CN114082309B - Polyphosphazene amide nanofiltration membrane with high-valence charge group on surface and preparation method thereof - Google Patents
Polyphosphazene amide nanofiltration membrane with high-valence charge group on surface and preparation method thereof Download PDFInfo
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- CN114082309B CN114082309B CN202111345289.7A CN202111345289A CN114082309B CN 114082309 B CN114082309 B CN 114082309B CN 202111345289 A CN202111345289 A CN 202111345289A CN 114082309 B CN114082309 B CN 114082309B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
Abstract
The invention relates to a polyphosphazene amide nanofiltration membrane with a high-valence charge group on the surface and a preparation method thereof, and solves the technical problem that the traditional nanofiltration membrane material with a monovalent negative group (carboxyl and sulfonic group) on the surface has poor selectivity on organic matters/salts interception in the prior art by adopting the nanofiltration membrane prepared by the preparation method of the polyphosphazene amide nanofiltration membrane with the high-valence charge group on the surface.
Description
Technical Field
The invention relates to the technical field of water treatment membranes, in particular to a polyphosphazene nanofiltration membrane with a high-valence charge group on the surface and a preparation method thereof.
Background
The traditional nanofiltration membrane material is a polyamide nanofiltration membrane with excessive monovalent negative charge groups on the surface, and is mainly prepared by interfacial polymerization of carbonic acid derivative acyl chloride (such as trimesoyl chloride) or sulfonyl chloride oil-soluble monomers and amine water-soluble monomers (such as piperazine, m/p-phenylenediamine and the like). The polyamide desalting layer generated by the reaction has excessive (sulfonyl) chloride groups which are hydrolyzed to generate carboxyl or sulfonic acid groups which are monovalent anions, so that the surface of the membrane is negatively charged, and the ion trapping effect is influenced by the southward effect. Therefore, the nanofiltration membrane technology can realize the selective separation of organic matters with different molecular weights and ions with different valence states, and is widely applied to the fields of water treatment, biological medicine, food industry and the like.
In order to increase the selectivity of organic matter/salt interception, the traditional nanofiltration membrane material with monovalent and negative electric groups (carboxyl groups and sulfonic groups) on the surface needs to greatly change the charge quantity of a membrane desalination layer by various complicated means so as to increase the charge density; for example, deng Huiyu (structure control and performance research of low-voltage charged nanofiltration membrane, doctor paper of Zhejiang university (2008)) is used for grafting methacryloyloxyethyl trimethyl ammonium chloride with high charge density onto the surface of polysulfone ultrafiltration membrane by an ultraviolet irradiation method to prepare a low-voltage monovalent charge group nanofiltration membrane; CN103240004B discloses a method of introducing a polymer with monovalent ionizable groups into the interior of a membrane material by a swelling embedding method to produce nanofiltration membranes of varying charge levels. However, according to the southward steric hindrance model, the strength of interaction between monovalent and monovalent, monovalent and higher valent anions (cations) is much smaller than the charge interactions between higher valent anions (cations). Therefore, the high-valence charge introduced into the nanofiltration membrane desalting layer can significantly change the selectivity of nanofiltration membrane ions, which is easier to realize than single surface charge amount (charge density) improvement, and the material has stronger long-time stability.
Therefore, in order to solve the above problems, the present invention is highly required to provide a method for preparing a polyphosphazene nanofiltration membrane having a high-valence charge group on the surface.
Disclosure of Invention
The invention aims to provide a preparation method of a polyphosphazene amide nanofiltration membrane with a high-valence charge group on the surface, which solves the technical problem that the traditional nanofiltration membrane material with a monovalent negative group (carboxyl and sulfonic group) on the surface has poor selectivity on organic matters/salts in the prior art by proposing the polyphosphazene amide nanofiltration membrane with the high-valence charge group on the surface.
The invention provides a polyphosphazene amide nanofiltration membrane with a high-valence charge group on the surface, which comprises at least one of a repeating unit structure shown in a formula 1, a formula 2, a formula 3, a formula 4 and a formula 5;
in the formulas 1-5, R1 is one of-O-, 1-8 straight chain or branched chain alkane groups or aromatic hydrocarbon groups;
r2 and R3 in the formula 1-formula 5 are one of-OH, -NH-, -N-, -Cl or-Br;
r4 in formula 1-formula 5 is-SO 3 One of H, -COOH or-H;
r5 in formula 5 may be one of a straight chain or branched alkyl group of-H, 1-8.
Preferably, the method comprises the steps of,
and->
The molar ratio of (3) is (20-80): (80-20).
Preferably, the phosphoramide polymer has a weight average molecular weight of from 2 to 100 tens of thousands.
The invention also provides a preparation method of the polyphosphazene amide nanofiltration membrane with the surface provided with the high-valence charge group, which comprises the following preparation steps:
dissolving a phosphoryl chloride reagent in an oil phase solvent, and uniformly mixing to obtain a phosphoryl chloride oil solution;
dissolving amine monomers in aqueous phase solution, and adding aqueous phase additives to obtain amine aqueous solution;
the phosphorus oxychloride oil solution and the amine aqueous solution are subjected to interfacial polymerization reaction on a porous base membrane to generate an amine phosphate desalting layer, so as to form a nascent nanofiltration membrane;
and drying the nascent state nanofiltration membrane to obtain the nanofiltration membrane.
Preferably, before the nascent nanofiltration membrane is dried, the surface of the nascent nanofiltration membrane is coated with phosphoryl chloride oil solution.
Preferably, the phosphoryl chloride-based reagent comprises at least one of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, O-dimethylphosphoryl chloride, phosphoryl chloride, pyrophosphoryl chloride, bis (dimethylamino) phosphoryl chloride and dichlorophosphoric acid ester;
preferably, the amine monomer comprises at least one of piperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, polyethyleneimine, phenylmethylamine, 2,5 diaminobenzenesulfonic acid, aliphatic diamine.
Preferably, the solid mass fraction of the phosphoryl chloride reagent is 0.05% -50%; the mass fraction of solids in the amine monomer is 0.1% -20%.
Preferably, the oil phase solvent is at least one of a straight or branched alkane containing 1 to 8 carbon atoms or a cycloalkane containing 6 to 10 carbon atoms.
Preferably, the porous base membrane is polysulfone, polyethersulfone, polyacrylonitrile, polyethylene, polypropylene; the phosphoryl chloride reagent is dip-coated on the surface of the nascent nanofiltration membrane for reaction for 30-1200s; the drying temperature is 50-90 ℃.
Compared with the prior art, the preparation method of the polyphosphazene amide nanofiltration membrane with the surface provided by the invention has the following steps:
the preparation method of the polyphosphoryl amide nanofiltration membrane with the high-valence charge groups on the surface selects the high-activity phosphoryl chloride reagent as an oil-soluble monomer, and generates a desalting layer of the phosphoramide substance on the porous base membrane through an interfacial polymerization reaction or a post-treatment process together with an amine aqueous solution monomer, and high-valence anions generated after partial hydrolysis of the phosphoryl chloride functional groups are introduced into the membrane surface to obtain the nanofiltration membrane with the high-valence negative charge groups on the surface and high organic matter/salt separation selectivity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of sample 1 and comparative example 1 according to example one, wherein a is sample 1 and b is comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyphosphazene amide nanofiltration membrane with a high-valence charge group on the surface, which comprises at least one of a repeating unit structure shown in a formula 1, a formula 2, a formula 3, a formula 4 and a formula 5;
in the formulas 1-5, R1 is one of-O-, 1-8 straight chain or branched chain alkane groups or aromatic hydrocarbon groups;
r2 and R3 in the formula 1-formula 5 are one of-OH, -NH-, -N-, -Cl or-Br;
r4 in formula 1-formula 5 is-SO 3 One of H, -COOH or-H;
r5 in formula 5 may be one of a straight chain or branched alkyl group of-H, 1-8.
In particular, the method comprises the steps of,
and->
The molar ratio of (3) is (20-80): (80-20).
Specifically, the phosphoramide polymer has a weight average molecular weight of 2 to 100 tens of thousands.
The invention also provides a preparation method of the polyphosphazene amide nanofiltration membrane with the surface provided with the high-valence charge group, which comprises the following preparation steps:
s1) dissolving a phosphoryl chloride reagent in an oil phase solvent, and uniformly mixing to obtain a phosphoryl chloride oil solution;
s2) dissolving amine monomers in an aqueous phase solution, and adding an aqueous phase additive to obtain an amine aqueous solution;
s3) carrying out interfacial polymerization reaction on the phosphorus oxychloride oil solution and the amine water solution on the porous base membrane to generate an amine phosphate desalting layer, so as to form a nascent nanofiltration membrane;
s4) drying the nascent state nanofiltration membrane to obtain the nanofiltration membrane.
Specifically, before the nascent nanofiltration membrane is dried, the surface of the nascent nanofiltration membrane is coated with phosphoryl chloride oil solution.
Specifically, the phosphoryl chloride reagent comprises at least one of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, O-dimethylphosphoryl chloride, phosphoryl chloride, pyrophosphoryl chloride, bis (dimethylamino) phosphoryl chloride and dichlorophosphate;
the amine monomer comprises at least one of piperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, polyethyleneimine, phenylmethylamine, 2, 5-diaminobenzene sulfonic acid and aliphatic diamine.
Specifically, the solid mass fraction of the phosphoryl chloride reagent is 0.05% -50%; the mass fraction of solids in the amine monomer is 0.1% -20%.
Specifically, the oil phase solvent is at least one of a straight-chain or branched alkane containing 1-8 carbon atoms or a cycloalkane containing 6-10 carbon atoms.
Specifically, the porous base membrane is polysulfone, polyethersulfone, polyacrylonitrile, polyethylene and polypropylene; the phosphoryl chloride reagent is dip-coated on the surface of the nascent nanofiltration membrane for reaction for 30-1200s; the drying temperature is 50-90 ℃.
Example 1
The preparation process of the polyphosphazene amide nanofiltration membrane (sample 1) with the high-valence charge groups on the surface comprises the following preparation steps:
101 Dissolving pyrophosphoryl chloride in Isopar G (isoparaffin solvent), uniformly mixing, and preparing Isopar G solution of 0.2wt% of pyrophosphoryl chloride;
102 0.2wt% of an aqueous amine solution is prepared;
103 Pouring 0.2 weight percent of amine aqueous solution on the surface of the polysulfone porous base membrane for 30S, rolling the surface of a dry film sheet by using rubber, pouring 0.2 weight percent of Isopar G solution of pyrophosphoryl chloride on the surface of the polysulfone porous base membrane for reaction for 90S, and generating an amine phosphate desalting layer through interfacial polymerization reaction to form a nascent nanofiltration membrane;
104 The nascent state nanofiltration membrane is put into a 60 ℃ oven to be dried for 300s, and the nanofiltration membrane (sample 1) is obtained.
Taking 500mg/L calcium chloride and 500mg/L glucose aqueous solution as representative feed liquid, adopting a self-made flat membrane evaluation device to measure the interception performance of the nanofiltration membrane, and adopting a commercial digital conductivity analyzer to measure the conductivity of the calcium chloride feed liquid and the conductivity of the exudates; the organic carbon content and the effusion of the organic matter solution feed liquid are analyzed and measured by adopting a test method of the total organic carbon content
From these conductivity or organic carbon content measurement values, the retention rate R of calcium chloride and organic matters was calculated according to the following formula (1).
Wherein: c (C) f Is the concentration of the feed solution; c (C) p Is the permeate concentration.
Sample 1 had a 500mg/L calcium chloride solution retention of 27.84% and an organic retention of 93.32% at a pressure of 0.48 MPa; as shown by a in fig. 1, the scanning electron microscope photograph shows that the surface of the sample 1 is smooth and flat.
Comparative example 1 was prepared, comparative example 1 was identical to the preparation procedure of sample 1, except that the oil phase solution was formulated as Isopar G solution formulated with 0.2wt% trimesoyl chloride.
The nanofiltration membrane performance of the obtained comparative example 1, which contains monovalent carboxyl groups in the desalting layer, has a retention rate of 36.80% of 500mg/L calcium chloride solution and a retention rate of 67.31% of organic matters under the pressure of 0.48 MPa. As shown in b of FIG. 1, the scanning electron microscope photo shows that the surface of the membrane has a more hundred-nanometer-sized fold structure
Sample 1 is lower in calcium chloride solution retention rate and higher in organic retention rate than comparative example 1, and the difference between the calcium chloride solution retention rate and the organic retention rate is large, which indicates that the nanofiltration membrane with high valence negative charge groups has higher organic/salt separation selectivity, i.e. has very low salt retention characteristics under the condition of high organic retention.
Isopar G is a commercial isoparaffin solvent from ExxonMobil.
Example two
The preparation process of the polyphosphazene amide nanofiltration membrane (sample 2) with the high-valence charge groups on the surface comprises the following preparation steps:
201 Dissolving trimesoyl chloride in Isopar G solvent, uniformly mixing, and preparing Isopar G solution of 0.5wt% of trimesoyl chloride;
202 1wt% of an aqueous amine solution is prepared;
203 Pouring 1wt% of amine aqueous solution on the surface of the polysulfone porous base membrane for 30S, rolling the surface of a dry film sheet by using rubber, pouring 0.5wt% of Isopar G solution of pyrophosphoryl chloride on the surface of the polysulfone porous base membrane for reaction for 90S, and generating an amine phosphate desalting layer through interfacial polymerization reaction to form a nascent nanofiltration membrane;
204 Preparing Isopar G solution of 0.1wt% phosphoryl chloride, pouring Isopar G solution of 0.1wt% phosphoryl chloride onto nascent nanofiltration membrane, reacting for 90s, and drying in oven at 60deg.C for 300s to obtain nanofiltration membrane (sample 2)
Sample 2 had a 500mg/L calcium chloride solution retention of 35.97% and an organic retention of 95.35% at a pressure of 0.48 MPa; scanning electron micrographs showed that sample 2 had a smooth and even surface.
Comparative example 2 the preparation of comparative example 2 was identical to that of sample 2 except that in step 204, isopar G solution of 0.1wt% trimesoyl chloride was prepared and Isopar G solution of 0.1wt% trimesoyl chloride was poured onto the nascent nanofiltration membrane.
The nanofiltration membrane performance of the desalting layer of the obtained comparative example 2 containing monovalent carboxyl groups; the retention rate of 500mg/L calcium chloride solution of the nanofiltration membrane is 83.01 percent and the retention rate of organic matters is 89.15 percent under the pressure of 0.48 MPa.
Comparative example 3, comparative example 2 was prepared by the same method as sample 2 except that in step 202, an aqueous solution of 1.5wt% m-phenylenediamine was prepared; in step 204, a 0.1wt% Isopar G solution of trimesoyl chloride was prepared and poured onto the nascent nanofiltration membrane.
Comparative example 3 nanofiltration membrane performance with monovalent carboxyl groups in the desalting layer: the retention rate of 500mg/L calcium chloride solution of the nanofiltration membrane is 97.52 percent and the retention rate of organic matters is 96.64 percent under the pressure of 0.48 MPa.
Sample 2 was lower in calcium chloride solution rejection and higher in organic rejection than comparative examples 2 and 3, showing that nanofiltration membranes with high valence negative charge groups have higher selectivity for organic/salt separation, i.e., have very low salt rejection characteristics with high organic rejection.
Example III
The preparation process of the polyphosphazene amide nanofiltration membrane (sample 3) with the high-valence charge groups on the surface comprises the following preparation steps:
301 Dissolving phosphoryl chloride and pyrophosphoryl chloride in normal hexane solvent, uniformly mixing, and preparing normal hexane mixed solution of 0.5wt% of phosphoryl chloride and pyrophosphoryl chloride;
302 1.5wt% of m-phenylenediamine aqueous solution is prepared;
303 Pouring 1.5 weight percent of m-phenylenediamine aqueous solution on the surface of a polysulfone porous base membrane for 30S, rolling the surface of a dry film sheet by using rubber, pouring 0.5 weight percent of n-hexane mixed solution of phosphoryl chloride and pyrophosphoryl chloride on the surface of the polysulfone porous base membrane for 90S, and generating an amine phosphate desalting layer through interfacial polymerization reaction to form a nascent nanofiltration membrane;
304 Preparing Isopar G solution of 0.1wt% phosphoryl chloride, pouring Isopar G solution of 0.1wt% phosphoryl chloride onto nascent nanofiltration membrane, reacting for 90s, and drying in oven at 60deg.C for 200s to obtain nanofiltration membrane (sample 3)
Sample 3 had a 500mg/L calcium chloride solution rejection of 44.4% and an organic rejection of 96.28% at a pressure of 0.48 MPa; scanning electron micrographs showed that sample 2 had a smooth and even surface.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A polyphosphazene nanofiltration membrane with high-valence charge groups on the surface is characterized in that: comprises at least one of the repeating unit structures shown in the formula 1, the formula 2, the formula 3, the formula 4 and the formula 5;
in the formulas 1-5, R1 is one of-O-, 1-8 straight chain or branched chain alkane groups or aromatic hydrocarbon groups;
r2 and R3 in the formula 1-formula 5 are one of-OH, -NH-, -N-, -Cl or-Br;
r4 in formula 1-formula 5 is-SO 3 One of H, -COOH or-H;
r5 in formula 5 may be one of a straight chain or branched alkyl group of-H, 1-8.
2. The polyphosphazene nanofiltration membrane with high valence charge groups on the surface of the membrane according to claim 1, wherein the membrane comprises:
and->
The molar ratio of (3) is (20-80): (80-20).
3. The polyphosphazene nanofiltration membrane with high valence charge groups on the surface of the membrane according to claim 1, wherein the membrane comprises: the weight average molecular weight of the phosphoramide polymer is 2 ten thousand to 100 ten thousand.
4. A method for preparing a polyphosphazene nanofiltration membrane with high valence charge groups on the surface based on any one of claims 1-3, characterized by: the preparation method comprises the following preparation steps:
dissolving a phosphoryl chloride reagent in an oil phase solvent, and uniformly mixing to obtain a phosphoryl chloride oil solution;
dissolving amine monomers in aqueous phase solution, and adding aqueous phase additives to obtain amine aqueous solution;
the phosphorus oxychloride oil solution and the amine aqueous solution are subjected to interfacial polymerization reaction on a porous base membrane to generate an amine phosphate desalting layer to form a nascent nanofiltration membrane, and the surface of the nascent nanofiltration membrane is coated with the phosphorus oxychloride oil solution;
and (3) drying the nascent nanofiltration membrane to obtain the polyphosphazene nanofiltration membrane with the surface provided with the high-valence charge groups.
5. The method of manufacturing according to claim 4, wherein: the phosphoryl chloride reagent comprises at least one of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, O-dimethyl phosphoryl chloride, pyrophosphoryl chloride, bis (dimethylamino) phosphoryl chloride and dichloro phosphate.
6. The method of manufacturing according to claim 4, wherein: the amine monomer comprises at least one of piperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, polyethyleneimine, phenylmethylamine, 2, 5-diaminobenzene sulfonic acid and aliphatic diamine.
7. The method of manufacturing according to claim 4, wherein: the solid mass fraction of the phosphoryl chloride reagent is 0.05% -50%; the mass fraction of solids in the amine monomer is 0.1% -20%.
8. The method of manufacturing according to claim 4, wherein: the oil phase solvent is at least one of straight chain or branched chain alkane containing 1-7 carbon atoms or cycloalkane containing 6-10 carbon atoms.
9. The method of manufacturing according to claim 4, wherein: the porous base membrane is at least one of polysulfone, polyethersulfone, polyacrylonitrile, polyethylene or polypropylene; the interface reaction time is 30-1200s; the drying temperature is 50-90 ℃.
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| US20080135482A1 (en) * | 2006-11-27 | 2008-06-12 | Kripal Singh | Polyamide nanofiltration membrane useful for the removal of phospholipids |
| KR20150005330A (en) * | 2013-07-05 | 2015-01-14 | 한국화학연구원 | Preparation method of polyamide nanofiltration composite membrane and the polyamide nanofiltration composite membrane thereby |
| CN110960991A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Composite nanofiltration membrane, preparation method and application |
| CN112090282A (en) * | 2019-06-17 | 2020-12-18 | 天津工业大学 | High-selectivity polyamide nanofiltration membrane and preparation method thereof |
| CN112108020A (en) * | 2020-09-10 | 2020-12-22 | 中国科学院过程工程研究所 | Polyamide nanofiltration membrane and preparation method and application thereof |
| CN113368694A (en) * | 2021-08-11 | 2021-09-10 | 湖南澳维新材料技术有限公司 | Solvent-resistant composite nanofiltration membrane and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080135482A1 (en) * | 2006-11-27 | 2008-06-12 | Kripal Singh | Polyamide nanofiltration membrane useful for the removal of phospholipids |
| KR20150005330A (en) * | 2013-07-05 | 2015-01-14 | 한국화학연구원 | Preparation method of polyamide nanofiltration composite membrane and the polyamide nanofiltration composite membrane thereby |
| CN110960991A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Composite nanofiltration membrane, preparation method and application |
| CN112090282A (en) * | 2019-06-17 | 2020-12-18 | 天津工业大学 | High-selectivity polyamide nanofiltration membrane and preparation method thereof |
| CN112108020A (en) * | 2020-09-10 | 2020-12-22 | 中国科学院过程工程研究所 | Polyamide nanofiltration membrane and preparation method and application thereof |
| CN113368694A (en) * | 2021-08-11 | 2021-09-10 | 湖南澳维新材料技术有限公司 | Solvent-resistant composite nanofiltration membrane and preparation method thereof |
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