CN114159979A - Method for preparing amphiphilic pollution-resistant reverse osmosis membrane through grafting reaction - Google Patents
Method for preparing amphiphilic pollution-resistant reverse osmosis membrane through grafting reaction Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 30
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 25
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000010612 desalination reaction Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000000614 phase inversion technique Methods 0.000 claims abstract description 7
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 6
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007790 scraping Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 20
- 229920001184 polypeptide Polymers 0.000 claims description 19
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 19
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 125000000539 amino acid group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000012695 Interfacial polymerization Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing an amphiphilic pollution-resistant reverse osmosis membrane by a grafting reaction, which specifically comprises the following steps: (1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water; (2) preparing a water phase solution and an oil phase solution, and adjusting the mass concentration fractions of the water phase solution and the oil phase solution to obtain a high-desalination reverse osmosis membrane; (3) preparing an amphiphilic solution, carrying out ultraviolet curing grafting reaction on the reverse osmosis membrane obtained in the step (2), and then cleaning, heating and drying; (4) and (4) drying the membrane in the step (3) to obtain the waterproof oil-resistant amphiphilic pollution-resistant composite reverse osmosis membrane. The method has the characteristics of simple operation, controllable reaction, great improvement of flux and hydrophobic and oleophobic resistance of the reverse osmosis membrane, enlargement of the application range of the reverse osmosis membrane in sewage and oil, great improvement of pollution resistance, great improvement of flow rate and the like, and is particularly suitable for the field of pollution-resistant reverse osmosis membranes.
Description
Technical Field
The invention relates to the field of reverse osmosis membrane preparation, in particular to a method for preparing an amphiphilic pollution-resistant reverse osmosis membrane through a grafting reaction.
Background
In the early 80 s of the 20 th century, the defects of cellulose materials were overcome in the United states, and a composite polyamide membrane with high water flux and high salt interception rate was developed, so that the reverse osmosis technology was widely applied to the industrial field. The application of the method in the living fields of seawater and brackish water desalination and pure water production is developed to the environmental protection field of wastewater treatment and reuse. At present, on the one hand, water resources are lacked, and a water source with lower quality than the prior water source is required to be continuously developed and utilized; on the other hand, the pressure applied by the government environmental protection department and the public demand on high-quality drinking water require the treatment method to be updated and the treatment degree to be improved, which brings huge market potential and development space for the membrane separation technology, especially the anti-pollution reverse osmosis membrane technology;
the existing anti-pollution reverse osmosis membrane is mainly applied to the fields of brackish water desalination drinking water, sewage reuse, sea water desalination primary effluent and the like, the water quality is often between 2000ppm and 30000ppm, the water quality condition is severe, the requirement of reverse osmosis membrane inflow on water quality is high, more pretreatment processes are often required to be added in front of the reverse osmosis membrane, the economic efficiency is low, in addition, the requirement of conventional reverse osmosis membrane inflow on oil in water is high, a higher deoiling and degreasing pretreatment process procedure is required to be added, the higher oil in water can not only damage a reverse osmosis membrane polyamide layer, but also oil hydrocarbon substances are difficult to remove to influence the water quality of reverse osmosis membrane effluent, and the requirements on anti-pollution performance and desalination flow stability of the reverse osmosis membrane are increasingly outstanding.
In order to solve the problems, the traditional reverse osmosis membrane preparation method is improved, and a method for preparing an amphiphilic pollution-resistant reverse osmosis membrane through a grafting reaction is provided.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing an amphiphilic pollution-resistant reverse osmosis membrane by a grafting reaction, which has the characteristics of simple operation, controllable reaction, great improvement on flux and hydrophobic and oleophobic resistance of the reverse osmosis membrane, enlarged application range of the reverse osmosis membrane in sewage and oil, great improvement on pollution resistance, great flow improvement and the like, and is particularly suitable for the field of pollution-resistant reverse osmosis membranes.
In order to achieve the aim of the invention, the invention adopts the specific scheme that:
a method for preparing an amphiphilic pollution-resistant reverse osmosis membrane through a grafting reaction comprises the following steps of firstly obtaining a polysulfone ultrafiltration membrane with a non-woven fabric and polysulfone double-layer structure by adopting an L-S phase inversion method, secondly obtaining a reverse osmosis membrane with a polyamide layer through interfacial polymerization, and finally obtaining an anti-pollution nanofiltration membrane through a grafting reaction with an amphiphilic group, wherein the method specifically comprises the following steps:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting the mass concentration fractions of the water phase solution and the oil phase solution to obtain a high-desalination reverse osmosis membrane;
(3) preparing an amphiphilic solution, carrying out ultraviolet curing grafting reaction on the reverse osmosis membrane obtained in the step (2), and then cleaning, heating and drying;
(4) and (4) drying the membrane in the step (3) to obtain the waterproof oil-resistant amphiphilic pollution-resistant composite reverse osmosis membrane.
Preferably, the ultrafiltration membrane used in step (1) has a molecular weight cut-off distribution of 5-12 ten thousand, and the specific step of step (1) comprises: stirring and dissolving the ultrafiltration membrane in a DMAc solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on a non-woven fabric, and then putting the non-woven fabric in cold water at the temperature of 9-16 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution is 15-20%;
the ultrafiltration membrane material used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the ultrafiltration membrane material is 70-120 g.
Preferably, the aqueous phase solution prepared in the step (2) comprises one or more of m-phenylenediamine, p-phenylenediamine and m-benzenetriol; the water phase mixed solution comprises one or more of DMSO, DMAc, DMF and triethylamine and a mixed solution of pure water; the oil phase solution is a mixed solution containing one or more of trimesoyl chloride (TMC), terephthaloyl chloride, m-benzenetricarboxy chloride, cyclohexane, acetonitrile, xylene, methylcyclohexane, Isopar G and Isopar E or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane;
in the step (2), the reaction time of the ultrafiltration membrane in the water phase is 0.5-2 minutes, and the reaction time in the oil phase is 0.5-2 minutes.
Preferably, the concentration of one or more of m-phenylenediamine, p-phenylenediamine and m-benzenetricarboxylic acid is 2-5%, the concentration of the water phase mixed solution comprises a mixed solution of one or more of DMSO, DMAc, DMF and triethylamine and pure water, the concentration is 1.5-5%, and the concentration of one or more of trimesoyl chloride (TMC), terephthaloyl chloride and m-benzenetricarboxylic acid chloride is 0.15-0.5%.
Preferably, in the step (3), the substance subjected to amphiphilic modification is an amphiphilic amino acid polypeptide, and the number of amino acid groups of the polypeptide is between 2 and 6; the polypeptide has hydrophilic amino acid and oleophobic amino acid group, and is obtained through solid phase reaction, and the end of the polypeptide has the group capable of reacting with amino and acyl chloride, and the group is subjected to curing grafting reaction under ultraviolet light and a catalyst.
Preferably, the concentration of the amphiphilic polypeptide is 0.1-0.5%, the concentration of the catalyst is 0.001-0.008%, the photocuring time is 5-10s, and the drying and crosslinking reaction time is 5-15 minutes.
Preferably, the method for preparing the amphiphilic pollution-resistant reverse osmosis membrane by the prepared composite nanofiltration membrane through one grafting reaction from inside to outside comprises a four-layer structure which is sequentially a non-woven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and an amphiphilic polypeptide amino acid modified layer.
The invention has the beneficial effects that:
the method has the characteristics of simple operation, controllable reaction, great improvement of flux and hydrophobic and oleophobic resistance of the reverse osmosis membrane, enlargement of the application range of the reverse osmosis membrane in sewage and oil, great improvement of pollution resistance, great improvement of flow rate and the like, and is particularly suitable for the field of pollution-resistant reverse osmosis membranes.
Detailed Description
The present invention is further described below by way of specific examples, but the present invention is not limited to only the following examples. Variations, combinations, or substitutions of the invention, which are within the scope of the invention or the spirit, scope of the invention, will be apparent to those of skill in the art and are within the scope of the invention.
A method for preparing an amphiphilic pollution-resistant reverse osmosis membrane through a grafting reaction comprises the following steps of firstly obtaining a polysulfone ultrafiltration membrane with a non-woven fabric and polysulfone double-layer structure by adopting an L-S phase inversion method, secondly obtaining a reverse osmosis membrane with a polyamide layer through interfacial polymerization, and finally obtaining an anti-pollution nanofiltration membrane through a grafting reaction with an amphiphilic group, wherein the method specifically comprises the following steps:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting the mass concentration fractions of the water phase solution and the oil phase solution to obtain a high-desalination reverse osmosis membrane;
(3) preparing an amphiphilic solution, carrying out ultraviolet curing grafting reaction on the reverse osmosis membrane obtained in the step (2), and then cleaning, heating and drying;
(4) and (4) drying the membrane in the step (3) to obtain the waterproof oil-resistant amphiphilic pollution-resistant composite reverse osmosis membrane.
The cut-off molecular weight distribution of the ultrafiltration membrane used in the step (1) is 5-12 ten thousand, and the step (1) comprises the following specific steps: stirring and dissolving the ultrafiltration membrane in a DMAc solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on a non-woven fabric, and then putting the non-woven fabric in cold water at the temperature of 9-16 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution is 15-20%;
the ultrafiltration membrane material used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the ultrafiltration membrane material is 70-120 g.
The aqueous phase solution prepared in the step (2) comprises one or more of m-phenylenediamine, p-phenylenediamine and m-benzenetriol; the water phase mixed solution comprises one or more of DMSO, DMAc, DMF and triethylamine and a mixed solution of pure water; the oil phase solution is a mixed solution containing one or more of trimesoyl chloride (TMC), terephthaloyl chloride, m-benzenetricarboxy chloride, cyclohexane, acetonitrile, xylene, methylcyclohexane, Isopar G and Isopar E or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane;
in the step (2), the reaction time of the ultrafiltration membrane in the water phase is 0.5-2 minutes, and the reaction time in the oil phase is 0.5-2 minutes.
One or more of m-phenylenediamine, p-phenylenediamine and m-phenylenediamine is 2-5% in concentration, the water phase mixed solution comprises one or more of DMSO, DMAc, DMF and triethylamine and pure water, the concentration is 1.5-5%, and one or more of trimesoyl chloride (TMC), terephthaloyl chloride and m-trimesoyl chloride is 0.15-0.5%.
In the step (3), the substance for performing amphiphilic modification is amphiphilic amino acid polypeptide, and the number of amino acid groups of the polypeptide is between 2 and 6; the polypeptide has hydrophilic amino acid and oleophobic amino acid group, and is obtained through solid phase reaction, and the end of the polypeptide has the group capable of reacting with amino and acyl chloride, and the group is subjected to curing grafting reaction under ultraviolet light and a catalyst.
The concentration of the amphiphilic polypeptide is 0.1-0.5%, the concentration of the catalyst is 0.001-0.008%, the photocuring time is 5-10s, and the drying and crosslinking reaction time is 5-15 minutes.
The method for preparing the amphiphilic pollution-resistant reverse osmosis membrane by the prepared composite nanofiltration membrane through a grafting reaction from inside to outside comprises a four-layer structure which is sequentially a non-woven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and an amphiphilic polypeptide amino acid modified layer.
Example 1:
1. preparing a mixed N, N-diethylamide (DMAc) solution and polysulfone particles, heating to 60 ℃, and stirring to obtain a homogeneous solution, wherein the mass ratio of the DMAc to the polyether sulfone is 85:15, and the molecular weight of the polyether sulfone is 5-12 ten thousand;
2. and (3) extruding the mixture through a precision slit, grinding a head, and mixing the mixture with S1 to coat the mixture on non-woven fabrics, wherein the thickness of the non-woven fabrics is 80-100 mu m, and the non-woven fabrics enter a cold water tank to be solidified and formed, and the temperature of the cold water tank is 10-20 ℃.
3. Preparing 0.2-0.5% anhydrous MPD and TEA 2.0g/L in the reaction tank A, dissolving in deionized water to prepare an aqueous phase solution, immersing the ultrafiltration membrane obtained in the step 2 in the reaction tank A, and taking out and drying surface water drops;
4. preparing 0.02-0.05% TMC and cyclohexane solution in the reaction tank B, immersing the ultrafiltration membrane obtained in the step S3 in the reaction tank B, taking out the reaction tank B, drying and cleaning;
5. soaking the reverse osmosis membrane obtained in the step 4 into the amphiphilic polypeptide solution obtained by synthesis, wetting and taking out, and performing infrared drying for 2-5min to obtain a grafted reverse osmosis membrane;
comparative example 1:
comparative example no step 5 of example 1 compared to example 1;
performance test:
the reverse osmosis membranes prepared in experimental example 1 and comparative example 1 were used to perform a desalination stability test on a membrane test bed. The test table is used for measuring the water flux and the desalination rate of the membrane after operation under the test conditions that the operating pressure is 0.6Mpa, the concentration is 1000PPM bovine serum albumin + pure water solution, the solution temperature is 25 ℃, and the PH value is 6.5-7.5, and the results are shown in the table 1-2:
| cumulative membrane run time | Experimental example 1 salt rejection | Comparative example 2 salt rejection | Experimental example 1 flow rate | Comparative example 2 flow rate |
| 1h | 99.08％ | 99.04％ | 28.57gfd | 29.03gfd |
| 24h | 99.06％ | 99.07％ | 28.09gfd | 26.43gfd |
| 48h(2d) | 99.04％ | 99.02％ | 28.34gfd | 24.09gfd |
| 96h(4d) | 99.02％ | 98.85％ | 28.26gfd | 21.09gfd |
| 6d | 99.02％ | 98.76％ | 28.219gfd | 17.09gfd |
| 10d | 98.96％ | 98.69％ | 28.13gfd | 16.09gfd |
| 30d | 98.92％ | 98.42％ | 27.32gfd | 15.97gfd |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for preparing an amphiphilic pollution-resistant reverse osmosis membrane through a grafting reaction is characterized in that a polysulfone ultrafiltration membrane with a non-woven fabric and polysulfone double-layer structure is obtained by adopting an L-S phase inversion method, then a reverse osmosis membrane with a polyamide layer is obtained through interfacial polymerization, and then an anti-pollution nanofiltration membrane is obtained through a grafting reaction with an amphiphilic group, and specifically comprises the following steps:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting the mass concentration fractions of the water phase solution and the oil phase solution to obtain a high-desalination reverse osmosis membrane;
(3) preparing an amphiphilic solution, carrying out ultraviolet curing grafting reaction on the reverse osmosis membrane obtained in the step (2), and then cleaning, heating and drying;
(4) and (4) drying the membrane in the step (3) to obtain the waterproof oil-resistant amphiphilic pollution-resistant composite reverse osmosis membrane.
2. The method for preparing the amphiphilic pollution-resistant reverse osmosis membrane by the grafting reaction according to claim 1, wherein the ultrafiltration membrane used in the step (1) has a molecular weight cut-off distribution of 5-12 ten thousand, and the step (1) comprises the following specific steps: stirring and dissolving the ultrafiltration membrane in a DMAc solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on a non-woven fabric, and then putting the non-woven fabric in cold water at the temperature of 9-16 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution is 15-20%;
the ultrafiltration membrane material used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the ultrafiltration membrane material is 70-120 g.
3. The method for preparing the amphiphilic fouling-resistant reverse osmosis membrane by a grafting reaction according to claim 1, wherein the aqueous solution prepared in the step (2) comprises one or more of m-phenylenediamine, p-phenylenediamine and m-benzenetriol; the water phase mixed solution comprises one or more of DMSO, DMAc, DMF and triethylamine and a mixed solution of pure water; the oil phase solution is a mixed solution containing one or more of trimesoyl chloride (TMC), terephthaloyl chloride, m-benzenetricarboxy chloride, cyclohexane, acetonitrile, xylene, methylcyclohexane, Isopar G and Isopar E or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane;
in the step (2), the reaction time of the ultrafiltration membrane in the water phase is 0.5-2 minutes, and the reaction time in the oil phase is 0.5-2 minutes.
4. The method for preparing an amphiphilic fouling-resistant reverse osmosis membrane according to claim 3, wherein the concentration of one or more of m-phenylenediamine, p-phenylenediamine and m-phenylenediamine is 2% -5%, the concentration of the mixed solution of water phase including one or more of DMSO, DMAc, DMF and triethylamine and pure water is 1.5% -5%, and the concentration of one or more of trimesoyl chloride (TMC), terephthaloyl chloride and m-trimesoyl chloride is 0.15% -0.5%.
5. The method for preparing the amphiphilic fouling resistant reverse osmosis membrane by grafting reaction according to claim 1, wherein in the step (3), the substance for amphiphilic modification is amphiphilic amino acid polypeptide, the number of amino acid groups of the polypeptide is 2-6; the polypeptide has hydrophilic amino acid and oleophobic amino acid group, and is obtained through solid phase reaction, and the end of the polypeptide has the group capable of reacting with amino and acyl chloride, and the group is subjected to curing grafting reaction under ultraviolet light and a catalyst.
6. The method for preparing the amphiphilic fouling resistant reverse osmosis membrane by the grafting reaction according to claim 5, wherein the amphiphilic polypeptide concentration is 0.1% -0.5%, the catalyst concentration is 0.001% -0.008%, the photocuring time is 5-10s, and the drying crosslinking reaction time is 5-15 minutes.
7. The method for preparing the amphiphilic fouling-resistant reverse osmosis membrane through the grafting reaction according to claim 1, wherein the prepared composite nanofiltration membrane comprises a four-layer structure comprising a non-woven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and an amphiphilic polypeptide amino acid modified layer in sequence from inside to inside.
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| CN115282794A (en) * | 2022-08-19 | 2022-11-04 | 沃顿科技股份有限公司 | Pollution-resistant reverse osmosis membrane for seawater desalination and preparation method thereof |
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| CN110975644A (en) * | 2019-12-04 | 2020-04-10 | 自然资源部天津海水淡化与综合利用研究所 | Anti-pollution and anti-oxidation polyamide composite reverse osmosis membrane and preparation method thereof |
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| CN110975644A (en) * | 2019-12-04 | 2020-04-10 | 自然资源部天津海水淡化与综合利用研究所 | Anti-pollution and anti-oxidation polyamide composite reverse osmosis membrane and preparation method thereof |
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| CN115282794A (en) * | 2022-08-19 | 2022-11-04 | 沃顿科技股份有限公司 | Pollution-resistant reverse osmosis membrane for seawater desalination and preparation method thereof |
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