CN106582314A - Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation - Google Patents
Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation Download PDFInfo
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- CN106582314A CN106582314A CN201610943971.9A CN201610943971A CN106582314A CN 106582314 A CN106582314 A CN 106582314A CN 201610943971 A CN201610943971 A CN 201610943971A CN 106582314 A CN106582314 A CN 106582314A
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- polysulfones
- microporous membrane
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D61/364—Membrane distillation
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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
- B01D67/0002—Organic membrane manufacture
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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
The invention relates to a preparation method of a small-pore-size hydrophobic composite membrane used for membrane distillation. The method includes the steps of: with polysulfone as a membrane material and N,N-dimethylacetamide as a solvent, heating and stirring the components to form a transparent membrane casting solution; in an ethanol water solution, preparing a hydrophobic modifying liquid containing a silane coupling agent and hydroxyl silicone oil; with a polypropylene nonwoven cloth as a reinforcing material, preparing a nascent state polysulfone microporous membrane through a phase inversion process; soaking the nascent state polysulfone microporous membrane in the hydrophobic modifying liquid, and performing thermal treatment to produce the polysulfone microporous membrane having excellent hydrophobicity. With the polypropylene nonwoven cloth as the reinforcing material, through the phase separation-surface modification process, the pore diameter of the composite membrane is small and has narrow distribution. Hydrophobization of membrane surface is achieved and a membrane distillation process can be operated stably for a long time. The preparation method is simple. The small-pore-size hydrophobic composite membrane has wide applications.
Description
Technical field
The present invention relates to a kind of preparation method of small-bore hydrophobic composite membrane, belongs to technical field of separation membrane preparation, this is answered
Close film and have the advantages that micro-pore diameter is little, pore-size distribution is narrow, hydrophobic performance good, it is adaptable to the field such as Membrane Materials.
Background technology
Membrane Materials are a kind of membrane separating process with steam pressure difference as motive force, by hydrophobic microporous membrane by high-temperature feeding
Liquid is separated with low temperature osmotic liquid, and the vapour pressure surveyed using high-temperature feeding liquid is higher than the vapour pressure of low temperature osmotic liquid, forces steam
Molecule is migrated by the lateral penetrating fluid side of feeding liquid, so as to realize that feed liquid is separated.Because its equipment volume is less, operating pressure is relatively low
And the features such as almost retention entirely of fixedness component, gradually it is applied to separation concentration, the high-concentration waste of heat-sensitive substance
The fields such as the condensing crystallizing of water.
Although Membrane Materials have above advantage, so far Membrane Materials do not obtain yet relatively broad industrialization should
With this is primarily due to the special film preparation of Membrane Materials, membrane module structure design, membrane distillation technique process optimization, steam phase heating
The aspects such as amount recovery have much room for improvement, and wherein Membrane Materials dedicated film needs to meet multinomial requirement, wherein the most key is high
Hydrophobicity, high porosity and narrow pore-size distribution, improve the flux of Membrane Materials process and effectively prevent the moistening during use from asking
Topic.
The hydrophobic porous film that at this stage Membrane Materials process is used mainly has politef, polypropylene, polyethylene, poly- inclined
Fluorothene etc..Wherein politef, polypropylene and polyethylene are due to without suitable solvent, can only typically pass through fusion drawn
Method prepares perforated membrane, not only the flux of porosity lower limit Membrane Materials process, while also easily producing many macropores of quantity
Affect to produce water quality and long-time stability；Kynoar can adopt non-solvent to cause phase inversion to prepare the porous of unsymmetric structure
Film, but the hydrophobicity of its material is poor and often add hydrophilic porogen, therefore the perforated membrane phase for preparing in preparation process
To more hydrophilic, easily there is fenestra wetting phenomena in actual use, it is difficult to meet the requirement of operation steady in a long-term.
Used as widely used engineering plastics, polysulfones has good chemical stability, mechanical strength and is soluble in
The advantages of conventional organic solvent, be one of common used material that phase inversion prepares ultra filtration perforated membrane；Simultaneously polysulfones has suitable again
In thermal conductance and hydrophobicity, be a kind of potential Membrane Materials membrane material.Patent (publication number：CN 102631844A) adopt
Phase inversion prepares polysulfones microporous membrane, and it is micro- to improve polysulfones by polysulfones solid content in reduction casting solution and addition small molecule alcohol
The Static water contact angles of pore membrane, but the means can reduce the mechanical strength of polysulfones microporous membrane, increase film surface micropore diameter, and
Static water contact angles are improved by changing film surface microstructure, and the hydrophobic performance of membrane material itself is not carried
It is high.Therefore, when high saliferous feeding liquid is processed, inorganic salt molecule is easily because micro-pore diameter is larger, membrane material hydrophobicity is not good
In fenestra interior suction adventitious deposit, there is fenestra moistening and plug-hole phenomenon, so as to affect separating effect；Simultaneously the thickness of the microporous membrane is
Hundreds of microns, with higher osmotic resistance, limit the further lifting of flux of membrane distillation.
The present invention is with polysulfones as membrane material, with non-woven fabrics as reinforcing material, to be modified containing the hydrophobic material of active group
Agent, the micro-pore diameter for being applied to Membrane Materials using the preparation of phase separation-surface-modification method is little, pore-size distribution is narrow, hydrophobic performance good
Composite flat membrane.
The content of the invention
The purpose of the present invention is can not still to meet Membrane Materials particular demands for existing business hydrophobic microporous membrane this shows
A kind of shape, there is provided small-bore hydrophobic composite membrane preparation method for Membrane Materials, porous composite film prepared by the method has micro-
The features such as bore dia is little, pore-size distribution is narrow, hydrophobic performance is good, function stratum disjunctum is thin, it is adaptable to Membrane Materials process, it is ensured that excellent
Separating effect and long-term stable operation.
Hydrophobic composite membrane preparation method in small-bore of the present invention, is realized by phase separation-surface grafting, including following step
Suddenly：
(1) preparation of casting solution：With polysulfones as membrane material, N,N-dimethylacetamide as solvent, heated and stirred to formed
Transparent casting solution, and standing and defoaming, it is stand-by；
(2) preparation of hydrophobically modified liquid：It is 1 in volume ratio:In 1 ethanol water, Deca dilute acetic acid solution makes its pH
Most 4.0, stir at 70 DEG C be added dropwise over after 30min silane coupler, 0.01% that mass concentration is 0.1%～10%～
1.0% hydroxy silicon oil, continues to stir 30min, stand-by；
(3) preparation of polysulfones microporous membrane：Using scraper by the casting solution prepared in step (1) in polypropylene (PP) non-woven fabrics
Surface spreading forms 50 μm of thin layer, immerses after stopping 5s in the case where relative humidity is for the air atmosphere of 60-80% in deionized water,
Take out after solidification 30min, obtain nascent state polysulfones microporous membrane；
(4) hydrophobic modification of polysulfones microporous membrane：Nascent state polysulfones microporous membrane prepared by step (3) is in hydrophobically modified liquid
Take out after middle immersion 2h, and be heat-treated in 70 DEG C of vacuum drying oven dry, that is, obtain the good polysulfones microporous membrane of hydrophobicity.
The preparation method of above-mentioned small-bore hydrophobic composite membrane, wherein：In casting solution, the molecular weight of polysulfones is about 80kDa,
Mass concentration is 16.0%.
The preparation method of above-mentioned small-bore hydrophobic composite membrane, wherein：Silane coupler in hydrophobically modified liquid is methyl
Triethoxysilane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, n-octytriethoxysilane, γ-
One or more in methacryloxypropyl trimethoxy silane.
Beneficial effect：
The present invention compared with prior art, with PP non-woven fabrics as reinforcing material, causes phase inversion to prepare and obtains by non-solvent
Micro-pore diameter is little, pore-size distribution is narrow, the composite micro porous film that polysulfones layer is thin, afterwards using gradually water under silane coupler acid condition
Solution from coalescence and hydroxyl react the characteristics of, while introduce the hydroxy silicon oil containing active group, so as to multiple in nascent state polysulfones
Close microporous membrane surface depositing ultrathin hydrophobic layer.With PP non-woven fabrics as reinforcing material, composite membrane machine tool intensity was both can guarantee that, and can have been dropped
The thickness of oligomeric sulfone functional layer, reduces osmotic resistance, increases flux of membrane distillation；It is modified with reference to phase separation-surface, obtaining diameter
While little, narrowly distributing surface micropore, moreover it is possible to realize the hydrophobization on film surface, be conducive to the fortune steady in a long-term of Membrane Materials process
OK.
Description of the drawings
The polysulfones microporous membrane surface scan electron microscope of Fig. 1 embodiment of the present invention 4；
The polysulfones microporous membrane profile scanning electron microscope of Fig. 2 embodiment of the present invention 4；
The polysulfones microporous membrane surface apertures scattergram of Fig. 3 embodiment of the present invention 4.
Specific embodiment
Comparative example 1
The N,N-dimethylacetamide of the polysulfones of 16.0wt% and 84.0wt% is mixed, 80 DEG C is heated with stirring to and is kept
12h, obtains the casting solution of homogeneous transparent, retells casting solution and is placed in 60 DEG C of baking oven and stands 24h so as to fully ripening, deaeration,
It is stand-by；In the case where relative humidity is for the air atmosphere of 60-80%, polysulfones casting solution is sprawled into shape in PP nonwoven surfaces using scraper
Into 50 μm of thin layer, stop after 5s and immerse in deionized water, take out after solidification 30min, obtain nascent state polysulfones microporous membrane；Finally
Nascent state polysulfones microporous membrane is placed in 70 DEG C of vacuum drying oven and is heat-treated to dry, that is, obtain original polysulfones microporous membrane.
Jing is tested, and the surface water contact angle of the polysulfones microporous membrane is 78 °, and average pore size is 0.023 μm, vacuum membrane distillation
When, pure water flux 9.8kg/m2H (feeding liquid is 60 DEG C of 5wt%NaCl aqueous solutions, and per-meate side vacuum is -0.095MPa).
Embodiment 1-5
The N,N-dimethylacetamide of the polysulfones of 16.0wt% and 84.0wt% is mixed, 80 DEG C is heated with stirring to and is kept
12h, obtains the casting solution of homogeneous transparent, retells casting solution and is placed in 60 DEG C of baking oven and stands 24h so as to fully ripening, deaeration,
It is stand-by；It is 1 in volume ratio:In 1 ethanol water, Deca dilute acetic acid solution makes its pH most 4.0, and at 70 DEG C 30min is stirred
Be added dropwise over afterwards silane coupler that mass concentration is 5.0% (MTES, dodecyltrimethoxysilane,
Hexadecyl trimethoxy silane, n-octytriethoxysilane or γ-methacryloxypropyl trimethoxy silane),
0.05% hydroxy silicon oil, continues to stir 30min, stand-by；In the case where relative humidity is for the air atmosphere of 60-80%, using scraper
Polysulfones casting solution is sprawled the thin layer to form 50 μm in PP nonwoven surfaces, is stopped after 5s and is immersed in deionized water, solidify 30min
After take out, obtain nascent state polysulfones microporous membrane；The polysulfones microporous membrane impregnated in again the ethanol of dodecyltrimethoxysilane
In aqueous solution, take out after 2 hours and be placed in being heat-treated in 70 DEG C of vacuum drying oven dry, that is, obtain the good polysulfones of hydrophobicity micro-
Pore membrane.
Test surface contact angle, average pore size and the vacuum membrane distillation pure water flux of prepared modified polysulfone microporous membrane
(feeding liquid is 60 DEG C of 5wt%NaCl aqueous solutions, and per-meate side vacuum is -0.095MPa), concrete outcome is shown in Table 1.
The surface contact angle and membrane distillation properties of the polysulfones microporous membrane of table 1
From table 1 it follows that after silane coupler/hydroxy silicon oil process, the Static Water on polysulfones microporous membrane surface
Contact angle is increased to more than 110 ° from 78 °, illustrates that silane coupler and hydroxy silicon oil can give polysulfones microporous membrane surface preferable
Hydrophobic performance, and vacuum membrane distillation test show, feeding liquid be 60 DEG C 5wt%NaCl aqueous solutions, per-meate side vacuum for-
During 0.095MPa, the flux of membrane distillation change of polysulfones microporous membrane is little after before processing, in 9.5kg/m2H fluctuates up and down.
Fig. 1 is the polysulfones microporous membrane surface electron microscope of embodiment 4 of 20000 times of amplification, as we can see from the figure microporous membrane table
Face is uniformly distributed substantial amounts of micropore, Fig. 2 polysulfones microporous membrane profile scanning electron microscopes；And the polysulfone membrane surface apertures from Fig. 3 point
Cloth data, more can intuitively illustrate the micro-pore diameter of the polysulfone membrane surface more than 98% less than 31nm, and about 60% micropore is straight
Footpath concentrates on 25～30nm, far smaller than the 0.1 of document report μm, and the polysulfones microporous membrane is shown indirectly for Membrane Materials process
When, can ensure that long-term stable operation.
Claims (3)
1. a kind of small-bore hydrophobic composite membrane preparation method for Membrane Materials, it is characterised in that comprise the following steps：
(1) preparation of casting solution：With polysulfones as membrane material, N,N-dimethylacetamide as solvent, heated and stirred is transparent to being formed
Casting solution, and standing and defoaming is stand-by；
(2) preparation of hydrophobically modified liquid：It is 1 in volume ratio:In 1 ethanol water, Deca dilute acetic acid solution makes its pH most
Stir at 4.0,70 DEG C and a certain amount of silane coupler, hydroxy silicon oil are added dropwise over after 30min, continue to stir 30min, it is stand-by；
(3) preparation of polysulfones microporous membrane：Using scraper by the casting solution prepared in step (1) in polypropylene non-woven fabric surface spreading
50 μm of thin layer is formed, is immersed after stopping 5s in the case where relative humidity is for the air atmosphere of 60-80% in deionized water, solidification
Take out after 30min, obtain nascent state polysulfones microporous membrane；
(4) hydrophobic modification of polysulfones microporous membrane：Nascent state polysulfones microporous membrane prepared by step (3) is soaked in hydrophobically modified liquid
Take out after bubble 2h, and be heat-treated in 70 DEG C of vacuum drying oven dry, that is, obtain the good polysulfones microporous membrane of hydrophobicity.
2. the described small-bore hydrophobic composite membrane preparation method for Membrane Materials is required according to right 1, it is characterised in that：It is hydrophobic
Silane coupler in modification liquid is MTES, dodecyltrimethoxysilane, hexadecyl trimethoxy
One or more in silane, n-octytriethoxysilane or γ-methacryloxypropyl trimethoxy silane.
3. the described small-bore hydrophobic composite membrane preparation method for Membrane Materials is required according to right 1, it is characterised in that：It is hydrophobic
The mass concentration of silane coupler is 0.1%～10% in modification liquid, and the mass concentration of hydroxy silicon oil is 0.01%～1.0%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453669A (en) * | 2018-11-27 | 2019-03-12 | 上海交通大学 | The preparation method of the hydrophilic Electrospun nano-fibers composite membrane of super-hydrophobic and bilateral |
| CN111450707A (en) * | 2020-04-09 | 2020-07-28 | 中国科学院宁波材料技术与工程研究所 | Polymer microporous membrane, method for producing same, and water treatment apparatus |
| CN111450711A (en) * | 2020-05-22 | 2020-07-28 | 南京工业大学 | Method for preparing hydrophobic graphene membrane |
| CN112023728A (en) * | 2020-08-10 | 2020-12-04 | 天津科技大学 | PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation and preparation method thereof |
| CN113412148A (en) * | 2019-02-12 | 2021-09-17 | 昭和电工材料株式会社 | Separation membrane for membrane distillation and membrane distillation module |
| CN114672055A (en) * | 2022-04-25 | 2022-06-28 | 江南大学 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453669A (en) * | 2018-11-27 | 2019-03-12 | 上海交通大学 | The preparation method of the hydrophilic Electrospun nano-fibers composite membrane of super-hydrophobic and bilateral |
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| CN111450711A (en) * | 2020-05-22 | 2020-07-28 | 南京工业大学 | Method for preparing hydrophobic graphene membrane |
| CN111450711B (en) * | 2020-05-22 | 2022-03-01 | 南京工业大学 | Method for preparing hydrophobic graphene membrane |
| CN112023728A (en) * | 2020-08-10 | 2020-12-04 | 天津科技大学 | PBI hydrophobic microporous membrane for acid-resistant and oxidation-resistant membrane distillation and preparation method thereof |
| CN114672055A (en) * | 2022-04-25 | 2022-06-28 | 江南大学 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
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