CN114642967A - Nanofiltration membrane based on reactive supporting layer, preparation method and application - Google Patents
Nanofiltration membrane based on reactive supporting layer, preparation method and application Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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Abstract
The invention discloses a preparation method of a nanofiltration membrane based on a reactive supporting layer, which comprises the following steps: (1) carrying out amino grafting reaction on the porous support membrane to prepare a reactive support membrane; (2) preparing the nanofiltration membrane based on the reaction activity supporting layer by carrying out interfacial polymerization on the water phase solution and the oil phase solution containing the polyacyl chloride oil phase monomer on the reaction activity supporting membrane; the aqueous monomer in the aqueous solution is a semi-aromatic amine. According to the invention, the reactive support membrane is obtained by carrying out amino grafting reaction on the porous support membrane, and the interfacial polymerization is carried out on the surface of the reactive support membrane, so that the structure of the formed polyamide separation layer can be changed by the reactive support membrane, and further, the water permeability of the polyamide nanofiltration membrane is improved, and the ion selectivity of the polyamide nanofiltration membrane is improved. The method has low requirement on equipment, has simple process, is convenient to improve on the basis of the traditional preparation process of the polyamide nanofiltration composite membrane, and realizes industrial production.
Description
Technical Field
The invention relates to the technical field of water treatment membranes, in particular to a nanofiltration membrane based on a reaction activity supporting layer, a preparation method and application.
Background
With the development of membrane technology, reverse osmosis membrane technology tends to mature. However, reverse osmosis membranes have no selectivity for the retention of ions, so that the operating pressure of the membrane is high and the membrane flux is limited. And the relative molecular weight of the organic matters intercepted by the ultrafiltration membrane is larger. The nanofiltration technology is a novel separation technology between reverse osmosis and ultrafiltration, the nanofiltration membrane is suitable for running under lower operating pressure, the energy consumption and the cost are lower, the nanofiltration membrane is more suitable for treating industrial softened water, the aperture of the nanofiltration membrane is about several nanometers, divalent ions and above ions in a solution and substances with the relative molecular weight of more than 200 can be effectively removed, and the separation performance of the nanofiltration membrane is superior to that of the ultrafiltration membrane and the microfiltration membrane.
With the increasingly severe environmental protection situation in China, the market of wastewater resource is huge, the separation and concentration of the high-salinity wastewater treated by the prior art need the highest possible interception resolution ratio of the primary and the divalent ions, and a nanofiltration membrane product with high water flux is required to improve the separation efficiency of mixed components as much as possible.
Most of the current commercial nanofiltration membranes are of a composite structure of aromatic polyamide, and the nanofiltration membranes comprise a polyamide separation layer, a porous support layer and a non-woven fabric substrate. The polyamide separation layer plays an important role in the separation performance of the membrane, such as water flux and ion selectivity, and most of researches in recent years focus on adjusting reaction parameters of an interfacial polymerization process, such as reaction monomers, reaction time, temperature, solution concentration, diffusion rate and the like, so as to optimize the structure of the polyamide separation layer and improve the osmotic selectivity of the membrane. However, the characteristics of the support layer (pore size, roughness, hydrophilicity, etc.) as a carrier for interfacial polymerization also have a great influence on the interfacial polymerization process.
Chinese patent publication No. CN111437732A discloses a method for preparing a high-selectivity high-flux nanofiltration membrane, which comprises adding one or more alkyl acids into an aqueous phase formula solution containing polyamine to regulate the pH value of the aqueous phase, and carrying out interfacial reaction with an organic phase monomer aromatic polybasic acyl chloride solution to form a polyamide ultrathin separation layer on a porous support layer. The composite nanofiltration membrane prepared by the method has higher water flux and high retention rate on sulfate radical, but has higher retention rate on chloride ions, more than 30 percent, and the ion selectivity needs to be improved.
Chinese patent publication No. CN109126463A discloses a method for preparing a high-flux nanofiltration membrane containing a microporous intermediate layer, in which a microporous material dispersion is coated on a porous support layer to form an intermediate layer, and interfacial polymerization is performed on the intermediate layer to prepare a composite nanofiltration membrane. The nanofiltration membrane intermediate layer has a uniform pore structure, the water permeability of the nanofiltration membrane is obviously improved, but the thickness of the nanofiltration membrane is increased by introducing the intermediate layer.
Disclosure of Invention
In order to improve the water permeation flux of the nanofiltration membrane and simultaneously improve the ion selectivity of the nanofiltration membrane, the invention provides a preparation method of the nanofiltration membrane based on a reaction active support layer, the method has simple process and low equipment requirement, and the prepared nanofiltration membrane has high water permeation flux, good ion selectivity and strong rejection capability on divalent anion rejection capability.
The technical scheme is as follows:
a preparation method of a nanofiltration membrane based on a reactive support layer comprises the following steps:
(1) carrying out amino grafting reaction on the porous support membrane to prepare a reactive support membrane;
(2) preparing the nanofiltration membrane based on the reaction activity supporting layer by carrying out interfacial polymerization on the water phase solution and the oil phase solution containing the polyacyl chloride oil phase monomer on the reaction activity supporting membrane;
in the aqueous phase solution, the aqueous phase monomer is a semi-aromatic amine monomer and is selected from at least one of piperazine, 2-methylpiperazine, 2, 5-dimethylpiperazine, 2, 6-dimethylpiperazine, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, ethylenediamine, N-bis (2-aminoethyl) ethylenediamine, diethylenetriamine and polyethyleneimine.
The porous support membrane comprises a non-woven fabric layer and a porous support layer, and is selected from one of a polysulfone ultrafiltration membrane, a polyether sulfone ultrafiltration membrane, a polyacrylonitrile ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane, a polypropylene ultrafiltration membrane, a polyethylene ultrafiltration membrane, a polystyrene ultrafiltration membrane or a polyimide ultrafiltration membrane.
According to the invention, the porous support membrane is subjected to amino grafting reaction, amino groups are introduced into the porous support layer with reaction inertia, the reaction active support membrane is constructed and subjected to interfacial polymerization on the surface thereof, and the reaction active support membrane can change the structure of the formed polyamide separation layer, so that the water permeability of the polyamide nanofiltration membrane is improved, the ion selectivity of the polyamide nanofiltration membrane is improved, and the preparation of the high-performance nanofiltration membrane is further realized.
Preferably, in the step (1), the porous support membrane is immersed in a reaction solution containing an amino monomer to perform an amino grafting reaction, wherein the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine; in the reaction liquid containing the amino monomer, the content of the amino monomer is 10-15 wt%. The aminolysis speed is too high due to the excessively high content of the amino monomer, and the content of the amino grafted on the surface of the porous support membrane is difficult to control; the content of the amino monomer is too low, and the problems of incomplete grafting or too long grafting time are easy to occur.
Further preferably, the amino grafting reaction conditions are as follows: the temperature is 90-160 ℃, and the time is 24-72 h.
In the oil phase solution, the oil phase monomer is at least one of trimesoyl chloride, paraphthaloyl chloride, phthaloyl chloride, pyromellitic chloride, malonyl chloride, glutaryl chloride and fumaroyl chloride; the solvent of the oil phase monomer is at least one of n-hexane, cyclohexane, n-heptane, toluene, benzene, isopar G, isopar E, isopar H, isopar L and isopar M.
Preferably, the content of the water phase monomer in the water phase solution is 0.1-0.5 wt%, and the content of the oil phase monomer in the oil phase solution is 0.01-0.05 wt%.
Preferably, in the step (2), the interfacial polymerization film-forming process includes:
1) pouring the aqueous phase solution on the surface of the reactive support membrane, and removing the redundant liquid on the surface of the membrane after the aqueous phase solution is in contact and stands for 1-10 min;
2) pouring the oil phase solution containing the polyacyl chloride oil phase monomer on the membrane surface obtained in the step 1), and removing the redundant liquid on the membrane surface after the contact and standing for 0.5-5 min;
3) and (3) carrying out water bath heat treatment on the membrane obtained in the step 2) to obtain the nanofiltration membrane based on the reactive active support layer.
The method of the invention carries out interfacial polymerization reaction on the reactive support membrane to prepare the polyamide separation layer, the amino group introduced on the reactive support membrane can react with the polybasic acyl chloride oil phase monomer to participate in the interfacial polymerization process, thereby improving the defect generation in the formation process of the polyamide separation layer, and meanwhile, the reactive support membrane introduced with the amino group can prevent the polyamide layer from infiltrating into the pore canal of the support layer, reducing the actual thickness of the formed polyamide separation layer, reducing the water permeation resistance and improving the water permeation performance of the membrane.
Preferably, in step 3), the conditions of the water bath heat treatment are as follows: 50-80 deg.C, 5-20 min.
The invention also provides the nanofiltration membrane based on the reactive supporting layer, which is prepared by the preparation method of the nanofiltration membrane based on the reactive supporting layer.
The nanofiltration membrane based on the reaction active support layer comprises a non-woven fabric layer, the reaction active support layer and a polyamide separation layer, and the water flux is more than 18 L.m-2·h-1·bar-1The ion selectivity is good, the retention rate to divalent anions is more than 90 percent, and the retention rate to monovalent anions is less than 25 percent.
The invention also provides application of the nanofiltration membrane based on the reactive support layer in the field of water treatment application, in particular to the field of water treatment such as hard water softening and organic matter removal.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method prepares the reactive support membrane containing amino groups through amino grafting reaction, so that the porous support membrane which is originally inert to reaction can also participate in interfacial polymerization reaction, and more polymerization reaction sites are provided, thereby improving the generation of defects in the formation process of the polyamide separation layer, further preventing the polyamide layer from infiltrating into the pore channels of the support layer due to the existence of the reactive support membrane, reducing the actual thickness of the polyamide layer, and reducing the water permeation resistance, therefore, the prepared nanofiltration membrane has high flux and divalent anion interception capability, and has effective separation selection capability.
(2) The method has low requirement on equipment, the preparation method of the reactive support membrane is simple, the improvement is convenient on the basis of the traditional polyamide nanofiltration composite membrane preparation process, the amplified preparation production is realized, and the prepared high-performance nanofiltration membrane has wide application prospect in the field of water treatment.
(3) The nanofiltration membrane provided by the invention has excellent water permeation flux and ion selectivity, and the water flux is more than 18 L.m-2·h-1·bar-1The retention rate for divalent anions is more than 90 percent, and the retention rate for monovalent anions is less than 25 percent.
Drawings
Fig. 1 is an SEM picture of the surface of the nanofiltration membrane based on the reactive support layer in example 1.
Fig. 2 is an SEM picture of the nanofiltration membrane cross-section based on the reactive support layer in example 1.
Detailed Description
The invention is further elucidated with reference to the following figures and 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.
Example 1
Immersing a commercial polyethersulfone ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 10 wt% of diethylenetriamine, taking out after amination grafting reaction is carried out for 24 hours at 90 ℃, and washing the surface of the membrane by absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane containing amino on the surface; subsequently, an aqueous solution containing 0.1 wt% of piperazine was poured onto the surface of the reactive support membrane, and after standing for 1min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.01 wt% of trimesoyl chloride to the surface of the membrane, after contacting and standing for 0.5min, pouring out the redundant solution, and removing the residual liquid on the surface; and carrying out heat treatment on the obtained membrane for 5min under the condition of 50 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 2
Immersing a commercial polyethersulfone ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 15 wt% of diethylenetriamine, taking out the porous support membrane after amination grafting reaction for 72h at 90 ℃, and washing the surface of the membrane by using absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.1 wt% of piperazine was poured onto the surface of the reactive support membrane, and after standing for 1min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.01 wt% of trimesoyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept still for 0.5min, pouring out the redundant solution, and removing the residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 20min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 3
Immersing a commercial polyethersulfone ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 15 wt% of ethylenediamine, carrying out amination grafting reaction at 160 ℃ for 24h, taking out, and washing the surface of the membrane with absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.5 wt% of piperazine was poured onto the surface of the reactive support membrane, and after standing for 5 minutes in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.05 wt% of trimesoyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept still for 2.5min, pouring out the redundant solution, and removing the residual liquid on the surface; and carrying out heat treatment on the obtained membrane for 5min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 4
Immersing a commercial polyethersulfone ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 10 wt% of hexamethylenediamine, taking out the porous support membrane after amination grafting reaction for 48 hours at 160 ℃, and washing the surface of the membrane by using absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.1 wt% of piperazine was poured onto the surface of the reactive support membrane, and after standing for 10min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.01 wt% of trimesoyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept stand for 5min, pouring out the redundant solution, and removing the residual liquid on the surface; and carrying out heat treatment on the obtained membrane for 15min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 5
Immersing a commercial polyethersulfone ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 15 wt% of diethylenetriamine, taking out the porous support membrane after amination grafting reaction for 72h at 90 ℃, and washing the surface of the membrane by using absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.5 wt% of piperazine was poured on the surface of the reaction active support film, and after standing for 10min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.05 wt% of trimesoyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept stand for 5min, pouring out the redundant solution, and removing the residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 20min under the condition of 50 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 6
Immersing the porous support membrane into an aqueous solution containing 10 wt% of ethylenediamine, performing amination grafting reaction for 24 hours at 90 ℃, taking out, and washing the surface of the membrane by using absolute ethyl alcohol and deionized water successively to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.5 wt% of piperazine was poured onto the surface of the reactive support membrane, and after standing for 1min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring isopar G solution containing 0.05 wt% of trimesoyl chloride onto the surface of the membrane, after the membrane is contacted and kept still for 0.5min, pouring out excessive solution, and removing residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 10min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reactive active support layer.
Example 7
Immersing a commercial polyvinylidene fluoride ultrafiltration membrane serving as a porous support membrane in an aqueous solution containing 15 wt% of triethylene tetramine, taking out the porous support membrane after amination grafting reaction for 72h at 90 ℃, and washing the surface of the membrane by using absolute ethyl alcohol and deionized water in sequence to obtain a reactive active support membrane with amino on the surface; subsequently, an aqueous solution containing 0.5 wt% of 2-methylpiperazine was poured onto the surface of the reaction active support film, and after standing for 5 minutes in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a cyclohexane solution containing 0.05 wt% of phthaloyl chloride onto the surface of the membrane, after the cyclohexane solution is contacted and kept stand for 2min, pouring out the redundant solution, and removing the residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 5min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reaction activity support layer.
Example 8
Immersing a commercial polypropylene ultrafiltration membrane serving as a porous support membrane into an aqueous solution containing 15 wt% of ethylenediamine, taking out after amination grafting reaction is carried out for 24 hours at 90 ℃, and washing the surface of the membrane by absolute ethyl alcohol and deionized water in sequence to obtain a reactive support membrane with amino on the surface; subsequently, an aqueous solution containing 0.5 wt% of 2-methylpiperazine was poured onto the surface of the reaction active support film, and after standing for 2min in contact, the excess solution was poured off, and the liquid remaining on the surface was removed. Then, pouring a normal hexane solution containing 0.05 wt% of terephthaloyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept stand for 1min, pouring out the redundant solution, and removing the residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 20min under the condition of 80 ℃ water bath to obtain the nanofiltration membrane based on the reaction activity support layer.
Comparative example 1
Pouring an aqueous solution containing 0.5 wt% of piperazine on the surface of a porous support membrane by using a commercial polyethersulfone ultrafiltration membrane as the porous support membrane, after the solution is contacted and kept still for 2min, pouring off the redundant solution, and removing the residual liquid on the surface. Then, pouring a normal hexane solution containing 0.05 wt% of trimesoyl chloride to the surface of the membrane, after the normal hexane solution is contacted and kept stand for 1min, pouring out the redundant solution, and removing the residual liquid on the surface; and then carrying out heat treatment on the obtained membrane for 10min under the condition of 50 ℃ water bath to obtain the nanofiltration membrane of which the supporting layer does not contain reactive groups.
Sample analysis
The micro-morphology of the nanofiltration membrane based on the reactive support layer prepared in example 1 is analyzed, the surface SEM result and the cross-section SEM result are respectively shown in fig. 1 and fig. 2, the vesicle structure of the nanofiltration membrane polyamide layer prepared after amination of the porous support membrane is smaller and more uniform, and the polyamide layer is thinner.
The performance of the nanofiltration membranes prepared in examples 1 to 8 and comparative example 1 was tested at room temperature using a cross-flow flat sheet membrane performance evaluation apparatus, and the pure water flux and 2000ppm of Na to the product membranes were measured2SO4The results of the tests on the retention of the aqueous solution and the retention of the aqueous NaCl solution at 2000ppm (test temperature 25 ℃ C., pressure 5bar) are shown in Table 1.
TABLE 1 nanofiltration Membrane Performance test results obtained in examples 1-8 and comparative example 1
As shown in table 1, the examples demonstrate that the pure water flux of the nanofiltration membrane prepared by the method of the present invention is significantly increased compared to the comparative examples, because the reactive support layer reduces the inward permeation of the polyamide layer into the support layer pore channels, reduces the thickness of the polyamide layer, and improves the water permeability; in addition, the nanofiltration membrane based on the reactive support layer in the embodiment has better mono/divalent anion selectivity, because the crosslinking degree of the polyamide layer in the embodiment is slightly reduced compared with that in the comparative example, the polyamide layer of the nanofiltration membrane in the embodiment has larger effective pore radius and more negative membrane surface charge, and the ion selectivity of the nanofiltration membrane is improved.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a nanofiltration membrane based on a reactive supporting layer is characterized by comprising the following steps:
(1) carrying out amino grafting reaction on the porous support membrane to prepare a reactive support membrane;
(2) preparing the nanofiltration membrane based on the reaction activity supporting layer by carrying out interfacial polymerization on the water phase solution and the oil phase solution containing the polyacyl chloride oil phase monomer on the reaction activity supporting membrane;
in the aqueous phase solution, the aqueous phase monomer is at least one of piperazine, 2-methyl piperazine, 2, 5-dimethyl piperazine, 2, 6-dimethyl piperazine, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, ethylenediamine, N-bis (2-aminoethyl) ethylenediamine, divinyl triamine and polyethyleneimine.
2. The preparation method of a nanofiltration membrane based on a reaction active support layer according to claim 1, wherein the porous support membrane is one selected from a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane, a polyacrylonitrile ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane, a polypropylene ultrafiltration membrane, a polyethylene ultrafiltration membrane, a polystyrene ultrafiltration membrane and a polyimide ultrafiltration membrane.
3. The method for preparing a nanofiltration membrane based on a reactive support layer according to claim 1, wherein in the step (1), the porous support membrane is immersed in a reaction solution containing an amino monomer for an amino grafting reaction, wherein the amino monomer is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine; in the reaction liquid containing the amino monomer, the content of the amino monomer is 10-15 wt%.
4. The method for preparing a nanofiltration membrane based on a reactive support layer according to claim 1, wherein the amino grafting reaction conditions are as follows: the temperature is 90-160 ℃, and the time is 24-72 h.
5. The method for preparing a nanofiltration membrane based on a reactive support layer according to claim 1, wherein in the oil phase solution, the oil phase monomer is at least one of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride, pyromellitic chloride, malonyl chloride, glutaryl chloride and fumaroyl chloride.
6. The method of claim 1, wherein the aqueous phase solution contains 0.1-0.5 wt% of the aqueous phase monomer, and the oil phase solution contains 0.01-0.05 wt% of the oil phase monomer.
7. The method for preparing a nanofiltration membrane based on a reactive support layer according to claim 1, wherein in the step (2), the interfacial polymerization membrane preparation process comprises:
1) pouring the aqueous phase solution on the surface of the reactive support membrane, and removing the redundant liquid on the surface of the membrane after the aqueous phase solution is in contact and stands for 1-10 min;
2) pouring an oil phase solution containing a polyacyl chloride oil phase monomer onto the surface of the membrane obtained in the step 1), and removing redundant liquid on the surface of the membrane after the solution is contacted and kept stand for 0.5-5 min;
3) and (3) carrying out water bath heat treatment on the membrane obtained in the step 2) to obtain the nanofiltration membrane based on the reactive active support layer.
8. The method for preparing a nanofiltration membrane based on a reactive support layer according to claim 7, wherein the conditions of the water bath heat treatment in the step 3) are as follows: 50-80 deg.C, 5-20 min.
9. According to the claimsThe nanofiltration membrane based on the reaction active support layer prepared by the preparation method of the nanofiltration membrane based on the reaction active support layer, which is described in any one of 1 to 8, is characterized in that the water flux is more than 18 L.m-2·h-1·bar-1。
10. Use of nanofiltration membranes based on a reactive support layer according to claim 9 in water treatment applications.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888441A (en) * | 2023-01-06 | 2023-04-04 | 湖南沁森高科新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
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