CN111589310A - Strong anti-pollution composite gradient ultrafiltration membrane and preparation method thereof - Google Patents
Strong anti-pollution composite gradient ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The ultrafiltration membrane is prepared by chemically bonding the surface of graphene oxide with magnetic nanoparticles to form a graphene oxide-magnetic nanoparticle hybrid, uniformly dispersing the graphene oxide-magnetic nanoparticle hybrid, organic fluorosilane and a pore-forming agent in a high-molecular polysulfone PSf solution, adopting the solution to cast a membrane forming method, and carrying out magnetic field assisted non-solvent induced phase conversion. Can overcome the defects that organic pollutants are easy to adhere to and block membrane pores, the separation efficiency is low, the membrane is not easy to clean, the flux recovery rate is low and the like in the ultrafiltration separation process of the traditional polymer membrane material.
Description
Technical Field
The invention belongs to the technical field of functional high-molecular-weight membrane materials, and particularly relates to a gradient ultrafiltration membrane based on magnetic field induction and in-situ hydrolysis and a preparation method thereof, namely a strong anti-pollution composite gradient ultrafiltration membrane and a preparation method thereof.
Background
The safety and shortage of water resources have been recognized as one of the important factors for human basic survival and global development. Nearly 80% of wastewater in the world is directly discharged without being treated, and the human health and the natural ecosystem are seriously threatened. The traditional water purification technologies such as flocculation, adsorption and distillation severely limit the practical application range due to complex process, large energy consumption and high cost. In order to pursue more economical and practical high-efficiency water treatment technology, membrane separation technology attracts attention due to its strong adaptability, low energy consumption, high selectivity and simple operation, is a high and new technology developed in recent ten years, and has been widely applied in the fields of food, medicine, seawater desalination, petrochemical industry and the like. However, the inherent hydrophobicity of the traditional polymer membrane material is easy to cause membrane pollution in the sewage treatment process, which causes the problems of membrane pore blockage, water flux reduction, separation efficiency reduction, difficult cleaning and the like, and thus the application of the membrane separation technology is greatly limited. Therefore, the construction of an effective membrane fouling defense mechanism is of great significance for the preparation of ultrafiltration membranes for water purification and regeneration.
Graphene oxide GO is an important and widely researched graphene derivative, and the surface of the graphene oxide GO contains a large number of polar groups such as hydroxyl, carboxyl, epoxy and the like, so that the graphene oxide GO can stably exist in an aqueous solution for a long time. The GO is introduced into an ultrafiltration membrane matrix by utilizing the characteristics of good hydrophilic performance and easy chemical modification of the surface of GO, so that the excellent anti-pollution performance of the ultrafiltration membrane becomes an important strategy for designing and preparing the strong anti-pollution ultrafiltration membrane. Patent CN106582327A reports the introduction of silver-loaded GO into polyvinyl alcohol ultrafiltration membranes, resulting in membrane separation materials with excellent anti-fouling properties.
However, the hydrophilic components introduced by conventional blending methods are mostly uniformly dispersed in the ultrafiltration membrane matrix. Compared with the interior of a membrane matrix, the membrane surface is a main place for membrane pollution, so that the introduced anti-pollution components are mainly gathered on the membrane surface and are not uniformly dispersed in the whole membrane material, the anti-pollution performance of the membrane can be effectively improved, the dosage of expensive nano hydrophilic components is greatly reduced, and the performance benefit is maximized. In addition, in order to improve the recycling rate of the ultrafiltration membrane, the design and development of an anti-pollution ultrafiltration membrane with high water flux recovery rate are also important points of attention.
Disclosure of Invention
The invention provides a strong anti-pollution composite gradient ultrafiltration membrane and a preparation method thereof, aiming at the defects that organic pollutants are easy to adhere to block membrane pores, the separation efficiency is low, the membrane pores are difficult to clean, the flux recovery rate is low and the like in the ultrafiltration separation process of the traditional polymer membrane material.
In order to achieve the purpose, the invention adopts the technical scheme that: a strong anti-pollution composite gradient ultrafiltration membrane is prepared by chemically bonding magnetic nano particles on the surface of graphene oxide to form a graphene oxide-magnetic nano particle hybrid, uniformly dispersing the graphene oxide-magnetic nano particle hybrid, organic fluorosilane and a pore-forming agent in a high-molecular polysulfone PSf solution, adopting a solution casting film-forming method, and carrying out magnetic field assisted non-solvent induced phase conversion.
Preferably, the magnetic nanoparticles are ferroferric oxide (Fe)3O4) Cobalt tetraoxydi ferrite (CoFe)2O4) And nickel ferrite (NiFe)2O4) One or more of the above, preferably ferroferric oxide Fe3O4。
Preferably, the organofluorosilane of the present invention is one or more of heptadecafluorodecyltrimethoxysilane (FAS), tridecafluorooctyltriethoxysilane (FOS) and nonafluorohexyltrimethoxysilane (FHS), and the preferred organofluorosilane is heptadecafluorodecyltrimethoxysilane (FAS).
The pore-forming agent is one or more of PEG2000, PVP K30 and LiCl, and the preferred pore-forming agent is PVPK 30.
The invention also provides a preparation method of the strong anti-pollution composite gradient ultrafiltration membrane, which comprises the following specific steps:
(1) grafting magnetic nanoparticles on the surface of graphene oxide: uniformly dispersing graphene oxide GO in an aqueous solution by using ultrasound, adding GO with carboxyl functional groups on the surface activated by an NHS/EDC catalyst, adding magnetic nanoparticles, and violently stirring to obtain a graphene oxide-magnetic nanoparticle hybrid;
(2) selecting a high molecular polymer PSf as a membrane matrix, dissolving the high molecular polymer PSf in N, N-dimethylacetamide (DMAc), and then adding the graphene oxide-magnetic nanoparticle hybrid prepared by the method in the step (1), organic fluorosilane and a pore-foaming agent; ultrasonic dispersion, standing and vacuum defoaming are carried out, then the mixed solution is poured on a glass plate under the action of a magnetic field, a liquid film with a specified thickness is scraped, and then the mixed solution is immersed into a coagulating bath to be solidified into a film, so that the composite gradient ultrafiltration membrane is obtained.
Preferably, the mass ratio of GO to magnetic nanoparticles in the step (1) is 5: 1-1: 5, and more preferably 1: 3.
Preferably, the mass ratio of the graphene oxide-magnetic nanoparticle hybrid to the organofluorosilane in the step (2) is 5: 1-1: 5, and more preferably 1: 1.
Preferably, the magnetic field auxiliary time in the step (2) is 30-90 s, and more preferably 60 s.
Preferably, the addition amounts of the graphene oxide-magnetic nanoparticle hybrid and the organofluorosilane in the mixed solution in the step (2) are respectively 0.1-0.5 wt% (the concentrations of the graphene oxide-magnetic nanoparticle hybrid and the organofluorosilane in the mixed solution are both 0.1-0.5 wt%), and more preferably 0.3 wt%.
Preferably, the coagulation bath in step (2) is one or more of deionized water, ethanol and isobutanol, and further preferably deionized water.
In the step (2), the adding amount of the pore-foaming agent is 1-5% (by mass in the mixed solution).
In the step (2), the magnetic field preferably adopts a neodymium iron boron permanent magnet with the coercive force of 868KA/m, and the neodymium iron boron permanent magnet is placed 5cm above a glass plate paved with pouring liquid during film making.
Compared with the traditional solution blending technology, the invention has the following remarkable beneficial effects:
1. the GO-magnetic nano particle hybrid is induced to migrate directionally and anchored on the surface of the membrane by a magnetic field for the first time, and in the phase transformation process, a long-chain fluoroalkyl chain generated by in-situ hydrolysis of organic fluorosilane can be combined with the GO-magnetic nano particle hybrid, so that better hydrophilic performance and pollution resistance are provided for the GO-magnetic nano particle hybrid, the reaction condition is mild, and the operation is simple and convenient.
2. The gradient ultrafiltration membrane prepared by the method has large water flux (the highest pure water flux is 323.2 L.m)-2·h-1) The removal rate of organic pollutants is high (the highest retention rate of bovine serum albumin BSA is 98%), the cleaning is easy after pollution, the recovery rate of water flux is high (the lowest irreversible pollution proportion is 2%, the highest recovery rate of water flux is 98%), and the like. In addition, the ultrafiltration membrane still keeps higher membrane flux and anti-pollution performance after multiple tests, the preparation process of the ultrafiltration membrane is simple, the repeatability is good, and the large-scale production is easy to realize, so that the ultrafiltration membrane can be called as a strong anti-pollution gradient ultrafiltration membrane.
3. The ultrafiltration membrane of the application is different from the traditional graphene-Fe3O4Magnetic aerogel of this graphene-Fe3O4Magnetic aerogel is used for adsorbing the dyestuff pollutant, relies on the porous structure of aerogel to adsorb the material, and magnetism plays the separation of convenient follow-up aerogel and retrieves, and the core is the aerogel. The application of the magnetic graphene-Fe3O4The nano filler is introduced into the ultrafiltration membrane as a nano filler, and is relatively gathered near the surface of the ultrafiltration membrane by utilizing the characteristic that the nano filler can directionally move under the action of a magnetic field, so that the ultrafiltration membrane is endowed with larger water flux and better pollution resistance, and the core of the technical scheme of the application is the pollution-resistant ultrafiltration membrane. Further magnetic graphene-Fe in the present application3O4Because a large number of carboxyl functional groups exist on the surface of the nano hybrid, organic fluorosilane in the film casting liquid can generate hydrolysis reaction when being immersed into water to form a film, and further the fluoroalkyl with low surface energy is bonded to graphene-Fe in a long chain manner3O4On the nano hybrid, the anti-pollution performance of the final ultrafiltration membrane can be further improved. In summary, this patent refers to graphene-Fe3O4The final surface of the nano hybrid is also chemically embedded with fluoroalkyl long chain generated by hydrolysis of fluorosilane, and graphene-Fe mentioned in the above patent3O4And are not the same.
4. In the prior art, magnetic nanoparticles are dispersed in a polymer solution and then cast on a glass plate, and then a pervaporation hybrid membrane is prepared through the whole action of a magnetic field and forced air drying. The anti-pollution ultrafiltration membrane prepared by the method is an asymmetric porous membrane, a large number of pore channels are formed in the membrane, and a magnetic field is not continuously applied but is applied for a period of time in the membrane preparation process, so that the magnetic nanoparticles can be non-uniformly dispersed in the ultrafiltration membrane in a gradient manner, namely when graphene-Fe is used3O4After the magnetic nanoparticles and the polymer solution are mixed, the mixed solution is placed in a magnetic field for a period of time to enable the magnetic nanoparticles to migrate directionally, but the viscosity of the polymer solution is high, the migration of the magnetic nanoparticles is delayed by the viscosity of the solution, so that the magnetic nanoparticles are finally distributed in the polymer solution in a non-uniform mode (the relative content of the magnetic particles in the area close to the surface of the solution is higher than that in the area far from the surface of the solution), then the magnetic field is removed, the casting solution is immersed in water to form a film, and in the process, the organic fluorosilane in the casting solution can form a film in the magnetic graphene-Fe3O4Hydrolysis reaction is carried out under the action of a large number of functional groups such as carboxyl on the surface, and further the fluoroalkyl with low surface energy is bonded to the graphene-Fe in a long chain manner3O4And on the magnetic nano hybrid, the final ultrafiltration membrane is endowed with better anti-pollution performance. In summary, the present application prepares a porous film rather than the existing dense film, the magnetic field of the present application is applied in a partial process, and in addition, the magnetic particles induced by the magnetic field of the present application can be further bonded with fluoroalkyl long chains in the film forming process.
Drawings
FIG. 1PSf Ultrafiltration Membrane (M0), PSf/GO-Fe3O4FAS ultrafiltration membrane (M2) and PSf/GO-Fe3O4Surface, cross-sectional SEM, AFM and EDX profiles of/FAS gradient ultrafiltration membrane (MM 2).
FIG. 2PSf Ultrafiltration Membrane (M0), PSf/GO-Fe3O4FAS ultrafiltration membrane (M2) and PSf/GO-Fe3O4Water flux and BSA retention for a/FAS gradient ultrafiltration membrane (MM2) are plotted.
FIG. 3 is a graph comparing the water flux recovery rate and the reversible fouling rate of PSf ultrafiltration membrane (M0), PSf/GO-Fe3O4/FAS ultrafiltration membrane (M2) and PSf/GO-Fe3O4/FAS gradient ultrafiltration membrane (MM 2).
Wherein M0 is a pure PSf ultrafiltration membrane and does not contain any magnetic nanoparticles; m2 is an ultrafiltration membrane prepared without applying a magnetic field, and the magnetic nano hybrid is uniformly distributed in the membrane matrix; MM2 is an ultrafiltration membrane prepared under the application of a magnetic field, and the magnetic nano-hybrids are non-uniformly gradient distributed in the membrane matrix.
Detailed Description
The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples.
The ultrasonic wave of this application adopts probe formula ultrasonic wave dispersion appearance, and power 600W adopts intermittent type formula supersound mode (supersound 10s, pauses 2s), and the supersound time 30min can satisfy the requirement.
Example 1
GO surface grafting Fe3O4: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. Followed by the addition of 50mg of Fe3O4Stirring for 24h at normal temperature, centrifuging, washing with water, and drying to obtain GO-Fe3O4A nano hybrid.
Preparing a PSf-based composite gradient ultrafiltration membrane: 0.3 wt% of GO-Fe3O40.3 wt% of FAS is ultrasonically and uniformly dispersed in DMAc (N, N-dimethylacetamide) solution with the concentration of 19% of polysulfone PSf, 3% of PVP-K30 pore-forming agent is added at the same time, after the solution is completely dissolved, the solution is kept stand and defoamed for 8 hours, pouring liquid on a glass plate, and scraping the film to the thickness of the pouring liquidControlling the thickness to be 200 mu m, then placing a neodymium iron boron permanent magnet with the coercive force of 868KA/m above the glass plate by 5cm, immersing the glass plate into deionized water after 60s, and preparing to obtain PSf/GO-Fe3O4a/FAS composite gradient ultrafiltration membrane. The pure water flux of the ultrafiltration membrane is 323.2 L.m-2·h-1The retention rate of BSA is 98%, the irreversible contamination ratio is 2%, and the recovery rate of water flux is 98%.
The relevant membrane separation and anti-pollution performance tests show that (figures 2 and 3): compared with pure PSf ultrafiltration membrane (M0) and PSf/GO-Fe without magnetic field application3O4FAS ultrafiltration membrane (M2), PSf/GO-Fe prepared by the patent3O4The composite gradient ultrafiltration membrane/FAS (MM2) has larger water flux, higher water flux recovery rate and lower irreversible pollution rate, and simultaneously maintains excellent pollutant (BSA) retention rate, which indicates that the composite gradient ultrafiltration membrane prepared by the method has excellent membrane separation and anti-pollution performance.
Example 2
GO surface grafting Fe3O4: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. Followed by the addition of 50mg of Fe3O4Stirring for 24h at normal temperature, centrifuging, washing with water, and drying to obtain GO-Fe3O4A nano hybrid.
Preparing a PSf-based composite gradient ultrafiltration membrane: 0.3 wt% of GO-Fe3O4Uniformly dispersing 0.3 wt% of FOS in a DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping a film to control the thickness to be 200 mu m, then placing a neodymium iron boron permanent magnet with the coercive force of 868KA/m above the glass plate by 5cm, immersing the glass plate into deionized water after 60 seconds, and preparing to obtain PSf/GO-Fe3O4the/FOS composite gradient ultrafiltration membrane. The pure water flux of the ultrafiltration membrane is 284.6 L.m-2·h-1The retention rate of BSA is 97%, the irreversible contamination ratio is 5%, and the recovery rate of water flux is 95%.
Example 3
GO surface grafted CoFe2O4: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. Followed by the addition of 50mg of CoFe2O4Stirring for 24h at normal temperature, centrifuging, washing with water, and drying to obtain GO-CoFe2O4A nano hybrid.
Preparing a PSf-based composite gradient ultrafiltration membrane: 0.3 wt% of GO-CoFe2O40.3 wt% of FAS is ultrasonically and uniformly dispersed in a DMAc solution with the concentration of 19% of polysulfone PSf, 3% of PEG2000 pore-forming agent is added at the same time, after the FAS is completely dissolved, the mixture is kept stand and defoamed for 8 hours, pouring liquid onto a glass plate, scraping a film, controlling the thickness to be 200 mu m, then placing a neodymium iron boron permanent magnet with the coercive force of 868KA/m above the glass plate by 5cm, and after 60 seconds, immersing the glass plate into deionized water to prepare PSf/GO-CoFe2O4a/FAS composite gradient ultrafiltration membrane. The pure water flux of the ultrafiltration membrane was 185.4 L.m-2·h-1The retention rate of BSA is 98%, the irreversible contamination ratio is 6%, and the recovery rate of water flux is 94%.
Example 4
GO surface grafted NiFe2O4: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. Followed by the addition of 50mg of NiFe2O4Stirring for 24h at normal temperature, centrifuging, washing with water, and drying to obtain GO-NiFe2O4A nano hybrid.
Preparing a PSf-based composite gradient ultrafiltration membrane: 0.3 wt% of GO-NiFe2O4Uniformly dispersing 0.3 wt% of FHS in a DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of LiCl pore-forming agent, standing and defoaming for 8 hours after the FHS is completely dissolved, pouring liquid on a glass plate, scraping a film, controlling the thickness to be 200 mu m, then placing a neodymium iron boron permanent magnet with the coercive force of 868KA/m above the glass plate by 5cm, and immersing the glass plate into deionized water after 60 seconds to prepare the PSf/GO-NiFe2O4the/FHS composite gradient ultrafiltration membrane. The pure water flux of the ultrafiltration membrane is 271.8 L.m-2·h-1The retention rate of BSA is 96%, the irreversible contamination ratio is 9%, and the recovery rate of water flux is 91%.
Furthermore, by assaying different ultrafiltration membranes, comparative analysis of the data measured in FIGS. 1-3 can be understood: fig. 1SEM shows that MM2 ultrafiltration membranes have significantly increased surface pore density and uniform cross-sectional finger-like pore shape compared to M0 and M2, which contributes to increased water flux of the ultrafiltration membrane. As can be seen in AFM, the surface roughness of MM2 is greatest, which helps the film adsorb water molecules, increasing water flux. And the EDX analysis of the membrane surface proves that the content of the magnetic nano hybrid on the surface of the MM2 membrane is higher under the action of a magnetic field. Figure 2 illustrates that MM2 ultrafiltration membranes under magnetic field have higher water flux while maintaining good contaminant rejection compared to M0 and M2. Fig. 3 shows that the MM2 ultrafiltration membrane under the action of the magnetic field has the highest recovery rate of water flux and the lowest irreversible contamination rate, compared with M0 and M2, which indicates that the MM2 ultrafiltration membrane has more excellent anti-contamination performance.
In the three drawings, M2 is an ultrafiltration membrane prepared under the condition of not applying a magnetic field, the anti-pollution components in the membrane are uniformly dispersed in a membrane matrix, and MM2 is an ultrafiltration membrane prepared after applying a magnetic field, the anti-pollution components in the membrane are non-uniformly dispersed in the membrane matrix in a gradient manner, as can be seen from the attached drawings 2 and 3, MM2 is superior to M2 in terms of water flux, water flux recovery rate and reversible pollution rate, and conversely, the fact that the anti-pollution components required by the MM2 ultrafiltration membrane are less than those required by the M2 ultrafiltration membrane if the same anti-pollution performance is achieved can be inferred. This particular ultrafiltration membrane and processing regime of the present application is well established as superior to conventional ultrafiltration membranes.
Claims (10)
1. A strong anti-pollution composite gradient ultrafiltration membrane is characterized in that: the ultrafiltration membrane is prepared by chemically bonding the surface of graphene oxide with magnetic nanoparticles to form a graphene oxide-magnetic nanoparticle hybrid, then uniformly dispersing the graphene oxide-magnetic nanoparticle hybrid, organic fluorosilane and a pore-forming agent in a high-molecular polysulfone PSf solution, and performing magnetic field assisted non-solvent induced phase conversion by adopting a solution casting method.
2. The strong anti-pollution composite gradient ultrafiltration membrane according to claim 1, wherein: the magnetic nano particles are one or more of ferroferric oxide, cobalt ferrate and nickel ferrite, and the ferroferric oxide is preferably selected.
3. The strong anti-pollution composite gradient ultrafiltration membrane according to claim 1, wherein: the organic fluorosilane is one or more of heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane and nonafluorohexyltrimethoxysilane; preferred is heptadecafluorodecyltrimethoxysilane.
4. The strong anti-pollution composite gradient ultrafiltration membrane according to claim 1, wherein: the pore-forming agent is one or more of PEG2000, PVP K30 and LiCl; preferably PVP K30.
5. A preparation method of a strong anti-pollution composite gradient ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following specific steps:
(1) grafting magnetic nanoparticles on the surface of graphene oxide: uniformly dispersing graphene oxide GO in an aqueous solution by using ultrasound, adding GO with carboxyl functional groups on the surface activated by an NHS/EDC catalyst, adding magnetic nanoparticles, and violently stirring to obtain a graphene oxide-magnetic nanoparticle hybrid;
(2) selecting a high molecular polymer PSf as a membrane matrix, dissolving the high molecular polymer PSf in N, N-dimethylacetamide (DMAc), and then adding the graphene oxide-magnetic nanoparticle hybrid prepared by the method in the step (1), organic fluorosilane and a pore-foaming agent; ultrasonic dispersion, standing and vacuum defoaming are carried out, then the mixed solution is poured on a glass plate under the action of a magnetic field, a liquid film with a specified thickness is scraped, and then the mixed solution is immersed into a coagulating bath to be solidified into a film, so that the composite gradient ultrafiltration membrane is obtained.
6. The preparation method of the strong anti-pollution composite gradient ultrafiltration membrane according to claim 5, characterized in that: in the step (1), the mass ratio of GO to the magnetic nanoparticles is 5: 1-1: 5.
7. The preparation method of the strong anti-pollution composite gradient ultrafiltration membrane according to claim 5, characterized in that: in the step (2), the mass ratio of the graphene oxide-magnetic nanoparticle hybrid to the organofluorosilane is 5: 1-1: 5.
8. The preparation method of the strong anti-pollution composite gradient ultrafiltration membrane according to claim 5, characterized in that: the magnetic field auxiliary time in the step (2) is 30-90 s, and more preferably 60 s.
9. The preparation method of the strong anti-pollution composite gradient ultrafiltration membrane according to claim 5, characterized in that: the addition amounts of the graphene oxide-magnetic nanoparticle hybrid and the organofluorosilane in the mixed solution obtained in the step (2) are respectively 0.1-0.5 wt%.
10. The preparation method of the strong anti-pollution composite gradient ultrafiltration membrane according to claim 5, characterized in that: in the step (2), the coagulating bath is one or more of deionized water, ethanol and isobutanol; in the step (2), the adding amount of the pore-foaming agent is 1-5%; and (3) in the step (2), the magnetic field adopts a neodymium iron boron permanent magnet with the coercive force of 868KA/m, and the neodymium iron boron permanent magnet is placed 5cm above the glass plate paved with the pouring liquid during film preparation.
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Cited By (5)
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| CN113289506A (en) * | 2021-06-15 | 2021-08-24 | 江南大学 | Asymmetric magnetic oxygen-nitrogen separation membrane and preparation method thereof |
| CN113318611A (en) * | 2021-05-31 | 2021-08-31 | 天津工业大学 | Hollow fiber ultrafiltration membrane with lasting high pollution resistance and preparation method thereof |
| CN114797472A (en) * | 2022-05-20 | 2022-07-29 | 北京赛诺膜技术有限公司 | Forward osmosis composite membrane prepared by magnetic field assisted thermally induced phase separation method and preparation method thereof |
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| CN114797472A (en) * | 2022-05-20 | 2022-07-29 | 北京赛诺膜技术有限公司 | Forward osmosis composite membrane prepared by magnetic field assisted thermally induced phase separation method and preparation method thereof |
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