CN105617875A - High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof - Google Patents
High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-throughput hollow fiber composite nanofiltration membrane. The high-throughput hollow fiber composite nanofiltration membrane is composed of a supporting layer and a separating layer; the supporting layer is prepared from a higher molecular hollow fiber ultrafiltration membrane; the separating layer is a polyamide layer obtained via interfacial polymerization of multi-amines and multi-acyl chlorides; pure water flux of the high-throughput hollow fiber composite nanofiltration membrane is high, and removing rates of the high-throughput hollow fiber composite nanofiltration membrane on NaCl in NaCl aqueous solution, and MgSO4 in MgSO4 aqueous solution are both high. A preparation method of the high-throughput hollow fiber composite nanofiltration membrane comprises following steps: nonsolvent induced phase separation method is adopted so prepare a high molecular hollow fiber ultrafiltration membrane; the high molecular hollow fiber ultrafiltration membrane is immersed into a multi-amine aqueous solution containing an acid-binding agent so as to obtain a nanofiltration memebrane precursor; the nanofiltration memebrane precursor is contacted with an organic solution of multi-acyl chlorides so as to form the polyamide separation layer and obtain hollow fiber composite nanofiltration membrane wires; and at last an oxidizing agent is used for oxidation treatment, and curing treatment is carried out so as to obtain a finished product. The high-throughput hollow fiber composite nanofiltration membrane is high in water flux, low in cost, and excellent in performance, and is convenient to prepare.
Description
Technical field
The present invention relates to a kind of NF membrane and preparation technology thereof, particularly relate to a kind of hollow fiber compound nanofiltration membrane and preparation method thereof.
Background technology
Nanofiltration (NF) is a kind of pressure-driven membrane separating process between reverse osmosis (RO) and ultrafiltration (UF), is one of the most rapid membrane separation technique of current development. It is generally believed that the separation aperture of NF membrane at 0.5��2nm, can be used for molecular weight between 200��2000 the separation of small organic molecule or purification; There is charged group in the film surface of major part NF membrane or membrane body, can realize different valence state ion separation (to bivalence and more high price salt there is higher rejection, and monovalent salt is had medium rejection), therefore otherwise referred to as " selectivity reverse osmosis ".
The separation effect of material is simultaneously based on charge effect and sieve effect by NF membrane, owing to not only having the fine separation performance of effectively catching small organic molecule, the salt of different valence state can be had again different cutoff performance, thus have application in special separation fields such as bio-pharmaceuticals, fine chemistry industry, food processings more. In water treatment field, NF membrane is mainly used in drink water purifying, wastewater treatment and Treated sewage reusing, water softening, brackish water desalination etc.
At present, NF membrane market is monopolized by several offshore companies, and only have flat board rolling NF membrane product, the preparation method of commercial flat board NF membrane, mainly having cladding process and interfacial polymerization two kinds, cladding process is to be coated with a floor height molecular solution on basement membrane or supporter, passes through forming film with phase transformation method, control the separation aperture of film, the NF membrane material that preparation is required; Interfacial polymerization is first dip-coating one monomer on basement membrane or supporter, after certain PROCESS FOR TREATMENT, then dip-coating another kind monomer, there is polyreaction in interface in two kinds of monomers of successively dip-coating, inversion of phases, the NF membrane material that preparation is required occur simultaneously. Relatively low water flux is one of bottleneck of existing NF membrane practical application, which limit the marketing of Nanofiltration-membrane technique and product.
Compared with flat board rolled membrane module, hollow fiber form membrane module has that specific surface area is big, take up an area the remarkable advantages such as little, self-supporting, cost are low, and the water flux of single membrane module is far above flat board rolling NF membrane. But owing to hollow fiber nanofiltration membrane prepares difficulty height, complex process, have no hollow fiber nanofiltration membrane product in the market on sale. The syntheti c route of hollow fiber nanofiltration membrane, is often also referred to cladding process or interfacial polymerization that flat board rolling NF membrane adopts.
CN1872400A Chinese patent literature discloses one " preparation method of Nano filtering composite membrane of hollow fiber ", which describe at polyvinylidene fluoride hollow fiber coating on base films one strata methylacrylate aminoester class composite, cross-link with dialkyl reagent again, prepare Nano filtering composite membrane of hollow fiber. CN102151499A Chinese patent literature discloses " a kind of polyamide composite nanofiltration membrane and preparation method thereof ", which describes the interface polymerization reaction of a kind of aliphatic macromole polyvinylamine and polynary acyl chlorides. CN102489187A Chinese patent literature discloses " preparation method of a kind of composite nanometer filtering film ", which describe the interface polymerization reaction of a kind of polyethylene polyamine comprising multiple ethylenediamine structure and pyromellitic trimethylsilyl chloride, again through heat treated, obtain composite nanometer filtering film. CN103041713A Chinese patent literature discloses " preparation method of a kind of hollow fiber nanofiltration membrane ", which describing by electrolyte aqueous slkali is hollow fiber ultrafiltration membrane prepared by outer coagulating bath, again on its surface by the interface polymerization reaction of polyamine with pyromellitic trimethylsilyl chloride, dry solidification obtains composite nanometer filtering film.
Above-mentioned existing hollow fiber nanofiltration membrane preparation technology not yet realizes industrialization, also fail to effectively to obtain can business application hollow fiber nanofiltration membrane additionally, nanometer filtering film water flux prepared by prior art is low, adds the use cost of user, constrains the application of Nanofiltration-membrane technique.
Summary of the invention
The technical problem to be solved is, overcome the deficiency and defect mentioned in background above technology, there is provided a kind of water flux height, cost is low, it is easy to prepare, performance is good high flux hollow fibre composite nanometer filtering film, the preparation method correspondingly providing this high flux hollow fibre composite nanometer filtering film.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of high flux hollow fibre composite nanometer filtering film, described hollow fiber compound nanofiltration membrane is mainly made up of supporting layer and stratum disjunctum, described supporting layer is polymeric hollow fiber ultrafiltration membrane, and described stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization; The pure water flux of described hollow fiber compound nanofiltration membrane reaches 45L m-2��h-1Above, it is more than 40% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be more than 90%.
In above-mentioned high flux hollow fibre composite nanometer filtering film, preferably, the masking polymer of described polymeric hollow fiber ultrafiltration membrane is one or more mixing in polysulfones, polyether sulfone, sulfonated polyether sulfone, Kynoar, polyacrylonitrile, it is particularly preferred that be carry out interfacial polymerization on the basis of Kynoar (PVDF basement membrane) to prepare hollow fiber compound nanofiltration membrane; Its weight average molecular weight is 30000��500000 (being more preferably 30000��100000); The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.03��0.5 ��m (being more preferably 0.03��0.1 ��m).
The said goods of the present invention is with macromolecule (polysulfones, polyether sulfone, sulfonated polyether sulfone, Kynoar, polyacrylonitrile etc.) hollow fiber ultrafiltration membrane for basement membrane, by comprising the amine monomers of little molecule aromatic polyamine and polynary acyl chlorides generation interfacial polymerization, separating. functional layer is prepared in membrane surface, then through oxidative work-up, and then obtain composite nanometer filtering film product.
Conceive as a total technology, the preparation method that the present invention also provides for a kind of above-mentioned high flux hollow fibre composite nanometer filtering film, comprise the following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first high molecular polymer, additive and solvent (with the mixture of aprotic solvent and water for outer coagulating bath) are fully dissolved or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, make preparation liquid pass through spinning head and enter in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtains the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: is immersed in the polyamine aqueous solution containing acid binding agent by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, removes unnecessary solution, obtain the NF membrane precursor of surface amine groups after reaction;
(3) prepared by stratum disjunctum: contacted with the organic solution of polynary acyl chlorides by above-mentioned prepared NF membrane precursor again, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with oxidant, described hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
In above-mentioned preparation method, it is preferred that the preparation liquid of described polymeric hollow fiber ultrafiltration membrane is mainly made up of the high molecular polymer of 15wt%��30wt%, the additive of 10wt%��30wt% and the solvent of 50wt%��70wt%.
In above-mentioned preparation method, it is preferred that the additive in described preparation liquid is organic additive and/or inorganic molecules additive;
Described organic additive includes the mixture of one or more in ethanol, ethylene glycol, diethylene glycol, isopropanol, glycerol, butanol, different molecular weight Polyethylene Glycol, different molecular weight polyvinyl pyrrolidone;
Described inorganic molecules additive includes one or more mixing in water, lithium chloride, lithium nitrate, lithium perchlorate or nano-sized hydrophobic calcium carbonate.
In above-mentioned preparation method, it is preferred that the solvent in described preparation liquid is the mixture of one or more in N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone, dimethyl sulfoxide.
In above-mentioned preparation method, it is preferred that described acid binding agent is the mixture of one or more in triethylamine, sodium hydroxide, sodium carbonate or tertiary sodium phosphate, and acid binding agent concentration in polyamine aqueous solution is 0.1wt%��3wt%.
In above-mentioned preparation method, preferably, described polyamine aqueous solution is the mixture of one or more in piperazine aqueous solution, p-phenylenediamine aqueous solution, m-diaminobenzene. aqueous solution, o-phenylenediamine aqueous solution, diethylenetriamine aqueous solution or triethylene tetramine aqueous solution, and the concentration of polyamine is 0.1wt%��5wt%.
In above-mentioned preparation method, it is preferred that described polynary acyl chlorides is the mixture of one or more in m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, pyromellitic trimethylsilyl chloride, 5-isocyanates-isophthaloyl chlorine or 2,4-diisocyanate; The organic solvent used in the organic solution of described polynary acyl chlorides is the mixture of one or more in Isopars (the IsoparG solvent that such as Exxon Mobil company produces), trifluorotrichloroethane, hexamethylene, normal hexane or heptane, and the concentration that polynary acyl chlorides is in organic solution is 0.05wt%��5wt%.
In above-mentioned preparation method, it is preferred that described oxidant is bleaching powder, sodium hypochlorite, hydrogen peroxide, ozone or chlorine, oxidant equivalent concentration is 0.01��1g/L.
In the preparation method that the present invention is above-mentioned, polymeric hollow fiber ultrafiltration membrane is to prepare with the mixture of aprotic solvent Yu water for outer coagulating bath, and by comprising the amine monomers of little molecule aromatic polyamine and polynary acyl chlorides through interfacial polymerization after membrane surface forms separating. functional layer, then through oxidative work-up, obtain high-throughout composite nanometer filtering film.
Compared with prior art, it is an advantage of the current invention that:
(1) method of the present invention adopts oxidant that NF membrane functional layer is carried out controllable oxidization process, reduce the degree of cross linking of aromatic polyamide in separating. functional layer, osmotic resistance when reducing fluid by NF membrane, thus while ensureing that NF membrane has setting cutoff performance and certain salt rejection rate, reach to improve the purpose of working water flux, there is the aquifer yield of higher per membrane area;
(2) compared with the existing products such as flat board rolling NF membrane, high flux hollow fibre composite nanometer filtering film provided by the invention has that surface area is big, take up an area the remarkable advantages such as little, self-supporting, cost are low, the water flux of single membrane module, far above flat board rolling NF membrane, is greatly improved the application and popularization value of Nanofiltration-membrane technique;
(3) compared with preparing the existing techniques such as hollow fiber nanofiltration membrane material with use coating processes, the hollow fiber compound nanofiltration membrane that the present invention is prepared by interfacial polymerization not only can realize the separation to small organic molecule, also can realize divalent salts and monovalent salt retaining in various degree, it is achieved specifically retain purpose;
(4) the high flux hollow fibre composite nanometer filtering film of the present invention adopts the film-forming method of interfacial polymerization, and technique is easily operated, and continuous production efficiency is high, and constant product quality, technical scheme has good industrialization advantage and commercial applications prospect.
Generally speaking, high flux hollow fibre composite nanometer filtering film prepared by the present invention has water flux height, cost is low, prepare the remarkable advantages such as easy, can commercial application implement.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the microphotograph of the high flux hollow fibre composite nanometer filtering film that embodiment 1 prepares in the specific embodiment of the invention.
Fig. 2 be in Fig. 1 high flux hollow fibre composite nanometer filtering film local amplification microphotograph.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more comprehensively, describes meticulously, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical. Technical term used herein is intended merely to the purpose describing specific embodiment, is not intended to limit the scope of the invention.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can be commercially available by market or can be prepared by existing method.
Embodiment 1:
The high flux hollow fibre composite nanometer filtering film of a kind of present invention as shown in Figure 1 and Figure 2, it is mainly made up of supporting layer and stratum disjunctum, and supporting layer is polymeric hollow fiber ultrafiltration membrane, and stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization. The masking polymer of polymeric hollow fiber ultrafiltration membrane is Kynoar, and its weight average molecular weight is 440000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.08 ��m.
The preparation method of the high flux hollow fibre composite nanometer filtering film of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first the Kynoar of 15wt%, the PEG400 of 10wt%, the lithium chloride of 5wt% and the N,N-dimethylacetamide of 70wt% are fully dissolved or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, preparation liquid is made to extrude in coagulating bath by hollow spinning head, then through coagulation forming in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtain the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: is immersed in the polyamine aqueous solution containing 1wt% triethylamine and 5wt% piperazine by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, removes unnecessary solution, obtain the NF membrane precursor of surface amine groups after reaction;
(3) prepared by stratum disjunctum: immerse in the hexane solution containing pyromellitic trimethylsilyl chloride 3wt% by above-mentioned prepared NF membrane precursor again, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with the Eusol of 0.5g/L, above-mentioned hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
After testing, the high flux hollow fibre composite nanometer filtering film that the present embodiment prepares 25 DEG C, under the operation pressure of 0.5MPa, pure water flux is 45L m-2��h-1; It is 49% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be 95%.
Embodiment 2:
The high flux hollow fibre composite nanometer filtering film of a kind of present invention, it is mainly made up of supporting layer and stratum disjunctum, and supporting layer is polymeric hollow fiber ultrafiltration membrane, and stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization. The masking polymer of polymeric hollow fiber ultrafiltration membrane is polysulfones, and its weight average molecular weight is 80000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.04 ��m.
The preparation method of the high flux hollow fibre composite nanometer filtering film of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first the polysulfones of 20wt%, the polyvinyl pyrrolidone of 15wt%, the lithium nitrate of 5wt% and the DMF of 60wt% are fully dissolved or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, preparation liquid is made to extrude in coagulating bath by hollow spinning head, then through coagulation forming in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtain the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: is immersed in the polyamine aqueous solution containing 0.5wt% sodium hydroxide and 4wt% p-phenylenediamine by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, removes unnecessary solution, obtain the NF membrane precursor of surface amine groups after reaction;
(3) prepared by stratum disjunctum: immerse in the hexane solution containing m-phthaloyl chloride 2wt% by above-mentioned prepared NF membrane precursor again, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with the liquor natrii hypochloritis of 0.8g/L, above-mentioned hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
After testing, the high flux hollow fibre composite nanometer filtering film that the present embodiment prepares 25 DEG C, under the operation pressure of 0.5MPa, pure water flux is 62L m-2��h-1; It is 42% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be 91%.
Embodiment 3:
The high flux hollow fibre composite nanometer filtering film of a kind of present invention, it is mainly made up of supporting layer and stratum disjunctum, and supporting layer is polymeric hollow fiber ultrafiltration membrane, and stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization. The masking polymer of polymeric hollow fiber ultrafiltration membrane is polyether sulfone, and its weight average molecular weight is 60000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.04 ��m.
The preparation method of the high flux hollow fibre composite nanometer filtering film of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first the polyether sulfone of 24wt%, the PEG400 of 10wt%, the nano-sized hydrophobic calcium carbonate of 3wt% and the N-Methyl pyrrolidone of 63wt% are fully dissolved or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, preparation liquid is made to extrude in coagulating bath by hollow spinning head, then through coagulation forming in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtain the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: is immersed in the polyamine aqueous solution containing 1.5wt% sodium carbonate and the m-diaminobenzene. of 5wt% by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, removes unnecessary solution, obtain the NF membrane precursor of surface amine groups after reaction;
(3) prepared by stratum disjunctum: immerse in the n-heptane solution containing o-phthaloyl chloride 5wt% by above-mentioned prepared NF membrane precursor again, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with the Eusol of 0.4g/L, above-mentioned hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
After testing, the high flux hollow fibre composite nanometer filtering film that the present embodiment prepares 25 DEG C, under the operation pressure of 0.5MPa, pure water flux is 47L m-2��h-1; It is 51% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be 96%.
Embodiment 4:
The high flux hollow fibre composite nanometer filtering film of a kind of present invention, it is mainly made up of supporting layer and stratum disjunctum, and supporting layer is polymeric hollow fiber ultrafiltration membrane, and stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization. The masking polymer of polymeric hollow fiber ultrafiltration membrane is sulfonated polyether sulfone, and its weight average molecular weight is 35000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.03 ��m.
The preparation method of the high flux hollow fibre composite nanometer filtering film of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first incite somebody to action: the sulfonated polyether sulfone of 22wt%, the diethylene glycol of 16wt%, the lithium perchlorate of 4wt% and the dimethyl sulfoxide of 58wt% fully dissolve or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, preparation liquid is made to extrude in coagulating bath by hollow spinning head, then through coagulation forming in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtain the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: is immersed in the polyamine aqueous solution containing 1.5wt% tertiary sodium phosphate and 4wt% o-phenylenediamine by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, removes unnecessary solution, obtain the NF membrane precursor of surface amine groups after reaction;
(3) prepared by stratum disjunctum: immerse in the trifluorotrichloroethane solution containing paraphthaloyl chloride 3wt% by above-mentioned prepared NF membrane precursor again, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with the liquor natrii hypochloritis of 0.5g/L, above-mentioned hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
After testing, the high flux hollow fibre composite nanometer filtering film that the present embodiment prepares 25 DEG C, under the operation pressure of 0.5MPa, pure water flux is 54L m-2��h-1; It is 48% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be 94%.
Embodiment 5:
The high flux hollow fibre composite nanometer filtering film of a kind of present invention, it is mainly made up of supporting layer and stratum disjunctum, and supporting layer is polymeric hollow fiber ultrafiltration membrane, and stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization. The masking polymer of polymeric hollow fiber ultrafiltration membrane is polyacrylonitrile, and its weight average molecular weight is 70000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.06 ��m.
The preparation method of the high flux hollow fibre composite nanometer filtering film of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by supporting layer: first adopt phase separation method to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film; Specifically first the polyacrylonitrile of 18wt%, the isopropanol of 15wt%, the lithium nitrate of 6wt% and the N,N-dimethylacetamide of 61wt% are fully dissolved or dispersion at 50 DEG C��85 DEG C, then remove the gas of dissolving, obtain preparation liquid; Under the discharging speed set and core liquid speed, preparation liquid is made to extrude in coagulating bath by hollow spinning head, then through coagulation forming in coagulating bath, after abundant phase transformation, film silk is carried out rolling and post processing, obtain the hollow fiber nanofiltration membrane supporting layer that average pore size is 0.03��0.5 ��m;
(2) prepared by separation layer precursor: immerse in the polyamine aqueous solution containing 0.5wt% sodium hydroxide and the diethylenetriamine of 3wt% by above-mentioned prepared polymeric hollow fiber ultrafiltration membrane, remove unnecessary solution after reaction, obtain the NF membrane precursor of surface amine groups;
(3) prepared by stratum disjunctum: immerse above-mentioned prepared NF membrane precursor containing 2 again, in the IsoparG solution of 4-diisocyanate 4wt%, acid chloride group and amido is made to be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, remove unnecessary solution, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) oxidative work-up: finally with the hydrogenperoxide steam generator of 0.5g/L, above-mentioned hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
After testing, the high flux hollow fibre composite nanometer filtering film that the present embodiment prepares 25 DEG C, under the operation pressure of 0.5MPa, pure water flux is 63L m-2��h-1; It is 41% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be 90%.
The high flux hollow fibre composite nanometer filtering film that the various embodiments described above prepare be all 25 DEG C, 0.5MPa operate under pressure, NaCl and the MgSO to 1.0g/L4Aqueous solution carry out salt rejection rate and pure water flux is tested.
Salt rejection rate is to evaluate the index that nano filter membrane separating property is the most frequently used, with R0Representing, computing formula is as follows:
C in formula0Represent water inlet conductance, unit �� s/cm; CfRepresent that producing water power leads, unit �� s/cm.
Pure water flux refers to that unit is in a hurry interior by the water yield of per membrane area, represents with J, unit L m-2��h-1, wherein:
J=Q/ (A �� t);
In formula, Q represents the water yield in the t time through membrane area A; A represents effective film area, unit m2; T express time, unit h.
Claims (10)
1. a high flux hollow fibre composite nanometer filtering film, it is characterized in that, described hollow fiber compound nanofiltration membrane is mainly made up of supporting layer and stratum disjunctum, and described supporting layer is polymeric hollow fiber ultrafiltration membrane, and described stratum disjunctum is polyamine and the polynary acyl chlorides aramid layer through interfacial polymerization; The pure water flux of described hollow fiber compound nanofiltration membrane reaches 45L m-2��h-1Above, it is more than 40% to the removal efficiency of NaCl in 1.0g/LNaCl aqueous solution, to 1.0g/LMgSO4MgSO in aqueous solution4Removal efficiency be more than 90%.
2. high flux hollow fibre composite nanometer filtering film according to claim 1, it is characterized in that, the masking polymer of described polymeric hollow fiber ultrafiltration membrane is one or more mixing in polysulfones, polyether sulfone, sulfonated polyether sulfone, Kynoar, polyacrylonitrile, and its weight average molecular weight is 30000��500000; The average pore size of polymeric hollow fiber ultrafiltration membrane is 0.03��0.5 ��m.
3. a preparation method for high flux hollow fibre composite nanometer filtering film as claimed in claim 1 or 2, comprises the following steps:
(1) phase separation method is first adopted to prepare polymeric hollow fiber ultrafiltration membrane, as the supporting layer of composite nanometer filtering film;
(2) above-mentioned prepared polymeric hollow fiber ultrafiltration membrane is immersed in the polyamine aqueous solution containing acid binding agent, obtain the NF membrane precursor of surface amine groups;
(3) more above-mentioned prepared NF membrane precursor is contacted with the organic solution of polynary acyl chlorides, make acid chloride group and amido be polymerized in the interface of aqueous phase and organic facies, form polyamide stratum disjunctum, obtain the hollow fiber compound nanofiltration membrane silk of nascent state;
(4) finally with oxidant, described hollow fiber compound nanofiltration membrane silk is carried out oxidation processes, then carry out post processing solidification, obtain high flux hollow fibre composite nanometer filtering film.
4. preparation method according to claim 3, it is characterised in that the preparation liquid of described polymeric hollow fiber ultrafiltration membrane is mainly made up of the high molecular polymer of 15wt%��30wt%, the additive of 10wt%��30wt% and the solvent of 50wt%��70wt%.
5. preparation method according to claim 4, it is characterised in that the additive in described preparation liquid is organic additive and/or inorganic molecules additive;
Described organic additive includes the mixture of one or more in ethanol, ethylene glycol, diethylene glycol, isopropanol, glycerol, butanol, different molecular weight Polyethylene Glycol, different molecular weight polyvinyl pyrrolidone;
Described inorganic molecules additive includes one or more mixing in water, lithium chloride, lithium nitrate, lithium perchlorate or nano-sized hydrophobic calcium carbonate.
6. preparation method according to claim 4, it is characterised in that the solvent in described preparation liquid is the mixture of one or more in N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone, dimethyl sulfoxide.
7. the preparation method according to any one of claim 3��6, it is characterized in that, described acid binding agent is the mixture of one or more in triethylamine, sodium hydroxide, sodium carbonate or tertiary sodium phosphate, and acid binding agent concentration in polyamine aqueous solution is 0.1wt%��3wt%.
8. the preparation method according to any one of claim 3��6, it is characterized in that, described polyamine aqueous solution is the mixture of one or more in piperazine aqueous solution, p-phenylenediamine aqueous solution, m-diaminobenzene. aqueous solution, o-phenylenediamine aqueous solution, diethylenetriamine aqueous solution or triethylene tetramine aqueous solution, and the concentration of polyamine is 0.1wt%��5wt%.
9. the preparation method according to any one of claim 3��6, it is characterized in that, described polynary acyl chlorides is the mixture of one or more in m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, pyromellitic trimethylsilyl chloride, 5-isocyanates-isophthaloyl chlorine or 2,4-diisocyanate; The organic solvent used in the organic solution of described polynary acyl chlorides is the mixture of one or more in Isopars, trifluorotrichloroethane, hexamethylene, normal hexane or heptane, and the concentration that polynary acyl chlorides is in organic solution is 0.05wt%��5wt%.
10. the preparation method according to any one of claim 3��6, it is characterised in that described oxidant is bleaching powder, sodium hypochlorite, hydrogen peroxide, ozone or chlorine, oxidant equivalent concentration is 0.01��1g/L.
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