CN115155340B - Polyamide composite nanofiltration membrane containing antibacterial interlayer and preparation method thereof - Google Patents
Polyamide composite nanofiltration membrane containing antibacterial interlayer and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 258
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 88
- 239000004952 Polyamide Substances 0.000 title claims abstract description 86
- 229920002647 polyamide Polymers 0.000 title claims abstract description 86
- 239000011229 interlayer Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 45
- 230000004907 flux Effects 0.000 claims abstract description 38
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 33
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012965 benzophenone Substances 0.000 claims abstract description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- 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 abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
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- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- 239000000654 additive Substances 0.000 claims description 3
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- 239000000835 fiber Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- 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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyamide composite nanofiltration membrane containing an antibacterial interlayer and a preparation method thereof. The preparation method comprises the steps of A, taking a polysulfone ultrafiltration membrane as a substrate, placing the substrate on the surface of a solution containing silver nitrate and benzophenone, enabling an effective filtration surface to be downward, enabling the solution to fully wet the substrate, and sealing to obtain a closed reaction system; B. placing the closed reaction system under ultraviolet light irradiation to deposit silver nano particles on the surface of the polysulfone ultrafiltration membrane to obtain a PSF-Ag ultrafiltration membrane; C. cleaning the PSF-Ag ultrafiltration membrane to obtain a C product; D. and (3) clamping the product C between film-making frames, airing, pouring the piperazine solution into the film-making frames, enabling the product C to be in contact with the piperazine solution, pouring out the residual solution, airing, pouring the trimesic acid chloride solution into the film-making frames, pouring out the residual solution after the contact, carrying out heat treatment, and taking out to obtain a finished product. The polyamide composite nanofiltration membrane containing the antibacterial interlayer has better stain resistance, can delay the decline of permeation separation performance, prolongs the service life and greatly improves the membrane flux.
Description
Technical Field
The invention relates to the technical field of composite nanofiltration membranes, in particular to a polyamide composite nanofiltration membrane containing an antibacterial interlayer and a preparation method thereof.
Background
Nanofiltration membranes (NF) are an important component of separation membranes, being a pressure driven selective separation membrane between reverse osmosis membranes (RO) and ultrafiltration membranes (UF). The nanofiltration membrane has more high salt rejection rate than the ultrafiltration membrane and higher permeation flux than the reverse osmosis membrane. The method is widely applied to the fields of seawater desalination, hard water softening, wastewater recycling and the like by virtue of the advantages of low cost, low energy consumption, high efficiency, easiness in control and the like. Although polyamide composite nanofiltration membranes (TFC) have significant advantages over conventional asymmetric membranes in terms of mechanical stability, separability performance, permeation flux, etc., in terms of current situation, polyamide nanofiltration membranes still have problems of easy membrane pollution, easy degradation of permeation separation performance, and insufficient membrane flux in the application process, and membrane damage is easily caused by flushing due to membrane pollution, so that the service life of the membranes is shortened. Therefore, the research on improving the fouling resistance, delaying the decline of the permeation separation performance, prolonging the service life and improving the membrane flux has very important significance.
Disclosure of Invention
The invention aims to provide a polyamide composite nanofiltration membrane containing an antibacterial interlayer and a preparation method thereof. The polyamide composite nanofiltration membrane containing the antibacterial interlayer has better stain resistance, can delay the decline of permeation separation performance, prolongs the service life and greatly improves the membrane flux.
The technical scheme of the invention is as follows: a preparation method of a polyamide composite nanofiltration membrane containing an antibacterial interlayer, which comprises the following steps,
A. taking a polysulfone ultrafiltration membrane as a base material, placing the polysulfone ultrafiltration membrane on the surface of an ethanol solution containing silver nitrate and benzophenone, enabling an effective filtration surface to contact the solution downwards, enabling the solution to fully wet the base material, and capping and sealing to obtain a closed reaction system;
B. placing the closed reaction system under ultraviolet light for irradiation for 5-90min, reducing silver ions into silver nano particles by free radicals generated by benzophenone cleavage, and depositing the silver nano particles on the surface of the polysulfone ultrafiltration membrane to obtain a PSF-Ag ultrafiltration membrane;
C. washing the PSF-Ag ultrafiltration membrane to remove unreacted complete solution and possible blockage and other sediments on the surface of the membrane to obtain a C product;
D. and (3) clamping the C product between film making frames, airing, pouring the piperazine aqueous solution into the film making frames, enabling the C product to be in contact with the piperazine aqueous solution for 5-20min, pouring out the residual solution, airing the C product for 3-15min, removing the residual solution, pouring the trimesoyl chloride n-hexane solution into the surface of the C product treated by the piperazine aqueous solution, pouring out the residual solution after being in contact with the surface for 30-120s, carrying out heat treatment on the C product at 60-80 ℃ for 10-30min, and taking out to obtain the polyamide composite nanofiltration film containing the antibacterial interlayer.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the concentration of the silver nitrate is 10-100mM, and the concentration of the benzophenone is 10-100mM.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the concentration of the silver nitrate in the step A is 60mM, and the concentration of the benzophenone in the step A is 60mM.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, in the step B, the closed reaction system is irradiated under ultraviolet light for 60 minutes.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the wavelength of ultraviolet light is 355-390nm.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the wavelength of ultraviolet light is 365nm.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the step C is to repeatedly wash the PSF-Ag ultrafiltration membrane with ethanol and deionized water to remove the solution which is not completely reacted on the surface of the membrane, and wash the membrane with ultrasonic waves for 10-40min to remove the possible blockage and other sediments, so as to obtain a product C.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the step C is to repeatedly wash the PSF-Ag ultrafiltration membrane with ethanol and deionized water to remove the solution which is not completely reacted on the surface of the membrane, and wash the membrane with ultrasonic waves for 30min to remove the possible blockage and other sediments, thus obtaining the product C.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the concentration of the piperazine aqueous solution in the step D is 0.05-0.4wt%, and the concentration of the trimesoyl chloride n-hexane solution is 0.05-0.4wt%.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, in the step D, the concentration of the piperazine aqueous solution is 0.1wt%, and the concentration of the trimesoyl chloride n-hexane solution is 0.1wt%.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the contact time of the C product and the piperazine aqueous solution is 15min, and the contact time of the C product and the trimesoyl chloride n-hexane solution is 90s.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the molecular weight cut-off of the polysulfone ultrafiltration membrane is 50000-70000, and the pure water flux is 200-400L m -2 ·h -1 。
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the molecular weight cut-off of the polysulfone ultrafiltration membrane is 60000, and the pure water flux is 300L.m -2 ·h -1 。
The polyamide composite nanofiltration membrane containing the antibacterial interlayer is prepared by the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer.
Compared with the prior art, the invention loads nano silver particles on the surface of the polysulfone ultrafiltration membrane, and further carries out interfacial polymerization reaction on the surface of the nano silver particles to generate a polyamide separation layer, thus preparing the polyamide composite nanofiltration membrane containing the antibacterial interlayer. The polysulfone ultrafiltration membrane is loaded with a large number of nano silver particles on the surface. The nano silver particles are loaded to greatly improve the antibacterial property and the hydrophilicity of the membrane, so that the membrane has better stain resistance, the flux recovery rate is obviously improved when the sewage and wastewater are filtered, the antibacterial rate of the membrane to escherichia coli can be more than 86%, and the flux recovery rate can be more than 86%. The improvement of the stain resistance can delay the performance decline and prolong the service life of the membrane. The loading of the nano silver particles can not be influencedAnd the nano silver particles are used as an interlayer to construct a large number of cavity structures between the polysulfone ultrafiltration membrane and the polyamide separation layer, and the existence of the cavity structures obviously increases the effective filtration area of the polyamide separation layer, so that the permeability of the membrane is improved, and the pure water flux improvement rate of the membrane can reach 59% at most. The polyamide composite nanofiltration membrane containing the antibacterial interlayer has better separation performance, and can be used for Na 2 SO 4 The retention rate of the catalyst can reach more than 97 percent. The nano silver particles in the polyamide composite nanofiltration membrane containing the antibacterial interlayer have better stability. The polyamide composite nanofiltration membrane containing the antibacterial interlayer has better stain resistance, can delay the decline of permeation separation performance, prolongs the service life and greatly improves the membrane flux.
Drawings
FIG. 1 is a scanning image of SEM analysis of a polyamide composite nanofiltration membrane containing an antibacterial interlayer in an embodiment of the invention;
FIG. 2 is a diagram of an energy spectrum analysis of a PSF-Ag ultrafiltration membrane in an embodiment of the invention;
FIG. 3 is an optical view of a plate count method of a polyamide composite nanofiltration membrane containing an antibacterial interlayer in an embodiment of the invention;
FIG. 4 is an optical diagram of a polyamide composite nanofiltration membrane bacteriostasis zone assay containing an antibacterial interlayer in an embodiment of the invention.
Description of the embodiments
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Example 1. Preparation of polysulfone ultrafiltration membrane
The polysulfone raw material, namely, suweiudel P-3500 LCD MB7 (PSF), is placed in a vacuum drying oven to dry 4h to remove water in the material, the material is dissolved in N, N-dimethylacetamide (DMAc) solvent, PEG400 is added as an additive (PSF in casting solution contains 26 percent, PEG400 contains 10 percent and DMAc contains 64 percent), and the mixture is heated in a drying oven at 70 ℃ until the mixture is completely mixed and then subjected to vacuum defoaming. The L-S phase inversion method is adopted to prepare the polysulfone membrane. The method comprises the steps of using a pretreated PET non-woven fabric (the thickness is 0.15 mm) (which is cleaned by hydrochloric acid solution, acetone solution, deionized water and alcohol respectively, no foreign matter is blocked in a fiber bundle net and no other sediment) as a supporting layer, cutting the cut non-woven fabric into a proper size, placing the proper size on a horizontal film scraping machine table surface, setting the scraper speed to be 3 m/min, adjusting the height between the scraper and the non-woven fabric to be 100 mu m, pouring the casting solution on the PET non-woven fabric slowly and uniformly, waiting for a film scraping machine to uniformly coat the casting solution on the non-woven fabric, placing the PET non-woven fabric coated with the casting solution into a coagulating bath at 25 ℃ for coagulating and forming a film (about 5 min) after 10s, transferring the film into pure water for 24h (time-changing water) after the film is completely and autonomously separated from a glass plate, and removing undissolved solvents and additives. The prepared membrane was stored in pure water for testing.
Example 2. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) Taking the polysulfone ultrafiltration membrane prepared in the example 1 as a substrate, placing the substrate on the surface of an ethanol solution containing 10mM silver nitrate source and 10mM photoinitiator benzophenone, enabling an effective filtration surface to contact the solution downwards, enabling the solution to fully wet the substrate, and sealing the substrate by a light-transmitting plate to obtain a closed reaction system;
2) The airtight reaction system in the step 1) is placed under an ultraviolet LED light source with the power of 50W and the wavelength of 355nm for irradiation, the irradiation is carried out for 90min, and the free radicals generated by the cracking of the diphenyl ketone are reduced into silver nano particles and deposited on the surface of the polysulfone membrane, so that the PSF-Ag ultrafiltration membrane is obtained;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove solution which is not completely reacted on the surface of the membrane, and storing the prepared membrane sample in the deionized water for later use;
4) Ultrasonically cleaning the PSF-Ag ultrafiltration membrane prepared in the step 3) for 10min to remove possible blockage and other sediments, and clamping the cleaned membrane onto two membrane frames (epoxy resin material, inner frame specification: 5cm x 7.5cm, outer frame specification: 10 cm. Times.12.5 cm, frame thickness: 4.5 cm), cutting into membrane frame size (smaller than the outer frame and larger than the inner frame to ensure no leakage of liquid when being filled into the membrane frame), pouring PIP solution with concentration of 0.05wt% into the membrane frame after airing, fully contacting with PSF-Ag bottom membrane for 20min, pouring out along one corner of the membrane frame, pouring out, naturally airing for 3min, and sucking the residual solution with filter paper. Pouring TMC oil phase solution with the concentration of 0.05wt% into the surface of the membrane treated by the PIP water phase solution, carefully pouring out after 120s contact, then placing into a baking oven with the temperature of 60 ℃ for heat treatment for 30min, taking out the membrane, and cleaning with deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) with the antibacterial interlayer.
Example 3. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) Taking the polysulfone ultrafiltration membrane prepared in the example 1 as a substrate, placing the substrate on the surface of an ethanol solution containing 100mM silver nitrate source and 100mM photoinitiator benzophenone, enabling an effective filtration surface to contact the solution downwards, enabling the solution to fully wet the substrate, and sealing the substrate by a light-transmitting plate to obtain a closed reaction system;
2) The airtight reaction system in the step 1) is placed under an ultraviolet LED light source with the power of 50W and the wavelength of 390nm for irradiation, the irradiation is carried out for 5min, and the free radicals generated by the cracking of the diphenyl ketone are reduced into silver nano particles and deposited on the surface of the polysulfone membrane, so that the PSF-Ag ultrafiltration membrane is obtained;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove solution which is not completely reacted on the surface of the membrane, and storing the prepared membrane sample in the deionized water for later use;
4) Ultrasonically cleaning the PSF-Ag ultrafiltration membrane prepared in the step 3) for 40min to remove possible blockage and other sediments, and clamping the cleaned membrane onto two membrane frames (epoxy resin material, inner frame specification: 5cm x 7.5cm, outer frame specification: 10 cm. Times.12.5 cm, frame thickness: 4.5 cm), cutting into membrane frame size (smaller than the outer frame and larger than the inner frame to ensure no leakage of liquid in the membrane frame), pouring PIP solution with concentration of 0.4wt% into the membrane frame after airing, fully contacting with PSF-Ag bottom membrane for 5min, pouring out along one corner of the membrane frame, naturally airing for 15min, and sucking the residual solution with filter paper. Pouring TMC oil phase solution with the concentration of 0.4wt% into the surface of the membrane treated by the PIP water phase solution, carefully pouring out after 30s contact, then placing the membrane into an oven with the temperature of 80 ℃ for heat treatment for 10min, taking out the membrane, and cleaning the membrane by using deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) with the antibacterial interlayer.
Example 4. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) The polysulfone ultrafiltration membrane prepared in the example 1 is taken as a substrate, placed on the surface of an ethanol solution containing 60mM silver nitrate source and 60mM photoinitiator benzophenone, and contacted with the solution with an effective filtration surface downwards, so that the substrate is fully wetted by the solution, and a light-transmitting plate is covered for sealing to obtain a closed reaction system;
2) The airtight reaction system in the step 1) is placed under an ultraviolet LED light source with the power of 50W and the wavelength of 365nm for irradiation, the irradiation is carried out for 60min, and the free radicals generated by the cracking of the diphenyl ketone are reduced into silver nano particles and deposited on the surface of the polysulfone membrane, so that the PSF-Ag ultrafiltration membrane is obtained;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove solution which is not completely reacted on the surface of the membrane, and storing the prepared membrane sample in the deionized water for later use;
4) Ultrasonically cleaning the PSF-Ag ultrafiltration membrane prepared in the step 3) for 30min to remove possible blockage and other sediments, and clamping the cleaned membrane onto two membrane frames (epoxy resin material, inner frame specification: 5cm x 7.5cm, outer frame specification: 10 cm. Times.12.5 cm, frame thickness: 4.5 cm), cutting into membrane frame size (smaller than the outer frame and larger than the inner frame to ensure no leakage of liquid when being filled into the membrane frame), pouring PIP solution with concentration of 0.1wt% into the membrane frame after airing, fully contacting the PIP solution with PSF-Ag bottom membrane for 15min, pouring out along one corner of the membrane frame, pouring out, naturally airing for 10min, and sucking the residual solution with filter paper. Pouring TMC oil phase solution with the concentration of 0.1wt% into the surface of the membrane treated by the PIP water phase solution, carefully pouring out after 90s contact, then placing the membrane into a baking oven with the temperature of 60 ℃ for heat treatment for 15min, taking out the membrane, and cleaning the membrane by using deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) with the antibacterial interlayer.
Experimental example.
1. Morphology graph of polyamide composite nanofiltration membrane containing antibacterial interlayer
The surface and cross section of the polyamide composite nanofiltration membrane containing the antimicrobial interlayer were characterized using a Zeiss Supra 55 electron scanning microscope. When the sample is prepared, the sample is kept clean and dry, cut into small pieces, then stuck on a non-woven fabric supporting layer on the surface of the torn composite film with the right side facing upwards, and is brittle broken by liquid nitrogen, and then the sample is stuck on an aluminum sample table by conductive adhesive. The sample stage was placed in a high vacuum evaporator, and after the metal spraying and vacuum pumping, the sample film was scanned and observed at an accelerating voltage of 10 kv.
The scan results of the corresponding film samples in example 2 are shown in fig. 1. Wherein a and d are respectively the surface and the section electron microscope images of the polysulfone ultrafiltration membrane, b and e are respectively the surface and the section electron microscope images of the PSF-Ag ultrafiltration membrane, and c and f are respectively the surface and the section electron microscope images of the TFN-Ag composite nanofiltration membrane. It can be seen that uniform membrane pores are distributed on the surface of the polysulfone ultrafiltration membrane, agNPs with the diameter of about 70-150nm are distributed on the surface of the PSF-Ag ultrafiltration membrane, and the polyamide separation layer in the TFN-Ag composite nanofiltration membrane is covered on the PSF-Ag membrane. The energy spectrum analysis of the PSF-Ag ultrafiltration membrane surface is shown in FIG. 2, and the Ag content of the membrane material surface is 0%, which shows that the polyamide separation layer is completely covered on the PSF-Ag ultrafiltration membrane.
2. Determination of surface water contact angle of polyamide composite nanofiltration membrane containing antibacterial interlayer
The Contact Angle (CA) can characterize the wettability of the sample surface. In the experiment, an SDC-100 contact angle measuring instrument is adopted to represent the wettability of the surface of the film, and the larger CA is, the worse the hydrophilicity of the surface of the sample is; conversely, the smaller the CA, the better the hydrophilicity of the sample surface. Before testing, the sample to be tested is cut into a square with the size of 2 multiplied by 2cm, and is cleaned by ultrasonic treatment with deionized water for 10min and dried. Ensuring the flatness of the surface of the test sample, carefully dripping 5 mu L of pure water on the surface of the film sample by a liquid-transferring gun at 25 ℃ each time, immediately preserving the image after dripping, and obtaining contact angle data by three-point method point-taking calculation according to computer calculation. Each sample was measured 5 times in parallel and averaged.
The water contact angles of the polyamide composite nanofiltration membranes containing the antibacterial interlayer in examples 2 to 4 and the polysulfone-based polyamide composite nanofiltration membrane (TFC membrane) prepared under the same conditions and not containing the antibacterial interlayer were measured, and the results were: in example 2, the water contact angle of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 56.6 °, and the water contact angle of the TFC membrane was 78.3 °; in example 3, the water contact angle of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 55.4 °, and the water contact angle of the TFC membrane was 76.9 °; in example 4, the water contact angle of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 44.2 °, and the water contact angle of the TFC membrane was 77.4 °. The hydrophilicity of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is obviously improved.
3. Permeation flux and separation performance test of polyamide composite nanofiltration membrane containing antibacterial interlayer
The permeate flux and separation performance of the membrane samples were tested using FlowMen0021 triple high pressure flat plate membrane pilot plant. The membrane samples were washed several times with pure water and placed in a test cell having a size of 4cm×6cm for the measurement of separation performance and permeation flux. In order to ensure stable testing performance of the composite membrane, the sample to be tested is pre-pressed for 10min under 0.6MPa before each test to achieve flux stability, and the effective filtering area A=24cm of the sample 2 The circulation flow is 5LPM and the test temperature is 25+ -0.5deg.C. During the experiment, the volume V of feed solution was taken and the time t required for it was recorded with a stopwatch, and the permeate flux J was calculated according to equation 1. The results were averaged over three runs.
Equation 1
Wherein the permeation flux of the J-membrane, L.m -2 ·h -1 ；
V-permeate volume, L;
a-effective membrane area, m 2 ；
T-test time, h.
The water flux of the polyamide composite nanofiltration membranes containing the antimicrobial interlayer in examples 2-4 and the TFC membranes prepared under the same conditions and without the antimicrobial interlayer were measured, and the result was: in example 2, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 63.25 L.m -2 ·h -1 The water flux of the TFC film is 47.86 L.m -2 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the In example 3, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 66.23 L.m -2 ·h -1 The water flux of the TFC film is 45.54 L.m -2 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the In example 4, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 68.87 L.m -2 ·h -1 The water flux of the TFC film is 43.15L.m -2 ·h -1 。
The corresponding separation performance was also tested using a FlowMen0021 triple high pressure flat membrane pilot plant using the rejection R as a parameter to evaluate the separation performance of the membrane samples. The rejection rate refers to the percentage of chemical removal from the feed solution by the separation membrane during membrane separation. In this experiment, a salt solution (Na 2 SO 4 ) And (3) for the feed liquid, respectively testing the conductivity of the feed liquid and the permeate liquid, and searching the corresponding concentration according to a conductivity-concentration standard curve. The calculation formula of the retention rate is shown in formula 2.
Equation 2
Wherein: r-retention,%;
concentration of solute in C-filtrate, mg/L;
C 0 -concentration of solute in feed solution, mg/L.
The retention rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in examples 2 to 4 was measured, and the result was: in example 2, the rejection rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 95.67%; in example 3, the retention rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 98.23 percent; in example 4, the rejection rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer was 97.56%.
4. Antibacterial performance test of polyamide composite nanofiltration membrane containing antibacterial interlayer
Gram negative escherichia coli (E.coli, ATCC 25922) is selected as a target strain, and the antibacterial performance of the composite membrane is evaluated through a plate counting method and a bacteriostasis zone experiment.
The bacteriostasis rate is measured by a plate counting method, and a film sample to be measured is cut into a film sample with the diameter of 2cmAnd (3) cleaning the wafer with deionized water for 30min, placing the wafer in a 50 ℃ oven for drying, and sterilizing by 2h ultraviolet for later use. 400 mu L of the mixture was taken at a concentration of 2.5X10 5 -10×10 5 The CFU/mL bacterial suspension is dripped on a sterile culture dish, and the sterilized sample to be tested is flatly paved and covered on the bacterial suspension with sterile forceps with the effective filtering surface facing downwards, so that the bacterial suspension is uniformly contacted with the sample to be tested. A petri dish without a film sample was taken and subjected to the same operation as a blank. The petri dish was placed in a constant temperature incubator at 37℃for 2 hours, and then taken out, and the membrane sample and petri dish were eluted with 10mL of PBS, respectively, and the eluents were uniformly mixed. The eluate was serially diluted multiple times with PBS to prepare 10-fold serial gradient dilutions. 100. Mu.L of the eluent and each of the gradient dilutions were removed by a pipette, and the resulting sterile solid culture plates were plated with a coated glass rod and incubated at 37℃for 24 hours. Taking out the cultured culture dish to count the colonies, and counting the number of the colonies of the sample to be detected as N A The number of blank colonies was counted as N B . The antibacterial rate eta of the sample to be tested is calculated according to a formula 3.
Equation 3
Wherein: eta-escherichia coli antibacterial rate,%;
N B -colony count after incubation of the control test bacteria, CFU;
N A -colony count, CFU, of the test sample after contact culture with the test bacteria.
The antibacterial condition of the corresponding sample in example 4 is shown in fig. 3, wherein a is a blank control sample, b is a polysulfone membrane sample, c is a TFC membrane sample, and d is a polyamide composite nanofiltration membrane sample containing an antibacterial interlayer. It can be seen that the polysulfone membrane and the TFC membrane have no antibacterial effect, and the antibacterial effect of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is remarkable. Specifically, the antibacterial rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 2 is 83.8%; the antibacterial rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 3 is 85.6%; the antibacterial rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 4 is 88.6%.
And (3) measuring a bacteriostasis area: cutting a sample to be tested into a wafer with the diameter of 6.00 and mm, cleaning impurities remained on the membrane by using deionized water through ultrasonic for 30min, placing the wafer in a 50-DEG C oven for drying, and sterilizing by using ultraviolet for 2h for later use. Diluting the activated strain with LB broth to 1×10 4 -3×10 4 CFU/mL. 100. Mu.L of the bacterial liquid was removed by a sterilized pipette to a prepared sterile solid culture plate, and the bacteria were dispersed uniformly by gentle shaking and applied by an applicator. And (3) taking a treated film sample, placing the test surface in a plate downwards, uniformly contacting the test surface with bacterial liquid, culturing at a constant temperature of 37 ℃ for 24h, and observing whether a bacteriostasis ring appears around the sample and measuring the diameter of the bacteriostasis ring.
The conditions of the inhibition zones of the corresponding samples in example 4 are shown in fig. 4, wherein e is a polysulfone membrane sample, f is a TFC membrane sample, and g is a polyamide composite nanofiltration membrane sample containing an antibacterial interlayer. It can be seen that no zone of inhibition appears near polysulfone and TFC membranes, whereas a distinct zone of inhibition appears near polyamide composite nanofiltration membranes containing antimicrobial interlayers. The antibacterial circle diameter of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 2 is 6.8mm, the antibacterial circle diameter of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 3 is 7.2mm, and the antibacterial circle diameter of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 4 is 7.5mm.
5. Anti-fouling performance test of polyamide composite nanofiltration membrane containing antibacterial interlayer
In the stain resistance test, BSA is selected to simulate the protein in natural water, and evaluation is carried out by measuring the condition of flux change with time in the filtration cycle. In each filtration cycle x, the sample to be tested is pre-pressed with pure water for 20min to reach flux stability, and the pure water flux J is recorded wx Then, the pure water in the feed liquid barrel was drained, 500ppm of BSA solution was added for filtration for 15min, the flux was recorded every 3min, the filtration flux Jpx of BSA was recorded, and then the membrane sample was backwashed with pure water for 30 min. J (J) w2 Ratio J w1 The ratio of (2) is the flux recovery rate. As a control, the same test was performed on TFC membranes prepared under the same conditions.
The test result shows that the flux recovery rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the example 2 is 74.5%, and the flux recovery rate of the TFC membrane is 46.8%; the flux recovery of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 3 was 76.3% and the flux recovery of the TFC membrane was 43.9%; the flux recovery of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 4 was 82.6%, and the flux recovery of the TFC membrane was 47.8%.
6. Stability test of polyamide composite nanofiltration membrane containing antibacterial interlayer
The stability of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is measured through a static soaking experiment and a dynamic filtration experiment.
Static experiment: the film sample was cut to 4cm by 6cm, placed in 2L deionized water, 5mL samples were taken from the soak every 24h, and 3,5-Br was used as a basis 2 Determination of Ag by PADAP spectrophotometry + The content is as follows.
Dynamic experiment: cutting a membrane sample into 4cm multiplied by 6cm (keeping the actual filtering area consistent with that of a static test membrane sample), placing the membrane sample in FlowMen0021 triple high-pressure flat membrane small test equipment, keeping the deionized water volume in a feed liquid tank at 2L during each operation, operating at 0.6MPa and test temperature of 25+/-0.5 ℃, operating 10 cycles, firstly emptying the original liquid in the feed liquid tank during each cycle, adding 2L of pure water, operating the equipment for 30min, taking the filtrate, and measuring the Ag of the filtrate + The concentration is closed, the equipment is closed for 30min, and then a proper amount of feed liquid in a feed liquid tank is taken to measure Ag + Concentration.
The polyamide composite nanofiltration membrane containing the antibacterial interlayer in the embodiments 2-4 of the invention is used for measuring silver in a water sample in a static experiment + The concentration is lower than 0.03mg/L and lower than 0.1mg/L specified by the drinking water quality guidance standard of the world health organization. In the dynamic circulating filtration experiment, in the previous three times of circulation, the filtrate and Ag in the circulating liquid + The concentration was maintained at approximately the level of 0.05 mg/L. After three cycles, either the circulating liquid or the Ag in the filtered liquid + The concentration is lower than 0.04mg/L. The polyamide composite nanofiltration membrane containing the antibacterial interlayer prepared by the invention has excellent metal stability.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A preparation method of a polyamide composite nanofiltration membrane containing an antibacterial interlayer is characterized by comprising the following steps: comprises the steps of,
A. taking a polysulfone ultrafiltration membrane as a base material, placing the polysulfone ultrafiltration membrane on the surface of an ethanol solution containing 60mM silver nitrate and 60mM benzophenone, enabling an effective filtration surface to contact the solution downwards, enabling the solution to fully wet the base material, and capping and sealing to obtain a closed reaction system; the preparation method of the polysulfone ultrafiltration membrane comprises the following steps: the preparation method comprises the steps of placing a polysulfone raw material, namely, suweidel P-3500 LCD MB7, in a vacuum drying oven, drying 4h to remove water in the material, dissolving in an N, N-dimethylacetamide solvent, adding PEG400 as an additive, preserving heat in a 70 ℃ oven until the mixture is completely mixed, then conducting vacuum defoaming, adopting an L-S phase inversion method to prepare a polysulfone membrane, using a pretreated PET non-woven fabric as a supporting layer, wherein the thickness of the PET non-woven fabric is 0.15mm, respectively washing the pretreated non-woven fabric with hydrochloric acid solution, acetone solution, deionized water and alcohol until the fiber bundle net is free from foreign matter blockage and other deposits, cutting the cut non-woven fabric into a proper size, placing the fiber bundle net on a table top of a horizontal doctor blade, setting the doctor blade speed to be 3 m/min, regulating the height between the doctor blade and the non-woven fabric to be 100 mu m, slowly pouring a casting film liquid onto the PET non-woven fabric at a uniform speed, waiting for a doctor blade machine to uniformly coat the casting film liquid onto the non-woven fabric, placing the non-woven fabric coated with the casting film liquid into a coagulating bath at 25 ℃ for about 5min to coagulate to form a film after 10S, after the non-woven fabric is completely separated from a glass plate, transferring the membrane to an autonomous membrane, and transferring the membrane to a membrane, and removing the solvent after 24h independently from the membrane and the solvent is removed;
B. placing the closed reaction system under an ultraviolet LED light source with the power of 50W and the wavelength of 365nm for irradiation for 60min, reducing silver ions into silver nano particles by free radicals generated by the cracking of benzophenone, and depositing the silver nano particles on the surface of the polysulfone ultrafiltration membrane to obtain a PSF-Ag ultrafiltration membrane;
C. repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove the solution which is not completely reacted on the membrane surface, so as to obtain a C product;
D. ultrasonically cleaning a C product for 30min to remove possible blockage and other deposits, clamping the cleaned membrane between two membrane frames, wherein the membrane frames are made of epoxy resin, the inner frame is made of 5cm multiplied by 7.5cm, the outer frame is made of 10cm multiplied by 12.5 cm, the frame thickness is 4.5cm, cutting the membrane frames into the size, airing the membrane frames, pouring piperazine aqueous solution with the concentration of 0.1wt% into the membrane frames, fully contacting the piperazine aqueous solution with PSF-Ag bottom membrane for 15min, carefully pouring the piperazine aqueous solution along one corner of the membrane frames, naturally airing the membrane frames for 10min, sucking the residual solution with filter paper, pouring trimesoyl chloride n-hexane solution with the concentration of 0.1wt% into the membrane surface treated by the piperazine aqueous solution, carefully pouring the membrane surfaces after the membrane surfaces are contacted for 90s, then placing the membrane into an oven at 60 ℃ for heat treatment for 15min, taking the membrane out, and cleaning the membrane with deionized water to obtain the polyamide composite containing the antibacterial interlayer.
2. The method for preparing the polyamide composite nanofiltration membrane with the antibacterial interlayer according to claim 1, wherein the method comprises the following steps: the molecular weight cut-off of the polysulfone ultrafiltration membrane is 50000-70000, and the pure water flux is 200-400 L.m ﹣2 •h ﹣1 。
3. A polyamide composite nanofiltration membrane containing an antibacterial interlayer is characterized in that: the polyamide composite nanofiltration membrane containing the antibacterial interlayer is prepared by the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in any one of claims 1-2.
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