CN115155340A - 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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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
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- 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
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- 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
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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
- B01D71/02—Inorganic material
- B01D71/022—Metals
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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
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- 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 following steps of A, taking a polysulfone ultrafiltration membrane as a base material, placing the polysulfone ultrafiltration membrane on the surface of a solution containing silver nitrate and benzophenone, enabling an effective filtering surface to face downwards, enabling the solution to fully wet the base material, and sealing to obtain a closed reaction system; B. irradiating the closed reaction system under ultraviolet light to deposit silver nanoparticles 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 product C; D. clamping the product C between film-making frames, air drying, pouring the piperazine solution into the film-making frames, contacting the product C with the piperazine solution, pouring out the residual solution, air drying, pouring the trimesoyl chloride solution, pouring out the residual solution after contacting, carrying out heat treatment, and taking out to obtain the finished product. The polyamide composite nanofiltration membrane containing the antibacterial interlayer prepared by the invention has better stain resistance, can delay the decline of the permeation and 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, which are pressure-driven selective separation membranes between Reverse Osmosis (RO) and Ultrafiltration (UF) membranes. The nanofiltration membrane has more high-valence salt rejection rate than the ultrafiltration membrane and has 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, less energy consumption, high efficiency, easiness in control and the like. Although polyamide composite nanofiltration membranes (TFC) have remarkable advantages in mechanical stability, separability, permeation flux and the like compared with conventional asymmetric membranes, the polyamide composite nanofiltration membranes still have the problems of easy membrane pollution, easy decline of permeation and separation performance and insufficient membrane flux in the application process, and the service life of the polyamide composite nanofiltration membranes is shortened due to easy membrane damage caused by flushing due to membrane pollution. Therefore, the method has very important significance in the research on improving the stain resistance, delaying the decline of the permeation separation performance, prolonging the service life and improving the membrane flux.
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, which is prepared by the invention, has better stain resistance, can delay the decline of the permeation and 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 comprises the following steps,
A. the polysulfone ultrafiltration membrane is used as a base material and is placed on the surface of an ethanol solution containing silver nitrate and benzophenone, the effective filtering surface is downward to contact the solution, so that the solution fully wets the base material, and the closed reaction system is obtained by covering and sealing;
B. placing the closed reaction system under ultraviolet light for irradiating for 5-90min, 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. cleaning the PSF-Ag ultrafiltration membrane to remove the solution which is not completely reacted on the surface of the membrane and possible blockage and other sediments to obtain a product C;
D. clamping the product C between membrane preparation frames, airing, pouring a piperazine aqueous solution into the membrane preparation frames, allowing the product C to contact with the piperazine aqueous solution for 5-20min, pouring out a residual solution, air-drying the product C for 3-15min, removing the residual solution, pouring a trimesoyl chloride n-hexane solution onto the surface of the product C treated by the piperazine aqueous solution, allowing the product C to contact with the surface of the product C for 30-120s, pouring out the residual solution, performing heat treatment on the product C at 60-80 ℃ for 10-30min, and taking out the product C to obtain the polyamide composite nanofiltration membrane 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 silver nitrate is 10-100mM, and the concentration of benzophenone is 10-100mM.
In the preparation method of the polyamide composite nanofiltration membrane with the antibacterial interlayer, in the step A, the concentration of silver nitrate is 60mM, and the concentration of benzophenone is 60mM.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A and the step B, the closed reaction system is irradiated for 60Min under ultraviolet light.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the wavelength of the 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 the ultraviolet light is 365nm.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the PSF-Ag ultrafiltration membrane is repeatedly cleaned by ethanol and deionized water to remove the solution which is not completely reacted on the surface of the membrane, and the solution is cleaned by ultrasonic for 10-40min to remove possible blockage and other sediments, so as to obtain the product C.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the PSF-Ag ultrafiltration membrane is repeatedly cleaned by ethanol and deionized water to remove the solution which is not completely reacted on the surface of the membrane, and the solution is cleaned by ultrasonic for 30min to remove possible blockage and other sediments to obtain the product C.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A and the step D, the concentration of the piperazine aqueous solution 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 and 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 product C and a piperazine water solution is 15min, and the contact time of the product C and a 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 cut-off molecular weight of the polysulfone ultrafiltration membrane is 50000-70000, and the pure water flux is 200-400 L.m-2.H-1.
In the preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer, in the step A, the cut-off molecular weight of the polysulfone ultrafiltration membrane is 60000, and the pure water flux is 300 L.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 nano silver particles are loaded on the surface of the polysulfone ultrafiltration membrane, and the interface polymerization reaction is further carried out on the surfaces of the nano silver particles to generate the polyamide separation layer, so that the polyamide composite nanofiltration membrane containing the antibacterial interlayer is prepared. The surface of the polysulfone ultrafiltration membrane is loaded with a large number of nano silver particles. The load of the nano silver particles greatly improves the antibacterial property and the hydrophilicity of the membrane, so that the membrane has better pollution resistance, the flux recovery rate is obviously improved when the polluted wastewater is filtered, the antibacterial rate of the membrane to escherichia coli can reach more than 86%, and the flux recovery rate can reach more than 86%. The improvement of the stain resistance can delay the performance decline and prolong the service life of the film. The load of the nano silver particles does not influence the composition of the polyamide separation layer on the surface of the polysulfone ultrafiltration membrane, the load of the nano silver particles on the polysulfone ultrafiltration membrane increases the roughness of the surface of the membrane, the nano silver particles are used as interlayers 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 of the membrane can be improved by over 37 percent. The polyamide composite nanofiltration membrane containing the antibacterial interlayer also has good separation performance, and the Na2SO4 rejection rate of the composite nanofiltration membrane can reach more than 97%. The nano silver particles in the polyamide composite nanofiltration membrane containing the antibacterial interlayer also have better stability. The polyamide composite nanofiltration membrane containing the antibacterial interlayer prepared by the invention has better stain resistance, can delay the decline of the permeation and separation performance, prolongs the service life and greatly improves the membrane flux.
Drawings
FIG. 1 is a SEM scanning analysis view of a polyamide composite nanofiltration membrane containing an antibacterial interlayer in an embodiment of the present invention;
FIG. 2 is a graph showing an energy spectrum analysis of a PSF-Ag ultrafiltration membrane according to an embodiment of the present invention;
FIG. 3 is an optical diagram of the polyamide composite nanofiltration membrane flat plate counting method measurement with the antibacterial interlayer in the embodiment of the invention;
fig. 4 is an optical diagram of the determination of the inhibition zone of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the embodiment of the invention.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1. Preparation of polysulfone ultrafiltration membrane
Putting a polysulfone raw material Suwei udel P-3500 LCD MB7 (PSF) into a vacuum drying oven, drying for 4 hours to remove water in the material, dissolving the material into N, N-dimethylacetamide (DMAc) solvent, adding PEG400 serving as an additive (the content of PSF in casting solution is 26%, the content of PEG400 in DMAc in the casting solution), preserving the temperature in an oven at 70 ℃ until the mixture is completely mixed, and then carrying out vacuum defoamation. Preparing the polysulfone membrane by adopting an L-S phase inversion method. Using a pretreated PET non-woven fabric (the thickness of which is 0.15 mm) (which is respectively cleaned by hydrochloric acid solution, acetone solution, deionized water and alcohol and has no foreign object blockage or other sediments in a fiber bundle net) as a supporting layer, cutting the cut non-woven fabric into a proper size, placing the non-woven fabric on the table top of a horizontal film scraping machine, setting the speed of a scraper at 3 m/min, adjusting the height between the scraper and the non-woven fabric to be 100 mu m, slowly pouring the film casting solution onto the PET non-woven fabric at a constant speed, waiting for the film scraping machine to uniformly coat the film casting solution on the non-woven fabric, placing the PET non-woven fabric coated with the film casting solution into a solidification bath at 25 ℃ for solidification to form a film (about 5 min) after the film completely and automatically breaks away from a glass plate, transferring the film into pure water for soaking for 24h (regularly changing water) to remove undissolved solvents and additives. The resulting film pieces were stored in pure water for testing.
Example 2. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) The polysulfone ultrafiltration membrane prepared in example 1 is used as a substrate, the polysulfone ultrafiltration membrane is placed on the surface of an ethanol solution containing 10mM silver source silver nitrate and 10mM photoinitiator benzophenone, the effective filtering surface of the polysulfone ultrafiltration membrane is downward to contact the solution, so that the solution fully wets the substrate, and a light-transmitting plate is covered for sealing to obtain a closed reaction system;
2) Placing the closed reaction system in the step 1) under an ultraviolet LED light source with the power of 50W and the wavelength of 355nm for irradiation, wherein the irradiation is carried out for 90min, and free radicals generated by the cracking of benzophenone of silver ions are reduced into silver nano particles and are deposited on the surface of a polysulfone membrane to obtain a PSF-Ag ultrafiltration membrane;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove the 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 deposits, clamping the cleaned membrane between two membrane making frames (epoxy resin material, inner frame specification: 5cm × 7.5cm, outer frame specification: 10cm × 12.5 cm, frame thickness: 4.5 cm), cutting into the size of a film-making frame (smaller than the outer frame and larger than the inner frame so as to ensure that the film-making frame is filled with the PIP solution without leakage), pouring the PIP solution with the concentration of 0.05wt% into the film-making frame after air drying so as to fully contact with the PSF-Ag basement membrane for 20min, pouring out the PIP solution carefully along one corner of the film-making frame, naturally air drying for 3min, and sucking the residual solution with filter paper. And pouring the TMC oil phase solution with the concentration of 0.05wt% onto the surface of the membrane treated by the PIP water phase solution, carefully pouring out after contacting for 120s, then putting the membrane into a drying oven with the temperature of 60 ℃ for heat treatment for 30min, then taking out the membrane, and cleaning the membrane by using deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) containing the antibacterial interlayer.
Example 3. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) The polysulfone ultrafiltration membrane prepared in example 1 is used as a substrate, the polysulfone ultrafiltration membrane is placed on the surface of an ethanol solution containing 100mM silver source silver nitrate and 100mM photoinitiator benzophenone, the effective filtering surface of the polysulfone ultrafiltration membrane is downward to contact the solution, so that the solution fully wets the substrate, and a light-transmitting plate is covered for sealing to obtain a closed reaction system;
2) Placing the closed reaction system in the step 1) under an ultraviolet LED light source with the power of 50W and the wavelength of 390nm for irradiation, wherein the irradiation is carried out for 5min, and free radicals generated by the cracking of the benzophenone of silver ions are reduced into silver nano particles and deposited on the surface of the polysulfone membrane to obtain a PSF-Ag ultrafiltration membrane;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove the 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, clamping the cleaned membrane between two membrane making frames (made of epoxy resin, the specification of an inner frame: 5cm × 7.5cm, outer frame specification: 10cm × 12.5 cm, frame thickness: 4.5 cm), cutting into the size of a film-making frame (smaller than the outer frame and larger than the inner frame so as to ensure that the film-making frame is filled with the PIP solution without leakage), pouring the PIP solution with the concentration of 0.4wt% into the film-making frame after air drying so as to fully contact with the PSF-Ag basement membrane for 5min, pouring out the PIP solution carefully along one corner of the film-making frame, pouring out the PIP solution, naturally air drying for 15min, and sucking the residual solution with filter paper. And pouring the TMC oil phase solution with the concentration of 0.4wt% onto the surface of the membrane treated by the PIP water phase solution, carefully pouring out after contacting for 30s, then placing the membrane into an oven with the temperature of 80 ℃ for heat treatment for 10min, then taking out the membrane, and cleaning the membrane by using deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) containing the antibacterial interlayer.
Example 4. Preparation method of polyamide composite nanofiltration membrane containing antibacterial interlayer
1) The polysulfone ultrafiltration membrane prepared in example 1 is used as a substrate, the polysulfone ultrafiltration membrane is placed on the surface of an ethanol solution containing 60mM silver source silver nitrate and 60mM photoinitiator benzophenone, the effective filtering surface of the polysulfone ultrafiltration membrane is downward to contact the solution, so that the solution fully wets the substrate, and a light-transmitting plate is covered for sealing to obtain a closed reaction system;
2) Placing the closed reaction system in the step 1) under an ultraviolet LED light source with the power of 50W and the wavelength of 365nm for irradiation, wherein the irradiation is carried out for 60min, and free radicals generated by the cracking of the benzophenone of silver ions are reduced into silver nano particles and are deposited on the surface of a polysulfone membrane to obtain a PSF-Ag ultrafiltration membrane;
3) Repeatedly cleaning the PSF-Ag ultrafiltration membrane by using ethanol and deionized water to remove the 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, clamping the cleaned membrane between two membrane making frames (made of epoxy resin, the specification of an inner frame: 5cm × 7.5cm, outer frame specification: 10cm × 12.5 cm, frame thickness: 4.5 cm), cutting into the size of a film-making frame (smaller than the outer frame and larger than the inner frame to ensure that the film-making frame is filled with the PIP solution without leakage), pouring the PIP solution with the concentration of 0.1wt% into the film-making frame after air drying, enabling the PIP solution to be fully contacted with the PSF-Ag base film for 15min, pouring out the PIP solution carefully along one corner of the film-making frame, naturally air-drying for 10min, and sucking the residual solution with filter paper. And pouring the TMC oil phase solution with the concentration of 0.1wt% onto the surface of the membrane treated by the PIP water phase solution, carefully pouring out after contacting for 90s, then placing the membrane into a drying oven with the temperature of 60 ℃ for heat treatment for 15min, then taking out the membrane, and cleaning the membrane by using deionized water to obtain the polyamide composite nanofiltration membrane (TFN-Ag composite nanofiltration membrane) containing the antibacterial interlayer.
Examples of the experiments.
1. Appearance diagram of polyamide composite nanofiltration membrane containing antibacterial interlayer
The surface and the section of the polyamide composite nanofiltration membrane containing the antibacterial interlayer are characterized by a Zeiss Supra 55 electron scanning microscope. When preparing a sample, keeping the sample clean and dry, cutting the sample into small pieces, sticking the small pieces right side up to the non-woven fabric supporting layer on the surface of the torn composite film, brittle-breaking the small pieces with liquid nitrogen, and then sticking the sample on an aluminum sample table with conductive adhesive. And (3) placing the sample stage in a high vacuum evaporator, spraying gold, vacuumizing, and scanning and observing a sample membrane under the acceleration voltage of 10 kv.
The scanning results of the corresponding film samples in example 2 are shown in fig. 1. Wherein a and d are respectively the surface and section electron microscope pictures of the polysulfone ultrafiltration membrane, b and e are respectively the surface and section electron microscope pictures of the PSF-Ag ultrafiltration membrane, and c and f are respectively the surface and section electron microscope pictures 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 a polyamide separation layer in the TFN-Ag composite nanofiltration membrane is covered on the PSF-Ag membrane. Energy spectrum analysis of the surface of the PSF-Ag ultrafiltration membrane as shown in fig. 2, it can be seen that the Ag content of the surface of the membrane material was 0%, indicating that the polyamide separation layer had completely covered the PSF-Ag ultrafiltration membrane.
2. Determination of surface water contact angle of polyamide composite nanofiltration membrane containing antibacterial interlayer
The Contact Angle (CA) may characterize the wetting properties 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 membrane, and the larger the CA is, the poorer the hydrophilicity of the surface of the sample is; conversely, the smaller the CA, the more hydrophilic the sample surface. Before testing, a sample to be tested is cut into a square of 2 multiplied by 2cm, cleaned by deionized water ultrasound for 10min and dried. Ensuring the smoothness of the surface of the test sample, using a liquid transfer gun to transfer 5 mu L of pure water each time to carefully drop on the surface of the film sample at 25 ℃, immediately storing an image after dropping, and obtaining contact angle data by point taking calculation according to a three-point method calculated by a computer. Each specimen was measured in duplicate 5 times and averaged.
The water contact angles of the polyamide composite nanofiltration membranes containing the antibacterial interlayers in examples 2 to 4 and the polysulfone-based polyamide composite nanofiltration membranes (TFC membranes) prepared under the same conditions and without the antibacterial interlayers 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 °. Therefore, 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 permeation flux and separation performance of the membrane samples were tested using a FlowMen0021 triple high pressure flat sheet membrane bench. The membrane samples were rinsed several times with pure water and placed in test cells measuring 4cm x 6cm for testing of separation performance and permeation flux. In order to ensure the stable test performance of the composite membrane, a sample to be tested is pre-pressed for 10min before 0.6MPa before each test so as to achieve the stable flux, the effective filtration area A =24cm < 2 >, the circulation flow is 5LPM, and the test temperature is 25 +/-0.5 ℃. In the experimental process, the feed liquid with the volume V is taken, the required time Δ t is recorded by a stopwatch, and the permeation flux J is calculated according to the formula 1. Results were averaged over three trials.
Equation 1
Wherein, the permeation flux of the J-membrane is L.m-2.h-1;
v-permeate volume, L;
a-effective membrane area, m2;
Δ t-test time, h.
The water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in examples 2 to 4 and the TFC membrane without the antibacterial interlayer prepared under the same conditions was measured, and the results were: in example 2, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 63.25L.m-2.h-1, and the water flux of the TFC membrane is 47.86L.m-2.h-1; in example 3, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 66.23L.m-2.h-1, and the water flux of the TFC membrane is 45.54L.m-2.h-1; in example 4, the water flux of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 68.87L.m-2.H-1, and the water flux of the TFC membrane is 43.15 L.m-2.H-1.
The corresponding separation performance is also tested by using FlowMen0021 triple high-pressure flat membrane small-scale equipment, and the separation performance of the membrane sample is judged by using the retention rate R as a parameter. Rejection refers to the percentage of chemical removed from the feed stream by the separation membrane during the membrane separation process. In the experiment, salt solution (Na 2SO 4) with a certain concentration is used as a feeding liquid, the conductivity of the feeding liquid and the conductivity of penetrating fluid are respectively tested, and the corresponding concentration is searched according to a conductivity-concentration standard curve. The calculation formula of the rejection rate is shown in formula 2.
Equation 2
In the formula: r-retention,%;
c-solute concentration in the filtrate, mg/L;
c0-solute concentration in feed solution, mg/L.
The retention rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the examples 2 to 4 is measured, and the results are as follows: in example 2, the rejection rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 95.67%; in example 3, the rejection rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 98.23%; in example 4, the rejection rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 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 by a plate counting method and a zone of inhibition experiment.
Measuring the antibacterial rate by a flat plate counting method, cutting a film sample to be measured into a wafer with the diameter of 2cm, cleaning impurities remained on the film by deionized water ultrasound for 30min, drying in an oven at 50 ℃, and performing ultraviolet sterilization for 2h for later use. And (3) dropwise adding 400 mu L of bacterial suspension with the concentration of 2.5X 105-10X 105CFU/mL on a sterile culture dish, and using a sterile forceps to downwards spread and cover the sterilized sample to be detected on the bacterial suspension so as to enable the bacterial suspension to uniformly contact the membrane sample to be detected. A petri dish without the membrane sample was used for the same operation as a blank. And (3) putting the culture dish into a constant-temperature incubator, culturing at 37 ℃ for 2 hours, taking out, eluting the membrane sample and the culture dish with 10mL of PBS respectively, and uniformly mixing the eluates. The eluate was diluted with PBS several times to prepare 10-fold serial gradient dilutions. Transferring 100 μ L of the eluate and each gradient diluent to a prepared sterile solid culture plate with a pipette, uniformly coating the plate with a coated glass rod, and culturing at 37 deg.C for 24h. And taking out the cultured culture dish for colony counting, and recording the colony number of the sample to be detected as NA and the colony number of the blank control as NB. The antibacterial rate eta of the sample to be detected is calculated according to the formula 3.
Equation 3
In the formula: eta-antibacterial rate of Escherichia coli,%;
NB-blank control test bacteria colony number after culture, CFU;
NA-the colony number, CFU, of the tested sample after contact culture with the tested bacteria.
The bacteriostasis of the corresponding samples 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. As can be seen, the polysulfone membrane and the TFC membrane have no bacteriostatic effect, and the polyamide composite nanofiltration membrane containing the antibacterial interlayer has a remarkable bacteriostatic effect. Specifically, the bacteriostasis rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the embodiment 2 is 83.8%; the bacteriostasis rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the embodiment 3 is 85.6 percent; in example 4, the bacteriostasis rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 88.6%.
And (3) determining the inhibition zone: cutting a sample to be tested into a wafer with the diameter of 6.00 mm, ultrasonically cleaning impurities remained on the wafer for 30min by using deionized water, then drying the wafer in a 50-DEG oven, and carrying out ultraviolet sterilization for 2h for later use. The activated strain was diluted to a concentration of 1X 104 to 3X 104CFU/mL with LB broth. Transfer 100. Mu.L of the inoculum to a prepared sterile solid culture plate using a sterile pipette, gently shake it to disperse the bacteria uniformly, and apply it using an applicator. And (3) taking the processed membrane sample, placing the membrane sample in a plate with the test surface facing downwards to enable the membrane sample to be in uniform contact with bacterial liquid, culturing for 24 hours at the constant temperature of 37 ℃, observing whether a bacteriostatic circle appears around the sample or not, and measuring the diameter of the bacteriostatic circle.
The inhibition zone of the corresponding sample in example 4 is shown in fig. 4, where 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. Therefore, no inhibition zone appears near the polysulfone membrane and the TFC membrane, and an obvious inhibition zone appears near the polyamide composite nanofiltration membrane containing the antibacterial interlayer. The diameter of the inhibition zone of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 2 is 6.8mm, the diameter of the inhibition zone of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 3 is 7.2mm, and the diameter of the inhibition zone of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 4 is 7.5mm.
5. Stain resistance test of polyamide composite nanofiltration membrane containing antibacterial interlayer
In the stain resistance test, protein in BSA simulated natural water is selected, and the evaluation is carried out by measuring the change of flux in a filtration cycle along with time. In each filtration cycle x, a sample to be measured is pre-pressed for 20min by pure water to achieve stable flux, pure water flux Jwx is recorded, then pure water in a feed liquid barrel is drained, 500ppm of BSA solution is added for filtration, the filtration time is 15min, the flux is recorded every 3min, the filtration flux Jpx of BSA is recorded, and then the membrane sample is subjected to 30min back washing by pure water. The ratio of Jw2 to Jw1 is the flux recovery rate. As a control, the same test was performed on TFC membranes made under the same conditions.
The test result shows that the flux recovery rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer in example 2 is 74.5%, and the flux recovery rate of the TFC membrane is 46.8%; in example 3, the flux recovery rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 76.3%, and the flux recovery rate of the TFC membrane is 43.9%; in example 4, the flux recovery rate of the polyamide composite nanofiltration membrane containing the antibacterial interlayer is 82.6%, and the flux recovery rate of the TFC membrane is 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 determined through a static immersion experiment and a dynamic filtration experiment.
Static state experiment: the membrane sample was cut to 4cm × 6cm, placed in 2L of deionized water, 5mL samples were taken from the soak solution every 24h, and the Ag + content was determined according to 3,5-Br2-PADAP spectrophotometry.
Dynamic experiment: the membrane sample is cut into 4cm multiplied by 6cm (the actual filtering area of the membrane sample is kept consistent with that of a static testing membrane sample), the membrane sample is placed in FlowMen0021 triple high-pressure flat-plate membrane small-scale test equipment, the volume of deionized water in a feed liquid tank is kept to be 2L in each operation, the operation pressure is 0.6MPa, the testing temperature is 25 +/-0.5 ℃,10 cycles are operated, in each cycle, original liquid in the feed liquid tank is firstly emptied, 2L of pure water is added, the equipment is operated for 30min, filtrate is taken to measure the Ag + concentration of the filtrate, then the equipment is closed, and the equipment is kept stand for 30min, and then a proper amount of feed liquid in the feed liquid tank is taken to measure the Ag + concentration.
In the polyamide composite nanofiltration membrane containing the antibacterial interlayer in the embodiments 2-4, the silver concentration in a water sample measured in a static experiment 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 circulation filtration experiment, the Ag + concentration in the filtrate and the circulating solution was maintained at a level of approximately 0.05mg/L in the first three cycles. After three cycles, the Ag + concentration in both the circulating solution and the filtrate was less than 0.04mg/L. The polyamide composite nanofiltration membrane containing the antibacterial interlayer has excellent metal stability.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. A preparation method of a polyamide composite nanofiltration membrane containing an antibacterial interlayer is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
A. the polysulfone ultrafiltration membrane is used as a base material and is placed on the surface of an ethanol solution containing silver nitrate and benzophenone, the effective filtering surface is downward to contact the solution, so that the solution fully wets the base material, and the closed reaction system is obtained by covering and sealing;
B. placing the closed reaction system under ultraviolet light for irradiation for 5-90min, reducing silver ions into silver nanoparticles by free radicals generated by the cracking of benzophenone and depositing the silver nanoparticles on the surface of the polysulfone ultrafiltration membrane to obtain a PSF-Ag ultrafiltration membrane;
C. cleaning the PSF-Ag ultrafiltration membrane to remove the solution which is not completely reacted on the surface of the membrane and possible blockage and other sediments to obtain a product C;
D. clamping the product C between membrane preparation frames, airing, pouring a piperazine aqueous solution into the membrane preparation frames, contacting the product C with the piperazine aqueous solution for 5-20min, pouring out a residual solution, air-drying the product C for 3-15min, removing the residual solution, pouring a trimesoyl chloride n-hexane solution onto the surface of the product C treated by the piperazine aqueous solution, contacting for 30-120s, pouring out the residual solution, carrying out heat treatment on the product C at 60-80 ℃ for 10-30min, and taking out to obtain the polyamide composite nanofiltration membrane containing the antibacterial interlayer.
2. The cut-off molecular weight of the polysulfone ultrafiltration membrane is 50000-70000, and the pure water flux is 200-400 L.m-2.H-1.
3. The cut-off molecular weight of the polysulfone ultrafiltration membrane is 60000, and the pure water flux is 300 L.m-2.h-1.
4. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: in the step A, the concentration of the silver nitrate is 10-100mM, and the concentration of the benzophenone is 10-100mM.
5. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 2, wherein the preparation method comprises the following steps: in the step A, the concentration of the silver nitrate is 60mM, and the concentration of the benzophenone is 60mM.
6. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: and in the step B, the closed reaction system is placed under ultraviolet light to irradiate for 60 Min.
7. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: the wavelength of the ultraviolet light is 355-390nm.
8. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: and 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 surface of the membrane, and ultrasonically cleaning for 10-40min to remove possible blockage and other sediments to obtain a product C.
9. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: in the step D, the concentration of the piperazine water solution is 0.05-0.4wt%, and the concentration of the trimesoyl chloride n-hexane solution is 0.05-0.4wt%.
10. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer of claim 7, wherein the preparation method comprises the following steps: 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%.
11. The preparation method of the polyamide composite nanofiltration membrane containing the antibacterial interlayer according to claim 1, wherein the preparation method comprises the following steps: and the contact time of the product C and the piperazine water solution is 15min, and the contact time of the product C and the trimesoyl chloride n-hexane solution is 90s.
12. 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 as claimed in any one of claims 1 to 9.
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