CN110721599B - Preparation method and application of SGO-ZnO-PSF composite ultrafiltration membrane - Google Patents
Preparation method and application of SGO-ZnO-PSF composite ultrafiltration membrane Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/02—Inorganic material
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- 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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- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the technical field of material preparation and separation, and particularly relates to a preparation method and application of an SGO-ZnO-PSF composite ultrafiltration membrane. According to the invention, ZnO nanoparticles are dispersed on the SGO sheet layer by an immersion precipitation phase inversion method to prepare the SGO-ZnO composite nanomaterial blend modified PSF ultrafiltration membrane, so that the pollution of humic acid with negative electricity to the membrane can be effectively prevented, and the PSF ultrafiltration membrane is used for separating humic acid in water. The SGO-ZnO-PSF composite ultrafiltration membrane prepared by the method has good pollution resistance, and simultaneously solves the problems of easy agglomeration and the like caused by inorganic material doping modification, and the modified composite membrane can effectively prevent humic acid with negative electricity from polluting the membrane.
Description
Technical Field
The invention belongs to the technical field of material preparation and separation, and particularly relates to a preparation method and application of an SGO-ZnO-PSF composite ultrafiltration membrane.
Background
The inability to obtain clean drinking water is a global problem, even in developed countries, where there is a lack of water management infrastructure. The Natural Organic Matter (NOM) mainly refers to macromolecular organic matter generated after animal and plant residues are decomposed in a natural circulation process, and comprises humus, microbial secretion, dissolved animal tissues, animal wastes and the like. NOM is widely present in water and is a causative substance of chromaticity, offensive odor, corrosion of the pipe wall of water distribution pipes, and carcinogenic organic compounds are formed when NOM-contaminated water is treated with disinfectants such as chlorine-based compounds. Humic Acid (HA) is an important component of natural organic matter, being the main component of dissolved organic matter found in surface/groundwater, and is involved in bacterial growth in water. In addition, HA is also present in combination with heavy metal ions, pesticides and herbicides in contaminated water, sometimes producing complex substances at high concentrations. Therefore, minimization of HA in surface or groundwater is very significant for water treatment.
Ultrafiltration (UF) and Microfiltration (MF) are currently commonly used in drinking water treatment. UF is widely used in the treatment of surface and ground water containing particles, microorganisms and organic matter. However, the UF membrane having large pores does not have a high removal rate of HA from water, and HA increases the membrane contamination. Therefore, how to improve the HA retention rate and the anti-pollution performance of UF attracts the extensive attention and reports of domestic and foreign researchers, wherein the modification of the traditional UF membrane to improve the HA separation performance is one of the current research hotspots.
Research on the membrane fouling process found that accumulation of bacteria on the membrane surface is mainly through two processes: adhesion and propagation. Numerous studies have shown that the bioadhesion of the membrane surface depends mainly on the nature of the adsorption surface, the solution and the microbiological properties. Wherein, the hydrophilic and hydrophobic property and the charge of the membrane material have larger influence on the adhesion of bacteria on the surface of the membrane, the stronger the hydrophilic property of the surface of the membrane is, the stronger the anti-bacterial adhesion capability is, and the weaker the anti-bacterial adhesion capability is otherwise. The more negative the membrane surface, the greater the antimicrobial anti-fouling capacity (most of the bacterial cytoplasm or proteins are negatively charged). Therefore, the membrane with hydrophilicity and negative charges on the surface is an effective way for relieving the membrane pollution problem through modification and construction. In recent years, Graphene Oxide (GO) has become a popular material in the field of film modification due to its good hydrophilicity and electronegativity. However, GO is also an amphiphilic material at the same time, which means that hydrophobic contaminants (proteins) can be adsorbed on the membrane surface, affecting the separation performance of the membrane.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of an SGO-ZnO-PSF composite ultrafiltration membrane. According to the invention, ZnO nanoparticles are dispersed on an SGO sheet layer by an immersion precipitation phase inversion method to prepare the SGO-ZnO composite nanomaterial blend modified Polysulfone (PSF) ultrafiltration membrane for separating humic acid in water. The modified PSF ultrafiltration membrane can effectively prevent humic acid with negative electricity from polluting the membrane and enhance the anti-pollution performance of the ultrafiltration membrane.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of an SGO-ZnO-PSF composite ultrafiltration membrane, which comprises the following steps:
(1) preparing an SGO-ZnO composite nano material:
adding the Sulfonated Graphene Oxide (SGO)/ethanol solution into the zinc acetate/ethanol solution, stirring, cooling to room temperature, adding hexane, sealing, refrigerating overnight in a refrigerator, centrifugally washing, and drying in vacuum to obtain a sulfonated graphene oxide-zinc oxide (SGO-ZnO) composite nano material;
(2) preparing an SGO-ZnO-PSF composite ultrafiltration membrane:
dissolving the SGO-ZnO composite nano material prepared in the step (1) in N, N-Dimethylformamide (DMF), performing ultrasonic dispersion, adding a certain amount of PSF and polyvinylpyrrolidone (PVP) to form a blending system, stirring and dissolving the blending system in a water bath at a certain temperature to obtain a uniform solution, performing ultrasonic treatment to obtain a casting solution, coating the casting solution on a glass plate by a tape casting method to form a film, quickly putting the film into a prepared coagulating bath for phase splitting and forming, taking out after soaking for a period of time, and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane.
The zinc acetate/ethanol solution in the step (1) is prepared by adding 1.0-3.0 g of anhydrous zinc acetate into 100 mL of anhydrous ethanol, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃.
The SGO/ethanol solution in the step (1) is prepared by dispersing SGO in absolute ethyl alcohol, and adding lithium hydroxide after uniform ultrasonic dispersion; the dosage ratio of the SGO, the absolute ethyl alcohol and the lithium hydroxide is 0.1-0.2 g, 50mL and 0.3 g.
The volume ratio of the zinc acetate/ethanol solution to the hexane in the step (1) is 1: 2.
In the blending system in the step (2), the concentration of the SGO-ZnO composite nano material is 0.05-0.3 wt%, the concentration of PVP is 1-3 wt%, and the content of PSF is 18-20 wt%.
And (3) when the SGO-ZnO composite nano material in the step (2) is dissolved in DMF, the ultrasonic dispersion time is 1-3 h.
The temperature of the water bath in the step (2) is 60-80 ℃, and the stirring time is 5 h.
The coagulating bath in step (2) is distilled water, sodium dodecyl sulfate and DMF according to a volume ratio of 2L: 5 g: 20 g of the mixture.
The time for the impregnation in the step (2) is 30 min.
The invention also provides application of the sulfonated graphene oxide/zinc oxide composite ultrafiltration membrane prepared by the invention in separation of humic acid in water.
Compared with the prior art, the invention has the technical advantages that:
sulfonated Graphene Oxide (SGO), as a graphene derivative, not only relays useful functional groups from graphene oxide, but also strongly charged-SO 3 has better compatibility with the polymer matrix. Thus, the hydrophilicity of GO can be further increased by substituting the hydroxyl/epoxy groups of GO with-SO 3H groups. According to the invention, ZnO nanoparticles are dispersed on the SGO sheet layer by an immersion precipitation phase inversion method to prepare the SGO-ZnO composite nanomaterial blend modified PSF ultrafiltration membrane, so that the pollution of humic acid with negative electricity to the membrane can be effectively prevented, and the PSF ultrafiltration membrane is used for separating humic acid in water. GO can easily interact with sulfonic acid groups without affecting its morphology. ZnO is dispersed in the SGO sheet layer, so that the excellent performances of the two materials can be combined at the same time, and the problem of agglomeration of ZnO nanoparticles dispersed in a polymer can be solved. On one hand, the hydrophilicity of the ultrafiltration membrane is greatly increased by doping the inorganic hybrid material SGO-ZnO, so that the pure water flux of the ultrafiltration membrane can be improved. On the other hand, the problem of agglomeration of ZnO in a polymer matrix is effectively relieved by compositing SGO and ZnO, the antifouling performance of the membrane can be improved by both SGO and ZnO, the antifouling performance of the modified ultrafiltration membrane is greatly improved, the modified ultrafiltration membrane has high flux for humic acid solution and high retention rate for humic acid, and the modified ultrafiltration membrane has great application value in the field of water treatment, especially in the field of removing humic acid in water.
Drawings
FIG. 1 is a comparison graph of pure water flux test results of an SGO-ZnO-PSF composite ultrafiltration membrane and other PSF ultrafiltration membranes;
FIG. 2 is a graph showing the change in pure water flux before and after the SG-Z/M3 ultrafiltration membrane and other PSF ultrafiltration membranes continuously filtering a BSA solution;
FIG. 3 is a graph of the flux recovery of SG-Z/M3 ultrafiltration membranes with other PSF ultrafiltration membranes;
FIG. 4 is a graph of the variation of the fouling parameters of SG-Z/M3 ultrafiltration membrane and other PSF ultrafiltration membranes;
FIG. 5 is a graph comparing the test results of the flux and rejection rate of humic acid solution for SGO-ZnO-PSF composite ultrafiltration membrane and other PSF ultrafiltration membranes;
FIG. 6 is a graph showing the flux change of the SG-Z/M2 ultrafiltration membrane and other PSF ultrafiltration membranes for the continuous filtration of humic acid solution.
Detailed Description
In order to further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available.
Example 1
(1) Preparing an SGO-ZnO composite nano material: adding 2.0 g of anhydrous zinc acetate into 100 mL of anhydrous ethanol to form a zinc acetate/ethanol solution, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃; meanwhile, 0.15 g of SGO is taken and dispersed in 50mL of absolute ethyl alcohol, ultrasonic treatment is carried out for 30 min, then 0.3g of lithium hydroxide is added to obtain an SGO/ethyl alcohol solution, and the mixture is stirred for 30 min in a water bath at 50 ℃; then adding the SGO/ethanol solution into the zinc acetate/ethanol solution, and continuing stirring in a water bath at 50 ℃ for 40 min; and naturally cooling the mixed solution to room temperature, adding 200 mL of hexane, sealing, placing in a refrigerator for refrigeration overnight, centrifuging, washing with deionized water and ethanol for three times respectively, and vacuum-drying at the temperature of 45 ℃ for 12 hours to obtain the SGO-ZnO composite nano material.
(2) Preparing an SGO-ZnO-PSF composite ultrafiltration membrane: dissolving 0.01 g of SGO-ZnO composite nano material (0.05 wt.%) prepared in the step (1) in 16.19 g of DMF, performing strong ultrasonic treatment for 1 h, adding 3.6 g of PSF and 0.2g of PVP into the solution to form a blending system, stirring at 70 ℃ for 5h to dissolve the blending system to form a uniform solution, performing strong ultrasonic treatment for 1 h to defoam and disperse inorganic materials to obtain a casting solution, coating the casting solution on a glass plate by using a tape casting method to form a film, quickly putting the film into a prepared coagulating bath for phase separation and forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), soaking for 30 min, taking out, and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane with the membrane thickness of 200 mu M, wherein the SGO-ZnO-PSF composite ultrafiltration membrane is marked as SG-Z/M1. And storing the prepared SGO-ZnO-PSF composite ultrafiltration membrane in distilled water.
The separation performance testing device with the membrane is characterized in that the prepared SG-Z/M1 ultrafiltration membrane is assembled into a membrane pool, deionized water is used as a to-be-filtered liquid to measure the pure water flux of the membrane, and the testing result is that the flux is 387.1 +/-41.6L M-2 h-1。
Example 2
(1) Preparing an SGO-ZnO composite nano material: adding 3.0g of anhydrous zinc acetate into 100 mL of anhydrous ethanol to form a zinc acetate/ethanol solution, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃; meanwhile, 0.2g of SGO is taken and dispersed in 50mL of absolute ethyl alcohol, ultrasonic treatment is carried out for 30 min, then 0.3g of lithium hydroxide is added to obtain an SGO/ethyl alcohol solution, and the mixture is stirred for 30 min in a water bath at 50 ℃; and then adding the SGO/ethanol solution into the zinc acetate/ethanol solution to form a mixed solution, continuing stirring in a water bath at 50 ℃ for 40 min, naturally cooling the mixed solution to room temperature, adding 200 mL of hexane, sealing, placing in a refrigerator for refrigeration overnight, centrifuging, washing with deionized water and ethanol for three times respectively, and performing vacuum drying at 45 ℃ for 12 h to obtain the SGO-ZnO composite nano material.
(2) Preparing an SGO-ZnO-PSF composite ultrafiltration membrane: taking 0.02g of SGO-ZnO composite nano material (0.1 wt.%) prepared in the step (1) to dissolve in 16.18g of DMF, performing strong ultrasound for 1 h, then adding 3.6 g of PSF and 0.2g of PVP into the solution to form a blending system, stirring for 5h at 70 ℃ to dissolve the blending system to form a uniform solution, performing strong ultrasound for 1 h to defoam and disperse inorganic materials to obtain a casting solution, coating the casting solution on a glass plate to form a film by a tape casting method, quickly putting the film into a prepared coagulating bath for phase separation molding (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), soaking for 30 min, taking out and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane with the membrane thickness of 200 mu M, and marking the SGO-ZnO-PSF composite ultrafiltration membrane as SG-Z/M2. And storing the prepared SGO-ZnO-PSF composite ultrafiltration membrane in distilled water.
The separation performance testing device with the membrane is characterized in that an SG-Z/M2 ultrafiltration membrane is assembled into a membrane pool, and deionized water is used as a to-be-filtered liquid to measure the pure water flux of the membrane. The test results are: flux 468.6 + -47.3L m-2 h-1。
Example 3
(1) Preparing an SGO-ZnO composite nano material: adding 1.0 g of anhydrous zinc acetate into 100 mL of anhydrous ethanol to form a zinc acetate/ethanol solution, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃; meanwhile, 0.1 g of SGO is taken and dispersed in 50mL of absolute ethyl alcohol, ultrasonic treatment is carried out for 30 min, then 0.3g of lithium hydroxide is added to obtain an SGO/ethyl alcohol solution, and the mixture is stirred for 30 min in a water bath at 50 ℃; and then adding the SGO/ethanol solution into the zinc acetate/ethanol solution to form a mixed solution, continuing stirring in a water bath at 50 ℃ for 40 min, naturally cooling the mixed solution to room temperature, adding 200 mL of hexane, sealing, placing in a refrigerator for refrigeration overnight, centrifuging, washing with deionized water and ethanol for three times respectively, and performing vacuum drying at 45 ℃ for 12 h to obtain the SGO-ZnO composite nano material.
(2) Preparing an SGO-ZnO-PSF composite ultrafiltration membrane: taking 0.04 g of SGO-ZnO composite nano material (0.2 wt.%) prepared in the step (1) to be dissolved in 15.96 g of DMF, performing strong ultrasonic treatment for 1 h, then adding 3.6 g of PSF and 0.4 g of PVP into the solution to form a blending system, stirring for 5h at 60 ℃ to be dissolved into a uniform solution, performing strong ultrasonic treatment for 1 h to be used for defoaming and dispersing inorganic materials to obtain a casting solution, coating the casting solution on a glass plate to form a film through a tape casting method, quickly putting the film into a prepared coagulating bath for phase separation and forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), soaking for 30 min, taking out and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane with the membrane thickness of 200 mu M, and marking the SGO-ZnO-PSF composite ultrafiltration membrane as SG-Z/M3. And storing the prepared SGO-ZnO-PSF composite ultrafiltration membrane in distilled water.
The separation performance testing device with the membrane is characterized in that the prepared SG-Z/M3 ultrafiltration membrane is assembled into a membrane pool, deionized water is used as a to-be-filtered liquid to measure the pure water flux of the membrane, and the detection result is the flux 601 +/-51.8L M-2 h-1. The protein pollution resistance of the membrane is detected by taking 2g/L BSA solution as a to-be-filtered solution, and the detection result is FRR = 88.6%.
The method for separating humic acid in water by using the SGO-ZnO-PSF composite ultrafiltration membrane comprises the following steps: preparing 10 mg/L humic acid solution as a to-be-filtered solution, assembling SG-Z/M3 ultrafiltration membranes into a membrane pool, and continuously filtering the humic acid solution. The flux change of the membrane to the humic acid solution was measured over 180 min with sampling intervals of 10 min.
Example 4
(1) Preparing an SGO-ZnO composite nano material: adding 2.0 g of anhydrous zinc acetate into 100 mL of anhydrous ethanol to form a zinc acetate/ethanol solution, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃; meanwhile, 0.2g of SGO is taken and dispersed in 50mL of absolute ethyl alcohol, ultrasonic treatment is carried out for 30 min, then 0.3g of lithium hydroxide is added to obtain an SGO/ethyl alcohol solution, and the mixture is stirred for 30 min in a water bath at 50 ℃; then adding the SGO/ethanol solution into the zinc acetate/ethanol solution, and continuing stirring in a water bath at 50 ℃ for 40 min; and naturally cooling the mixed solution to room temperature, adding 200 mL of hexane, sealing, placing in a refrigerator for refrigeration overnight, centrifuging, washing with deionized water and ethanol for three times respectively, and vacuum-drying at the temperature of 45 ℃ for 12 hours to obtain the SGO-ZnO composite nano material.
(2) Preparing an SGO-ZnO-PSF composite ultrafiltration membrane: taking 0.06g of SGO-ZnO composite nano material (0.3 wt.%) prepared in the step (1) to dissolve in 15.74g of DMF, performing strong ultrasound for 1 h, then adding 3.6 g of PSF and 0.6 g of PVP into the solution to form a blending system, stirring for 5h at 80 ℃ to dissolve the blending system to form a uniform solution, performing strong ultrasound for 1 h to defoam and disperse inorganic materials to obtain a casting solution, coating the casting solution on a glass plate to form a film by a tape casting method, quickly putting the film into a prepared coagulating bath for phase separation molding (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), soaking for 30 min, taking out and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane with the membrane thickness of 200 mu M, and marking the SGO-ZnO-PSF composite ultrafiltration membrane as SG-Z/M4. And storing the prepared SGO-ZnO-PSF composite ultrafiltration membrane in distilled water.
The separation performance testing device with the membrane is characterized in that an SG-Z/M4 ultrafiltration membrane is assembled into a membrane pool, and deionized water is used as a to-be-filtered liquid to measure the pure water flux of the membrane. The test results are: flux 524.6 + -36.2L m-2 h-1。
Example 5
This example performs a comparative test on the separation performance of other existing PSF ultrafiltration membranes (pure PSF ultrafiltration membranes, GO/PSF ultrafiltration membranes, SGO/PSF ultrafiltration membranes, and ZnO/PSF ultrafiltration membranes).
Preparation of pure PSF ultrafiltration membrane: 3.6 g of PSF and 0.4 g of PVP are taken and mixed with 16 g of DMF to form a blending system, the blending system is stirred at 60 ℃ for 5 hours to be dissolved into a uniform solution, and the solution is subjected to strong ultrasound for 1 hour to be defoamed to obtain a casting solution. The casting solution is scraped on a glass plate to form a film by a tape casting method, the film is quickly placed into a prepared coagulating bath for split-phase forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), the film is taken out after being soaked for 30 min and washed by a large amount of distilled water, the film is stored in the distilled water, and the thickness of the prepared modified PSF ultrafiltration film is 200 mu m and is marked as PSF.
Preparing a GO-PSF ultrafiltration membrane: 0.04 g of GO is dissolved in 15.96 g of DMF, and strong ultrasound is carried out for 1 h. And then adding 3.6 g of PSF and 0.4 g of PVP into the solution to form a blending system, stirring at 60 ℃ for 5 hours to dissolve the PSF and the PVP into a uniform solution, and performing powerful ultrasound on the solution for 1 hour to defoam and disperse the inorganic materials to obtain a casting solution. The casting solution is scraped on a glass plate to form a film by a tape casting method, the film is quickly placed into a prepared coagulating bath for split-phase forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), the film is taken out after being soaked for 30 min and washed by a large amount of distilled water, the film is stored in the distilled water, the thickness of the prepared modified PSF ultrafiltration film is 200 mu M, and the mark is GO/M.
Preparation of SGO-PSF ultrafiltration membrane: 0.04 g of SGO was dissolved in 15.96 g of DMF and subjected to vigorous sonication for 1 hour. Then, 3.6 g of PSF and 0.4 g of PVP were added to the solution to form a mixed system. Stirring at 60 ℃ for 5h to dissolve the mixture into a uniform solution, and performing powerful ultrasound on the solution for 1 h to defoam and disperse the inorganic material to obtain a membrane casting solution. The casting solution is scraped on a glass plate to form a film by a tape casting method, the film is quickly placed into a prepared coagulating bath for split-phase forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), the film is taken out after being soaked for 30 min and washed by a large amount of distilled water, the film is stored in the distilled water, the thickness of the prepared modified PSF ultrafiltration film is 200 mu M, and the mark is SGO/M.
Preparing a ZnO-PSF ultrafiltration membrane: 0.04 g of ZnO is dissolved in 15.96 g of DMF and is subjected to strong ultrasound for 1 h. Then 3.6 g of PSF, 0.4 g of PVP were added to the solution to form a blended system. Stirring at 60 ℃ for 5h to dissolve the mixture into a uniform solution, and performing powerful ultrasound on the solution for 1 h to defoam and disperse the inorganic material to obtain a membrane casting solution. The casting solution is scraped on a glass plate to form a film by a tape casting method, is quickly put into a prepared coagulating bath for split-phase forming (the proportion of the coagulating bath is 2L of distilled water, 5 g of SDS and 20 g of DMF), is taken out after being soaked for 30 min and is washed by a large amount of distilled water, and is stored in the distilled water. The thickness of the prepared modified PSF ultrafiltration membrane is 200 mu M, and the label is ZnO/M.
The separation performance testing device with the membrane is characterized in that prepared PSF and GO/M, SGO/M, ZnO/M are respectively assembled into a membrane pool, and deionized water is used as a liquid to be filtered to measure the pure water flux of the membrane. The flux of the test result is 229.2 +/-50.2L m-2h-1、402.3±44.7 L m-2 h-1、519.5±60.1 L m-2 h-1、346.3±28.9 L m-2 h-1. FIG. 1 is a comparison graph of pure water flux test results of the SGO-ZnO-PSF composite ultrafiltration membrane prepared in the invention and other PSF ultrafiltration membranes; as can be seen from FIG. 1, the pure PSF ultrafiltration membrane has a water flux of 229.2L m-2 h-1The maximum flux of the PSF ultrafiltration membrane modified by SGO-ZnO can reach 601L m-2 h-1The PSF ultrafiltration membrane modified by GO and ZnO is greatly improved in flux performance.
The separation performance testing device of the loaded membrane respectively assembles the prepared PSF, GO/M, SGO/M, ZnO/M and SG-Z/M3 into a membrane pool, and detects the protein pollution resistance of the membrane by taking 2g/L BSA solution as a to-be-filtered solution. FIG. 2 is a graph showing the change in pure water Flux (Flux) before and after (1g/L) continuous filtration of a BSA solution; FIG. 3 is a graph of flux recovery efficiency versus time; FIG. 4 is a graph of contamination parameter variation; as can be seen from FIGS. 2 to 4, the flux recovery of the prepared SG-Z/M3 ultrafiltration membrane reaches 88.6%, and the SG-Z/M3 ultrafiltration membrane is proved to have excellent filtration performance after continuous filtration and excellent anti-pollution performance compared with other PSF ultrafiltration membranes.
Preparing 10 mg/L humic acid solution as a to-be-filtered solution, respectively assembling SGO/M, ZnO/M into membrane tanks, and continuously filtering the humic acid solution. The flux change of the membrane to the humic acid solution was measured over 180 min with sampling intervals of 10 min. FIG. 5 is a graph comparing the test results of the flux and rejection rate of humic acid solution of the SGO-ZnO-PSF composite ultrafiltration membrane prepared in the invention and other PSF ultrafiltration membranes. As can be seen from FIG. 5, the SGO-ZnO-PSF composite ultrafiltration membrane prepared by the method has high flux on humic acid solution, and simultaneously maintains higher rejection rate. FIG. 6 is a graph showing the flux change of the SG-Z/M2 ultrafiltration membrane and other PSF ultrafiltration membranes for the continuous filtration of humic acid solution. It can be seen that the flux of the pure PSF ultrafiltration membrane/pure water flux (J/J) is 180 min later0) Only about 65 percent of pure water flux, while the maximum flux of the SG-Z/M2 ultrafiltration membrane prepared by the method is about 90 percent of the pure water flux, and the anti-fouling effect is obvious.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (8)
1. A preparation method of the SGO-ZnO-PSF composite ultrafiltration membrane is characterized by comprising the following steps:
(1) preparing an SGO-ZnO composite nano material:
adding the SGO/ethanol solution into the zinc acetate/ethanol solution, stirring, cooling to room temperature, adding hexane, sealing, refrigerating overnight in a refrigerator, centrifugally washing, and drying in vacuum to obtain the SGO-ZnO composite nano material;
(2) preparing an SGO-ZnO-PSF composite ultrafiltration membrane:
dissolving the SGO-ZnO composite nano material prepared in the step (1) in DMF (dimethyl formamide), performing ultrasonic dispersion, adding PSF (phosphosilicate fluoride) and PVP (polyvinyl pyrrolidone) to form a blending system, stirring and dissolving the blending system in a water bath to obtain a uniform solution, performing ultrasonic treatment to obtain a casting solution, coating the casting solution on a glass plate by a tape casting method to form a film, quickly putting the film into a prepared coagulating bath for phase separation and forming, taking out after dipping, and washing with a large amount of distilled water to obtain the SGO-ZnO-PSF composite ultrafiltration membrane; the SGO/ethanol solution in the step (1) is prepared by dispersing SGO in absolute ethyl alcohol, and adding lithium hydroxide after uniform ultrasonic dispersion; the dosage ratio of the SGO to the absolute ethyl alcohol to the lithium hydroxide is 0.1-0.2 g to 50mL to 0.3 g; the coagulating bath in step (2) is distilled water, sodium dodecyl sulfate and DMF according to a volume ratio of 2L: 5 g: 20 g of the mixture.
2. The preparation method of the composite ultrafiltration membrane according to claim 1, wherein the zinc acetate/ethanol solution in the step (1) is prepared by adding 1.0-3.0 g of anhydrous zinc acetate into 100 mL of anhydrous ethanol, refluxing at 80 ℃ for 20 min, and cooling to 50 ℃.
3. The method for preparing the composite ultrafiltration membrane according to claim 1, wherein the volume ratio of the zinc acetate/ethanol solution to the hexane in the step (1) is 1: 2.
4. The preparation method of the composite ultrafiltration membrane according to claim 1, wherein the concentration of the SGO-ZnO composite nanomaterial in the blending system in the step (2) is 0.05-0.3 wt%, the concentration of PVP is 1-3 wt%, and the content of PSF is 18-20 wt%.
5. The preparation method of the composite ultrafiltration membrane according to claim 1, wherein the ultrasonic dispersion time is 1-3 h when the SGO-ZnO composite nanomaterial in the step (2) is dissolved in DMF.
6. The preparation method of the composite ultrafiltration membrane according to claim 1, wherein the temperature of the water bath in the step (2) is 60-80 ℃, and the stirring time is 5 hours.
7. The method for preparing the composite ultrafiltration membrane according to claim 1, wherein the time for the immersion in the step (2) is 30 min.
8. Use of the SGO-ZnO-PSF composite ultrafiltration membrane prepared by the preparation method of the composite ultrafiltration membrane according to any one of claims 1 to 7 in separation of humic acid in water.
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