CN104841295A - Mesoporous silica sphere/semi-aromatic polyamide nano-composite reverse osmosis membrane and preparation method thereof - Google Patents
Mesoporous silica sphere/semi-aromatic polyamide nano-composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of water treatment membranes, and discloses a mesoporous silica sphere/semi-aromatic polyamide nano-composite reverse osmosis membrane. The nano-composite reverse osmosis membrane is obtained through the forming of a layer of semi-aromatic polyamide macromolecular function separating layer embedded with a mesoporous silica sphere on an ultra-filtration support membrane. The mesoporous silica sphere can be effectively introduced into a semi-aromatic polyamide macromolecule layer so as to obtain the nano-composite reverse osmosis membrane with excellent performance. Strong hydrogen bonds between the mesoporous silica sphere and the semi-aromatic polyamide macromolecule in the nano-composite reverse osmosis membrane can be uniformly and stably dispersed in the semi-aromatic polyamide macromolecular function separating layer, so that the water flux of the composite reverse osmosis membrane is greatly promoted, the separating performance is obviously improved, and the separating stability and the membrane surface hydrophilicity are good; and meanwhile, the preparation method is simple, strong in operability, and low in production cost, and has good industrial application prospect.
Description
Technical field
The invention belongs to membrane for water treatment technical field, be specifically related to a kind of nano combined reverse osmosis membrane and preparation method thereof.
Background technology
Complex reverse osmosis membrane primarily of separating layer, supporting layer and nonwoven layer three part composition, wherein separating layer has been the functional layer of centrifugation.Polyamide complex reverse osmosis membrane can be applicable to the fields such as brackish water desalination, desalinization and wastewater treatment, has broad application prospects.Such reverse osmosis membrane usually with organic acyl chlorides and organic amine for primary raw material monomer is prepared by interfacial polymerization.Interfacial polymerization is dissolved in by two kinds of very high for reactivity monomers in two kinds of immiscible solvents respectively, by generating the method for macromolecule member materials at two kinds of solvent interface polymerization reaction take places; The method is widely used in prepares complex reverse osmosis membrane.Current business-like main flow membrane material is aromatic polyamides type reverse osmosis membrane, and it is obtained by interface polymerization reaction as reaction monomers by pyromellitic trimethylsilyl chloride and m-phenylene diamine (MPD) usually.In recent years by development of new membrane material, improve the separating property of complex reverse osmosis membrane thus reduce its energy consumption in membrane separating process and cost, becoming one of study hotspot of novel trans permeable membrane.
So-called semi-aromatic polyamide refers to that the two kinds of organic monomers (organic amine and organic amide) participating in reaction only have one to have armaticity, the polyamide material obtained by this two kinds of monomer polymerization reaction take places.Semi-aromatic polyamide is compared with aromatic polyamides, and the former macromolecular chain has better flexible and hydrone permeability, and this material has good hydrophily.Therefore, semi-aromatic polyamide is applied to water flux and the hydrophily that reverse osmosis membrane preparation can significantly improve membrane material.Mesopore silicon oxide spheres has good hydrophilic property, porosity is high, aperture is homogeneous, pattern is regular, prepare the advantages such as simple; Therefore by means of design features such as mesopore silicon oxide spheres good hydrophilic property, porosity height, in complex reverse osmosis membrane preparation process, additive is it can be used as to be incorporated in the separating layer of membrane material, the high porosity of mesopore silicon oxide spheres will significantly improve the hydrone permeability of separating layer, and the introducing of mesopore silicon oxide spheres is also expected to make the degree of cross linking of reverse osmosis membrane separation layer itself be optimized further, and then greatly promote the water flux of complex reverse osmosis membrane, thus separating property raising is made to become possibility.But, have not yet to see the relevant report be incorporated into by mesopore silicon oxide in semi-aromatic polyamide reverse osmosis membrane.
Summary of the invention
To be solved by this invention is the technical problem how improving complex reverse osmosis membrane separating property, nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide and preparation method thereof is provided, contain the semi-aromatic polyamide function separating layer of mesopore silicon oxide spheres by interfacial polymerization at ultrafiltration support membrane surface formation one deck and obtain, because meso-porous nano silicon oxide ball surface is with abundant silicone hydroxyl functional group, therefore and between semi-aromatic polyamide separating layer there is stronger hydrogen bond action, therefore Absorbable organic halogens is scattered in semi-aromatic polyamide separating layer, make this complex reverse osmosis membrane water flux high, stable performance, good hydrophilic property, its preparation method process is simple simultaneously, workable, and preparation condition is easy to control, and has wide scale application prospect.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
The nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide, the semi-aromatic polyamide function separating layer that this complex reverse osmosis membrane contains mesopore silicon oxide spheres by interfacial polymerization at ultrafiltration support membrane Surface Creation one deck is formed, and is specifically obtained by following preparation method:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine, dipping 0.5-10 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of m-phenylene diamine (MPD) is 0.5-5.0w/v%, and the concentration of camphorsulfonic acid is 0.5-4.6w/v%, and the concentration of triethylamine is 0.6-3.5w/v%;
(2) cyclohexyl-1,3,5-tri-formyl chloride and mesopore silicon oxide spheres to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of the formyl chloride of cyclohexyl-1,3,5-tri-described in described oil-phase solution is 0.05-0.6w/v%; The concentration of described mesopore silicon oxide spheres is 0.01-0.1w/v%; Described mesopore silicon oxide spheres is of a size of 20-200 nanometer, and mesoporous pore size is 2-20 nanometer;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.4-8 minute, thus the semi-aromatic polyamide Motor cortex of mesopore silicon oxide spheres is embedded with at ultrafiltration support membrane Surface Creation one deck, form the nano combined reverse osmosis membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined reverse osmosis membrane surface is excessive, heat-treat, heat treatment temperature is 70-90 DEG C, heat treatment time is 3-20 minute, finally can obtain mesopore silicon oxide spheres/semi-aromatic polyamide complex reverse osmosis membrane with deionized water rinsing.
Wherein, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
Wherein, the aperture of described polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane is 40-100 nanometer.
Wherein, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
Preferably, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%; In oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%, and the concentration of mesopore silicon oxide spheres is 0.04w/v%.
A preparation method for the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, the method is carried out according to following steps:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine, dipping 0.5-10 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of m-phenylene diamine (MPD) is 0.5-5.0w/v%, and the concentration of camphorsulfonic acid is 0.5-4.6w/v%, and the concentration of triethylamine is 0.6-3.5w/v%;
(2) cyclohexyl-1,3,5-tri-formyl chloride and mesopore silicon oxide spheres to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of the formyl chloride of cyclohexyl-1,3,5-tri-described in described oil-phase solution is 0.05-0.6w/v%; The concentration of described mesopore silicon oxide spheres is 0.01-0.1w/v%; Described mesopore silicon oxide spheres is of a size of 20-200 nanometer, and mesoporous pore size is 2-20 nanometer;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.4-8 minute, thus the semi-aromatic polyamide Motor cortex of mesopore silicon oxide spheres is embedded with at ultrafiltration support membrane Surface Creation one deck, form the nano combined reverse osmosis membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined reverse osmosis membrane surface is excessive, heat-treat, heat treatment temperature is 70-90 DEG C, heat treatment time is 3-20 minute, finally can obtain the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide with deionized water rinsing.
Wherein, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
Wherein, the aperture of described polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane is 40-100 nanometer.
Wherein, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
Preferably, it is characterized in that, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%; In oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%, and the concentration of mesopore silicon oxide spheres is 0.04w/v%.
The invention has the beneficial effects as follows:
Mesopore silicon oxide spheres is incorporated in semi-aromatic polyamide separating layer by interfacial polymerization by the present invention, due in preparation process to containing mesopore silicon oxide spheres and cyclohexyl-1,3, the oil-phase solution of 5-tri-formyl chloride has carried out ultrasonic disperse process, and mesopore silicon oxide spheres can be dispersed in the semi-aromatic polyamide separating layer of nano combined reverse osmosis membrane; In addition, owing to having stronger hydrogen bond action between the silicone hydroxyl on mesopore silicon oxide spheres surface and the amido link of semi-aromatic polyamide, the mesopore silicon oxide spheres formed/semi-aromatic polyamide reverse osmosis membrane has stable separating property; Its preparation method process is simple simultaneously, workable, and preparation condition is easy to control, and has wide scale application prospect.
The nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide prepared by the present invention, due to mesopore silicon oxide spheres have stronger hydrophily, high porosity and and suitable aperture size, be introduced in semi-aromatic polyamide separating layer, the hydrophily of reverse osmosis membrane and hydrone permeability can be made to be improved significantly; Thus improve the water flux of the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, and then make its separating property be improved significantly.In addition, mesopore silicon oxide spheres be introduced in the degree of cross linking reducing semi-aromatic polyamide separating layer to a certain extent, this is also conducive to the raising of water flux.
Experiment shows, under 2000mg/L sodium chloride solution, 1.5MPa test pressure and 25 DEG C of solution temperature test conditions, the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide prepared by the present invention, water flux can reach 28.21 ~ 85.43L/m
2h, salt rejection rate can reach 68.69 ~ 97.54%.When the present invention takes the concentration of m-phenylene diamine (MPD) to be 2.0w/v%, cyclohexyl-1,3, the concentration of 5-tri-formyl chloride is 0.1w/v%, when the concentration of mesopore silicon oxide spheres is 0.04w/v%, 1.49 times of the pure semi-aromatic polyamide reverse osmosis membrane that water flux is prepared under being about the same terms, its salt rejection rate still can remain on higher level.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail:
Following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
(1) in deionized water, a certain amount of m-phenylene diamine (MPD) monomer is added, its concentration is made to reach 2w/v%, a certain amount of camphorsulfonic acid and triethylamine is added again in this solution, its concentration is made to reach 2.3w/v% and 1.1w/v% respectively, mix formation aqueous phase solution, then be that the polysulfones ultrafiltration support membrane of 60 nanometers is immersed in this aqueous phase solution by aperture, flood 2 minutes, then polysulfones ultrafiltration support membrane is taken out, remove the aqueous phase solution of its excess surface.
(2) cyclohexyl-1,3,5-tri-formyl chloride is joined in Isopar G type hydrocarbon mixture, be mixed with the oil-phase solution of concentration 0.1w/v%; Add wherein again and be of a size of 100 nanometers and the nanosilica white sphere that mesoporous pore size is 2 nanometers makes its concentration reach 0.04w/v%, and within 40 minutes, form uniform oil-phase solution by ultrasonic process; Again the polysulfones ultrafiltration support membrane that step (1) obtains is immersed in this oil-phase solution, reacted for 60 seconds, after taking-up, remove the oil-phase solution of film excess surface; Thus the semi-aromatic polyamide Motor cortex of mesopore silicon oxide spheres is embedded with at ultrafiltration support membrane Surface Creation one deck, form the nano combined reverse osmosis membrane of nascent state.
(3) by the complex reverse osmosis membrane of nascent state that obtains 80 DEG C of baking oven interior heats process 5 minutes, then taking-up with deionized water rinsing for several times, obtain the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide.
Embodiment 2:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the dip time in aqueous phase solution is 0.5 minute.
Embodiment 3:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the dip time in aqueous phase solution is 10 minutes.
Embodiment 4:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that m-phenylene diamine (MPD) concentration is 0.5w/v%.
Embodiment 5:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that m-phenylene diamine (MPD) concentration is 5.0w/v%.
Embodiment 6:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that camphorsulfonic acid concentration is 0.5w/v%.
Embodiment 7:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that camphorsulfonic acid concentration is 4.6w/v%.
Embodiment 8:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that triethylamine concentration is 0.6w/v%.
Embodiment 9:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that triethylamine concentration is 3.5w/v%.
Embodiment 10:
Adopt the method for embodiment 1 to prepare mesopore silicon oxide spheres/semi-aromatic polyamide composite Nano reverse osmosis membrane, its difference is only that the reaction time is 0.4 minute in oil-phase solution.
Embodiment 11:
Adopt the method for embodiment 1 to prepare mesopore silicon oxide spheres/semi-aromatic polyamide composite Nano reverse osmosis membrane, its difference is only that the reaction time is 8 minutes in oil-phase solution.
Embodiment 12:
Adopt the method for embodiment 1 to prepare mesopore silicon oxide spheres/semi-aromatic polyamide composite Nano reverse osmosis membrane, its difference is only that the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.05w/v%.
Embodiment 13:
Adopt the method for embodiment 1 to prepare mesopore silicon oxide spheres/semi-aromatic polyamide composite Nano reverse osmosis membrane, its difference is only that the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.6w/v%.
Embodiment 14:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the concentration of mesopore silicon oxide spheres is 0.01w/v%.
Embodiment 15:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the concentration of mesopore silicon oxide spheres is 0.1w/v%.
Embodiment 16:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that mesopore silicon oxide spheres is of a size of 20 nanometers.
Embodiment 17:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that mesopore silicon oxide spheres is of a size of 200 nanometers.
Embodiment 18:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the mesoporous pore size of mesopore silicon oxide spheres is 5.5 nanometers.
Embodiment 19:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the mesoporous pore size of mesopore silicon oxide spheres is 20 nanometers.
Embodiment 20:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that heat treatment temperature is 70 DEG C.
Embodiment 21:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that heat treatment temperature is 90 DEG C.
Embodiment 22:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that heat treatment time is 3 minutes.
Embodiment 23:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that heat treatment time is 20 minutes.
Embodiment 24:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that ultrafiltration support membrane selects the polyether sulfone ultrafiltration support membrane of aperture 60 nanometer.
Embodiment 25:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that ultrafiltration support membrane selects the polyether sulfone ultrafiltration support membrane of aperture 40 nanometer.
Embodiment 26:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that ultrafiltration support membrane selects the polyether sulfone ultrafiltration support membrane of aperture 100 nanometer.
Embodiment 27:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the organic solvent of oil-phase solution is normal hexane.
Embodiment 28:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the organic solvent of oil-phase solution is normal heptane.
Embodiment 29:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the ultrasonic disperse time is 30 minutes.
Embodiment 30:
Adopt the method for embodiment 1 to prepare the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, its difference is only that the ultrasonic disperse time is 60 minutes.
Embodiment 31:
For showing the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide prepared by the present invention and the difference of pure semi-aromatic polyamide complex reverse osmosis membrane in separating property, adopt the method for embodiment 1 to prepare pure semi-aromatic polyamide complex reverse osmosis membrane, its difference is only not add mesopore silicon oxide spheres.
Complex reverse osmosis membrane the various embodiments described above prepared is kept in water, and test its water flux and salt rejection rate under 2000mg/L sodium chloride solution, 1.5MPa test pressure and 25 DEG C of solution temperatures, test result is in table 1.
The separating property parameter of complex reverse osmosis membrane under the different preparation condition of table 1
| Embodiment | Water flux (L/m 2h) | Salt rejection rate (%) |
| 1 | 69.09 | 93.89 |
| 2 | 75.23 | 70.40 |
| 3 | 58.67 | 95.33 |
| 4 | 85.22 | 68.69 |
| 5 | 51.09 | 95.88 |
| 6 | 60.56 | 89.96 |
| 7 | 66.78 | 93.58 |
| 8 | 50.46 | 90.15 |
| 9 | 61.85 | 92.34 |
| 10 | 79.80 | 87.46 |
| 11 | 28.21 | 97.43 |
| 12 | 75.21 | 73.37 |
| 13 | 33.65 | 96.90 |
| 14 | 45.34 | 95.87 |
| 15 | 85.43 | 83.42 |
| 16 | 57.08 | 94.93 |
| 17 | 74.12 | 89.40 |
| 18 | 72.33 | 90.56 |
| 19 | 81.20 | 85.70 |
| 20 | 73.20 | 90.19 |
| 21 | 58.12 | 94.96 |
| 22 | 75.35 | 90.56 |
| 23 | 54.19 | 96.39 |
| 24 | 67.09 | 93.56 |
| 25 | 57.34 | 92.84 |
| 26 | 72.30 | 91.08 |
| 27 | 58.34 | 93.57 |
| 28 | 62.09 | 92.61 |
| 29 | 71.23 | 89.40 |
| 30 | 67.92 | 92.05 |
| 31 | 46.30 | 97.54 |
Result shows, m-phenylene diamine (MPD), cyclohexyl-1,3,5-tri-formyl chloride and mesopore silicon oxide spheres concentration all have material impact to the separating property of the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide; With the increase of m-phenylene diamine (MPD) and cyclohexyl-1,3,5-tri-formyl chloride concentration, the salt rejection rate of the nano combined reverse osmosis membrane of gained increases gradually, and water flux reduces gradually; With the increase of mesopore silicon oxide spheres concentration, the salt rejection rate of the nano combined reverse osmosis membrane of gained reduces gradually, and water flux increases gradually; Be 2w/v% in m-phenylene diamine (MPD) concentration, pyromellitic trimethylsilyl chloride is 0.1w/v%, and when mesopore silicon oxide spheres concentration is 0.04w/v%, the separating property of the nano combined reverse osmosis membrane of gained mesopore silicon oxide spheres/semi-aromatic polyamide is optimized the most.In addition, the concentration of camphorsulfonic acid and triethylamine, ultrafiltration support membrane aperture, oil phase solvent kind, the dip time in aqueous phase, the reaction time in oil phase and heat treatment temperature and time also have certain influence to the separating property of this nano combined reverse osmosis membrane.Compared with the pure semi-aromatic polyamide complex reverse osmosis membrane obtained under identical preparation condition, the separating property of this nano combined reverse osmosis membrane significantly improves, its water flux is about 1.49 times of pure semi-aromatic polyamide complex reverse osmosis membrane, and salt rejection rate still can remain on higher level.
Claims (10)
1. the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, it is characterized in that, the semi-aromatic polyamide function separating layer that this nano combined reverse osmosis membrane contains mesopore silicon oxide spheres by interfacial polymerization at ultrafiltration support membrane Surface Creation one deck is formed, and is specifically obtained by following preparation method:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine, dipping 0.5-10 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of m-phenylene diamine (MPD) is 0.5-5.0w/v%, and the concentration of camphorsulfonic acid is 0.5-4.6w/v%, and the concentration of triethylamine is 0.6-3.5w/v%;
(2) cyclohexyl-1,3,5-tri-formyl chloride and mesopore silicon oxide spheres to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of the formyl chloride of cyclohexyl-1,3,5-tri-described in described oil-phase solution is 0.05-0.6w/v%; The concentration of described mesopore silicon oxide spheres is 0.01-0.1w/v%; Described mesopore silicon oxide spheres is of a size of 20-200 nanometer, and mesoporous pore size is 2-20 nanometer;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.4-8 minute, thus the semi-aromatic polyamide Motor cortex of mesopore silicon oxide spheres is embedded with at ultrafiltration support membrane Surface Creation one deck, form the nano combined reverse osmosis membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined reverse osmosis membrane surface is excessive, heat-treat, heat treatment temperature is 70-90 DEG C, heat treatment time is 3-20 minute, finally can obtain the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide with deionized water rinsing.
2. the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 1, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
3. the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 2, is characterized in that, the aperture of described polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane is 40-100 nanometer.
4. the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 1, is characterized in that, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
5. the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 1, is characterized in that, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%; In oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%, and the concentration of mesopore silicon oxide spheres is 0.04w/v%.
6. a preparation method for the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide, is characterized in that, the method is carried out according to following steps:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine, dipping 0.5-10 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of m-phenylene diamine (MPD) is 0.5-5.0w/v%, and the concentration of camphorsulfonic acid is 0.5-4.6w/v%, and the concentration of triethylamine is 0.6-3.5w/v%;
(2) cyclohexyl-1,3,5-tri-formyl chloride and mesopore silicon oxide spheres to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of the formyl chloride of cyclohexyl-1,3,5-tri-described in described oil-phase solution is 0.05-0.6w/v%; The concentration of described mesopore silicon oxide spheres is 0.01-0.1w/v%; Described mesopore silicon oxide spheres is of a size of 20-200 nanometer, and mesoporous pore size is 2-20 nanometer;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.4-8 minute, thus the semi-aromatic polyamide Motor cortex of mesopore silicon oxide spheres is embedded with at ultrafiltration support membrane Surface Creation one deck, form the nano combined reverse osmosis membrane of nascent state;
(3) oil-phase solution that after taking out, removing described nascent state complex reverse osmosis membrane surface is excessive, heat-treat, heat treatment temperature is 70-90 DEG C, heat treatment time is 3-20 minute, finally can obtain the nano combined reverse osmosis membrane of mesopore silicon oxide spheres/semi-aromatic polyamide with deionized water rinsing.
7. the preparation method of the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 6, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
8. the preparation method of the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 6, is characterized in that, the aperture of described polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane is 40-100 nanometer.
9. the preparation method of the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 6, is characterized in that, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
10. the preparation method of the nano combined reverse osmosis membrane of a kind of mesopore silicon oxide spheres/semi-aromatic polyamide according to claim 6, is characterized in that, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%; In oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%, and the concentration of mesopore silicon oxide spheres is 0.04w/v%.
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