CN114011255A - Base membrane of reverse osmosis membrane and preparation method thereof - Google Patents

Base membrane of reverse osmosis membrane and preparation method thereof Download PDF

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Publication number
CN114011255A
CN114011255A CN202111384106.2A CN202111384106A CN114011255A CN 114011255 A CN114011255 A CN 114011255A CN 202111384106 A CN202111384106 A CN 202111384106A CN 114011255 A CN114011255 A CN 114011255A
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membrane
reverse osmosis
osmosis membrane
solution
base
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蔡相宇
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Tianjin Tianyuan New Material Technology Co ltd
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Tianjin Tianyuan New Material Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/66Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68Polysulfones; Polyethersulfones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0006Organic membrane manufacture by chemical reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride

Abstract

The invention discloses a base membrane of a reverse osmosis membrane and a preparation method thereof, wherein the base membrane comprises non-woven fabrics and a membrane casting material layer, the membrane casting material layer is a membrane casting agent coated on the non-woven fabrics and dried, the membrane casting agent consists of a supporting layer polymer and a pore-forming agent, the supporting layer polymer is one of polyether sulfone, polysulfone or polyvinylidene fluoride, and the concentration of the supporting layer polymer in a solution is 12-25 wt.%, and the invention relates to the technical field of reverse osmosis membranes and preparation. The base membrane of the reverse osmosis membrane and the preparation method thereof can realize better reverse osmosis filtration treatment, the service life is greatly prolonged, the base membrane of the reverse osmosis membrane is well improved, the weather resistance of the reverse osmosis membrane is improved, meanwhile, the preparation method of the reverse osmosis membrane is simple, the rapid production and preparation through a simple preparation process are realized, the production efficiency is greatly improved, the reverse osmosis membrane structure is enriched, the reverse osmosis effect is good, and therefore the reverse osmosis membrane production work of production personnel is greatly facilitated.

Description

Base membrane of reverse osmosis membrane and preparation method thereof
Technical Field
The invention relates to the technical field of reverse osmosis membranes and preparation, in particular to a base membrane of a reverse osmosis membrane and a preparation method thereof.
Background
The reverse osmosis membrane is an artificial semipermeable membrane with certain characteristics and is made by simulating a biological semipermeable membrane, and is a core component of a reverse osmosis technology, the principle of the reverse osmosis technology is that under the action of osmotic pressure higher than that of a solution, substances and water are separated from each other according to the fact that other substances cannot permeate the semipermeable membrane, and the membrane aperture of the reverse osmosis membrane is very small, so that dissolved salts, colloids, microorganisms and organic matters in the water can be effectively removed, the system has the advantages of good water quality, low energy consumption, no pollution, simple process and simplicity and convenience in operation, and the reverse osmosis membrane is a core element for realizing reverse osmosis and is an artificial semipermeable membrane with certain characteristics and made by simulating a biological semipermeable membrane. The membrane is generally made of high molecular materials, such as cellulose acetate membrane, aromatic polyhydrazide membrane and aromatic polyamide membrane, the diameter of surface micropores is generally between 0.5 and 10nm, the permeability is related to the chemical structure of the membrane, some high molecular materials have good salt repellency, the water permeation speed is not good, and the chemical structure of some high molecular materials has more hydrophilic groups, so the water permeation speed is relatively fast, therefore, a satisfactory reverse osmosis membrane has proper permeability or desalination rate, and the reverse osmosis membrane has the following characteristics: (1) high salt rejection at high flow rates; (2) the mechanical strength is high and the service life is long; (3) can function under lower operating pressure.
The current reverse osmosis membrane has a single structure, the reverse osmosis effect is poor, better reverse osmosis filtration treatment cannot be realized, the service life is short, the improvement on the base membrane of the reverse osmosis membrane cannot be realized, the weather resistance of the reverse osmosis membrane is improved, meanwhile, the preparation method of the current reverse osmosis membrane is complex, the rapid production preparation cannot be realized through a simple preparation process, the production efficiency is greatly reduced, and therefore, the production work of the reverse osmosis membrane for production personnel is greatly inconvenient.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a base membrane of a reverse osmosis membrane and a preparation method thereof, and solves the problems that the existing reverse osmosis membrane has a single structure, is poor in reverse osmosis effect, cannot realize better reverse osmosis filtration treatment, is short in service life, cannot improve the weather resistance of the reverse osmosis membrane, is complex in preparation method, cannot realize rapid production and preparation through a simple preparation process, and greatly reduces the production efficiency.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the membrane casting material layer is a membrane casting agent coated on the non-woven fabric and dried, and the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent.
Preferably, the support layer polymer is one of polyethersulfone, polysulfone or polyvinylidene fluoride, and has a concentration in the solution of 12wt.% to 25 wt.%.
Preferably, the porogen is one of PEO, PVP, PEG, glycerol or glycol, and its concentration in the solution is 0.1wt.% to 8 wt.%.
The invention also provides a preparation method of the reverse osmosis membrane, which is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the membrane casting solution prepared in the step S1 on non-woven fabrics by using an automatic membrane coater, scraping the membrane, immersing the membrane casting solution into water for coagulation bath to form a membrane casting material layer () on the non-woven fabrics, preparing a reverse osmosis membrane base membrane by using a dipping-precipitation phase conversion method, and then putting the reverse osmosis membrane base membrane into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (4) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in an oven at the temperature of 30-60 ℃ for 5-10min to prepare the reverse osmosis membrane, and putting the reverse osmosis membrane into deionized water for later use.
Preferably, the aqueous solution in step S3 is one of m-phenylenediamine, p-phenylenediamine or xylylenediamine, and the concentration of the aqueous solution in the solution is 0.5wt.% to 6 wt.%.
Preferably, the oil phase solution in step S3 is one of trimesoyl chloride, phthaloyl chloride, terephthaloyl chloride or isophthaloyl chloride, and the concentration thereof in the solution is 0.02wt.% to 0.5 wt.%.
(III) advantageous effects
The invention provides a base membrane of a reverse osmosis membrane and a preparation method thereof. Compared with the prior art, the method has the following beneficial effects: the base membrane of the reverse osmosis membrane and the preparation method thereof comprise a non-woven fabric and a membrane casting material layer, wherein the membrane casting material layer is a membrane casting agent coated on the non-woven fabric after drying, and the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent, so that better reverse osmosis filtration treatment can be realized, the service life is greatly prolonged, the base membrane of the reverse osmosis membrane is well improved, the weather resistance of the reverse osmosis membrane is improved, meanwhile, the preparation method of the reverse osmosis membrane is simple, the rapid production and preparation through a simple preparation process are realized, the production efficiency is greatly improved, the reverse osmosis membrane structure is enriched, the reverse osmosis effect is good, and therefore, the reverse osmosis membrane production work of production personnel is greatly facilitated.
Drawings
FIG. 1 is a schematic view of the structure of the base film of the present invention.
In the figure, 1 a nonwoven fabric and 2 a cast film material layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the embodiment of the present invention provides four technical solutions: a base membrane of a reverse osmosis membrane and a preparation method thereof specifically comprise the following embodiments:
example 1
The base membrane of the reverse osmosis membrane comprises a non-woven fabric 1 and a membrane casting material layer 2, wherein the membrane casting material layer 2 is a membrane casting agent coated on the non-woven fabric 1 and dried, the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent, the supporting layer polymer is polyether sulfone, the concentration of the polyether casting agent in a solution is 12wt.%, the pore-forming agent is PEO, and the concentration of the polyether casting agent in the solution is 0.1 wt.%.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the membrane casting solution prepared in the step S1 on the non-woven fabric 1 by using an automatic membrane coater, scraping the membrane, immersing the membrane casting solution into water for coagulation bath to form a membrane casting material layer 2 on the non-woven fabric 1, preparing a reverse osmosis membrane base membrane by using an immersion-precipitation phase conversion method, and then putting the reverse osmosis membrane base membrane into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (2) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in a 30 ℃ oven for 5min to prepare the reverse osmosis membrane, and placing the reverse osmosis membrane into deionized water for later use, wherein the water phase solution is m-phenylenediamine and has a concentration of 0.5wt.% in the solution, and the oil phase solution is trimesoyl chloride and has a concentration of 0.02wt.% in the solution.
Example 2
A base membrane of a reverse osmosis membrane comprises a non-woven fabric 1 and a membrane casting material layer 2, wherein the membrane casting material layer 2 is a membrane casting agent coated on the non-woven fabric 1 and dried, the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent, the supporting layer polymer is polysulfone, the concentration of the polysulfone in a solution is 16wt.%, the pore-forming agent is PVP, and the concentration of the polysulfone in the solution is 3 wt.%.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the membrane casting solution prepared in the step S1 on the non-woven fabric 1 by using an automatic membrane coater, scraping the membrane, immersing the membrane casting solution into water for coagulation bath to form a membrane casting material layer 2 on the non-woven fabric 1, preparing a reverse osmosis membrane base membrane by using an immersion-precipitation phase conversion method, and then putting the reverse osmosis membrane base membrane into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (3) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in a 40 ℃ oven for 7min to prepare the reverse osmosis membrane, and placing the reverse osmosis membrane into deionized water for later use, wherein the water phase solution is p-phenylenediamine and the concentration of the p-phenylenediamine in the solution is 2wt.%, and the oil phase solution is phthaloyl chloride and the concentration of the phthaloyl chloride in the solution is 0.2 wt.%.
Example 3
The base membrane of the reverse osmosis membrane comprises a non-woven fabric 1 and a membrane casting material layer 2, wherein the membrane casting material layer 2 is a membrane casting agent coated on the non-woven fabric 1 after being dried, the membrane casting agent consists of a supporting layer polymer and a pore-forming agent, the supporting layer polymer is polyvinylidene fluoride, the concentration of the supporting layer polymer in a solution is 22wt.%, the pore-forming agent is PEG, and the concentration of the pore-forming agent in the solution is 6 wt.%.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the membrane casting solution prepared in the step S1 on the non-woven fabric 1 by using an automatic membrane coater, scraping the membrane, immersing the membrane casting solution into water for coagulation bath to form a membrane casting material layer 2 on the non-woven fabric 1, preparing a reverse osmosis membrane base membrane by using an immersion-precipitation phase conversion method, and then putting the reverse osmosis membrane base membrane into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (3) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in a 50 ℃ oven for 8min to prepare the reverse osmosis membrane, and placing the reverse osmosis membrane into deionized water for later use, wherein the water phase solution is xylylenediamine, the concentration of which in the solution is 4wt.%, and the oil phase solution is terephthaloyl chloride, and the concentration of which in the solution is 0.35 wt.%.
Example 4
The base membrane of the reverse osmosis membrane comprises a non-woven fabric 1 and a membrane casting material layer 2, wherein the membrane casting material layer 2 is a membrane casting agent coated on the non-woven fabric 1 and dried, the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent, the supporting layer polymer is polyether sulfone, the concentration of the polyether sulfone in a solution is 25wt.%, the pore-forming agent is glycerol, and the concentration of the polyether sulfone in the solution is 8 wt.%.
The embodiment of the invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the membrane casting solution prepared in the step S1 on the non-woven fabric 1 by using an automatic membrane coater, scraping the membrane, immersing the membrane casting solution into water for coagulation bath to form a membrane casting material layer 2 on the non-woven fabric 1, preparing a reverse osmosis membrane base membrane by using an immersion-precipitation phase conversion method, and then putting the reverse osmosis membrane base membrane into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (3) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in a 60 ℃ oven for 10min to prepare the reverse osmosis membrane, and placing the reverse osmosis membrane into deionized water for later use, wherein the water phase solution is m-phenylenediamine and has a concentration of 6wt.% in the solution, and the oil phase solution is isophthaloyl dichloride and has a concentration of 0.5wt.% in the solution.
Comparative experiment
The reverse osmosis membranes of the same type in the existing market are selected as comparative examples for experiments, the nanofiltration membranes prepared in the examples 1-4 and the comparative examples are sampled, immersed in bovine serum albumin culture solution, cultured for 24 hours at 37 ℃, taken out, tested by a membrane test bench, and tested by 3000ppm sodium chloride raw water solution under the test conditions of operating pressure of 0.6MPa, temperature of 25 ℃ and pH of 6.5-7.5 for the desalination rate, water flux and tensile strength of the membrane after 30min of operation. The results of the experiments are summarized in table 1.
TABLE 1 Water flux, salt rejection and tensile Strength of membranes
Test sample Water flux (GFD) Salt rejection ratio (wt%) Tensile Strength (N/50 mm)
Example 1 44.1 73.5 89
Example 2 46.9 77.6 92
Example 3 41.9 72.6 90
Example 4 46.1 78.7 91
Comparative example 1 20.7 61.3 78
In conclusion, the reverse osmosis membrane can realize better reverse osmosis filtration treatment, the service life is greatly prolonged, the weather resistance of the reverse osmosis membrane is improved by improving the base membrane of the reverse osmosis membrane, meanwhile, the preparation method of the reverse osmosis membrane is simple, the rapid production and preparation through a simple preparation process are realized, the production efficiency is greatly improved, the reverse osmosis membrane structure is enriched, the reverse osmosis effect is good, and therefore the reverse osmosis membrane production work of production personnel is greatly facilitated.
And those not described in detail in this specification are well within the skill of those in the art.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. A base membrane of a reverse osmosis membrane, characterized in that: the pore-forming membrane comprises a non-woven fabric (1) and a membrane casting material layer (2), wherein the membrane casting material layer (2) is a membrane casting agent coated on the non-woven fabric (1) after drying, and the membrane casting agent is composed of a supporting layer polymer and a pore-forming agent.
2. A base membrane of a reverse osmosis membrane according to claim 1, wherein: the support layer polymer is one of polyether sulfone, polysulfone or polyvinylidene fluoride, and the concentration of the support layer polymer in the solution is 12-25 wt.%.
3. A base membrane of a reverse osmosis membrane according to claim 1, wherein: the pore-forming agent is one of PEO, PVP, PEG, glycerol or dihydric alcohol, and the concentration of the pore-forming agent in the solution is 0.1wt.% to 8 wt.%.
4. A method of preparing a reverse osmosis membrane using a base membrane of the reverse osmosis membrane of claim 1, wherein: the method specifically comprises the following steps:
s1, preparing a polymer mixed solution: at room temperature, adding a polymer into a solvent, stirring vigorously for 15min, then stirring the mixed solution at the rotating speed of 120rpm for 24h, standing and defoaming, and finally preparing a casting solution;
s2, preparation of a reverse osmosis membrane base membrane: coating the casting solution prepared in the step S1 on non-woven fabric (1) by using an automatic film coater, scraping the film, immersing the film into water for coagulation bath to form a casting material layer (2) on the non-woven fabric (1), preparing a reverse osmosis membrane base film by using a dipping-precipitation phase conversion method, and then putting the reverse osmosis membrane base film into deionized water for later use;
s3, preparing a reverse osmosis membrane: and (4) vertically drying the base membrane prepared in the step (S2) in the shade, coating a water phase solution on the surface, vertically drying in the shade, coating an oil phase solution for interfacial polymerization, pouring out the solution, drying in an oven at the temperature of 30-60 ℃ for 5-10min to prepare the reverse osmosis membrane, and putting the reverse osmosis membrane into deionized water for later use.
5. The method of preparing a reverse osmosis membrane according to claim 4, wherein: the aqueous phase solution in the step S3 is one of m-phenylenediamine, p-phenylenediamine or xylylenediamine, and the concentration of the aqueous phase solution in the solution is 0.5wt.% to 6 wt.%.
6. The method of preparing a reverse osmosis membrane according to claim 4, wherein: the oil phase solution in the step S3 is one of trimesoyl chloride, phthaloyl chloride, terephthaloyl chloride or isophthaloyl chloride, and the concentration of the oil phase solution in the solution is 0.02wt.% to 0.5 wt.%.
CN202111384106.2A 2021-11-19 2021-11-19 Base membrane of reverse osmosis membrane and preparation method thereof Pending CN114011255A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107486041A (en) * 2017-10-17 2017-12-19 常州市美纤膜技术有限公司 A kind of ultralow pressure complex reverse osmosis membrane and preparation method thereof
CN108671755A (en) * 2018-05-16 2018-10-19 南京帝膜净水材料开发有限公司 A kind of preparation method of complex reverse osmosis membrane
CN110385046A (en) * 2018-12-29 2019-10-29 启成(江苏)净化科技有限公司 A method of big flux RO membrane is prepared with more acyl chlorides substituted cyclic macromoleculars
CN111001298A (en) * 2019-12-30 2020-04-14 天津天元新材料科技有限公司 Preparation method of modified reverse osmosis membrane
CN111974230A (en) * 2020-08-31 2020-11-24 启成(江苏)净化科技有限公司 Preparation method of hydrophilic base membrane for preparing high-flux reverse osmosis membrane
AU2020104003A4 (en) * 2020-12-10 2021-02-18 Ocean University Of China Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107486041A (en) * 2017-10-17 2017-12-19 常州市美纤膜技术有限公司 A kind of ultralow pressure complex reverse osmosis membrane and preparation method thereof
CN108671755A (en) * 2018-05-16 2018-10-19 南京帝膜净水材料开发有限公司 A kind of preparation method of complex reverse osmosis membrane
CN110385046A (en) * 2018-12-29 2019-10-29 启成(江苏)净化科技有限公司 A method of big flux RO membrane is prepared with more acyl chlorides substituted cyclic macromoleculars
CN111001298A (en) * 2019-12-30 2020-04-14 天津天元新材料科技有限公司 Preparation method of modified reverse osmosis membrane
CN111974230A (en) * 2020-08-31 2020-11-24 启成(江苏)净化科技有限公司 Preparation method of hydrophilic base membrane for preparing high-flux reverse osmosis membrane
AU2020104003A4 (en) * 2020-12-10 2021-02-18 Ocean University Of China Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof

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