopolarity
Dyestuff (Crosslinking of modified poly (etheretherketone) membranes for are detached in solvent
Use in solvent resistant nanofiltration, 447,212-221,2013).
Document《Acid and alkali-resistance high temperature resistant NF membrane HYDRACoRe70pHT for sugar industry spent lye recycle, membrane science with
Technology, 32,11-15,2006》Middle report：The sulfonated polyether sulfone class composite nanometer filtering film being commercialized is by day east electrician Hai De
The HYDRACoRe series that energy company develops, can use in strong acid, strong base solution, be widely used in the recycling of salkali waste.
The acidproof NF membrane Duracid NF1812C that GE companies develop be three-layer composite structure, can 20% hydrochloric acid,
It keeps stablizing under the conditions of sulfuric acid and phosphoric acid, and remains to keep stablizing under the conditions of 70 DEG C, the sulfuric acid of 20% concentration.
Being reported in the patent No. US5265734, EP0392982 (A3) can receive what pH=0~14 were run steadily in the long term
Filter membrane only has the SelRO MPS34 that KOCH companies develop, it is developed by Israel scientist earliest, and material is silicon
Rubber is applied to infiltration evaporation earliest.
Polyvinyl alcohol (PVA) is a kind of water-soluble polymer, has good film forming, cohesion, emulsibility, remarkable
Grease resistance and solvent resistance and good acid-fast alkali-proof performance.Chemical crosslinking can reduce the crystallinity of PVA, improve film
Mechanical strength, increase film to the rejection of salt ion, and the performance with better acid and alkali-resistance and solvent.Last century 80
Crosslinked PVA/PAN (polyacrylonitrile) composite membrane is used for ethanol dehydration, infiltrating and vaporizing membrane is made to have obtained work by age, GFT companies
The application of industry.Currently, the infiltrating and vaporizing membrane of commercialization is mainly PVA film.Due to PVA good dissolubilities and film forming,
The reverse osmosis field of nanofiltration is had been applied to, for improving the resistance tocrocking of film.Its method is multiple mainly in polyamide functional layer
Unify layer PVA, then heat cross-linking is carried out by crosslinking agent, detailed process is shown in CN101462024.Utilize crosslinked PVA functional layer systems
Standby composite nanometer filtering film is also it has been reported that still since its poor salt-stopping rate is (generally to Na2SO4Rejection be less than
90%) fail to realize industrialization.
Silane coupling agent is a kind of silane with organo-functional group, has energy and inanimate matter material simultaneously in the molecule thereof
(such as glass, silica sand, metal) chemically combined reactive group and chemically combined anti-with organic material (synthetic resin etc.)
Answer group.Main application is in adhesive field.
Therefore, how silane coupling agent to be introduced into and prepares a kind of acidproof composite nanometer filtering film in PVA systems and need
In further R and D.
Invention content
The purpose of the invention is to overcome the defect of existing NF membrane acid resistance difference, and provide a kind of composite nanometer filtering film
And preparation method thereof and the composite nanometer filtering film and composite nanometer filtering film the answering in water treatment field that is prepared by this method
With.
To achieve the goals above, the present invention provides a kind of composite nanometer filtering film, and the composite nanometer filtering film includes being stacked in one
The supporting layer and separating layer risen, wherein the separating layer is that the polymer containing hydroxyl and the silane coupling agent containing amino are molten
Solution is in solvent by forming the cross-linked network structure being located in the support layer surface after sol-gel and heat cross-linking reaction
Composite nanometer filtering film, then the initial composite NF membrane carries out to post-processing is modified to be obtained in sultones.
The present invention also provides a kind of preparation methods of composite nanometer filtering film, and this approach includes the following steps：
(1) polymer containing hydroxyl, the silane coupling agent containing amino are dissolved in solvent and are prepared into coating liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) by step (2) be formed with initial film supporting layer immerse the solution containing crosslinking agent and crosslinking catalyst in into
Row cross-linking reaction, obtain include supporting layer and the cross-linked network in the support layer surface initial composite NF membrane；
(4) the initial composite NF membrane in sultones is subjected to post-processing modification, obtains modified compound receive
Filter membrane.
The present invention also provides the composite nanometer filtering films being prepared by the above method.
The composite nanometer filtering film being prepared the present invention also provides above-mentioned composite nanometer filtering film and by the above method is in water process
Application in field.
The present inventor by further investigation find, on the one hand, the polymer of the present invention containing hydroxyl with
Silane coupling agent containing amino all has stronger acid resistance；On the other hand, the polymer containing hydroxyl and contain amino
Silane coupling agent after sol-gel and heat cross-linking reaction by foring cross-linked network structure, then, initial multiple by what is obtained
It closes NF membrane and further carries out post-processing modification in the sultones of specific temperature, arrived by necleophilic reaction by sulfonic group is branched
Nanofiltration film surface obtains modified composite nanometer filtering film, not only increases the mechanical property of film, and also increases to inorganic salts
And the cutoff performance of organic molecule.In conclusion separating layer of the present invention be by the polymer containing hydroxyl with contain
It is formed after thering is the silane coupling agent of amino to be post-processed by sol-gel, heat cross-linking reaction and with sultones；This hair
The bright composite nanometer filtering film not only has higher salt rejection rate and water penetration (water flux), also has stronger acid resistance, and
And preparation method is simple, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the forming process schematic diagram of the composite nanometer filtering film prepared by the present invention.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of composite nanometer filtering film, the composite nanometer filtering film includes the supporting layer to stack together and separation
Layer, wherein the separating layer is that the polymer containing hydroxyl is dissolved in solvent with the silane coupling agent containing amino by molten
The initial composite nanofiltration for the cross-linked network structure being located in the support layer surface is formed after glue-gel and heat cross-linking reaction
Film, then the initial composite NF membrane is carried out what post-processing modification obtained in sultones.
According to the present invention, the sultones can be 1,3- propyl sulfonic acids lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and 1,8-
It is one or more in naphthalene sulfonic acids lactone.
According to the present invention, the polymer containing hydroxyl is polyethylene glycol, polyvinyl alcohol, chitosan, chitosan quaternary ammonium
It is one or more in salt, polyether polyol and polyester polyol；From the point of view of raw material is ready availability, it is preferable that described to contain
It is one or more in polyethylene glycol, polyvinyl alcohol and chitosan to have the polymer of hydroxyl.In the present invention, the chitosan
(chitosan) it is also known as chitosan, is that the chitin (chitin) being widely present by nature is obtained by deacetylation
It arrives, chemical name is Chitosan (1-4) -2- amino-B-D glucose.
According to the present invention, the silane coupling agent containing amino can include all silane coupling agents containing amino,
From the point of view of raw material is ready availability, the silane coupling agent containing amino can be gamma-amino propyl trimethoxy silicane,
γ aminopropyltriethoxy silane (KH550), N- (β-aminoethyl)-γ-aminopropyls front three (second) oxysilane, N- (β-ammonia
Ethyl)-γ-aminopropyltriethoxies dimethoxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino hydroxypropyl methyl two
One in methoxy silane, dimethylaminopropyl trimethoxy silane and 4- amino -3,3- dimethylbutyl trimethoxy silanes
Kind is a variety of；Preferably, the silane coupling agent containing amino is gamma-amino propyl trimethoxy silicane and/or gamma-amino
Propyl-triethoxysilicane.
According to the present invention, the thickness of the supporting layer and separating layer is not particularly limited, and can be the routine of this field
Selection, but in order to enable this two layers can play the role of better coordinated, so as to get composite nanometer filtering film can be preferably
Have both excellent acid resistance, higher water flux and salt rejection rate, under preferable case, the thickness of the supporting layer is that 90-150 is micro-
The thickness of rice, the separating layer is 0.05-0.5 microns；In the case of more preferably, the thickness of the supporting layer is 100-120 microns,
The thickness of the separating layer is 0.1-0.3 microns.
According to the present invention, the supporting layer is not particularly limited, can be by existing various with certain intensity and energy
Be enough in nanofiltration, the material of reverse osmosis membrane is made, usually can be by polyacrylonitrile, Kynoar, the non-sulfonated poly- virtue of phenolphthalein type
One or more in ether sulfone, polyether sulfone and bisphenol-a polysulfone are made, and can know to this those skilled in the art, herein will
It repeats no more.
It is described to contain on the basis of the solvent of 100 parts by weight in the forming process of the separating layer according to the present invention
The dosage of the polymer of hydroxyl can be 0.1-50 parts by weight, and the dosage of the silane coupling agent containing amino can be
0.01-50 parts by weight；In the case of more preferably, on the basis of the solvent of 100 parts by weight, the dosage of the polymer containing hydroxyl
Dosage for 0.25-25 parts by weight, the silane coupling agent containing amino is 0.025-25 parts by weight.
The present invention also provides a kind of preparation methods of composite nanometer filtering film, and this approach includes the following steps：
(1) polymer containing hydroxyl, the silane coupling agent containing amino are dissolved in solvent and are prepared into coating liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) by step (2) be formed with initial film supporting layer immerse the solution containing crosslinking agent and crosslinking catalyst in into
Row cross-linking reaction, obtain include supporting layer and the cross-linked network structure in the support layer surface initial composite nanofiltration
Film；
(4) the initial composite NF membrane in sultones is subjected to post-processing modification, obtains modified compound receive
Filter membrane.
According to the present invention, the present invention in the coating liquid the polymer containing hydroxyl, contain the silane coupled of amino
The dosage of agent and solvent is not particularly limited, if the NF membrane enabled to can have both excellent acid resistance, compared with
High water flux and salt rejection rate, for example, in step (1), it is described to contain hydroxyl on the basis of the solvent of 100 parts by weight
The dosage of polymer can be 0.1-50 parts by weight, preferably 0.25-25 parts by weight；The silane coupling agent containing amino
Dosage can be 0.01-50 parts by weight, preferably 0.025-25 parts by weight；In the present invention, the preparation of the coating liquid
Cheng Youxuan is carried out in the presence of the catalyst for sol-gel, and the catalyst of the sol-gel is not particularly limited,
Can be one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, preferably hydrochloric acid, and with 100 parts by weight
On the basis of solvent, the dosage of the catalyst of the sol-gel is 0.01-50 parts by weight, preferably 0.025-25 parts by weight.Separately
Outside, in the present invention, the concentration of the hydrochloric acid is not particularly limited, it is preferable that a concentration of 0.5-1.5mol/L of the hydrochloric acid,
It is highly preferred that a concentration of 1mol/L of the hydrochloric acid.
According to the present invention, the present invention is not particularly limited the pH value of the coating liquid, it is preferable that the pH of the coating liquid
Value is 1-4.
According to the present invention, the polymer containing hydroxyl, the silane coupling agent containing amino are being dissolved in solvent by the present invention
During, it preferably carries out under stirring conditions, the present invention is not specific to the condition of the stirring and the equipment of stirring
It limits, the conventional mixing plant that can be well known to those skilled in the art carries out under stirring condition appropriate, as long as energy
The polymer containing hydroxyl, the silane coupling agent containing amino is enough set to be completely dissolved in solvent.In addition, the present invention is inciting somebody to action
The process that polymer containing hydroxyl, the silane coupling agent containing amino are dissolved in solvent carries out at normal temperatures.
According to the present invention, the present invention is not particularly limited the thickness of the supporting layer, can be the routine of this field
Selection, but in order to enable the supporting layer and the separating layer can play the role of better coordinated, make it is compound
NF membrane can preferably have both excellent acid resistance, higher water flux and salt rejection rate, under preferable case, the supporting layer
Thickness be 90-150 microns, preferably 100-120 microns.
According to the present invention, the present invention is not particularly limited the dosage of the coating liquid, but in order to enable the nanofiltration arrived
Film can preferably have both excellent acid resistance, higher water flux and salt rejection rate, under preferable case, the use of the coating liquid
Amount is so that the thickness of the separating layer is 0.05-0.5 microns, preferably 0.1-0.3 microns.
Do not had coated in the present invention to described during the coating liquid is coated in supporting layer according to the present invention
It is specific to limit, in the spraying that can be well known to those skilled in the art, blade coating, spin coating etc. any one.
According to the present invention, after coating liquid is coated uniformly on supporting layer, under preferable case, this is coated with coating liquid
Supporting layer to be put into baking oven complete solvent therein to volatilize, do not have to its temperature and time in an oven in the present invention
Body limits, as long as can ensure that solvent volatilization is complete, under preferable case, and the dry 20- in the baking oven that temperature is 50-70 DEG C
It is 40 minutes, 25-35 minutes dry in the baking oven that temperature is 55-65 DEG C in the case of more preferable.
According to the present invention, the present invention is not particularly limited the type of the solvent, as long as described contain can be dissolved
The polymer of hydroxyl and silane coupling agent containing amino, for example, in step (1), the solvent can be water, first
It is one or more in alcohol, ethyl alcohol, acetone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), it is preferable that the solvent is
The mixed solvent of water, ethyl alcohol and dimethyl sulfoxide (DMSO), and in the in the mixed solvent, water, ethyl alcohol and dimethyl sulfoxide (DMSO) weight ratio
Can be 1-50：1-30：1, preferably 1-25：1-20：1.It is more advantageous to using the mixed solvent of water, ethyl alcohol and dimethyl sulfoxide (DMSO)
Above-mentioned several substances dissolving, and the coating liquid of preparation can be made preferably to be coated on supporting layer, and what is enabled to are received
Filter membrane can preferably have both excellent acid resistance, higher water flux and salt rejection rate.
According to the present invention, in step (3), the condition of the cross-linking reaction may include：Crosslinking temperature is 20-100 DEG C,
Crosslinking time is -48 hours 10 minutes；Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is -24 hours 20 minutes.
According to the present invention, the crosslinking agent contained in crosslinker solution of the present invention can be common aldehydes, such as can be
It is one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, malonaldehyde, butanedial and glutaraldehyde, preferably first
It is one or more in aldehyde, acetaldehyde, propionic aldehyde and butyraldehyde, more preferably formaldehyde.
According to the present invention, a kind of crosslinking catalyst contained in crosslinker solution of the present invention can be customary acid class,
Can be such as one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, preferably in sulfuric acid, hydrochloric acid and acetic acid
One or more, more preferably sulfuric acid；In addition, another crosslinking catalyst contained in crosslinker solution of the present invention can
Think Sulfates, such as can be it is one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate, preferably sodium sulphate,
It is one or more in sulphate of potash and magesium, more preferably sodium sulphate.
According to the present invention, the present invention is not special to the dosage of crosslinking agent and crosslinking catalyst in the crosslinker solution
Ground limits, as long as the composite nanometer filtering film enabled to can have both excellent acid resistance, higher water flux and salt rejection rate
.In the present invention, on the basis of the total weight of the solvent, the dosage of the crosslinking agent is 1-100 weight %, preferably
10-50 weight %；The dosage of the acids is 1-98 weight %, preferably 5-80 weight %；The dosage of the Sulfates is
1-60 weight %, preferably 5-50 weight %.
According to the present invention, in step (4), the initial composite NF membrane is impregnated in sultones and is post-processed
It is modified, it is by necleophilic reaction that sulfonic group is branched to nanofiltration film surface, obtain modified composite nanometer filtering film；Wherein, described first
The condition that beginning composite nanometer filtering film is post-processed in sultones includes：Temperature can be 25-100 DEG C, and the time can be 1 point
Clock -10 hours；Preferably, temperature is 30-80 DEG C, and the time is -5 hours 10 minutes；Wherein, the initial composite NF membrane is existed
The mode impregnated in sultones is not particularly limited, as long as the initial composite NF membrane is completely infused in sultones
.Under this condition by nucleophilic substitution, nanofiltration film surface is arrived by sulfonic group is branched, obtains composite nanometer filtering film, it can
The composite nanometer filtering film enable has both excellent acid resistance, higher water flux and salt rejection rate.
It is difficult in a solvent since the polymer containing hydroxyl has higher molecular weight according to the present invention
Be completely dissolved, therefore, in order to enable to cross-linked network structure be more uniformly distributed, and improve the composite nanometer filtering film performance stablize
Property, under preferable case, the preparation method of the composite nanometer filtering film further includes that will the coating liquid be coated on supporting layer it
Before, the coating liquid is filtered.In specific operation process, first by the polymer containing hydroxyl and amino can be contained
Silane coupling agent be dissolved in solvent and filter, obtain the coating liquid of homogeneous transparent；In addition, also not having for the filtering
Body limits, the filter method and equipment that can be well known to those skilled in the art.
According to the present invention, in order to enable the composite nanometer filtering film arrived is more smooth, it is preferable that composite nanometer filter provided by the invention
The preparation method of film further includes that the supporting layer is fixed on a glass or applied before coating liquid is coated on supporting layer
On film machine.
The present invention also provides the composite nanometer filtering films being prepared by preparation method provided by the present invention.
The present invention also provides by composite nanometer filtering film of the present invention and by the preparation method system of the present invention
Application of the standby composite nanometer filtering film in water treatment field.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples：
(1) water flux of composite nanometer filtering film is tested obtain by the following method：Composite nanometer filter permeable membrane is fitted into membrane cisterna,
Under 1.2MPa after precompressed 0.5 hour, under pressure is 2.0MPa, temperature be 25 DEG C under the conditions of measure the water of the NF membrane in 1h
Transit dose, and be calculated by the following formula to obtain：
J=Q/ (At), wherein J is water flux, and Q is water transit dose (L), and A is effective membrane area of composite nanometer filtering film
(m2), t is the time (h)；
(2) salt rejection rate of composite nanometer filtering film tests obtain by the following method：Composite nanometer filtering film is fitted into membrane cisterna,
Under 1.2MPa after precompressed 0.5h, under pressure is 2.0MPa, temperature be 25 DEG C under the conditions of to measure initial concentration in 1h be 2000ppm
Sodium sulphate raw water solution and permeate in the concentration of sodium sulphate change, and be calculated by the following formula to obtain：
R=(Cp-Cf)/Cp× 100%, wherein R is salt rejection rate, CpFor the concentration of sodium sulphate in stoste, CfFor in permeate
The concentration of sodium sulphate；
(3) the acid resistance test of composite nanometer filtering film：It is by composite nanometer filtering film diaphragm containing 10 mass %H2SO4Aqueous solution
In impregnate one month, the then variation of the water flux and salt-stopping rate of test compound NF membrane week about.
In addition, in the following Examples and Comparative Examples：
Polyvinyl alcohol (PVA) is purchased from lark prestige Science and Technology Ltd. (alcoholysis degree 95%, weight average molecular weight 95000),
γ aminopropyltriethoxy silane (KH550), 1,3- propyl sulfonic acid lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and 1,8- naphthalene sulfonic acids
Lactone is purchased from lark prestige Science and Technology Ltd.；Polysulfones counterdie is purchased from Hangzhou Mei Yi films Science and Technology Ltd., and thickness is 120 micro-
Rice；Formaldehyde, the concentrated sulfuric acid, sodium sulphate, ethyl alcohol, hydrochloric acid etc. are purchased from Sinopharm Chemical Reagent Co., Ltd..
Embodiment 1
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
By the γ aminopropyltriethoxy silane (KH550) of 1.0g polyvinyl alcohol (PVA), 1.0g be dissolved in 100g go from
In sub- water, the dilute hydrochloric acid of 1mol/L is then instilled under stiring, and the pH value for adjusting solution is 1.At normal temperatures, after stirring for 24 hours, mistake
Filter obtains clarification coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, it is then placed in 60 DEG C of baking oven and heats 30min, really
It is complete to protect solvent volatilization；Again by obtained initial composite NF membrane be immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and
In the solution of 15g sodium sulphate, at 60 DEG C, after heating 30min, which is taken out, is immersed in after washing
In deionized water, for future use；
Obtained initial composite NF membrane is immersed in 1,3- propyl sulfonic acid lactones, is obtained after 1h is heated under the conditions of 50 DEG C
To modified composite nanometer filtering film, which is taken out, is rinsed well with deionized water, impregnated in deionized water.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite membrane 10 mass % H2SO4It is 2.0MPa, temperature in pressure after being impregnated one month in aqueous solution
Degree measures water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Fig. 1 gives the forming process of the composite nanometer filtering film of the present invention, is by the silane coupling agent water containing amino first
It solves and simultaneously interacts with polyhydroxylated polymer polyethylene, then by acid condition, utilize the anti-of formaldehyde and hydroxyl
It answers so that the silane coupling agent containing amino reacts to form cross-linked network structure with polyhydroxylated polymer；It finally, will be crosslinked
Perfect initial composite NF membrane carries out post-processing modification in sultones, by necleophilic reaction that sulfonic group is branched to nanofiltration
Film surface obtains composite nanometer filtering film.
Embodiment 2
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
The gamma-amino propyl trimethoxy silicane (KH540) of 1.0g PVA, 0.5g are dissolved in 100g deionized waters, so
The dilute hydrochloric acid for instilling 1mol/L under stiring afterwards, the pH value for adjusting solution are 3.At normal temperatures, it after stirring for 24 hours, is obtained by filtration clear
Clear coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, it is then placed in 60 DEG C of baking oven and heats 30min, really
It is complete to protect solvent volatilization；Again by obtained initial composite NF membrane be immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and
In the solution of 15g sodium sulphate, at 60 DEG C, after heating 30min, which is taken out, is immersed in after washing
In deionized water, for future use；
Obtained initial composite NF membrane is immersed in Isosorbide-5-Nitrae-butyl sulfonic acid lactone, is obtained after 2h is heated under the conditions of 50 DEG C
To modified composite nanometer filtering film, which is taken out, is rinsed well with deionized water, impregnated in deionized water.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite membrane 10 mass % H2SO4It is 2.0MPa, temperature in pressure after being impregnated one month in aqueous solution
Degree measures water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 3
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
By N- (β-aminoethyl)-γ-aminopropyls front three (second) oxysilane of PVA, 1.5g of 1.0g be dissolved in 100g go from
In sub- water, the dilute hydrochloric acid of 1mol/L is then instilled under stiring, and the pH value for adjusting solution is 4.At normal temperatures, after stirring for 24 hours, mistake
Filter obtains clarification coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, it is then placed in 50 DEG C of baking oven and heats 30min, really
It is complete to protect solvent volatilization；Again by obtained initial composite NF membrane be immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and
In the solution of 15g sodium sulphate, at 60 DEG C, after heating 30min, which is taken out, is immersed in after washing
In deionized water, for future use；
Obtained initial composite NF membrane is immersed in 1,8- naphthalene sulfonic acids lactones, is obtained after heating 2h under the conditions of 60 DEG C
The composite nanometer filtering film is taken out, is rinsed well with deionized water by modified composite nanometer filtering film, is impregnated in deionized water.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 4
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, initial answered what is obtained
It closes NF membrane to be immersed in 1,3- propyl sulfonic acid lactones, modified composite nanometer filtering film is obtained after heating 1h at 40 DEG C.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 5
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, initial answered what is obtained
It closes NF membrane to be immersed in 1,3- propyl sulfonic acid lactones, modified composite nanometer filtering film is obtained after heating 1h at 60 DEG C.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 6
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, initial answered what is obtained
It closes NF membrane to be immersed in 1,3- propyl sulfonic acid lactones, modified composite nanometer filtering film is obtained after heating 0.5h at 50 DEG C.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 7
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, initial answered what is obtained
It closes NF membrane to be immersed in 1,3- propyl sulfonic acid lactones, modified composite nanometer filtering film is obtained after heating 2h at 50 DEG C.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 8
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, initial answered what is obtained
It closes NF membrane to be immersed in 1,3- propyl sulfonic acid lactones, modified composite nanometer filtering film is obtained after heating 3h at 50 DEG C.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 9
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, the polyhydroxy in coating liquid
Based polyalcohol substitutes polyvinyl alcohol with chitosan.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Embodiment 10
The embodiment is for illustrating composite nanometer filtering film provided by the invention and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, the polyhydroxy in coating liquid
Based polyalcohol substitutes polyvinyl alcohol with chitosan quaternary ammonium salt.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Comparative example 1
The comparative example is used to illustrate the composite nanometer filtering film and preparation method thereof that the prior art provides.
According to prepare the preparation method of composite nanometer filtering film identical with implementing 1, institute the difference is that, not in sulfonic acid
The post-processing of ester is modified.
After obtained composite nanometer filtering film is impregnated 24 hours in water, then pressure is 2.0MPa, temperature is 25 DEG C of items
Water flux and salt rejection rate are measured under part, the results are shown in Table 1.
In addition, by the composite nanometer filtering film 10 mass % H2SO4After being impregnated one month in aqueous solution, it is in pressure
2.0MPa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and the results are shown in Table 1.
Table 1
Can be seen that composite nanometer filtering film provided by the invention from the result of above example 1-10 has excellent water flux
And salt-stopping rate, and before being handled with soda acid and with 10 weight %H2SO4Result after handling 30 days can be seen that the present invention and carry
The composite nanometer filtering film of confession has acid resistance well, and preparation method is simple, great prospects for commercial application.
Further, it can be seen that from the comparing result of embodiment 1-10 and comparative example 1 without will be initial with sultones
The water flux that composite nanometer filtering film carries out the modified composite nanometer filtering film of post-processing is relatively low, can reduce the application of the composite nanometer filtering film in this way
Efficiency, waste of energy largely limit the commercial Application of this composite nanometer filtering film.
In addition, Fig. 1 is the forming process schematic diagram of the composite nanometer filtering film prepared by the present invention, and as seen from Figure 1, this hair
It is bright by the way that initial composite NF membrane is carried out post-processing modification with sultones, can be by hydrophilic sulfonic acid by necleophilic reaction
Base is introduced on the surface of composite nanometer filtering film, is effectively improved the water flux of the composite nanometer filtering film.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (20)
1. a kind of composite nanometer filtering film, the composite nanometer filtering film includes the supporting layer to stack together and separating layer, which is characterized in that
The separating layer be the polymer containing hydroxyl and the silane coupling agent containing amino be dissolved in solvent by sol-gel with
And the initial composite NF membrane for the cross-linked network structure being located in the support layer surface is formed after heat cross-linking reaction, then will be described
Initial composite NF membrane carries out what post-processing modification obtained in sultones；
Wherein, the sultones is 1,3- propyl sulfonic acids lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and 1, in 8- naphthalene sulfonic acids lactones
It is one or more；
Wherein, the thickness of the supporting layer is 90-150 microns；The thickness of the separating layer is 0.05-0.5 microns；
Wherein, the polymer containing hydroxyl is polyethylene glycol, polyvinyl alcohol, chitosan, chitosan quaternary ammonium salt, polyether polyols
It is one or more in alcohol and polyester polyol；
Wherein, the silane coupling agent containing amino is gamma-amino propyl trimethoxy silicane, three ethoxy of gamma-amino propyl
Base silane, N- (β-aminoethyl)-γ-aminopropyls front three (second) oxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy diformazans
Oxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, Y- aminopropylmethyldimethoxysilanes, dimethylaminopropyl
It is one or more in trimethoxy silane and 4- amino -3,3- dimethylbutyl trimethoxy silanes.
2. composite nanometer filtering film according to claim 1, wherein the thickness of the supporting layer is 100-120 microns；Described point
The thickness of absciss layer is 0.1-0.3 microns.
3. composite nanometer filtering film according to claim 1, wherein in the forming process of the separating layer, with 100 parts by weight
Solvent on the basis of, the dosage of the polymer containing hydroxyl is 0.1-50 parts by weight；It is described to contain the silane coupled of amino
The dosage of agent is 0.01-50 parts by weight.
4. composite nanometer filtering film according to claim 3, wherein described to contain hydroxyl on the basis of the solvent of 100 parts by weight
Polymer dosage be 0.25-25 parts by weight；The dosage of the silane coupling agent containing amino is 0.025-25 parts by weight.
5. composite nanometer filtering film according to claim 1, wherein the polymer containing hydroxyl be polyethylene glycol and/or
Chitosan.
6. composite nanometer filtering film according to claim 1, wherein the silane coupling agent containing amino is gamma-amino third
Base trimethoxy silane.
7. the preparation method of the composite nanometer filtering film described in any one of claim 1-6, this approach includes the following steps：
(1) polymer containing hydroxyl, the silane coupling agent containing amino are dissolved in solvent and are prepared into coating liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) step (2) is formed in solution of the supporting layer immersion containing crosslinking agent and crosslinking catalyst of initial film and is handed over
Connection reaction, obtain include supporting layer and the cross-linked network structure in the support layer surface initial composite NF membrane；
(4) the initial composite NF membrane in sultones is subjected to post-processing modification, obtains modified composite nanometer filtering film.
8. preparation method according to claim 7, wherein in step (1), the solvent is water, methanol, ethyl alcohol, third
It is one or more in ketone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO).
9. preparation method according to claim 8, wherein in step (1), the solvent is water, ethyl alcohol and dimethyl
The mixed solvent of sulfoxide.
10. preparation method according to claim 9, wherein in the in the mixed solvent, water, ethyl alcohol and dimethyl sulfoxide (DMSO)
Weight ratio be 1-50：1-30：1.
11. preparation method according to claim 10, wherein in the in the mixed solvent, water, ethyl alcohol and dimethyl sulfoxide (DMSO)
Weight ratio be 1-25：1-20：1.
12. preparation method according to claim 7, wherein in step (3), the condition of the cross-linking reaction includes：It hands over
It is 20-100 DEG C to join temperature, and crosslinking time is -48 hours 10 minutes.
13. preparation method according to claim 12, wherein in step (3), the condition of the cross-linking reaction includes：
Crosslinking temperature is 40-80 DEG C, and crosslinking time is -24 hours 20 minutes.
14. preparation method according to claim 7, wherein in the cross-linking reaction, the crosslinking agent is formaldehyde, second
It is one or more in aldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, malonaldehyde, butanedial and glutaraldehyde；The crosslinking catalyst is
It is one or more in acids and Sulfates；And on the basis of the total weight of the solvent, the dosage of the crosslinking agent is 1-
100 weight %；The dosage of the acids is 1-98 weight %；The dosage of the Sulfates is 1-60 weight %.
15. preparation method according to claim 14, wherein on the basis of the total weight of the solvent, the crosslinking agent
Dosage be 10-50 weight %；The dosage of the acids is 5-80 weight %；The dosage of the Sulfates is 5-50 weights
Measure %.
16. preparation method according to claim 15, wherein the acids be sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and
It is one or more in nitric acid；The Sulfates are one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate.
17. preparation method according to claim 7, wherein in step (4), the initial composite NF membrane is in sulfonic acid
Lactone carries out the modified condition of post-processing：Temperature is 25-100 DEG C, and the time is -10 hours 1 minute.
18. preparation method according to claim 17, wherein in step (4), the initial composite NF membrane is in sulfonic acid
Lactone carries out the modified condition of post-processing：Temperature is 30-80 DEG C, and the time is -5 hours 10 minutes.
19. the composite nanometer filtering film being prepared by the preparation method described in any one of claim 7-18.
20. by application of the composite nanometer filtering film described in claim 1 or 19 in water treatment field.
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