CN102886207A - Preparation method of composite reverse osmosis membrane - Google Patents
Preparation method of composite reverse osmosis membrane Download PDFInfo
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- CN102886207A CN102886207A CN2012104059931A CN201210405993A CN102886207A CN 102886207 A CN102886207 A CN 102886207A CN 2012104059931 A CN2012104059931 A CN 2012104059931A CN 201210405993 A CN201210405993 A CN 201210405993A CN 102886207 A CN102886207 A CN 102886207A
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Abstract
The invention discloses a preparation method of a composite reverse osmosis membrane, and particularly relates to a preparation method of an organic acylating chlorination nanometer titania modified aramid composite reverse osmosis membrane. The preparation method comprises the following steps of: preparing organic phase solution of trimesoyl chloride; then adding acylating chlorination modified nanometer titania into the organic phase solution to prepare uniform suspension liquid; soaking backup polysulfone supporting membrane in m-phenylenediamine (MPD) aqueous solution with the mass concentration of 0.5% to 3%, wherein the aqueous solution contains sodium dodecyl sulfate (SDS); then rolling through a rubber roller to remove excessive solution; after drying the solution, contacting the dried solution with the organic phase solution that is subjected to ultrasonic dispersion just now for 10 to 120 seconds; and finally, drying the solution in vacuum to obtain the product. The preparation method of the composite reverse osmosis membrane disclosed by the invention has the advantages that a stable structure is formed in the reaction, therefore, the mechanical strength of the reverse osmosis membrane can be improved, and meanwhile, the flux of pure water of the membrane can be improved by virtue of nano particles while an original high salt removing rate is maintained. The preparation method is simple and is easy to implement.
Description
Technical field
The present invention relates to a kind of preparation method of polymer compound film, specifically refer to the preparation method of the nano-titanium dioxide modified aromatic polyamide composite reverse osmosis membrane of a kind of organic chloride.
Background technology
High-flux reverse osmosis membrane is needing of modern industry application, at present, the improvement of reverse osmosis membrane is mainly concentrated on new monomer development, surface modification and adds the aspect such as organic molecule, although obtained certain effect, can not fundamentally reach requirement.In recent years along with the maturation of inorganic nano material technology of preparing, the research of inorganic particle filled interfacial polymerization counter-infiltration is also become one of study hotspot of reverse osmosis membrane performance.
The preparation process of counter-infiltration interfacial polymerization film is special, and nano particle is also different from Blending Processes in the interpolation of reverse osmosis membrane, needs to add nano particle to oil phase or aqueous phase, and the process of two kinds of method film forming and the separating effect of film will be different.
Common nano-titania particle surface is with a large amount of hydroxyls, adds in water or the oil phase hydrophily that the existence of hydroxyl after the film forming can weaken reverse osmosis membrane.And add by the nano particle after organically-modified in the oil phase of interfacial polymerization, thereby in interfacial polymerization process can and monomer reaction between organic phase and inorganic phase, obtain a kind of nano modification film with covalent bonds, organically-modified nano particle has the film properties after the existence of hydrophilic radical also can improve film forming in membrane structure simultaneously.
Summary of the invention
The present invention is directed to the less deficiency of present organic reverse osmosis membrane flux, in the reverse osmosis membrane preparation process, add a kind of organic chloride modified nano-titanium dioxide particle reverse osmosis membrane has been carried out modification, proposed the preparation method of the nano-titanium dioxide modified aromatic polyamide composite reverse osmosis membrane of a kind of organic chloride.The present invention is achieved by the following technical programs:
A kind of preparation method of complex reverse osmosis membrane, its feature may further comprise the steps:
(1) first configuration quality concentration is 0.05%-0.2% pyromellitic trimethylsilyl chloride (TMC) organic phase solution, wherein solvent is IsoparG oil, then add the chloride modified nano-titanium dioxide, ultrasonic dispersion 1 hour is made into mass concentration and is 0.005%-0.2% unit for uniform suspension;
(2) polysulfones support membrane for subsequent use being put into mass concentration is that 0.5%-3% m-phenylene diamine (MPD) (MPD) aqueous solution soaked 30-180 seconds, wherein contains mass concentration in the aqueous solution and be 0.1% dodecyl sodium sulfate (SDS);
Unnecessary solution is removed in the polysulfones support membrane rubber rollers roll extrusion of (3) soaking through m-phenylene diamine (MPD) solution;
(4) after solution was done, the organic phase solution of finishing with firm ultrasonic dispersion contacted 10-120 seconds;
(5) film that said process is made is put into 80-100 ℃ vacuum drying oven and was kept dry getting final product 10-15 minutes.
As preferably, the mass concentration of chloride modified nano-titanium dioxide is 0.005%-0.2% in the preparation method's of above-mentioned a kind of complex reverse osmosis membrane the step (1).
As preferably, the preparation method of above-mentioned a kind of complex reverse osmosis membrane the chloride modified nano-titanium dioxide with two kinds of groups: phenyl ring and acid chloride groups.
Be the material of industry routine in the present invention for the chloride modified nano-titanium dioxide, can realize titanium dioxide is carried out modification by open source information, be used in the present invention.
Beneficial effect: the nano titanium oxide with acid chloride groups forms amido link with the m-phenylene diamine (MPD) reaction in interface polymerization reaction, form rock-steady structure, can improve the mechanical strength of reverse osmosis membrane, when keeping original equipment with high desalinization, the existence of nano particle can improve the film pure water flux simultaneously.And this preparation method is simple, and operation is easily gone.
The specific embodiment
The below specifies enforcement of the present invention, but protection scope of the present invention is not limited to this:
Embodiment 1
Configuration quality concentration is 0.1% pyromellitic trimethylsilyl chloride (TMC) organic phase solution, and wherein solvent is IsoparG, then adds a certain amount of TMC modified nano-titanium dioxide particle, and ultrasonic dispersion 1 hour is made into mass concentration and is 0.005% unit for uniform suspension; It is that 2% m-phenylene diamine (MPD) (MPD) aqueous solution soaked 120 seconds that the polysulfones support membrane is put into mass concentration, wherein then uses rubber rollers roll extrusion polysulfones support membrane, removes unnecessary solution; After solution was done, the organic phase solution of finishing with firm ultrasonic dispersion contacted 20 seconds; The vacuum drying oven of this film being put into 90 ℃ kept 15 minutes, and drying makes hybridized composite reverse osmosis membrane.With the initial performance of sodium-chloride water solution test membrane under 1MPa pressure of 2000ppm, the salt rejection rate of this film is 98.8%, and flux is 25.47L/h/m
2
Embodiment 2
Do not add the modified nano-titanium dioxide particle, all the other operating procedures are identical with embodiment 1, and the preparation composite membrane is also tested, and the diaphragm pure water flux is 11.21 L/h/m
2, rejection is 98.1%.
Embodiment 3-7
Change the mass concentration of the contained TMC modified nano-titanium dioxide particle of organic phase solution, the method for operating that other steps and embodiment 1 are identical, the preparation composite membrane is also tested, and obtains result such as following table:
| Embodiment | 3 | 4 | 5 | 6 | 7 |
| Nano-TiO 2Concentration | 0.01% | 0.03% | 0.05% | 0.07% | 0.1% |
| Flux L/h/m 2 | 28.02 | 29.55 | 32.61 | 33.14 | 33.34 |
| Salt rejection rate | 98.8% | 99.0% | 98.7% | 97.9% | 97.1% |
Embodiment 8-10
Change the mass concentration of the contained TMC of organic phase solution, the method for operating that other steps and embodiment 1 are identical, the preparation composite membrane is also tested, and obtains result such as following table:
| Embodiment | 8 | 9 | 10 |
| TMC concentration | 0.05% | 0.15% | 0.2% |
| Flux L/h/m 2 | 23.45 | 24.63 | 21.40 |
| Salt rejection rate | 97.2% | 93.1% | 92.1% |
Embodiment 11-15
Change the mass concentration of the contained m-phenylene diamine (MPD) of aqueous phase solution, the method for operating that other steps and embodiment 1 are identical, the preparation composite membrane is also tested, and obtains result such as following table:
| Embodiment | 11 | 12 | 13 | 14 | 15 |
| M-phenylene diamine (MPD) concentration | 0.5% | 1% | 1.5% | 2.5% | 3% |
| Flux L/h/m 2 | 24.50 | 24.84 | 25.10 | 26.22 | 28.30 |
| Salt rejection rate | 95.3% | 96.7% | 97.3% | 98.9% | 98.9% |
Claims (3)
1. the preparation method of a complex reverse osmosis membrane, its feature may further comprise the steps:
(1) first configuration quality concentration is 0.05%-0.2% pyromellitic trimethylsilyl chloride organic phase solution, wherein solvent is IsoparG oil, then add the chloride modified nano-titanium dioxide, ultrasonic dispersion 1 hour is made into mass concentration and is 0.005%-0.2% unit for uniform suspension;
(2) polysulfones support membrane for subsequent use being put into mass concentration is that 0.5%-3% the m-phenylene diamine (MPD) aqueous solution soaked 30-180 seconds, wherein contains mass concentration in the aqueous solution and be 0.1% dodecyl sodium sulfate;
Unnecessary solution is removed in the polysulfones support membrane rubber rollers roll extrusion of (3) soaking through m-phenylene diamine (MPD) solution;
(4) after solution was done, the organic phase solution of finishing with firm ultrasonic dispersion contacted 10-120 seconds;
(5) film that said process is made is put into 80-100 ℃ vacuum drying oven and was kept dry getting final product 10-15 minutes.
2. the preparation method of a kind of complex reverse osmosis membrane according to claim 1 is characterized in that the mass concentration of chloride modified nano-titanium dioxide in the described step (1) is 0.005%-0.2%.
3. the preparation method of a kind of complex reverse osmosis membrane according to claim 1 is characterized in that described chloride modified nano-titanium dioxide is with two kinds of groups: phenyl ring and acid chloride groups.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111196A (en) * | 2013-03-04 | 2013-05-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nanofiltration membrane |
| CN103301756A (en) * | 2013-07-01 | 2013-09-18 | 苏州瀚海高分子有限公司 | Preparation method of nanometer TiO2-PA laminated film |
| CN103877872A (en) * | 2014-03-28 | 2014-06-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nano material modified poly piperazine amide nanofiltration membrane |
| CN103990385A (en) * | 2014-05-20 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Preparation method of novel polyamide composite separation membrane |
| CN104624066A (en) * | 2014-12-18 | 2015-05-20 | 浙江工业大学 | Preparation method of high-flux mixed matrix composite film |
| CN107158974A (en) * | 2017-05-21 | 2017-09-15 | 南京悠谷环保科技有限公司 | A kind of high intensity hydrophily NF membrane and preparation method thereof and the application in protein solution desalination processes |
| CN109382001A (en) * | 2018-11-26 | 2019-02-26 | 常州星源新能源材料有限公司 | A kind of reverse osmosis membrane and preparation method thereof |
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| CN101745325A (en) * | 2008-12-10 | 2010-06-23 | 王志梅 | Method for synthesizing polyesteramide reverse osmosis membrane |
| CN102091540A (en) * | 2010-12-28 | 2011-06-15 | 中国石油大学(华东) | Preparation method of sulfonated polyethersulfone/TiO2 nano composite ultrafiltration membrane |
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- 2012-10-23 CN CN2012104059931A patent/CN102886207A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101745325A (en) * | 2008-12-10 | 2010-06-23 | 王志梅 | Method for synthesizing polyesteramide reverse osmosis membrane |
| CN102091540A (en) * | 2010-12-28 | 2011-06-15 | 中国石油大学(华东) | Preparation method of sulfonated polyethersulfone/TiO2 nano composite ultrafiltration membrane |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111196A (en) * | 2013-03-04 | 2013-05-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nanofiltration membrane |
| CN103301756A (en) * | 2013-07-01 | 2013-09-18 | 苏州瀚海高分子有限公司 | Preparation method of nanometer TiO2-PA laminated film |
| CN103877872A (en) * | 2014-03-28 | 2014-06-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nano material modified poly piperazine amide nanofiltration membrane |
| CN103877872B (en) * | 2014-03-28 | 2016-03-09 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of nano-material modified polypiperazine-amide nanofiltration membrane |
| CN103990385A (en) * | 2014-05-20 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Preparation method of novel polyamide composite separation membrane |
| CN104624066A (en) * | 2014-12-18 | 2015-05-20 | 浙江工业大学 | Preparation method of high-flux mixed matrix composite film |
| CN107158974A (en) * | 2017-05-21 | 2017-09-15 | 南京悠谷环保科技有限公司 | A kind of high intensity hydrophily NF membrane and preparation method thereof and the application in protein solution desalination processes |
| CN107158974B (en) * | 2017-05-21 | 2019-12-24 | 泰州龙谷信息科技有限公司 | High-strength hydrophilic nanofiltration membrane, preparation method thereof and application thereof in protein solution desalination process |
| CN109382001A (en) * | 2018-11-26 | 2019-02-26 | 常州星源新能源材料有限公司 | A kind of reverse osmosis membrane and preparation method thereof |
| CN109382001B (en) * | 2018-11-26 | 2021-07-13 | 常州星源新能源材料有限公司 | Reverse osmosis membrane and preparation method thereof |
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Application publication date: 20130123 |