CN114259880B - Reverse osmosis membrane, preparation method and device thereof - Google Patents
Reverse osmosis membrane, preparation method and device thereof Download PDFInfo
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- CN114259880B CN114259880B CN202111636146.1A CN202111636146A CN114259880B CN 114259880 B CN114259880 B CN 114259880B CN 202111636146 A CN202111636146 A CN 202111636146A CN 114259880 B CN114259880 B CN 114259880B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The application discloses a preparation method of a reverse osmosis membrane, which comprises the following steps: respectively preparing a water phase solution and an oil phase solution; immersing a basement membrane into the aqueous phase solution, keeping the solution for 10 to 60 seconds, and then carrying out surface drying treatment on the basement membrane; coating the basement membrane with the dried surface with an oil phase solution under the conditions that the temperature is 20-25 ℃ and the humidity is 45-70 RH percent, and then removing the redundant oil phase solution; and carrying out heat treatment on the membrane, rinsing, glycerol soaking, protective layer coating and drying to obtain the reverse osmosis membrane. The application also provides a membrane, and a reverse osmosis membrane preparation apparatus. According to the reverse osmosis membrane preparation method, the prepared membrane and the reverse osmosis membrane preparation device, the temperature and the humidity during oil phase solution coating are controlled, so that the oil phase reaction monomers can be prevented from being hydrolyzed by free water in the air, the effective concentration of the oil phase reaction monomers is stabilized, the interface polymerization reaction is ensured to be fully performed, and the reverse osmosis membrane with higher crosslinking degree and good stability is obtained.
Description
Technical Field
The application relates to the technical field of reverse osmosis membrane preparation, in particular to a reverse osmosis membrane, and a preparation method and a device thereof.
Background
Reverse osmosis, also known as reverse osmosis, is a membrane separation operation that uses a pressure differential as a driving force to separate a solvent from a solution. Pressure is applied to the feed solution on one side of the reverse osmosis membrane and when the pressure exceeds its osmotic pressure, the solvent will reverse osmosis against the direction of natural osmosis. Thereby obtaining a permeated solvent, i.e., permeate, at the low pressure side of the reverse osmosis membrane; the high pressure side yields a concentrated solution, i.e. a concentrate. If seawater is treated by reverse osmosis, fresh water is obtained at the low pressure side of the reverse osmosis membrane, and brine is obtained at the high pressure side.
The reverse osmosis membrane has no phase change and chemical reaction in the application process, does not destroy the biological activity, has the characteristics of low energy consumption, small equipment volume, simple operation, strong adaptability and the like, and is widely applied to the fields of seawater desalination, brackish water desalination, industrial, commercial and household pure water preparation, sewage treatment, reclaimed water recycling, concentration and separation and the like.
The conventional reverse osmosis membrane is usually prepared by adopting an interfacial polymerization method, a layer of polysulfone basement membrane is coated on non-woven fabrics firstly in the preparation process, the basement membrane is coated by a water phase and an oil phase, and the interface is polymerized to obtain the reverse osmosis membrane. However, the membrane prepared by the method has loose structure, low degree of crosslinking and poor stability.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a method for preparing a reverse osmosis membrane; the second object of the present invention is to provide a reverse osmosis membrane prepared by the above method; the third purpose of the invention is to provide a reverse osmosis membrane preparation device. According to the reverse osmosis membrane preparation method, the prepared membrane and the reverse osmosis membrane preparation device, the temperature and the humidity during oil phase solution coating are controlled, the oil phase reaction monomer can be prevented from being hydrolyzed by free water in the air, the effective concentration of the oil phase reaction monomer is stabilized, the full proceeding of interfacial polymerization reaction is ensured, the reverse osmosis membrane with higher crosslinking degree and good stability is obtained, and the desalination rate and the stability of the reverse osmosis membrane are improved.
The technical scheme provided by the invention is as follows:
a preparation method of a reverse osmosis membrane comprises the following steps:
respectively preparing a water phase solution and an oil phase solution;
immersing a basement membrane into the aqueous phase solution, keeping the solution for 10 to 60 seconds, and then carrying out surface drying treatment on the basement membrane;
coating the basement membrane with the dried surface with an oil phase solution under the conditions that the temperature is 20-25 ℃ and the humidity is 45-70 RH percent, and then removing the redundant oil phase solution;
and carrying out heat treatment on the membrane, rinsing, glycerol soaking, protective layer coating and drying to obtain the reverse osmosis membrane.
Preferably, the oil phase solution is applied to the surface-dried base film at 20 to 23 ℃ and 45 to 65 RH%.
Preferably, the surface drying treatment of the base film specifically comprises the following steps: vacuum water absorption is carried out on the basement membrane immersed in the water phase;
the method for removing the redundant oil phase solution specifically comprises the following steps: and removing the oil phase solution on the surface of the bottom film by using an oil-driving roller.
Preferably, the base membrane is specifically polyether sulfone base membrane with molecular weight cutoff of 3-5 ten thousand;
the aqueous phase solution is prepared by dissolving aqueous phase reaction monomers, a surfactant and inorganic base in water, wherein the concentration of the aqueous phase reaction monomers is 1-3 wt%, the concentration of the surfactant is 0.02-0.08 wt%, and the concentration of the inorganic base is 0.2-1.0 wt%;
the oil phase solution is prepared by dissolving oil phase reaction monomers in an organic solvent, wherein the concentration of the oil phase reaction monomers is 0.1-0.5 wt%.
Preferably, the water-phase reaction monomer is one or more of triethanolamine, methyldiethanolamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
the oil phase reaction monomer is one or more of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or pyromellitic chloride.
Preferably, the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate and hexadecyl trimethyl ammonium bromide;
the inorganic base is one or more of sodium hydroxide and potassium hydroxide;
the organic solvent is one or more of trifluorotrichloroethane, n-hexane, cyclohexane or heptane.
A reverse osmosis membrane prepared by the preparation method of any one of the above.
A reverse osmosis membrane production apparatus comprising: the device comprises a bottom film transmission mechanism, a water phase treatment mechanism, an oil phase treatment mechanism, a first oven, a rinsing mechanism, a protective layer coating mechanism and a second oven;
the basement membrane transmission mechanism is used for transmitting the basement membrane to sequentially pass through the water phase treatment mechanism, the oil phase treatment mechanism, the first drying oven, the rinsing mechanism, the protective layer coating mechanism and the second drying oven;
the oil phase processing mechanism comprises a cover body, a bottom plate, an oil phase coating mechanism and a temperature and humidity control mechanism;
the base plate and the oil phase coating mechanism are positioned in the cover body, and the oil phase coating mechanism is positioned above the base membrane and is used for coating the oil phase solution on the base membrane; the bottom plate is positioned below the bottom film and used for supporting the bottom film.
Preferably, the oil phase coating mechanism comprises an oil phase solution storage tank and an oil phase solution coating head, wherein the oil phase solution coating head is positioned in the housing and communicated to the oil phase solution storage tank through a pipeline; and/or the presence of a gas in the gas,
the temperature and humidity control mechanism is specifically a constant temperature and humidity machine.
Preferably, the aqueous treatment mechanism comprises an aqueous phase soaking tank and a vacuum water absorption box; and/or the presence of a gas in the gas,
the oil phase processing mechanism also comprises an oil driving roller.
The applicant analyzes the problems of loose structure, low crosslinking degree and poor stability of the prepared film, a water-phase reaction monomer (such as m-phenylenediamine) has two functional groups, an oil-phase reaction monomer (such as trimesoyl chloride) has three functional groups, and interfacial polymerization reaction is carried out, namely the two functional groups react to generate a reticular polyamide structure with a certain crosslinking degree. Further analysis finds that the acyl chloride functional group of the oil phase reaction monomer trimesoyl chloride is easily hydrolyzed by free water molecules in the air and is changed into carboxyl, so that the dissolution and the diffusion of the oil phase reaction monomer in the oil phase are influenced, the reaction activity of the monomer is influenced, the crosslinking degree of the polymer is reduced, and the performance of the formed polyamide reverse osmosis membrane is finally influenced.
The prior preparation method does not consider the influence of hydrolysis of oil phase reaction monomers on interfacial polymerization reaction. In order to solve the problem, the applicant researches and controls the temperature and the humidity during the oil phase solution coating, so that the oil phase reaction monomer can be prevented from being hydrolyzed by free water in the air, the effective concentration of the oil phase reaction monomer is stabilized, the oil phase reaction monomer can be effectively diffused to the interface of a water phase and an oil phase, the full progress of interfacial polymerization reaction is ensured, the polyamide structure has higher crosslinking degree and is more compact, the reverse osmosis membrane with higher crosslinking degree and good stability is obtained, and the desalination rate and the stability of the reverse osmosis membrane are improved. Specifically, the temperature and the humidity when the oil phase solution is coated are controlled to be 20-25 ℃ and 45-70 RH%; and after the basement membrane is controlled to be immersed into the aqueous phase solution, the basement membrane is subjected to surface drying treatment, so that adverse effects on subsequent oil phase coating are avoided.
More preferably, the oil phase solution is applied to the surface-dried primary coating at 20 to 23 ℃ and a humidity of 45 to 65 RH%.
The aqueous solution is subjected to a surface drying treatment, preferably by means of vacuum water absorption, to facilitate the permeation of the aqueous solution into the polysulfone layer, and the polyamide structure formed is more tightly connected to the polysulfone layer. Preferably, the vacuum water absorption is performed by vacuum water absorption of the back surface of the base film by using a vacuum water absorption box. And the oil displacement roller can be used for removing the redundant oil phase solution on the surface of the basement membrane.
The method provided by the application is suitable for quality control of common oil phase reaction monomers, and the oil phase reaction monomers are preferably one or more of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or pyromellitic chloride. The oil phase reaction monomer and the oil phase additive are dissolved in the organic solvent together to prepare oil phase solution for use. The organic solvent is one or more of trifluorotrichloroethane, n-hexane, cyclohexane or heptane. The water phase can be prepared by dissolving water phase reaction monomers, a surfactant and inorganic base in water; the water phase reaction monomer is one or more of triethanolamine, methyldiethanolamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine, one or more of surfactant sodium dodecyl sulfate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide, and the inorganic alkali is one or more of sodium hydroxide and potassium hydroxide. When preparing the aqueous solution, RO water is preferably used.
The application also provides a reverse osmosis membrane prepared by the preparation method.
The application also provides a reverse osmosis membrane preparation device, which comprises a bottom membrane transmission mechanism, a water phase treatment mechanism, an oil phase treatment mechanism, a first oven, a rinsing mechanism, a protective layer coating mechanism and a second oven, wherein the oil phase treatment mechanism comprises a cover body, a bottom plate, an oil phase coating mechanism and a temperature and humidity control mechanism; the base plate and the oil phase coating mechanism are positioned in the cover body, and the oil phase coating mechanism is positioned above the basement membrane and is used for coating the oil phase solution on the basement membrane; the bottom plate is located below the bottom film and used for supporting the bottom film, the temperature and the humidity in the cover body are controlled through the temperature and humidity control mechanism, the bottom plate is located in a proper range, and the effective reaction concentration of the oil phase reaction monomer during oil phase coating is guaranteed.
Further, the oil phase coating mechanism comprises an oil phase solution storage tank and an oil phase solution coating head, wherein the oil phase solution coating head is positioned in the cover body and communicated with the oil phase solution storage tank through a pipeline. The oil phase solution storage tank prevents free water from entering the tank through a filtering mechanism, and the stability of the oil phase solution is kept; when the device is used, an oil phase solution enters the oil phase solution coating head through a pipeline, the basement membrane is coated in the cover body, and the temperature and humidity range is in a controllable range. Further, the temperature and humidity control mechanism is preferably a constant temperature and humidity machine. The cover body supplies the entry and the export of basement membrane business turn over, can introduce the air to the cover body in, takes out the high temperature and high humidity's of the internal high temperature and humidity's of cover through the constant temperature and humidity machine, and in sending into the cover body again with the air of low temperature and low humidity after the constant temperature and humidity machine is handled to reach the stability of stabilizing the compartment humiture.
Preferably, the water-based treatment mechanism comprises a water-phase soaking tank and a vacuum water absorption box, wherein the basement membrane is fully contacted with the water phase in the water-phase soaking tank, and then the vacuum water absorption box is used for carrying out vacuum water absorption on the back surface of the basement membrane; the oil phase processing mechanism also comprises an oil driving roller which is used for removing the redundant oil phase solution on the surface of the basement membrane.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural view of a reverse osmosis membrane production apparatus according to an embodiment of the present invention;
reference numerals are as follows: 1-basement membrane transport mechanism; 2-a water phase treatment mechanism; 21-water phase soaking tank; 22-vacuum suction box; 3-an oil phase treatment mechanism; 31-a cover; 32-a bottom plate; 33-oil phase coating mechanism; 34-a temperature and humidity control mechanism; 35-an oil displacement roller; 4-a first oven; 5-a rinsing mechanism; 6-protective layer coating mechanism; 7-a second oven; a-a bottom film.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly disposed on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It will be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings to facilitate the description of the application and to simplify the description, and are not intended to indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be constructed in operation as a limitation of the application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, the meaning of a plurality or a plurality is two or more unless explicitly defined otherwise.
It should be understood that the structures, ratios, sizes, and the like shown in the drawings are only used for matching the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the practical limit conditions of the present application, so that the modifications of the structures, the changes of the ratio relationships, or the adjustment of the sizes, do not have the technical essence, and the modifications, the changes of the ratio relationships, or the adjustment of the sizes, are all within the scope of the technical contents disclosed in the present application without affecting the efficacy and the achievable purpose of the present application.
Example 1
1) Preparing an aqueous phase solution: dissolving m-phenylenediamine, sodium dodecyl sulfate and sodium hydroxide in RO water to prepare an aqueous solution with the concentration of 1.8wt% of the m-phenylenediamine, the concentration of 0.04wt% of the sodium dodecyl sulfate and the concentration of 0.5wt% of the sodium hydroxide;
2) Preparing an oil phase solution: dissolving trimesoyl chloride in n-hexane to prepare a solution with the concentration of 0.2 wt%;
3) Directly immersing a polyether sulfone basement membrane with the molecular weight cutoff of 3-5 ten thousand into an aqueous phase solution, keeping for 10-60 s, and then carrying out surface drying treatment on the basement membrane through vacuum water absorption;
4) The basement membrane after the surface drying enters an oil phase reaction area with the temperature of 22.5 ℃ and the humidity of 70RH percent for oil phase coating, and the redundant oil phase is removed;
5) And (3) carrying out heat treatment on the membrane, rinsing, soaking in glycerol, coating with PVA, and drying to obtain the reverse osmosis membrane.
Example 2
The reverse osmosis membrane was produced using the reverse osmosis membrane production apparatus shown in fig. 1. The reverse osmosis membrane preparation device comprises: a basement membrane transmission mechanism 1, a water phase treatment mechanism 2, an oil phase treatment mechanism 3, a first oven 4, a rinsing mechanism 5, a protective layer coating mechanism 6 and a second oven 7; the basement membrane transmission mechanism 1 is used for transmitting the basement membrane to sequentially pass through the water phase treatment mechanism 2, the oil phase treatment mechanism 3, the first drying oven 4, the rinsing mechanism 5, the protective layer coating mechanism 6 and the second drying oven 7; the water-based treatment mechanism 2 comprises a water-phase soaking tank 21 and a vacuum water absorption box 22; the oil phase processing mechanism 3 comprises a cover body 31, a bottom plate 32, an oil phase coating mechanism 33, a temperature and humidity control mechanism 34 and an oil displacement roller 35; the base plate 32 and the oil phase coating mechanism 33 are positioned in the cover body 31, and the oil phase coating mechanism 33 is positioned above the basement membrane and is used for coating the oil phase solution on the basement membrane; the bottom plate 32 is positioned below the bottom film and is used for supporting the bottom film; the oil phase coating mechanism 33 comprises an oil phase solution storage tank and an oil phase solution coating head, wherein the oil phase solution coating head is positioned in the cover body 31 and communicated to the oil phase solution storage tank through a pipeline; the temperature and humidity control mechanism 34 is specifically a constant temperature and humidity machine; the oil-driving roller 35 is located in the housing 31 and is used for taking out the excess oil phase on the surface of the basement membrane.
The preparation steps are as follows:
1) Preparing an aqueous phase solution: dissolving m-phenylenediamine, sodium dodecyl sulfate and sodium hydroxide in RO water to prepare an aqueous solution with the concentration of 1.8wt% of the m-phenylenediamine, the concentration of 0.04wt% of the sodium dodecyl sulfate and the concentration of 0.5wt% of the sodium hydroxide, and storing the aqueous solution in an aqueous phase processing mechanism 2;
2) Preparing an oil phase solution: dissolving trimesoyl chloride in normal hexane to prepare a solution with the concentration of 0.2wt%, and storing the solution in an oil phase solution storage tank;
3) Moving a polyether sulfone basement membrane with the molecular weight cutoff of 3-5 ten thousand through a basement membrane transmission mechanism 1, immersing the basement membrane into an aqueous phase solution in an aqueous phase treatment mechanism 2, keeping for 10-60 s, and then drying the surface of the basement membrane through vacuum water absorption;
4) The basement membrane with the dried surface enters the oil phase treatment mechanism 3, the temperature and humidity in the cover body 31 are controlled to be 22.5 ℃ and the humidity is 60RH% through the temperature and humidity control mechanism 34, oil phase coating is carried out by using the oil phase solution coating head, meanwhile, the basement membrane is supported by the bottom plate 32, and then the redundant oil phase is removed;
5) And (3) conveying the membrane into a first oven for heat treatment, then conveying the membrane into a rinsing mechanism 5 for rinsing and glycerol soaking treatment, then coating PVA on a protective layer coating mechanism 6, and then conveying the membrane into a second oven 7 for drying treatment to obtain the reverse osmosis membrane.
Example 3
The same procedure as in example 1 was repeated except that the surface of the base film was dried, and the base film was subjected to oil-phase coating in an oil-phase reaction zone at 21.8 ℃ and 48 RH%.
Comparative example 1
The same procedure as in example 1 was repeated except that the surface of the base film was dried, and the base film was subjected to oil-phase coating in an oil-phase reaction zone at 25.0 ℃ and a humidity of 76 RH%.
Comparative example 2
The same procedure as in example 1 was repeated except that the surface of the base film was dried, and the base film was subjected to oil-phase coating in an oil-phase reaction zone at 24.8 ℃ and a humidity of 78 RH%.
The films prepared in examples 1-3 and comparative examples 1-2 were tested under the following conditions:
a 2000mg/L aqueous NaCl solution was tested at a pressure of 225psi, a test solution temperature of 25 ± 1 ℃, a test solution pH = 7.5-8.0.
The crosslinking degree test method comprises the following steps:
the degree of crosslinking was calculated by measuring the percentage contents of C, O, N elements on the film surface by XPS (X-ray photoelectron spectroscopy).
The test results are shown in the following table:
the results show that the present application can increase the degree of crosslinking of the polyamide structure and further increase the salt rejection and stability of the membrane by controlling the temperature and humidity of the oil phase reaction zone, while comparative examples 1-2 show that the membrane prepared has a low salt rejection and a low degree of crosslinking under high humidity conditions, indicating that the humidity has a greater effect on the quality of the membrane.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A preparation method of a reverse osmosis membrane is characterized by comprising the following steps:
respectively preparing a water phase solution and an oil phase solution;
immersing the basement membrane into the aqueous solution, keeping the solution for 10 to 60s, and then carrying out vacuum water absorption on the basement membrane;
coating the oil phase solution on the basement membrane with the dried surface under the conditions that the temperature is 20 to 23 ℃ and the humidity is 45 to 65RH percent, and then removing the redundant oil phase solution;
and carrying out heat treatment on the membrane, rinsing, glycerol soaking, protective layer coating and drying to obtain the reverse osmosis membrane.
2. The method of preparing a reverse osmosis membrane according to claim 1,
the method for removing the redundant oil phase solution comprises the following steps: and removing the oil phase solution on the surface of the basement membrane by using an oil-repelling roller.
3. The preparation method of a reverse osmosis membrane according to claim 1, characterized in that the base membrane is specifically a polyethersulfone base membrane with the molecular weight cutoff of 3-5 ten thousand;
the aqueous phase solution is prepared by dissolving an aqueous phase reaction monomer, a surfactant and an inorganic base in water, wherein the concentration of the aqueous phase reaction monomer is 1 to 3wt%, the concentration of the surfactant is 0.02 to 0.08wt%, and the concentration of the inorganic base is 0.2 to 1.0wt%;
the oil phase solution is prepared by dissolving oil phase reaction monomers in an organic solvent, wherein the concentration of the oil phase reaction monomers is 0.1 to 0.5wt%.
4. A method for preparing a reverse osmosis membrane according to claim 3, characterized in that the aqueous phase reaction monomer is one or more of triethanolamine, methyldiethanolamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
the oil phase reaction monomer is one or more of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride or pyromellitic chloride.
5. The method for preparing a reverse osmosis membrane according to claim 3, wherein the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate and cetyl trimethyl ammonium bromide;
the inorganic base is one or more of sodium hydroxide and potassium hydroxide;
the organic solvent is one or more of trifluorotrichloroethane, n-hexane, cyclohexane or heptane.
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| JPH01123824A (en) * | 1987-11-09 | 1989-05-16 | Tokyo Inst Of Technol | Production of polysiloxane/polyamide block copolymer |
| CN105848767A (en) * | 2013-12-26 | 2016-08-10 | 株式会社Lg化学 | High-functional polyamide-based dry water treatment separator and method for manufacturing same |
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| CN105289334B (en) * | 2015-11-25 | 2018-06-26 | 华东理工大学 | A kind of compound forward osmosis membrane and preparation method thereof |
| CN105749768A (en) * | 2016-04-15 | 2016-07-13 | 湖南沁森环保高科技有限公司 | Composite reverse osmosis membrane with high salt removing rate and controllable flux and method for preparing composite reverse osmosis membrane |
| CN109999665A (en) * | 2019-04-30 | 2019-07-12 | 中国科学院生态环境研究中心 | Lotus positive electricity anti-acid nanofiltration membrane, preparation method and application |
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| CN111229053B (en) * | 2020-02-17 | 2022-03-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-flux nanofiltration membrane, and preparation method and application thereof |
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| JPH01123824A (en) * | 1987-11-09 | 1989-05-16 | Tokyo Inst Of Technol | Production of polysiloxane/polyamide block copolymer |
| CN105848767A (en) * | 2013-12-26 | 2016-08-10 | 株式会社Lg化学 | High-functional polyamide-based dry water treatment separator and method for manufacturing same |
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