CN105561805A - Composite nanofiltration membrane as well as preparation method and application thereof - Google Patents
Composite nanofiltration membrane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite nanofiltration membrane which comprises a support layer and a separate layer which are superposed together, wherein the separate layer is a composite nanofiltration membrane body adopting a cross-linked network structure formed on the surface of the support layer by dissolving one or more polymers containing hydroxyl groups and a silane coupling agent containing sulfonic groups in a solvent and carrying out a sol-gel reaction and a thermo-crosslinking reaction. The composite nanofiltration membrane is not only relatively high in desalinization ratio, water permeability (water flux), and acid resistance, but also simple in preparation method, thereby having a wide prospect in industrial application.
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 is polyamide structure mostly, and it is high that it has salt-stopping rate, the advantage that water flux is large, and its operating pressure is also relatively low.But, due to the polyamide structure of himself, can only stable operation in the scope of pH=2 ~ 11, under the pH environment of harshness, the structure of film can be destroyed, and performance will significantly decline.Therefore, which limits the range of application of polyamide nanofiltration membrane.In many industries, such as: concentrated, the printing and dyeing of concentrated, the alkali of papermaking, acid and metallurgy etc. all require that film itself has very strong acidproof or alkali resistance.According to these special needs above, abroad some major companies also have developed a series of acid and alkali-resistance NF membrane product in succession.But owing to belonging to trade secret, the material of these films, formula and production technology are all open.Therefore, the NF membrane material tool developing a kind of acid and alkali-resistance is of great significance.
Polyvinyl alcohol (PVA) has good acid resistance, and its good film forming, and hydrophily becomes the study hotspot in nanofiltration and counter-infiltration material.But a lot of research shows to take PVA as the standard that its salt-stopping rate of NF membrane of obtaining of material and water flux do not reach product film, limits its large-scale production application.
Therefore, how to prepare a kind of acidproof composite nanometer filtering film 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 sulfonic silane coupler to described separating layer.
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 sulfonic 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 composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked network structure in described support layer surface.
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 sulfonic silane coupler; On the other hand, polymer containing hydroxyl with containing sulfonic silane coupler reacted by sol-gel and heat cross-linking after define cross-linked network structure, 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 is formed with being reacted by sol-gel, heat cross-linking containing sulfonic silane coupler by the polymer containing hydroxyl; 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 containing sulfonic silane coupler prepared by the present invention;
Fig. 2 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 composite nanometer filtering film forming the cross-linked network structure be positioned in described support layer surface afterwards with being dissolved in solvent containing sulfonic silane coupler to described separating layer.
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 sulfonic 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 sulfonic silane coupler is 0.025-25 weight portion.
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 be by reacting to prepare by containing amino silane coupler and sultones containing sulfonic silane coupler.
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 (KH602), dimethylaminopropyl trimethoxy silane and 4-amino-3, one or more in 3-dimethylbutyl trimethoxy silane, preferably, described is gamma-amino propyl trimethoxy silicane (KH540) and/or γ aminopropyltriethoxy silane containing amino silane coupler.
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.
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 sulfonic 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 composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked network structure in described support layer surface.
According to the present invention, the present invention is to being not particularly limited containing the polymer of hydroxyl, the consumption containing sulfonic silane coupler and solvent in described coating liquid, 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 sulfonic 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 sulfonic 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 sulfonic silane coupler.In addition, the polymer containing hydroxyl, the process that is dissolved in solvent containing sulfonic 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 contain the polymer of hydroxyl described in can dissolving and contain sulfonic silane coupler, 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, 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: loaded by composite nanometer filtering film 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), 1,3-propyl sulfonic acid lactone, Isosorbide-5-Nitrae-butyl sulfonic acid lactone, 1,8-naphthalene sulfonic acids lactone, γ aminopropyltriethoxy silane (KH550) is 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.
Preparation example 1
This preparation example is for illustration of the preparation method containing sulfonic silane coupler (SKH550).
In the conical flask being furnished with magnetic agitation, add the KH550 of 5g, then, instill Isosorbide-5-Nitrae-butyl sulfonic acid lactone 3g under agitation, obtain containing sulfonic silane coupler after normal-temperature reaction 24h; Shown in the forming process schematic diagram containing sulfonic silane coupler of this course of reaction prepared by Fig. 1 the present invention.
Preparation example 2
This preparation example is for illustration of the preparation method containing sulfonic silane coupler (SKH540).
In the conical flask being furnished with magnetic agitation, add the KH540 of 5g, then, instill 1,3-propyl sulfonic acid lactone 2g under agitation, obtain after normal-temperature reaction 24h containing sulfonic silane coupler.
Preparation example 3
This preparation example is for illustration of the preparation method containing sulfonic silane coupler (SKH602).
In the conical flask being furnished with magnetic agitation, add the KH602 of 5g, then, instill 1,8-naphthalene sulfonic acids lactone 4g under agitation, obtain after normal-temperature reaction 24h containing sulfonic silane coupler.
Embodiment 1
Be dissolved in 100g deionized water by the sulfonic silane coupler (SKH550) that 1.0g polyvinyl alcohol (PVA), 0.6g contain preparation example 1 preparation, 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 film 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;
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. 2 gives the forming process of composite nanometer filtering film of the present invention, first be to be hydrolyzed containing sulfonic silane coupler and to interact with polyhydroxylated polymer polyvinyl alcohol, then pass through in acid condition, utilize the reaction of formaldehyde and hydroxyl, make to react containing sulfonic silane coupler and polyhydroxylated polymer to form cross-linked network structure, 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.
1.0g shitosan, 0.8g are contained sulfonic silane coupler (SKH550) and be dissolved in 100g deionized water, then under agitation instills the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 2.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 film obtained is immersed in the solution containing 100g water, the 15g concentrated sulfuric acid, 15g formaldehyde and 20g sodium sulphate, at 60 DEG C, after heating 45min, this initial composite NF membrane is taken out, soak in deionized water after washing, for future use;
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
1.0g chitosan quaternary ammonium salt, 1.0g are contained sulfonic silane coupler (SKH550) and be dissolved in 100g deionized water, then under agitation instills 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 film obtained is immersed in the solution containing 100g water, the 20g concentrated sulfuric acid, 20g formaldehyde and 25g sodium sulphate, at 60 DEG C, after heating 60min, this initial composite NF membrane is taken out, soak in deionized water after washing, for future use;
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 4
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the quality containing sulfonic silane coupler (SKH550) in casting solution is 0.2g.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the quality containing sulfonic silane coupler (SKH550) in casting solution is 0.4g.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the quality containing sulfonic silane coupler (SKH550) in casting solution is 0.8g.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the quality containing sulfonic silane coupler (SKH550) in casting solution is 1.0g.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the SKH540 prepared containing sulfonic silane coupler preparation example 2 in casting solution replaces SKH550.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the SKH602 prepared containing sulfonic silane coupler preparation example 3 in casting solution replaces SKH550.
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
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, substitutes containing sulfonic silane coupler (SKH550) in casting solution with gamma-aminopropyl-triethoxy-silane (KH550).
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 1-8, 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 1-8 and comparative example 1, do not adopt the water flux of the composite nanometer filtering film prepared containing sulfonic silane coupler and salt-stopping rate 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. 2 prepared by the present invention, as seen from Figure 2, first the present invention will be hydrolyzed containing sulfonic silane coupler and interact with polyhydroxylated polymer polyvinyl alcohol, then pass through in acid condition, utilize the reaction of formaldehyde and hydroxyl, make to react containing sulfonic silane coupler and polyhydroxylated polymer to form cross-linked network structure, obtain 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 composite nanometer filtering film forming the cross-linked network structure be positioned in described support layer surface afterwards with being dissolved in solvent containing sulfonic silane coupler to described separating layer.
2. 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.
3. 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 sulfonic silane coupler is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
4. the composite nanometer filtering film according to claim 1 or 3, 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.
5. composite nanometer filtering film according to claim 1, wherein, described is by reacting to prepare by containing amino silane coupler and sultones containing sulfonic silane coupler.
6. composite nanometer filtering film according to claim 5, 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. composite nanometer filtering film according to claim 5, 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.
8. the preparation method of the composite nanometer filtering film in claim 1-7 described in any one, the method comprises the following steps:
(1) by the polymer containing hydroxyl, to be dissolved in solvent containing sulfonic 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 composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked network structure in described support layer surface.
9. preparation method according to claim 8, 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 sulfonic silane coupler is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
10. preparation method according to claim 8, 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.
11. preparation methods according to claim 8 or claim 9, 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).
12. preparation methods according to claim 11, 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.
13. preparation methods according to claim 8, 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.
Preparation method described in 14. according to Claim 8 or 13, 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.
15. preparation methods according to claim 14, 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.
16. composite nanometer filtering films prepared by the preparation method in claim 8-15 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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| CN115970508A (en) * | 2023-01-03 | 2023-04-18 | 浙江大学 | Nanofiber membrane with gel network, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107970793A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
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| CN115970508B (en) * | 2023-01-03 | 2024-04-19 | 浙江大学 | Nanofiber membrane with gel network, preparation method and application |
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