CN1257748A - Alcohol-water system modifying process for inner interface of inverse osmosis membrane - Google Patents
Alcohol-water system modifying process for inner interface of inverse osmosis membrane Download PDFInfo
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- CN1257748A CN1257748A CN 98125653 CN98125653A CN1257748A CN 1257748 A CN1257748 A CN 1257748A CN 98125653 CN98125653 CN 98125653 CN 98125653 A CN98125653 A CN 98125653A CN 1257748 A CN1257748 A CN 1257748A
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- alcohol
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Abstract
An alcohol-water system process for modifying the reverse osmotic composite membrane features that the reverse osmotic composite membrane is prepared through three steps of preparing porous bearing layer, treating inner interface with alcohol-water system and forming super-thin function layer. The resultant membrane has high salt intercepting rate up to 94.5-99.5% increased by 17% and high water-outputting rate up to 0.5-0.85 sq.m/sq.m.d increased by over 70%. Its advantages are mild reaction condition controlled easily, simple and safe operation and low cost of reagent.
Description
The invention belongs to reverse osmosis and lure composite membrane by inner interface alcohol-water system modifying process.
1981, J.E.Cadotte is at U.S.Pat.4, the polyamide composite film of 259,183 reports is reflected at polysulfones porous support layer surface by aromatic diamines and fragrant acyl chlorides by interfacial polycondensation and forms, and has high yield water rate, high salt-stopping rate and good physical and mechanical properties simultaneously.People are generally by the physical aspect of control ultrathin functional layer and the performance of chemical constitution control reverse osmosis composite membrane: 1991, S.A.Sundet is at U.S.Pat.5,019,264 usefulness 5-isocyanic acid phenyl-diformyl and m-phenylene diamine (MPD) prepare high performance composite membrane by interfacial polycondensation; 1996, M.Hirose reported in Journal of Membrane Science (121:209) by add isopropyl alcohol in complex liquid and controls the degree of roughness of ultrathin functional layer to improve the composite membrane performance; But these methods all make the prescription and the process complications of complex liquid, and some adding ingredients cost an arm and a leg, and the source approach is few, is difficult to obtain; Arylamine and fragrant acyl chlorides price are more expensive, and the arylamine and the operation of fragrant acyl chlorides of preparation labyrinth are also very complicated.
The object of the invention provides a kind of reverse osmosis composite membrane by inner interface alcohol-water system modifying process, by the performance of the inner boundary between usefulness alcohol-aqueous systems processing porous support layer and ultrathin functional layer with the raising reverse osmosis composite membrane; The preparation of composite membrane is divided into preparation, inner boundary alcohol-aqueous systems processing, the ultrathin functional layer formation three phases of porous support layer in the inventive method.
The character appreciable impact composite membrane performance of the inner boundary in the composite membrane between ultrathin functional layer and porous support layer.Thereby alcohol-aqueous systems changes the performance of composite membrane to the swelling action of the fine and close epidermal area of porous support layer and character that the reversing effect can change composite membrane by inner interface: swelling action makes that distance increases between the strand of the fine and close epidermal area of porous support layer, polarity strengthens the interaction ability that makes film and hydrone and strengthens, and the two acting in conjunction increases the permeable amount of composite membrane; When the variation of solute migration rate was very little, this variation caused the salt-stopping rate of composite membrane to increase.
The present invention adopts following steps to form reverse osmosis composite membrane:
1). the preparation of asymmetric porous support layer
Casting solution is dissolved in N by 13.5%～18% bisphenol a polysulfone and 2%～10% tributyl phosphate, and dinethylformamide is formed, and prepares asymmetric porous membrane by the Loeb-sourirajan method on polyester non-woven fabric;
2). the fine and close epidermal area alcohol-water system modifying of porous support layer
The volume fraction of alcohol is alcohol-aqueous systems of 0.02～0.95 in the preparation liquid system, and the structure of the alcohol of employing is as follows:
CH
3(CH
2)
n(OH) n＝0～3 HO(CH
2)
mOH m＝2～3
(CH
3)
2CHOH，HOCH
2CH(OH)CH
2OH
The temperature of alcohol-aqueous systems is 10～100 ℃, makes the fine and close epidermal area of porous support layer after the abundant drip washing be dipped in alcohol-aqueous systems 5 minutes～10 days, and it is standby to take out afterwash;
3). the formation of ultrathin functional layer
Ultrathin functional layer forms on the fine and close epidermal area after the processing, and the composition of the complex liquid of ultrathin functional layer is divided into A liquid: 2%～2.5% m-phenylene diamine (MPD) aqueous solution; B liquid: the hexane solution of 0.1%～0.25% acyl chlorides, wherein, the ratio of diacid chloride and three acyl chlorides is 2: 3～3: 2; C liquid: 0.1%～0.5% polyvinyl alcohol water solution; Porous support layer was soaked A liquid 3～6 minutes, dry, soaked B liquid 0.5～1.5 minute, soaked C liquid again 0.5～1.5 minute, at last in 95 ± 5 ℃ of following post processings 5～10 minutes;
Composite membrane performance with the inventive method preparation: salt-stopping rate 94.5%～99.5%, producing water ratio 0.50m
3/ m
2.d～0.85m
3/ m
2.d; Salt-stopping rate raising rate relatively can reach 17%, and producing water ratio raising rate relatively can reach more than 70%;
The gentle easily control of reaction condition of the present invention, safety simple to operate, reagent is cheap and easy to get, and toxicity is little, and corrosivity is little, and equipment is not had specific (special) requirements; Because it is the character gentleness of alcohol obviously weakens the stable nothing of the physical mechanical of porous support layer, little to the chemical stability influence of composite membrane simultaneously; The present invention makes reverse osmosis composite membrane can obtain good separating property under simple formulation and the process conditions very much, and prepared reverse osmosis composite membrane performance has reached higher level.
Embodiment provided by the invention is as follows:
Embodiment 1: formula of casting is a bisphenol a polysulfone 15%, tributyl phosphate 5%, and porous support layer was handled 1 day with methyl alcohol-aqueous systems of 20 ℃, and the methyl alcohol volume fraction is 0.1 in the liquid system; A liquid is the 2% m-phenylene diamine (MPD) aqueous solution, and B liquid is 0.15% solution of acid chloride, isophthaloyl chloride: trimesoyl chloride=3: 2, C liquid are 0.1% polyvinyl alcohol water solution.Soaked A liquid 3 minutes, soaked B liquid 40 seconds, soaked C liquid 1 minute, handled 10 minutes for 95 ± 2 ℃.Gained composite membrane performance: salt-stopping rate=95.3%, producing water ratio=0.60m
3/ m
2.d.
Embodiment 2: all the other conditions are with 1, and the temperature that only changes methyl alcohol-water is 40 ℃, gained composite membrane performance: salt-stopping rate=96.5%, producing water ratio=0.62m
3/ m
2.d.
Embodiment 3: formula of casting is a bisphenol a polysulfone 14%, tributyl phosphate 2%, and porous support layer was handled 3 days with isopropyl alcohol-aqueous systems of 15 ℃, and the volume fraction of isopropyl alcohol is 0.2 in the liquid system; A liquid is the 2% m-phenylene diamine (MPD) aqueous solution, and B liquid is 0.2% solution of acid chloride, isophthaloyl chloride: trimesoyl chloride=3: 2, C liquid are 0.3% polyvinyl alcohol water solution.Soaked A liquid 3 minutes, soaked B liquid 1 minute, soaked C liquid 1 minute, handled 7 minutes for 97 ± 2 ℃.Gained composite membrane performance: salt-stopping rate=99.0%, producing water ratio=0.60m
3/ m
2.d.
Embodiment 4: all the other conditions are with 3, and only changing the processing time is 5 days; Gained composite membrane performance: salt-stopping rate=97.3%, producing water ratio=0.58m
3/ m
2.d.
Embodiment 5: all the other conditions are with 3, and the change liquid system is that the volume fraction of propyl alcohol accounts for 0.05, gained composite membrane performance: salt-stopping rate=97.1%, producing water ratio=0.84m
3/ m
2.d.
Embodiment 6: all the other conditions are with 3, and the change liquid system is that the volume fraction of butanols accounts for 0.8, and gained composite membrane performance is: salt-stopping rate=97.3%, producing water ratio=0.50m
3/ m
2.d.
Embodiment 7: formula of casting is a bisphenol a polysulfone 16%, tributyl phosphate 10%, porous support layer with 50 ℃ ethanol-aqueous systems handled 2 hours, the ethanol volume fraction is 0.2 in the liquid system; A liquid is the 2% m-phenylene diamine (MPD) aqueous solution, and B liquid is 0.15% solution of acid chloride, isophthaloyl chloride: trimesoyl chloride=3: 2, C liquid are 0.5% polyvinyl alcohol water solution.Soaked A liquid 3 minutes, soaked B liquid 1.5 minutes, soaked C liquid 1 minute, handled 10 minutes for 95 ± 2 ℃.Gained composite membrane performance: salt-stopping rate=95.8%, producing water ratio=0.50m
3/ m
2.d.
Embodiment 8: change into ethylene glycol-aqueous systems, its temperature is 70 ℃, and the volume fraction of ethylene glycol is 0.3 in the liquid system, and the processing time is 30 minutes, and all the other conditions are with 6, gained composite membrane performance: salt-stopping rate=96.3%, producing water ratio=0.55m
3/ m
2.d.
Embodiment 9: formula of casting is a bisphenol a polysulfone 14%, tributyl phosphate 2%, porous support layer with 100 ℃ glycerine-aqueous systems handled 10 minutes, the glycerine volume fraction is 0.2 in the liquid system; A liquid is the 2% m-phenylene diamine (MPD) aqueous solution, and B liquid is 0.25% solution of acid chloride, isophthaloyl chloride: trimesoyl chloride=3: 2, C liquid are 0.3% polyvinyl alcohol water solution.Soaked A liquid 3 minutes, soaked B liquid 1 minute, soaked C liquid 1 minute, handled 8 minutes for 96 ± 2 ℃; Gained composite membrane performance: salt-stopping rate=96.8%, producing water ratio=0.64m
3/ m
2.d.
Claims (1)
1. alcohol-the water system modifying process of a reverse osmosis composite membrane by inner interface is characterized in that adopting following steps to form reverse osmosis composite membrane:
1). the preparation of asymmetric porous support layer
Casting solution is dissolved in N by 13.5%～18% bisphenol a polysulfone and 2%～10% tributyl phosphate, and dinethylformamide is formed, and prepares asymmetric porous membrane by the Loeb-sourirajan method on polyester non-woven fabric;
2). the fine and close epidermal area alcohol-water system modifying of porous support layer
The volume fraction of alcohol is alcohol-aqueous systems of 0.02～0.95 in the preparation liquid system, and the structure of the alcohol of employing is as follows:
CH
3(CH
2)
n(OH) n＝0～3 HO(CH
2)
mOH m＝2～3
(CH
3)
2CHOH，HOCH
2CH(OH)CH
2OH
The temperature of alcohol-aqueous systems is 10～100 ℃, makes the fine and close epidermal area of porous support layer after the abundant drip washing be dipped in alcohol-aqueous systems 5 minutes～10 days, and it is standby to take out afterwash;
3). the formation of ultrathin functional layer
Ultrathin functional layer forms on the fine and close epidermal area after the processing, and the complex liquid of ultrathin functional layer is formed and is divided into A liquid: 2%～2.5% m-phenylene diamine (MPD) aqueous solution; B liquid: the hexane solution of 0.1%～0.25% acyl chlorides, wherein, the ratio of diacid chloride and three acyl chlorides is 2: 3～3: 2; C liquid: 0.1%～0.5% polyvinyl alcohol water solution; Porous support layer was soaked A liquid 3～6 minutes, dry, soaked B liquid 0.5～1.5 minute, soaked C liquid again 0.5～1.5 minute, at last in 95 ± 5 ℃ of following post processings 5～10 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125653 CN1257748A (en) | 1998-12-24 | 1998-12-24 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125653 CN1257748A (en) | 1998-12-24 | 1998-12-24 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
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| Publication Number | Publication Date |
|---|---|
| CN1257748A true CN1257748A (en) | 2000-06-28 |
Family
ID=5229258
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| CN 98125653 Pending CN1257748A (en) | 1998-12-24 | 1998-12-24 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321727C (en) * | 2004-11-12 | 2007-06-20 | 国家海洋局杭州水处理技术研究开发中心 | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method |
| CN100540126C (en) * | 2006-08-30 | 2009-09-16 | 贵阳时代汇通膜科技有限公司 | The production method of light-pollution reverse osmosis composite film |
| CN101804304A (en) * | 2010-04-09 | 2010-08-18 | 北京化工大学 | Modification method of reverse osmosis membrane surface |
| CN102921315A (en) * | 2012-11-02 | 2013-02-13 | 北京碧水源膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN104289116A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Composite reverse osmosis membrane and preparation method thereof |
| CN105080369A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | High rejection rate composite reverse osmosis membrane and preparation method thereof |
| CN106563360A (en) * | 2016-11-02 | 2017-04-19 | 浙江理工大学 | Preparation method of low-charge reverse osmosis composite film |
| CN109499395A (en) * | 2018-11-16 | 2019-03-22 | 杭州华滤膜科技有限公司 | A kind of preparation method of the reverse osmosis seawater film of high throughput |
| CN111359456A (en) * | 2020-04-13 | 2020-07-03 | 北京化工大学 | Linear-crosslinked multi-component copolymerized polyamide reverse osmosis membrane for seawater desalination and preparation method thereof |
-
1998
- 1998-12-24 CN CN 98125653 patent/CN1257748A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321727C (en) * | 2004-11-12 | 2007-06-20 | 国家海洋局杭州水处理技术研究开发中心 | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method |
| CN100540126C (en) * | 2006-08-30 | 2009-09-16 | 贵阳时代汇通膜科技有限公司 | The production method of light-pollution reverse osmosis composite film |
| CN101804304A (en) * | 2010-04-09 | 2010-08-18 | 北京化工大学 | Modification method of reverse osmosis membrane surface |
| CN102921315A (en) * | 2012-11-02 | 2013-02-13 | 北京碧水源膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN102921315B (en) * | 2012-11-02 | 2014-12-10 | 北京碧水源膜科技有限公司 | Anti-pollution reverse osmosis membrane and preparation method thereof |
| CN104289116A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Composite reverse osmosis membrane and preparation method thereof |
| CN105080369A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | High rejection rate composite reverse osmosis membrane and preparation method thereof |
| CN106563360A (en) * | 2016-11-02 | 2017-04-19 | 浙江理工大学 | Preparation method of low-charge reverse osmosis composite film |
| CN109499395A (en) * | 2018-11-16 | 2019-03-22 | 杭州华滤膜科技有限公司 | A kind of preparation method of the reverse osmosis seawater film of high throughput |
| CN111359456A (en) * | 2020-04-13 | 2020-07-03 | 北京化工大学 | Linear-crosslinked multi-component copolymerized polyamide reverse osmosis membrane for seawater desalination and preparation method thereof |
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