CN114432900B - Preparation method of anti-pollution composite reverse osmosis membrane and anti-pollution composite reverse osmosis membrane prepared by same - Google Patents
Preparation method of anti-pollution composite reverse osmosis membrane and anti-pollution composite reverse osmosis membrane prepared by same Download PDFInfo
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Abstract
The invention relates to a preparation method of an anti-pollution composite reverse osmosis membrane and the anti-pollution composite reverse osmosis membrane prepared by the method. The preparation method comprises the following steps: (1) Preparing a polymer solution as a casting solution, coating the casting solution on a reinforced material, and then curing in a coagulating bath to form a film, thereby forming a polymer porous supporting layer on the reinforced material; (2) Contacting the reinforcing material with the polymer porous supporting layer obtained in the step (1) with an aqueous phase solution containing amine monomers, and then contacting with an oil phase solution containing acyl chloride monomers, so as to form a polyamide layer on the polymer porous supporting layer; (3) Contacting the reinforcing material obtained in step (2) with a polyamide layer and a polymer porous support layer in sequence with a post-grafting treatment aqueous solution; and (4) cleaning and drying to obtain the anti-pollution composite reverse osmosis membrane. The anti-pollution composite reverse osmosis membrane prepared by the method has the advantages that the anti-pollution performance is obviously improved, and the service life is greatly prolonged.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membranes, in particular to a preparation method of an anti-pollution composite reverse osmosis membrane and the anti-pollution composite reverse osmosis membrane prepared by the preparation method.
Background
The reverse osmosis technology is widely applied to the fields of water treatment, chemical industry, food, medicine and the like, but the reverse osmosis membrane has the problem of pollution in the using process. In order to improve the anti-pollution performance of the reverse osmosis membrane, researchers have made many studies on the anti-pollution performance of the reverse osmosis membrane, and found that physical properties of the membrane surface such as roughness, hydrophilicity and charge property all affect the pollution of the membrane, the smoother the membrane surface is, the less the membrane is easily polluted, and the hydrophilic surface can reduce the pollution of hydrophobic substances and increase the pollution of hydrophilic substances. Therefore, the anti-pollution performance of the membrane can be effectively improved by changing the surface property of the membrane through the membrane material and the surface modification.
In patent US7913857B2, a composite reverse osmosis membrane with high contamination resistance is prepared by coating the surface of a membrane with a hydrophilic compound containing an amine group and a hydroxyl group, the compound is connected by the covalent bond action of the amine group and residual acyl chloride, so that the compound can be well fixed on the surface of the membrane, and the hydroxyl group contained in the compound can change the hydrophilicity of the membrane. After 4 hours of protein contamination, the optimal modified membrane flux decayed 0.9% while the control decayed 21.8%. This indicates that coating with hydrophilic substances increases the resistance of the membrane to contamination by proteinaceous substances. The amino and residual acyl chloride are covalently linked to the surface of the membrane, and because the number of the residual acyl chloride is limited and the acyl chloride is easy to hydrolyze into carboxyl in aqueous solution, so that the number of the amino grafted to the surface of the membrane through covalent bonding on the surface of the membrane is limited, and the method has a limited effect on improving the anti-pollution performance of the membrane.
CN101439271B hydrophilic antipollution reverse osmosis membrane preparation method adopts N-hydroxy thiosuccinimide sodium salt, N-hydroxy thiosuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to graft- (CH) on polyamide cortex 2 CH 2 O) n-macromolecule hydrophilic chain, and improves the anti-pollution performance of the composite reverse osmosis membrane. The method mainly adopts N-hydroxy sulphosuccinimide sodium salt, N-hydroxy sulphosuccinimide and 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to activate polyethylene glycol, amino polyethylene glycol and polyvinyl alcohol so as to form amide with terminal amine groups on the surface of the membrane and graft the amide on the surface of the reverse osmosis membrane. The grafting process in this context requires the treatment of the polyamide composite membrane in an acidic solution with a pH of 1 to 3 and the activation and grafting processes in this context are carried out in stages, which undoubtedly increases the operational risks and the cost of recycling the waste liquid, and also increases the difficulty of controlling the reaction time and stability, which is disadvantageousIs suitable for large-scale production.
In patent CN108057348A, a hydrophilic bactericidal antipollution reverse osmosis membrane and a preparation method thereof, a bactericidal high molecular polymer and an antibacterial polymer are grafted on the surface of the reverse osmosis membrane by a reversible addition-fragmentation chain transfer polymerization activity polymerization method, and the prepared antipollution reverse osmosis membrane has excellent antipollution performance and bacterial growth inhibition performance on the premise of ensuring the original membrane performance. Dicyclohexylcarbodiimide is used herein to graft monomers to the surface of the composite membrane in an organic solvent.
In patent CN108126530a "a method for preparing an anti-pollution reverse osmosis composite membrane and a reverse osmosis composite membrane", a cross-linked anti-pollution coating is formed on the surface of a polyamide desalting layer, so that the service life and the anti-pollution performance of the membrane are improved, and the anti-pollution coating liquid is an acidic mixed solution containing polyacrylamide and aldehydes.
The article "Surface grafting of polyvinyl alcohol (PVA) with cross-linking of cellulose polymer (GA) to improve resistance to contamination of aromatic polyamide composite membranes using a microbial membrane bioreactor" ("Godwill Kasong et al"; water Practice and Technology (2019) 14 (3): 614-624) uses glutaraldehyde cross-linked PVA to coat the Surface of an aromatic polyamide composite membrane to improve its anti-contamination properties. The result shows that the structural morphology and the chemical property of the modified membrane are changed, the pollution resistance is obviously improved, the flux attenuation is reduced from 46.04% to 25.94% after modification, but the salt rejection rate of the membrane is slightly reduced, which has a certain limit for pursuing the membrane with high salt rejection rate.
In the article Surface modification on thin-film composite reverse osmosis membrane by location modification for anti-pollution (Zhang Yang et al; journal of Polymer Research 26 (3). March 2019), polyethylene glycol is used to modify the Surface of the reverse osmosis membrane so as to make the reverse osmosis membrane have more excellent anti-pollution performance. The polyethylene glycol is chelated and fixed on the surface of the polyamide membrane through the ion dipole effect between ether oxygen atoms in a PEG skeleton and-COONa in a PA layer, the flux attenuation of the membrane is 19 percent after 12 hours of bovine serum albumin pollution modification, the flux attenuation of an original membrane is 40 percent, and the contact angle of the modified membrane is reduced from 60.2 +/-2.12 degrees to 12.9 +/-0.25 degrees, which shows that the cationic complex polyethylene glycol modified reverse osmosis membrane can increase the hydrophilicity and the pollution resistance of the membrane. However, in this method, polyethylene glycol is attached to the membrane surface mainly by chelation, which may have a certain limitation in long-term operation stability of the membrane.
The article "Surface ionization of Chloroflexine a reverse osmosis membranes for in-situ biologicling control" (Kim Taek-Seung et al; journal of Membrane Science 576. April 2019) uses glutaraldehyde as a cross-linking agent to fix Chlorodidine on the Surface of a reverse osmosis Membrane by a molecular layer-by-layer self-assembly technique, which is expected to improve the anti-pollution performance of the Membrane. The results show that the chlorohexidine can be stably present on the surface of the membrane and the modified membrane has excellent anti-pollution performance and stability. In this method, chlorhexidine is fixed on the surface of the reverse osmosis membrane by glutaraldehyde crosslinking, and the acting force of chlorhexidine to the surface of the membrane is small, which is disadvantageous for long-term operation.
The article "In situ modification of the polyamide reverse osmosis membrane module for improved fouling resistance of the membrane (Liu Meihong et al; chemical Engineering Research and Design, volume 141, january 2019, pages 402-412) uses a reverse osmosis membrane module In situ modification process to activate the amidated carboxyl grafted sulfamic acid, diethanolamine and piperazine with 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and N-methylsuccinamide to improve the fouling resistance of the membrane. The result shows that the pollution resistance of the modified membrane to bovine serum albumin, sodium alginate and dodecyl ammonium bromide is obviously improved. The membrane component is adopted for modification, the component needs to be cleaned for at least 10 hours before modification to remove residues in the membrane component, the cleaned component is treated in a solution which takes 2-morpholine ethanesulfonic acid with pH of 4 as a buffer reagent and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and N-methylsuccinamide for 4 hours, the temperature is kept at 30 ℃, deionized water is used for cleaning after activation is finished, and finally a modified monomer is added for reaction for 9 hours at 30 ℃.
To date, the following needs still exist: the method can improve the pollution resistance of the reverse osmosis membrane, ensure the long-term stable operation of the reverse osmosis membrane, reduce the reaction time, and is simple in process and suitable for industrial large-scale production.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the problems in the prior art and provides a preparation method of an anti-pollution composite reverse osmosis membrane and the anti-pollution composite reverse osmosis membrane prepared by the preparation method.
Means for solving the problems
The inventors of the present invention have made extensive studies to achieve the above object and have found that a hydrophilic substance containing at least one amine group is grafted onto the surface of a composite reverse osmosis membrane by amide crosslinking in the presence of a pyridine catalyst through surface grafting post-treatment, and a hydantoin-based antibacterial substance is introduced to further improve the anti-fouling performance of the membrane, so that the flux decay of the membrane after fouling is reduced and the service life is greatly improved. This method greatly reduces the reaction time. The anti-pollution performance of the membrane is expected to be improved by performing surface grafting post-treatment on the reverse osmosis membrane, and a substance for post-treatment can stably exist on the surface of the membrane to ensure the long-term operation stability of the membrane.
One aspect of the present invention relates to a method for preparing an anti-fouling composite reverse osmosis membrane, comprising the steps of:
(1) Dissolving a polymer in a solvent to prepare a polymer solution serving as a membrane casting solution, coating the membrane casting solution on a reinforced material, and then curing in a coagulating bath to form a membrane, thereby forming a polymer porous supporting layer on the reinforced material;
(2) Contacting the reinforcing material with the polymer porous supporting layer obtained in the step (1) with an aqueous phase solution containing amine monomers, and then with an oil phase solution containing acyl chloride monomers, so as to form a polyamide layer on the polymer porous supporting layer;
(3) Contacting the reinforcing material having the polyamide layer and the polymer porous support layer obtained in (2) in this order with a post-grafting treatment aqueous solution containing a pyridine compound, an antibacterial substance, and a hydrophilic compound containing at least one amine group;
(4) And cleaning and drying to obtain the anti-pollution composite reverse osmosis membrane.
The method of preparing an anti-fouling composite reverse osmosis membrane according to the present application, wherein the polymer is one or more of polysulfone, polyethersulfone, polyacrylonitrile, sulfonated polyethersulfone, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide, and the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, chloroform, and dimethylsulfoxide, preferably, the concentration of the polymer is 10 to 30wt% based on the total weight of the polymer solution; preferably, the reinforcing material is a non-woven fabric and the coagulation bath is a water bath.
The method of making an anti-fouling composite reverse osmosis membrane according to the present application wherein the amine monomer is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, sym-phenylenediamine, polyetheramine, 3-fluoroaniline, 3-chloroaniline, aminopiperazine, 2,3-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminobenzenesulphonic acid, N-phenyl-p-phenylenediamine, 1,4-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-diaminoanisole, 3,4' -diaminodiphenyl ether, 23 zxft 5623-propylenediamine, 1,3-propylenediamine, diisobutylamine, 1,2-cyclohexanediamine, N-hexylamine, heptylamine, cycloheptylamine, 3456-zzylamine, 3456-octylenediamine, dodecylenediamine, N-butylenediamine, 655795, N-butylenediamine, 655749, N-butylenediamine, 655795, N-butylenediamine, 6538, N-butylenediamin, 6525, one or more of N-diethyl-p-phenylenediamine, 2-hydroxyethylpropylamine, 1,3-diamino-2-propanol, and 3,3',5,5' -tetramethylbenzidine, preferably, the amine monomer is present in a concentration of 1.0 to 8.0wt% based on the total weight of the aqueous solution.
The method of preparing an anti-fouling composite reverse osmosis membrane according to the present application, wherein the acyl chloride monomer is trimesoyl chloride, terephthaloyl chloride, oxalyl chloride, 3-bromopropionyl chloride, undecanoyl chloride, dodecanoyl chloride, n-valeroyl chloride, 3-fluorobenzoyl chloride, 4-methoxybenzoyl chloride, 4-phenylbenzoyl chloride, p-fluorobenzoyl chloride, isovaleroyl chloride, o-chlorobenzoyl chloride, isophthaloyl chloride, succinoyl chloride, 1,7-heptanedioyl chloride, malonic acid monoethyl ester chloride, m-methylbenzoyl chloride, 2-methoxybenzoyl chloride, 4-phenylbenzoyl chloride, 3,4-dimethoxybenzoyl chloride, cyclopentoyl chloride, cyclopropylformyl chloride, heptanooyl chloride, 3-phenylpropionoyl chloride, o-fluorobenzoyl chloride, p-ethylbenzoyl chloride, perfluorooctane sulfonyl chloride, 3 zxft 3963-trichlorobenzoyl chloride, 4-bromo-2-fluorobenzoyl chloride, 4325 zxft 3525, 3536-chlorobenzoyl chloride, preferably the concentration of n-butylbenzoyl chloride in the oil phase is 3926 wt% or 3926 wt% based on the total weight of the oil phase of the benzoyl chloride monomer; preferably, the solvent in the oil phase solution is one or more of ethylcyclohexane, ISOPAR G, ISOPAR E, pentane, hexane, octane, heptane, dichloromethane, carbon tetrachloride, toluene, xylene, propylene oxide, and cyclohexanone.
The method of making an anti-fouling composite reverse osmosis membrane according to the present application wherein the pyridine compound is one or more of 3-iodo-4-aminopyridine, 2-bromo-4-aminopyridine, 4-pyrrolidinylpyridine, 4-dimethylaminopyridine, 4-amino-3-nitropyridine, 4-amino-2-chloropyridine, 4-amino-3,5-dichloropyridine, 4-amino-2,6-dichloropyridine, 4-amino-2,6-dimethylpyridine, 4-methylaminopyridine, 2-amino-4-bromopyridine, 2-bromo-4-aminopyridine, 3-amino-4-bromopyridine, 4-amino-2-methoxypyridine, 3-amino-4-methylpyridine, 4-pyridinecarboxamide, 2-amino-3-hydroxypyridine, 2-aminopyridine, 3-aminopyridine, 2-amino-4-methylpyridine, and 2-amino-3-methylpyridine, preferably at a concentration of the grafted pyridine compound of from 0.10wt% based on the total weight of the aqueous solution.
The method for preparing an anti-fouling composite reverse osmosis membrane according to the present application, wherein the antibacterial substance is one or more of hydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1-aminohydantoin hydrochloride, 2-thiohydantoin and 3-allyl-5,5-dimethylhydantoin, preferably, the concentration of the antibacterial substance is 0.01wt% to 15wt% based on the total weight of the post-grafting treatment aqueous solution.
The method of making an anti-fouling composite reverse osmosis membrane according to the present application wherein the hydrophilic compound containing at least one amine group is one or more of 2- (propylamino) ethanol, 2-ethylamino ethanol, N-phenylethanolamine, methoxypolyethyleneglycol amine, hydroxylamine-O-sulfonic acid, 2-hydroxyethylamine, isopropanolamine, phenylethanolamine, polyetheramine, N-methyl-D-glucamine, aminopiperazine, 2-aminopyridine, 2,6-diaminopyridine, diethanolamine, ethanolamine, m-phenylenediamine, polyethyleneamine, polyethyleneimine, N-butyldiethanolamine, N-phenyldiethanolamine, O-phosphoethanolamine, diaminobenzenesulfonic acid, 2-amino-1-phenylethanol, 2-amino-3-hydroxypyridine, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, diethylene glycol di (3-aminopropyl) ether, propanolamine, and 1-aminocyclopropanecarboxylic acid, preferably, the hydrophilic compound containing at least one amine group is present at a concentration of 0.01 to 10wt%, based on the total weight of the post-grafting aqueous solution.
Another aspect of the invention is directed to an anti-fouling composite reverse osmosis membrane prepared according to the method of the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the preparation method of the anti-pollution composite reverse osmosis membrane, the hydrophilic substance containing at least one amino group is grafted to the surface of the composite reverse osmosis membrane through amide crosslinking in the presence of a pyridine catalyst through surface grafting post treatment, and meanwhile, a hydantoin antibacterial substance is introduced to further improve the anti-pollution performance of the membrane, so that the flux attenuation of the membrane is reduced after the membrane is polluted, and the service life of the membrane is greatly prolonged. This method greatly reduces the reaction time. The anti-pollution performance of the membrane is expected to be improved by performing surface grafting post-treatment on the reverse osmosis membrane, and a substance for post-treatment can stably exist on the surface of the membrane to ensure the long-term operation stability of the membrane.
Drawings
FIG. 1 is a schematic sectional view of an anti-contamination composite reverse osmosis membrane provided by the present invention.
FIG. 2 is an SEM scan of a composite reverse osmosis membrane prepared in a comparative example.
FIG. 3 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 1.
FIG. 4 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared according to example 2.
FIG. 5 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 3.
FIG. 6 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 4.
FIG. 7 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 5.
FIG. 8 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 6.
FIG. 9 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared according to example 7.
FIG. 10 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 8.
FIG. 11 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 9.
FIG. 12 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 10.
FIG. 13 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared in example 11.
FIG. 14 is an SEM scan of an anti-fouling composite reverse osmosis membrane prepared according to example 12.
Detailed Description
The invention relates to a preparation method of an anti-pollution composite reverse osmosis membrane, which is characterized by comprising the following steps:
(1) Dissolving a polymer in a solvent to prepare a polymer solution serving as a membrane casting solution, coating the membrane casting solution on a reinforced material, and then curing in a coagulating bath to form a membrane, thereby forming a polymer porous supporting layer on the reinforced material; preferably, the coagulation bath is a water bath, the temperature of the coagulation bath being from 10 ℃ to 25 ℃;
(2) Contacting the reinforcing material with the polymer porous support layer obtained in (1) with an aqueous solution containing amine monomers, preferably at room temperature, preferably for 10-30 seconds, and removing the aqueous solution remained on the surface after the contact; then contacting with an oil phase solution containing acyl chloride monomers to form a polyamide layer on the polymer porous supporting layer, preferably, contacting at room temperature for 10-60 seconds, and removing the residual oil phase solution on the surface after contacting;
(3) Contacting the reinforcing material having the polyamide layer and the polymer porous support layer obtained in (2) in this order with a post-grafting treatment aqueous solution containing a pyridine compound, an antibacterial substance, and a hydrophilic compound containing at least one amine group; preferably, the contacting may be carried out at 50 ℃ to 90 ℃ for a time preferably of 0.5 minutes to 20 minutes; preferably, the pH of the aqueous graft post-treatment solution is in the range of 6 to 8.
(4) And cleaning and drying to obtain the composite reverse osmosis membrane.
In the preparation method of the present invention, the polymer is one or more of polysulfone, polyethersulfone, polyacrylonitrile, sulfonated polyethersulfone, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide, and the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, chloroform, and dimethylsulfoxide, preferably, the concentration of the polymer is 10wt% to 30wt%, more preferably, the concentration of the polymer is 10wt% to 20wt%, based on the total weight of the polymer solution; if the concentration of the polymer is less than 10wt%, the prepared membrane has larger pore size and higher pure water flux and lower mechanical strength, and if the concentration of the polymer is more than 30wt%, the prepared membrane has smaller pore size and lower pure water flux. Either a lower or higher concentration of polymer is detrimental to the performance of the composite membrane.
In the production method of the present invention, the reinforcing material is preferably a nonwoven fabric, and the material of the nonwoven fabric is not particularly limited, and may be polypropylene (PP), polyester (PET), polyamide (PA), viscose, acrylic, polyethylene (HDPE), polyvinyl chloride (PVC), cellulose or a derivative thereof, and the like, and is preferably a polypropylene (PP) nonwoven fabric and a Polyester (PET) nonwoven fabric, and more preferably a polypropylene (PP) nonwoven fabric.
In the preparation method of the invention, the amine monomer is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, sym-phenylenediamine, polyether amine, 3-fluoroaniline, 3-chloroaniline, aminopiperazine, 2,3-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminobenzenesulphonic acid, N-phenyl-p-phenylenediamine, 1,4-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-diaminoanisole, 3,4' -diaminodiphenyl ether, 56zxft 5623-propylenediamine, 1,3-propylenediamine, diisobutylamine, 56 zxft-cyclohexanediamine, N-hexylamine, heptylamine, cycloheptylamine, 3456 zxft 5656-octyldiamine, decylamine, dodecylenediamine, N-ethylethylenediamine, N-butylenediamine, 6538-diaminonaphthalene, 6595-diaminonaphthalene 5749, N-dimethyl-38xft 5795-diaminonaphthalene, one or more of N-diethyl-p-phenylenediamine, 2-hydroxyethylpropylamine, 1,3-diamino-2-propanol, and 3,3',5,5' -tetramethylbenzidine, preferably, the amine monomer concentration is from 1.0wt% to 8.0wt%, more preferably, the amine monomer concentration is from 2.0wt% to 5.0wt%, based on the total weight of the aqueous phase solution; if the concentration of the amine monomer is lower than 1.0wt%, the salt rejection rate of the obtained composite membrane is low, and if the concentration of the amine monomer is higher than 8.0wt%, the water flux of the obtained composite membrane is low.
In the preparation method of the present invention, preferably, a pH adjusting agent is added to the aqueous phase solution to adjust the pH value of the solution to be in the range of 8 to 10, and preferably, the pH adjusting agent is one or any of NaOH, KOH, sodium phosphate, disodium hydrogen phosphate, sodium sulfite, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium citrate, potassium citrate, sodium bisulfite and triethylamine. The pH regulator is used for absorbing redundant acid generated by interfacial polymerization and promoting the continuous forward reaction of the interfacial polymerization.
In the preparation method, the acyl chloride monomer is one or more of trimesoyl chloride, terephthaloyl chloride, oxalyl chloride, 3-bromopropionyl chloride, undecanoyl chloride, dodecanoyl chloride, n-valeroyl chloride, 3-fluorobenzoyl chloride, 4-methoxybenzoyl chloride, 4-phenylbenzoyl chloride, p-fluorobenzoyl chloride, isovaleroyl chloride, o-chlorobenzoyl chloride, isophthaloyl chloride, succinoyl chloride, 1,7-pimeloyl chloride, malonic acid monoethyl ester chloride, m-methylbenzoyl chloride, 2-methoxybenzoyl chloride, 4-phenylbenzoyl chloride, 3,4-dimethoxybenzoyl chloride, cyclopentylcarbonyl chloride, cyclopropylformyl chloride, heptanoyl chloride, 3-phenylpropionoyl chloride, o-fluorobenzoyl chloride, p-ethylbenzoyl chloride, perfluorooctane sulfonyl chloride, 3963 zxft-trichlorobenzoyl chloride, 4-bromo-2-fluorobenzoyl chloride, 3,5-difluorobenzoyl chloride, 3536-chlorobenzoyl chloride, n-butylbenzoyl chloride, 3926-n-butylbenzoyl chloride, 3926 chloride and 3926. Preferably, the concentration of the acyl chloride monomer is 0.01wt% to 2wt%, more preferably, the concentration of the acyl chloride monomer is 0.10wt% to 0.25wt%, based on the total weight of the oil phase solution; if the concentration of the acyl chloride monomer is lower than 0.01wt%, the prepared composite membrane is thin and has low salt rejection rate, and if the concentration of the acyl chloride monomer is higher than 2wt%, the prepared composite membrane is thick and has low water flux. Preferably, the solvent in the oil phase solution is one or more of ethylcyclohexane, ISOPAR G, ISOPAR E, pentane, hexane, octane, heptane, dichloromethane, carbon tetrachloride, toluene, xylene, propylene oxide, and cyclohexanone.
In the production method of the present invention, the pyridine compound is one or more of 3-iodo-4-aminopyridine, 2-bromo-4-aminopyridine, 4-pyrrolidinylpyridine, 4-dimethylaminopyridine, 4-amino-3-nitropyridine, 4-amino-2-chloropyridine, 4-amino-3,5-dichloropyridine, 4-amino-2,6-dichloropyridine, 4-amino-2,6-dimethylpyridine, 4-methylaminopyridine, 2-amino-4-bromopyridine, 2-bromo-4-aminopyridine, 3-amino-4-bromopyridine, 4-amino-2-methoxypyridine, 3-amino-4-methylpyridine, 4-pyridinecarboxamide, 2-amino-3-hydroxypyridine, 2-aminopyridine, 3-aminopyridine, 2-amino-4-methylpyridine and 2-amino-3-methylpyridine, preferably, the concentration of the pyridine compound is 0.10wt% based on the total weight of the aqueous solution after treatment, and more preferably the concentration of the pyridine compound is 0.1 to 10wt%. If the concentration of the pyridine compound is less than 0.1wt%, the anti-pollution performance of the composite membrane is poor, and if the concentration of the pyridine compound is more than 10wt%, the water flux of the composite membrane is low.
In the preparation method, the pyridine compound plays a role in catalyzing an acylation reaction between the hydrophilic compound containing at least one amino group and the polyamide, so that the hydrophilic compound containing at least one amino group is grafted to the surface of the polyamide layer through the acylation reaction, and the anti-fouling performance and the water flux of the reverse osmosis membrane are improved.
In the preparation method, the antibacterial substance is one or more of hydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1-aminohydantoin hydrochloride, 2-thiohydantoin and 3-allyl-5,5-dimethylhydantoin.
The hydantoin ring belongs to a heterocyclic ring, and the alpha carbon atom adjacent to the nitrogen atom on the hydantoin ring is provided with two electron-donating methyl groups, so that-NH on the hydantoin derivative has higher activity and can react with an acyl chloride group on the surface of the polyamide layer formed by interfacial polymerization, so that hydantoin substances are grafted to the surface of the polyamide layer, and the anti-pollution performance of the reverse osmosis membrane is remarkably improved. Preferably, the concentration of the antibacterial substance is 0.01 to 15wt%, more preferably, 0.05 to 5wt%, based on the total weight of the aqueous graft post-treatment solution. If the concentration of the antibacterial substance is less than 0.01wt%, the anti-pollution performance of the composite membrane is poor, and if the concentration of the antibacterial substance is more than 15wt%, the water flux of the composite membrane is low.
In the preparation method of the present invention, the hydrophilic compound containing at least one amine group is one or more of 2- (propylamino) ethanol, 2-ethylamino ethanol, N-phenylethanolamine, methoxypolyethyleneglycol amine, hydroxylamine-O-sulfonic acid, 2-hydroxyethylamine, isopropanolamine, phenylethanolamine, polyetheramine, N-methyl-D-glucamine, aminopiperazine, 2-aminopyridine, 2,6-diaminopyridine, diethanolamine, ethanolamine, m-phenylenediamine, polyvinylamine, polyethyleneimine, N-butyldiethanolamine, N-phenyldiethanolamine, O-phosphoethanolamine, diaminobenzenesulfonic acid, 2-amino-1-phenylethanol, 2-amino-3-hydroxypyridine, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, diethylene glycol di (3-aminopropyl) ether, propanolamine and 1-aminocyclopropanecarboxylic acid), preferably, the hydrophilic compound is present at a concentration of 0.01 to 10wt%, more preferably, the hydrophilic compound is present at a concentration of 0.01 to 5wt%, based on the total weight of the aqueous solution after-grafting. If the concentration of the hydrophilic compound is less than 0.01wt%, the contamination resistance of the composite membrane is poor and the salt rejection rate is low, and if the concentration of the hydrophilic compound is more than 10wt%, the water flux of the composite membrane is low.
In the production method of the present invention, the washing is performed, for example, by soaking in deionized water. The drying temperature is not particularly limited, and is usually 60 to 100 ℃; the drying time is also not particularly limited, and is usually 5 to 60 minutes.
The present invention also relates to a composite reverse osmosis membrane prepared by the preparation method according to the present invention, preferably, as shown in fig. 1, which may include: the anti-pollution composite material comprises a non-woven fabric layer, a polymer porous supporting layer, a polyamide layer formed on the polymer porous supporting layer and an anti-pollution layer formed by grafting post-treatment on the polyamide layer.
Examples
The present invention will be described in further detail with reference to specific examples, but the present invention is by no means limited to the following examples. It should be noted that the reagents and raw materials used in the examples of the present invention are commercially available conventional products unless otherwise specified.
Comparative example
(1) Preparation of a polymeric porous support layer
Dissolving polysulfone (purchased from Solvay, udel P-3500LCD MB7) in N, N-dimethylformamide to prepare a membrane casting solution with the concentration of 18wt%, uniformly scraping the membrane casting solution on the surface of a PP non-woven fabric by using a membrane scraping machine, then immersing the PP non-woven fabric in an aqueous solution with the temperature of 20 +/-3 ℃, and solidifying for 60 seconds;
(2) Interfacial polymerization preparation of composite reverse osmosis membrane
Immersing the membrane prepared in the step (1) into an aqueous phase solution containing 3.5wt% of m-phenylenediamine (pH value is adjusted to 10 by using NaOH) for 10 seconds, taking out the membrane, blowing off redundant solution by using nitrogen, immersing the membrane into an ISOPAR G oil phase solution containing 0.18wt% of trimesoyl chloride and 0.045wt% of isophthaloyl dichloride for 15 seconds, taking out the membrane, washing the membrane by using deionized water, and drying the membrane in an oven at 80 ℃ to obtain the composite reverse osmosis membrane;
(3) Cleaning and drying post-treatment
And (3) soaking the composite reverse osmosis membrane prepared in the step (2) in pure water at the temperature of 75 +/-5 ℃ for 5 minutes, taking out and drying in an oven at the temperature of 80 ℃.
Example 1
(1) Preparation of a polymeric porous support layer
Dissolving polysulfone (purchased from Solvay, udel P-3500LCD MB7) in N, N-dimethylformamide to prepare a membrane casting solution with the concentration of 18wt%, uniformly scraping the membrane casting solution on the surface of a PP non-woven fabric by using a membrane scraping machine, and then immersing the PP non-woven fabric in an aqueous solution with the temperature of 15 +/-3 ℃ for solidification;
(2) Interfacial polymerization preparation of composite reverse osmosis membrane
Immersing the membrane prepared in the step (1) into an aqueous phase solution containing 3.5wt% of m-phenylenediamine (pH value is adjusted to 10 by using NaOH) for 10 seconds, taking out the membrane, blowing off redundant solution by using nitrogen, immersing the membrane into an ISOPAR G oil phase solution containing 0.18wt% of trimesoyl chloride and 0.045wt% of isophthaloyl dichloride for 15 seconds, taking out the membrane, washing the membrane by using deionized water, and drying the membrane in an oven at 80 ℃ to obtain the composite reverse osmosis membrane;
(3) Preparation of anti-pollution composite reverse osmosis membrane by grafting post-treatment
Soaking the composite reverse osmosis membrane prepared in the step (2) in a grafting post-treatment water solution with the temperature of 70 +/-5 ℃ and the pH value of 6.5 for 5 minutes, wherein the grafting post-treatment water solution contains 0.1wt% of 4-dimethylaminopyridine, 5wt% of 3-hydroxymethyl-5,5-dimethylhydantoin and 1wt% of diethanolamine;
(4) Cleaning and drying post-treatment
And (4) soaking the anti-pollution composite reverse osmosis membrane prepared in the step (3) in pure water at the temperature of 75 +/-5 ℃ for 5 minutes, taking out and drying in an oven at the temperature of 80 ℃.
Example 2
Example 2 was performed in the same manner as in example 1, except that the concentration of 4-dimethylaminopyridine was changed to 1wt% in step (3).
Example 3
Example 3 was carried out in the same manner as in example 1, except that the concentration of 4-dimethylaminopyridine was changed to 3wt% in step (3).
Example 4
Example 4 was performed in the same manner as in example 2, except that the temperature of the aqueous solution of the post-grafting treatment was changed to 75. + -. 5 ℃ in step (3), and the concentration of 3-hydroxymethyl-5,5-dimethylhydantoin was changed to 0.1 wt%.
Example 5
Example 5 was carried out in the same manner as in example 4 except that the concentration of 3-hydroxymethyl-5,5-dimethylhydantoin was changed to 5wt% in step (3).
Example 6
Example 6 was carried out in the same manner as in example 4 except that the concentration of 3-hydroxymethyl-5,5-dimethylhydantoin was changed to 15wt% in step (3).
Example 7
Example 7 was carried out in the same manner as in example 5 except that 1wt% of 4-dimethylaminopyridine was changed to 1wt% of 4-aminopyridine and 1wt% of diethanolamine was changed to 0.1wt% of ethanolamine in step (3).
Example 8
Example 8 was carried out in the same manner as in example 7, except that the concentration of ethanolamine was changed to 3% by weight in step (3).
Example 9
Example 9 was carried out in the same manner as in example 7, except that the concentration of ethanolamine was changed to 5% by weight in step (3).
Example 10
Example 10 was conducted in the same manner as example 5 except that 1wt% of 4-dimethylaminopyridine was changed to 1wt% of 2-bromo-4-aminopyridine and 1wt% of diethanolamine was changed to 0.1wt% of polyethyleneimine (available from michelin, E808878) in step (3).
Example 11
Example 11 was performed in the same manner as example 10, except that the concentration of polyethyleneimine was changed to 3wt% in step (3).
Example 12
Example 12 was performed in the same manner as in example 10, except that the concentration of polyethyleneimine was changed to 5wt% in step (3).
The hydrophilicity was evaluated as follows for the composite reverse osmosis membrane prepared in the comparative example and the anti-contamination composite reverse osmosis membranes prepared in examples 1 to 12.
Using the composite reverse osmosis membrane prepared in the comparative example and the anti-contamination composite reverse osmosis membranes prepared in examples 1 to 12, water drop contact angles were measured as follows: the membrane samples were soaked in purified water for 24 hours and air dried at 20 ℃. The contact angle tester has the following model: german KRUSS DSA30 research type contact angle measuring instrument. The membrane sample was laid flat on a test table, pure water was dropped onto the membrane with the needle of a contact angle measuring instrument, and the contact angle of the drop was recorded 10 seconds after the drop was dropped onto the membrane. The volume of each drop of pure water was about 3 μ L, five random spots were tested for each sample, and the data were averaged. The results are summarized in table 1 below.
The composite reverse osmosis membrane prepared in the comparative example and the anti-contamination composite reverse osmosis membranes prepared in examples 1 to 12 were respectively tested in a membrane test station, an initial flux and an initial salt rejection rate were tested under test conditions of an operating pressure of 150psi, a temperature of 23 + -2 deg.C, 2000ppm NaCl aqueous solution, and then the flux of the contaminated membrane was tested and the flux decay rate was calculated by contaminating the 50ppm bovine serum albumin for 12 hours, and the results are summarized in Table 1 below.
TABLE 1
As can be seen from the results shown in table 1, the anti-contamination composite reverse osmosis membrane prepared in the example still maintained a higher flux and increased hydrophilicity, thus reducing contamination with hydrophobic substances, and the flux decay rate before and after contamination was significantly reduced, that is, the flux decay was reduced after contamination, relative to the composite reverse osmosis membrane of the comparative example. The anti-pollution performance of the membrane is improved by carrying out surface grafting post-treatment on the composite reverse osmosis membrane, and the anti-pollution performance of the composite membrane is favorably influenced by adjusting the respective types and concentrations of the pyridine compound, the antibacterial substance and the hydrophilic compound in the water solution after grafting post-treatment.
The morphology of the composite reverse osmosis membrane prepared in the comparative example and the anti-contamination composite reverse osmosis membranes prepared in examples 1 to 12 were observed using SEM (JEOL 7500F, japan Electron Ltd.) and are shown in FIGS. 2 to 14, respectively. As can be seen from a comparison of fig. 2 with fig. 3 to 14, the leaf-like structure of the surface of the anti-contamination composite reverse osmosis membrane obtained through the post-grafting treatment shows a large difference from the structure of the surface of the composite reverse osmosis membrane obtained in the comparative example, which indicates that the post-grafting treatment is effective, and the surface morphology of the anti-contamination composite reverse osmosis membrane differs depending on the kind and concentration of the pyridine compound, the kind and concentration of the antibacterial substance, and the kind and concentration of the hydrophilic compound.
Industrial applicability
The preparation method of the anti-pollution reverse osmosis membrane can reduce the reaction time, has simple process and is suitable for industrial large-scale production, the anti-pollution performance of the anti-pollution composite reverse osmosis membrane prepared by the method is obviously improved, the anti-pollution composite reverse osmosis membrane can stably run for a long time, the flux attenuation of the membrane after being polluted is reduced, and the service life is greatly prolonged. Therefore, the method has positive significance for water treatment, industrial or urban wastewater treatment, food processing and pharmaceutical industry.
Claims (10)
1. The preparation method of the anti-pollution composite reverse osmosis membrane is characterized by comprising the following steps:
(1) Dissolving a polymer in a solvent to prepare a polymer solution serving as a membrane casting solution, coating the membrane casting solution on a reinforced material, and then curing in a coagulating bath to form a membrane, thereby forming a polymer porous supporting layer on the reinforced material;
(2) Contacting the reinforcing material with the polymer porous supporting layer obtained in the step (1) with an aqueous phase solution containing amine monomers, and then with an oil phase solution containing acyl chloride monomers, so as to form a polyamide layer on the polymer porous supporting layer;
(3) Contacting the reinforcing material having the polyamide layer and the polymer porous support layer obtained in (2) in this order with a post-grafting treatment aqueous solution containing a pyridine compound, an antibacterial substance, and a hydrophilic compound containing at least one amine group;
wherein the pyridine is one or more of 3-iodo-4-aminopyridine, 2-bromo-4-aminopyridine, 4-pyrrolidinylpyridine, 4-dimethylaminopyridine, 4-amino-3-nitropyridine, 4-amino-2-chloropyridine, 4-amino-3,5-dichloropyridine, 4-amino-2,6-dichloropyridine, 4-amino-2,6-dimethylpyridine, 4-methylaminopyridine, 2-amino-4-bromopyridine, 2-bromo-4-aminopyridine, 3-amino-4-bromopyridine, 4-amino-2-methoxypyridine, 3-amino-4-methylpyridine, 4-pyridinecarboxamide, 2-amino-3-hydroxypyridine, 2-aminopyridine, 3-aminopyridine, 2-amino-4-methylpyridine, and 2-amino-3-methylpyridine, the concentration of the pyridine is from 0.1wt% to 10wt% based on the total weight of the post-grafting aqueous solution;
the antibacterial substance is one or more of hydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1-aminohydantoin hydrochloride, 2-thiohydantoin and 3-allyl-5,5-dimethylhydantoin, and the concentration of the antibacterial substance is 0.01wt% to 15wt% based on the total weight of the post-grafting treatment aqueous solution;
the hydrophilic compound containing at least one amine group is one or more of 2- (propylamino) ethanol, 2-ethylamino ethanol, N-phenylethanolamine, methoxypolyethyleneglycol amine, hydroxylamine-O-sulfonic acid, 2-hydroxyethylamine, isopropanolamine, phenylethanolamine, polyetheramine, N-methyl-D-glucamine, aminopiperazine, 2-aminopyridine, 2,6-diaminopyridine, diethanolamine, ethanolamine, m-phenylenediamine, polyethyleneamine, polyethyleneimine, N-butyldiethanolamine, N-phenyldiethanolamine, O-phosphoethanolamine, diaminobenzenesulfonic acid, 2-amino-1-phenylethanol, 2-amino-3-hydroxypyridine, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, diethylene glycol bis (3-aminopropyl) ether, propanolamine, and 1-aminocyclopropanecarboxylic acid, the concentration of the hydrophilic compound containing at least one amine group being 0.01 to 10wt% based on the total weight of the post-grafting aqueous solution;
(4) And cleaning and drying to obtain the anti-pollution composite reverse osmosis membrane.
2. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1, wherein said polymer is one or more of polysulfone, polyethersulfone, polyacrylonitrile, sulfonated polyethersulfone, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide, and said solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, chloroform, and dimethylsulfoxide.
3. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1 wherein the concentration of said polymer is from 10 to 30 weight percent based on the total weight of said polymer solution.
4. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1, wherein the reinforcement material is a nonwoven fabric and the coagulation bath is a water bath.
5. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1 wherein the amine monomer is selected from the group consisting of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, sym-phenylenediamine, polyetheramine, 3-fluoroaniline, 3-chloroaniline, aminopiperazine, 2,3-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminobenzenesulphonic acid, N-phenyl-p-phenylenediamine, 1,4-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-diaminoanisole, 3,4' -diaminodiphenyl ether, 23 zxft 5623-propylenediamine, 1,3-propylenediamine, diisobutylamine, 1,2-cyclohexanediamine, N-hexylamine, heptylamine, cycloheptylamine, 3456-octylenediamine, dodecylamine, N-dodecylenediamine, N-385749, N-diethylbutylenediamine, N-butylenediamine, 345795, 345798, N-diethylphenylenethylenediamine, 345795, 3495, 345798, 3495, 3450, N-diethylphenylenethylenediamine, 345795, 345798, and N-diethylphenylenethylenediamine.
6. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1, wherein the amine-based monomer is present at a concentration of 1.0 to 8.0wt% based on the total weight of the aqueous phase solution.
7. <xnotran> 1 , , , ,3- , , , ,3- ,4- ,4- , , , , , , 3245 zxft 3245- , , ,2- ,4- ,4- , 3732 zxft 3732- , , , ,3- , , , , 3963 zxft 3963- ,4- -2- , 4325 zxft 4325- , 3536 zxft 3536- , 3926 zxft 3926- ,4- , 2- . </xnotran>
8. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1, wherein the concentration of the acyl chloride monomer is 0.01 to 2wt% based on the total weight of the oil phase solution.
9. The method of preparing an anti-fouling composite reverse osmosis membrane according to claim 1, wherein the solvent in the oil phase solution is one or more of ethylcyclohexane, ISOPAR G, ISOPAR E, pentane, hexane, octane, heptane, dichloromethane, carbon tetrachloride, toluene, xylene, propylene oxide, and cyclohexanone.
10. An anti-contamination composite reverse osmosis membrane prepared by the preparation method according to any one of claims 1 to 9.
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