CN106492646B - A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly - Google Patents
A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, belongs to technical field of membrane separation.Its step includes: to prepare mesoporous sphere SiO by template of cetyl trimethylammonium bromide2Nanoparticle, and carried out hydrophobic modification.It is doped in the casting solution of dimethyl silicone polymer, SiO is prepared using ultrasonic immersing method2The hybridized film prepared is put into heat cross-linking in baking oven and forms dense film by/PDMS hybridized film.The present invention provides a kind of preparation methods for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, and hybridized film infiltration evaporation obtained is functional, selection separation property with higher.
Description
Technical field
The present invention relates to the preparation methods for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, belong to film point
From technical field.
Background technique
With the aggravation of global energy crisis and environmental crisis, bio-ethanol fuel is as a kind of potential fuel instead stone
The non-renewable energy resources such as oil have highlighted potential advantage, cause the extensive concern of countries in the world.Industrial production biology
Ethyl alcohol mostly uses fermentation method, during the fermentation, with the increase of concentration of alcohol in fermentation liquid, will lead in microbial fermentation bacterium
Poison failure, strong inhibition generate the fermentation reaction of ethyl alcohol.The separation of ethanol in fermentation liquid is gone out using infiltration evaporation isolation technics
Come, it is possible to prevente effectively from inhibiting effect of the ethyl alcohol to reaction, improves the production capacity of fermentor, while obtaining high concentration ethanol,
Therefore preparation has the preferential alcohol infiltrating and vaporizing membrane of excellent release energy at key to solve this problem.
Currently, infiltration evaporation membrane material includes machine polymer, inorganic material and organic/inorganic hybridization material, organic/nothing
Machine hybridized film combines the advantages of organic film and inoranic membrane, can overcome organic polymer films mechanical strength and poor chemical stability
The disadvantages of, to widely be paid close attention to.For it is preferential thoroughly alcohol hybridized film use inorganic particulate mainly include zeolite, MOF,
Carbon molecular sieve, silica etc..Wherein, mesoporous sphere silica has a uniform nondirectional pore size distribution, biggish surface area,
The advantages that surface is easily modified, high thermal stability and mechanical stability can be used for the preparation of hybridized film.
The present invention provides a kind of preparation methods for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, should
Method
Summary of the invention
The object of the present invention is to provide a kind of preparations for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly
Method, further increases the separating property of ethanol/water, prepares mesoporous sphere by template of cetyl trimethylammonium bromide
SiO2Nanoparticle, using ultrasonic blending method by mesoporous sphere SiO2Nanoparticle is evenly spread in PDMS solution, passes through ultrasound
Infusion process composite S iO on polysulfones basement membrane2/ PDMS separating layer, the heat cross-linking in vacuum drying oven, form dense uniform has
Machine/inorganic hybrid membrane.The organic/inorganic hybrid membrane of this method preparation has excellent preferential Methanol permeability.
A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, which is characterized in that packet
Include following steps:
(1) ethyl alcohol, CTBA (cetyl trimethylammonium bromide), DEA (diethanol amine), water are added to reaction vessel
In, heating stirring makes it be uniformly mixed (stirring 30min such as at 60 DEG C is uniformly mixed it)；It is then slowly added into TEOS (just
Silester) stirring 2h, silica product is washed three times respectively with ethanol water, is dried in drying box stand-by；
(2) product that step (1) is dried is calcined into Muffle furnace 6h, removes template agent removing；
(3) the meso-porous titanium dioxide silicon particle for going template agent removing to obtain in (2) is added in normal heptane, stirs 2h, then
Silane coupling agent is added to continue to stir 5h, mass percentage of the silane coupling agent in normal heptane is 1-60%, and washing is stand-by,
Obtain modified mesoporous sphere SiO2Nanoparticle；
(4) polysulfones basement membrane is placed in ethanol/water and (is such as placed in 2h in 30wt% ethanol/water), remove membrane surface has
Then it is stand-by to impregnate suction filtration 4h in deionized water for machine object；
(5) normal heptane, polymer, crosslinking agent, catalyst are configured to solution by a certain percentage, then change step (3)
Mesoporous sphere SiO after property2Nanoparticle evenly spreads in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is made
SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on heat cross-linking in vacuum drying oven；
(8) step (6), (7) are repeated several times.
Mass ratio=1:0.1~1:10 of TEOS:CTBA in step (1).
Ethyl alcohol in further preferred step (1), the CTBA aqueous solution of mass percentage 25%, DEA (diethanol amine),
Water, TEOS (ethyl orthosilicate) dosage relation be 4.5g:5.2-10.4g:0.1g:32ml:3-5ml (preferably 3.65ml).
Step (2) calcination temperature is 400 DEG C~900 DEG C；
Step (3) silane coupling agent is selected from 1,13,3- tetramethyl-disilazane, perfluoro capryl triethoxysilane, ethylene
Base trimethoxy silane, (the third amino of 3-) trimethoxy silane.
Normal heptane in step (5), polymer, crosslinking agent, catalyst proportionate relationship be 100:10:1:0.05, crosslinking agent
For the crosslinking agent of this field routine, such as ethyl orthosilicate；Catalyst is the catalyst of this field routine, such as di lauric dibutyl
Tin.
Dip time described in step (6) is 0.1~30min in the methods of the invention, and dipping time is 1~30 time.
Step (6) mesoporous sphere SiO during preparation method of the invention2Nanoparticle be polymer 0.1wt%~
60wt%.
Mesoporous sphere SiO is prepared in the method for the present invention2Hybridized film is for alcohol/water separation.
SiO of the present invention2/ PDMS hybridized film is used for separating alcohol/aqueous systems, and the separation temperature of mixed system is 30~90
℃。
The principle of the present invention is: using ethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, and preparation is situated between
Hole spherical shape (SiO2) nanoparticle, then by SiO2Particle carries out hydrophobically modified.By modified SiO2Nanoparticle is evenly dispersed
Casting solution is formed into dimethyl silicone polymer/normal heptane/ethyl orthosilicate/dibutyl tin dilaurate solution, using dipping
Method makes SiO2/ PDMS is compounded in membrane surface, and fine and close evaporation alcohol permselective membrane is formed by heat cross-linking.
The present invention is prepared for mesoporous sphere silica (SiO by template of cetyl trimethylammonium bromide2) nanometer
Particle, using hydrophobic silane coupling agent to SiO2Nanoparticle carries out hydrophobic modification, and modifying agent is selected from 1,1,3,3- tetra-
Methyl disilazane, perfluoro capryl triethoxysilane, (the third amino of 3-) trimethoxy silane, vinyltrimethoxysilane,
By modified SiO2Nanoparticle evenly spread to normal heptane, polymer, crosslinking agent, in catalyst mixed solution, using super
Sound infusion process prepares the mesoporous SiO of favorable dispersibility2/ PDMS hybridized film.The hybridized film effectively raises the separation of ethanol/water
Performance has biggish application potential.
The present invention is for the first time by hydrophobic mesoporous sphere SiO2It is dispersed in polymer and is applied to preferential alcohol infiltration evaporation thoroughly
In the preparation of film, a kind of environmentally protective, simple and effective nano hybridization membrane preparation method is provided, composite membrane is effectively increased
Separating effect.
Detailed description of the invention
Fig. 1 is the mesoporous sphere SiO of embodiment 12Particle transmission electron microscope picture；
Specific embodiment
It elaborates in the following with reference to the drawings and specific embodiments to the present invention, but the present invention is not limited to following implementations
Example.
Embodiment 1
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it.It is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, it is dry
It is dried in case.
(2) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(3) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous sphere SiO for then preparing step (1)2Nanoparticle (SiO2Nanoparticle is polymer
10wt%) uniform particle is distributed in this solution and forms casting solution；
(4) at room temperature, the polysulfones plate membrane that step (2) has pre-processed is impregnated into the casting solution in step (3), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface.
(5) SiO for preparing step (4)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 823gm-2·h-1, separation factor 8.90.
Embodiment 2
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it.It is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, it is dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 550 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 2h is added 10% silane coupling agent, 1,1,3,3- tetramethyl-disilazane and continues to stir 4h, is washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
5wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1736gm-2·h-1, separation factor 9.3.
Embodiment 3
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 10.4g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it.It is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, it is dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 550 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 2h is added 10% silane coupling agent, 1,1,3,3- tetramethyl-disilazane and continues to stir 4h, is washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
5wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1621gm-2·h-1, separation factor 9.4.
Embodiment 4
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it.It is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, it is dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 500 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 2h is added 10% silane coupling agent, 1,1,3,3- tetramethyl-disilazane and continues to stir 4h, is washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
5wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1436gm-2·h-1, separation factor 9.1.
Embodiment 5
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it, is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 550 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 2h is added 10% silane coupling agent, 1,1,3,3- tetramethyl-disilazane and continues to stir 4h, is washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
10wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (5)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1897gm-2·h-1, separation factor 10.5.
Embodiment 6
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it, is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 550 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 10% silane coupling agent perfluoro capryl triethoxysilane 4h is added in 2h, be washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
10wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1554gm-2·h-1, separation factor 9.1.
Embodiment 7
Use basement membrane for polysulfone material, flat plate ultrafiltration membrane, membrane area 28cm2, high molecular polymer is poly dimethyl silicon
Oxygen alkane, solvent are normal heptane.
Preparation condition and method:
(1) by 4.5g ethyl alcohol, 5.2g 25%CTBA, 0.1g DEA, 32ml water is added in 50ml beaker, stirs at 60 DEG C
Mixing 30min is uniformly mixed it, is then slowly added into 3.65ml TEOS (in 2min), is washed respectively with ethanol water three times, dry
It is dried in case；
(2) the mesoporous sphere SiO that will be prepared2Nanoparticle is put into 550 DEG C of Muffle furnaces and calcines 6h, removes template agent removing；
(3) the mesoporous sphere silica of template agent removing will be gone to be added in 300ml normal heptane in (2), is stirred at 60 DEG C
Then 10% silane coupling agent vinyl trimethoxy silane 4h is added in 2h, be washed out stand-by；
(4) polysulfones basement membrane is placed in 2h in 30wt% ethanol/water, removes the organic matter of membrane surface, is then immersed in
It is stand-by that 4h is filtered in ionized water；
(5) by normal heptane, dimethyl silicone polymer, ethyl orthosilicate, dibutyl tin dilaurate 100:10:1 in proportion:
0.05 is configured to solution, the mesoporous SiO of hydrophobic spherical for then preparing step (3)2(SiO2Nanoparticle is polymer
10wt%) uniform particle is distributed in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), is soaked
Stain 1min makes SiO2/ PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on 80 DEG C of vacuum drying oven crosslinking 12h；
By the SiO of above-mentioned preparation2/ PDMS hybridized film carries out infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test
Condition are as follows: material liquid is the ethanol/water system that ethanol content is 5wt%, and feed liquid temperature is 60 DEG C, and film downstream lateral pressure is
240Pa。
The infiltration evaporation film properties measured are as follows: permeation flux 1975gm-2·h-1, separation factor 10.1.
Claims (10)
1. a kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly, which is characterized in that including
Following steps:
(1) ethyl alcohol, CTBA (cetyl trimethylammonium bromide), DEA (diethanol amine), water are added in reaction vessel, are added
Thermal agitation is uniformly mixed it；It is then slowly added into TEOS (ethyl orthosilicate) stirring 2h, by silica product ethanol water
It washs three times, is dried in drying box stand-by respectively；
(2) product that step (1) is dried is calcined into Muffle furnace 6h, removes template agent removing；
(3) the meso-porous titanium dioxide silicon particle for going template agent removing to obtain in (2) is added in normal heptane, stirs 2h, is then added
Hydrophobic silane coupling agent continues to stir 5h, carries out hydrophobically modified, mass percentage of the silane coupling agent in normal heptane
For 1-60%, washing is stand-by, obtains modified mesoporous sphere SiO2Nanoparticle；
(4) polysulfones basement membrane is placed in ethanol/water, removes the organic matter of membrane surface, then impregnates and filter in deionized water
4h is stand-by；
(5) normal heptane, polymer, crosslinking agent, catalyst are configured to solution by a certain percentage, it is then that step (3) is modified
Mesoporous sphere SiO2Nanoparticle evenly spreads in this solution and forms casting solution；
(6) at room temperature, the polysulfones plate membrane that step (4) has pre-processed is impregnated into the casting solution in step (5), makes SiO2/
PDMS is combined to polysulfones membrane surface；
(7) SiO for preparing step (6)2/ PDMS hybridized film is placed on heat cross-linking in vacuum drying oven.
2. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that repeat step (6), (7) several times.
3. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that mass ratio=1:0.1~1:10 of TEOS:CTBA in step (1).
4. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that ethyl alcohol in step (1), the CTBA aqueous solution of mass percentage 25%, DEA, water, TEOS dosage close
System is 4.5g:5.2-10.4g:0.1g:32ml:3-5ml.
5. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that ethyl alcohol in step (1), the CTBA aqueous solution of mass percentage 25%, DEA, water, TEOS dosage close
System is 4.5g:5.2-10.4g:0.1g:32ml:3.65ml.
6. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that step (2) calcination temperature is 400 DEG C~900 DEG C.
7. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that step (3) silane coupling agent is selected from 1,13,3- tetramethyl-disilazanes, perfluoro capryl triethoxysilicane
Alkane, vinyltrimethoxysilane, (the third amino of 3-) trimethoxy silane.
8. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that step (6) mesoporous sphere SiO2Nanoparticle is 0.1wt%~80wt% of polymer.
9. a kind of preparation side for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly described in accordance with the claim 1
Method, which is characterized in that the heating stirring in step (1) is uniformly mixed it to stir 30min at 60 DEG C and being uniformly mixed it；
Polysulfones basement membrane being placed in ethanol/water to be placed in 2h in 30wt% ethanol/water in step (4).
10. the mesoporous silicon oxide for preferential alcohol infiltration evaporation thoroughly being prepared according to any one of claim 1-9 method
The application of hybridized film, for alcohol/water separation.
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| CN109289531A (en) * | 2018-09-30 | 2019-02-01 | 北京工业大学 | A kind of preparation method of the dimethyl silicone polymer for organic solvent nanofiltration/meso-porous nano silicon composite membrane |
| CN111036089A (en) * | 2018-10-15 | 2020-04-21 | 武汉智宏思博环保科技有限公司 | Preparation method of modified PDMS/ZIF pervaporation hybrid membrane |
| CN110180414B (en) * | 2019-06-06 | 2021-12-31 | 上海电气集团股份有限公司 | Pervaporation membrane material and preparation method thereof |
| 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 |
| CN111871227B (en) * | 2020-07-20 | 2022-07-12 | 浙江师范大学 | Fluorosilicone composite membrane for emulsion separation and preparation method thereof |
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| CN113509845B (en) * | 2021-04-27 | 2022-06-24 | 北京工业大学 | Graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation, preparation and application |
| CN113509846B (en) * | 2021-04-27 | 2023-03-10 | 北京工业大学 | Method for preparing polydimethylsiloxane composite membrane through water surface spreading method and application |
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