CN103691325B - A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly - Google Patents
A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly Download PDFInfo
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Abstract
A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly, belongs to infiltration evaporation technical field of membrane separation.The film liquid that preparation Kynoar (PVDF), inorganic particulate, additive, solvent mix, stir at a certain temperature, deaeration, non-woven fabrics supporting layer applies knifing, take water as coagulation bath, adopts immersion precipitation phase inversion process to obtain inorganic particulate/PVDF composite membrane.The inorganic particulate that the present invention obtains/PVDF composite membrane is excellent for the preferential Methanol permeability of the low-concentration ethanol aqueous solution (1wt% ~ 30wt%), and be 10wt% ethanol water for concentration, permeation flux is up to J=21.1kg/m
2h, separation factor alpha=6.2.
Description
Technical field
The present invention relates to the preparation method that one can be used for evaporation alcohol permselective inorganic particulate/PVDF composite membrane, belong to infiltrating and vaporizing membrane separation field.
Background technology
The preferential alcohol infiltrating and vaporizing membrane thoroughly of research both at home and abroad at present, be mostly hydrophobicity dense film, as dimethyl silicone polymer, poly-trimethyl silicane propine etc., due to himself hydrophobicity, and the swellbility of dense film in the low-concentration ethanol aqueous solution is lower, Small molecular resistance to mass tranfer in dense film is comparatively large, causes dense film permeation flux all lower, generally all lower than 2.0kg/m
2h, cannot meet the commercial Application requirement of evaporation alcohol permselective membrane.Key of the present invention is to adopt with porous inorganic particle and hydrophobicity PVDF for raw material, and employing immersion precipitation phase inversion process prepares inorganic particulate/PVDF composite membrane.Composite membrane obtained on the one hand has porous asymmetric structure, greatly reduce the resistance to mass tranfer of Small molecular in film, inorganic particulate also plays humidification to PVDF on the other hand, the loose structure of inorganic particulate is utilized to improve ethanol/water separation factor to the preference of ethanol, can on the basis keeping certain separative efficiency, realize increasing substantially of alcohol permselective membrane flux, to break through the comprehensive separating property of existing dense film.
Summary of the invention
The object of the invention is the preparation method providing a kind of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly for above-mentioned key technical problem.This composite membrane on the basis keeping certain separative efficiency, can realize increasing substantially of permeation flux, breaches the comprehensive separating property of dense film.This inorganic particulate/PVDF composite membrane permeation flux can up to J=21.1kg/m
2h, separation factor alpha=6.2, have good prospects for commercial application.
A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly, is characterized in that comprising the following steps:
Step 1: the preparation method of inorganic particulate/pvdf membrane liquid, by Kynoar (PVDF), inorganic particulate, additive, solvent mixing, 12-48h is stirred at 70-90 DEG C, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The mass ratio of Kynoar, inorganic particulate, additive, solvent is 10:(0.05-3): (0.05-5): (30-130);
Step 2: immersion precipitation phase inversion process prepares inorganic particulate/PVDF composite membrane, the film liquid obtained in step 1 being applied knifing on polyester non-woven fabric, is immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 8-24h under 20-60 DEG C of environment.
Kynoar weight average molecular weight described in step 1 is 20000-400000.
Inorganic particulate described in step 1 is any one in silica, ZSM-5 zeolite, Silicalite-1 zeolite, polysilsesquioxane.
Additive described in step 1 is any one in polyethylene glycol-200 (PEG-200), polyethylene glycol-300 (PEG-300), PEG-4000 (PEG-400), polyethylene glycol-600 (PEG-600), polyethylene glycol-700 (PEG-700).
Solvent described in step 1 is any one in triethyl phosphate, DMF, DMA, 1-METHYLPYRROLIDONE.
Polyester non-woven fabric described in step 2 is the whole polyester non-woven fabrics of the model NAS-222 that Ao Long company provides.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is done to the explanation of a step:
Embodiment 1
1) by weight average molecular weight be 20000 PVDF, ZSM-5 zeolite, PEG-200, triethyl phosphate mixing, at 70 DEG C, stir 16h, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The quality of PVDF, ZSM-5 zeolite, PEG-200, triethyl phosphate is respectively 10g, 0.05g, 0.05g, 30g;
2) by 1) in the film liquid that obtains on polyester non-woven fabric, apply knifing, being immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 24h under 20 DEG C of environment.
Inorganic particulate/PVDF the composite membrane obtained is measured Pervaporation Separation, and be 40 DEG C in operating temperature, when in feed liquid, concentration of alcohol is 1wt%, separation factor is 8.7, and permeation flux is 3.3kg/m
2h.
Embodiment 2
1) by weight average molecular weight be 50000 PVDF, ZSM-5 zeolite, PEG-400, triethyl phosphate mixing, at 70 DEG C, stir 18h, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The quality of PVDF, ZSM-5 zeolite, PEG-200, triethyl phosphate is respectively 10g, 2g, 3g, 70g;
2) by 1) in the film liquid that obtains on polyester non-woven fabric, apply knifing, being immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 12h under 40 DEG C of environment.
Inorganic particulate/PVDF the composite membrane obtained is measured Pervaporation Separation, and be 40 DEG C in operating temperature, when in feed liquid, concentration of alcohol is 30wt%, separation factor is 4.5, and permeation flux is 17.9kg/m
2h.
Embodiment 3
1) by weight average molecular weight be 100000 PVDF, polysilsesquioxane, PEG-600, DMA mixing, at 90 DEG C, stir 12h, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The quality of PVDF, ZSM-5 zeolite, PEG-200, triethyl phosphate is respectively 10g, 0.1g, 2g, 90g;
2) by 1) in the film liquid that obtains on polyester non-woven fabric, apply knifing, being immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 24h under 30 DEG C of environment.
Inorganic particulate/PVDF the composite membrane obtained is measured Pervaporation Separation, and be 40 DEG C in operating temperature, when in feed liquid, concentration of alcohol is 10wt%, separation factor is 6.2, and permeation flux is 21.1kg/m
2h.
Embodiment 4
1) by weight average molecular weight be 120000 PVDF, Silicalite-1 zeolite, PEG-600, DMF mixing, at 80 DEG C, stir 16h, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The quality of PVDF, Silicalite-1 zeolite, PEG-600, DMF is respectively 10g, 3g, 5g, 90g;
2) by 1) in the film liquid that obtains on polyester non-woven fabric, apply knifing, being immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 12h under 50 DEG C of environment.
Inorganic particulate/PVDF the composite membrane obtained is measured Pervaporation Separation, and be 40 DEG C in operating temperature, when in feed liquid, concentration of alcohol is 10wt%, separation factor is 6.8, and permeation flux is 12.5kg/m
2h.
Embodiment 5
1) by weight average molecular weight be 400000 PVDF, silica, PEG-700,1-METHYLPYRROLIDONE mixing, at 70 DEG C, stir 48h, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The quality of PVDF, silica, PEG-700,1-METHYLPYRROLIDONE is respectively 10g, 1g, 3g, 130g;
2) by 1) in the film liquid that obtains on polyester non-woven fabric, apply knifing, being immersed in the water film forming, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 8h under 60 DEG C of environment.
Inorganic particulate/PVDF the composite membrane obtained is measured Pervaporation Separation, and be 40 DEG C in operating temperature, when in feed liquid, concentration of alcohol is 5wt%, separation factor is 7.3, and permeation flux is 7.2kg/m
2h.
Claims (5)
1. a preparation method for preferential alcohol inorganic particulate/PVDF composite membrane thoroughly, is characterized in that: said method comprising the steps of:
Step 1: the preparation method of inorganic particulate/pvdf membrane liquid, by Kynoar (PVDF), inorganic particulate, additive, solvent mixing, 12-48h is stirred at 70-90 DEG C, even to film liquid, be then placed in vacuum drying oven deaeration and obtain inorganic particulate/pvdf membrane liquid; The mass ratio of Kynoar, inorganic particulate, additive, solvent is 10:(0.05-3): (0.05-5): (30-130), described inorganic particulate is containing loose structure;
Step 2: immersion precipitation phase inversion process prepares inorganic particulate/PVDF composite membrane, applies knifing by the film liquid obtained in step 1, is immersed in the water film forming on polyester non-woven fabric, take water as coagulation bath, until solvent in film liquid and water coke slurry thoroughly after, dry 8-24h under 20-60 DEG C of environment
Wherein, described inorganic particulate/PVDF composite membrane has porous asymmetric structure.
2. according to the preparation method described in claim 1, it is characterized in that: the Kynoar weight average molecular weight described in step 1 is 20000-400000.
3. according to the preparation method described in claim 1, it is characterized in that: the inorganic particulate described in step 1 is any one in silica, ZSM-5 zeolite, Silicalite-1 zeolite and polysilsesquioxane.
4. according to the preparation method described in claim 1, it is characterized in that: the additive described in step 1 is any one in polyethylene glycol-200 (PEG-200), polyethylene glycol-300 (PEG-300), PEG-4000 (PEG-400), polyethylene glycol-600 (PEG-600) and polyethylene glycol-700 (PEG-700).
5. according to the preparation method described in claim 1, it is characterized in that: solvent described in step 1 is any one in triethyl phosphate, DMF, DMA and 1-METHYLPYRROLIDONE.
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| CN106378015B (en) * | 2016-11-09 | 2021-07-27 | 北京工商大学 | Polysilsesquioxane modified zeolite/silicone rubber composite membrane and application 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 |
| CN108822449A (en) * | 2018-06-05 | 2018-11-16 | 哈尔滨工业大学 | A kind of nano hybridization polyvinylidene fluoride copolymer composite membrane and its preparation method and application |
| CN111569673B (en) * | 2020-05-30 | 2021-10-19 | 杨笃云 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
| CN111533642B (en) * | 2020-05-30 | 2021-06-11 | 广西英和药业有限公司 | Method for recovering ethanol from ethanol/water solution |
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| JP2000334881A (en) * | 1999-05-28 | 2000-12-05 | Konica Corp | Cage-shaped silsesquioxane-containing film |
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
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| CN101143305A (en) * | 2007-07-06 | 2008-03-19 | 清华大学 | Priority dealcoholization PDMS/PVDF multi-layer compound film and preparation method thereof |
| CN101157764A (en) * | 2007-09-26 | 2008-04-09 | 天津工业大学 | Method for preparing inorganic matter micropowder hybrid polyvinylidene fluoride |
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| JP2000334881A (en) * | 1999-05-28 | 2000-12-05 | Konica Corp | Cage-shaped silsesquioxane-containing film |
| CN101039798A (en) * | 2004-10-06 | 2007-09-19 | 纽约州立大学研究基金会 | High flux and low fouling filtration media |
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
| CN101143305A (en) * | 2007-07-06 | 2008-03-19 | 清华大学 | Priority dealcoholization PDMS/PVDF multi-layer compound film and preparation method thereof |
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