CN111437725A - Preparation method of graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane - Google Patents
Preparation method of graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane Download PDFInfo
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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
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
A preparation method of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane comprises the following steps: carrying out esterification reaction on graphene oxide and polyethylene glycol to form graphene oxide-polyethylene glycol serving as a hydrophilic material for later use; dissolving a set amount of graphene oxide-polyethylene glycol in an N, N-dimethylformamide solvent, and performing ultrasonic dispersion; adding a set amount of polyvinylidene fluoride and polyvinylpyrrolidone into the solution subjected to ultrasonic dispersion to form a blending system, stirring and dissolving the blending system in a water bath at a set temperature to obtain a uniform solution, standing and defoaming to obtain a membrane casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into a coagulating bath for split-phase forming, taking out after soaking for 2 hours, washing with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing in the distilled water. The composite ultrafiltration membrane prepared by the method has the advantages that the water flux is greatly improved, the hydrophilicity is obviously enhanced, and the composite ultrafiltration membrane has excellent anti-pollution performance.
Description
Technical Field
The invention relates to a preparation method of a composite ultrafiltration membrane. In particular to a preparation method of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane.
Background
In recent years, membrane separation techniques have attracted considerable attention from water treatment engineers and researchers. The ultrafiltration membrane separation technology has wide application prospect in the industries of food, medicine, biology, environmental protection, chemical industry, energy, petroleum, water treatment and the like. Polyvinylidene fluoride (PVDF) has the advantages of high mechanical strength, good chemical stability, good thermal stability, good film forming property and the like, and is widely applied to the preparation of ultrafiltration membranes. Although the PVDF ultrafiltration membrane has good application performance, the main defect of hydrophobicity is that serious membrane pollution is caused, so that the flux of the membrane is reduced, and the energy consumption in the operation process of the membrane is increased. This major drawback of PVDF ultrafiltration membranes seriously threatens their application and popularization. Therefore, membrane researchers have conducted extensive studies to improve the hydrophilicity of PVDF ultrafiltration membranes and to control membrane fouling. Membrane hydrophilic modification is the most direct and effective method developed for this purpose, because it can not only improve the hydrophilicity of the membrane, but also improve the physicochemical properties of the membrane, thereby contributing to the improvement of the antifouling property of the membrane.
The addition of hydrophilic polymers or mixing of inorganic nanoparticles with cast membrane solutions is the most reported technique to date for improving membrane hydrophilicity and controlling fouling. Interestingly, a number of studies have indicated that the incorporation of such organic polymers into PVDF membranes can be effective in improving their hydrophilicity and anti-fouling properties. However, it has been reported that some hydrophilic polymers are easily lost during phase transition, resulting in a decrease in the hydrophilic properties of the membrane. In addition, the hydrophilicity, water flux and rejection rate of the organic polymer membrane can be improved by adding various inorganic nanoparticles. While this method of incorporating inorganic nanoparticles into organic polymer films has these advantages, it has been reported to have a disadvantage. When nanoparticles having a relatively low specific surface area are added to the casting solution, the desired high concentration of nanoparticles causes them to aggregate. Razmjou and Mansour reported that the aggregation of nanoparticles in polyvinylidene fluoride membranes adversely affected the mechanical strength of the membranes. Therefore, further exploration of ideal hydrophilic additives to overcome these disadvantages is an important research topic.
In recent years, a novel multifunctional carbon nanomaterial Graphene Oxide (GO) has been widely used as a film additive with its unique structure and excellent properties. On one hand, the graphene oxide has good hydrophilicity due to a large number of oxygen-containing functional groups (hydroxyl, carboxyl and epoxy) on the surface, so that the graphene oxide can improve the hydrophilicity and the organic pollution resistance of the membrane. On the other hand, the graphene oxide has a high specific surface area and excellent mechanical properties, and the mechanical strength of the polymer matrix can be optimized by adding a certain amount of graphene oxide into the polymer matrix. Graphene oxide, however, is amphiphilic, which limits its ability to improve membrane hydrophilicity to some extent. This means that hydrophobic contaminants (proteins) can be adsorbed to the surface of the composite membrane. Subsequently, many studies found that the improvement of the hydrophilicity of the modified graphene oxide is more advantageous to increase the hydrophilicity and stain resistance of the membrane. Ayyaru and Ahn use Sulfonated Graphene Oxide (SGO) as an additive to prepare a membrane with higher hydrophilicity, higher permeability and better antifouling property than a PVDF/GO nano composite membrane. Xu prepares modified graphene oxide to blend into the PVDFUF membrane, and the hydrophilicity and the anti-pollution performance of the membrane are superior to those of the membrane of unmodified graphene oxide. The hydrophilicity of the Graphene Oxide (GO) can be further enhanced through the esterification reaction between the Graphene Oxide (GO) and a hydrophilic substance polyethylene glycol (PEG).
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, which can improve the flux, hydrophilicity and pollution resistance of the ultrafiltration membrane.
The technical scheme adopted by the invention is as follows: a preparation method of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane comprises the following steps:
1) carrying out esterification reaction on graphene oxide and polyethylene glycol to form graphene oxide-polyethylene glycol serving as a hydrophilic material for later use;
2) dissolving a set amount of graphene oxide-polyethylene glycol in an N, N-dimethylformamide solvent, and performing ultrasonic dispersion;
3) adding a set amount of polyvinylidene fluoride and polyvinylpyrrolidone into the solution subjected to ultrasonic dispersion to form a blending system, stirring and dissolving the blending system in a water bath at a set temperature to obtain a uniform solution, standing and defoaming to obtain a membrane casting solution;
4) and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into a coagulating bath for split-phase forming, taking out after soaking for 2 hours, washing with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing in the distilled water.
The step 1) comprises the following steps:
(1) dissolving 0.1-0.2g of graphene oxide in 200ml of N, N-dimethylformamide solvent, and performing ultrasonic treatment for 30min to induce to form a homogeneous solution;
(2) 2.4g of polyethylene glycol 6000(PEG-6000) and 200m of L graphene oxide dispersion liquid are respectively added into a flask, and after 15min of ultrasonic treatment, 0.083g of N, N' -dicyclohexylcarbodiimide and 0.01g of 4-dimethylaminopyridine are respectively added;
(3) the solution is subjected to ultrasonic treatment for 30 minutes and is placed in a forced air drying oven to react for 12 hours at the temperature of 60 ℃;
(4) putting the homogeneous solution into a dialysis bag for dialysis for 3 days;
(5) and (5) freeze-drying to obtain the graphene oxide-polyethylene glycol.
The ultrasonic dispersion time in the step 2) is 1-3 h.
In the blending system in the step 3), the content of polyvinylpyrrolidone is 1-3 wt%, the content of polyvinylidene fluoride is 20 wt%, the content of N, N-dimethylformamide solvent is 77-79 wt%, wherein the content of graphene oxide-polyethylene glycol is 0.3-1.0% of the mass of polyvinylidene fluoride.
Drying the polyvinylidene fluoride in the step 3) in a vacuum drying oven at 60 ℃ for 12 hours before each use.
Stirring and dissolving in the water bath at the set temperature in the step 3) until the set temperature of the uniform solution is 60-65 ℃, and stirring for more than 12 hours.
The standing and defoaming time in the step 3) is more than 12 h.
The coagulating bath in the step 4) is distilled water, and the temperature is 18-22 ℃.
The thickness of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200-250 mu m.
The graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is used for separating bovine serum albumin.
According to the preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, the water flux of the prepared composite ultrafiltration membrane is greatly improved, the hydrophilicity is obviously enhanced, and the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane shows excellent anti-pollution performance. Is expected to be used for wastewater treatment. The invention has the beneficial effects that:
1. the hydrophilic composite material graphene oxide-polyethylene glycol is doped, so that the hydrophilicity of the ultrafiltration membrane is greatly increased, the flux of the ultrafiltration membrane can be improved, and the pollution resistance of the ultrafiltration membrane is also greatly improved.
2. The graphene oxide is modified by the hydrophilic substance polyethylene glycol, so that the defect of amphipathy of the graphene oxide is effectively alleviated, and the capability of improving the hydrophilicity of the membrane is improved.
Drawings
FIG. 1a is a scanning electron microscope surface view of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method of the invention in example 2;
FIG. 1b is a cross-sectional view of FIG. 1 a;
FIG. 2 is an infrared spectrum of graphene oxide-polyethylene glycol prepared by the method of the present invention;
FIG. 3 is a graph showing the results of flux measurements on different ultrafiltration membranes prepared in examples 1 to 5;
FIG. 4 is a graph showing the results of retention tests for different ultrafiltration membranes prepared in examples 1 to 5;
FIG. 5 is a graph showing the fouling resistance values of different ultrafiltration membranes prepared in examples 1 to 5;
FIG. 6 is a graph showing the flux recovery of different ultrafiltration membranes prepared in examples 1 to 5.
Detailed Description
The following describes the preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to the present invention in detail with reference to the examples and the accompanying drawings.
The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane comprises the following steps:
1) carrying out esterification reaction on Graphene Oxide (GO) and polyethylene glycol (PEG) to form graphene oxide-polyethylene glycol (P-GO) serving as a hydrophilic material for later use; the method comprises the following steps:
(1) dissolving 0.1-0.2g of graphene oxide in 200ml of N, N-Dimethylformamide (DMF) amine solvent, and performing ultrasonic treatment for 30min to induce to form a homogeneous solution;
(2) 2.4g of polyethylene glycol 6000(PEG-6000) and 200m of L graphene oxide dispersion are respectively added into a flask, and after 15min of ultrasonic treatment, 0.083g of N, N' -Dicyclohexylcarbodiimide (DCC) and 0.01g of 4-Dimethylaminopyridine (DAMP) are respectively added;
(3) the solution is subjected to ultrasonic treatment for 30 minutes and is placed in a forced air drying oven to react for 12 hours at the temperature of 60 ℃;
(4) putting the homogeneous solution into a dialysis bag for dialysis for 3 days so as to completely remove free polyethylene glycol and catalyst;
(5) graphene oxide-polyethylene glycol (P-GO) is obtained after freeze drying, and the synthesis of the P-GO is proved in figure 2.
2) Dissolving a set amount of graphene oxide-polyethylene glycol in an N, N-dimethylformamide solvent, and performing ultrasonic dispersion for 1-3 h;
3) adding a set amount of polyvinylidene fluoride (PVDF) and polyvinylpyrrolidone (PVP) into the solution subjected to ultrasonic dispersion to form a blending system, wherein in the blending system, the content of polyvinylpyrrolidone is 1-3 wt%, the content of polyvinylidene fluoride is 20 wt%, and the content of N, N-dimethylformamide solvent is 77-79 wt%, wherein the content of graphene oxide-polyethylene glycol is 0.3-1.0% of the mass of polyvinylidene fluoride, stirring and dissolving the mixture in a water bath at a set temperature to obtain a uniform solution, and standing and defoaming to obtain a casting solution;
the polyvinylidene fluoride (PVDF) is dried in a vacuum drying oven at 60 ℃ for 12 hours before each use.
The solution is stirred and dissolved in the water bath at the set temperature until the set temperature of the uniform solution is 60-65 ℃, the stirring time is more than 12 hours, and the standing and defoaming time is more than 12 hours.
4) And coating the casting film liquid on a glass plate through a film scraper to form a film, putting the film into a coagulating bath for split-phase forming, wherein the coagulating bath is distilled water, is taken out after being soaked for 2 hours at the temperature of about 18-22 ℃, is washed by distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration film, and is stored in distilled water. The thickness of the prepared graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200-250 mu m.
The graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is used for separating Bovine Serum Albumin (BSA).
Examples are given below:
example 1
1. The preparation method of the hydrophilic composite material P-GO comprises the steps of firstly dissolving 0.1g of Graphene Oxide (GO) in 200ml of N, N-Dimethylformamide (DMF) amine solvent, performing ultrasonic treatment for 30min to induce and form a homogeneous solution, respectively adding 122.4g of polyethylene glycol 6000(PEG-6000) and 200m of L Graphene Oxide (GO) dispersion liquid into a flask, performing ultrasonic treatment for 15min, respectively adding 0.083g of N, N' -Dicyclohexylcarbodiimide (DCC) and 0.01g of 4-Dimethylaminopyridine (DAMP), then performing ultrasonic treatment for 30min, placing the solution into a blast drying box to react for 12h at 60 ℃, filling the homogeneous solution into a dialysis bag to perform dialysis for 3 days to completely remove free polyethylene glycol and catalyst, and finally performing freeze drying on the homogeneous solution to obtain the graphene oxide-polyethylene glycol (P-GO).
2. Preparing a composite ultrafiltration membrane: polyvinylidene fluoride (PVDF) was dried in a vacuum oven at 60 ℃ for 12h before each use. Dissolving 0.06g of graphene oxide-polyethylene glycol (P-GO) in 79g of N, N-Dimethylformamide (DMF) solvent, strongly performing ultrasonic treatment for 1h, then adding 20g of polyvinylidene fluoride (PVDF) and 1g of polyvinylpyrrolidone (PVP) into the solution to form a blending system, stirring the blending system in a water bath at the temperature of 60-65 ℃ for 12h to dissolve the blending system into a uniform solution, standing and defoaming for 12h to obtain a casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into distilled water for split-phase forming, taking out the membrane after soaking for 2 hours, washing the membrane with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing the membrane in distilled water at 4 ℃. The thickness of the prepared graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200 mu m, and the membrane is marked as P/0.3P-GO.
3. Preparing 0.5 g/L Bovine Serum Albumin (BSA) solution, carrying a membrane separation performance testing device, separating distilled water and the BSA solution sequentially by using a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, wherein the result of the separation performance test of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is that the flux is 80 +/-6L m-2·h-1The retention rate: 95 plus or minus 0.95 percent.
Example 2
1. The preparation method of the hydrophilic composite material P-GO comprises the steps of firstly dissolving 0.15g of Graphene Oxide (GO) in 200ml of N, N-Dimethylformamide (DMF) amine solvent, performing ultrasonic treatment for 30min to induce and form a homogeneous solution, respectively adding 122.4g of polyethylene glycol 6000(PEG-6000) and 200m of L Graphene Oxide (GO) dispersion liquid into a flask, performing ultrasonic treatment for 15min, respectively adding 0.083g of N, N' -Dicyclohexylcarbodiimide (DCC) and 0.01g of 4-Dimethylaminopyridine (DAMP), then performing ultrasonic treatment for 30min, placing the solution into a blast drying box to react for 12h at 60 ℃, filling the homogeneous solution into a dialysis bag to perform dialysis for 3 days to completely remove free polyethylene glycol and catalyst, and finally performing freeze drying on the homogeneous solution to obtain the graphene oxide-polyethylene glycol (P-GO).
2. Preparing a composite ultrafiltration membrane: polyvinylidene fluoride (PVDF) was dried in a vacuum oven at 60 ℃ for 12h before each use. Dissolving 0.1g of graphene oxide-polyethylene glycol (P-GO) in 78g of N, N-Dimethylformamide (DMF) solvent, strongly performing ultrasonic treatment for 1h, then adding 20g of polyvinylidene fluoride (PVDF) and 2g of polyvinylpyrrolidone (PVP) into the solution to form a blending system, stirring the blending system in a water bath at the temperature of 60-65 ℃ for 12h to dissolve the blending system into a uniform solution, standing and defoaming for 12h to obtain a casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into distilled water for split-phase forming, taking out the membrane after soaking for 2 hours, washing the membrane with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing the membrane in distilled water at 4 ℃. The thickness of the prepared graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200 mu m, and the membrane is marked as P/0.5P-GO.
3. Preparing Bovine Serum Albumin (BSA) solution of 0.5 g/L, loading a separation performance testing device of the membrane, separating distilled water and the BSA solution by a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane in sequence, wherein the result of the separation performance test of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is that the flux is 91 +/-10L m-2·h-1The retention rate: 94 +/-1.41 percent.
Example 3
1. The preparation method of the hydrophilic composite material P-GO comprises the steps of firstly dissolving 0.2g of Graphene Oxide (GO) in 200ml of N, N-Dimethylformamide (DMF) amine solvent, performing ultrasonic treatment for 30min to induce and form a homogeneous solution, respectively adding 2.4g of polyethylene glycol 6000(PEG-6000) and 200m of L Graphene Oxide (GO) dispersion liquid into a flask, performing ultrasonic treatment for 15min, respectively adding 0.083g of N, N' -Dicyclohexylcarbodiimide (DCC) and 0.01g of 4-Dimethylaminopyridine (DAMP), then performing ultrasonic treatment for 30min, placing the solution into a blast drying box to react for 12h at 60 ℃, filling the homogeneous solution into a dialysis bag to perform dialysis for 3 days to completely remove free polyethylene glycol and catalyst, and finally performing freeze drying on the homogeneous solution to obtain the graphene oxide-polyethylene glycol (P-GO).
2. Preparing a composite ultrafiltration membrane: polyvinylidene fluoride (PVDF) was dried in a vacuum oven at 60 ℃ for 12h before each use. Dissolving 0.2g of graphene oxide-polyethylene glycol (P-GO) in 77g of N, N-Dimethylformamide (DMF) solvent, strongly performing ultrasonic treatment for 1h, then adding 20g of polyvinylidene fluoride (PVDF) and 3g of polyvinylpyrrolidone (PVP) into the solution to form a blending system, stirring the blending system in a water bath at the temperature of 60-65 ℃ for 12h to dissolve the blending system into a uniform solution, standing and defoaming for 12h to obtain a casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into distilled water for split-phase forming, taking out the membrane after soaking for 2 hours, washing the membrane with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing the membrane in distilled water at 4 ℃. The thickness of the prepared graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200 mu m, and the membrane is marked as P/1.0P-GO.
3. Preparing Bovine Serum Albumin (BSA) solution of 0.5 g/L, loading a separation performance testing device of the membrane, separating distilled water and the BSA solution by a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane in sequence, wherein the result of the separation performance test of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is that the flux is 70 +/-7L m-2·h-1The retention rate: 95 +/-4.24 percent.
Example 4 (polyvinylidene fluoride Ultrafiltration Membrane not prepared by the method of the invention)
Preparing a polyvinylidene fluoride ultrafiltration membrane: polyvinylidene fluoride (PVDF) was dried in a vacuum oven at 60 ℃ for 12h before each use. Adding 20g of polyvinylidene fluoride (PVDF) and 2g of polyvinylpyrrolidone (PVP) into 78g of N, N-Dimethylformamide (DMF) solvent to form a blending system, stirring the blending system in a water bath at the temperature of 60-65 ℃ for 12 hours to dissolve the mixture into a uniform solution, standing and defoaming the uniform solution for 12 hours to obtain a membrane casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into distilled water for split-phase forming, taking out the membrane after soaking for 2 hours, washing the membrane with distilled water to prepare the polyvinylidene fluoride ultrafiltration membrane, and storing the polyvinylidene fluoride ultrafiltration membrane in distilled water at 4 ℃. The prepared polyvinylidene fluoride (PVDF) ultrafiltration membrane has the thickness of 200 mu m and is marked as PVDF.
Example 5 (graphene oxide-polyvinylidene fluoride Ultrafiltration Membrane not prepared by the method of the invention)
Preparing a graphene oxide-polyvinylidene fluoride composite ultrafiltration membrane: polyvinylidene fluoride (PVDF) was dried in a vacuum oven at 60 ℃ for 12h before each use. Dissolving 0.1g of Graphene Oxide (GO) in 78g of N, N-Dimethylformamide (DMF) solvent, performing strong ultrasonic treatment for 1h, adding 20g of polyvinylidene fluoride (PVDF) and 2g of polyvinylpyrrolidone (PVP) into the solution to form a blending system, stirring the blending system in a water bath at the temperature of 60-65 ℃ for 12h to dissolve the mixture into a uniform solution, standing and defoaming the uniform solution for 12h to obtain a casting solution; and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into distilled water for split-phase forming, taking out the membrane after soaking for 2 hours, washing the membrane with the distilled water to prepare the graphene oxide-polyvinylidene fluoride composite ultrafiltration membrane, and storing the membrane in the distilled water at 4 ℃. The thickness of the prepared graphene oxide-polyvinylidene fluoride composite ultrafiltration membrane is 200 mu m, and the membrane is marked as P/0.5 GO.
FIG. 1a is a scanning electron microscope surface view of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method of the present invention in example 2. Fig. 1a shows that the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method of the invention has a significant microporous structure, and the cross-sectional view of fig. 1b also shows a typical finger-shaped pore structure.
FIG. 3 is a graph showing the results of the flux tests of different ultrafiltration membranes prepared in examples 1 to 5. from FIG. 3, it can be seen that the water flux of the polyvinylidene fluoride ultrafiltration membrane prepared in example 4 was 45. + -. 5.5L. m-2·h-1The maximum flux of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared in the embodiment 2 can reach 91 +/-10L m-2·h-1. The flux performance of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method is greatly improved.
Fig. 4 is a graph showing the results of retention tests for different ultrafiltration membranes prepared in examples 1-5. As can be seen from FIG. 4, the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method of the invention has ultrahigh flux, and meanwhile, the rejection rate is obviously reduced, and the excellent separation performance is shown.
From fig. 5 and fig. 6, it can be seen that the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane prepared by the method of the present invention has excellent anti-pollution performance.
Claims (10)
1. A preparation method of a graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is characterized by comprising the following steps:
1) carrying out esterification reaction on graphene oxide and polyethylene glycol to form graphene oxide-polyethylene glycol serving as a hydrophilic material for later use;
2) dissolving a set amount of graphene oxide-polyethylene glycol in an N, N-dimethylformamide solvent, and performing ultrasonic dispersion;
3) adding a set amount of polyvinylidene fluoride and polyvinylpyrrolidone into the solution subjected to ultrasonic dispersion to form a blending system, stirring and dissolving the blending system in a water bath at a set temperature to obtain a uniform solution, standing and defoaming to obtain a membrane casting solution;
4) and (3) coating the membrane casting solution on a glass plate by a membrane scraper to form a membrane, putting the membrane casting solution into a coagulating bath for split-phase forming, taking out after soaking for 2 hours, washing with distilled water to prepare the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane, and storing in the distilled water.
2. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the step 1) comprises the following steps:
(1) dissolving 0.1-0.2g of graphene oxide in 200ml of N, N-dimethylformamide solvent, and performing ultrasonic treatment for 30min to induce to form a homogeneous solution;
(2) 2.4g of polyethylene glycol 6000(PEG-6000) and 200m of L graphene oxide dispersion liquid are respectively added into a flask, and after 15min of ultrasonic treatment, 0.083g of N, N' -dicyclohexylcarbodiimide and 0.01g of 4-dimethylaminopyridine are respectively added;
(3) the solution is subjected to ultrasonic treatment for 30 minutes and is placed in a forced air drying oven to react for 12 hours at the temperature of 60 ℃;
(4) putting the homogeneous solution into a dialysis bag for dialysis for 3 days;
(5) and (5) freeze-drying to obtain the graphene oxide-polyethylene glycol.
3. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the ultrasonic dispersion time in the step 2) is 1-3 h.
4. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein in the blending system in the step 3), the content of polyvinylpyrrolidone is 1-3 wt%, the content of polyvinylidene fluoride is 20 wt%, the content of N, N-dimethylformamide solvent is 77-79 wt%, and the content of graphene oxide-polyethylene glycol is 0.3-1.0% of the mass of polyvinylidene fluoride.
5. The method for preparing the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the polyvinylidene fluoride in the step 3) is dried in a vacuum drying oven at 60 ℃ for 12 hours before each use.
6. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the temperature of the uniform solution in the step 3) is 60-65 ℃ in a water bath at a set temperature, and the stirring time is more than 12 hours.
7. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the standing and defoaming time in the step 3) is more than 12 hours.
8. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the coagulation bath in the step 4) is distilled water at a temperature of 18 ℃ to 22 ℃.
9. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the thickness of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is 200-250 um.
10. The preparation method of the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane according to claim 1, wherein the graphene oxide-polyethylene glycol/polyvinylidene fluoride composite ultrafiltration membrane is used for separating bovine serum albumin.
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| CN115155328A (en) * | 2022-07-08 | 2022-10-11 | 安庆市鑫祥瑞环保科技有限公司 | Polymer ultrafiltration membrane for sewage treatment and preparation method thereof |
| CN115155328B (en) * | 2022-07-08 | 2024-04-19 | 安庆市鑫祥瑞环保科技有限公司 | Polymer ultrafiltration membrane for sewage treatment and preparation method thereof |
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Application publication date: 20200724 |