CN111282440B - Composite nanofiltration membrane with environmental responsiveness and preparation method thereof - Google Patents
Composite nanofiltration membrane with environmental responsiveness and preparation method thereof Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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Abstract
The invention relates to a composite nanofiltration membrane with environmental responsiveness and a preparation method thereof. The composite nanofiltration membrane has excellent separation performance, has unique environmental responsiveness, and can realize controllable adjustment of permeability on the premise of maintaining selectivity; the preparation method is simple and convenient to operate, mild in reaction conditions and good in application prospect.
Description
Technical Field
The invention belongs to the field of nanofiltration membranes, and particularly relates to a composite nanofiltration membrane with environmental responsiveness and a preparation method thereof.
Background
The nanofiltration membrane has the aperture within the nanometer range and the molecular weight cutoff of 200-1000 Da, can efficiently separate salts of univalent or multivalent ions, and is widely applied to water treatment. The traditional nanofiltration membrane is mainly formed by interfacial polymerization of diamine and acyl chloride on a porous support layer.
In recent years, in order to further improve the separation performance of the nanofiltration membrane, researchers have introduced an intermediate layer between the support layer and the polyamide layer for control. The middle layer can control the interfacial polymerization process to reduce the thickness of the polyamide layer and reduce the water transportation resistance, and can increase the surface roughness and the permeation surface area. Interfacial polymerization on a porous support layer carrying a cadmium hydroxide nanowire intermediate layer was first reported in Science,2015,348,1347, to produce a rugged polyamide layer with wrinkles less than 10nm thick. Cadmium hydroxide nanowires can also be dissolved with HCl solution to form additional nanochannels. However, the cadmium hydroxide nanowires can be removed only by using HCl solution, which is not environment-friendly. Chemical Science (Chemical Science,2019,10,9077) reports a two-in-one strategy to prepare hyper-osmotic nanofiltration membranes using Covalent Organic Framework (COF) nanofiber scaffold mediated interfacial polymerization. The COF nanofiber support not only regulates and controls the interfacial polymerization process to generate an ultrathin polyamide layer, but also provides a rough substrate for the expansion of the actual area of the polyamide layer due to the fact that the COF nanofiber support can spontaneously change into an uneven structure, and the water permeation area is increased. However, the process of preparing COFs is complicated.
For the improvement of membrane performance, it is also generally involved in the development of its functionality, such as the development of a membrane with environmental stimulus responsiveness. For example, Journal of membrane science (2019,580,117) forms a dense PAA @ PS layer by depositing PAA @ PS core-shell nanoparticles on a porous base film to obtain a pH-responsive membrane with a nanostructure. The permeation flux of the membrane varies at different pH, while also exhibiting different selectivity for different sized particles. P (NIPAM-co-4VP) nanoparticles of PNIPAM shell P4VP core were blended with polyvinylidene fluoride in Journal of Membrane science (Journal of membrane science,2018,564,53) to prepare a rapidly reversible temperature and pH dual-response gated membrane by phase inversion. The aperture of the prepared membrane is increased along with the increase of temperature and pH, so that the water flux is increased, and meanwhile, the release of lysozyme can be realized.
Generally, the larger the pore size, the greater the permeability, however the pore size also determines the selectivity of the membrane for the separation of particles of different particle size. Therefore, the existing separation membrane with environmental responsiveness is often accompanied by selectivity change while permeability changes under the stimulation of environment, and the controllable regulation transmission of the separation membrane under different environments is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a composite nanofiltration membrane with environmental responsiveness and a preparation method thereof, wherein the composite nanofiltration membrane has a wrinkled ultrathin separation surface layer and excellent separation performance; by using external environmental stimulation, the permeability can be effectively regulated and controlled, and meanwhile, the selectivity is kept unchanged.
The invention provides a composite nanofiltration membrane with environmental responsiveness, which comprises a porous support membrane, an environmental responsiveness nano particle intermediate layer and a separation surface layer.
The porous support membrane is polysulfone, polyethersulfone, polyacrylonitrile, polyvinylidene fluoride porous membrane or ultrafiltration membrane with surface modified by hydrophilic.
The environment-responsive nanoparticles are core-shell structure nanoparticles with hard sphere nanoparticles as cores and environment-responsive polymers as shells or nanoparticles directly formed by the environment-responsive polymers. The size of the environment-responsive nanoparticles is 1-800 nm.
The hard spherical nano particles are silicon dioxide SiO2One or more of polystyrene PS and polymethyl methacrylate PMMA; the environment-responsive polymer is one of a temperature-responsive polymer, a pH-responsive polymer, and a temperature-pH dual-responsive copolymer.
The temperature-responsive polymer is one or more of poly (N-isopropylacrylamide) PNIPAM, poly N, N-diethylacrylamide PDEAM, poly (N-vinylcaprolactam) PVCL, polymethyl vinyl ether PVME, polyoxypropylene PPO and polyoxyethylene PEO; the pH responsive polymer is one or more of polyacrylic acid (PAA), polymethacrylic acid (PMAA), polydimethylaminoethyl methacrylate (PDMAEMA), poly-4-vinylpyridine (P4 VP) and poly-2-vinylpyridine (P2 VP); the temperature and pH dual-responsive copolymer is one or more of P (DEAM-co-AA), P (NIPAM-co-4VP), P (DEAM-co-MAA), P (NIPAM-co-AA) and P (NIPAM-co-MAA).
The invention also provides a preparation method of the composite nanofiltration membrane with environmental responsiveness, which comprises the following steps:
(1) depositing the environmentally responsive nanoparticles onto the porous support film to form an intermediate layer;
(2) and sequentially immersing the obtained porous support membrane loaded with the environmental-responsive nano particles into a solution containing a water-phase reaction monomer and a solution containing an oil-phase reaction monomer, carrying out interfacial polymerization reaction, and finally rinsing to obtain the nanofiltration membrane with environmental responsiveness.
The deposition method in the step (1) is one of a gravity deposition method, a suction filtration method, a vertical deposition method and a vertical pulling method; the load capacity of the environmental-responsive nanoparticles is 0.1-500 mu g/cm2。
The water phase reaction monomer in the step (2) is one or more of piperazine, m-phenylenediamine, polyethyleneimine, o-phenylenediamine, N-diaminopiperazine, 1, 4-bis (3-aminopropyl) -piperazine, triethanolamine, N- (2-aminopropyl) -piperazine, methyldiethanolamine, diethylenetriamine and triethylene tetramine; the concentration of the water-phase reaction monomer is 0.01-5.0 w/v%. The time for immersing the solution containing the aqueous phase reaction monomer is 1-30 minutes.
The oil phase reaction monomer in the step (2) is one or more of trimesoyl chloride, pyromellitic chloride, phthaloyl chloride, isophthaloyl chloride and terephthaloyl chloride; the solvent adopted by the oil phase reaction monomer solution is one or more of cyclohexane, normal hexane, trichlorotrifluoroethane and heptane; the concentration of the oil phase reaction monomer is 0.01-2.0 w/v%.
The interfacial polymerization reaction time in the step (2) is 1-120 seconds.
Advantageous effects
(1) According to the invention, the environment-responsive nano particle intermediate layer is introduced into the membrane structure, so that on one hand, the intermediate layer can effectively regulate and control the interfacial polymerization process, the thickness of the polyamide separation layer is reduced, and the water transmission resistance is reduced; on the other hand, the surface roughness of the polyamide separation layer can be increased by the middle layer, and the effective permeation area is increased, so that the permeability of the membrane is remarkably improved. Secondly, the size of the environmental responsive nanoparticles can change under the environmental stimulus, so that an additional nano-channel is introduced into the membrane intermediate structure, and the selectivity is not influenced while the permeability of the membrane is enhanced.
(2) The invention has excellent separation performance, and the separation performance has unique environmental responsiveness, and can realize controllable adjustment of permeability on the premise of maintaining selectivity; the preparation method is simple and convenient to operate, mild in reaction conditions and good in application prospect.
Drawings
FIG. 1 is a surface SEM image of environmentally responsive nanoparticles P (St-co-AA) deposited in example 7.
Figure 2 is a surface SEM image of a composite nanofiltration membrane prepared after deposition of the environmentally responsive nanoparticles P (St-co-AA) in example 7.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Examples 1 to 4
(1) Taking temperature responsive SiO2The @ PNIPAM nano-particle is loaded on the polysulfone membrane in a suction filtration mode, and the loading amount is 2.97 mu g/cm2、5.94μg/cm2、8.91μg/cm2And 11.9. mu.g/cm2Wherein SiO is2@ PNIPAM is SiO2The PNIPAM is a core-shell structure nano particle with a shell.
(2) Soaking the prepared base membrane loaded with the nano particles in 0.3% w/v piperazine/water solution for 5 minutes, taking out and removing the excessive water phase solution on the surface until no obvious water drops exist;
(3) and (3) immersing the membrane into an oil phase solution of 0.15 w/v% trimesoyl chloride/cyclohexane, carrying out interfacial polymerization reaction for 1 minute to obtain a composite nanofiltration membrane, and immersing the composite nanofiltration membrane into deionized water for testing.
Examples 5 to 7
Examples 5 to 7 are substantially the same as example 1 except that the nanoparticles to be supported were pH-responsive P (St-co-AA) and the supporting masses were 9.82. mu.g/cm, respectively2、19.6μg/cm2、49.1μg/cm2. Wherein, P (St-co-AA) is a core-shell structure nano particle with PS as a core and PAA as a shell.
Examples 8 to 10
Examples 8 to 10 were substantially the same as in example 1, except that the nanoparticles were supported by P (NIPAM-co-AA) responding to both temperature and pH, and the supported masses were 8.26. mu.g/cm, respectively2、16.5μg/cm2、33.0μg/cm2。
Examples 11 to 13
Examples 11-13 are essentially the same as example 1, except that the supported nanoparticlesThe particles are P (NIPAM-co-AA) @ PNIPAM with temperature and pH simultaneously responding, and the load mass is 9.61 mu g/cm2、19.2μg/cm2、38.5μg/cm2. Wherein, the P (NIPAM-co-AA) @ PNIPAM is a core-shell structured nano particle taking the P (NIPAM-co-AA) as a core and taking the PNIPAM as a shell.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that it is not loaded with environmentally responsive nanoparticles.
The surface morphology of the membrane after deposition of the P (St-co-AA) nanoparticles and of the composite nanofiltration membrane in example 7 was determined by SEM. The results are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that the nanoparticles are arranged in a monolayer order on the surface of the membrane. As can be seen from fig. 2, after the nanoparticle intermediate layer is loaded, the surface of the nanofiltration membrane has a large wrinkle appearance.
SiO in the test examples by dynamic light scattering2The particle size of @ PNIPAM, P (St-co-AA), P (NIPAM-co-AA) and P (NIPAM-co-AA) @ PNIPAM nanoparticles vary with temperature, pH and temperature and pH, respectively. The results are shown in tables 1 to 3, respectively. It can be seen from the table that the radius of the particles decreases with increasing temperature or decreasing pH of the nanoparticles.
Examples 1 to 4 and comparative example 1 were tested for pure water permeability and desalting performance at temperatures of 25 ℃ and 50 ℃ under an operating pressure of 0.5MPa with a sodium sulfate aqueous solution of 1.0 g/L; examples 5-7 and comparative example 1 were tested for pure water permeability and desalting performance at pH 6 and 2; examples 8 to 13 were tested for pure water permeation performance and desalting performance at a temperature of 25 c, pH 6 and 2, and 50 c, pH 6, and the results are shown in tables 4 to 6, respectively.
TABLE 1 SiO2Variation of particle size of @ PNIPAM with temperature
TABLE 2P (St-co-AA) particle size as a function of pH
TABLE 3 variation of particle size of P (NIPAM-co-AA) and P (NIPAM-co-AA) @ PNIPAM with temperature and pH
TABLE 4 different SiO2Influence of @ PNIPAM loading capacity on performance of composite nanofiltration membrane
TABLE 5 Effect of different P (St-co-AA) loadings on the Performance of composite nanofiltration membranes
TABLE 6 influence of different load amounts of P (NIPAM-co-AA) and P (NIPAM-co-AA) @ PNIPAM on the performance of the composite nanofiltration membrane
As can be seen from tables 4-6, when the environmentally responsive nanoparticles were loaded, the water flux was significantly increased compared to the membrane without the nanoparticles under the same preparation conditions, e.g., 8.91. mu.g/cm deposition2 SiO2At @ PNIPAM, the water flux can be from 25L/m2H increases to 65.4L/m2H, when the test temperature is increased to 50 ℃, the water flux of the prepared composite nanofiltration membrane is further and remarkably increased to 108L/m2H while for 1.0g/L Na2SO4The retention of the aqueous solution can still be kept above 90%. Then, for example, 38.4. mu.g/cm was deposited2P (NIPAM-co-AA) @ PNIPAM, the water flux is increasedAdding to 96.9L/m2H, when the testing temperature is increased to 50 ℃, the water flux of the prepared composite nanofiltration membrane is further and remarkably increased to 180L/m2H; the water flux can be increased to 108L/m by reducing the pH2H. The results show that the separation performance of the membrane can be obviously improved by introducing the environment-responsive middle layer, the separation performance of the membrane also has environment responsiveness, and the permeability can be changed according to the change of the external environment, and meanwhile, the selectivity is not influenced, so that the controllable adjustment and transmission of the nanofiltration membrane are realized.
Claims (6)
1. A composite nanofiltration membrane with environmental responsiveness is characterized in that: the porous support membrane, the environment-responsive nanoparticle intermediate layer and the separation surface layer are included; the composite nanofiltration membrane is provided with a wrinkled ultrathin separation surface layer; the porous support membrane is polysulfone, polyethersulfone, polyacrylonitrile, polyvinylidene fluoride porous membrane or ultrafiltration membrane with surface modified by hydrophilic; the environment-responsive nanoparticles are core-shell structure nanoparticles with hard sphere nanoparticles as cores and environment-responsive polymers as shells or nanoparticles directly formed by the environment-responsive polymers; the size of the environment-responsive nanoparticles is 1-800 nm; the hard spherical nano particles are silicon dioxide SiO2One or more of polystyrene PS and polymethyl methacrylate PMMA; the environment-responsive polymer is one of a temperature-responsive polymer, a pH-responsive polymer and a temperature-pH dual-responsive copolymer; the temperature-responsive polymer is one or more of poly (N-isopropylacrylamide) PNIPAM, poly N, N-diethylacrylamide PDEAM, poly (N-vinylcaprolactam) PVCL, polymethyl vinyl ether PVME, polyoxypropylene PPO and polyoxyethylene PEO; the pH responsive polymer is one or more of polyacrylic acid (PAA), polymethacrylic acid (PMAA), polydimethylaminoethyl methacrylate (PDMAEMA), poly-4-vinylpyridine (P4 VP) and poly-2-vinylpyridine (P2 VP); the temperature and pH dual-responsive copolymer is one or more of P (DEAM-co-AA), P (NIPAM-co-4VP), P (DEAM-co-MAA), P (NIPAM-co-AA) and P (NIPAM-co-MAA).
2. A method for preparing the composite nanofiltration membrane with environmental responsiveness as claimed in claim 1, comprising the following steps:
(1) depositing the environmentally responsive nanoparticles onto the porous support film to form an intermediate layer;
(2) and sequentially immersing the obtained porous support membrane loaded with the environment-responsive nano particles into a solution containing a water-phase reaction monomer and a solution containing an oil-phase reaction monomer, carrying out interfacial polymerization reaction, and finally rinsing to obtain the composite nanofiltration membrane with environment responsiveness.
3. The method of claim 2, wherein: the deposition method in the step (1) is one of a gravity deposition method, a suction filtration method, a vertical deposition method and a vertical pulling method; the load capacity of the environmental-responsive nanoparticles is 0.1-500 mu g/cm2。
4. The method of claim 2, wherein: the water phase reaction monomer in the step (2) is one or more of piperazine, m-phenylenediamine, polyethyleneimine, o-phenylenediamine, N-diaminopiperazine, 1, 4-bis (3-aminopropyl) -piperazine, triethanolamine, N- (2-aminopropyl) -piperazine, methyldiethanolamine, diethylenetriamine and triethylene tetramine; the concentration of the water-phase reaction monomer is 0.01-5.0 w/v%.
5. The method of claim 2, wherein: the oil phase reaction monomer in the step (2) is one or more of trimesoyl chloride, pyromellitic chloride, phthaloyl chloride, isophthaloyl chloride and terephthaloyl chloride; the solvent adopted by the oil phase reaction monomer solution is one or more of cyclohexane, normal hexane, trichlorotrifluoroethane and heptane; the concentration of the oil phase reaction monomer is 0.01-2.0 w/v%.
6. The method of claim 2, wherein: the time for immersing the solution containing the water-phase reaction monomer in the step (2) is 1-30 minutes; the interfacial polymerization reaction time is 1-120 seconds.
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