CN108380060A - A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film and preparation method thereof - Google Patents

A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film and preparation method thereof Download PDF

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Publication number
CN108380060A
CN108380060A CN201810201087.7A CN201810201087A CN108380060A CN 108380060 A CN108380060 A CN 108380060A CN 201810201087 A CN201810201087 A CN 201810201087A CN 108380060 A CN108380060 A CN 108380060A
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polyacrylonitrile
filtering film
composite nanometer
ultrafiltration membranes
nanometer filtering
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赵志云
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Changxin Science & Technology Consulting Co Ltd
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Changxin Science & Technology Consulting Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/18—Membrane materials having mixed charged functional groups

Abstract

The present invention relates to water process environmental technology field, a kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film and preparation method thereof is disclosed.The composite nanometer filtering film includes polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, the cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, polyacrylonitrile ultrafiltration membranes upper surface is covered with anion selection separating layer, and the anion selection separating layer is prepared by interfacial polymerization with triamine benzene by pyromellitic trimethylsilyl chloride.Composite nanometer filtering film of the present invention can retain the anion and cation of high price simultaneously, simplify filter progress, and the rejection effect and water flux of NF membrane are improved by addition modified zeolite in selecting separating layer in anion.

Description

A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film and preparation method thereof
Technical field
The present invention relates to water process environmental technology fields, and anion and cation can be retained simultaneously more particularly, to one kind Band both sexes charge polyacrylonitrile flat composite nanometer filtering film and preparation method thereof.
Background technology
The aperture of NF membrane or separation accuracy between ultrafiltration and it is reverse osmosis between, to the interception of molecule 200~ Between 1000Da, and the aperture of film can be used for detaching small molecule organic material and ion, and with behaviour in 1 ran It is low to make pressure, the characteristics of low energy consumption.NF membrane is widely used to sewage disposal, water demineralization and food, dyestuff etc. at present Industry isolates and purifies process etc., compares chemical treatment method, passes through the method environmental protection of physical filtering, unharmful substance production It is raw.The technology of preparing of NF membrane include phase inversion, blending method, composite algorithm, thermal induction phase inversion, chemic modified method, etc. from Daughter method and sol-gel method for inoranic membrane.Wherein, composite algorithm is the most and most effective of current preparation NF membrane Method.The ultra-thin molecular layer in the compound aperture with Nano grade, common complex method typically on the basement membrane with micropore There are surface cladding process, interfacial polymerization, situ aggregation method, Plasma Polymerization, uv photo initiated grafting method and power formation method etc..Directly Till now, interfacial polymerization is still the most important method for preparing composite nanometer filtering film, it can form one on porous basement membrane The ultra-thin separating layer of layer, and can realize the best separation property of composite membrane by optimizing the structure of both basement membrane and separating layer Energy.However presently, there are the problem of to be positively charged composite nanometer filtering film can only retain high-valence cationic, to the rejection of anion compared with Low, negatively charged composite nanometer filtering film can only retain high-valence anion, relatively low to cationic rejection, when existed simultaneously in water body high price Multiple working procedure is needed to be filtered when cation and anion, flow is complicated, and equipment cost is high.
Invention content
The present invention is to overcome the problems, such as that prior art composite nanometer filtering film retention zwitterion is single, and providing one kind can The composite nanometer filtering film of anion and cation is retained simultaneously, reduces filtering process, reduces the poly- with both sexes charge of production cost Acrylonitrile composite nanometer filtering film.
The present invention also provides a kind of preparation methods of the polyacrylonitrile composite nanometer filtering film with both sexes charge.
To achieve the goals above, the present invention uses following technical scheme：A kind of band both sexes charge polyacrylonitrile flat is multiple NF membrane, including polyacrylonitrile ultrafiltration membranes are closed, polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separation Layer, the cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, institute It states polyacrylonitrile ultrafiltration membranes upper surface and is covered with anion selection separating layer, the anion selection separating layer is by equal benzene Three formyl chlorides are prepared with triamine benzene by interfacial polymerization.
The present invention by the method for pouring soln in the lower surface of polyacrylonitrile ultrafiltration membranes by preparing cation selective Separating layer, the height that interface polymerization reaction generation lotus positive electricity occurs with three formyl chloride of polyphenyl in basement membrane lower surface for polyethylene polyamine are poly- Object, i.e. cation selective separating layer, according to Donnan effect, under the action of electrostatic repulsion the separating layer of lotus positive electricity to high price sun from Son has higher rejection, so basement membrane lower surface can have higher rejection to calcium ion, magnesium ion；Triamine benzene and equal benzene In basement membrane upper surface the high polymer that interface polymerization reaction generates bear electricity, bear under the action of electrostatic repulsion occur for three formyl chlorides The separating layer of electricity has higher rejection, such as SO to high-valence anion4 2-；To reach simultaneously by the height in staying water Valence ion remaval.It is a small number of in the prior art to there is the high polymer by the high polymer of lotus positive electricity and bear electricity to mix, in basement membrane Surface only covers one layer of zwitterion selection separating layer, although preparation method simplifies and has simultaneously to high price zwitterion certain Rejection, but the rejection effect of high price zwitterion not rationality, because if simultaneous with just in selection separating layer Electricity and negative electricity will produce charging neutrality effect, such as will produce positive charge and repel cation, and negative electrical charge attracts cation, can not Effectively cation is retained, the present invention by assigning negative electrical charge and positive charge, positive and negative charge point respectively in the upper and lower surface of basement membrane The both sides of cloth and basement membrane avoid the neutralizing effect for generating charge, greatly improve the rejection to high price zwitterion.
Preferably, the average pore size of the polyacrylonitrile ultrafiltration membranes is 0.04~0.1 micron.
Preferably, containing modified zeolite in the anion selection separating layer.
Modified zeolite is dispersed in the through-hole structure that molecular layer can be reduced in anion selection separating layer, increases separating layer Rejection；In addition zeolite has porous structure, has preferable adsorption effect to heavy metal ion, when there are heavy metals in water body When ion, zeolite has the function of secondary removing heavy metal ion, and the content of heavy metal ion is preferably minimized.
Preferably, the preparation method of modified zeolite is：By 4~5 parts by weight zeolites and 1~2 weight account polyethylene imines It is added in 15~20 parts by weight of deionized water, 2~3h of sonic oscillation, then adds 0.2~0.3 parts by weight of ethylene base, three second Oxysilane stirs 3~5h, modified zeolite is obtained by filtration.
It, can using vinyltriethoxysilane coupling agent by the grafting polyethylene imine of long-chain to zeolite granular surface The surface energy for reducing zeolite makes zeolite be easier to select the polymer phase of molecular layer to mix with anion, improves separating layer material Uniformity, zeolite also have certain hydrophilic effect, improve the hydrophily of molecular layer；At high water pressures due to composite nanometer filtering film It is unstable in anion selects separation one polymer to run zeolite, there is a large amount of amino, energy on polyethyleneimine strand It is enough to be crosslinked with pyromellitic trimethylsilyl chloride, to which zeolite to be firmly fixed in the polymer that anion selects separating layer, prevent The movement polymerization of defervescence stone, causes zeolite dispersion uneven, a large amount of hydrophilic additionally, due to containing in polyethyleneimine macromolecular chain Amino can improve the hydrophily of composite nanometer filtering film, to promote its water flux.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 1~2 day into the water, naturally dry after taking-up obtains clean polyacrylonitrile Ultrafiltration membranes；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, 3~5h of heating stirring, it is 0.2~0.5% organic phase to obtain mass fraction Solution；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.1~ 0.3, zeolite granular is then added, triamine benzene is 1 with modified zeolite mass ratio:0.8~1,30~40min is stirred, water phase A is obtained Solution；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.2~0.4, obtain aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 8~15min is infiltrated, outwells polyacrylonitrile ultrafiltration base Then aqueous phase B solution is poured on the lower surface of polyacrylonitrile ultrafiltration membranes by the upper surface water phase solution A of film, infiltrate 2~4min, The lower surface aqueous phase B solution for outwelling polyacrylonitrile ultrafiltration membranes, then wipes polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Redundant solution and put it into and carry out interface polymerization reaction in organic phase solution, put it into baking oven and carry out after completion of the reaction Solidification crosslinking obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
The upper and lower surface of polyacrylonitrile ultrafiltration membranes is first infiltrated into water phase solution A and aqueous phase B solution respectively in the present invention, so It immerses in organic phase solution again afterwards, reduces reaction step, preparation method is easy.
Preferably, the middle triamine benzene mass fraction of water phase solution A is 2~5% in the step 3).
The present invention is higher by middle triamine benzene mass fraction, this is to select molecular layer to improve basement membrane upper surface anion Compactness and thickness make the aperture of molecular layer become smaller and thicken with thickness, increase its rejection to low price zwitterion, because logical The zwitterion of high price can only be retained by crossing the charge effect on separating layer surface, and the zwitterion of low price only passes through Physical entrapment Effect the anion of low price is removed, this requires separating layer apertures to want small, thickness wants thick, but aperture becomes slight and thickness Thickeing can cause the water flux of NF membrane to reduce, and influence its filter efficiency, and the present invention is carried by the hydrophilic interaction of modified zeolite The hydrophily of macromolecule layer, to improve its water flux, elimination separating layer aperture is small and thickness thickness causes lacking for water flux reduction It falls into.
Preferably, the mass fraction of polyethylene polyamine is 0.2~0.5% in aqueous phase B solution in the step 4).
Preferably, solidification crosslinking temperature is 50~60 DEG C in the step 5).
Preferably, solidification crosslinking time is 10~20min in the step 5).
Preferably, step 5) median surface polymerization reaction time is 30~60s, polymeric reaction temperature is 20~30 ℃。
Therefore, the present invention has the advantages that：Composite nanometer filtering film can retain simultaneously high price anion and sun from Son simplifies filter progress；By anion select separating layer in addition modified zeolite come improve NF membrane rejection effect and Water flux.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention is described further.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art, Method in embodiment is unless otherwise instructed the conventional method of this field.
Embodiment 1
A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration base The average pore size of film is 0.04 micron, and polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, described Cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, the polypropylene Nitrile ultrafiltration membranes upper surface is covered with anion selection separating layer, and the anion selection separating layer is to pass through pyromellitic trimethylsilyl chloride It is prepared by interfacial polymerization with triamine benzene, contains modified zeolite, the system of modified zeolite in the anion selection separating layer Preparation Method is：4 parts by weight zeolites and 1 weight account polyethylene imines are added in 15 parts by weight of deionized water, sonic oscillation 2h, Then 0.2 parts by weight vinyltriethoxysilane is added, 3h is stirred, modified zeolite is obtained by filtration.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 1 day into the water, naturally dry after taking-up, obtains clean polyacrylonitrile ultrafiltration Basement membrane；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 3h, it is 0.2% organic phase solution to obtain mass fraction；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.1, then Zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:0.8,30min is stirred, water phase solution A, water phase solution A are obtained Middle triamine benzene mass fraction be 2%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.2, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.2% in aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 8min is infiltrated, outwells polyacrylonitrile ultrafiltration membranes Then aqueous phase B solution is poured on the lower surface of polyacrylonitrile ultrafiltration membranes by upper surface water phase solution A, infiltrate 2min, outwell poly- third The lower surface aqueous phase B solution of alkene nitrile ultrafiltration membranes, then wipes the extra molten of polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Liquid simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, and the interface polymerization reaction time is 30s, and polymeric reaction temperature is It 20 DEG C, puts it into carry out solidification crosslinking in baking oven after completion of the reaction, solidification crosslinking temperature is 50 DEG C, and solidification crosslinking time is 10min obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
Embodiment 2
A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration base The average pore size of film is 0.06 micron, and polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, described Cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, the polypropylene Nitrile ultrafiltration membranes upper surface is covered with anion selection separating layer, and the anion selection separating layer is to pass through pyromellitic trimethylsilyl chloride It is prepared by interfacial polymerization with triamine benzene, contains modified zeolite, the system of modified zeolite in the anion selection separating layer Preparation Method is：4.2 parts by weight zeolites and 1.5 weight account polyethylene imines are added in 16 parts by weight of deionized water, ultrasound is shaken 2.3h is swung, 0.23 parts by weight vinyltriethoxysilane is then added, 3.5h is stirred, modified zeolite is obtained by filtration.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 1 day into the water, naturally dry after taking-up, obtains clean polyacrylonitrile ultrafiltration Basement membrane；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 3.5h, it is 0.3% organic phase solution to obtain mass fraction；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.15, so After be added zeolite granular, triamine benzene is 1 with modified zeolite mass ratio:0.82,33min is stirred, obtains water phase solution A, water phase A is molten The middle triamine benzene mass fraction of liquid is 3%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.25, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.3% in aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 9min is infiltrated, outwells polyacrylonitrile ultrafiltration membranes Then aqueous phase B solution is poured on the lower surface of polyacrylonitrile ultrafiltration membranes by upper surface water phase solution A, infiltrate 2.5min, outwell poly- The lower surface aqueous phase B solution of acrylonitrile ultrafiltration membranes, then wipes the extra of polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Solution simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, and the interface polymerization reaction time is 40s, polymeric reaction temperature It is 22 DEG C, puts it into carry out solidification crosslinking in baking oven after completion of the reaction, solidification crosslinking temperature is 53 DEG C, and solidification crosslinking time is 14min obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
Embodiment 3
A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration base The average pore size of film is 0.07 micron, and polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, described Cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, the polypropylene Nitrile ultrafiltration membranes upper surface is covered with anion selection separating layer, and the anion selection separating layer is to pass through pyromellitic trimethylsilyl chloride It is prepared by interfacial polymerization with triamine benzene, contains modified zeolite, the system of modified zeolite in the anion selection separating layer Preparation Method is：4.5 parts by weight zeolites and 1.6 weight account polyethylene imines are added in 18 parts by weight of deionized water, ultrasound is shaken 2.5h is swung, 0.26 parts by weight vinyltriethoxysilane is then added, 4h is stirred, modified zeolite is obtained by filtration.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 1.5 days into the water, naturally dry after taking-up, it is super obtains clean polyacrylonitrile Filter basement membrane；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 4h, it is 0.35% organic phase solution to obtain mass fraction；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.2, then Zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:0.9,34min is stirred, water phase solution A, water phase solution A are obtained Middle triamine benzene mass fraction be 3.5%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.3, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.35% in aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 10min is infiltrated, outwells polyacrylonitrile ultrafiltration membranes Upper surface water phase solution A, then aqueous phase B solution is poured on to the lower surface of polyacrylonitrile ultrafiltration membranes, infiltrate 3min, outwell poly- The lower surface aqueous phase B solution of acrylonitrile ultrafiltration membranes, then wipes the extra of polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Solution simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, and the interface polymerization reaction time is 46s, polymeric reaction temperature It is 24 DEG C, puts it into carry out solidification crosslinking in baking oven after completion of the reaction, solidification crosslinking temperature is 55 DEG C, and solidification crosslinking time is 15min obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
Embodiment 4
A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration base The average pore size of film is 0.08 micron, and polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, described Cation selective separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, the polypropylene Nitrile ultrafiltration membranes upper surface is covered with anion selection separating layer, and the anion selection separating layer is to pass through pyromellitic trimethylsilyl chloride It is prepared by interfacial polymerization with triamine benzene, contains modified zeolite, the system of modified zeolite in the anion selection separating layer Preparation Method is：4.8 parts by weight zeolites and 1.7 weight account polyethylene imines are added in 19 parts by weight of deionized water, ultrasound is shaken 2.7h is swung, 0.27 parts by weight vinyltriethoxysilane is then added, 4.5h is stirred, modified zeolite is obtained by filtration.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 2 days into the water, naturally dry after taking-up, obtains clean polyacrylonitrile ultrafiltration Basement membrane；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 4.5h, it is 0.4% organic phase solution to obtain mass fraction；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.25, so After be added zeolite granular, triamine benzene is 1 with modified zeolite mass ratio:0.95,37min is stirred, obtains water phase solution A, water phase A is molten The middle triamine benzene mass fraction of liquid is 4%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.35, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.4% in aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 12min is infiltrated, outwells polyacrylonitrile ultrafiltration membranes Upper surface water phase solution A, then aqueous phase B solution is poured on to the lower surface of polyacrylonitrile ultrafiltration membranes, infiltrate 3.5min, outwell The lower surface aqueous phase B solution of polyacrylonitrile ultrafiltration membranes, then wipes the more of polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Remaining solution simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, and the interface polymerization reaction time is 50s, polymerisation temperature Degree is 27 DEG C, puts it into carry out solidification crosslinking in baking oven after completion of the reaction, and solidification crosslinking temperature is 57 DEG C, cures crosslinking time For 16min, band both sexes charge polyacrylonitrile flat composite nanometer filtering film is obtained.
Embodiment 5
A kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, polyacrylonitrile ultrafiltration base The average pore size of film is 0.1 micron, and polyacrylonitrile ultrafiltration membranes lower surface is covered with cation selective separating layer, the sun Ion, which selects separating layer, to be prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, the polyacrylonitrile Ultrafiltration membranes upper surface is covered with anion selection separating layer, anion selection separating layer be by pyromellitic trimethylsilyl chloride with Triamine benzene is prepared by interfacial polymerization, contains modified zeolite, the preparation of modified zeolite in the anion selection separating layer Method is：5 parts by weight zeolites and 2 weight account polyethylene imines are added in 20 parts by weight of deionized water, sonic oscillation 3h, so After add 0.3 parts by weight vinyltriethoxysilane, stir 5h, modified zeolite be obtained by filtration.
A kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile ultrafiltration membranes are impregnated 2 days into the water, naturally dry after taking-up, obtains clean polyacrylonitrile ultrafiltration Basement membrane；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 5h, it is 0.5% organic phase solution to obtain mass fraction；
3) triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.3, then Zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:1,40min is stirred, water phase solution A is obtained, water phase solution A Middle triamine benzene mass fraction is 5%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.4, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.5% in aqueous phase B solution；
5) water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 15min is infiltrated, outwells polyacrylonitrile ultrafiltration membranes Upper surface water phase solution A, then aqueous phase B solution is poured on to the lower surface of polyacrylonitrile ultrafiltration membranes, infiltrate 4min, outwell poly- The lower surface aqueous phase B solution of acrylonitrile ultrafiltration membranes, then wipes the extra of polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Solution simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, and the interface polymerization reaction time is 60s, polymeric reaction temperature It is 30 DEG C, puts it into carry out solidification crosslinking in baking oven after completion of the reaction, solidification crosslinking temperature is 60 DEG C, and solidification crosslinking time is 20min obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
Test：
Examples 1 to 5 composite nanometer filtering film and the polyacrylonitrile composite nanometer filtering film bought in the market are tested, film properties are packed into Rejection and water flux test are carried out in evaluating apparatus, test condition is set as hydraulic pressure 0.4MPa, and test temperature is 25 DEG C, respectively To the Na of a concentration of 1000mg/L2SO4With the MgCl of a concentration of 1000mg/L2Progress rejection test, testing time 8h, so Afterwards in hydraulic pressure 0.4MPa, test temperature is the water flux of test compound NF membrane under the conditions of 25 DEG C, and test result is as follows：
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 NF membrane purchased in market
Na2SO4(%) 95.12 96.57 95.30 95.42 95.84 95.48
MgCl2(%) 92.33 93.52 93.42 93.47 93.96 66.54
Water flux (L/m2h) 20.14 21.38 22.47 21.87 22.66 16.18
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, although this Invention is disclosed above with preferred embodiment, and however, it is not intended to limit the invention, any person skilled in the art, It does not depart within the scope of technical solution of the present invention, when the technology contents using the disclosure above make a little change or are modified to equivalent The equivalent embodiment of variation, as long as being without departing from technical solution of the present invention content, according to the technical essence of the invention to above real Any simple modification, equivalent change and modification made by example are applied, in the range of still falling within technical solution of the present invention.

Claims (10)

1. a kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film, including polyacrylonitrile ultrafiltration membranes, which is characterized in that institute It states polyacrylonitrile ultrafiltration membranes lower surface and is covered with cation selective separating layer, the cation selective separating layer is by equal benzene Three formyl chlorides are prepared with polyethylene polyamine by interfacial polymerization, polyacrylonitrile ultrafiltration membranes upper surface be covered with it is cloudy from Son selection separating layer, anion selection separating layer be by pyromellitic trimethylsilyl chloride and triamine benzene by prepared by interfacial polymerization At.
2. a kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 1, which is characterized in that described The average pore size of polyacrylonitrile ultrafiltration membranes is 0.04 ~ 0.1 micron.
3. a kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 1, which is characterized in that described Contain modified zeolite in anion selection separating layer.
4. a kind of band both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 3, which is characterized in that described The preparation method of modified zeolite is：4 ~ 5 parts by weight zeolites and 1 ~ 2 weight account polyethylene imines are added to 15 ~ 20 parts by weight In ionized water, then 2 ~ 3h of sonic oscillation adds 0.2 ~ 0.3 parts by weight vinyltriethoxysilane, stir 3 ~ 5h, mistake Filter obtains modified zeolite.
5. a kind of preparation side with both sexes charge polyacrylonitrile flat composite nanometer filtering film as claimed in claim 1 or 2 or 3 or 4 Method, which is characterized in that include the following steps：
1）Polyacrylonitrile ultrafiltration membranes are impregnated 1 ~ 2 day into the water, naturally dry after taking-up, it is super to obtain clean polyacrylonitrile Filter basement membrane；
2）Pyromellitic trimethylsilyl chloride is added in n-hexane, 3 ~ 5h of heating stirring, it is 0.2 ~ 0.5% organic to mix to obtain mass fraction Liquid；
3）Triamine benzene, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of triamine benzene and triethylamine is 1:0.1 ~ 0.3, Then zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:0.8 ~ 1,30 ~ 40min is stirred, water phase solution A is obtained；
4）Polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.2 ~ 0.4, obtain aqueous phase B solution；
5）Water phase solution A is poured on to the upper surface of polyacrylonitrile ultrafiltration membranes, 8 ~ 15min is infiltrated, outwells polyacrylonitrile ultrafiltration base Then aqueous phase B solution is poured on the lower surface of polyacrylonitrile ultrafiltration membranes by the upper surface water phase solution A of film, infiltrate 2 ~ 4min, The lower surface aqueous phase B solution for falling polyacrylonitrile ultrafiltration membranes, then wipes polyacrylonitrile ultrafiltration membranes upper and lower surface with filter paper Redundant solution simultaneously puts it into and carries out interface polymerization reaction in organic phase solution, puts it into baking oven consolidated after completion of the reaction Change crosslinking, obtains band both sexes charge polyacrylonitrile flat composite nanometer filtering film.
6. a kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 5, special Sign is, the step 3）The mass fraction of triamine benzene is 2 ~ 5% in middle water phase solution A.
7. a kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 5, special Sign is, the step 4）The mass fraction of polyethylene polyamine is 0.2 ~ 0.5% in middle aqueous phase B solution.
8. a kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 5, special Sign is, the step 5）Middle solidification crosslinking temperature is 50 ~ 60 DEG C.
9. a kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 5, special Sign is, the step 5）Middle solidification crosslinking time is 10 ~ 20min.
10. a kind of preparation method with both sexes charge polyacrylonitrile flat composite nanometer filtering film according to claim 5, special Sign is, the step 5）Median surface polymerization reaction time is 30 ~ 60s, and polymeric reaction temperature is 20 ~ 30 DEG C.
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