CN105498549A - Composite nano-filtration membrane, preparation method and applications thereof - Google Patents
Composite nano-filtration membrane, preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a composite nano-filtration membrane. The composite nano-filtration membrane comprises a supporting layer and a separating layer, which are laminated together. The separating layer is prepared by the following steps: dissolving a polymer containing hydroxyl groups and a silane coupling agent containing amino groups into a solvent, carrying out sol-gel and thermo-crosslinking reactions so as to form a primary composite nano-filtration membrane, which is formed on the surface of the supporting layer and has a crosslinked network structure, and then subjecting the primary composite nano-filtration membrane to a post treatment in sultone. The composite nano-filtration membrane has the advantages of high desalting rate, high water flux, strong acid resistant performance, simple preparation method, and good industrial application prospect.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering film and preparation method thereof, and the application of this composite nanometer filtering film in water treatment field.
Background technology
Nanofiltration is a kind of pressure-driven membrane separating process between counter-infiltration and ultrafiltration, the pore diameter range of NF membrane is at a few ran, organic matter monovalention and molecular weight being less than to 200 removes poor, and has higher removal efficiency to divalence or multivalent ion and the organic matter of molecular weight between 200 ~ 500.Can be widely used in that fresh water is softening, seawater softening, drink water purifying, water correction, water-oil separating, wastewater treatment and recycling, and the classification of the heavy chemicals such as dyestuff, antibiotic, polypeptide and polysaccharide, purifying and the field such as concentrated.
At present, commercial nanofiltration membrane greatly mainly with polysulphone super-filter membrane as supporting layer, carry out the interfacial polymerization of polyamine aqueous phase and polynary acyl chlorides organic phase in milipore filter upper surface original position, final product is composite nanometer filtering film.Common aqueous phase monomers is that piperazine or piperazine replace amine, organic phase is pyromellitic trimethylsilyl chloride or a kind of multifunctional carboxylic acid halides, as the content of report disclosed in patent No. US4769148 and US4859384, a large amount of unreacted acid chloride groups is hydrolyzed into carboxylic acid, make NF membrane surface band negative electricity, utilize charge effect, polypiperazine-amide composite nanometer filtering film has higher rejection to high-valence anion, has adjustable rejection to monovalent anion.In addition, patent No. US4765897, US4812270 and US4824574 additionally provide a kind of method how polyamide composite reverse osmosis membrane being transformed into NF membrane.But, due to the restriction of material self character, under extreme pH environments, particularly under basic conditions, traditional polyamide-based NF membrane can be degraded, because the use pH scope of polyamide nanofiltration membrane is generally 2 ~ 11, so neutral medium or the weak acid and weak base medium close to neutrality can only be used for.
In recent years, researchers develop multiple NF membrane, and occur multiple commercial product.In addition, a lot of new material, such as sulfonated polyether ketone, sulfonated polyether sulfone etc. are also applied to nanofiltration field.
Document " Acidstablethin-filmcompositemembranefornanofiltrationpre paredfromnaphthalene-1,3,6-trisulfonylchloride (NTSC) andpiperazine (PIP), J.Membr.Sci., 415-416,122-131,2012 " report in: sulfonamide material has very strong acid resistance, and the composite nanometer filtering film utilizing polynary sulfonic acid chloride monomer and piperazine to be obtained by interfacial polymerization can keep stable separating property in pH=0 environment.
Document " Sulfonatedpoly (etheretherketone) basedcompositemembranesfornanofiltrationofacidicandalkal inemedia, J.Membr.Sci., 381, 81-89, 2011 " report in: sulfonated polyether-ether-ketone both had acid resistance, there is again very strong alkali resistance, by the crosslinked NF membrane material that more can obtain cutoff performance excellence, and, polyetheretherketonematerials materials after crosslinked has very strong solvent resistance, dyestuff (Crosslinkingofmodifiedpoly (etheretherketone) membranesforuseinsolventresistantnanofiltration can be separated in isopropyl alcohol with acetone polar solvent, 447, 212-221, 2013).
" acid and alkali-resistance is high temperature resistant, and NF membrane HYDRACoRe70pHT is used for the recovery of sugar industry spent lye to document, membrane science and technology, 32,11-15,2006 " report in: commercial sulfonated polyether sulfone class composite nanometer filtering film is the HYDRACoRe series developed by day east electrician's Hydranautics company, can use in strong acid, strong base solution, be widely used in the recovery of salkali waste.
The acidproof NF membrane DuracidNF1812C that GE company develops is three-layer composite structure, can 20% hydrochloric acid, keep stable under sulfuric acid and phosphoric acid condition, and at 70 DEG C, still can keep stable under the sulfuric acid condition of 20% concentration.
Patent No. US5265734, the SelROMPS34 that KOCH company can be only had to develop in the NF membrane of pH=0 ~ 14 long-term stability operation is reported in EP0392982 (A3), it is developed by Israel scientist the earliest, and material is silicon rubber, is applied to infiltration evaporation the 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 degree of crystallinity of PVA, improves the mechanical strength of film, increases film to the rejection of salt ion, and has the performance of better acid and alkali-resistance and solvent.The eighties in last century, crosslinked PVA/PAN (polyacrylonitrile) composite membrane is used for ethanol dehydration by GFT company, makes infiltrating and vaporizing membrane obtain industrialized application.At present, commercial infiltrating and vaporizing membrane is mainly PVA film.The dissolubility good due to PVA and film forming, be applied to nanofiltration counter-infiltration field, is used for improving the resistance tocrocking of film.Its method is compound one deck PVA in polyamide functional layer mainly, then carries out heat cross-linking by crosslinking agent, and detailed process is shown in CN101462024.The composite nanometer filtering film utilizing crosslinked PVA functional layer to prepare also has bibliographical information, but because its poor salt-stopping rate is (generally to Na
2sO
4rejection lower than 90%) fail to realize industrialization.
Silane coupler is the silane that a class has organo-functional group, have in the molecule thereof simultaneously can and inanimate matter material (as glass, silica sand, metal etc.) chemically combined reactive group and with organic material (synthetic resin etc.) chemically combined reactive group.It is mainly used in adhesive field.
Therefore, how silane coupler is incorporated in PVA system and prepares a kind of acidproof composite nanometer filtering film and to need further R and D.
Summary of the invention
The object of the invention is the defect in order to overcome existing NF membrane acid resistance difference, and a kind of composite nanometer filtering film and preparation method thereof is provided, and this composite nanometer filtering film and the application of composite nanometer filtering film in water treatment field that prepared by the method.
To achieve these goals, the invention provides a kind of composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, wherein, to be polymer containing hydroxyl react by sol-gel and heat cross-linking the composite nanometer filtering film forming the cross-linked network structure be positioned in described support layer surface afterwards with being dissolved in solvent containing amino silane coupler to described separating layer, more described initial composite NF membrane is carried out in sultones post processing modification obtains.
Present invention also offers a kind of preparation method of composite nanometer filtering film, the method comprises the following steps:
(1) by the polymer containing hydroxyl, to be dissolved in solvent containing amino silane coupler and to be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the initial composite NF membrane comprising supporting layer He be positioned at the cross-linked network in described support layer surface;
(4) described initial composite NF membrane is carried out post processing modification in sultones, obtain modified composite nanometer filtering film.
Present invention also offers the composite nanometer filtering film prepared by said method.
The application of composite nanometer filtering film in water treatment field that present invention also offers above-mentioned composite nanometer filtering film and prepared by said method.
The present inventor finds through further investigation, and on the one hand, the polymer containing hydroxyl of the present invention all has stronger acid resistance with containing amino silane coupler; On the other hand, cross-linked network structure is defined after polymer containing hydroxyl and the silane coupler containing amino are reacted by sol-gel and heat cross-linking, then, the initial composite NF membrane obtained is carried out post processing modification further in the sultones of specified temp, by necleophilic reaction, sulfonic group branching is surperficial to NF membrane, obtain modified composite nanometer filtering film, not only increase the mechanical property of film, and also increase the cutoff performance to inorganic salts and organic molecule.In sum, separating layer of the present invention be by the polymer containing hydroxyl with to be reacted by sol-gel, heat cross-linking containing amino silane coupler and formed after carrying out post processing with sultones; 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 its preparation method is simple, has prospects for commercial application.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the forming process schematic diagram of the composite nanometer filtering film prepared by the present invention.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, wherein, to be polymer containing hydroxyl react by sol-gel and heat cross-linking the initial composite NF membrane forming the cross-linked network structure be positioned in described support layer surface afterwards with being dissolved in solvent containing amino silane coupler to described separating layer, more described initial composite NF membrane is carried out in sultones post processing modification obtains.
According to the present invention, described sultones can be one or more in 1,3-propyl sulfonic acid lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and 1,8-naphthalene sulfonic acids lactone.
According to the present invention, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol, shitosan, chitosan quaternary ammonium salt, PPG and PEPA; From the angle consideration that raw material is ready availability, preferably, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol and shitosan.In the present invention, described shitosan (chitosan) is also known as chitosan, be that the chitin (chitin) extensively existed by nature obtains through deacetylation, chemical name is Chitosan (1-4)-2-amino-B-D glucose.
According to the present invention, described can comprising containing amino silane coupler contains all amino silane couplers, the angle ready availability from raw material is considered, described can be gamma-amino propyl trimethoxy silicane containing amino silane coupler, γ aminopropyltriethoxy silane (KH550), N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, dimethylaminopropyl trimethoxy silane and 4-amino-3, one or more in 3-dimethylbutyl trimethoxy silane, preferably, described is gamma-amino propyl trimethoxy silicane and/or γ aminopropyltriethoxy silane containing amino silane coupler.
According to the present invention, the thickness of described supporting layer and separating layer is not particularly limited, it can be the routine selection of this area, but two-layerly can play better coordinated effect to make this, the composite nanometer filtering film obtained is enable to have excellent acid resistance, higher water flux and salt rejection rate better concurrently, under preferable case, the thickness of described supporting layer is 90-150 micron, and the thickness of described separating layer is 0.05-0.5 micron; More preferably in situation, the thickness of described supporting layer is 100-120 micron, and the thickness of described separating layer is 0.1-0.3 micron.
According to the present invention, described supporting layer is not particularly limited, can by existing various there is certain intensity and can be used in nanofiltration, the material of reverse osmosis membrane makes, usually can be made up of one or more in polyacrylonitrile, Kynoar, phenolphthalein type non-sulfonated polyether sulphone, polyether sulfone and bisphenol-a polysulfone, all can know these those skilled in the art, will repeat no more at this.
According to the present invention, in the forming process of described separating layer, with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl can be 0.1-50 weight portion, and the described consumption containing amino silane coupler can be 0.01-50 weight portion; More preferably in situation, with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.25-25 weight portion, and the described consumption containing amino silane coupler is 0.025-25 weight portion.
Present invention also offers a kind of preparation method of composite nanometer filtering film, the method comprises the following steps:
(1) by the polymer containing hydroxyl, to be dissolved in solvent containing amino silane coupler and to be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the initial composite NF membrane comprising supporting layer He be positioned at the cross-linked network structure in described support layer surface;
(4) described initial composite NF membrane is carried out post processing modification in sultones, obtain modified composite nanometer filtering film.
According to the present invention, the present invention is not particularly limited the polymer containing hydroxyl in described coating liquid, consumption containing amino silane coupler and solvent, as long as the NF membrane obtained can be enable to have excellent acid resistance, higher water flux and salt rejection rate concurrently, such as, in step (1), with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl can be 0.1-50 weight portion, is preferably 0.25-25 weight portion; The described consumption containing amino silane coupler can be 0.01-50 weight portion, is preferably 0.025-25 weight portion; In the present invention, the preparation process of described coating liquid is preferably carried out under the existence of the catalyst for sol-gel, the catalyst of described 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, be preferably hydrochloric acid, and with the solvent of 100 weight portions for benchmark, the consumption of the catalyst of described sol-gel is 0.01-50 weight portion, be preferably 0.025-25 weight portion.In addition, in the present invention, the concentration of described hydrochloric acid is not particularly limited, and preferably, the concentration of described hydrochloric acid is 0.5-1.5mol/L, and more preferably, the concentration of described hydrochloric acid is 1mol/L.
According to the present invention, the pH value of the present invention to described coating liquid is not particularly limited, and preferably, the pH value of described coating liquid is 1-4.
According to the present invention, the present invention is by the polymer containing hydroxyl, be dissolved in the process of solvent containing amino silane coupler, preferably carry out under the condition stirred, the present invention is not particularly limited the condition of described stirring and the equipment of stirring, the mixing plant of the routine that can be well known to those skilled in the art carries out under suitable stirring condition, as long as can make the polymer containing hydroxyl, be fully dissolved in solvent containing amino silane coupler.In addition, the polymer containing hydroxyl, the process that is dissolved in solvent containing amino silane coupler are being carried out by the present invention at normal temperatures.
According to the present invention, the thickness of the present invention to described supporting layer is not particularly limited, it can be the routine selection of this area, but better coordinated effect can be played in order to make described supporting layer and described separating layer, enabling the composite nanometer filtering film obtained have excellent acid resistance, higher water flux and salt rejection rate better concurrently, under preferable case, the thickness of described supporting layer is 90-150 micron, is preferably 100-120 micron.
According to the present invention, the consumption of the present invention to described coating liquid is not particularly limited, but have excellent acid resistance, higher water flux and salt rejection rate better concurrently to enable the NF membrane obtained, under preferable case, the consumption of described coating liquid makes the thickness of described separating layer be 0.05-0.5 micron, is preferably 0.1-0.3 micron.
According to the present invention, described coating liquid is being coated in the process of supporting layer, the described the present invention of being coated in is being not particularly limited, any one in the spraying that can be well known to those skilled in the art, blade coating, spin coating etc.
According to the present invention, coating liquid is evenly being coated in after on supporting layer, under preferable case, the supporting layer this being coated with coating liquid puts into baking oven with by solvent volatilization wherein completely, is not particularly limited, as long as can guarantee solvent volatilization completely its temperature and time in an oven in the present invention, under preferable case, being dry 20-40 minute in the baking oven of 50-70 DEG C in temperature, more preferably in situation, is dry 25-35 minute in the baking oven of 55-65 DEG C in temperature.
According to the present invention, the kind of the present invention to described solvent is not particularly limited, as long as the described polymer containing hydroxyl and the silane coupler containing amino can be dissolved, such as, in step (1), described solvent can be water, methyl alcohol, ethanol, acetone, glycol monoethyl ether, one or more in ethylene glycol and dimethyl sulfoxide (DMSO), preferably, described solvent is water, the mixed solvent of ethanol and dimethyl sulfoxide (DMSO), and in described mixed solvent, water, the weight ratio of ethanol and dimethyl sulfoxide (DMSO) can be 1-50:1-30:1, be preferably 1-25:1-20:1.The mixed solvent of water, ethanol and dimethyl sulfoxide (DMSO) is adopted more to be conducive to above-mentioned several substance dissolves, and the coating liquid of preparation can be made to be coated on supporting layer better, and the NF membrane obtained can be enable to have excellent acid resistance, higher water flux and salt rejection rate better concurrently.
According to the present invention, in step (3), the condition of described cross-linking reaction can comprise: crosslinking temperature is 20-100 DEG C, and crosslinking time is 10 minutes-48 hours; Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is 20 minutes-24 hours.
According to the present invention, the crosslinking agent contained in crosslinker solution of the present invention can be conventional aldehydes, as being one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde, be preferably in formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde one or more, be 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, as being one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, being preferably one or more in sulfuric acid, hydrochloric acid and acetic acid, being more preferably sulfuric acid; In addition, the another kind of crosslinking catalyst contained in crosslinker solution of the present invention can be Sulfates, as being one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate, being preferably one or more in sodium sulphate, sulphate of potash and magesium, being more preferably sodium sulphate.
According to the present invention, the consumption of the present invention to the crosslinking agent in described crosslinker solution and crosslinking catalyst is not particularly limited, as long as the composite nanometer filtering film obtained can be enable to have excellent acid resistance, higher water flux and salt rejection rate concurrently.In the present invention, with the gross weight of described solvent for benchmark, the consumption of described crosslinking agent is 1-100 % by weight, is preferably 10-50 % by weight; The consumption of described acids is 1-98 % by weight, is preferably 5-80 % by weight; The consumption of described Sulfates is 1-60 % by weight, is preferably 5-50 % by weight.
According to the present invention, in step (4), described initial composite NF membrane is soaked in sultones and carries out post processing modification, by necleophilic reaction, sulfonic group branching is surperficial to NF membrane, obtain modified composite nanometer filtering film; Wherein, the condition that described initial composite NF membrane carries out post processing in sultones comprises: temperature can be 25-100 DEG C, and the time can be 1 minute-10 hours; Preferably, temperature is 30-80 DEG C, and the time is 10 minutes-5 hours; Wherein, the mode that described initial composite NF membrane is soaked in sultones is not particularly limited, as long as described initial composite NF membrane is completely infused in sultones.Under this condition by nucleophilic substitution, by sulfonic group branching to NF membrane surface, obtain composite nanometer filtering film, the composite nanometer filtering film obtained can be enable to have excellent acid resistance, higher water flux and salt rejection rate concurrently.
According to the present invention, because the described polymer containing hydroxyl has higher molecular weight, it is difficult to dissolve completely in a solvent, therefore, in order to make the cross-linked network structure that obtains more even, and improve the stability of described composite nanometer filtering film, under preferable case, the preparation method of described composite nanometer filtering film also comprises before being coated on supporting layer by described coating liquid, is filtered by described coating liquid.In specific operation process, first by described polymer containing hydroxyl and to be dissolved in solvent containing amino silane coupler and to filter, the coating liquid of homogeneous transparent can be obtained; In addition, described filtration is also not particularly limited, the filter method that can be well known to those skilled in the art and equipment.
According to the present invention, in order to make the composite nanometer filtering film that obtains more smooth, preferably, before the preparation method of composite nanometer filtering film provided by the invention is also included in and is coated on supporting layer by coating liquid, by fixing for described supporting layer on a glass or on film machine.
Present invention also offers the composite nanometer filtering film prepared by preparation method provided by the present invention.
Present invention also offers by composite nanometer filtering film of the present invention and the application of composite nanometer filtering film in water treatment field prepared by described preparation method of the present invention.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples:
(1) water flux of composite nanometer filtering film is tested by the following method and is obtained: composite nanometer filter permeable membrane loaded in membrane cisterna, under 1.2MPa, precompressed is after 0.5 hour, at the water transit dose that pressure is under 2.0MPa, temperature records described NF membrane in 1h under being 25 DEG C of conditions, and obtained by following formulae discovery:
J=Q/ (At), wherein, J is water flux, the effective film area (m of Q to be water transit dose (L), A be composite nanometer filtering film
2), t is the time (h);
(2) salt rejection rate of composite nanometer filtering film is tested by the following method and is obtained: loaded by composite nanometer filtering film in membrane cisterna, under 1.2MPa after precompressed 0.5h, in the change in concentration that pressure is under 2.0MPa, temperature records sodium sulphate in the former aqueous solution of sodium sulphate and permeate that initial concentration in 1h is 2000ppm under being 25 DEG C of conditions, and obtained by following formulae discovery:
R=(C
p-C
f)/C
p× 100%, wherein, R is salt rejection rate, C
pfor the concentration of sodium sulphate in stoste, C
ffor the concentration of sodium sulphate in permeate;
(3) the acid resistance test of composite nanometer filtering film: be that composite nanometer filtering film diaphragm is being contained 10 quality %H
2sO
4soak one month in the aqueous solution, the then water flux of test compound NF membrane and the change of salt-stopping rate week about.
In addition, in the following Examples and Comparative Examples:
Purchased from lark prestige Science and Technology Ltd., (alcoholysis degree is 95% to polyvinyl alcohol (PVA), weight average molecular weight is 95000), γ aminopropyltriethoxy silane (KH550), 1,3-propyl sulfonic acid lactone, 1,4-butyl sulfonic acid lactone and 1,8-naphthalene sulfonic acids lactone are all purchased from lark prestige Science and Technology Ltd.; Polysulfones counterdie is purchased from Hangzhou Mei Yi film Science and Technology Ltd., and thickness is 120 microns; Formaldehyde, the concentrated sulfuric acid, sodium sulphate, ethanol, hydrochloric acid etc. are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water by the γ aminopropyltriethoxy silane (KH550) of 1.0g polyvinyl alcohol (PVA), 1.0g, then under agitation instill the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 1.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 60 DEG C heats 30min, guarantees solvent volatilization completely; Again the initial composite NF membrane obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this initial composite NF membrane is taken out, soak in deionized water after washing, for future use;
The initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, heat 1h under 50 DEG C of conditions after, obtains modified composite nanometer filtering film, this composite nanometer filtering film is taken out, clean with deionized water rinsing, soak in deionized water.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Fig. 1 gives the forming process of composite nanometer filtering film of the present invention, first be to be hydrolyzed containing amino silane coupler and to interact with polyhydroxylated polymer polyethylene, then pass through in acid condition, utilize the reaction of formaldehyde and hydroxyl, make to react containing amino silane coupler and polyhydroxylated polymer to form cross-linked network structure; Finally, in sultones, carry out post processing modification by being cross-linked perfect initial composite NF membrane, by necleophilic reaction, sulfonic group branching is surperficial to NF membrane, obtain composite nanometer filtering film.
Embodiment 2
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water by the gamma-amino propyl trimethoxy silicane (KH540) of 1.0gPVA, 0.5g, then under agitation instill the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 3.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 60 DEG C heats 30min, guarantees solvent volatilization completely; Again the initial composite NF membrane obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this initial composite NF membrane is taken out, soak in deionized water after washing, for future use;
The initial composite NF membrane obtained is immersed in Isosorbide-5-Nitrae-butyl sulfonic acid lactone, heat 2h under 50 DEG C of conditions after, obtains modified composite nanometer filtering film, this composite nanometer filtering film is taken out, clean with deionized water rinsing, soak in deionized water.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 3
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water, then under agitation instill the watery hydrochloric acid of 1mol/L by N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS of PVA, 1.5g of 1.0g, the pH value regulating solution is 4.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 50 DEG C heats 30min, guarantees solvent volatilization completely; Again the initial composite NF membrane obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this initial composite NF membrane is taken out, soak in deionized water after washing, for future use;
The initial composite NF membrane obtained is immersed in 1,8-naphthalene sulfonic acids lactone, heat 2h under 60 DEG C of conditions after, obtains modified composite nanometer filtering film, this composite nanometer filtering film is taken out, clean with deionized water rinsing, soak in deionized water.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 4
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, obtains the composite nanometer filtering film of modification at 40 DEG C after heating 1h.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 5
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, obtains the composite nanometer filtering film of modification at 60 DEG C after heating 1h.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 6
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, obtains the composite nanometer filtering film of modification at 50 DEG C after heating 0.5h.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 7
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, obtains the composite nanometer filtering film of modification at 50 DEG C after heating 2h.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 8
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the initial composite NF membrane obtained is immersed in 1,3-propyl sulfonic acid lactone, obtains the composite nanometer filtering film of modification at 50 DEG C after heating 3h.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 9
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the chitosan to replace polyvinyl alcohol of the polyhydroxylated polymer in coating liquid.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 10
This embodiment is for illustration of 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 enforcement 1, institute's difference is, the polyhydroxylated polymer chitosan quaternary ammonium salt in coating liquid substitutes polyvinyl alcohol.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Comparative example 1
Composite nanometer filtering film that this comparative example provides for illustration of prior art and preparation method thereof.
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, not by the post processing modification of sultones.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite nanometer filtering film at 10 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Table 1
As can be seen from the result of above embodiment 1-10, composite nanometer filtering film provided by the invention has excellent water flux and salt-stopping rate, and from before soda acid process and with 10 % by weight H
2sO
4process the result after 30 days can find out, composite nanometer filtering film provided by the invention there is acid resistance well, and preparation method is simple, has prospects for commercial application.
Further, as can be seen from the comparing result of embodiment 1-10 and comparative example 1, water flux without the composite nanometer filtering film with sultones, initial composite NF membrane being carried out post processing modification is lower, the application efficiency of this composite nanometer filtering film can be reduced like this, waste energy, limit the commercial Application of this composite nanometer filtering film to a great extent.
In addition, the forming process schematic diagram of the composite nanometer filtering film of Fig. 1 prepared by the present invention, as seen from Figure 1, the present invention is by carrying out post processing modification with sultones by initial composite NF membrane, pass through necleophilic reaction, hydrophilic sulfonic group can be incorporated on the surface of composite nanometer filtering film, effectively improve the water flux of this composite nanometer filtering film.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (17)
1. a composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, it is characterized in that, to be polymer containing hydroxyl react by sol-gel and heat cross-linking the initial composite NF membrane forming the cross-linked network structure be positioned in described support layer surface afterwards with being dissolved in solvent containing amino silane coupler to described separating layer, more described initial composite NF membrane is carried out in sultones post processing modification obtains.
2. composite nanometer filtering film according to claim 1, wherein, described sultones is one or more in 1,3-propyl sulfonic acid lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and 1,8-naphthalene sulfonic acids lactone.
3. composite nanometer filtering film according to claim 1, wherein, the thickness of described supporting layer is 90-150 micron, is preferably 100-120 micron; The thickness of described separating layer is 0.05-0.5 micron, is preferably 0.1-0.3 micron.
4. composite nanometer filtering film according to claim 1, wherein, in the forming process of described separating layer, with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.1-50 weight portion, is preferably 0.25-25 weight portion; The described consumption containing amino silane coupler is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
5. the composite nanometer filtering film according to claim 1 or 4, wherein, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol, shitosan, chitosan quaternary ammonium salt, PPG and PEPA; Be preferably in polyethylene glycol, polyvinyl alcohol and shitosan one or more.
6. the composite nanometer filtering film according to claim 1 or 4, wherein, described is one or more in amino-3, the 3-dimethylbutyl trimethoxy silanes of gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, Y-amino propyl methyl dimethoxysilane, dimethylaminopropyl trimethoxy silane and 4-containing amino silane coupler; Be preferably gamma-amino propyl trimethoxy silicane and/or γ aminopropyltriethoxy silane.
7. the preparation method of the composite nanometer filtering film in claim 1-6 described in any one, the method comprises the following steps:
(1) by the polymer containing hydroxyl, to be dissolved in solvent containing amino silane coupler and to be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the initial composite NF membrane comprising supporting layer He be positioned at the cross-linked network structure in described support layer surface;
(4) described initial composite NF membrane is carried out post processing modification in sultones, obtain modified composite nanometer filtering film.
8. preparation method according to claim 7, wherein, in step (1), with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.1-50 weight portion, is preferably 0.25-25 weight portion; The described consumption containing amino silane coupler is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
9. preparation method according to claim 7, wherein, the thickness of described supporting layer is 90-150 micron, is preferably 100-120 micron; The consumption of described coating liquid makes the thickness of described separating layer be 0.05-0.5 micron, is preferably 0.1-0.3 micron.
10. the preparation method according to claim 7 or 8, wherein, in step (1), described solvent is one or more in water, methyl alcohol, ethanol, acetone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), preferably, described solvent is the mixed solvent of water, ethanol and dimethyl sulfoxide (DMSO).
11. preparation methods according to claim 10, wherein, in described mixed solvent, the weight ratio of water, ethanol and dimethyl sulfoxide (DMSO) is 1-50:1-30:1, is preferably 1-25:1-20:1.
12. preparation methods according to claim 7, wherein, in step (3), the condition of described cross-linking reaction comprises: crosslinking temperature is 20-100 DEG C, and crosslinking time is 10 minutes-48 hours; Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is 20 minutes-24 hours.
13. preparation methods according to claim 7 or 12, wherein, in described cross-linking reaction, described crosslinking agent is one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde; Described crosslinking catalyst is one or more in acids and Sulfates; And with the gross weight of described solvent for benchmark, the consumption of described crosslinking agent is 1-100 % by weight, be preferably 10-50 % by weight; The consumption of described acids is 1-98 % by weight, is preferably 5-80 % by weight; The consumption of described Sulfates is 1-60 % by weight, is preferably 5-50 % by weight.
14. preparation methods according to claim 13, wherein, described acids is one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid; Described Sulfates is one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate.
15. preparation methods according to claim 7, wherein, in step (4), the condition that described initial composite NF membrane carries out post processing modification at sultones comprises: temperature is 25-100 DEG C, and the time is 1 minute-10 hours; Preferably, temperature is 30-80 DEG C, and the time is 10 minutes-5 hours.
16. composite nanometer filtering films prepared by the preparation method in claim 7-15 described in any one.
17. by the application of the composite nanometer filtering film described in claim 1 or 16 in water treatment field.
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