CN114177786B - Preparation method of multilayer polyamide composite reverse osmosis membrane - Google Patents
Preparation method of multilayer polyamide composite reverse osmosis membrane Download PDFInfo
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- CN114177786B CN114177786B CN202111279786.1A CN202111279786A CN114177786B CN 114177786 B CN114177786 B CN 114177786B CN 202111279786 A CN202111279786 A CN 202111279786A CN 114177786 B CN114177786 B CN 114177786B
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- 239000012528 membrane Substances 0.000 title claims abstract description 126
- 239000004952 Polyamide Substances 0.000 title claims abstract description 62
- 229920002647 polyamide Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 29
- 229920001690 polydopamine Polymers 0.000 claims abstract description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 25
- 239000011241 protective layer Substances 0.000 claims abstract description 22
- 229960003638 dopamine Drugs 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 105
- 210000004379 membrane Anatomy 0.000 claims description 100
- 239000012071 phase Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- GSZQTIFGANBTNF-UHFFFAOYSA-N (3-aminopropyl)phosphonic acid Chemical compound NCCCP(O)(O)=O GSZQTIFGANBTNF-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 239000004745 nonwoven fabric Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- -1 phosphonic acid modified graphene Chemical class 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001266 acyl halides Chemical class 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 210000002469 basement membrane Anatomy 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000009849 vacuum degassing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 5
- 125000003368 amide group Chemical group 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009292 forward osmosis Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SMKZBQZAMSKHNS-UHFFFAOYSA-M sodium;2-sulfoacetate Chemical compound [Na+].OS(=O)(=O)CC([O-])=O SMKZBQZAMSKHNS-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
- B01D2325/48—Antimicrobial properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a multilayer polyamide composite reverse osmosis membrane, which is characterized in that polyvinyl alcohol or polyvinylpyrrolidone is added into a polysulfone membrane, dopamine solution is pressed on the polysulfone membrane in a pressing mode, the dopamine solution reacts to form a polydopamine layer on the surface and in membrane pores of the membrane, then a base membrane with the polydopamine layer is sequentially immersed into low-concentration water phase solution and oil phase solution, and because the water phase solution and the oil phase solution are low in concentration, part of amido groups carried by the polydopamine layer are remained on the surface of the membrane after the water phase is immersed, the amido groups can react with the following oil phase acyl chloride to generate amido bonds, so that an interpenetration structure is formed, and the relation between the polyamide layer and the polysulfone base membrane layer can be enlarged. And a polydopamine layer and a polyamide structure are formed in pores of the porous base membrane, so that the membrane flux is increased, and the rejection rate of the membrane is increased. The glutaraldehyde cross-linked chitosan complex silver is used as a polyamide protective layer, the chitosan surface has a plurality of hydroxyl groups and amino groups, so that the attack of chlorine can be prevented, the chlorine resistance of the membrane is improved, and the antibacterial property of the membrane is improved due to the antibacterial property of the silver.
Description
Technical Field
The invention relates to a multilayer polyamide film preparation process and a corresponding film product.
Background
The membrane technology is a common water treatment technology, and the conventional membrane technology is divided into reverse osmosis, forward osmosis, nanofiltration, ultrafiltration and the like. The reverse osmosis technology is a separation method for separating solute from solvent in solution by means of selective interception of reverse osmosis membrane under the action of certain pressure, and compared with other membrane types (nanofiltration, ultrafiltration, forward osmosis, microfiltration and the like), the reverse osmosis technology has smaller membrane pore size and can effectively remove impurities such as salts, organic matters, colloids, bacteria and the like in water. Polyamide is a common reverse osmosis membrane material, interfacial polymerization is a polyamide preparation method of manufacturers, but the conventional interfacial polymerization has the defects of weak contact force between a base membrane and an active layer, low water flux, reduced rejection rate while increasing the water flux and poor antibacterial performance.
In the prior art, the permeability and rejection rate of a polyamide reverse osmosis membrane are increased by adopting a surface treatment and mixed doping mode, but the conventional rejection rate and permeability cannot be simultaneously improved due to the TRADE-OFF effect, and a membrane with high antibacterial performance, which can increase the flux and rejection rate of the reverse osmosis membrane and increase the binding force between a polyamide layer and a supporting layer, is urgently needed.
Disclosure of Invention
The present invention aims to provide a stable reverse osmosis membrane having high rejection rate, high permeability and strong antibacterial property.
The application provides a preparation method of a composite reverse osmosis membrane, which comprises the following steps:
a) Preparation of a base film: weighing 17-19 wt% of polysulfone resin, dissolving the polysulfone resin in N, N-dimethylformamide, adding 4.0-5.0 wt% of additive, stirring for 3-6h at 50-100 ℃ to prepare uniformly dispersed solution; filtering, vacuum degassing, uniformly coating on non-woven fabric, wherein the thickness of a wet film is about 100-200 μm, immediately immersing in pure water at 20-30 ℃ for gel curing to form a film, and spraying 30-60% sulfuric acid solution at 25-50 ℃ on a polysulfone film to obtain a polysulfone base film;
b) Preparing a basement membrane surface modification layer, weighing 6.0-8.5g of trihydroxymethyl aminomethane into a beaker, adding a proper amount of ultrapure water for dissolving, transferring into a 1L volumetric flask, fixing the volume, and adjusting the pH to 6.0-8.0 by using hydrochloric acid to obtain the trihydroxymethyl aminomethane-hydrochloric acid buffer solution. Weighing 0.2-0.4g of dopamine, adding the dopamine into the buffer solution to form a dopamine modified solution, and pressurizing and filtering the dopamine modified solution on a polysulfone basal membrane to form a polydopamine layer on the surface of the membrane and in membrane pores.
C) Preparation of the bottom polyamide layer. Preparing aqueous phase liquid: dissolving aromatic polyfunctional amine and a surfactant in water in sequence, stirring uniformly, and adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6-10 to obtain an aqueous phase solution, wherein the aromatic polyfunctional amine accounts for 0.06-0.10% of the mass concentration of the aqueous solution, and the surfactant accounts for 0.5% of the mass concentration of the aqueous solution; preparing an oil phase solution: dissolving aromatic polyfunctional acyl halide in naphtha, stirring uniformly to obtain oil phase liquid, wherein the mass concentration of the aromatic polyfunctional acyl halide in the oil solution is 0.01-0.03%, immersing the base film with the formed polydopamine layer in a water phase solution for 30-60 seconds, removing the excessive water phase liquid on the surface of the non-woven fabric base film by using a surface-polished stainless steel roller, immersing the base film in the oil phase liquid for 40-60 seconds, removing the residual oil phase liquid on the surface, then putting the base film in an oven at 60-90 ℃ for 4-8 minutes, and then cleaning to obtain a bottom polyamide layer.
D) A top polyamide layer.
And (3) ultrasonically dispersing 0.1-0.5g of graphene oxide in 100mL of water to prepare the graphene oxide/water dispersion. 0.1-0.5g of 3-aminopropylphosphonic acid was dissolved in 40mL of ethanol to prepare a 3-aminopropylphosphonic acid/ethanol solution. Adding the 3-aminopropyl phosphonic acid/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 10-15h at the temperature of 80-95 ℃. And (4) carrying out suction filtration, and washing filter residues in ethanol to obtain the phosphonic acid modified graphene oxide.
Preparing aqueous phase liquid: dissolving aromatic polyfunctional amine and a surfactant in water in sequence, stirring uniformly, adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6-10 to obtain an aqueous phase solution, wherein the mass concentration of the aromatic polyfunctional amine in the aqueous solution is 0.3-0.5%, then adding the phosphonic acid modified graphene oxide, and stirring uniformly. Preparing an oil phase solution: dissolving aromatic polyfunctional acyl halide in naphtha, stirring uniformly to obtain oil phase liquid, wherein the mass concentration of the aromatic polyfunctional acyl halide in the oil solution is 0.1-0.3%, immersing the base membrane with the bottom polyamide layer into the water phase solution for 30-60 seconds, removing the redundant water phase liquid on the surface of the non-woven fabric base membrane by using a stainless steel roller with polished surface, immersing the base membrane into the oil phase liquid for 40-80 seconds, removing the residual oil phase liquid on the surface, then putting the base membrane into an oven with the temperature of 60-90 ℃ for 5 minutes, and then cleaning to obtain the membrane with the top polyamide layer.
E) And (4) preparing a protective layer.
Preparing a chitosan complex silver antibacterial agent, weighing soluble silver salt and chitosan according to the weight ratio of 1: 10-70, firstly adding water into a reaction kettle, starting a stirrer, controlling the reaction pH value to be 3.6-8.5, controlling the reaction temperature to be-16-70 ℃, slowly adding chitosan, stirring until the chitosan is completely dissolved to form a solution with the mass concentration of 0.3-0.9, then adding the soluble silver salt, stirring for reaction for 0.2-20 hours, adding glutaraldehyde, and preparing a protective layer modified solution with the mass concentration of 0.2-0.8% of glutaraldehyde.
And (3) immersing the membrane containing the top polyamide layer into a protective layer modification solution for 0.2-4h, and performing a crosslinking reaction to obtain the polyamide membrane of the surface-modified chitosan protective layer.
Preferably, the soluble silver salt comprises a nitrate, acetate or citrate salt.
Preferably, the surfactant is sodium benzene sulfonate, sodium dodecyl benzene sulfonate or sodium carboxymethyl sulfonate.
Preferably, the additive is polyvinyl alcohol or polyvinylpyrrolidone.
Preferably, the aromatic polyfunctional amine is p-phenylenediamine or m-phenylenediamine.
Preferably, the aromatic polyfunctional acid chloride is trimesoyl chloride.
Advantageous effects
According to the method, polyvinyl alcohol or polyvinylpyrrolidone is added into a polysulfone membrane, the porosity of the membrane is increased, the flux of the membrane is increased, a dopamine solution is filter-pressed on the polysulfone membrane in a pressing-in mode, a polydopamine layer is formed on the surface of the membrane and in membrane pores through reaction, then a base membrane with the polydopamine layer is sequentially immersed into a water phase solution and an oil phase solution, the water phase solution and the oil phase solution are low in concentration, after the water phase is immersed, part of amido groups carried by the polydopamine layer are arranged on the surface of the membrane, the amido groups can react with the following oil phase acyl chloride to generate amido bonds, an interpenetration structure is formed, and the relation between the membrane polyamide layer and the base membrane layer can be increased. And a polydopamine layer and a polyamide structure are formed in pores of the porous base membrane, so that the membrane flux is increased, and the rejection rate of the membrane is increased.
The concentration of the monomers applied in the preparation process of the top layer polyamide is higher than that of the monomers applied in the bottom layer, so that a compact polyamide layer is conveniently formed on the top layer, the retention rate of the membrane is ensured, meanwhile, in the preparation process of the top layer membrane, the phosphonic acid modified graphene oxide is added into the water phase monomers, the hydrophilicity of the membrane is increased, partial channels are provided, the treatment flux of the membrane is increased, and meanwhile, the phosphonic acid groups can be complexed with the acyl chloride groups, so that the acyl chloride groups are prevented from being hydrolyzed, the formation amount of the polyamide is increased, and the retention rate of the membrane is increased. In the membrane preparation process, the concentration applied in the bottom layer polyamide preparation process is low, amino exposed points of polydopamine exist on the membrane surface after the membrane surface is coated with the aqueous solution, a polyamide mechanism is formed by the amino exposed points and acyl chloride groups, a penetrating layer is formed, the connecting force of a polyamide layer and a base layer is increased, the polydopamine layer is generated by polymerization reaction of monomer dopamine on the polysulfone membrane, and the connecting force of the polydopamine layer and the polysulfone layer is enhanced.
Glutaraldehyde crosslinked chitosan complexed silver is used as a polyamide protective layer, and the chitosan surface has a plurality of hydroxyl groups and amino groups, so that chlorine attack can be prevented, the chlorine resistance of the membrane is improved, and the antibacterial property of the membrane is improved due to the antibacterial property of the silver.
Detailed Description
Example 1
The application provides a preparation method of a composite reverse osmosis membrane, which comprises the following steps:
a) Preparation of a base film: weighing polysulfone resin with the weight ratio of 18 percent, dissolving the polysulfone resin in N, N-dimethylformamide, adding polyvinyl alcohol with the weight ratio of 4.0 percent, stirring for 3 hours at the temperature of 60 ℃ to prepare uniformly dispersed solution; filtering, vacuum degassing, uniformly coating on non-woven fabric, wherein the thickness of a wet film is about 100 μm, immediately immersing in pure water at 20 ℃ for gel curing to form a film, and spraying 30% sulfuric acid solution at 25 ℃ on a polysulfone film to obtain a polysulfone base film;
b) Preparing a basement membrane surface modification layer, weighing 6.0g of tris (hydroxymethyl) aminomethane into a beaker, adding a proper amount of ultrapure water for dissolving, transferring into a 1L volumetric flask, fixing the volume, and adjusting the pH to 6.0 by using hydrochloric acid to obtain tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution. Weighing 0.2g of dopamine, adding the dopamine into the buffer solution to form a dopamine modified solution, and performing pressure filtration on the dopamine modified solution on a polysulfone basal membrane for 0.5h to obtain a polydopamine layer formed on the surface and in the pores of the membrane.
C) Preparation of the bottom polyamide layer. Preparing an aqueous phase liquid: sequentially dissolving p-phenylenediamine and sodium benzenesulfonate in water, stirring uniformly, and adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 7 to obtain an aqueous phase solution, wherein the mass concentration of the p-phenylenediamine in the aqueous solution is 0.06%, and the mass concentration of the surfactant in the aqueous solution is 0.5%; preparing an oil phase solution: dissolving trimesoyl chloride in naphtha, uniformly stirring to obtain an oil phase solution, wherein the mass concentration of the trimesoyl chloride in the oil solution is 0.01%, immersing the base membrane with the formed poly dopamine layer into the water phase solution for 30 seconds, removing the redundant water phase solution on the surface of the non-woven fabric base membrane by using a stainless steel roller with a polished surface, immersing the base membrane into the oil phase solution for 40 seconds, removing the residual oil phase solution on the surface, then, putting the base membrane into a 60 ℃ oven for 4 minutes, and then, cleaning to obtain a bottom polyamide layer.
D) A top polyamide layer.
0.1g of graphene oxide is dispersed in 100mL of water by ultrasonic to prepare graphene oxide/water dispersion. 0.1g of 3-aminopropyl phosphonic acid was dissolved in 40mL of ethanol to prepare a 3-aminopropyl phosphonic acid/ethanol solution. Adding the 3-aminopropyl phosphonic acid/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 10 hours at 80 ℃. And (4) carrying out suction filtration, and washing filter residues in ethanol to obtain the phosphonic acid modified graphene oxide.
Preparing aqueous phase liquid: sequentially dissolving p-phenylenediamine and sodium benzenesulfonate in water, stirring uniformly, adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6 to obtain an aqueous phase solution, wherein the mass concentration of the p-phenylenediamine in the aqueous solution is 0.3%, the phosphonic acid modified graphene oxide accounting for 5% of the total mass of the aqueous phase solution is added, and stirring uniformly. Preparing an oil phase solution: dissolving trimesoyl chloride in naphtha, uniformly stirring to obtain an oil phase solution, wherein the mass concentration of the trimesoyl chloride in the oil solution is 0.1%, immersing the base membrane with the bottom polyamide layer into the water phase solution for 30 seconds, removing the redundant water phase solution on the surface of the non-woven fabric base membrane by using a stainless steel roller with a polished surface, immersing the base membrane into the oil phase solution for 40 seconds, removing the residual oil phase solution on the surface, then putting the base membrane into a 60 ℃ oven for 5 minutes, and then cleaning to obtain the membrane with the top polyamide layer.
E) And (4) preparing a protective layer.
Preparing a chitosan silver complex antibacterial agent, weighing silver nitrate and chitosan in a weight ratio of 1: 20, firstly adding water into a reaction kettle, starting a stirrer, controlling the reaction pH value to be 3.6, controlling the reaction temperature to be 20 ℃, slowly adding the chitosan, stirring until the chitosan is completely dissolved to prepare a chitosan solution with the mass concentration of 3%, then adding the silver nitrate, stirring for reaction for 0.3 hour, adding glutaraldehyde, and preparing a protective layer modified solution with the mass concentration of 0.3%.
And (3) immersing the membrane containing the top polyamide layer into a protective layer modification solution for 1h, and carrying out crosslinking reaction to obtain the polyamide membrane with the surface modified chitosan protective layer.
Example 2
A) Preparation of a base film: weighing 18 wt% of polysulfone resin, dissolving the polysulfone resin in N, N-dimethylformamide, adding 4.0 wt% of polyvinylpyrrolidone, and stirring at 60 ℃ for 3 hours to prepare a uniformly dispersed solution; filtering, vacuum degassing, uniformly coating on non-woven fabric, wherein the thickness of a wet film is about 100 μm, immediately immersing in pure water at 20 ℃ for gel curing to form a film, and spraying 30% sulfuric acid solution at 25 ℃ on a polysulfone film to obtain a polysulfone base film;
b) Preparing a basement membrane surface modification layer, weighing 6.0g of tris (hydroxymethyl) aminomethane into a beaker, adding a proper amount of ultrapure water for dissolving, transferring into a 1L volumetric flask, fixing the volume, and adjusting the pH to 6.0 by using hydrochloric acid to obtain tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution. Weighing 0.2g of dopamine, adding the dopamine into the buffer solution to form dopamine modified solution, and performing pressure filtration on the dopamine modified solution on a polysulfone basal membrane for 0.5h to obtain a membrane surface and a membrane hole to form a polydopamine layer.
C) Preparation of the bottom polyamide layer. Preparing an aqueous phase liquid: sequentially dissolving p-phenylenediamine and sodium dodecyl benzene sulfonate in water, uniformly stirring, and adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 7 to obtain an aqueous phase solution, wherein the m-phenylenediamine accounts for 0.06% of the mass concentration of the aqueous solution, and the surfactant accounts for 0.5% of the mass concentration of the aqueous solution; preparing an oil phase solution: dissolving trimesoyl chloride in naphtha, uniformly stirring to obtain an oil phase solution, wherein the mass concentration of the trimesoyl chloride in the oil solution is 0.01%, immersing the base membrane with the formed poly dopamine layer into the water phase solution for 30 seconds, removing the redundant water phase solution on the surface of the non-woven fabric base membrane by using a stainless steel roller with a polished surface, immersing the base membrane into the oil phase solution for 40 seconds, removing the residual oil phase solution on the surface, then, putting the base membrane into a 60 ℃ oven for 4 minutes, and then, cleaning to obtain a bottom polyamide layer.
D) A top polyamide layer.
0.1g of graphene oxide is dispersed in 100mL of water by ultrasonic to prepare graphene oxide/water dispersion. 0.1g of 3-aminopropyl phosphonic acid was dissolved in 40mL of ethanol to prepare a 3-aminopropyl phosphonic acid/ethanol solution. Adding the 3-aminopropyl phosphonic acid/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 10 hours at 80 ℃. And (4) carrying out suction filtration, and washing filter residues in ethanol to obtain the phosphonic acid modified graphene oxide.
Preparing aqueous phase liquid: sequentially dissolving p-phenylenediamine and sodium dodecyl benzene sulfonate in water, stirring uniformly, adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6 to obtain an aqueous phase solution, wherein the mass concentration of the p-phenylenediamine in the aqueous solution is 0.3%, the phosphonic acid modified graphene oxide accounting for 5% of the total mass of the aqueous phase solution is added, and stirring uniformly. Preparing an oil phase solution: dissolving trimesoyl chloride in naphtha, uniformly stirring to obtain an oil phase solution, wherein the mass concentration of the trimesoyl chloride in the oil solution is 0.1%, immersing the base membrane with the bottom polyamide layer into the water phase solution for 30 seconds, removing the redundant water phase solution on the surface of the non-woven fabric base membrane by using a stainless steel roller with a polished surface, immersing the base membrane into the oil phase solution for 40 seconds, removing the residual oil phase solution on the surface, then putting the base membrane into a 60 ℃ oven for 5 minutes, and then cleaning to obtain the membrane with the top polyamide layer.
E) And (4) preparing a protective layer.
Preparing a chitosan complex silver antibacterial agent, weighing silver acetate and chitosan in a weight ratio of 1: 20, firstly adding water into a reaction kettle, starting a stirrer, controlling the reaction pH value to be 3.6, controlling the reaction temperature to be 20 ℃, slowly adding chitosan, stirring until the chitosan is completely dissolved to prepare a chitosan solution with the mass concentration of 3%, then adding the silver acetate, stirring for reaction for 0.3 hour, adding glutaraldehyde, and preparing a protective layer modified solution with the mass concentration of 0.3%.
And (3) immersing the membrane containing the top polyamide layer into a protective layer modification solution for 1h, and carrying out crosslinking reaction to obtain the polyamide membrane with the surface modified chitosan protective layer.
Comparative example 1
The other process was the same as in example 1 except that a 30% sulfuric acid solution at 25 ℃ was not sprayed on the polysulfone film during the preparation of the polysulfone-based film
Comparative example 2
The rest of the process is the same as that of example 1, except that in the preparation process of the bottom polyamide layer, the mass concentration of the p-phenylenediamine in the aqueous solution is 0.3%, and the mass concentration of the surfactant in the aqueous solution is 0.5%; the mass concentration of trimesoyl chloride in the oil solution is 0.1%.
Comparative example 3
Otherwise, the same as example 1 was repeated, except that a protective layer was not formed.
Comparative example 4
The procedure of example 1 was repeated except that the phosphonic acid-modified graphene oxide was not added to the aqueous solution in the top polyamide layer.
Comparative example 5
The rest was the same as example 1 except that the bottom polyamide layer was not formed.
Comparative example 6
The rest was the same as example 1 except that the polydopamine layer was not formed.
Comparative example 7
The procedure of example 1 was repeated, except that the polydopamine layer was not subjected to pressure filtration.
The membranes of the above examples and comparative examples were tested under 1400ppm sodium chloride solution at pH 7.5 at 20 ℃ under 150psi test pressure, and after running for a long time under 1500ppm active chlorine attack, the membrane properties were again measured as shown in Table 1
Table 1:
it can be seen that the base membrane is not subjected to acid treatment, the rejection rate and the water flux of the membrane are reduced, the main reason is that the porosity of the membrane is increased by the acid treatment, the membrane pores which are not subjected to the acid treatment are small, the amount of the dopamine solution entering the membrane pores is small in the suction filtration process, so that a polydopamine layer and a polyamide layer are not formed in part of the membrane pores, and the rejection rate of the membrane is reduced.
When the underlayer coating was treated with a high concentration polyamide, the salt rejection rate was high in comparative example 2, but the underlayer coating was formed by using a high concentration polyamide in successive layers. The rejection rate of the membrane is reduced.
As can be seen from comparison of comparative example 3 with example 1, the rejection rate of the membrane without the protective layer formed decreases more rapidly by the attack of active chlorine, further illustrating that the establishment of the protective layer has the property of making the membrane more resistant to chlorine attack.
As can be seen from comparison of comparative example 4 with example 1, the phosphonic acid-modified graphene oxide was not added, and both the rejection rate and flux of the membrane were reduced due to the fact that the phosphonic acid-modified graphene oxide can increase the hydrophilicity of the membrane and the phosphoric acid groups can form a complex with the amide to prevent hydrolysis of the amide during the reaction.
As can be seen from comparison between comparative example 5 and example 1, the rejection of the membrane is reduced without forming the bottom polyamide layer, the flux change is not large, and the bottom polyamide layer and the polydopamine layer form coupling penetration, so that the corresponding rejection is reduced without the bottom polyamide layer.
As can be seen from comparison between comparative example 6 and example 1, the non-formed polydopamine layer is not formed, the rejection rate of the membrane is reduced, the flux change is not large, and the main reason is that the bottom polyamide and the polydopamine layer can form coupling insertion, so that after the non-formed polydopamine layer does not exist, the corresponding coupling effect disappears, and the rejection rate is reduced.
As can be seen from comparison between comparative example 7 and example 1, the rejection of the membrane is reduced without filter pressing, the flux change is not large, and the corresponding rejection is reduced mainly when excessive poly-dopamine layers and polyamide layers are not formed in the corresponding membrane pores without filter pressing.
The membranes were also tested for long-term operation, and after 100 days at a temperature of 20 ℃ and a working pressure of 150psi at a pH of 7.5 in 1400ppm NaCl solution, the corresponding membrane properties are shown in Table 2:
TABLE 2
| Case(s) | Rate of decrease in rejection | Membrane crusherDamage ratio (ratio of film damage area to overall area) |
| Example 1 | 0.7% | 0.02% |
| Example 2 | 0.6% | 0.02% |
| Comparative example 1 | 2.0% | 1.0% |
| Comparative example 2 | 1.7% | 1.3% |
| Comparative example 3 | 2.1% | 0.5% |
| Comparative example 4 | 1.2% | 0.4% |
| Comparative example 5 | 1.6% | 1.4% |
| Comparative example 6 | 1.1% | 1.2% |
| Comparative example 7 | 1.0% | 0.5% |
As can be seen from the table 2, due to the chemical bonding between the bottom layer and the polyamide layer in the technical scheme of the application, the service life of the membrane is greatly prolonged, and the lower membrane breakage rate and rejection rate reduction rate can be ensured under the long-term operation of the membrane.
Film antibacterial property test experiment
Gram-negative escherichia coli and gram-positive staphylococcus aureus are used as bacterial models, the antibacterial performance of the membranes of the embodiment 1, the comparative example 4 and the comparative example 5 is tested by adopting a bacterial liquid oscillation method according to the national standard (GB/T20944.3-2008), a group of blank controls are set, and the calculation formula of the sterilization rate is as follows: ((A-B)/A) × 100%, A being the number of colonies of the bacteria in the blank control group, B being the number of colonies of the bacteria in the solution at each sampling. The performance of each film versus table 2:
table 2:
| case(s) | Sterilizing rate of Escherichia coli | Staphylococcus aureus bactericidal rate |
| Example 1 | 98.7% | 97.5% |
| Comparative example 3 | 94.7% | 92.7% |
| Commercially available polyamide membranes | 93.5% | 91.7% |
As can be seen from table 2, the formation of the protective layer during the film preparation process can increase the antibacterial performance of the film.
Claims (4)
1. A preparation method of a multilayer polyamide membrane composite reverse osmosis membrane comprises the following steps:
a) Preparation of a base film: weighing 17-19 wt% of polysulfone resin, dissolving the polysulfone resin in N, N-dimethylformamide, adding 4.0-5.0 wt% of additive, stirring for 3-6h at 50-100 ℃ to prepare uniformly dispersed solution; filtering, vacuum degassing, uniformly coating on non-woven fabric, wherein the thickness of a wet film is 100-200 μm, immediately immersing in pure water at 20-30 ℃ for gel curing to form a film, and spraying 30-60% sulfuric acid solution at 25-50 ℃ on a polysulfone film to obtain a polysulfone base film;
b) Preparing a base membrane surface modification layer, weighing 6.0-8.5g of tris (hydroxymethyl) aminomethane in a beaker, adding a proper amount of ultrapure water for dissolving, transferring to a 1L volumetric flask, fixing the volume, and adjusting the pH to 6.0-8.0 by using hydrochloric acid to obtain tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution; weighing 0.2-0.4g of dopamine, adding the dopamine into the buffer solution to form dopamine modified solution, and performing pressure filtration on the dopamine modified solution on a polysulfone basal membrane to form a polydopamine layer on the surface of the membrane and in membrane pores;
c) Preparing a bottom polyamide layer; preparing an aqueous phase liquid: dissolving aromatic polyfunctional amine and a surfactant in water in sequence, stirring uniformly, and adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6-10 to obtain an aqueous phase solution, wherein the aromatic polyfunctional amine accounts for 0.06-0.10% of the aqueous solution by mass, and the surfactant accounts for 0.5% of the aqueous solution by mass; preparing an oil phase solution: dissolving aromatic polyfunctional acyl halide in naphtha, and uniformly stirring to obtain oil phase liquid, wherein the aromatic polyfunctional acyl halide accounts for 0.01-0.03% of the mass of the oil solution; immersing the basement membrane with the polydopamine layer into a water phase solution for 30-60 seconds, removing excessive water phase liquid on the surface of the non-woven fabric basement membrane by using a stainless steel roller with a polished surface, immersing the basement membrane into oil phase liquid for 40-60 seconds, removing residual oil phase liquid on the surface, then putting the basement membrane into a drying oven at 60-90 ℃ for 4-8 minutes, and then cleaning to obtain bottom polyamide;
d) A top polyamide layer; 0.1-0.5g of graphene oxide is placed in 100mL of water and subjected to ultrasonic dispersion to prepare graphene oxide/water dispersion; dissolving 0.1-0.5g of 3-aminopropyl phosphonic acid in 40mL of ethanol to prepare a 3-aminopropyl phosphonic acid/ethanol solution; adding the 3-aminopropyl phosphonic acid/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 10-15h at the temperature of 80-95 ℃; performing suction filtration, and washing filter residues in ethanol to obtain phosphonic acid modified graphene oxide; preparing aqueous phase liquid: sequentially dissolving aromatic polyfunctional amine and a surfactant in water, stirring uniformly, adding sodium hydroxide into the obtained aqueous solution to adjust the pH value of the solution to 6-10 to obtain an aqueous phase solution, wherein the aromatic polyfunctional amine accounts for 0.3-0.5% of the aqueous solution by mass, adding the phosphonic acid modified graphene oxide, and stirring uniformly; preparing an oil phase solution: dissolving aromatic polyfunctional acyl halide in naphtha, and uniformly stirring to obtain an oil phase liquid, wherein the aromatic polyfunctional acyl halide accounts for 0.1-0.3% of the oil phase liquid by mass; immersing the base film with the bottom polyamide layer into the aqueous phase solution for 30-60 seconds, removing excessive aqueous phase liquid on the surface of the non-woven fabric base film by using a stainless steel roller with a polished surface, immersing the base film into the oil phase liquid for 40-80 seconds, removing the residual oil phase liquid on the surface, then putting the base film into an oven at 60-90 ℃ for 5 minutes, and then cleaning to obtain the film with the top polyamide layer;
e) Preparing a protective layer; preparing a chitosan-silver complex antibacterial agent, weighing soluble silver salt and chitosan in a weight ratio of 1: 10-70, adding water into a reaction kettle, starting a stirrer, controlling the reaction pH value to be 3.6, controlling the reaction temperature to be-16-70 ℃, slowly adding chitosan, stirring until the chitosan is completely dissolved to form a solution with the mass ratio of 3%, adding the soluble silver salt, stirring for reaction for 0.2-20 hours, adding glutaraldehyde, and preparing a protective layer modified solution with the mass ratio of 0.2-0.8% of glutaraldehyde; and (3) immersing the membrane containing the top polyamide layer into a protective layer modification solution for 0.2-4h, and performing a crosslinking reaction to obtain the polyamide membrane of the surface-modified chitosan protective layer.
2. A method of preparing a composite reverse osmosis membrane according to claim 1 wherein said soluble silver salt comprises a nitrate, acetate or citrate salt.
3. A method of preparing a composite reverse osmosis membrane according to claim 1 wherein said surfactant is sodium benzene sulfonate or sodium dodecyl benzene sulfonate.
4. A method of preparing a composite reverse osmosis membrane according to claim 1 wherein the additive is polyvinyl alcohol or polyvinyl pyrrolidone.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001259388A (en) * | 2000-03-23 | 2001-09-25 | Nitto Denko Corp | Composite reverse osmosis membrane and method for producing the same |
| CN101185849A (en) * | 2007-09-11 | 2008-05-28 | 浙江工商大学 | Preparation method of polyamide/polyvinyl alcohol/polyamide composite membrane whose separation layer is multi-layer alternate compounding |
| CN109847586A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | High-flux reverse osmosis membrane and its preparation method and application |
| CN111203106A (en) * | 2020-02-04 | 2020-05-29 | 厦门江天智能仿生科技有限公司 | Multilayer reverse osmosis composite membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008093544A (en) * | 2006-10-10 | 2008-04-24 | Nitto Denko Corp | Composite semipermeable membrane and method for producing the same |
| EP2318126B1 (en) * | 2008-07-10 | 2018-08-22 | Board Of Regents, The University Of Texas System | Water purification membranes with improved fouling resistance |
| US10384171B2 (en) * | 2012-11-23 | 2019-08-20 | Council Of Scientific & Industrial Research | Modified thin film composite reverse osmosis membrane and a process for preparation thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001259388A (en) * | 2000-03-23 | 2001-09-25 | Nitto Denko Corp | Composite reverse osmosis membrane and method for producing the same |
| CN101185849A (en) * | 2007-09-11 | 2008-05-28 | 浙江工商大学 | Preparation method of polyamide/polyvinyl alcohol/polyamide composite membrane whose separation layer is multi-layer alternate compounding |
| CN109847586A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | High-flux reverse osmosis membrane and its preparation method and application |
| CN111203106A (en) * | 2020-02-04 | 2020-05-29 | 厦门江天智能仿生科技有限公司 | Multilayer reverse osmosis composite membrane |
Non-Patent Citations (2)
| Title |
|---|
| Polyamide thin-film composite membrane fabricated through interfacial polymerization coupled with surface amidation for improved reverse osmosis performance;Chuang Yu等;《Journal of Membrane Science》;20180904;第566卷;第87-95页 * |
| 聚酰胺反渗透膜复合膜改性研究进展;刘兆峰 等;《化工新型材料》;20201031;第48卷(第10期);第54-57+63页 * |
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