CN101545213A - Method for preparing PDMS/PVDF composite membrane - Google Patents
Method for preparing PDMS/PVDF composite membrane Download PDFInfo
- Publication number
- CN101545213A CN101545213A CN200910097955A CN200910097955A CN101545213A CN 101545213 A CN101545213 A CN 101545213A CN 200910097955 A CN200910097955 A CN 200910097955A CN 200910097955 A CN200910097955 A CN 200910097955A CN 101545213 A CN101545213 A CN 101545213A
- Authority
- CN
- China
- Prior art keywords
- pdms
- pvdf
- acetone
- mixed liquor
- composite membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method for preparing a PDMS/PVDF composite membrane. The method comprises the following steps: firstly, preparing a poly(vinylidene fluoride) basement membrane, namely, dissolving PVDF in a triethylphosphate solvent to prepare a solution of the PVDF and wiping a membrane on one side of a non-woven fabric; secondly, preparing a polydimethylsiloxane layer, namely first dissolving PDMS in a n-hexane solvent and then adding a triethoxyoctylsilane cross linker and a dibutyltin dilaurate catalyst into the solvent; and finally, after the stirring, centrifugation, filtration and deaeration of the mixed solution, directly wiping the mixed solution on the poly(vinylidene fluoride) basement membrane and obtaining the PDMS/PVDF composite membrane after drying. The method has the advantages that: the process is simple; the production cost is low; and the prepared composite membrane has excellent thermal stability, excellent penetrating quality and good ethanol, acetone and butanol selectivity and is not contaminated by liquid.
Description
Technical field
The present invention relates to a kind of preparation method who can be used for the organic PDMS/PVDF of infiltration evaporation penetrated preferably (dimethyl silicone polymer/Kynoar) film, be used for the separation of acetone product, belong to the infiltrating and vaporizing membrane separation field.
Background technology
Arrival along with global energy crisis and environmental crisis; force people to exist new forms of energy to replace non-renewable energy resources such as oil; wherein biological butanol fuel (biobutanol) not only can replace traditional petroleum-based energy as a kind of clean energy resource, and can significantly reduce the pollution of environment.At present, developed countries such as American-European Japan in various degree with biological butanol instead of part oil, and be devoted to produce extensive biological butanol fuel to solve energy crisis.
As far back as the seventies in 19th century, Pasteur just finds that bacterium can produce butanols, to the twenties in 20th century, Chaim Weizmann found that Clostridium.acetobutylicum can utilize amylofermentation to produce butanols and ethanol, and had set up first acetone factory in U.S. Indiana State in 1918.To the forties, the fermentation of acetone-butanols has become the second largest fermentation industry that is only second to alcoholic fermentation.But to the sixties, because fermenting and producing butanols, acetone, ethanol be than traditional chemical industry method production cost height, efficient is lower, and therefore development is very slow.Up to last century end, oil price is constantly soaring, and acetone is subject to people's attention again.
Biological fermentation process prepares and also comprises a large amount of acetone and a spot of ethanol (product general designation ABE) etc. in the product of butanols.Whole fermentation process can be subjected to serious product and suppress, when product A BE concentration reached certain value, microorganism stopped growing, and therefore must adopt effective method that product A BE is removed from zymotic fluid, reduce product and suppress, reduce industrial cost thereby improve fermentation production rate.Being applied to the technology that acetone butanol fermentation separates at present mainly comprises: gas is carried, liquid-liquid extraction, absorption, infiltration evaporation etc., wherein infiltration evaporation is because characteristics such as its high selectivity, economy, simplicity obtain extensive studies (Tong Cancan, Yang Lirong, Wu Jian equality. the progress of acetone separation coupling technology [J]. chemical industry progress .2008,27 (11): 1783-1789).Infiltration evaporation (Pervaporation) demonstrates special advantages as one of membrane separation technique new branch in the fields such as separation of the reluctant azeotropic mixture of traditional separation means, nearly boiling point system; Its separation is not limited by VLE, first separation degree height, simple, pollution-free, the low energy consumption of facility, can carry out integrated with traditional separation means such as rectifying, extraction, absorption, crystallizations, be easy to be coupled with chemical reaction, be suitable for and various production scales, become the up-and-coming youngster in the separation unit operation family.The macromolecule member material that is applied to infiltrating and vaporizing membrane acetone/butanols at present is less, and PEBA is wherein a kind of important macromolecular material, its to the separation factor of acetone about 5～10, to separation factor (Liu, FF about 8～15 of butanols; Liu, L; Feng, XS.Separation of acetone-butanol-ethanol (ABE) from dilute aqueoussolutions by pervaporation[J] .Sep.Purif.Technol.2005,42 (3): 273-282); Meagher etc. discloses a kind of inoranic membrane (Silicalte membrane andmethod for the selective recovery and concentration of acetone andbutanol from model ABE solutions and fermentation broth in addition, US005755967A), its selectivity to acetone is better, flux is big, but inorganic material film cost costliness has limited its industrial applications.In addition, liquid film also is applied in the organic matter separation of the acetone aqueous solution, Thogsukmak etc. utilize trioctylamine liquid film acetone/butanols from acetone-butanols aqueous solution, the acetone separation factor is 70～75, the butanols separation factor is 100～105, but it exists the less stable film easily to run off and pollutes defective (Thongsukmak A such as zymotic fluid easily, Sirkar K K.Pervaporation membranes highly selective for solvents present infermentation broths[J] .J.Mem.Sci., 2007,302:45-58), limited greatly in industrial application.
Summary of the invention
The objective of the invention is at above-mentioned technical problem, a kind of preparation method who can be used for the PDMS/PVDF composite membrane of penetrated preferably ethanol/acetone/butanols is provided.
The inventive method may further comprise the steps:
Step (1). preparation Kynoar counterdie: PVDF (Kynoar) is dissolved in the triethyl phosphate solvent is mixed with PVDF solution, the concentration of PVDF is 10～20wt% in the PVDF solution; Stir under 50～80 ℃, filter, discontinuous degassing is poured on the nonwoven fabric, and the side knifing at nonwoven fabric dries then naturally;
Step (2). preparation dimethyl silicone polymer layer: PDMS (dimethyl silicone polymer) is dissolved in the n-hexane solvent, add the crosslinking agent octyltri-ethoxysilane again, octyltri-ethoxysilane that adds and the mass ratio of PDMS are 0.04～0.1:1, and mixed liquor is stirred 0.5～1h;
The catalyst dibutyl tin laurate is joined in the mixed liquor, and the dibutyl tin laurate of adding and the mass ratio of PDMS are 0.01～0.08:1; The concentration of PDMS is 5～30wt% in the mixed liquor;
Step (3). mixed liquor is stirred 0.5～3h,, again mixed liquor is directly scraped on the Kynoar counterdie through centrifugal, filtration, deaeration, dry at normal temperatures, put into vacuum drying oven then at 30～110 ℃ of following vacuumize 1～10h, crosslinked fully, obtain the PDMS/PVDF composite membrane.
The PDMS/PVDF composite membrane that the present invention is prepared, production technology is simpler, production cost is lower, be used for the preferential saturating ethanol/acetone/butanols of aqueous acetone solution, the butanols aqueous solution, ethanol/acetone/butanols aqueous solution and acetone liquid, for concentration is the aqueous acetone solution of 0.4～0.6wt%, its separation factor alpha under 45 ℃=18～20; For concentration is the butanols aqueous solution of 0.8～1.1wt%, its separation factor alpha under 45 ℃=20～23; For the organic matter total concentration is ethanol/acetone/butanols aqueous solution of 1.8～2.0wt%, the separation factor of its ethanol, acetone and butanols is respectively under 45 ℃: 4～7,21～23 and 23～25, and separate back ethanol/acetone/butanols total concentration and can reach 30～35wt%.
The PDMS/PVDF composite membrane of the inventive method preparation, can from ethanol/acetone/butanols aqueous solution, isolate ethanol/acetone/butanols, the saturating ethanol/acetone of infiltration evaporation/butanols effect with excellent performance, be applied to acetone simultaneously, effectively reduced the inhibitory action of tunning (acetone), its production cost is lower, has the large-scale industrial application prospect.Ethanol/acetone/butanols PDMS/PVDF composite membrane is a dense film, has good heat endurance and excellent permeability energy, and is good to the selectivity of ethanol/acetone/butanols for this method preparation preferential saturating, and is not subjected to the pollution of feed liquid.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Embodiment 1
1). preparation Kynoar counterdie: 7gPVDF is dissolved in the triethyl phosphate solvent is mixed with PVDF solution, the concentration of PVDF is 10wt% in the PVDF solution; Stir under 50 ℃, filter, discontinuous degassing is poured on the nonwoven fabric, and the side knifing at nonwoven fabric dries then naturally;
2). preparation dimethyl silicone polymer layer: 5g PDMS is dissolved in the n-hexane solvent, adds 0.2g crosslinking agent octyltri-ethoxysilane again, mixed liquor is stirred 0.5h;
0.05g catalyst dibutyl tin laurate is joined in the mixed liquor; The concentration of PDMS is 5wt% in the mixed liquor;
3). mixed liquor is stirred 0.5h,, again mixed liquor is directly scraped on the Kynoar counterdie, dry at normal temperatures, put into vacuum drying oven then at 50 ℃ of following vacuumize 4h through centrifugal, filtration, deaeration, crosslinked fully, obtain the PDMS/PVDF composite membrane.
Embodiment 2
1). preparation Kynoar counterdie: 7gPVDF is dissolved in the triethyl phosphate solvent is mixed with PVDF solution, the concentration of PVDF is 15wt% in the PVDF solution; Stir under 70 ℃, filter, discontinuous degassing is poured on the nonwoven fabric, and the side knifing at nonwoven fabric dries then naturally;
2). preparation dimethyl silicone polymer layer: 5g PDMS is dissolved in the n-hexane solvent, adds 0.4g crosslinking agent octyltri-ethoxysilane again, mixed liquor is stirred 1h;
0.15g catalyst dibutyl tin laurate is joined in the mixed liquor; The concentration of PDMS is 25wt% in the mixed liquor;
3). mixed liquor is stirred 3h,, again mixed liquor is directly scraped on the Kynoar counterdie, dry at normal temperatures, put into vacuum drying oven then at 30 ℃ of following vacuumize 10h through centrifugal, filtration, deaeration, crosslinked fully, obtain the PDMS/PVDF composite membrane.
Embodiment 3
1). preparation Kynoar counterdie: 7g PVDF is dissolved in the triethyl phosphate solvent is mixed with PVDF solution, the concentration of PVDF is 20wt% in the PVDF solution; Stir under 80 ℃, filter, discontinuous degassing is poured on the nonwoven fabric, and the side knifing at nonwoven fabric dries then naturally;
2). preparation dimethyl silicone polymer layer: 5g PDMS is dissolved in the n-hexane solvent, adds 0.5g crosslinking agent octyltri-ethoxysilane again, mixed liquor is stirred 40min;
0.4g catalyst dibutyl tin laurate is joined in the mixed liquor; The concentration of PDMS is 30wt% in the mixed liquor;
3). mixed liquor is stirred 2h,, again mixed liquor is directly scraped on the Kynoar counterdie, dry at normal temperatures, put into vacuum drying oven then at 110 ℃ of following vacuumize 1h through centrifugal, filtration, deaeration, crosslinked fully, obtain the PDMS/PVDF composite membrane.
Utilize the PDMS/PVDF composite membrane of example 1 to investigate to the membrane separating property of concentration for the aqueous acetone solution of 0.2wt%.The result shows: absolute pressure 0.3MP behind 40 ℃, film, and the separation factor of acetone is 13.5; Total permeation flux is: 35.7gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of concentration for the aqueous acetone solution of 0.5wt%.The result shows: absolute pressure 0.3MP behind 45 ℃, film, and the separation factor of acetone is 19.8; Total permeation flux is: 47.5gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of concentration for the aqueous acetone solution of 10wt%.The result shows: absolute pressure 0.3MP behind 60 ℃, film, and the separation factor of acetone is 9.6; Total permeation flux is: 255.8gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of concentration for the butanols aqueous solution of 0.3wt%.The result shows: absolute pressure 0.3MP behind 30 ℃, film, and the separation factor of butanols is 14.7; Total permeation flux is: 25.7gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of concentration for the butanols aqueous solution of 1.1wt%.The result shows: absolute pressure 0.3MP behind 40 ℃, film, and the separation factor of acetone is 15.7; Total permeation flux is: 50.9gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of concentration for the butanols aqueous solution of 6.5wt%.The result shows: absolute pressure 0.3MP behind 30 ℃, film, and the separation factor of butanols is 20.9; Total permeation flux is: 285.1gm
-2h
-1
Utilize the PDMS/PVDF film of example 2 to investigate to the membrane separating property of total concentration for ethanol-acetone-butanols aqueous solution of 1.9wt%.The result shows: absolute pressure 0.3MP behind 45 ℃, film, and the separation factor of ethanol, acetone and butanols is 4.7,21.1 and 23.2; Total permeation flux is: 68.1gm
-2h
-
Utilize the PDMS/PVDF film of example 3 to investigate to the membrane separating property of total concentration for ethanol-acetone-butanols aqueous solution of 20wt%.The result shows: absolute pressure 0.3MP behind 40 ℃, film, and the separation factor of ethanol, acetone and butanols is 2.8,12.1 and 24.9; Total permeation flux is: 659.3gm
-2h
-1
Utilize the PDMS/PVDF film of example 3 to investigate to the membrane separating property of total concentration for ethanol-acetone-butanols aqueous solution of 10wt%.The result shows: absolute pressure 0.3MP behind 45 ℃, film, and the separation factor of ethanol, acetone and butanols is 3.7,17.2 and 25.4; Total permeation flux is: 376.5gm
-2h
-1
Claims (1)
1, a kind of preparation method of PDMS/PVDF composite membrane is characterized in that this method may further comprise the steps:
Step (1). preparation Kynoar counterdie: Kynoar is dissolved in the triethyl phosphate solvent is mixed with Kynoar solution, the concentration of Kynoar is 10～20wt% in the Kynoar solution; Stir under 50～80 ℃, filter, discontinuous degassing is poured on the nonwoven fabric, and the side knifing at nonwoven fabric dries then naturally;
Step (2). preparation dimethyl silicone polymer layer: dimethyl silicone polymer is dissolved in the n-hexane solvent, add the crosslinking agent octyltri-ethoxysilane again, the octyltri-ethoxysilane that adds and the mass ratio of dimethyl silicone polymer are 0.04～0.1:1, and mixed liquor was stirred 0.5～1 hour;
The catalyst dibutyl tin laurate is joined in the mixed liquor, and the dibutyl tin laurate of adding and the mass ratio of dimethyl silicone polymer are 0.01～0.08:1; The concentration of dimethyl silicone polymer is 5～30wt% in the mixed liquor;
Step (3). mixed liquor was stirred 0.5～3 hour, through centrifugal, filtration, deaeration, again mixed liquor is directly scraped on the Kynoar counterdie, dry at normal temperatures, put into vacuum drying oven then 30～110 ℃ of following vacuumizes 1～10 hour, crosslinked fully, obtain the PDMS/PVDF composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097955A CN101545213A (en) | 2009-04-27 | 2009-04-27 | Method for preparing PDMS/PVDF composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097955A CN101545213A (en) | 2009-04-27 | 2009-04-27 | Method for preparing PDMS/PVDF composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101545213A true CN101545213A (en) | 2009-09-30 |
Family
ID=41192571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910097955A Pending CN101545213A (en) | 2009-04-27 | 2009-04-27 | Method for preparing PDMS/PVDF composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101545213A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050954A (en) * | 2010-11-12 | 2011-05-11 | 北京工业大学 | Preparation method of environment-friendly silicone rubber composite membrane |
| CN102806024A (en) * | 2012-08-29 | 2012-12-05 | 江南大学 | Method for preparing high-permeability polydimethylsiloxane gas separation membrane and application thereof |
| CN103285751A (en) * | 2013-06-28 | 2013-09-11 | 清华大学 | PDMS (Polydimethylsiloxane)-PVDF (Polyvinylidene Fluoride) composite membrane for separating organic vapor and modification-preparation method thereof |
| CN106582332A (en) * | 2016-12-19 | 2017-04-26 | 河北工业大学 | Method for preparing superhydrophobic composite microporous membrane |
| CN106831287A (en) * | 2017-01-09 | 2017-06-13 | 北京化工大学 | A kind of system and method for preparing bio-based butadiene |
| CN110143851A (en) * | 2019-06-06 | 2019-08-20 | 太仓沪试试剂有限公司 | A method of n-butanol is purified using membrane separation technique |
-
2009
- 2009-04-27 CN CN200910097955A patent/CN101545213A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050954A (en) * | 2010-11-12 | 2011-05-11 | 北京工业大学 | Preparation method of environment-friendly silicone rubber composite membrane |
| CN102806024A (en) * | 2012-08-29 | 2012-12-05 | 江南大学 | Method for preparing high-permeability polydimethylsiloxane gas separation membrane and application thereof |
| CN103285751A (en) * | 2013-06-28 | 2013-09-11 | 清华大学 | PDMS (Polydimethylsiloxane)-PVDF (Polyvinylidene Fluoride) composite membrane for separating organic vapor and modification-preparation method thereof |
| CN103285751B (en) * | 2013-06-28 | 2015-12-09 | 清华大学 | A kind of PDMS-PVDF composite membrane of separating organic steam and modification method for preparing thereof |
| CN106582332A (en) * | 2016-12-19 | 2017-04-26 | 河北工业大学 | Method for preparing superhydrophobic composite microporous membrane |
| CN106582332B (en) * | 2016-12-19 | 2019-09-06 | 河北工业大学 | A kind of preparation method of super-hydrophobic composite micro porous film |
| CN106831287A (en) * | 2017-01-09 | 2017-06-13 | 北京化工大学 | A kind of system and method for preparing bio-based butadiene |
| CN106831287B (en) * | 2017-01-09 | 2020-07-03 | 北京化工大学 | System and method for preparing bio-based butadiene |
| CN110143851A (en) * | 2019-06-06 | 2019-08-20 | 太仓沪试试剂有限公司 | A method of n-butanol is purified using membrane separation technique |
| CN110143851B (en) * | 2019-06-06 | 2022-06-07 | 太仓沪试试剂有限公司 | Method for purifying n-butanol by membrane separation technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102000516B (en) | Method for preparing polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film | |
| Huang et al. | Separation and purification of biobutanol during bioconversion of biomass | |
| CN101545213A (en) | Method for preparing PDMS/PVDF composite membrane | |
| CN104117297B (en) | A kind of preparation method of hydrophobically modified nanon calcium carbonatefilled osmosis vaporizing compound membrane | |
| CN100569349C (en) | A kind of priority dealcoholization PDMS/PVDF multilayer complex films and preparation method thereof | |
| CN101279212B (en) | Preparation of intercrossed network water dealcoholizing pervaporation membrane | |
| CN104084052B (en) | A kind of preparation method of silicone rubber composite hollow fiber membrane | |
| Zheng et al. | The potential of pervaporation for biofuel recovery from fermentation: An energy consumption point of view | |
| Saha et al. | Continuous production of bioethanol from sugarcane bagasse and downstream purification using membrane integrated bioreactor | |
| CN104084059B (en) | A kind of preparation method of hydrophobically modified nanon calcium carbonatefilled composite silicone rubber membrane | |
| CN101269304A (en) | Method for preparing pervaporation membrane for separating alcohol-water system | |
| CN101480582B (en) | Method for preparing polyurethane film based on hydroxy-terminated polybutadiene | |
| CN104138717B (en) | A kind of preparation method of PDMS/PAN infiltration evaporation hollow-fibre membrane | |
| CN103877874A (en) | Preparation method of polydimethylsiloxane-carbon nano tube composite membrane, composite membrane and method for separating and purifying butyl alcohol | |
| JPWO2015005410A1 (en) | Method for producing alcohol from cellulose-containing biomass | |
| CN102191340B (en) | Method for removing inhibitors in prehydrolysis liquid of lignocellulose | |
| Si et al. | Recovery of ethanol via vapor phase by polydimethylsiloxane membrane with excellent performance | |
| CN104151585A (en) | Preparation method of hydrophobic nano-grade calcium carbonate filled polyurethane pervaporation membrane | |
| Serna-Vazquez et al. | Simultaneous production and extraction of bio-chemicals produced from fermentations via pervaporation | |
| CN103420793B (en) | The method of a kind of polyvinylidene difluoride (PVDF)-polydimethylsiloxane composite membrane separation and purification butanols | |
| CN104107644B (en) | A kind of preparation method of alcohol permselective silicon rubber composite membrane | |
| CN102371078B (en) | Recovery method for ionic liquid solvent generated from homogeneous acylation reaction of cellulose | |
| CN110743372A (en) | Device and process for preparing methanol and butyl acetate | |
| CN101816897A (en) | ZSM-5 molecular sieve filled silicon rubber/cellulose acetate composite membrane and preparation method thereof | |
| CN104138718B (en) | A kind of preparation method of modification polybutadiene polyurethane infiltrating and vaporizing membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090930 |