CN102430349A - Reverse osmosis composite membrane and preparation method thereof - Google Patents
Reverse osmosis composite membrane and preparation method thereof Download PDFInfo
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- CN102430349A CN102430349A CN2011104356331A CN201110435633A CN102430349A CN 102430349 A CN102430349 A CN 102430349A CN 2011104356331 A CN2011104356331 A CN 2011104356331A CN 201110435633 A CN201110435633 A CN 201110435633A CN 102430349 A CN102430349 A CN 102430349A
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Abstract
The invention relates to spherical monodisperse amino functionalized mesoporous SiO2 nano particles and a reverse osmosis composite membrane prepared from the mesoporous SiO2 nano particles. An organic group functionalized mesoporous SiO2 material contained in the reverse osmosis composite membrane breakthroughs the limitation of a zeolite molecular sieve which has under-sized aperture, and the aperture is widened to the mesoporous field from the microporous field; and organic groups in the material can react with organic monomer molecules in the process of interfacial polymerization so that a molecular sieve can be firmly introduced into the membrane in a manner of chemical bonding. The invention provides a new design scheme for the development of the high-performance reverse osmosis composite membrane. The organic group functionalized mesoporous SiO2 material can be designed individually and the organic groups in the material can be selected according to the requirement of the organic monomer molecules in the polymerization process. On one hand, the molecular sieve can be firmly introduced into the membrane; and on the other hand, the molecular sieve is endowed with different properties by different organic groups and the application scope of the reverse osmosis composite membrane can be widened.
Description
Technical field
The invention belongs to the reverse osmosis composite membrane technical field, be specifically related to a kind of response type amino functional mesoporous silicon oxide/polyamide reverse osmosis composite film and preparation method thereof.
Background technology
China's water resource per capita is very poor, and the economic growth of high speed makes China's exsiccosis severe more in addition.Therefore, how obtaining water purification and freshwater resources has at low cost become China and has had one of research topic of its own strategic significance, is regarded as the effective way of alleviating water resource pressure and obtain fresh water through reverse osmosis technology.
The research of reverse osmosis composite membrane and application are the most valued research directions in present reverse osmosis technology field; Composite membrane has overcome the shortcoming of the easy densification of asymmetric membrane; Make both performances reach best through preparing supporter and surperficial superthin layer respectively, thereby improved the performance of permeable membrane.Use maximum aromatic polyamide membranes at present and have excellent chemical stability, anti-biological corrosion, operating pressure requires advantages such as low.But deficiency such as in reverse osmosis process, still have energy consumption height, poor selectivity, be prone to pollute, flux is limited makes cost that reverse osmosis membrane technology obtains fresh water still than higher.Therefore, the exploitation energy consumption is low, water flux is big, selectivity good, the demand of resistant to pollution desalination membrane is just very urgent.Byeong-Heon in 2007 etc. have reported a kind of new technology (Journal of Membrane Science of interfacial polymerization nano molecular sieve composite membrane; 2007; 294:1); Successfully develop the novel reverse osmosis composite membrane that contains zeolite molecular sieve material, the hole of zeolite possess hydrophilic property makes the water flux of film increase, and salt rejection rate does not significantly descend.But still there is the too small restriction of molecular sieve bore diameter in the novel reverse osmosis composite membrane of zeolite molecular sieve material.And at present bibliographical information all is that mode through physically trapping is incorporated into inorganic nanoparticles in organic film, makes inorganic nanoparticles stable limited in film.Therefore, be badly in need of developing high performance mesoporous reverse osmosis composite membrane and satisfy the requirement on using.
Summary of the invention
The purpose of this invention is to provide a kind of response type amino functional mesoporous silicon oxide/polyamide reverse osmosis composite film and preparation method thereof, promptly a kind of mesoporous SiO of amino functional that contains
2The reverse osmosis composite membrane of molecular sieve, the aperture that can effectively improve molecular sieve.
One aspect of the invention relates to the mesoporous SiO of a kind of monodisperse spherical amino functional
2Nano particle; Adopt following method preparation: at first softex kw is dissolved in the deionized water; Processing concentration is the CTAB aqueous solution of 5.7～16mmol/L, adds ethanol and NaOH again, under 80～100 ℃, is stirred to the solution clear; Under agitation add the mixture of positive tetraethyl orthosilicate and 3-aminopropyl triethoxysilane rapidly, continue to stir; Reactant mixture is successively through the dry material that obtains containing template under filtration, washing with alcohol, the vacuum environment; The material that will contain template again with absolute ethyl alcohol and concentrated hydrochloric acid agitation and filtration after, fully wash the back drying with absolute ethyl alcohol and make the mesoporous SiO of monodisperse spherical amino functional
2Nano particle.
The additional proportion of ethanol and NaOH is following in the above-mentioned CTAB aqueous solution: adding 9.6ml ethanol and 0.7ml concentration are the NaOH of 2mol/L in the 86.4mlCTAB aqueous solution.
The above-mentioned 3-aminopropyl triethoxysilane and the mass ratio of softex kw are 0.5～1.5: 1, and the mass volume ratio g/ml of 3-aminopropyl triethoxysilane and positive tetraethyl orthosilicate is 1～2: 1.
Another aspect of the present invention relates to a kind of reverse osmosis composite membrane, and its preparation method comprises the steps:
1) at first with the mesoporous SiO of monodisperse spherical amino functional
2Nano particle is ultrasonic to be dispersed in the hexane solution of pyromellitic trimethylsilyl chloride as oil phase.
2) then the polysulfones basement membrane and the water m-phenylene diamine (MPD) aqueous solution of hygrometric state is fully acted on, water is drained,
3) with step 2) oil phase for preparing in the polysulfones basement membrane handled well and the step 1) carries out interface polymerization reaction, and reaction finishes the back at air drying, heat-treats at last again and makes the mesoporous SiO of amino functional of the present invention
2Molecular sieve/reverse osmosis composite membrane.
Above-mentioned steps 1) the mesoporous SiO of monodisperse spherical amino functional in
2The mass and size percentage g/ml of nano particle in the hexane solution of pyromellitic trimethylsilyl chloride is 0.1%.
The mass and size specific concentration g/ml of the hexane solution of above-mentioned pyromellitic trimethylsilyl chloride is 0.1%.
The mass and size specific concentration g/ml of the aqueous solution of above-mentioned m-phenylene diamine (MPD) (MPD) is 2%.
Above-mentioned steps 3) time of described interface polymerization reaction is 60s.
Described heat treatment is meant 110-120 ℃ of following 3min.
The reverse osmosis composite membrane use mass and size specific concentration g/ml that the present invention prepares is 1% solution of sodium bisulfite preservation.
The organic group functionized mesoporous earth silicon material that reverse osmosis composite membrane of the present invention contains has been broken through the too small restriction of zeolite molecules mesh size, and the aperture is expanded to mesoporous field from micropore.And the organic group in the material can react with the organic monomer molecule in the process of interfacial polymerization, makes molecular sieve with firm being incorporated in the film of the mode of chemical bonding.This provides a kind of new design for the exploitation of high-performance reverse osmosis composite membrane.Organic group functionized mesoporous silica material can design separately, and organic group wherein can be based on the requirement of organic monomer molecule in the polymerization process and select.Make that on the one hand different on the other hand organic groups gives molecular sieve different performances, can widen the range of application of reverse osmosis composite membrane in the introducing film that molecular sieve can be firm.
Description of drawings
Fig. 1: the nitrogen adsorption-desorption isotherm of the amino functional Metaporous silicon dioxide material of the present invention's preparation.
Fig. 2: the pore size distribution curve of the amino functional Metaporous silicon dioxide material of the present invention's preparation.
Fig. 3: the stereoscan photograph of the amino functional Metaporous silicon dioxide material of the present invention's preparation.
Fig. 4: the XRD figure of the amino functional Metaporous silicon dioxide material of the present invention's preparation.
Fig. 5: the stereoscan photograph of the amino functional Metaporous silicon dioxide material of the present invention's preparation.
Fig. 6: mesoporous material mass fraction of the present invention is the stereoscan photograph of the composite membrane surface texture of 0.05% (w/v).
Fig. 7: mesoporous material mass fraction of the present invention is the stereoscan photograph of the composite membrane surface texture of 0.1% (w/v).
Fig. 8: the graph of a relation that the water flux of composite membrane of the present invention and salt rejection rate change with molecular sieve content.
The specific embodiment
Following embodiment is of the present invention further specifying, rather than restriction protection scope of the present invention.
The mesoporous SiO of embodiment 1 monodisperse spherical amino functional
2The preparation of nano particle
3-aminopropyl triethoxysilane content is 10% the mesoporous SiO of amino functional in the initial reaction liquid
2The preparation of molecular sieve: 0.2000g softex kw (CTAB) is dissolved in the 86.4ml deionized water; Adding 9.6ml ethanol and 0.7ml concentration is the NaOH of 2mol/L; At 80 ℃ of following vigorous stirring to solution clears; The mixture that under agitation adds positive tetraethyl orthosilicate of 1.15ml and 0.1268g 3-aminopropyl triethoxysilane rapidly continued vigorous stirring 2 hours.Drying is 12 hours under reactant mixture process filtration successively, three times, 60 ℃ vacuum environments of washing with alcohol.Template remove the employing solvent extraction, in the 100mL conical flask, add the material, 30mL absolute ethyl alcohol and the 5ml concentrated hydrochloric acid (HCl36-38%) that contain template after the drying; Stir 6h down at 50 ℃; Filter, fully wash with absolute ethyl alcohol, and dry down in 45 ℃.The specific area of this material is 1007m
2/ g, the aperture is 2.7nm, pore volume is 0.88cm
3/ g, particle diameter are 192nm.Its pore structure has the ordered arrangement of two-dimentional six directions.The nitrogen adsorption of material-desorption curve such as Fig. 1, pore size distribution curve is seen Fig. 2, and ESEM is seen Fig. 3, and XRD figure is seen Fig. 4.
The mesoporous SiO of embodiment 2 monodisperse spherical amino functionals
2The preparation of nano particle
3-aminopropyl triethoxysilane content is 20% the mesoporous SiO of amino functional in the initial reaction liquid
2The preparation of molecular sieve: 0.2000g softex kw (CTAB) is dissolved in the 86.4ml deionized water; The NaOH that adds 9.6ml ethanol and 0.7ml2mol/L; At 80 ℃ of following vigorous stirring to solution clears; The mixture that under agitation adds positive tetraethyl orthosilicate of 1.02ml and 0.2536g 3-aminopropyl triethoxysilane rapidly continued vigorous stirring 2 hours.Drying is 12 hours under reactant mixture process filtration successively, three times, 60 ℃ vacuum environments of washing with alcohol.Template remove the employing solvent extraction, in the 100mL conical flask, add the material, 30mL absolute ethyl alcohol and the 5ml concentrated hydrochloric acid (HCl36-38%) that contain template after the drying; Stir 6h down at 50 ℃; Filter, fully wash with absolute ethyl alcohol, and dry down in 45 ℃.This material particle size is 240nm.ESEM is seen Fig. 5.
The mesoporous SiO of prepared amino functional
2Nano particle is bigger than existing zeolite molecules mesh size, helps mass transfer, with the SiO of conventional method preparation
2Particle is compared has more perfectly spherical morphology, evenly disperses when helping making film.
The preparation of embodiment 3 reverse osmosis composite membranes
With mass fraction is the mesoporous SiO of amino functional of 0.05% (w/v)
2Molecular sieve is distributed to (ultrasonic 1h under the room temperature) in the oil phase through ultrasonic.It is in 2% the m-phenylene diamine (MPD) solution (water) that the polysulfones basement membrane of hygrometric state is immersed in mass and size specific concentration g/ml; And roll with rubber bar and to make water fully and the support membrane effect; Water is drained back (time of draining is about 150s), and be dispersed with the mesoporous SiO of amino functional
2Interface polymerization reaction is carried out in the hexane solution contact of the pyromellitic trimethylsilyl chloride of molecular sieve (TMC), behind air drying 2min, under 110-120 ℃, heat-treats 3min again, makes molecular sieve/polyamide reverse osmosis composite film.As shown in Figure 5, stereoscan photograph shows the mesoporous SiO of amino functional
2Molecular sieve is combined on the film.The above-mentioned film that is used for analyzing that makes will be put into distilled water and soak more than the 24h, cleans with deionized water.The hexane solution of above-mentioned pyromellitic trimethylsilyl chloride (TMC) is to make solvent with n-hexane, is mixed with the TMC solution of (w/v 0.1%).The TMC facile hydrolysis is rotten, so should be rapid during weighing, and used graduated cylinder and reagent bottle all should dryings.Stereoscan photograph (Fig. 6) can be observed nano material and be incorporated in the membrane material.
The preparation of embodiment 4 reverse osmosis composite membranes
With mass fraction is the mesoporous SiO of amino functional of 0.1% (w/v)
2Molecular sieve is distributed to (ultrasonic 1h under the room temperature) in the oil phase through ultrasonic.It is in 2% the m-phenylene diamine (MPD) solution (water) that the polysulfones basement membrane of hygrometric state is immersed in mass and size specific concentration g/ml; And roll with rubber bar and to make water fully and the support membrane effect; Water is drained back (time of draining is about 150s), and be dispersed with the mesoporous SiO of amino functional
2Interface polymerization reaction is carried out in the hexane solution contact of the pyromellitic trimethylsilyl chloride of molecular sieve (TMC), behind air drying 2min, under 110-120 ℃, heat-treats 3min again, makes molecular sieve/polyamide reverse osmosis composite film.As shown in Figure 5, stereoscan photograph shows the mesoporous SiO of amino functional
2Molecular sieve is combined on the film.The above-mentioned film that is used for analyzing that makes will be put into distilled water and soak more than the 24h, cleans with deionized water.The hexane solution of above-mentioned pyromellitic trimethylsilyl chloride (TMC) is to make solvent with n-hexane, is mixed with the TMC solution of (w/v 0.1%).The TMC facile hydrolysis is rotten, so should be rapid during weighing, and used graduated cylinder and reagent bottle all should dryings.Stereoscan photograph (Fig. 7) can be observed nano material and be incorporated in the membrane material.
Embodiment 3,4 prepared composite membranes are packed in the film properties evaluating apparatus, use concentration to be 2000mgL then
-1Sodium chloride solution as material liquid, under 25 ℃, 1.6MPa, begin to measure in the certain hour t (h) through effective film area S (m behind the operation 30min
2) the volume V (L) of sodium chloride penetrating fluid, calculate the water flux (L/m of film
2H).Measure material liquid respectively and see through the electrical conductivity of liquid with conductivity meter, calculate the salt rejection rate (%) of film.As shown in Figure 8.With the mesoporous SiO of amino functional
2The water flux of the increase film of molecular sieve content increases, and salt rejection rate remains on more than 96%.Above-mentioned testing result shows that the composite membrane that the present invention prepares has good performance, has good popularization and application prospect.
Claims (10)
1. mesoporous SiO of monodisperse spherical amino functional
2Nano particle, described mesoporous SiO
2Nano particle prepares with following method: at first softex kw is dissolved in the deionized water; Processing concentration is the CTAB aqueous solution of 5.7～16mmol/L; Add ethanol and NaOH again; Under 80～100 ℃, be stirred to the solution clear, under agitation add the mixture of positive tetraethyl orthosilicate and 3-aminopropyl triethoxysilane rapidly, continue to stir; Reactant mixture is successively through the dry material that obtains containing template under filtration, washing with alcohol, the vacuum environment; The material that will contain template again with absolute ethyl alcohol and concentrated hydrochloric acid agitation and filtration after, fully wash the back drying with absolute ethyl alcohol and make the mesoporous SiO of monodisperse spherical amino functional
2Nano particle.
2. mesoporous SiO as claimed in claim 1
2Nano particle is characterized in that the additional proportion of ethanol and NaOH is following in the described CTAB aqueous solution: in the 86.4mlCTAB aqueous solution, add 9.6ml ethanol and 0.7ml concentration is the NaOH of 2mol/L.
3. mesoporous SiO as claimed in claim 1
2Nano particle, the mass ratio that it is characterized in that described 3-aminopropyl triethoxysilane and softex kw is 0.5～1.5: 1, and the mass volume ratio g/ml of 3-aminopropyl triethoxysilane and positive tetraethyl orthosilicate is 1～2: 1.
4. reverse osmosis composite membrane is with following method preparation:
1) at first with the mesoporous SiO of the described monodisperse spherical amino functional of claim 1
2Nano particle is ultrasonic to be dispersed in the hexane solution of pyromellitic trimethylsilyl chloride as oil phase.
2) then the polysulfones basement membrane and the water m-phenylene diamine (MPD) aqueous solution of hygrometric state is fully acted on, water is drained,
3) with step 2) oil phase for preparing in the polysulfones basement membrane handled well and the step 1) carries out interface polymerization reaction, and reaction finishes the back at air drying, heat-treats at last again and makes the mesoporous SiO of amino functional of the present invention
2Molecular sieve/reverse osmosis composite membrane.
5. reverse osmosis composite membrane as claimed in claim 4 is characterized in that the mesoporous SiO of monodisperse spherical amino functional in the described step 1)
2The mass and size percentage g/ml of nano particle in the pyromellitic trimethylsilyl chloride hexane solution is 0.1%.
6. reverse osmosis composite membrane as claimed in claim 5 is characterized in that the mass and size specific concentration g/ml of described pyromellitic trimethylsilyl chloride hexane solution is 0.1%.
7. reverse osmosis composite membrane as claimed in claim 4 is characterized in that described step 2) in the mass and size specific concentration g/ml of the m-phenylene diamine (MPD) aqueous solution be 2%.
8. reverse osmosis composite membrane as claimed in claim 4 is characterized in that the time of described step 3) median surface polymerisation is 60s.
9. reverse osmosis composite membrane as claimed in claim 4 is characterized in that heat treatment is meant 110-120 ℃ of following 3min in the described step 3).
10. the described reverse osmosis composite membrane use of claim 4 mass and size specific concentration g/ml is 1% solution of sodium bisulfite preservation.
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| CN102794116A (en) * | 2012-06-06 | 2012-11-28 | 复旦大学 | Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof |
| CN103906561A (en) * | 2012-06-08 | 2014-07-02 | Lg化学株式会社 | Reverse osmosis membrane with high permeation flux comprising surface-treated zeolite, and method for preparing the same |
| CN104174308A (en) * | 2014-09-04 | 2014-12-03 | 北京碧水源膜科技有限公司 | Preparation method and application of hybridization reverse osmosis membrane |
| CN104211073A (en) * | 2014-09-19 | 2014-12-17 | 熊仕显 | Preparation method of monodisperse nano spherical silicon dioxide and nano silicon dioxide |
| 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 |
| CN105347438A (en) * | 2014-12-18 | 2016-02-24 | 青岛木力新能源科技有限公司 | Sewage treatment equipment constructed by using reverse-osmosis hydrophilic material |
| CN105585073A (en) * | 2014-12-18 | 2016-05-18 | 青岛木力新能源科技有限公司 | Sea water desalination project built through reverse-osmosis hydrophilic materials |
| CN105585074A (en) * | 2014-12-18 | 2016-05-18 | 青岛木力新能源科技有限公司 | Sea water desalting equipment made of hydrophilic materials |
| CN106397801A (en) * | 2016-09-07 | 2017-02-15 | 辽宁石油化工大学 | Preparation method of fuel cell AEM (anion-exchange membrane) modified with mesoporous silica PSF (polysulfone) doped with and supported with G8-2-8/NaSal micellar system |
| CN106943902A (en) * | 2017-04-17 | 2017-07-14 | 中国海洋大学 | Ester modified polyamide reverse osmosis composite film of a kind of silicic acid and preparation method thereof |
| CN107140652A (en) * | 2017-05-27 | 2017-09-08 | 中山大学 | Azide mesoporous silica nano-particle and preparation method thereof |
| CN107349797A (en) * | 2016-05-10 | 2017-11-17 | 宁波水艺膜科技发展有限公司 | A kind of super hydrophilic polymer microporous film and its manufacture method |
| CN107970794A (en) * | 2017-11-22 | 2018-05-01 | 国家海洋局天津海水淡化与综合利用研究所 | A kind of hud typed hierarchical porous structure nano-particle and its modification reverse osmosis membrane of preparation |
| CN108579477A (en) * | 2018-05-16 | 2018-09-28 | 南京帝膜净水材料开发有限公司 | A kind of anti-pollution reverse osmosis composite membrane and preparation method thereof |
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| US10287184B2 (en) | 2016-11-16 | 2019-05-14 | University Of Dammam | Water filtration apparatus and a method of using thereof |
| CN109985531A (en) * | 2019-04-08 | 2019-07-09 | 天津大学 | A method of reverse osmosis membrane is prepared using silester as oily phase cosolvent |
| CN111001309A (en) * | 2019-12-16 | 2020-04-14 | 浙江工业大学 | Method for preparing mixed matrix reverse osmosis membrane by using amino modified mesoporous silicon nanospheres |
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| CN112675715A (en) * | 2019-10-18 | 2021-04-20 | 中国科学院青岛生物能源与过程研究所 | Polyamide nano composite film and preparation method and application thereof |
| CN111085117A (en) * | 2019-11-28 | 2020-05-01 | 丁水英 | High-water-permeability reverse osmosis membrane and preparation method thereof |
| CN111001309A (en) * | 2019-12-16 | 2020-04-14 | 浙江工业大学 | Method for preparing mixed matrix reverse osmosis membrane by using amino modified mesoporous silicon nanospheres |
| CN111317825A (en) * | 2020-03-06 | 2020-06-23 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
| CN111317825B (en) * | 2020-03-06 | 2021-08-24 | 南京市江宁医院 | Regularly folded ultra-small-size large-pore inorganic silicon macromolecular drug carrier, and preparation method and application thereof |
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Application publication date: 20120502 |