CN102210981A - Method for preparing polyamide reverse osmosis composite membrane - Google Patents
Method for preparing polyamide reverse osmosis composite membrane Download PDFInfo
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- CN102210981A CN102210981A CN2011101546438A CN201110154643A CN102210981A CN 102210981 A CN102210981 A CN 102210981A CN 2011101546438 A CN2011101546438 A CN 2011101546438A CN 201110154643 A CN201110154643 A CN 201110154643A CN 102210981 A CN102210981 A CN 102210981A
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- reverse osmosis
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- osmosis composite
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Abstract
The invention belongs to a method for preparing polyamide reverse osmosis composite membrane. The method comprises the following steps: fully contacting a porous supporting base membrane surface with a polyamine solution, and washing the membrane surface by utilizing water, ketone, alcohol, acid, aqueous alkali and the like; removing the polyamine at the membrane surface; performing interfacial polymerization reaction with a multivariant acyl chloride solution after the surface is semi-dried; and forming the polyamide reverse osmosis composite membrane at the surface of the base membrane.
Description
Technical field
The present invention relates to a kind of method of making polyamide reverse osmosis composite film, belong to preparation method's technical field of pellicle.
Background technology
Nanofiltration and reverse osmosis membrane are because of the separating property to the brilliance of organic molecule and inorganic ion, and safety, environmental friendliness, advantage such as easy to operate and become one of key technology of water treatment.Its application comprises the seawater and the bitter degree of saltinessization, water softening, and middle water reclaims, Industrial Wastewater Treatment, wide spectrums such as ultra-pure water preparation.Wherein composite membrane can be with the rejection of film because of it, water flux, performance optimization such as stability and become current with fastest developing speed, use maximum film kinds, surpassing 90% nanofiltration and reverse osmosis membrane in the market is composite membrane.Composite membrane is meant very thin, the different materials fine and close, that the special separation function is arranged of compound one deck on the support counterdie of porous.Compare with integrated film, the surface compact layer thickness of composite membrane is thinner, thereby makes film have the high solute separation rate and the transmission rates of water simultaneously, and optimizable physical chemistry structure, can satisfy various Selective Separation demand.The current composite membrane that is widely used in the water treatment field is mainly taked the mode of interfacial polymerization, polyamide film is compound to micropore supports the counterdie surface.Common technical process has detailed introduction at the United States Patent (USP) 4277344 of initiative.The micropore counterdie that at first polysulfones is coated on the polyester non-woven fabric and forms, be immersed in the diamines or the polyamines aqueous solution, drench by wind then, methods such as roll-in are removed the unnecessary amine aqueous solution in film surface, be immersed in again in organic non-polar solution of polynary acyl chlorides and acyl chlorides generation interface polymerization reaction, thereby form the fine and close polyamide ultrathin active layer with separation function on the surface, after the film forming, fully washing and suitable heat cure are handled and can be increased film properties.Film properties mainly comprises salt rejection rate and water flux, and based on the consideration of energy-conservation and efficient, the water flux that constantly improves film becomes one of main target of industry in recent years.Add the water flux (as US4872984, US4983291, US5207908, US6162358, US6024873, and US7598296) that additive and composite membrane-forming post processing can improve film in various degree in the monomer solution.
Summary of the invention
The present invention wants the technical solution problem to be: overcome the shortcoming of above-mentioned prior art, a kind of method of making polyamide reverse osmosis composite film is provided.
In order to solve above technical problem, a kind of method of making polyamide reverse osmosis composite film of the present invention is characterized in that:
The first step, polysulfones is supported counterdie be immersed in diamines or the polyamines solution;
The counterdie surface is washed in second step, taking-up back, removes the diamines or the polyamines on counterdie surface;
The 3rd step, half-dried back are carried out interface polymerization reaction to the organic solution that counterdie immerses polynary acyl chlorides monomer, form polyamide reverse osmosis composite film on the counterdie surface;
The 4th step, taking-up polyamide reverse osmosis composite film are also heat-treated or the UV processing.
In second step of the present invention, the cleaning fluid that is used to wash the counterdie surface is deionized water, water-soluble ketone and the aqueous solution thereof, water-soluble alcohol and the aqueous solution thereof, the water-soluble organic acid and the aqueous solution thereof, a kind of in the water-soluble inorganic acid and the aqueous solution thereof, water-soluble alkali and the aqueous solution thereof, water-soluble salt and the aqueous solution thereof.
Further, a kind of in spraying, spraying, scrub, embathe of described washing methods.
In second step, the wash time scope is: 1 second to 30 seconds.
The inventive method second is in the step, removes the diamines or the polyamines on counterdie surface by the method for washing, and its purpose is to remove the amine of counterdie outer surface, makes the amine that participates in interface polymerization reaction be only limited to amine molecule in the counterdie hole.
Thereby the water flux of the polyamide reverse osmosis composite film that obtains significantly improves, and the rejection of NaCl has also been obtained improvement to a certain degree.
The specific embodiment
Comparative Examples: the polysulfones counterdie of the about 200A of average pore size immersed contain in 2.0% the m-phenylene diamine (MPD) aqueous solution 2 minutes, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride with squeegee press mold surface to half-dried back.Put into 110 ℃ oven 10 minutes after the taking-up, use aqueous slkali then successively, acid solution, alcoholic solution and pure water thoroughly clean back test membrane performance.The composite membrane of this Comparative Examples gained is at 25 ℃, the 1500ppm NaCl aqueous solution, and under the 1.5MPa pressure test conditions, to the rejection 98.6% of NaCl, water flux is 0.82M
3/ M
2.d.
Embodiment 1, counterdie immersed 2.0% amine aqueous solution after 2 minutes, spend deionised water surface 5 seconds, place in the air 3 minutes half-dried to the film surface, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride then, other technology is identical with Comparative Examples, and test condition is identical with Comparative Examples, and the result lists table 1 in.
Embodiment 2, counterdie immersed 2.0% amine aqueous solution after 2 minutes, with washed with isopropyl alcohol surface 5 seconds, place in the air 3 minutes half-dried to the film surface, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride then, other technology is identical with Comparative Examples, and test condition is identical with Comparative Examples, and the result lists table 1 in.
Embodiment 3, counterdie immersed 2.0% amine aqueous solution after 2 minutes, with acetone washing surface 5 seconds, place in the air 3 minutes half-dried to the film surface, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride then, other technology is identical with Comparative Examples, and test condition is identical with Comparative Examples, and the result lists table 1 in.
Embodiment 4, counterdie immersed 2.0% amine aqueous solution after 2 minutes, the solution washing surface of watery hydrochloric acid 5 seconds with 1%, place in the air 3 minutes half-dried to the film surface, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride then, other technology is identical with Comparative Examples, and test condition is identical with Comparative Examples, and the result lists table 1 in.
Embodiment 5, counterdie immersed 2.0% amine aqueous solution after 2 minutes, NaOH solution washing surface with 0.1% 5 seconds, place in the air 3 minutes half-dried to the film surface, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride then, other technology is identical with Comparative Examples, and test condition is identical with Comparative Examples, and the result lists table 1 in.
Table 1
As can be known from the above table, use the present invention to make polyamide reverse osmosis composite film, the water flux and the desalting performance of gained composite membrane all are improved.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. method of making polyamide reverse osmosis composite film is characterized in that:
The first step, polysulfones is supported counterdie be immersed in diamines or the polyamines solution;
The counterdie surface is washed in second step, taking-up back, removes the diamines or the polyamines on counterdie surface;
The 3rd step, half-dried back are carried out interface polymerization reaction to the organic solution that counterdie immerses polynary acyl chlorides monomer, form polyamide reverse osmosis composite film on the counterdie surface;
The 4th step, taking-up polyamide reverse osmosis composite film are also heat-treated or the UV processing.
2. the method for manufacturing polyamide reverse osmosis composite film according to claim 1, it is characterized in that: in second step, the cleaning fluid that is used to wash the counterdie surface is deionized water, water-soluble ketone and the aqueous solution thereof, water-soluble alcohol and the aqueous solution thereof, the water-soluble organic acid and the aqueous solution thereof, a kind of in the water-soluble inorganic acid and the aqueous solution thereof, water-soluble alkali and the aqueous solution thereof, water-soluble salt and the aqueous solution thereof.
3. the method for manufacturing polyamide reverse osmosis composite film according to claim 1 is characterized in that: in described second step, and a kind of in spraying, spraying, scrub, embathe of washing methods.
4. the method for manufacturing polyamide reverse osmosis composite film according to claim 1 is characterized in that: in second step, the wash time scope is: 1 second to 30 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011101546438A CN102210981A (en) | 2011-06-10 | 2011-06-10 | Method for preparing polyamide reverse osmosis composite membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101546438A CN102210981A (en) | 2011-06-10 | 2011-06-10 | Method for preparing polyamide reverse osmosis composite membrane |
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| CN102210981A true CN102210981A (en) | 2011-10-12 |
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| CN2011101546438A Pending CN102210981A (en) | 2011-06-10 | 2011-06-10 | Method for preparing polyamide reverse osmosis composite membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657454A (en) * | 2013-12-17 | 2014-03-26 | 北京碧水源膜科技有限公司 | Preparation method for novel polyamide reverse osmosis membrane |
| CN104722218A (en) * | 2013-12-18 | 2015-06-24 | 天津大学 | Preparation method for solvent-resistant modified polyetherimide nanofiltration membrane |
| CN111036090A (en) * | 2019-12-26 | 2020-04-21 | 湖南沁森高科新材料有限公司 | Preparation method of aromatic polyamide composite reverse osmosis membrane and prepared reverse osmosis membrane |
| CN111111447A (en) * | 2019-12-26 | 2020-05-08 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane preparation method with adjustable and controllable desalination rate and prepared nanofiltration membrane |
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| US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| CN1292723A (en) * | 1999-01-14 | 2001-04-25 | 东丽株式会社 | Composite semipermeable membrane, procedss for producing the same, and method of purifying water with the same |
| WO2001091873A2 (en) * | 2000-05-23 | 2001-12-06 | Osmonics, Inc. | Polysulfonamide matrices |
| CN1631499A (en) * | 2004-11-12 | 2005-06-29 | 国家海洋局杭州水处理技术研究开发中心 | Novel compound nanometer filtering membrane of polyamide and its preparing method |
| CN1840230A (en) * | 2005-03-30 | 2006-10-04 | 世韩工业株式会社 | Composite polyamide reverse osmosis membrane and method of producing the same |
| CN102125809A (en) * | 2010-01-13 | 2011-07-20 | 武少禹 | Method for improving performance of reverse osmosis composite membrane through vapor treatment |
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2011
- 2011-06-10 CN CN2011101546438A patent/CN102210981A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| CN1292723A (en) * | 1999-01-14 | 2001-04-25 | 东丽株式会社 | Composite semipermeable membrane, procedss for producing the same, and method of purifying water with the same |
| WO2001091873A2 (en) * | 2000-05-23 | 2001-12-06 | Osmonics, Inc. | Polysulfonamide matrices |
| CN1631499A (en) * | 2004-11-12 | 2005-06-29 | 国家海洋局杭州水处理技术研究开发中心 | Novel compound nanometer filtering membrane of polyamide and its preparing method |
| CN1840230A (en) * | 2005-03-30 | 2006-10-04 | 世韩工业株式会社 | Composite polyamide reverse osmosis membrane and method of producing the same |
| CN102125809A (en) * | 2010-01-13 | 2011-07-20 | 武少禹 | Method for improving performance of reverse osmosis composite membrane through vapor treatment |
Non-Patent Citations (1)
| Title |
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| 汤蓓蓓等: "界面聚合法制备复合膜", 《化学进展》, no. 09, 24 September 2007 (2007-09-24) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657454A (en) * | 2013-12-17 | 2014-03-26 | 北京碧水源膜科技有限公司 | Preparation method for novel polyamide reverse osmosis membrane |
| CN103657454B (en) * | 2013-12-17 | 2015-12-30 | 北京碧水源膜科技有限公司 | A kind of preparation method of novel polyamide reverse osmosis membrane |
| CN104722218A (en) * | 2013-12-18 | 2015-06-24 | 天津大学 | Preparation method for solvent-resistant modified polyetherimide nanofiltration membrane |
| CN104722218B (en) * | 2013-12-18 | 2017-04-26 | 天津大学 | Preparation method for solvent-resistant modified polyetherimide nanofiltration membrane |
| CN111036090A (en) * | 2019-12-26 | 2020-04-21 | 湖南沁森高科新材料有限公司 | Preparation method of aromatic polyamide composite reverse osmosis membrane and prepared reverse osmosis membrane |
| CN111111447A (en) * | 2019-12-26 | 2020-05-08 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane preparation method with adjustable and controllable desalination rate and prepared nanofiltration membrane |
| CN111036090B (en) * | 2019-12-26 | 2022-03-22 | 湖南沁森高科新材料有限公司 | Preparation method of aromatic polyamide composite reverse osmosis membrane and prepared reverse osmosis membrane |
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Application publication date: 20111012 |