CN108465381A - A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film and preparation method thereof - Google Patents

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

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Publication number
CN108465381A
CN108465381A CN201810202197.5A CN201810202197A CN108465381A CN 108465381 A CN108465381 A CN 108465381A CN 201810202197 A CN201810202197 A CN 201810202197A CN 108465381 A CN108465381 A CN 108465381A
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hollow fiber
polyacrylonitrile hollow
ultrafiltration membranes
separating layer
polyacrylonitrile
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • 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
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The present invention relates to water process environmental technology field, a kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film and preparation method thereof is disclosed.The hollow fiber compound nanofiltration membrane includes polyacrylonitrile hollow fiber ultrafiltration membranes, polyacrylonitrile hollow fiber ultrafiltration membranes outer 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, the polyacrylonitrile hollow fiber ultrafiltration membranes inner 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.Hollow fiber compound nanofiltration membrane 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 hollow fiber 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 hollow fiber 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 hollow fibre of band both sexes charge polyacrylonitrile Tie up composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, polyacrylonitrile hollow fiber ultrafiltration membranes outer surface It is covered with cation selective separating layer, the cation selective separating layer is passed through by pyromellitic trimethylsilyl chloride and polyethylene polyamine Interfacial polymerization is prepared, and the polyacrylonitrile hollow fiber ultrafiltration membranes inner surface is covered with anion selection separating layer, institute Stating anion selection separating layer is prepared by interfacial polymerization with triamine benzene by pyromellitic trimethylsilyl chloride.
The present invention by the method for interfacial polymerization in the outer surface of polyacrylonitrile hollow fiber ultrafiltration membranes by preparing sun Ion selects separating layer, polyethylene polyamine that interface polymerization reaction occurs in basement membrane outer surface with three formyl chloride of polyphenyl and generates lotus positive electricity High polymer, i.e. cation selective separating layer, according to Donnan effect, the separating layer of lotus positive electricity is to height under the action of electrostatic repulsion Valence cation has higher rejection, so basement membrane outer surface can have higher rejection to calcium ion, magnesium ion；Triamine benzene The high polymer that interface polymerization reaction generates bear electricity occurs in basement membrane inner surface with pyromellitic trimethylsilyl chloride, in the effect of electrostatic repulsion The separating layer of lower bear electricity has higher rejection, such as SO to high-valence anion4 2-；To reach simultaneously by staying water In high valence ion removal.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, One layer of zwitterion is only covered in membrane surface and selects separating layer, although preparation method simplifies and has simultaneously to high price zwitterion There is certain rejection, but the effect is unsatisfactory for the rejection of high price zwitterion, because if simultaneously in selection separating layer Charging neutrality effect is will produce with positive electricity and negative electricity, such as will appear positive charge and repel cation, negative electrical charge attracts cation, Effectively cation can not be retained, the present invention assigns negative electrical charge and positive charge respectively by the inside and outside two sides in basement membrane, positive and negative Distribution of charges avoids the neutralizing effect for generating charge, greatly improves the rejection to high price zwitterion in the both sides of basement membrane.
Preferably, the average pore size of the polyacrylonitrile hollow fiber ultrafiltration membranes is 0.02~0.08 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 hollow fiber composite nanometer filtering film, includes the following steps
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 4~8h, then puts Enter 10~18h of immersion in water, clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, 3~5h of heating stirring, it is 0.3~0.6% 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~ 0.2, zeolite granular is then added, triamine benzene is 1 with modified zeolite mass ratio:0.6~0.8,35~40min is stirred, water is obtained Phase solution A；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.3~0.6, obtain aqueous phase B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 20~30min, Then rubber pipette bulb is used to blow out the water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, reusing syringe will The inside that organic phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out 2~3min of interface polymerization reaction, uses suction ear Ball blows out reaction solution, then is dipped in 5~10min in aqueous phase B solution, is then immersed in organic phase solution and carries out interfacial polymerization 20~30s is reacted, polyacrylonitrile hollow fiber ultrafiltration membranes are taken out and puts it into and carries out solidification crosslinking in baking oven, obtains band two Property charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Preferably, the middle triamine benzene mass fraction of water phase solution A is 4~6% 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 0.3~0.8% 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 20~30min in the step 5).
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 hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, in The average pore size of fibre ultrafiltration basement membrane is 0.02 micron, and polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with sun Ion selects separating layer, contains modified zeolite in the anion selection separating layer, the cation selective separating layer is to pass through Pyromellitic trimethylsilyl chloride is prepared with polyethylene polyamine by interfacial polymerization, table in the polyacrylonitrile hollow fiber ultrafiltration membranes Face is covered with anion selection separating layer, and the anion selection separating layer is to pass through boundary by pyromellitic trimethylsilyl chloride and triamine benzene Face polymerization is prepared.
Wherein, the preparation method of modified zeolite is：4 parts by weight zeolites and 1 weight account polyethylene imines are added to 15 weights It measures in part deionized water, sonic oscillation 2h, then adds 0.2 parts by weight vinyltriethoxysilane, stir 3h, filtering Obtain modified zeolite.
A kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 4h, is then placed in 10h is impregnated in water, and clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 3h, 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 1:0.1, then Zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:0.6,35min is stirred, water phase solution A, water phase solution A are obtained Middle triamine benzene mass fraction is 4%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.3, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.3% in B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 20min, then The water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes is blown out using rubber pipette bulb, reusing syringe will be organic The inside that phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out interface polymerization reaction 2min, will be reacted using rubber pipette bulb Liquid is blown out, then is dipped in 5min in aqueous phase B solution, is then immersed in progress interface polymerization reaction 20s in organic phase solution, is taken out Polyacrylonitrile hollow fiber ultrafiltration membranes simultaneously put it into and carry out solidification crosslinking in baking oven, and solidification crosslinking temperature is 50 DEG C, solidification Crosslinking time is 20min, obtains band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Embodiment 2
A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, in The average pore size of fibre ultrafiltration basement membrane is 0.03 micron, and polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with sun Ion selects separating layer, contains modified zeolite in the anion selection separating layer, the cation selective separating layer is to pass through Pyromellitic trimethylsilyl chloride is prepared with polyethylene polyamine by interfacial polymerization, table in the polyacrylonitrile hollow fiber ultrafiltration membranes Face is covered with anion selection separating layer, and the anion selection separating layer is to pass through boundary by pyromellitic trimethylsilyl chloride and triamine benzene Face polymerization is prepared.
Wherein, the preparation method of modified zeolite is：4.3 parts by weight zeolites and 1.2 weight account polyethylene imines are added to In 16 parts by weight of deionized water, then sonic oscillation 2.1h adds 0.22 parts by weight vinyltriethoxysilane, stirring Modified zeolite is obtained by filtration in 3.5h.
A kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 5h, is then placed in 12h is impregnated in water, and clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 3.5h, 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 1:0.14, so After be added zeolite granular, triamine benzene is 1 with modified zeolite mass ratio:0.65,36min is stirred, obtains water phase solution A, water phase A is molten Triamine benzene mass fraction is 4.5% in liquid；
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 0.4% in B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 22min, then The water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes is blown out using rubber pipette bulb, reusing syringe will be organic The inside that phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out interface polymerization reaction 2.3min, will be anti-using rubber pipette bulb It answers liquid to blow out, then is dipped in 6min in aqueous phase B solution, be then immersed in progress interface polymerization reaction 22s in organic phase solution, take Going out polyacrylonitrile hollow fiber ultrafiltration membranes and put it into and carries out solidification crosslinking in baking oven, solidification crosslinking temperature is 53 DEG C, Gu Change crosslinking time is 22min, obtains band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Embodiment 3
A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, in The average pore size of fibre ultrafiltration basement membrane is 0.05 micron, and polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with sun Ion selects separating layer, contains modified zeolite in the anion selection separating layer, the cation selective separating layer is to pass through Pyromellitic trimethylsilyl chloride is prepared with polyethylene polyamine by interfacial polymerization, table in the polyacrylonitrile hollow fiber ultrafiltration membranes Face is covered with anion selection separating layer, and the anion selection separating layer is to pass through boundary by pyromellitic trimethylsilyl chloride and triamine benzene Face polymerization is prepared.
Wherein, the preparation method of modified zeolite is：4.5 parts by weight zeolites and 1.6 weight account polyethylene imines are added to In 17 parts by weight of deionized water, then sonic oscillation 2.2h adds 0.24 parts by weight vinyltriethoxysilane, stirring Modified zeolite is obtained by filtration in 4h.
A kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 6h, is then placed in 14h is impregnated in water, and clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 4h, it is 0.45% 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 1:0.16, so After be added zeolite granular, triamine benzene is 1 with modified zeolite mass ratio:0.7,37min is stirred, obtains water phase solution A, water phase A is molten Triamine benzene mass fraction is 5% in liquid；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.45, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.5% in B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 25min, then The water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes is blown out using rubber pipette bulb, reusing syringe will be organic The inside that phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out interface polymerization reaction 2.6min, will be anti-using rubber pipette bulb It answers liquid to blow out, then is dipped in 7min in aqueous phase B solution, be then immersed in progress interface polymerization reaction 25s in organic phase solution, take Going out polyacrylonitrile hollow fiber ultrafiltration membranes and put it into and carries out solidification crosslinking in baking oven, solidification crosslinking temperature is 54 DEG C, Gu Change crosslinking time is 27min, obtains band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Embodiment 4
A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, in The average pore size of fibre ultrafiltration basement membrane is 0.07 micron, and polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with sun Ion selects separating layer, contains modified zeolite in the anion selection separating layer, the cation selective separating layer is to pass through Pyromellitic trimethylsilyl chloride is prepared with polyethylene polyamine by interfacial polymerization, table in the polyacrylonitrile hollow fiber ultrafiltration membranes Face is covered with anion selection separating layer, and the anion selection separating layer is to pass through boundary by pyromellitic trimethylsilyl chloride and triamine benzene Face polymerization is prepared.
Wherein, the preparation method of modified zeolite is：4.6 parts by weight zeolites and 1.8 weight account polyethylene imines are added to In 18 parts by weight of deionized water, then sonic oscillation 2.5h adds 0.26 parts by weight vinyltriethoxysilane, stirring Modified zeolite is obtained by filtration in 4.5h.
A kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 7h, is then placed in 16h is impregnated in water, and clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 4.5h, 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 1:0.18, so After be added zeolite granular, triamine benzene is 1 with modified zeolite mass ratio:0.75,38min is stirred, obtains water phase solution A, water phase A is molten Triamine benzene mass fraction is 5.5% in liquid；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.5, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.6% in B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 28min, then The water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes is blown out using rubber pipette bulb, reusing syringe will be organic The inside that phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out interface polymerization reaction 2.7min, will be anti-using rubber pipette bulb It answers liquid to blow out, then is dipped in 8min in aqueous phase B solution, be then immersed in progress interface polymerization reaction 27s in organic phase solution, take Going out polyacrylonitrile hollow fiber ultrafiltration membranes and put it into and carries out solidification crosslinking in baking oven, solidification crosslinking temperature is 56 DEG C, Gu Change crosslinking time is 28min, obtains band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Embodiment 5
A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, in The average pore size of fibre ultrafiltration basement membrane is 0.08 micron, and polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with sun Ion selects separating layer, contains modified zeolite in the anion selection separating layer, the cation selective separating layer is to pass through Pyromellitic trimethylsilyl chloride is prepared with polyethylene polyamine by interfacial polymerization, table in the polyacrylonitrile hollow fiber ultrafiltration membranes Face is covered with anion selection separating layer, and the anion selection separating layer is to pass through boundary by pyromellitic trimethylsilyl chloride and triamine benzene Face polymerization is prepared.
Wherein, the preparation method of modified zeolite is：5 parts by weight zeolites and 2 weight account polyethylene imines are added to 20 weights It measures in part deionized water, sonic oscillation 3h, then adds 0.3 parts by weight vinyltriethoxysilane, stir 5h, filtering Obtain modified zeolite.
A kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, includes the following steps：
1) polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, carry out water and recycle 8h, is then placed in 18h is impregnated in water, and clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2) pyromellitic trimethylsilyl chloride is added in n-hexane, heating stirring 5h, it is 0.6% 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:0.8,40min is stirred, water phase solution A, water phase solution A are obtained Middle triamine benzene mass fraction is 6%；
4) polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.6, obtain aqueous phase B solution, the mass fraction of polyethylene polyamine is 0.8% in B solution；
5) it uses syringe that water phase solution A is injected to the inside of polyacrylonitrile hollow fiber ultrafiltration membranes, infiltrates 30min, then The water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes is blown out using rubber pipette bulb, reusing syringe will be organic The inside that phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out interface polymerization reaction 3min, will be reacted using rubber pipette bulb Liquid is blown out, then is dipped in 10min in aqueous phase B solution, is then immersed in progress interface polymerization reaction 30s in organic phase solution, is taken Going out polyacrylonitrile hollow fiber ultrafiltration membranes and put it into and carries out solidification crosslinking in baking oven, solidification crosslinking temperature is 60 DEG C, Gu Change crosslinking time is 30min, obtains band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film.
Test：
To Examples 1 to 5 hollow fiber compound nanofiltration membrane and the polyacrylonitrile hollow fiber composite nanometer filtering film bought in the market into Row test is fitted into film properties evaluating apparatus and carries out rejection and water flux test, and test condition is set as hydraulic pressure 0.8MPa, surveys It is 25 DEG C to try temperature, respectively to the Na of a concentration of 1000mg/L2SO4With the MgCl of a concentration of 1000mg/L2Carry out rejection survey Examination, testing time 8h, then in hydraulic pressure 0.8MPa, test hollow fiber compound nanofiltration membrane under the conditions of test temperature is 25 DEG C Water flux, test result is as follows：
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 NF membrane purchased in market
Na2SO4(%) 96.33 97.15 96.43 96.25 97.20 96.52
MgCl2(%) 93.05 94.46 94.75 93.87 94.23 75.68
Water flux (L/m2h) 30.17 31.54 32.53 31.20 32.85 24.42
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 (9)

1. a kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film, including polyacrylonitrile hollow fiber ultrafiltration membranes, It is characterized in that, polyacrylonitrile hollow fiber ultrafiltration membranes outer surface is covered with cation selective separating layer, the sun from Son selection separating layer is prepared by interfacial polymerization with polyethylene polyamine by pyromellitic trimethylsilyl chloride, in the polyacrylonitrile Fibre ultrafiltration basement membrane inner surface is covered with anion selection separating layer, and the anion selection separating layer is by equal benzene front three Acyl chlorides is prepared with triamine benzene by interfacial polymerization.
2. a kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 1, which is characterized in that The average pore size of the polyacrylonitrile hollow fiber ultrafiltration membranes is 0.02 ~ 0.08 micron.
3. a kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 1, which is characterized in that Contain modified zeolite in the anion selection separating layer.
4. a kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 3, which is characterized in that The preparation method of the modified zeolite is：4 ~ 5 parts by weight zeolites and 1 ~ 2 weight account polyethylene imines are added to 15 ~ 20 weight In part deionized water, then 2 ~ 3h of sonic oscillation adds 0.2 ~ 0.3 parts by weight vinyltriethoxysilane, and stirring 3 ~ Modified zeolite is obtained by filtration in 5h.
5. a kind of system with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film as claimed in claim 1 or 2 or 3 or 4 Preparation Method, which is characterized in that include the following steps：
1）Polyacrylonitrile hollow fiber ultrafiltration membranes are connected in water circle device component, water is carried out and recycles 4 ~ 8h, then put Enter 10 ~ 18h of immersion in water, clean polyacrylonitrile hollow fiber ultrafiltration membranes are obtained after being placed in oven and dried；
2）Pyromellitic trimethylsilyl chloride is added in n-hexane, 3 ~ 5h of heating stirring, it is 0.3 ~ 0.6% 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 ~ 0.2, Then zeolite granular is added, triamine benzene is 1 with modified zeolite mass ratio:0.6 ~ 0.8,35 ~ 40min is stirred, it is molten to obtain water phase A Liquid；
4）Polyethylene polyamine, triethylamine are added to the water, sonic oscillation dissolving, the mass ratio of polyethylene polyamine and triethylamine is 1: 0.3 ~ 0.6, obtain aqueous phase B solution；
5）The inside that water phase solution A is injected to polyacrylonitrile hollow fiber ultrafiltration membranes using syringe, infiltrates 20 ~ 30min, so Rubber pipette bulb is used to blow out the water phase solution A of the inside of polyacrylonitrile hollow fiber ultrafiltration membranes afterwards, reusing syringe will have The inside that machine phase solution injects polyacrylonitrile hollow fiber ultrafiltration membranes carries out 2 ~ 3min of interface polymerization reaction, will using rubber pipette bulb Reaction solution
Blowout, then is dipped in 5 ~ 10min in aqueous phase B solution, be then immersed in organic phase solution carry out interface polymerization reaction 20 ~ 30s takes out polyacrylonitrile hollow fiber ultrafiltration membranes and puts it into and carry out solidification crosslinking in baking oven, and it is poly- to obtain band both sexes charge Acrylonitrile hollow fiber compound nanofiltration membrane.
6. a kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 5, It is characterized in that, the step 3）Triamine benzene mass fraction is 4 ~ 6% in middle water phase solution A.
7. a kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 5, It is characterized in that, the step 4）The mass fraction of polyethylene polyamine is 0.3 ~ 0.8% in middle aqueous phase B solution.
8. a kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 5, It is characterized in that, the step 5）Middle solidification crosslinking temperature is 50 ~ 60 DEG C.
9. a kind of preparation method with both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film according to claim 5, It is characterized in that, the step 5）Middle solidification crosslinking time is 20 ~ 30min.
CN201810202197.5A 2018-03-12 2018-03-12 A kind of band both sexes charge polyacrylonitrile hollow fiber composite nanometer filtering film and preparation method thereof Pending CN108465381A (en)

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Application publication date: 20180831