CN1748845A - Process for preparing organic-inorganic hybridized osmotic evaporation film - Google Patents
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- CN1748845A CN1748845A CN 200510014883 CN200510014883A CN1748845A CN 1748845 A CN1748845 A CN 1748845A CN 200510014883 CN200510014883 CN 200510014883 CN 200510014883 A CN200510014883 A CN 200510014883A CN 1748845 A CN1748845 A CN 1748845A
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Abstract
The preparation process of hybridized organic-inorganic pervaporation film includes the following steps: dissolving PVA of polymerization degree 1650-1900 into deionized water at 50-90 deg c to form 5-10 wt% concentration solution, cooling to room temperature, adding g-(2, 3-propylene oxide) propyl trimethoxy silane in 0-2 times weight of PVA and 1.0 M HCl solution in 0.5-2.0 ml, and stirring for over 12 hr to obtain casting solution; filtering, debubbling, scraping the casting solution with scraper onto organic glass plate, evaporating water and phase converting into film; and heat treatment at 80-160 deg.c for 0.1-24 hr to obtain the hybridized organic-inorganic pervaporation film. The prepared pervaporation film has high mechanical strength and excellent benzene/cyclohexane separating effect.
Description
Technical field
The present invention relates to a kind of preparation method of organic-inorganic hybridized osmotic evaporation film.Belong to the membrane separation technique of separating organic/organic (benzene/cyclohexane) mixture.
Background technology
Process of pervaporation is the purpose that reaches the separating liquid mixture by the selectivity of dense film.The pervaporation technology is mainly used in organics dehydration, water removes separating of organic matter and organic/organic mixture.This process has separation factor height, simple to operate, environmental friendliness, process and is not subjected to advantages such as VLE restriction.That pervaporation is based on component relative volatility to be separated unlike distillation technology is different and separated, but separates purpose because the dissolving of different component in film and diffusion difference reach.Utilize the pervaporation technology not only can not add the 3rd component, simplify flow process, the minimizing expense drops into, and is applicable to the occasion of different benzene content.Its separation factor is all greater than azeotropic distillation and extracting rectifying.
The pervaporation membrane technology adopts the macromolecule homogeneous membrane usually at present, because there is " Trade-off " phenomenon in polymeric membrane, be permeability of the membrane can and selectivity this grow that and disappear, so Many researchers has been developed the filled-type polymeric membrane of fillings such as inorganic medium such as zeolite molecular sieve, carbon molecular sieve, active carbon.But owing to interact to weak physical action between macromolecule and the inorganic particle, cause the defective hole between polymeric membrane and the inorganic particulate easily, influence the separating property of film; The dispersion of inorganic particle in macromolecule also is a difficult problem in the preparation process simultaneously, causes the reunion of inorganic particulate in polymeric membrane easily, equally also can influence the separating property of film.Therefore be necessary to develop the novel hybrid organic-inorganic film of a class fully, can address the above problem, can obtain pervaporation separating property preferably again.
Adopt sol-gel process to prepare hybrid organic-inorganic film bibliographical information has been arranged, what usually adopt is as inorganic precursor with ethyl orthosilicate or methyl silicate, such presoma is because itself structural reason, difficult control hydrolysis and condensation polymerization speed in the process of preparation macromolecule-inorganic hybridized film finally cause the structure of hybrid organic-inorganic film to be difficult to control.In contrast to this, select silane coupler g-(2, the 3-expoxy propane) propyl trimethoxy silicane (GPTMS) of hydrophilic long-chain to have following advantage: (1) GPTMS is a hydrophily, and coupling is better between hydrophilic macromolecule such as the polyvinyl alcohol; (2) epoxy radicals on the GPTMS can be in acidic aqueous solution open loop and polyvinyl alcohol can form covalent bond, increase the compatibility between organic and the inorganic component, (3) GPTMS is a fabric softening agent, can reach softening high-molecular polyvinyl alcohol chain, destroy the regular arrangement of macromolecular chain, to obtain higher permeation flux.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of organic-inorganic hybridized osmotic evaporation film.With the osmotic evaporation film of the method preparation, Separation of Benzene and cyclohexane mixture effectively, and also its separating effect obviously is better than extracting rectifying and azeotropic distillation method.
The present invention is achieved through the following technical solutions, (the preparation of (1) casting solution: the polyvinyl alcohol of the degree of polymerization 1650～1900 is dissolved in 50～90 ℃ of deionized waters, make mass concentration and be 5～10% solution, be cooled to after the room temperature mass ratio according to GPTMS and polyvinyl alcohol and be 0～2 and add GPTMS, add 0.5～2.0ml 1.0M HCl solution then, after fully stirring more than 12 hours, promptly obtain casting solution; (2) preparation of hybrid organic-inorganic film: with the casting solution for preparing with screen filtration to remove impurity, standing and defoaming is scraped casting solution on poly (methyl methacrylate) plate equably with scraper then, treats forming film with phase transformation method after the water evaporates; (3) under 80～160 ℃, heat-treated 0.1～24 hour, obtain organic-inorganic hybridized osmotic evaporation film.
The invention has the advantages that: the sol-gel technology of preparing is very easy, the pervaporation separating property of the polyvinyl alcohol that makes-GPTMS hybridized film increases considerably, prepared film has good separating effect to benzene and cyclohexane, and polyvinyl alcohol film only is 22.4g/ (m to total permeation flux of benzene and cyclohexane mixture
2And the prepared polyvinyl alcohol-GPTMS hybridized film of the present invention can reach 137g/ (m to the permeation flux of benzene and cyclohexane mixture h),
2H).
The specific embodiment
Embodiment one
The preparation of organic-inorganic hybridized osmotic evaporation film (film 1)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Under condition of stirring, in this polyvinyl alcohol water solution, add the GPTMS of 0.5g, add 1.0ml 1.0M hydrochloric acid solution again.Stir 12h mixed evenly after, preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 1h at 120 ℃.Can make hybrid organic-inorganic film (film 1).
Prepared film 1 is through ESEM and transmission electron microscope analysis, infrared spectrum analysis, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, the differential scanning calorimetric method is analyzed, dynamic thermomechanical property and X-ray diffraction analysis, this film compactness is good, the mechanical strength height, polyvinyl alcohol and g-(2, the 3-expoxy propane) compatibility is fine between the propyl trimethoxy silicane, forms covalent bond, and the non-oxidation silicon grain generates.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 96.8%, total permeation flux can reach 120g/ (m
2H) more than.
Embodiment two
The preparation of organic-inorganic hybridized osmotic evaporation film (film 2)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Under condition of stirring, in this polyvinyl alcohol water solution, add the GPTMS of 1g, add 1.0ml 1.0M hydrochloric acid solution again.Stir 12h above mixed evenly after, preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 1h at 120 ℃.Can make the required organic-inorganic hybridized osmotic evaporation film of this experiment (film 2).
Prepared film 2 is through ESEM and transmission electron microscope analysis, infrared spectrum analysis, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, the differential scanning calorimetric method is analyzed, dynamic thermomechanical property and X-ray diffraction analysis, and this film compactness is good, the mechanical strength height, compatibility is fine between polyvinyl alcohol and g-(2, the 3-expoxy propane) propyl trimethoxy silicane, forms covalent bond, and generate the silicon oxide particle of about 20 nanometers of size, nano oxidized silicon grain is uniformly dispersed in film.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 97.9%, total permeation flux can reach 137g/ (m
2H) more than.Be used for the Separation of Benzene mass concentration and be 10% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 92.4%,, total permeation flux can reach 97.3g/ (m
2H) more than.Be used for the Separation of Benzene mass concentration and be 90% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 99.2%,, total permeation flux can reach 158.5g/ (m
2H) more than.
Embodiment three
The preparation of organic-inorganic hybridized osmotic evaporation film (film 3)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Under condition of stirring, in this polyvinyl alcohol water solution, add the GPTMS of 2g, add 1.0ml 1.0M hydrochloric acid solution again.Stir 12h above mixed evenly after, preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 1h at 120 ℃.Can make the required organic-inorganic hybridized osmotic evaporation film of this experiment (film 3).
Prepared film 3 is through ESEM and transmission electron microscope analysis, infrared spectrum analysis, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, the differential scanning calorimetric method is analyzed, dynamic thermomechanical property and X-ray diffraction analysis, and this film compactness is good, the mechanical strength height, compatibility is fine between polyvinyl alcohol and g-(2, the 3-expoxy propane) propyl trimethoxy silicane, forms covalent bond, and generate the silicon oxide particle of about 20～50 nanometers of a large amount of sizes, nano oxidized silicon grain disperses more even in film.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 98.0%,, total permeation flux can reach 95.0g/ (m
2H) more than.
Embodiment four
The preparation of organic-inorganic hybridized osmotic evaporation film (film 4)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Under condition of stirring, in this polyvinyl alcohol water solution, add the GPTMS of 1g, add 1.0ml 1.0M hydrochloric acid solution again.Stir 12h above mixed evenly after, preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 0.5h at 120 ℃.Can make the required organic-inorganic hybridized osmotic evaporation film of this experiment (film 4).
Prepared film 4 is through ESEM and transmission electron microscope analysis, infrared spectrum analysis, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, the differential scanning calorimetric method is analyzed, dynamic thermomechanical property and X-ray diffraction analysis, and this film compactness is good, the mechanical strength height, compatibility is fine between polyvinyl alcohol and g-(2, the 3-expoxy propane) propyl trimethoxy silicane, forms covalent bond, and generate the silicon oxide particle of about 20 nanometers of a large amount of sizes, nano oxidized silicon grain is uniformly dispersed in film.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 96.8%,, total permeation flux can reach 145.6g/ (m
2H) more than.
Embodiment five
The preparation of organic-inorganic hybridized osmotic evaporation film (film 5)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Under condition of stirring, in this polyvinyl alcohol water solution, add the GPTMS of 1g, add 1.0ml 1.0M hydrochloric acid solution again.Stir 12h above mixed evenly after, preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 1h at 80 ℃.Can make the required organic-inorganic hybridized osmotic evaporation film of this experiment (film 5).
Prepared film 5 is through ESEM and transmission electron microscope analysis, infrared spectrum analysis, nuclear magnetic resonance spectroscopy, thermogravimetric analysis, the differential scanning calorimetric method is analyzed, dynamic thermomechanical property and X-ray diffraction analysis, and this film compactness is good, the mechanical strength height, compatibility is fine between polyvinyl alcohol and g-(2, the 3-expoxy propane) propyl trimethoxy silicane, forms covalent bond, and generate the silicon oxide particle of about 20 nanometers of a large amount of sizes, nano oxidized silicon grain is uniformly dispersed in film.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 96.2%, total permeation flux can reach 147.2g/ (m
2H) more than.
Comparative Examples one
The preparation of the blank polyvinyl alcohol osmotic evaporation film of non-hydridization type (film 6)
Taking by weighing the 2.5 gram degree of polymerization is that 1750 polyvinyl alcohol and 47.5 gram deionized waters are put into there-necked flask, puts into 90 ℃ water bath with thermostatic control and heats, and stirs the about 1h of dissolving down.All reduce to room temperature after the dissolving, make mass concentration and be 5% polyvinyl alcohol water solution.Preparation liquid is removed standing and defoaming behind the impurity with screen filtration.Then casting solution is poured on knifing on the poly (methyl methacrylate) plate, drying at room temperature 24h takes off film, puts into drying box then and heat-treats 1h at 120 ℃.Can make the required blank polyvinyl alcohol film of this experiment.
Prepared polyvinyl alcohol osmotic evaporation film process scanning electron microscope analysis, infrared spectrum analysis, thermogravimetric analysis, the differential scanning calorimetric method is analyzed and X-ray diffraction analysis, and this film densification is good.Be used for the Separation of Benzene mass concentration and be 50% benzene and cyclohexane mixture, the mass concentration of benzene is reached more than 90%, total permeation flux only reaches 22.4g/ (m
2H) more than.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, film 4, the pervaporation Separation of Benzene of the prepared film 6 of film 5 and Comparative Examples and the permeation flux of cyclohexane mixture and separation factor result.
Table 1
| Film number | GPTMS/PVA mass ratio | Heat treatment temperature (℃) | Heat treatment time (h) | Concentration of raw material (wt% benzene) | Separation factor | Permeation flux (the g/m of component 2.h) | |
| Benzene | Cyclohexane | ||||||
| Film 1 film 2 films 3 films 4 films 5 films 6 | 0.2 0.4 0.8 0.4 0.4 0 | 120 120 120 120 80 120 | 1 1 1 0.5 1 1 | 49.8 50.1 50.0 50.2 50.5 50.0 | 30.4 46.9 51.3 30.5 26.0 9.6 | 116.3 134.2 92.8 141.0 141.7 20.3 | 3.8 2.9 1.8 4.6 5.5 2.1 |
Claims (1)
1, a kind of preparation method of organic-inorganic hybridized osmotic evaporation film is characterized in that this method may further comprise the steps:
(1) preparation of casting solution: the polyvinyl alcohol of the degree of polymerization 1650～1900 is dissolved in 50～90 ℃ of deionized waters, make mass concentration and be 5～10% solution, be cooled to after the room temperature according to g-(2, the 3-expoxy propane) mass ratio of propyl trimethoxy silicane and polyvinyl alcohol is 0～2 adding g-(2, the 3-expoxy propane) propyl trimethoxy silicane, add 0.5～2.0ml 1.0M HCl solution then, fully stir more than 12 hours after, promptly obtain casting solution;
(2) preparation of hybrid organic-inorganic film: to remove impurity, scrape casting solution equably on poly (methyl methacrylate) plate with scraper then, treats to pass through forming film with phase transformation method after the water evaporates by standing and defoaming with screen filtration for the casting solution that step (1) is prepared;
(3) film that step (2) is made was heat-treated under 80～160 ℃ 0.1～24 hour, obtained polyvinyl alcohol-g-(2, the 3-expoxy propane) propyl trimethoxy silicane hybrid pervaporation membrane.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100518914C (en) * | 2006-10-27 | 2009-07-29 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
| CN102029115A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of ethanol pervaporation hybrid film used for removing methyl alcohol in wastewater |
| CN102029116A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of polyvinyl alcohol pervaporation hybrid membrane |
| CN102863647A (en) * | 2012-09-19 | 2013-01-09 | 合肥工业大学 | Preparation method of organic-inorganic hybrid ionic membrane |
| CN102908915A (en) * | 2012-10-31 | 2013-02-06 | 中国科学技术大学 | Diffusion and dialysis membrane for alkali recovery as well as preparation method and application of same |
| CN106000119A (en) * | 2016-06-06 | 2016-10-12 | 西北大学 | Polyethylene glycol desulphurization composite film filled with active carbon and preparation method thereof |
| CN107020016A (en) * | 2017-04-19 | 2017-08-08 | 盐城师范学院 | A kind of non-charged membrane and preparation method thereof, application |
| US11617989B1 (en) | 2020-09-04 | 2023-04-04 | King Saud University | Extraction of benzene from benzene/cyclohexane mixture |
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2005
- 2005-08-29 CN CN 200510014883 patent/CN1748845A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100518914C (en) * | 2006-10-27 | 2009-07-29 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
| CN102029115A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of ethanol pervaporation hybrid film used for removing methyl alcohol in wastewater |
| CN102029116A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of polyvinyl alcohol pervaporation hybrid membrane |
| CN102863647A (en) * | 2012-09-19 | 2013-01-09 | 合肥工业大学 | Preparation method of organic-inorganic hybrid ionic membrane |
| CN102908915A (en) * | 2012-10-31 | 2013-02-06 | 中国科学技术大学 | Diffusion and dialysis membrane for alkali recovery as well as preparation method and application of same |
| CN102908915B (en) * | 2012-10-31 | 2015-02-11 | 中国科学技术大学 | Preparation method of diffusion and dialysis membrane for alkali recovery |
| CN106000119A (en) * | 2016-06-06 | 2016-10-12 | 西北大学 | Polyethylene glycol desulphurization composite film filled with active carbon and preparation method thereof |
| CN107020016A (en) * | 2017-04-19 | 2017-08-08 | 盐城师范学院 | A kind of non-charged membrane and preparation method thereof, application |
| CN107020016B (en) * | 2017-04-19 | 2020-05-01 | 盐城师范学院 | Non-charged membrane and preparation method and application thereof |
| US11617989B1 (en) | 2020-09-04 | 2023-04-04 | King Saud University | Extraction of benzene from benzene/cyclohexane mixture |
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