CN104923086A - Semi-aromatic polyamide compound reverse osmosis membrane and preparation method thereof - Google Patents
Semi-aromatic polyamide compound 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 semi-aromatic polyamide compound reverse osmosis membrane and a preparation method thereof. The compound reverse osmosis membrane is prepared by interfacial polymerization reaction of m-phenylenediamine and cyclohexyl-1,3,5-tri-formyl chloride on an ultrafiltration supporting membrane to form a layer of semi-aromatic polyamide macromolecule function separating layer, and the ultrafiltration supporting membrane can be uniformly coated with the semi-aromatic polyamide macromolecule function separating layer so as to obtain the compound reverse osmosis membrane with good performance. The semi-aromatic polyamide macromolecule function separating layer of the compound reverse osmosis membrane has excellent water molecule permeability and hydrophilic performance; a semi-aromatic polyamide macromolecule chain has excellent flexibility and a stable structure, so that the compound reverse osmosis membrane has the characteristics of high water flux and stable separation performance; the preparation method is simple, the operability is strong, the production cost is low, and excellent industrialized application prospects are achieved.
Description
Technical field
The invention belongs to membrane for water treatment technical field, be specifically related to a kind of semi-aromatic polyamide complex 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, and have broad application prospects, therefore such material causes the extensive concern of membrane material manufacturing enterprise and research institution.Polyamide complex reverse osmosis membrane usually with organic acyl chlorides and organic amine for primary raw material monomer is obtained 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 water flux 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 material.
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.But still there is salt rejection rate or the water flux weak point waiting separation aspect of performance on the low side at present prepared semi-aromatic polyamide complex reverse osmosis membrane, thus causes such reverse osmosis membrane in use energy consumption and high expensive.
Summary of the invention
To be solved by this invention is the technical problem how improving semi-aromatic polyamide complex reverse osmosis membrane separating property, a kind of semi-aromatic polyamide complex reverse osmosis membrane and preparation method thereof is provided, form one deck uniform semi-aromatic polyamide fractionated polymer absciss layer by interfacial polymerization on ultrafiltration support membrane surface and obtain, because semi-aromatic polyamide function separating layer has good hydrone permeability and hydrophilicity, and semi-aromatic polyamide macromolecular chain has good flexibility, such that this complex reverse osmosis membrane water flux is high, hydrophily and having good stability; 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:
A kind of semi-aromatic polyamide complex reverse osmosis membrane, the semi-aromatic polyamide function separating layer that this semi-aromatic polyamide complex reverse osmosis membrane is evenly applied at ultrafiltration support membrane Surface Creation one deck by interfacial polymerization and being formed, 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 0.5-4.0w/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) be immersed in again concentration be 0.05-0.5w/v% containing cyclohexyl-1,3, in the oil-phase solution of 5-tri-formyl chloride, carry out interface polymerization reaction, reaction time is 0.4-8 minute, thus at ultrafiltration support membrane Surface Creation one deck semi-aromatic polyamide Motor cortex, form nascent state complex reverse osmosis membrane;
(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, and heat treatment time is 3-20 minute, finally can obtain 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 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%, and in oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%.
A preparation method for semi-aromatic polyamide complex reverse osmosis membrane, 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 0.5-4.0w/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) be immersed in again concentration be 0.05-0.5w/v% containing cyclohexyl-1,3, in the oil-phase solution of 5-tri-formyl chloride, carry out interface polymerization reaction, reaction time is 0.4-8 minute, thus at ultrafiltration support membrane Surface Creation one deck semi-aromatic polyamide Motor cortex, form nascent state complex reverse osmosis membrane;
(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, and heat treatment time is 3-20 minute, finally can obtain 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 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%, and in oil-phase solution described in step (2), the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%.
The invention has the beneficial effects as follows:
The present invention is with m-phenylene diamine (MPD) and cyclohexyl-1,3,5-tri-formyl chloride is respectively as aqueous phase and oil phase reaction monomers, by interfacial polymerization at oil-water interfaces, make amido functional group and the cyclohexyl-1 of m-phenylene diamine (MPD), there is linear and network polymerization reaction in the acyl chlorides functional group of 3,5-tri-formyl chloride, thus forms one deck uniform semi-aromatic polyamide fractionated polymer absciss layer on ultrafiltration support membrane surface.Because polyamide bond and polyamide macromolecular chain have well chemistry and structural stability, the semi-aromatic polyamide reverse osmosis membrane prepared by the present invention has good separating property stability; Its preparation method process is simple simultaneously, workable, and preparation condition is easy to control, and has wide scale application prospect.
Semi-aromatic polyamide complex reverse osmosis membrane prepared by the present invention is compared with traditional aromatic polyamides reverse osmosis membrane materials, due to the existence of cyclohexyl functional group, the rigidity of semi-aromatic polyamide molecular structure can obviously reduce, this makes the compactness of this membrane material decline to some extent to a certain extent, and then the water flux of semi-aromatic polyamide reverse osmosis membrane is significantly increased; In addition, because semi-aromatic polyamide material has stronger hydrophily, be applied to reverse osmosis membrane preparation, the surface hydrophilicity of complex reverse osmosis membrane can be made to be improved significantly; And hydrophilic raising enhances the active force of film surface and hydrone, thus be also conducive to the lifting of this complex reverse osmosis membrane water flux.
And, compared with the semi-aromatic polyamide complex reverse osmosis membrane reported before, semi-aromatic polyamide complex reverse osmosis membrane prepared by the present invention, due to the improvement in preparation method and optimization, and the introducing of camphorsulfonic acid and triethylamine additive, its salt rejection rate is got a promotion, and water flux still can remain on higher level simultaneously, thus significantly improves the separating property of semi-aromatic polyamide reverse osmosis membrane.
Experiment shows, under 2000mg/L sodium chloride solution, 1.5MPa test pressure and 25 DEG C of solution temperature test conditions, the semi-aromatic polyamide complex reverse osmosis membrane water flux prepared by the present invention can reach 21.76 ~ 78.07L/m
2h, salt rejection rate can reach 68.74 ~ 98.95%.When the present invention takes the concentration of m-phenylene diamine (MPD) to be 2.0w/v%, when the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.1w/v%, 1.88 times of the aromatic polyamides 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 that concentration is 0.1w/v%; Again the polysulfones ultrafiltration support membrane that step (1) obtains is immersed in this oil-phase solution, reacted for 60 seconds, after taking-up, get rid of the oil-phase solution except striping excess surface; Thus at polysulfones ultrafiltration support membrane Surface Creation one deck semi-aromatic polyamide Motor cortex, form nascent state complex reverse osmosis membrane.
(3) by the nascent state complex reverse osmosis membrane that obtains 80 DEG C of baking oven interior heats process 5 minutes, then taking-up with deionized water rinsing for several times, obtain semi-aromatic polyamide complex reverse osmosis membrane.
Embodiment 2:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of m-phenylene diamine (MPD) is 0.5w/v%.
Embodiment 3:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of m-phenylene diamine (MPD) is 4w/v%.
Embodiment 4:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.05w/v%.
Embodiment 5:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of cyclohexyl-1,3,5-tri-formyl chloride is 0.5w/v%.
Embodiment 6:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of camphorsulfonic acid is 0.5w/v%.
Embodiment 7:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of camphorsulfonic acid is 4.6w/v%.
Embodiment 8:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of triethylamine is 0.6w/v%.
Embodiment 9:
Adopt embodiment 1 method to be prepared, its difference is only that the concentration of triethylamine is 3.5w/v%.
Embodiment 10:
Adopt embodiment 1 method to be prepared, its difference is only that the dip time of polysulfones ultrafiltration support membrane in aqueous phase solution is 0.5 minute.
Embodiment 11:
Adopt embodiment 1 method to be prepared, its difference is only that the dip time of polysulfones ultrafiltration support membrane in aqueous phase solution is 10 minutes.
Embodiment 12:
Adopt embodiment 1 method to be prepared, its difference is only that the reaction time of polysulfones ultrafiltration support membrane in oil-phase solution is 0.4 minute.
Embodiment 13:
Adopt embodiment 1 method to be prepared, its difference is only that the reaction time of polysulfones ultrafiltration support membrane in oil-phase solution is 8 minutes.
Embodiment 14:
Adopt embodiment 1 method to be prepared, its difference is only that oven temperature is 70 DEG C.
Embodiment 15:
Adopt embodiment 1 method to be prepared, its difference is only that oven temperature is 90 DEG C.
Embodiment 16:
Adopt embodiment 1 method to be prepared, its difference is only that heat treatment temperature is 3 minutes.
Embodiment 17:
Adopt embodiment 1 method to be prepared, its difference is only that heat treatment temperature is 20 minutes.
Embodiment 18:
Adopt embodiment 1 method to be prepared, its difference is only that the aperture of polysulfones ultrafiltration support membrane is 40 nanometers.
Embodiment 19:
Adopt embodiment 1 method to be prepared, its difference is only that the aperture of polysulfones ultrafiltration support membrane is 100 nanometers.
Embodiment 20:
Adopt embodiment 1 method to be prepared, its difference is only that ultrafiltration support membrane selects aperture to be the polyether sulfone ultrafiltration support membrane of 40 nanometers.
Embodiment 21:
Adopt embodiment 1 method to be prepared, its difference is only that ultrafiltration support membrane selects aperture to be the polyether sulfone ultrafiltration support membrane of 60 nanometers.
Embodiment 22:
Adopt embodiment 1 method to be prepared, its difference is only that ultrafiltration support membrane selects aperture to be the polyether sulfone ultrafiltration support membrane of 100 nanometers.
Embodiment 23:
Adopt embodiment 1 method to be prepared, its difference is only that the solvent in oil-phase solution is normal hexane.
Embodiment 24:
Adopt embodiment 1 method to be prepared, its difference is only that the solvent in oil-phase solution is normal heptane.
Embodiment 25:
For the difference of aromatic polyamide composite reverse osmosis membrane in separating property prepared under showing semi-aromatic polyamide complex reverse osmosis membrane prepared by the present invention and the same terms, embodiment 1 method is adopted to prepare aromatic polyamide composite reverse osmosis membrane, its difference is only cyclohexyl-1,3,5-tri-formyl chloride changes pyromellitic trimethylsilyl chloride into.
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 | 46.30 | 97.54 |
| 2 | 78.07 | 68.74 |
| 3 | 41.57 | 97.89 |
| 4 | 67.34 | 79.34 |
| 5 | 21.79 | 98.21 |
| 6 | 40.12 | 94.24 |
| 7 | 48.32 | 96.60 |
| 8 | 39.67 | 95.31 |
| 9 | 41.65 | 92.45 |
| 10 | 59.26 | 87.77 |
| 11 | 45.10 | 97.84 |
| 12 | 61.34 | 82.33 |
| 13 | 21.76 | 98.95 |
| 14 | 49.53 | 94.12 |
| 15 | 41.34 | 98.09 |
| 16 | 47.88 | 96.72 |
| 17 | 37.86 | 97.82 |
| 18 | 45.28 | 97.44 |
| 19 | 47.13 | 97.56 |
| 20 | 42.51 | 96.21 |
| 21 | 44.36 | 96.98 |
| 22 | 46.88 | 97.32 |
| 23 | 44.30 | 96.84 |
| 24 | 45.43 | 97.32 |
| 25 | 24.62 | 98.33 |
Result shows, the separating property of m-phenylene diamine (MPD) and cyclohexyl-1,3,5-tri-formyl chloride concentration double aromatic polyamide composite reverse osmosis membrane has material impact; With the increase of both concentration, the salt rejection rate of gained semi-aromatic polyamide complex reverse osmosis membrane increases gradually, water flux reduces gradually, be 2w/v% in phenylenediamine concentration, cyclohexyl-1, when 3,5-tri-formyl chloride is 0.1w/v%, the separating property of gained semi-aromatic polyamide complex reverse osmosis membrane is optimized the most.In addition, the concentration of camphorsulfonic acid and triethylamine, ultrafiltration support membrane aperture, oil phase solvent kind, in aqueous phase, the separating property tool of dip time, reaction time in oil phase and heat treatment temperature and time also double aromatic polyamide composite reverse osmosis membrane has a certain impact.Compared with traditional aromatic polyamides reverse osmosis membrane, the separating property of semi-aromatic polyamide reverse osmosis membrane significantly improves, and its water flux is about 1.88 times of aromatic polyamides reverse osmosis membrane.
Claims (10)
1. a semi-aromatic polyamide complex reverse osmosis membrane, it is characterized in that, the semi-aromatic polyamide function separating layer that this semi-aromatic polyamide complex reverse osmosis membrane is evenly applied at ultrafiltration support membrane Surface Creation one deck by interfacial polymerization and being formed, 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 0.5-4.0w/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) be immersed in again concentration be 0.05-0.5w/v% containing cyclohexyl-1,3, in the oil-phase solution of 5-tri-formyl chloride, carry out interface polymerization reaction, reaction time is 0.4-8 minute, thus at ultrafiltration support membrane Surface Creation one deck semi-aromatic polyamide Motor cortex, form nascent state complex reverse osmosis membrane;
(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, and heat treatment time is 3-20 minute, finally can obtain semi-aromatic polyamide complex reverse osmosis membrane with deionized water rinsing.
2. a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
3. a kind of semi-aromatic polyamide complex reverse osmosis membrane 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. a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, is characterized in that, the solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
5. a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, it is characterized in that, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%, cyclohexyl-1 in oil-phase solution described in step (2), the concentration of 3,5-tri-formyl chloride is 0.1w/v%.
6. a preparation method for semi-aromatic polyamide complex reverse osmosis membrane, 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 0.5-4.0w/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) be immersed in again concentration be 0.05-0.5w/v% containing cyclohexyl-1,3, in the oil-phase solution of 5-tri-formyl chloride, carry out interface polymerization reaction, reaction time is 0.4-8 minute, thus at ultrafiltration support membrane Surface Creation one deck semi-aromatic polyamide Motor cortex, form nascent state complex reverse osmosis membrane;
(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, and heat treatment time is 3-20 minute, finally can obtain semi-aromatic polyamide complex reverse osmosis membrane with deionized water rinsing.
7. the preparation method of a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or polyether sulfone ultrafiltration support membrane.
8. the preparation method of a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 7, 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 a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, is characterized in that, the solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
10. a kind of semi-aromatic polyamide complex reverse osmosis membrane according to claim 1, it is characterized in that, in aqueous phase solution described in step (1), the concentration of m-phenylene diamine (MPD) is 2w/v%, cyclohexyl-1 in oil-phase solution described in step (2), the concentration of 3,5-tri-formyl chloride is 0.1w/v%.
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| CN107596930A (en) * | 2017-08-24 | 2018-01-19 | 江苏亚峰科技集团有限公司 | A kind of reverse osmosis film |
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| CN107737533A (en) * | 2017-10-25 | 2018-02-27 | 浙江工业大学 | A kind of preparation method of beta cyclodextrin reverse osmosis membrane |
| CN110252152A (en) * | 2019-07-03 | 2019-09-20 | 合肥学院 | It is a kind of with compared with the flexible organic solvent reverse osmosis membrane of high permeating flux, preparation method and application |
| CN110252152B (en) * | 2019-07-03 | 2021-05-25 | 合肥学院 | Flexible organic solvent reverse osmosis membrane with high permeation flux, preparation method and application |
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| CN111495217B (en) * | 2020-04-14 | 2022-07-08 | 北京上远科技有限公司 | Preparation method of surface-modified pollution-resistant composite nanofiltration membrane |
| CN115007004A (en) * | 2022-05-16 | 2022-09-06 | 天津工业大学 | Preparation method of hydrophilic charged high-pressure reverse osmosis membrane based on chicken protein/aromatic polyamide |
| CN115007004B (en) * | 2022-05-16 | 2023-12-26 | 天津工业大学 | Preparation method of hydrophilic charged high-voltage reverse osmosis membrane based on egg albumin/aromatic polyamide |
| CN118649565A (en) * | 2024-08-13 | 2024-09-17 | 自然资源部天津海水淡化与综合利用研究所 | High-pressure reverse osmosis membrane based on epsilon-caprolactam for accurately constructing polyamide network and preparation method thereof |
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