CN109985531A - A method of reverse osmosis membrane is prepared using silester as oily phase cosolvent - Google Patents
A method of reverse osmosis membrane is prepared using silester as oily phase cosolvent Download PDFInfo
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- CN109985531A CN109985531A CN201910275072.XA CN201910275072A CN109985531A CN 109985531 A CN109985531 A CN 109985531A CN 201910275072 A CN201910275072 A CN 201910275072A CN 109985531 A CN109985531 A CN 109985531A
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- reverse osmosis
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/56—Polyamides, e.g. polyester-amides
Abstract
The present invention relates to a kind of methods for preparing reverse osmosis membrane as oily phase cosolvent using silester.Support membrane is infiltrated in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution；Film is infiltrated in the Isopar G solution containing silester and pyromellitic trimethylsilyl chloride and causes interfacial polymerization to form aromatic polyamides separating layer；Film is placed at 70~90 DEG C and is heat-treated, aromatic polyamide composite reverse osmosis membrane is made.Preparation process of the present invention is simple, at low cost, easy to implement, and obtained aromatic polyamide composite reverse osmosis membrane has both high throughput >=3Lm‑2·h‑1·bar‑1With high rejection >=99.00%.In addition, the present invention can also offer reference for other high-performance aromatic polyamides compound-split film preparations.
Description
Technical field
The present invention relates to a kind of methods for preparing reverse osmosis membrane as oily phase cosolvent using silester, belong to compound anti-
Permeate field of membrane preparation.
Background technique
Reverse osmosis membrane technology is widely used in fields such as seawater/brackish water desalination, ultrapure water preparation and wastewater treatments,
It is the important means for alleviating water resources crisis.Preparation has both high throughput (>=3Lm-2·h-1·bar-1) and high rejection (>=
99.00%) reverse osmosis membrane helps that reverse osmosis membrane process energy consumption and cost is greatly reduced and improves producing water water quality (D.Cohen-
Tanugi,R.K.McGovern,S.H.Dave,J.H.Lienhard,J.C.Grossman,Quantifying the
potential of ultra-permeable membranes for water desalination,Energy&
Environmental Science,2014,7:1134-1141.)。
Aromatic polyamides thin layer composite reverse osmosis membrane is the reverse osmosis membrane of current main-stream.Aromatic polyamides thin layer composite reverse osmosis
The preparation process of permeable membrane is generally interfacial polymerization.It is generally believed that separating layer determines the separating property of film, and contribute the overwhelming majority
Resistance to mass tranfer.It therefore, is always research hotspot to the optimization of separating layer structure.Cosolvent is introduced in water phase or organic phase
It is currently used optimization separating layer structure method.This method is simple and effective, and at low cost.Water phase cosolvent may destroy
Membrane surface pore structure is supported, and then influences the performance of composite membrane, and oily phase cosolvent then will not influence support membrane surface pore structure,
This is because separating layer formation speed is very fast, hinders cosolvent and contact (Freger V., Nanoscale with support membrane
heterogeneity of polyamide membranes formed by interfacial polymerization,
Langmuir,19(2003)4791–4797.).Current best oily phase cosolvent be ethyl acetate (T.Kamada, T.Ohara,
T.Shintani,T.Tsuru,Controlled surface morphology of polyamide membranes via
the addition of co-solvent for improved permeate flux,Journal of Membrane
Science,467(2014)303-312.).However, ethyl acetate is volatile, and penetrating odor is strong, dangerous.This
Outside, the flux using reverse osmosis membrane prepared by ethyl acetate is not high enough (lower than 3Lm-2·h-1·bar-1)。
Summary of the invention
High throughput (>=3Lm is had both to be made-2·h-1·bar-1) and high rejection (>=99.00%) reverse osmosis membrane,
We conducted researchs and test, it was found that a kind of new oil phase cosolvent, i.e. silester.Silester is colourless liquid,
Smell is unobvious, and not volatile (165~169 DEG C of boiling point), highly-safe, structural formula is as follows:
High throughput (>=3Lm is had both using silester as oily phase cosolvent the purpose of the present invention is to provide a kind of-2·h-1·bar-1) and high rejection (>=99.00%) aromatic polyamides reverse osmosis membrane method.This method is simple, easy to operate.
This method can make made reverse osmosis membrane have both high throughput (>=3Lm-2·h-1·bar-1) and high rejection (>=99.00%).This
Invention is realized by the following technical scheme.
A kind of method preparing reverse osmosis membrane as oily phase cosolvent using silester of the invention, including following mistake
Journey:
1) support membrane is infiltrated in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution；
2) by film be infiltrated in the Isopar G solution containing silester and pyromellitic trimethylsilyl chloride cause interfacial polymerization with
Form aromatic polyamides separating layer；
3) film is placed at 70~90 DEG C and is heat-treated, aromatic polyamide composite reverse osmosis membrane is made.
The rapid support membrane 1) is infiltrated on 20~40s in aqueous phase solution.
It is 0.04 that Isopar G solution of the step 2) containing pyromellitic trimethylsilyl chloride and silester, which preferably contains concentration,
~0.20% pyromellitic trimethylsilyl chloride, 2~14% silester and 97.96~85.80% Isopar G solution.
Rapid 3) 4~the 6min of heat treatment.
The aromatic polyamide composite reverse osmosis membrane is sufficiently cleaned in rigid be made with deionized water.
Prepared reverse osmosis membrane has both high throughput >=3L m-2·h-1·bar-1；High salt rejection rate >=99.00%.
Silester has the characteristics that boiling point is high, not volatile gentle taste is unobvious, is a kind of more best than in report at present
The safer oily phase cosolvent of oily phase cosolvent ethyl acetate.In general, cosolvent can enhance the phase of water phase and oily phase
Capacitive is accelerated aqueous phase monomers and is mutually spread toward oil, separating layer crosslinking on the one hand can be made more abundant, to guarantee that film has high cut
Rate is stayed, reaction on the other hand can be made more violent, to increase separating layer surface roughness, that is, increases effective permeable face of film
Product, and then increase the flux of film.However, it is mutually deeper that aqueous phase monomers can be diffused into oil if aqueous phase monomers diffusion is too fast
Region is unfavorable for membrane flux raising to keep separating layer thicker.Relative to ethyl acetate, the water solubility of silester is lower,
It not will lead to separating layer thickness while increasing separating layer surface roughness to increase excessively.To sum up, relative to ethyl acetate, silicic acid
Ethyl ester has more advantage in terms of preparation has both high-throughput and high rejection reverse osmosis membrane.
The advantages that present invention has process simple, at low cost, easy to implement.In addition, prepared reverse osmosis membrane has both height
Flux (>=3Lm-2·h-1·bar-1) and high salt rejection rate (>=99.00%): it is 2000ppm aqueous sodium chloride in material liquid
Under the test condition that liquid, pressure are 15.5bar and temperature is 25 DEG C, water flux and salt rejection rate can reach 4.19Lm respectively-2·
h-1·bar-1With 99.36%.The present invention is not limited only to the preparation to aromatic polyamide composite reverse osmosis membrane, and is also applied for
Prepare other high-performance interfacial polymerization seperation films.
Detailed description of the invention
Fig. 1: for aromatic polyamide composite reverse osmosis membrane separating layer atomic force microscope made from embodiment 2；Made reverse osmosis
Permeable membrane surface is coarse, and roughness is up to 104.9nm.
Fig. 2: for aromatic polyamide composite reverse osmosis membrane separating layer atomic force transmission electron microscope picture made from embodiment 2；It is made
It is very thin that reverse osmosis membrane efficiently separates thickness degree, only 14nm.
Specific embodiment
Embodiment 1
Support film surface is infiltrated on 20s in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution.It then, will be molten
Liquid is outwelled.Then, after ensuring that film surface does not have visible liquid, film surface is infiltrated on containing 0.04% equal chlorobenzoyl chloride, 2%
Cause interfacial polymerization in silester and 97.96%Isopar G solution.It is heat-treated 4min finally, film is placed at 70 DEG C, is made
Aromatic polyamide composite reverse osmosis membrane is obtained, and is sufficiently cleaned with deionized water.
Filtered at 15.5bar, 25 DEG C 2000ppm sodium-chloride water solution test to obtain the complex reverse osmosis membrane flux and
Rejection is respectively 2.45Lm-2·h-1·bar-1With 99.25%.
Embodiment 2
Support film surface is infiltrated on 30s in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution.It then, will be molten
Liquid is outwelled.Then, after ensuring that film surface does not have visible liquid, film surface is infiltrated on containing 0.12% equal chlorobenzoyl chloride, 8%
Cause interfacial polymerization in silester and 91.88%Isopar G solution.It is heat-treated 5min finally, film is placed at 80 DEG C, is made
Aromatic polyamide composite reverse osmosis membrane is obtained, and is sufficiently cleaned with deionized water.Aromatic polyamides manufactured in the present embodiment are compound
Reverse osmosis membrane atomic force microscopy diagram shows that made reverse osmosis membrane rough surface, roughness is up to 104.9nm (attached drawing 1)；It is made
Aromatic polyamide composite reverse osmosis membrane transmission electron microscope picture show that it is very thin that made reverse osmosis membrane efficiently separates thickness degree, only
14nm (attached drawing 2).
Filtered at 15.5bar, 25 DEG C 2000ppm sodium-chloride water solution test to obtain the complex reverse osmosis membrane flux and
Rejection is respectively 4.19Lm-2·h-1·bar-1With 99.36%.
Embodiment 3
Support film surface is infiltrated on 40s in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution.It then, will be molten
Liquid is outwelled.Then, after ensuring that film surface does not have visible liquid, by film surface be infiltrated on containing 0.20% equal chlorobenzoyl chloride,
Cause interfacial polymerization in 14% silester and 85.80%Isopar G solution.It is heat-treated finally, film is placed at 90 DEG C
6min is made aromatic polyamide composite reverse osmosis membrane, and is sufficiently cleaned with deionized water.
Filtered at 15.5bar, 25 DEG C 2000ppm sodium-chloride water solution test to obtain the complex reverse osmosis membrane flux and
Rejection is respectively 2.84Lm-2·h-1·bar-1With 97.94%.
Comparative example 1
Existing best oily phase cosolvent (ethyl acetate) and silester are compared, as a result it is as shown in the table.1 in table
Respectively represented with 2 use ethyl acetate as the reverse osmosis membrane of oily phase cosolvent preparation with use silester as it is oily be mutually total to it is molten
The reverse osmosis membrane of agent preparation.As seen from table, use ethyl acetate not high enough as the reverse osmosis membrane flux of oily phase cosolvent preparation
(it is less than 3Lm-2·h-1·bar-1), flux and rejection are below and use silester as oily phase cosolvent preparation
The flux and rejection of reverse osmosis membrane.In addition, silester is used to have both high pass as the reverse osmosis membrane of oily phase cosolvent preparation
Measure (> 3Lm-2·h-1·bar-1) and high salt rejection rate (> 99.00%).To sum up, high-throughput and high retention is had both in preparation
In terms of rate reverse osmosis membrane, silester has more advantage than ethyl acetate.
| Film | Flux (Lm-2·h-1·bar-1) | Sodium chloride rejection (%) |
| 1 | 2.78 | 99.00 |
| 2 | 4.19 | 99.36 |
A kind of method for preparing reverse osmosis membrane as oily phase cosolvent using silester that the present invention is disclosed and proposed, this
Field technical staff can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although method of the invention and
Technology of preparing is described by preferred embodiment, and related technical personnel can obviously not depart from the content of present invention, essence
Methods and techniques described herein route is modified or is reconfigured in mind and range, to realize final technology of preparing.
In particular, it should be pointed out that all similar replacements and change are apparent to those skilled in the art, they
It is considered as being included in spirit of that invention, range and content.
Claims (5)
1. a kind of method for preparing reverse osmosis membrane as oily phase cosolvent using silester, it is characterized in that including the following steps:
1) support membrane is infiltrated in aqueous phase solution so that support membrane is sufficiently infiltrated by aqueous phase solution；
2) film is infiltrated in the Isopar G solution containing silester and pyromellitic trimethylsilyl chloride and causes interfacial polymerization to be formed
Aromatic polyamides separating layer；
3) film is placed at 70~90 DEG C and is heat-treated, aromatic polyamide composite reverse osmosis membrane is made.
2. the method as described in claim 1, it is characterized in that the rapid support membrane 1) is infiltrated on 20~40s in aqueous phase solution.
3. the method as described in claim 1, it is characterized in that the step 2) is containing pyromellitic trimethylsilyl chloride and silester
Isopar G solution is preferably pyromellitic trimethylsilyl chloride, 2~14% silester and 97.96 containing concentration for 0.04~0.20%
The solution of~85.80% Isopar G.
4. the method as described in claim 1, it is characterized in that the rapid 3) 4~6min of heat treatment.
5. the method as described in claim 1, it is characterized in that the aromatic polyamide composite reverse osmosis membrane of step 3) preparation spend from
Sub- water cleaning.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110960987A (en) * | 2019-12-11 | 2020-04-07 | 恩泰环保科技（常州）有限公司 | High-performance nano hybrid reverse osmosis membrane and preparation method thereof |
| CN111282453A (en) * | 2020-02-20 | 2020-06-16 | 汕头市奥斯博环保材料制造有限公司 | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
| CN114950165A (en) * | 2022-05-23 | 2022-08-30 | 天津工业大学 | Preparation method of high-pressure reverse osmosis membrane based on gamma-valerolactone interface auxiliary polymerization |
| CN116116244A (en) * | 2023-04-18 | 2023-05-16 | 蓝星（杭州）膜工业有限公司 | Composite membrane and preparation method and application thereof |
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Patent Citations (4)
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| US20120031833A1 (en) * | 2010-07-15 | 2012-02-09 | The Ohio State University Research Foundation | Systems, compositions, and methods for fluid purification |
| CN102430349A (en) * | 2011-12-22 | 2012-05-02 | 中国海洋大学 | Reverse osmosis composite membrane and preparation method thereof |
| CN104474910A (en) * | 2014-12-11 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of organic-inorganic composite separation membrane |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110960987A (en) * | 2019-12-11 | 2020-04-07 | 恩泰环保科技（常州）有限公司 | High-performance nano hybrid reverse osmosis membrane and preparation method thereof |
| CN110960987B (en) * | 2019-12-11 | 2022-05-03 | 恩泰环保科技（常州）有限公司 | High-performance nano hybrid reverse osmosis membrane and preparation method thereof |
| CN111282453A (en) * | 2020-02-20 | 2020-06-16 | 汕头市奥斯博环保材料制造有限公司 | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
| CN114950165A (en) * | 2022-05-23 | 2022-08-30 | 天津工业大学 | Preparation method of high-pressure reverse osmosis membrane based on gamma-valerolactone interface auxiliary polymerization |
| CN114950165B (en) * | 2022-05-23 | 2023-10-13 | 天津工业大学 | Preparation method of high-pressure reverse osmosis membrane based on gamma-valerolactone interface assisted polymerization |
| CN116116244A (en) * | 2023-04-18 | 2023-05-16 | 蓝星（杭州）膜工业有限公司 | Composite membrane and preparation method and application thereof |
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Application publication date: 20190709 |