CN103495350B - Hollow hydrophobic fiber membrane and preparation method thereof - Google Patents
Hollow hydrophobic fiber membrane and preparation method thereof Download PDFInfo
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- CN103495350B CN103495350B CN201310491584.2A CN201310491584A CN103495350B CN 103495350 B CN103495350 B CN 103495350B CN 201310491584 A CN201310491584 A CN 201310491584A CN 103495350 B CN103495350 B CN 103495350B
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Abstract
The invention discloses a hollow hydrophobic fiber membrane and a preparation method thereof, and provides a hollow hydrophobic fiber membrane with good hydrophobic performance and a preparation method thereof. The hydrophobic membrane comprises, by mass, 13-17% of polymers, 5-15% of inorganic nanoparticle nucleating agents, 1-5% of organic liquid nucleating agents, 60-66% of organic solvent and 5-15% of pore-forming additives. The preparation method includes evenly mixing the dried inorganic nanoparticle nucleating agents and the dried polymers at a high speed, evenly dispersing in the organic solvent while stirring, adding the pore-forming additives and organic liquid nucleating agents, mixing evenly and removing bubbles to obtain required membrane casting liquor, extruding the membrane casting liquor by a spinning jet, subjecting the membrane casting liquor to a coagulating bath at the temperature of 40-60 DEG C, fully rinsing in ethyl alcohol at the temperature of 10-60 DEG C after freezing, and drying at the temperature of 30-70 DEG C to obtain the hollow hydrophobic fiber membrane. During membrane forming, polyvinylidene fluoride forms crystalline structures in different sizes, so that high hydrophobization of the hollow hydrophobic fiber membrane is realized.
Description
Technical field
The present invention relates to technical field of membrane, particularly relate to a kind of hollow fiber hydrophobic membrane and preparation method thereof.
Background technology
Membrane Materials is a kind of liquid separation technology that Conventional espresso technique combines with membrane separation technique, Membrane Materials process is the hydrone carburation by evaporation of hot side liquid, through the micropore of hydrophobic membrane, in aqueous phase, the solute such as nonvolatile ion and molecule then can not through hydrophobic membrane, thus realizes that solution is separated, the concentrated or object of purifying.Membrane Materials is the membrane process having phase transformation, and the transmission of heat and quality occurs simultaneously, and the motive force of mass transfer is that hydrophobic membrane both sides are poor through the vapor partial pressure of component.
Hollow-fibre membrane hydrophobicity for Membrane Materials process is lower often in use easily wetted, causes that service time shortens, organic efficiency is low.Therefore, develop a kind of super-hydrophobic hollow-fibre membrane and can ensure that it has persistence difficulty and is infiltrated, improve the operating efficiency of diffusion barrier.
Publication number is CN102114390.A, a kind of hydrophobic membrane and preparation method thereof is disclosed in the patent document that invention and created name is " reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane and preparation method thereof ", adopt Kynoar as material of preparing, add hydrophobic type inorganic nano-particle, non-solvent, adopt solution phase inversion to obtain reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane.Owing to using hydrophobic type inorganic nano-particle, in film forming procedure, hydrophobic type inorganic nano-particle is only present in membranous wall inside, only plays humidification, less on the impact of hollow-fibre membrane hydrophobicity.
Summary of the invention
The object of the invention is the technological deficiency for existing in prior art, and the hollow fiber hydrophobic membrane that a kind of hydrophobic performance is good is provided.
It is simple that another object of the present invention is to provide a kind of technique, easy to operate, is easy to the preparation method of the hollow fiber hydrophobic membrane of suitability for industrialized production.
The technical scheme adopted for realizing object of the present invention is:
A kind of hollow fiber hydrophobic membrane, consists of by the raw material of mass fraction: polymer 13-17%, inorganic nano-particle nucleator 5-15%, organic liquid nucleator 1-5%, organic solvent 60-66%, becomes macroporous additive 5-15%.
A preparation method for hollow fiber hydrophobic membrane, comprises the steps:
(1) casting solution is configured: after being mixed with dry polymer high-speed uniform by the inorganic nano-particle nucleator of drying, under high velocity agitation, be evenly dispersed in organic solvent; And add into macroporous additive and organic liquid nucleator, mix, remove bubble, namely obtain required casting solution;
(2) shaping: to be extruded by spinning head by above-mentioned casting solution, entering temperature is in the coagulating bath of 40-60 DEG C, after solidifying, in 10-60 DEG C of ethanol after abundant rinsing, obtains hollow fiber hydrophobic membrane through 30-70 DEG C of drying.
Described polymer is Kynoar, and described organic liquid nucleator is any one material in adipic acid, sodium succinate, Sodium glutarate, and described one-tenth macroporous additive is any one material in ethylene glycol, diethylene glycol, glycerine.
Described inorganic nano-particle nucleator is any one material in nano-calcium carbonate, nanoclay, nano silicon.
Described organic solvent any one material that to be solvent be in dimethylacetylamide (DMAc), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO).
Compared with prior art, the invention has the beneficial effects as follows:
1, there is inorganic nano-particle nucleator and organic liquid nucleator in hollow fiber hydrophobic membrane of the present invention, utilize the difference of inorganic nano-particle nucleator and organic liquid nucleator film forming procedure, casting solution is extruded through spinning head, in inversion of phases film forming procedure, hollow-fibre membrane inside forms two kinds of structures, be take inorganic particulate as the nucleation structure of core, another kind is organic liquid nucleator induction nucleation.Inorganic nano-particle nucleator and organic liquid nucleator polymer (Kynoar) in film forming procedure is utilized to form the crystalline texture of different scale, then inorganic nano-particle nucleator forms uneven nanometer-sub-micron surface structure on gained film surface in the curing process, there is lotus leaf effect, control surface hydrophobicity, thus the high hydrophobization realizing hollow-fibre membrane.
2, hollow fiber hydrophobic membrane of the present invention utilizes low molecule pore-foaming agent to become macroporous additive to form micropore on film surface as pore-forming, due to inorganic particulate nucleator and the inhomogenous difference of organic liquid nucleator ambient polymer (PVDF) nucleation, utilize difference in shrinkage in dry run at different temperatures, form surface texture uneven in various degree, realize regulation and control hollow fiber hydrophobic membrane hydrophobicity, realize the high hydrophobization of hollow fiber film structure.
3, the film-forming process of this method is simple, easy to operate, is easy to realize suitability for industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
By the nano-calcium carbonate of 10% of drying process with 15% Kynoar high speed mixer mix after, join in the dimethylacetylamide of 60% under agitation, then add the ethylene glycol of 10% and the adipic acid of 5%, stirring and dissolving is even, after deaeration, make casting solution.
Above-mentioned casting solution is through spinning head spinning under measuring pump effect, and inside and outside coagulating bath is 60 DEG C of deionized waters, after gel completes, obtain spun filament.Gained spun filament after rinsing 24h, is dried for 70 DEG C and is namely obtained polyvinylidene fluoride hollow fiber hydrophobic membrane in 60 DEG C of ethanol.The external diameter of gained hollow fiber hydrophobic membrane is 1.2mm, and internal diameter is 0.7mm, and contact angle is 135 degree.
Embodiment 2
By the nanoclay of 5% of drying process with 17% Kynoar high speed mixer mix after, join in the dimethyl formamide of 60% under agitation, then add the sodium succinate of 15% diethylene glycol and 3%, stirring and dissolving is even, after deaeration, make casting solution.
Above-mentioned casting solution is through spinning head spinning under measuring pump effect, and inside and outside coagulating bath is 40 DEG C of deionized waters, after gel completes, obtain spun filament.Gained spun filament after rinsing 24h, is dried for 50 DEG C and is namely obtained polyvinylidene fluoride hollow fiber hydrophobic membrane in 30 DEG C of ethanol.Gained hollow fiber hydrophobic membrane external diameter is 1.2mm, and internal diameter is 0.7mm, and contact angle is 121 degree.
Embodiment 3
By the nano silicon of 15% of drying process with 13% Kynoar high speed mixer mix after, join in the dimethyl sulfoxide (DMSO) of 66% under agitation, then add 5% glycerine, the Sodium glutarate of 1%, stirring and dissolving is even, after deaeration, makes casting solution.
Above-mentioned casting solution is through spinning head spinning under measuring pump effect, and inside and outside coagulating bath is 50 DEG C of deionized waters, after gel completes, obtain spun filament.Gained spun filament after rinsing 24h, is dried for 30 DEG C and is namely obtained polyvinylidene fluoride hollow fiber hydrophobic membrane in 10 DEG C of ethanol.The external diameter of gained hollow fiber hydrophobic membrane is 1.2mm, and internal diameter is 0.7mm, and contact angle is 95 degree.
The present invention adds inorganic nano-particle and organic liquid nucleator in casting solution, utilize phase inversion spinning film forming, pass through technology controlling and process, in film forming procedure, Kynoar forms the crystalline texture of different scale, then form uneven nanometer-sub-micron surface structure on gained film surface in the curing process, thus realize the high hydrophobization of hollow-fibre membrane.The hydrophilic and hydrophobic of inorganic nano-particle nucleator does not affect resulting structures.This method film-forming process is simple, easy to operate, and gained hollow-fibre membrane hydrophobicity is strong, is easy to realize suitability for industrialized production.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a hollow fiber hydrophobic membrane, is characterized in that, consists of by the raw material of mass fraction: polymer 13-17%, inorganic nano-particle nucleator 5-15%, organic liquid nucleator 1-5%, organic solvent 60-66%, becomes macroporous additive 5-15%; Utilize inorganic nano-particle nucleator and organic liquid nucleator polymer in film forming procedure to form the crystalline texture of different scale, inorganic nano-particle nucleator forms uneven nanometer-sub-micron surface structure on gained film surface in the curing process then.
2. hollow fiber hydrophobic membrane according to claim 1, is characterized in that, described inorganic nano-particle nucleator is any one in nano-calcium carbonate, nanoclay and nano silicon.
3. hollow fiber hydrophobic membrane according to claim 1, is characterized in that, described organic liquid nucleator is any one in adipic acid, sodium succinate and Sodium glutarate.
4. hollow fiber hydrophobic membrane according to claim 1, is characterized in that, described one-tenth macroporous additive is any one in ethylene glycol, diethylene glycol and glycerine.
5. hollow fiber hydrophobic membrane according to claim 1, is characterized in that, described polymer is Kynoar.
6. hollow fiber hydrophobic membrane according to claim 1, is characterized in that, described organic solvent is any one in dimethylacetylamide, dimethyl formamide and dimethyl sulfoxide (DMSO).
7. the preparation method of a hollow fiber hydrophobic membrane according to claim 1, it is characterized in that, comprise the steps: (1) configuration casting solution: after being mixed with dry polymer uniform by the inorganic nano-particle nucleator of drying, under agitation, be evenly dispersed in organic solvent; And add into macroporous additive and organic liquid nucleator, mix, remove bubble, namely obtain required casting solution;
(2) shaping: to be extruded by spinning head by above-mentioned casting solution, entering temperature is in the coagulating bath of 40-60 DEG C, after gel completes, in the ethanol of 10-60 DEG C after abundant rinsing, obtains hollow fiber hydrophobic membrane through 30-70 DEG C of drying; Utilize inorganic nano-particle nucleator and organic liquid nucleator polymer in film forming procedure to form the crystalline texture of different scale, inorganic nano-particle nucleator forms uneven nanometer-sub-micron surface structure on gained film surface in the curing process then.
8. the preparation method of hollow fiber hydrophobic membrane according to claim 7, is characterized in that, described inorganic nano-particle nucleator is any one material in nano-calcium carbonate, nanoclay and nano silicon.
9. the preparation method of hollow fiber hydrophobic membrane according to claim 7, it is characterized in that, described polymer is Kynoar, described organic liquid nucleator is any one material in adipic acid, sodium succinate and Sodium glutarate, and described one-tenth macroporous additive is any one material in ethylene glycol, diethylene glycol and glycerine.
10. the preparation method of hollow fiber hydrophobic membrane according to claim 7, is characterized in that, described organic solvent is any one material in dimethylacetylamide, dimethyl formamide and dimethyl sulfoxide (DMSO).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10967331B2 (en) * | 2016-10-26 | 2021-04-06 | National University Of Singapore | Hollow fiber membrane |
| CN106362602A (en) * | 2016-11-21 | 2017-02-01 | 天津华清健坤膜科技有限公司 | Hollow fiber hydrophobic membrane and preparation method thereof |
| CN106731871B (en) * | 2016-12-15 | 2019-11-01 | 天津工业大学 | Inorganic particulate induction mutually separates the method for preparing super-hydrophobic mixed substrate membrane containing nano-grade molecular sieve |
| CN113549429B (en) * | 2021-08-19 | 2022-06-21 | 广东工业大学 | Controllable supercooling-degree phase change microcapsule and preparation method and application thereof |
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| CN1718627A (en) * | 2005-07-13 | 2006-01-11 | 南京工业大学 | Polypropylene micropore film and its preparation method |
| CN101590374A (en) * | 2008-05-27 | 2009-12-02 | 广州美能材料科技有限公司 | A kind of Kynoar hollow-fibre membrane and preparation method thereof |
| CN101890312A (en) * | 2010-04-23 | 2010-11-24 | 苏州膜华材料科技有限公司 | Hydrophilic PVDF ultrafiltration membrane and preparation method |
| CN102114390A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane and preparation method thereof |
| CN102228804A (en) * | 2011-04-15 | 2011-11-02 | 天津科技大学 | Method for preparing hydrophobic microporous membrane and membrane prepared by method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718627A (en) * | 2005-07-13 | 2006-01-11 | 南京工业大学 | Polypropylene micropore film and its preparation method |
| CN101590374A (en) * | 2008-05-27 | 2009-12-02 | 广州美能材料科技有限公司 | A kind of Kynoar hollow-fibre membrane and preparation method thereof |
| CN102114390A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane and preparation method thereof |
| CN101890312A (en) * | 2010-04-23 | 2010-11-24 | 苏州膜华材料科技有限公司 | Hydrophilic PVDF ultrafiltration membrane and preparation method |
| CN102228804A (en) * | 2011-04-15 | 2011-11-02 | 天津科技大学 | Method for preparing hydrophobic microporous membrane and membrane prepared by method |
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