CN103691325A - Preparation method of ethanol permselective inorganic particles/PVDF (Polyvinylidene Fluoride) composite membrane - Google Patents
Preparation method of ethanol permselective inorganic particles/PVDF (Polyvinylidene Fluoride) composite membrane Download PDFInfo
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- CN103691325A CN103691325A CN201310696862.8A CN201310696862A CN103691325A CN 103691325 A CN103691325 A CN 103691325A CN 201310696862 A CN201310696862 A CN 201310696862A CN 103691325 A CN103691325 A CN 103691325A
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- pvdf
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- inorganic particulate
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- composite membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010954 inorganic particle Substances 0.000 title abstract description 6
- 239000002033 PVDF binder Substances 0.000 title abstract 5
- 239000007788 liquid Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 12
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 9
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 8
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 claims description 4
- 229940068886 polyethylene glycol 300 Drugs 0.000 claims description 4
- 229940089985 polyethylene glycol 700 Drugs 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 15
- 230000004907 flux Effects 0.000 abstract description 10
- 238000005373 pervaporation Methods 0.000 abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 5
- -1 PEG-700 Chemical compound 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of an ethanol permselective inorganic particles/PVDF (Polyvinylidene Fluoride) composite membrane, belonging to the technical field of separation of pervaporation membranes. The preparation method comprises the following steps: preparing a membrane liquid mixed by PVDF, inorganic particles, an additive and a solvent; uniformly stirring and defoaming at a certain temperature; coating and knifing on a non-woven fabric support layer; and preparing the inorganic particles/PVDF composite membrane by adopting an immersion precipitation phase inversion method with water as a gel bath. The inorganic particles/PVDF composite membrane obtained by the invention is excellent in ethanol permselective performance on low-concentration ethanol water (1-30wt%), and the permeation flux reaches up to J which is equal to 21.1kg/m<2>h and the separation factor is alpha which is equal to 6.2 for 10wt% ethanol water.
Description
Technical field
The present invention relates to a kind of preparation method who 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, little molecule resistance to mass tranfer in dense film is larger, causes dense film permeation flux all lower, general 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 that to take porous inorganic particle be raw material with hydrophobicity PVDF, and employing immersion precipitation phase inversion is prepared inorganic particulate/PVDF composite membrane.The composite membrane making on the one hand has porous asymmetric structure, greatly reduced the resistance to mass tranfer of little molecule in film, inorganic particulate also plays humidification to PVDF on the other hand, utilize preferential selective the improve ethanol/water separation factor of the loose structure of inorganic particulate to ethanol, can keep on the basis of 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 provides a kind of preferential preparation method of alcohol inorganic particulate/PVDF composite membrane thoroughly for above-mentioned key technical problem.This composite membrane can, keeping, on the basis of certain separative efficiency, realizing increasing substantially of permeation flux, have been broken through the comprehensive separating property of dense film.This inorganic particulate/PVDF composite membrane permeation flux can be up to J=21.1kg/m
2h, separation factor alpha=6.2, have good prospects for commercial application.
A preferential preparation method for 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, at 70-90 ℃, stir 12-48h, 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 is prepared inorganic particulate/PVDF composite membrane, the film liquid obtaining in step 1 is applied to knifing on polyester non-woven fabric, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 8-24h under 20-60 ℃ 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, the whole polyester nonwoven of the model NAS-222 that Wei Aolong company provides.
The specific embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is done the explanation of a step:
embodiment 1
1) PVDF that is 20000 by weight average molecular weight, ZSM-5 zeolite, PEG-200, triethyl phosphate mix, and at 70 ℃, stir 16h, even to film liquid, are 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, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 24h under 20 ℃ of environment.
Inorganic particulate/PVDF the composite membrane obtaining is measured to Pervaporation Separation, is 40 ℃ in operating temperature, and 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) PVDF that is 50000 by weight average molecular weight, ZSM-5 zeolite, PEG-400, triethyl phosphate mix, and at 70 ℃, stir 18h, even to film liquid, are 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, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 12h under 40 ℃ of environment.
Inorganic particulate/PVDF the composite membrane obtaining is measured to Pervaporation Separation, is 40 ℃ in operating temperature, and 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) PVDF that is 100000 by weight average molecular weight, polysilsesquioxane, PEG-600, DMA mix, and at 90 ℃, stir 12h, even to film liquid, are 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, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 24h under 30 ℃ of environment.
Inorganic particulate/PVDF the composite membrane obtaining is measured to Pervaporation Separation, is 40 ℃ in operating temperature, and 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) PVDF that is 120000 by weight average molecular weight, Silicalite-1 zeolite, PEG-600, DMF mix, and at 80 ℃, stir 16h, even to film liquid, are 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, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 12h under 50 ℃ of environment.
Inorganic particulate/PVDF the composite membrane obtaining is measured to Pervaporation Separation, is 40 ℃ in operating temperature, and 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) PVDF that is 400000 by weight average molecular weight, silica, PEG-700,1-METHYLPYRROLIDONE mix, and at 70 ℃, stir 48h, even to film liquid, are 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, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 8h under 60 ℃ of environment.
Inorganic particulate/PVDF the composite membrane obtaining is measured to Pervaporation Separation, is 40 ℃ in operating temperature, and 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 preferential preparation method for 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, at 70-90 ℃, stir 12-48h, 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 is prepared inorganic particulate/PVDF composite membrane, the film liquid obtaining in step 1 is applied to knifing on polyester non-woven fabric, be immersed in the water film forming, take water as coagulation bath, after solvent in film liquid and water exchange thoroughly, dry 8-24h under 20-60 ℃ of environment.
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, 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), 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, 1-METHYLPYRROLIDONE.
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| CN201310696862.8A CN103691325B (en) | 2013-12-18 | 2013-12-18 | A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly |
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| CN201310696862.8A CN103691325B (en) | 2013-12-18 | 2013-12-18 | A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly |
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| CN103691325B CN103691325B (en) | 2016-04-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106378015A (en) * | 2016-11-09 | 2017-02-08 | 北京工商大学 | Polysilsesquioxane modified zeolite/silicon rubber composite film and application thereof |
| CN106731871A (en) * | 2016-12-15 | 2017-05-31 | 天津工业大学 | The method that inorganic particulate induction phase separation prepares 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 |
| CN111533642A (en) * | 2020-05-30 | 2020-08-14 | 青岛森晨环保科技有限责任公司 | Method for recovering ethanol from ethanol/water solution |
| CN111569673A (en) * | 2020-05-30 | 2020-08-25 | 青岛森晨环保科技有限责任公司 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378015A (en) * | 2016-11-09 | 2017-02-08 | 北京工商大学 | Polysilsesquioxane modified zeolite/silicon rubber composite film and application thereof |
| CN106378015B (en) * | 2016-11-09 | 2021-07-27 | 北京工商大学 | Polysilsesquioxane modified zeolite/silicone rubber composite membrane and application thereof |
| CN106731871A (en) * | 2016-12-15 | 2017-05-31 | 天津工业大学 | The method that inorganic particulate induction phase separation prepares 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 |
| CN111533642A (en) * | 2020-05-30 | 2020-08-14 | 青岛森晨环保科技有限责任公司 | Method for recovering ethanol from ethanol/water solution |
| CN111569673A (en) * | 2020-05-30 | 2020-08-25 | 青岛森晨环保科技有限责任公司 | 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 |
| CN111569673B (en) * | 2020-05-30 | 2021-10-19 | 杨笃云 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
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