CN106582314B - A kind of small-bore hydrophobic composite membrane preparation method for membrane distillation - Google Patents
A kind of small-bore hydrophobic composite membrane preparation method for membrane distillation Download PDFInfo
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- CN106582314B CN106582314B CN201610943971.9A CN201610943971A CN106582314B CN 106582314 B CN106582314 B CN 106582314B CN 201610943971 A CN201610943971 A CN 201610943971A CN 106582314 B CN106582314 B CN 106582314B
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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 present invention relates to a kind of small-bore hydrophobic composite membrane preparation method for membrane distillation, the present invention is by being solvent using polysulfones as membrane material, n,N-dimethylacetamide, and heating stirring is to forming transparent casting solution；In ethanol water, the hydrophobically modified liquid of silane-containing coupling agent and hydroxy silicon oil is configured；Using polypropylene non-woven fabric as reinforcing material, nascent state polysulfones microporous barrier is prepared using inversion of phases technique；Nascent state polysulfones microporous barrier is subjected to immersion treatment in hydrophobically modified liquid, obtains the good polysulfones microporous barrier of hydrophobicity by heat treatment.It is an advantage of the invention that using polypropylene non-woven fabric as reinforcing material, in conjunction with mutually separation-surface modification technology, while obtaining small micro-pore diameter, composite membrane of narrowly distributing, realizes the hydrophobization of film surface, be conducive to the operation steady in a long-term of membrane distillation process.Manufacturing method of the present invention is simple, and prepared small-bore hydrophobic composite membrane has wide purposes.
Description
Technical field
The present invention relates to a kind of preparation methods of small-bore hydrophobic composite membrane, belong to technical field of separation membrane preparation, this is multiple
Closing film has many advantages, such as that micro-pore diameter is small, pore-size distribution is narrow, hydrophobic performance is good, is suitable for the fields such as membrane distillation.
Background technique
Membrane distillation is a kind of using steam pressure difference as the membrane separating process of motive force, by hydrophobic microporous membrane by high-temperature feeding
Liquid is separated with low temperature osmotic liquid, and the vapour pressure of low temperature osmotic liquid is higher than using the vapour pressure that high-temperature feeding liquid is surveyed, forces steam
Molecule is migrated by the lateral penetrating fluid side of feeding liquid, to realize that feed liquid separates.Since its equipment volume is smaller, operating pressure is lower
And almost full the features such as retaining 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 distillation has the advantages that above, membrane distillation does not obtain relatively broad industrialization yet and answers so far
With this is primarily due to the dedicated film preparation of membrane distillation, membrane module structure design, membrane distillation technique process optimization, steam phase heating
Amount recycling etc. is to be improved, and wherein membrane distillation 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 distillation process and the wetting in use process are effectively prevent to ask
Topic.
The hydrophobic porous film that membrane distillation process uses at this stage mainly has polytetrafluoroethylene (PTFE), polypropylene, polyethylene, gathers partially
Vinyl fluoride etc..Wherein polytetrafluoroethylene (PTFE), polypropylene and polyethylene can only generally pass through fusion drawn due to unsuitable solvent
Method prepares perforated membrane, not only the flux of porosity lower limit membrane distillation process, while being also easy to produce many macropores of quantity
It influences to produce water quality and long-time stability；Kynoar can cause phase inversion to prepare the porous of unsymmetric structure using non-solvent
Film, but its material hydrophobicity is poor and the perforated membrane phase often adding hydrophilic pore-foaming agent during the preparation process, therefore be prepared
To more hydrophilic, fenestra wetting phenomena easily occurs in actual use, it is difficult to meet the requirement run steadily in the long term.
As widely used engineering plastics, polysulfones has good chemical stability, mechanical strength and is soluble in
The advantages that common organic solvent is one of the common used material of phase inversion preparation ultra filtration perforated membrane；Polysulfones has suitable again simultaneously
In thermal conductance and hydrophobicity, be a kind of potential membrane distillation membrane material.Patent (publication number: CN 102631844A) uses
Phase inversion prepares polysulfones microporous barrier, and micro- by reducing polysulfones solid content and addition small molecule alcohol raising polysulfones in casting solution
The Static water contact angles of pore membrane, but the means can reduce the mechanical strength of polysulfones microporous barrier, increase film surface micro-pore diameter, and
Static water contact angles are to be improved by changing film surface microstructure, and the hydrophobic performance of membrane material itself is not mentioned
It is high.Therefore, when handling high saliferous feeding liquid, inorganic salt molecule is easy due to micro-pore diameter is larger, membrane material hydrophobicity is bad
In fenestra interior suction adventitious deposit, fenestra wetting and plug-hole phenomenon occurs, to influence separating effect；Simultaneously the microporous barrier with a thickness of
Hundreds of microns, osmotic resistance with higher limit the further promotion of flux of membrane distillation.
The present invention using polysulfones as membrane material, using non-woven fabrics as reinforcing material, with the hydrophobic material containing active group be modified
Agent, the micro-pore diameter for being suitable for membrane distillation using mutually separation-surface-modification method preparation is small, pore-size distribution is narrow, hydrophobic performance is good
Composite flat membrane.
Summary of the invention
The purpose of the present invention is not being able to satisfy membrane distillation particular demands still for existing business hydrophobic microporous membrane, this is existing
Shape, provides a kind of small-bore hydrophobic composite membrane preparation method for membrane distillation, and the porous composite film of this method preparation has micro-
The features such as bore dia is small, pore-size distribution is narrow, hydrophobic performance is good, function separating layer is thin is suitable for membrane distillation 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, be by mutually separate-surface grafting realizes, including following step
It is rapid:
(1) preparation of casting solution: being solvent, heating stirring to formation by membrane material, n,N-dimethylacetamide of polysulfones
Transparent casting solution, and standing and defoaming, for use；
(2) preparation of hydrophobically modified liquid: in the ethanol water that volume ratio is 1:1, dilute acetic acid solution, which is added dropwise, makes its pH
Most 4.0, stir at 70 DEG C be added dropwise after 30min silane coupling agent, 0.01% that mass concentration is 0.1%~10%~
1.0% hydroxy silicon oil continues to stir 30min, for use；
(3) preparation of polysulfones microporous barrier: 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 in deionized water after stopping 5s under relative humidity is the air atmosphere of 60-80%,
It is taken out after solidification 30min, obtains nascent state polysulfones microporous barrier；
(4) hydrophobic modification of polysulfones microporous barrier: by the nascent state polysulfones microporous barrier of step (3) preparation in hydrophobically modified liquid
It is taken out after middle immersion 2h, and is heat-treated to and is done to get the good polysulfones microporous barrier of hydrophobicity is arrived in 70 DEG C of vacuum drying oven.
The preparation method of above-mentioned small-bore hydrophobic composite membrane, in which: 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, in which: the silane coupling agent in hydrophobically modified liquid is methyl
Triethoxysilane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, n-octytriethoxysilane, γ-
One of methacryloxypropyl trimethoxy silane is a variety of.
The utility model has the advantages that
Compared with prior art, the present invention causing phase inversion preparation to obtain by non-solvent using PP non-woven fabrics as reinforcing material
Micro-pore diameter is small, pore-size distribution is narrow, polysulfones layer is thin composite micro porous film, utilize gradually water under silane coupling agent acid condition afterwards
The characteristics of solving autohemagglutination and reacting with hydroxyl, while the hydroxy silicon oil containing active group is introduced, thus multiple in nascent state polysulfones
Close micropore film surface depositing ultrathin hydrophobic layer.Using PP non-woven fabrics as reinforcing material, composite membrane machine tool intensity not only can guarantee, but also can drop
The thickness of oligomeric sulfone functional layer reduces osmotic resistance, increases flux of membrane distillation；It is modified in conjunction with mutually separation-surface, obtaining diameter
While small, narrowly distributing surface micropore, moreover it is possible to which the hydrophobization for realizing film surface is conducive to the fortune steady in a long-term of membrane distillation process
Row.
Detailed description of the invention
4 polysulfones microporous barrier surface scan electron microscope of Fig. 1 embodiment of the present invention；
4 polysulfones microporous barrier profile scanning electron microscope of Fig. 2 embodiment of the present invention；
4 polysulfones microporous barrier surface apertures distribution map of Fig. 3 embodiment of the present invention.
Specific embodiment
Comparative example 1
The n,N-dimethylacetamide of the polysulfones of 16.0wt% and 84.0wt% are mixed, 80 DEG C is heated with stirring to and keeps
12h obtains the casting solution of homogeneous transparent, retells casting solution and is placed in 60 DEG C of baking oven and stands for 24 hours, cures it sufficiently, deaeration,
For use；In the case where relative humidity is the air atmosphere of 60-80%, polysulfones casting solution is sprawled into shape in PP nonwoven surface using scraper
At 50 μm of thin layer, is immersed in deionized water after stopping 5s, taken out after solidifying 30min, obtain nascent state polysulfones microporous barrier；Finally
Nascent state polysulfones microporous barrier is placed in 70 DEG C of vacuum drying oven to be heat-treated to and is done to get original polysulfones microporous barrier is arrived.
After tested, the surface water contact angle of the polysulfones microporous barrier is 78 °, and average pore size is 0.023 μm, vacuum membrane distillation
When, pure water flux 9.8kg/m2H (the 5wt%NaCl aqueous solution that feeding liquid is 60 DEG C, per-meate side vacuum degree are -0.095MPa).
Embodiment 1-5
The n,N-dimethylacetamide of the polysulfones of 16.0wt% and 84.0wt% are mixed, 80 DEG C is heated with stirring to and keeps
12h obtains the casting solution of homogeneous transparent, retells casting solution and is placed in 60 DEG C of baking oven and stands for 24 hours, cures it sufficiently, deaeration,
For use；In the ethanol water that volume ratio is 1:1, dilute acetic acid solution, which is added dropwise, makes its pH most 4.0, stirs 30min at 70 DEG C
Be added dropwise afterwards mass concentration be 5.0% silane coupling agent (methyltriethoxysilane, dodecyltrimethoxysilane,
Hexadecyl trimethoxy silane, n-octytriethoxysilane or γ-methacryloxypropyl trimethoxy silane),
0.05% hydroxy silicon oil continues to stir 30min, for use；In the case where relative humidity is the air atmosphere of 60-80%, scraper is utilized
Polysulfones casting solution is sprawled to form 50 μm of thin layer in PP nonwoven surface, is immersed in deionized water after stopping 5s, solidifies 30min
After take out, obtain nascent state polysulfones microporous barrier；The polysulfones microporous barrier is impregnated in the ethyl alcohol of dodecyltrimethoxysilane again
It takes out to be placed in 70 DEG C of vacuum drying oven to be heat-treated in aqueous solution, after 2 hours and do to get micro- to the good polysulfones of hydrophobicity
Pore membrane.
Surface contact angle, average pore size and the vacuum membrane distillation pure water flux of the prepared modified polysulfone microporous barrier of test
(the 5wt%NaCl aqueous solution that feeding liquid is 60 DEG C, per-meate side vacuum degree are -0.095MPa), concrete outcome is shown in Table 1.
The surface contact angle and membrane distillation properties of 1 polysulfones microporous barrier of table
From table 1 it follows that after silane coupling agent/hydroxy silicon oil processing, the Static Water of polysulfones micropore film surface
Contact angle is increased to 110 ° or more from 78 °, and it is preferable to illustrate that silane coupling agent and hydroxy silicon oil can assign polysulfones micropore film surface
Hydrophobic performance, and vacuum membrane distillation experiments have shown that, 5wt%NaCl aqueous solution that feeding liquid is 60 DEG C, per-meate side vacuum degree be-
When 0.095MPa, the flux of membrane distillation variation of polysulfones microporous barrier is little before and after the processing, in 9.5kg/m2H or more fluctuation.
Fig. 1 is the 4 polysulfones micropore film surface electron microscope of embodiment for amplifying 20000 times, as we can see from the figure microporous barrier table
Face is uniformly distributed a large amount of micropore, Fig. 2 polysulfones microporous barrier profile scanning electron microscope；And divide from the PS membrane surface apertures in Fig. 3
Cloth data more can intuitively illustrate that the polysulfones film surface is more than that 98% micro-pore diameter is less than 31nm, and about 60% micropore is straight
Diameter concentrates on 25~30nm, 0.1 μm far smaller than reported in the literature, shows the polysulfones microporous barrier for membrane distillation process indirectly
When, it can ensure that long-term stable operation.
Claims (3)
1. a kind of small-bore hydrophobic composite membrane preparation method for membrane distillation, which comprises the following steps:
(1) preparation of casting solution: being solvent by membrane material, n,N-dimethylacetamide of polysulfones, and heating stirring is transparent to being formed
Casting solution, and standing and defoaming, for use；
(2) preparation of hydrophobically modified liquid: in the ethanol water that volume ratio is 1:1, dilute acetic acid solution, which is added dropwise, makes its pH most
A certain amount of silane coupling agent, hydroxy silicon oil is added dropwise after stirring 30min at 4.0,70 DEG C, continues to stir 30min, for use；
(3) preparation of polysulfones microporous barrier: using scraper by the casting solution prepared in step (1) in polypropylene non-woven fabric surface spreading
The thin layer for forming 50 μm immerses in deionized water, solidification after stopping 5s under relative humidity is the air atmosphere of 60-80%
It is taken out after 30min, obtains nascent state polysulfones microporous barrier；
(4) hydrophobic modification of polysulfones microporous barrier: nascent state polysulfones microporous barrier prepared by step (3) is soaked in hydrophobically modified liquid
It is taken out after bubble 2h, and is heat-treated to and is done to get the good polysulfones microporous barrier of hydrophobicity is arrived in 70 DEG C of vacuum drying oven.
2. the small-bore hydrophobic composite membrane preparation method according to claim 1 for membrane distillation, it is characterised in that: hydrophobic
Silane coupling agent in modification liquid is methyltriethoxysilane, dodecyltrimethoxysilane, hexadecyl trimethoxy
One of silane, n-octytriethoxysilane or γ-methacryloxypropyl trimethoxy silane are a variety of.
3. the small-bore hydrophobic composite membrane preparation method according to claim 1 for membrane distillation, it is characterised in that: hydrophobic
The mass concentration of silane coupling agent is 0.1%~10% in modification liquid, and the mass concentration of hydroxy silicon oil is 0.01%~1.0%.
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| CN109453669B (en) * | 2018-11-27 | 2021-08-06 | 上海交通大学 | Preparation method of super-hydrophobic and double-sided hydrophilic electrostatic spinning nanofiber composite membrane |
| WO2020165956A1 (en) * | 2019-02-12 | 2020-08-20 | 日立化成株式会社 | Separation membrane for membrane distillation, and membrane distillation module |
| CN111450707B (en) * | 2020-04-09 | 2022-07-05 | 中国科学院宁波材料技术与工程研究所 | Polymer microporous membrane, method for producing the same, and water treatment apparatus |
| CN111450711B (en) * | 2020-05-22 | 2022-03-01 | 南京工业大学 | Method for preparing hydrophobic graphene membrane |
| CN112023728B (en) * | 2020-08-10 | 2022-02-22 | 天津科技大学 | PBI hydrophobic microporous membrane for high-acid-resistance and oxidation-resistance membrane distillation and preparation method thereof |
| CN114672055B (en) * | 2022-04-25 | 2023-01-03 | 安徽紫金新材料科技股份有限公司 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
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