CN103223300A - Hollow fiber type composite nano-filtration membrane and preparation method thereof - Google Patents
Hollow fiber type composite nano-filtration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hollow fiber type composite nano-filtration membrane and a preparation method thereof. The hollow fiber type composite nano-filtration membrane comprises a hollow fiber microporous base membrane adopted as a supporting layer, a polysulfone transition layer, and a polyamide composite layer, wherein the polysulfone transition layer is positioned inside membrane holes of the hollow fiber microporous base membrane, and the polyamide composite layer is positioned inside membrane holes of the polysulfone transition layer. The preparation method comprises: adopting a thermally induced phase separation method to obtain an asymmetric microporous base membrane, adopting an impregnation phase transformation method to obtain the polysulfone transition layer in the micro holes, and adopting pressure control and an interface condensation polymerization reaction to obtain the polyamide composite layer. The hollow fiber type composite nano-filtration membrane provides a sodium chloride salt solution entrapment rate of more than 90%, a divalent salt ion entrapment rate of more than 95%, and a pollutant entrapment rate of more than 99% under 0.2-0.8 MPa, such that the hollow fiber type composite nano-filtration membrane has characteristics of high strength, washing resistance, large flux and the like, wherein the pollutants have a molecular weight of 300-200,000 Daltons.
Description
Technical field
The present invention relates to a kind of hollow fiber type composite nanometer filtering film and preparation method thereof with processing suspended contaminant ability.
Background technology
The research and development of doughnut reverse osmosis membrane are expected to lead the future of membrane technology.Present commercial RO film adopts is compound rolled film, easily pollute with the difficult influent quality that cleans the RO film and proposed very high requirement, have to adopt doughnut super/micro-filtration (UF/MF) film is as the preliminary treatment of RO film, be so-called pair of embrane method (UF/MF-RO) water treatment integrated technique, seriously restricted the further reduction of embrane method cost of water treatment.Promote the film resistance tocrocking and can relax the influent quality requirement: this is that two embrane methods (UF/MF-RO) are integrated into, and super/micro-filtration water inlet directly obtains to meet the key that RO produces water quality standard.
Than compound rolled film, composite hollow fiber membrane can realize that resistance tocrocking and anti-washability improve, the compression strength of film is high very high with hot strength, hollow-fibre membrane can be done very carefully, make assembly hollow-fibre membrane loading density height afterwards like this, the effective filtration area of NF film is bigger in the same units volume.Hollow-fibre membrane can significantly promote effective film area in the unit volume, and the membrane structure of self-supporting makes backwash become possibility, effectively promotes the contamination resistance of film.But in the patent of reporting at present, the influent quality of hollow-fibre membrane requires suspension turbidity SDI＜3, all is subjected to the strictness restriction of feed water by reverse osmosis water quality requirement, and therefore the preliminary treatment to the RO water inlet remains necessary.
Anti-pollution type hollow fiber nanofiltration membrane has been reported in many work, wherein can be divided into two classes according to the position of separating layer: separating layer is positioned at the inner pressed hollow-fibre membrane of hollow-fibre membrane inner surface and the external-compression type hollow-fibre membrane that separating layer is positioned at the hollow-fibre membrane outer surface.Inner pressed when operation separating layer is subjected to flowing and washes away lessly, and resistance to pressure is higher, is therefore at first reported.Japan Patent (JP022842) has prepared the hollow fiber nanofiltration membrane of external-compression type and inner pressed.Owing to be subjected to the restriction of membrane material intensity and operating condition, tend to use the version of inner pressed in the patent application, when still adopting the hollow-fibre membrane of inner pressed, it can not get performance with respect to rolled film advantage structurally, has limited its application.
United States Patent (USP) (US5,784,079) has been reported the hollow-fibre membrane of external-compression type.In order to improve the stability of film under higher operating pressure, the basement membrane external diameter of employing is less, so the mechanical stability of film is relatively poor, in operation easy generation hollow-fibre membrane fracture in service.Owing to adopt the less fibre structure of external diameter, it is more strict on the contrary to make that membrane module requires the preliminary treatment of intaking, and is not easy to engineering and uses in addition.
Present known a kind of antipollution type hollow-fibre membrane (application number: 200810059988.3), form by three-decker.With polyolefin doughnut micropore basal membrane is supporting layer, is transition zone and is composite bed with the polyamide with polyvinyl alcohol crosslinked structure, has obtained a kind of external-compression type hollow fiber nanofiltration membrane.Composite bed with nanofiltration separation performance is positioned at the hollow-fibre membrane outer surface, in utilization and operation process and cleaning process, the phase mutual friction easily of hollow-fibre membrane surface, very easily damage the hollow-fibre membrane face coat, with piperazine and pyromellitic trimethylsilyl chloride be two phase reaction monomer especially respectively, the polyamide lamination layer structure that obtains loosens and easily comes off, and can have a strong impact on the separating property of film.
In addition, in this patent polyvinyl alcohol crosslinked structure is filled into hollow-fibre membrane fenestra inside,, has increased the resistance to mass tranfer of hydrone, be unfavorable for the lifting of pure water flux in film inside because polyvinyl alcohol has crystallinity and cross-linked structure compactness.Utilize piperazine to prepare composite bed as the water monomer in this patent, its structure only has cutoff performance about 90% to divalent ion, and is about 20% to monovalence sodium chloride salt ion rejection.
In sum, when composite bed was positioned at doughnut basement membrane inner surface, the inner pressed operation can't be brought into play its advantage with respect to rolled film; When composite bed was positioned at doughnut basement membrane outer surface, the external-compression type flushing operation can destroy lamination layer structure.Need the exploitation composite bed to be positioned at the hollow fiber type composite nanometer filtering film of the fenestra inside of hollow fiber basement membrane; reduce the film pollution to give full play to the hollow fiber type composite nanometer filtering film with periodicity air purge, backwash; because composite bed is subjected to doughnut micropore basal membrane structural defence, effectively widened the concentration of treatment scope of hollow-fibre membrane water inlet simultaneously.
Summary of the invention
The objective of the invention is problem at the poor-performing of anti-flushing of existing external-compression type hollow fiber nanofiltration membrane existence, a kind of preparation external-compression type of anti-flushing hollow fiber nanofiltration membrane and preparation method thereof is proposed, use this external-compression type hollow fiber nanofiltration membrane, can intake in micro-filtration membrane, prepare anti-ly wash away, big flux, high-intensity hollow fiber nanofiltration membrane.
Technical scheme of the present invention is as follows:
A kind of hollow fiber type composite nanometer filtering film, it is characterized in that: this hollow fiber type composite nanometer filtering film is made up of doughnut micropore basal membrane, polysulfones transition zone and polyamide composite bed as supporting layer, the polysulfones transition zone is positioned at the fenestra inside of hollow-fibre membrane micropore basal membrane, and the polyamide composite bed is positioned at the fenestra inside of polysulfones transition zone.
Doughnut micropore basal membrane of the present invention is a hollow fiber microporous membrane, and its external diameter is 0.6～1.8mm, and internal diameter is 0.3～1.2mm, and external diameter and internal diameter ratio are 1.5～2; The alcohol bubble point is 0.2～0.4MPa, and hot strength is at least 7MPa, and compression strength is at least 2MPa.
Polysulfones transition region thickness L2 of the present invention accounts for 5～25% of supporting layer thickness L1; Polyamide composite bed thickness L3 accounts for 1～10% of polysulfones transition region thickness L2; Supporting layer aperture D1 is at 100～150nm, and polysulfones transition zone aperture D2 is at 30～70nm, and polyamide composite bed aperture is at 0.5～2nm.
Polysulfones transition zone of the present invention is polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone; The polyamide composite bed is partially aromatic polyamide or the Wholly aromatic polyamide that aliphatic polyamine or aromatic polyamine and aromatic polycarboxylic acyl chlorides form through interface polymerization reaction.
The preparation method of a kind of hollow fiber type composite nanometer filtering film provided by the invention is characterized in that described method carries out according to the following steps:
1) at first the polysulfones casting solution of concentration between 2～20wt% is immersed in the fenestra of doughnut micropore basal membrane by dipping method, dipping method comprises: the doughnut micropore basal membrane is immersed in 0.5～10min in the casting solution, or make the doughnut micropore basal membrane, or make the doughnut micropore basal membrane in the rotation of casting solution surface by casting solution reservoir 0.5～10min;
2) hollow-fibre membrane that step 1) is obtained immerses 10～120min in the coagulating bath;
3) after hollow-fibre membrane takes out, be encapsulated into the modification hollow-fibre membrane that obtains in the fenestra of doughnut micropore basal membrane, to fill the polysulfones transition zone in the film device from coagulating bath;
4) be the polyamine aqueous phase solution of 0.2～5wt% in modification hollow-fibre membrane inner surface circulation concentration, the hollow-fibre membrane medial and lateral surface pressing difference that makes modification is at 0.01～0.3MPa, and pressure keeps 1～10min;
5) purge argon gas 0.5～10min or circulation organic solvent 5～30min at modification hollow-fibre membrane outer surface, modification hollow-fibre membrane outer surface circulation concentration is polynary acyl chlorides oil-phase solution 1～10min of 0.05～2wt% then, reacts;
6), clean modification doughnut basement membrane outer surface at modification hollow-fibre membrane outer surface circulation organic solvent;
7) the film device is put into baking oven, and heat treatment 5～30min between 40～90 ℃ further carries out with the reaction that promotes amine and acyl chlorides through heating, and removes the solvent acquisition hollow fiber type composite nanometer filtering film of reactant.
In above-mentioned preparation method, the solute of used casting solution is polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone in the step 1); The solvent of casting solution is N, dinethylformamide, N, in N-dimethylacetylamide, ethyl acetate, propyl acetate, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), chloroform, carbon tetrachloride, carrene and the dichloroethanes one or more mix, and the concentration of casting solution is between 2～10wt%; Step 2) coagulating bath described in is one or more mixing in water, ethanol, isopropyl alcohol, isobutanol, methyl-sulfoxide and the acetonitrile.Contain hydrophilic additive or pore additive in the described casting solution, hydrophilic additive is ethanol, isopropyl alcohol, n-butanol, tert-pentyl alcohol, 2 octanols or diglycol, and the quality percentage composition of hydrophilic additive is between 10～50wt%; The pore additive be molecular weight 300,000～900,000 daltonian polyethylene glycol or PVP, pore additive quality percentage composition is between 0.1～10wt%.In the described step 4), make modification hollow-fibre membrane medial and lateral surface pressing difference between 0.05～0.2MPa; The concentration of polyamine aqueous phase solution is 0.5～2wt%; Described polyamine is aliphatic polyamine or aromatic polyamine, and aliphatic polyamine is piperazine and derivative thereof; Described aromatic polyamine is the derivative of aromatic polycarboxylic amine or its sulfonic group, carboxylic acid group, sulfonate or metal carboxylate.The concentration of polynary acyl chlorides described in the step 5) in oil-phase solution is 0.05～0.6wt%, and polynary acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride, and the solvent of described oil-phase solution is n-hexane or cyclohexane; Employed organic solvent is cyclohexane or n-hexane; Purging the argon gas time at modification hollow-fibre membrane outer surface is 2～5min; The circulation organic solvent time is 15～30min; Reaction time is 5～10min.In the step 7), after reaction was carried out, the film post-processing temperature was at 50～70 ℃, and the post processing time is at 10～20min.
The present invention compared with prior art has the following advantages and the high-lighting effect: under 0.2～0.8MPa, to the rejection of sodium chloride salt solution〉90%; Rejection to the divalent salts ion〉95%; To molecular weight 300～200,000 daltonian pollutant cutoff performance〉99%.Described hollow fiber nanofiltration membrane possesses the characteristics of high strength, antiscour, big flux.
Description of drawings
Fig. 1 is a hollow fiber type composite nanometer filtering film sectional schematic diagram.
Fig. 2 is the vertical view of Fig. 1.
Fig. 3 is the stress strain diagram of doughnut basement membrane before and after the modification.
Nanofiltration performance when Fig. 4 is the operation of hollow fiber type composite nanometer filtering film long-term stability.
Fig. 5 is the anti-flushing performance and the antifouling property of dull and stereotyped NF membrane NF-90 of commercialization and hollow fiber type composite nanometer filtering film.
Fig. 6 is the relation of hollow fiber type composite nanometer filtering film pure water flux and sodium sulphate cutoff performance.
The specific embodiment
The present invention is described further below in conjunction with drawings and Examples.
Concretely, a kind of hollow fiber type composite nanometer filtering film provided by the invention be by doughnut micropore basal membrane supporting layer 1, be positioned at the hollow-fibre membrane micropore basal membrane fenestra inside polysulfones transition zone 2 and be positioned at the hollow fiber type composite nanometer filtering film (as shown in Figure 1, 2) that the polyamide composite bed 3 of the fenestra inside of polysulfones transition zone constitutes.
According to the present invention, the doughnut micropore basal membrane should have suitable interior external diameter.Its external diameter is 0.6～1.8mm, and internal diameter is 0.3～1.2mm, and external diameter and internal diameter ratio are 1.5～2.
According to the present invention, the alcohol bubble point of doughnut micropore basal membrane should be greater than 0.2MPa.If the alcohol bubble point of basement membrane is less than 0.2MPa, applied pressure destroyed when the composite bed of the hollow fiber type composite nanometer filtering film that obtains was in use filtered by nanofiltration easily, influenced its cutoff performance to salt ion.
Simultaneously, the hot strength of used basement membrane should be greater than 7MPa, and compression strength is at least 2MPa.If used basement membrane hot strength and compression strength are lower, then in the use of NF membrane, cause the fracture of hollow-fibre membrane easily because of the flushing of regular air water, cause the reduction of system effectiveness.
The doughnut micropore basal membrane adopts the polyolefin polymers of strong-hydrophobicity usually, can be respectively 25mN/m and 30mN/m as vinylidene, polyacrylic surface, and the polyamide composite bed is because amido link and the not influence of complete reaction carboxyl and amidine functional group, belong to have the surface can hydrophilic polymer.If directly compound in the polyolefin surfaces reaction, because the influence of surface energy, the nanofiltration composite bed is difficult for evenly applying in membrane surface, and the nanofiltration composite bed is relatively poor with combining of basement membrane, makes and easily peel off between prepare two-layer that character is held back in heavy damage.
In addition, the film hole diameter of doughnut micropore basal membrane still prepares the needed basement membrane film hole diameter of polyamide composite film usually at 30～70nm at 100～150nm.If directly adopt the bigger TPO micropore basal membrane in aperture to prepare composite nanometer filtering film, then in the use more than operating pressure 0.3MPa, the polyamide composite bed of composite nanometer filtering film is damaged easily, significantly reduces separating property.
Therefore, the NF membrane of holding dirty ability for the mechanical strength that makes full use of polyolefin film with preparation high strength, height, by interface polymerization reaction before the TPO membrane surface prepares composite bed, need modification doughnut micropore basal membrane, make and form transition zone in the fenestra of basement membrane.
Adopt polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone material preparation transition zone, adopt aliphatic polyamine or aromatic polyamine and aromatic polycarboxylic acyl chlorides to prepare the polyamide composite bed through partially aromatic polyamide or the Wholly aromatic polyamide that interface polymerization reaction forms.Polysulfones is compound in polyolefin datum hole inside afterwards through inversion of phases, and then by the method for interface polymerization reaction the polyamide composite bed is embedded membrane structure.It is characterized in that: polysulfones transition region thickness L2 accounts for 5～25% of supporting layer thickness L1; Polyamide composite bed thickness L3 accounts for 1～10% of polysulfones transition region thickness L2; Supporting layer aperture D1 is at 100～150nm, and polysulfones transition zone aperture D2 is at 30～70nm, and polyamide composite bed aperture is at 0.5～2nm.
The preparation method of hollow fiber type composite nanometer filtering film provided by the invention, this method is carried out according to the following steps:
1) at first the polysulfones casting solution of concentration between 2～20wt% is immersed in the fenestra of doughnut micropore basal membrane by dipping method, dipping method comprises: the doughnut micropore basal membrane is immersed in 0.5～10min in the casting solution, or make the doughnut micropore basal membrane, or make the doughnut micropore basal membrane in the rotation of casting solution surface by casting solution reservoir 0.5～10min;
2) hollow-fibre membrane that step 1) is obtained immerses 10～120min in the coagulating bath;
3) after hollow-fibre membrane takes out, be encapsulated into the modification hollow-fibre membrane that obtains in the fenestra of doughnut micropore basal membrane, to fill the polysulfones transition zone in the film device from coagulating bath;
4) be the polyamine aqueous phase solution of 0.2～5wt% in modification hollow-fibre membrane inner surface circulation concentration, make modification hollow-fibre membrane medial and lateral surface pressing difference between 0.01～0.3MPa, pressure keeps 1～10min;
5) purge argon gas 0.5～10min or circulation organic solvent 5～30min at modification hollow-fibre membrane outer surface, modification hollow-fibre membrane outer surface circulation concentration is polynary acyl chlorides oil-phase solution 1～10min of 0.05～2wt% then, reacts;
6), clean modification doughnut basement membrane outer surface at modification hollow-fibre membrane outer surface circulation organic solvent;
7) the film device is put into baking oven, and heat treatment 5～30min between 40～90 ℃ further carries out with the reaction that promotes amine and acyl chlorides through heating, and removes the solvent acquisition hollow fiber type composite nanometer filtering film of reactant.
The polysulfones transition zone prepares by following scheme among the present invention:
1) at first the polysulfones casting solution of concentration between 2～20wt% is immersed in the fenestra of doughnut micropore basal membrane by dipping method, dipping method comprises: the doughnut micropore basal membrane is immersed in 0.5～10min in the casting solution, or make the doughnut micropore basal membrane, or make the doughnut micropore basal membrane in the rotation of casting solution surface by casting solution reservoir 0.5～10min;
2) hollow-fibre membrane that step 1) is obtained immerses 10～120min in the coagulating bath;
3) after hollow-fibre membrane takes out, be encapsulated into the modification hollow-fibre membrane that obtains in the fenestra of doughnut micropore basal membrane, to fill the polysulfones transition zone in the film device from coagulating bath;
The solute of used casting solution is polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone in the step 1); The solvent of casting solution is N, dinethylformamide, N, in N-dimethylacetylamide, ethyl acetate, propyl acetate, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), chloroform, carbon tetrachloride, carrene and the dichloroethanes one or more mix, and the concentration of casting solution is between 2～10wt%; Described step 2) coagulating bath in is one or more mixing in water, ethanol, isopropyl alcohol, isobutanol, methyl-sulfoxide and the acetonitrile.
Casting solution contains hydrophilic additive or pore additive, and hydrophilic additive is ethanol, isopropyl alcohol, n-butanol, tert-pentyl alcohol, 2 octanols or diglycol, and the quality percentage composition of hydrophilic additive is between 10～50wt%; The pore additive be molecular weight 300,000～900,000 daltonian polyethylene glycol or PVP, pore additive quality percentage composition is between 0.1～10wt%.
The polyamide composite bed prepares by following scheme among the present invention:
1) be the polyamine aqueous phase solution of 0.2～5wt% in modification hollow-fibre membrane inner surface circulation concentration, make modification hollow-fibre membrane medial and lateral surface pressing difference between 0.01～0.3MPa, pressure keeps 1～10min;
2) purge argon gas 0.5～10min or circulation organic solvent 5～30min at modification hollow-fibre membrane outer surface, modification hollow-fibre membrane outer surface circulation concentration is polynary acyl chlorides oil-phase solution 1～10min of 0.05～2wt% then, reacts;
3), clean modification doughnut basement membrane outer surface at modification hollow-fibre membrane outer surface circulation organic solvent;
4) the film device is put into baking oven, and heat treatment 5～30min between 40～90 ℃ further carries out with the reaction that promotes amine and acyl chlorides through heating, and removes the solvent acquisition hollow fiber type composite nanometer filtering film of reactant.
In the step 1), it is 0.05～0.2MPa that the polyamine aqueous phase solution is exerted pressure; The concentration of polyamine aqueous phase solution is 0.5～2wt%; Described polyamine is aliphatic polyamine or aromatic polyamine, and aliphatic polyamine is piperazine and derivative thereof.
Aromatic polyamine is the derivative of aromatic polycarboxylic amine or its sulfonic group, carboxylic acid group, sulfonate, metal carboxylate; The concentration of polynary acyl chlorides in oil-phase solution is 0.05～0.6wt%; Described polynary acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride; The solvent of oil-phase solution is n-hexane or cyclohexane for not compatible and to using polyamine to have the organic solvent of certain solubility with water; Step 2) employed organic solvent is used identical with oil-phase solution; Purging the argon gas time is 2～5min; The circulation organic solvent time is 15～30min; Reaction time is 5～10min.In the step 7), after reaction was carried out, the film post-processing temperature was at 50～70 ℃, and the post processing time is at 10～20min.
The hollow fiber nanofiltration membrane that obtains through above reaction is to magnesium sulfate (2000ppm, 0.4MPa) rejection greater than 95%, greater than 99%, and (2000ppm, rejection 0.4MPa) is greater than 90% to the representative sodium chloride of monovalent salt to the rejection of suspended contaminant (SDI=5).The water flux of gained NF membrane is greater than 61Lm-2h-1MPa-1, more preferably greater than 102Lm
-2H
-1MPa
-1The water flux of NF membrane is high more, then under identical aquifer yield required, NF membrane can be moved under lower operating pressure, has reduced pollution that hollow-fibre membrane moves and to the destruction of hollow-fibre membrane under elevated pressures.The hollow-fibre membrane of preparation moves under the lower pressure of 0.1～0.8MPa usually.
Therefore because hollow fiber nanofiltration membrane of the present invention has higher mechanical strength simultaneously and separates through performance, keep higher separation to see through under the level can long-time running, the preliminary treatment of water inlet is required low, can hold dirty suspension pollutant (SDI=5).
Contain hydrophilic additive or pore additive in the used casting solution of preparation polysulfones transition zone, the quality percentage composition of hydrophilic additive as preferably, adds content between 10～30wt% between 10～50wt%; Pore additive quality percentage composition is between 0.1～10wt%, as preferably, between 0.1～5wt%.
The used polyamine of preparation polyamide composite bed is aliphatic polyamine or aromatic polyamine, and aliphatic polyamine is piperazine and derivative thereof.Aromatic polyamine is the derivative of aromatic polycarboxylic amine or its sulfonic group, carboxylic acid group, sulfonate, metal carboxylate, for example o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid triethylamine salt, 3,5-diaminobenzoic acid triethylamine salt, 2,4-diamino benzene sulfonic acid, 3,5-diamino benzene sulfonic acid, 2,4-diamino benzene sulfonic acid triethylamine salt, 3,5-diaminobenzene sulphur triethylamine salt etc.
The used polynary acyl chlorides of preparation polyamide composite bed is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride etc., preferred pyromellitic trimethylsilyl chloride.
Fig. 3 intercepts 5cm modification doughnut basement membrane as batten for AGS-J model tensilometer test modification doughnut basement membrane hot strength, obtains the stress strain diagram of different component modification doughnut basement membrane under the rate of extension of 10cm/min.
Shown in Figure 3, the mechanical strength of original PVDF doughnut micropore basal membrane is 11.65MPa, utilize that concentration is 2,5, the PES/NMP solution polysulfones solution modification doughnut basement membrane mechanical strength of 10w/v% rises to 11.66,13.07,15.68MPa, proves that modification doughnut basement membrane possesses excellent more mechanical property.
Fig. 4 is that the described method of patent obtains the hollow fiber type composite nanometer filtering film, the nanofiltration performance when testing its steady in a long-term operation, and in 40 hours test period, the water flux of NF membrane and basicly stable constant to the rejection of 2000ppm magnesium sulfate.
Fig. 5 is that to select the dull and stereotyped NF membrane NF-90 of commercialization for use be the anti-flushing performance and the antifouling property of the hollow fiber type composite nanometer filtering film that contrast characterized.Carry out 2.5 times loop test under the operating pressure of 25 ° of C and 0.4MPa, the cross-flow operation that two kinds of film devices all are in 1L/min is carried out nanofiltration experiment.Solution is the model molecule with bovine serum albumin (BSA), buffer solution adjusting pH=4.7 ± 0.1(pH=pIBSA).At first, with the MgSO of 2000ppm
4The aqueous solution is feeding liquid test water flux; Again with the MgSO of 2000ppm
4With the BSA mixed aqueous solution of 100ppm be feeding liquid, the test two kinds of films water flux; At last, wash with the flow velocity of deionized water with 5L/min.Through after above-mentioned 2.5 cyclings, the water flux data of acquisition are illustrated in pollutant with the ratio of initial water flux numerical value and have under the situation attenuation of water flux.
Below by several specific embodiments technical scheme of the present invention is described in further detail.
Adopt thermal phase separation process to prepare external diameter 1.2mm, the TPO hollow-fibre membrane of internal diameter 0.8mm is a basement membrane, alcohol bubble point 0.24～0.25MPa, and hot strength 9.5MPa has 1150.6Lm under the operating pressure of 0.01MPa
-2H
-1Pure water flux, elongation at break is 150%.
N-formyl sarcolysine base pyrrolidones (NMP) solution of preparation polysulfones-like polymer, compound concentration is the 25mL casting solution of 2w/v%, stirring at normal temperature was fully dissolved final vacuum baking oven 0.09MPa deaeration 30min in 24 hours.Curtain coating casting solution on clean glass plate with the casting solution edge rotation on glass plate of hollow-fibre membrane silk, makes and the interior solution that soaks into of film silk micropore took out in the film silk immersion deionized water in 1 hour after the abundant exchange of solvent, takes after normal temperature dries.
Preparation contains polynary two amine aqueous solutions of 2w/v%, contains the oil-phase solution of 0.1w/v%.With 4 long for having of 10cm applies the film silk system film forming devices of transition zone, the aqueous phase solution film silk internal membrane silk 1min that under 0.05MPa pressure, circulates.Use argon purge film device shell 2min subsequently, desciccator diaphragm silk surface.Film device circulation oil-phase solution generation interface polymerization reaction, n-hexane circulation film device shell 1min wash-out film silk surface little molecule of unreacted polyamide and reaction monomers behind the 10min.The film device is put into 60 ℃ of heat treatment 20min of baking oven.
Compacting 1 hour under 0.4MPa pressure after the preparation hollow fiber type composite nanometer filtering film, under 0.4MPa pressure, hold back the MgSO4 solution of 2000ppm afterwards, connect filter liquor after 1 hour, get 100 times of 0.5mL dilutions and make that magnesium ion reaches 1～10ppm order of magnitude in the solution, calculate magnesium ion concentration with magnesium ion 1～10ppm calibration curve among the ICP, hollow fiber type composite nanometer filtering film magnesium sulfate rejection rate is 1-filter liquor concentration/concentration of raw material.The hollow fiber type composite nanometer filtering film that test obtains the results are shown in Table 4.
Embodiment 2:
Adopt the basement membrane identical with embodiment 1.
Compound concentration is dimethyl sulfoxide (DMSO) (DMSO) casting solution of the polysulfones-like polymer of 10w/v%, and stirring at normal temperature was fully dissolved final vacuum baking oven 0.09MPa deaeration 30min in 24 hours.The film silk is immersed in 5min in the casting solution, makes to soak into solution in the film silk hole, and the film silk immerses in the deionized water and to take out after the abundant exchange of solvent in 2 hours, takes after normal temperature dries.
Preparation contains polynary two amine aqueous solutions of 2w/v%, contains the polynary acyl chlorides oil-phase solution of 0.1w/v%.With 4 long for having of 10cm applies the film silk system film forming devices of transition zone, make the aqueous phase solution film silk internal membrane silk 5min that under 0.2MPa pressure, circulates.Use argon purge film device 5min subsequently, desciccator diaphragm silk surface.Interface polymerization reaction takes place in film device shell circulation oil-phase solution 10min, n-hexane circulation film device shell 3min wash-out film silk surface little molecule of unreacted polyamide and reaction monomers.The film device is put into 60 ℃ of heat treatment 20min of baking oven.
The MgSO of 2000ppm is held back in compacting 1 hour under 0.4MPa pressure after the preparation hollow fiber type composite nanometer filtering film afterwards under 0.4MPa pressure
4Solution, connect filter liquor after 1 hour, get 100 times of 0.5mL dilutions and make that magnesium ion reaches 1～10ppm order of magnitude in the solution, calculate magnesium ion concentration with magnesium ion 1～10ppm calibration curve among the ICP, hollow fiber type composite nanometer filtering film magnesium sulfate rejection rate is 1-filter liquor concentration/concentration of raw material.
Hollow fiber type composite nanometer filtering film test with obtaining the results are shown in Table 4.
Compare with embodiment 1, except changing film silk dip time in casting solution, other reaction conditions are identical.NF membrane pure water flux that obtains and 2000ppm rejection relation are as shown in table 1.Dipping PES soaks in micropore, has promoted fenestra and to the support of composite bed rejection has been raise; When dip time was long, nmp solvent can destroy the membrane pore structure of PVDF doughnut micropore basal membrane, and the supporting layer aperture is excessive and can't support the structure of composite bed, destroys cutoff performance.
Table 1 film silk Immersion time is to the NF membrane performance impact
Adopt the basement membrane identical with embodiment 1.Compound concentration is dimethyl sulfoxide (DMSO) (DMSO) casting solution of the polysulfones-like polymer of 10w/v%, and the different additive (as shown in table 2) of the certain content of dissolving in the solution, stirring at normal temperature were fully dissolved final vacuum baking oven 0.09MPa deaeration 30min in 24 hours.The film silk is immersed in 5min in the casting solution, makes to soak into solution in the film silk hole, and the film silk immerses that 10min takes place to take out after the exchange of solvent in the deionized water.
Preparation contains the polynary diamines of 2w/v%, contains the polynary acyl chlorides oil-phase solution of 0.1w/v%.With 4 long for having of 10cm applies the film silk system film forming devices of transition zone, make the aqueous phase solution film silk internal membrane silk 5min that under 0.1MPa pressure, circulates.Use argon purge film device 5min subsequently, desciccator diaphragm silk surface.Film device shell is full of oil-phase solution 10min interface polymerization reaction takes place, n-hexane circulation film device shell 3min wash-out film silk surface little molecule of unreacted polyamide and reaction monomers.The film device is put into 60 ℃ of heat treatment 20min of baking oven.
It is as shown in the table for NF membrane pure water flux that obtains and 2000ppm rejection relation.As can be seen from Table 2, comparative example 2 water flux is higher, and this is relevant with additive change transition zone hydrophily and aperture structure; And the rejection variation is relevant with pore size.
Table 2 transition zone additive is to the nanofiltration Effect on Performance
aRelative molecular weight is 300,000 dalton
bRelative molecular weight is 900,000 dalton
Adopt the basement membrane identical with embodiment 1; Preparation polysulfones-like polymer concentration is dimethyl sulfoxide (DMSO) (DMSO) casting solution of 10w/v%, PVP-K30 content 0.1wt%, and stirring at normal temperature was fully dissolved final vacuum baking oven 0.09MPa deaeration 30min in 24 hours.The film silk is immersed in 5min in the casting solution, makes to soak into solution in the film silk hole, and the film silk immerses the water that volume ratio is 90:10/alcohol solidification and takes out behind the exchange of solvent 10min in bathing.
Preparation contains the polynary diamines of 2w/v%, contains the polynary acyl chlorides oil-phase solution of 0.1w/v%.With 4 long for having of 10cm applies the film silk system film forming devices of transition zone, make the aqueous phase solution film silk internal membrane silk 5min that under 0.1MPa pressure, circulates.Use argon purge film device 4min subsequently, desciccator diaphragm silk surface.Film device shell is full of oil-phase solution 5min interface polymerization reaction takes place, n-hexane circulation film device shell 3min wash-out film silk surface little molecule of unreacted polyamide and reaction monomers.The film device is put into 60 ℃ of heat treatment 20min of baking oven.
Compacting 1 hour under 0.4MPa pressure after the preparation hollow fiber type composite nanometer filtering film, afterwards under the pressure of 0.2～0.8MPa to the rejection of the metabisulfite solution of 2000ppm and pure water flux as shown in Figure 6.
Embodiment 6
The basement membrane identical with embodiment 1, the transition zone preparation method identical with embodiment 2.
Preparation contains 4w/v% piperazine solution, contains the polynary solution of acid chloride of 0.2w/v%.Film silk system film forming device with 4 long film silks that are coated with transition zone for 10cm, make the aqueous phase solution film silk internal membrane silk 5min that under 0.2MPa pressure, circulates, film device shell circulation organic solvent 15min, continue circulation oil phase reaction solution 10min afterwards interface polymerization reaction takes place, the aforementioned organic solvent film device shell 5min that circulates once more subsequently cleans.The film device is put into 50 ℃ of heat treatment 20min of baking oven.
Compacting 1 hour under 0.4MPa pressure the results are shown in Table 4 after the preparation hollow fiber type composite nanometer filtering film.
Embodiment 7
Adopt the basement membrane identical, the transition zone preparation method identical with embodiment 2 with embodiment 1.
Preparation contains the piperazine of the m-phenylene diamine (MPD) of 0.4w/v% and 0.1w/v% as aqueous phase reactions solution, and the polynary acyl chlorides that contains 0.05w/v% is an oil-phase solution.With 4 long be the modification doughnut basement membrane system film forming device of 10cm, with the pressure of 0.2MPa inner surface circulation aqueous phase solution 5min to modification doughnut basement membrane.Film device shell circulation organic solvent 30min continues circulation oil phase reaction solution 10min afterwards interface polymerization reaction takes place, and the aforementioned organic solvent film device shell 5min that circulates once more subsequently cleans.N-hexane circulation film device shell 3min wash-out modification doughnut basement membrane outer surface little molecule of unreacted polyamide and reaction monomers.The film device is put into 60 ℃ of heat treatment 20min of baking oven.
Compacting 1 hour under 0.4MPa pressure the results are shown in Table 4 after the preparation hollow fiber type composite nanometer filtering film.
Embodiment 8
Adopt the basement membrane identical, the transition zone preparation method identical with embodiment 2 with embodiment 1.
Preparation contains polynary two amine aqueous solutions of 2w/v%, contains the polynary acyl chlorides oil-phase solution of 0.6w/v%.With 4 long modification doughnut basement membrane system film forming devices that formed transition zone for 10cm, with the pressure of 0.2MPa inner surface circulation aqueous phase solution 5min to modification doughnut basement membrane, use argon purge film device shell 5min subsequently, interface polymerization reaction takes place in film device shell circulation oil-phase solution 5min, the outer surface of n-hexane circulation film device shell 5min flushing modification doughnut basement membrane.The film device is put into 70 ℃ of heat treatment 10min of baking oven.Hollow fiber type composite nanometer filtering film test with obtaining the results are shown in Table 4.
Embodiment 9
Adopt the basement membrane identical, the transition zone preparation method identical with embodiment 2 with embodiment 1.
Preparation contains the m-phenylene diamine (MPD) solution of 2w/v%, and the cyclohexane solution that contains the many first acyl chlorides of 0.2w/v% is an oil-phase solution.With 4 long be the modification doughnut basement membrane system film forming device of 10cm, with the pressure of 0.1MPa inner surface circulation aqueous phase solution 1min to modification doughnut basement membrane, use argon purge film device shell 5min subsequently, interface polymerization reaction takes place in film device shell circulation oil-phase solution 10min, the little molecule of outer surface unreacted polyamide and the reaction monomers of cyclohexane circulation film device shell 3min wash-out modification doughnut basement membrane.The film device is put into 50 ℃ of heat treatment 20min of baking oven.Hollow fiber type composite nanometer filtering film test with obtaining the results are shown in Table 4.
Adopt the basement membrane identical, the transition zone preparation method identical with embodiment 2 with embodiment 1.
Preparation contains the m-phenylene diamine (MPD) solution of 2w/v%, contains the polynary acyl chlorides oil-phase solution of 0.05w/v%.With 4 long be the modification doughnut basement membrane system film forming device of 10cm, with the pressure of 0.2MPa inner surface circulation aqueous phase solution 1min to modification doughnut basement membrane, use argon purge film device shell 5min subsequently, interface polymerization reaction takes place in film device shell circulation oil-phase solution 10min, and n-hexane circulation film device shell 3min cleans the outer surface of modification doughnut basement membrane.The film device is put into 70 ℃ of heat treatment 20min of baking oven.With the test of the hollow fiber type composite nanometer filtering film that obtains, lower pure water flux has formed finer and close aramid layer during with this temperature and has formed relevantly, sees Table 4.
Each embodiment hollow fiber type composite nanometer filtering film results of property of table 4 gathers
aKynoar doughnut micropore basal membrane
bPolysulfones modification doughnut basement membrane.
Claims (10)
1. hollow fiber type composite nanometer filtering film, it is characterized in that: this hollow fiber type composite nanometer filtering film is made up of doughnut micropore basal membrane, polysulfones transition zone (2) and polyamide composite bed (3) as supporting layer (1), the polysulfones transition zone is positioned at the fenestra inside of hollow-fibre membrane micropore basal membrane, and the polyamide composite bed is positioned at the fenestra inside of polysulfones transition zone.
2. hollow fiber type composite nanometer filtering film according to claim 1 is characterized in that: described doughnut micropore basal membrane is a hollow fiber microporous membrane, and its external diameter is 0.6～1.8mm, and internal diameter is 0.3～1.2mm, and external diameter and internal diameter ratio are 1.5～2; The alcohol bubble point is 0.2～0.4MPa, and hot strength is at least 7MPa, and compression strength is at least 2MPa.
3. according to the hollow fiber type composite nanometer filtering film described in the claim 1, it is characterized in that: polysulfones transition region thickness L2 accounts for 5～25% of supporting layer thickness L1; Polyamide composite bed thickness L3 accounts for 1～10% of polysulfones transition region thickness L2; Supporting layer aperture D1 is at 100～150nm, and polysulfones transition zone aperture D2 is at 30～70nm, and polyamide composite bed aperture is at 0.5～2nm.
4. hollow fiber type composite nanometer filtering film according to claim 1 is characterized in that: the polysulfones transition zone is polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone; The polyamide composite bed is half aromatics or the Wholly aromatic polyamide that aliphatic polyamine or aromatic polyamine and aromatic polycarboxylic acyl chlorides form through interface polymerization reaction.
5. as the preparation method of the described a kind of hollow fiber type composite nanometer filtering film of the arbitrary claim of claim 1～4, it is characterized in that described method carries out according to the following steps:
1) at first the polysulfones casting solution of concentration between 2～20wt% is immersed in the fenestra of doughnut micropore basal membrane by dipping method, dipping method comprises: the doughnut micropore basal membrane is immersed in 0.5～10min in the casting solution, or make the doughnut micropore basal membrane, or make the doughnut micropore basal membrane in the rotation of casting solution surface by casting solution reservoir 0.5～10min;
2) hollow-fibre membrane that step 1) is obtained immerses 10～120min in the coagulating bath;
3) after hollow-fibre membrane takes out, be encapsulated into the modification hollow-fibre membrane that obtains in the fenestra of doughnut micropore basal membrane, to fill the polysulfones transition zone in the film device from coagulating bath;
4) be the polyamine aqueous phase solution of 0.2～5wt% in modification hollow-fibre membrane inner surface circulation concentration, make modification hollow-fibre membrane medial and lateral surface pressing difference between 0.01～0.3MPa, pressure keeps 1～10min;
5) purge argon gas 0.5～10min or circulation organic solvent 5～30min at modification hollow-fibre membrane outer surface, modification hollow-fibre membrane outer surface circulation concentration is polynary acyl chlorides oil-phase solution 1～10min of 0.05～2wt% then, reacts;
6), clean modification doughnut basement membrane outer surface at modification hollow-fibre membrane outer surface circulation organic solvent;
7) the film device is put into baking oven, and heat treatment 5～30min between 40～90 ℃ further carries out with the reaction that promotes amine and acyl chlorides through heating, and removes the solvent acquisition hollow fiber type composite nanometer filtering film of reactant.
6. the preparation method of hollow fiber type composite nanometer filtering film as claimed in claim 5 is characterized in that: the solute of used casting solution is polysulfones, polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, SPSF, sulfonated polyether sulfone or sulfonated polyether-ether-ketone in the step 1); The solvent of casting solution is N, dinethylformamide, N, in N-dimethylacetylamide, ethyl acetate, propyl acetate, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), chloroform, carbon tetrachloride, carrene and the dichloroethanes one or more mix, and the concentration of casting solution is between 2～10wt%; Step 2) coagulating bath described in is one or more mixing in water, ethanol, isopropyl alcohol, isobutanol, methyl-sulfoxide and the acetonitrile.
7. the preparation method of hollow fiber type composite nanometer filtering film as claimed in claim 6, it is characterized in that: contain hydrophilic additive or pore additive described in the step 1) in the casting solution, hydrophilic additive is ethanol, isopropyl alcohol, n-butanol, tert-pentyl alcohol, 2 octanols or diglycol, and the quality percentage composition of hydrophilic additive is between 10～50wt%; The pore additive be molecular weight 300,000～900,000 daltonian polyethylene glycol or PVP, pore additive quality percentage composition is between 0.1～10wt%.
8. the preparation method of hollow fiber type composite nanometer filtering film as claimed in claim 5 is characterized in that: in the described step 4), make modification hollow-fibre membrane medial and lateral surface pressing difference between 0.01～0.3MPa; The concentration of polyamine aqueous phase solution is 0.5～2wt%; Described polyamine is aliphatic polyamine or aromatic polyamine, and aliphatic polyamine is piperazine and derivative thereof; Described aromatic polyamine is the derivative of aromatic polycarboxylic amine or its sulfonic group, carboxylic acid group, sulfonate or metal carboxylate.
9. the preparation method of hollow fiber type composite nanometer filtering film as claimed in claim 5, it is characterized in that: the concentration of polynary acyl chlorides described in the step 5) in oil-phase solution is 0.05～0.6wt%, polynary acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride, and the solvent of described oil-phase solution is n-hexane or cyclohexane; Employed organic solvent is used identical with oil-phase solution; Purging the argon gas time at modification hollow-fibre membrane outer surface is 2～5min; The circulation organic solvent time is 15～30min; Reaction time is 5～10min.
10. the preparation method of hollow fiber type composite nanometer filtering film as claimed in claim 5 is characterized in that: in the described step 7), after reaction was carried out, the film post-processing temperature was at 50～70 ℃, and the post processing time is at 10～20min.
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| CN115090130B (en) * | 2021-09-13 | 2023-04-25 | 浙江美易膜科技有限公司 | Nanofiltration membrane containing silica gel nanoparticle intermediate layer and preparation method thereof |
| CN114534521A (en) * | 2022-03-23 | 2022-05-27 | 烟台大学 | Cross-linked polyether-ether-ketone hollow fiber composite nanofiltration membrane and preparation method thereof |
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