CN111790274A - Preparation method of anti-pollution polysulfone composite nanofiltration membrane for water body filtration - Google Patents
Preparation method of anti-pollution polysulfone composite nanofiltration membrane for water body filtration Download PDFInfo
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Abstract
The invention relates to the technical field of membrane separation, and discloses a preparation method of an anti-pollution polysulfone composite nanofiltration membrane for water filtration. The method comprises the following steps: 1) adding a polyethylene glycol pore-foaming agent and nano titanium dioxide composite particles into a polysulfone solution, and standing and defoaming at room temperature to obtain a membrane casting solution; 2) coating the casting solution on the side surface of a glass plate in a blade mode, and immersing the glass plate into deionized water coagulation bath to form a film so as to obtain a polysulfone base film; 3) soaking a polysulfone base membrane in an aqueous phase solution, taking out, wiping with a sponge to remove excess aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and carrying out interfacial polymerization reaction at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane; 4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for thermosetting crosslinking reaction to obtain the anti-pollution polysulfone composite nanofiltration membrane. The composite nanofiltration membrane prepared by the invention has excellent anti-pollution performance and membrane stability.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method of an anti-pollution polysulfone composite nanofiltration membrane for water filtration.
Background
The membrane separation technology is a technology for separating substances and water in a mixed aqueous solution by the selective permeation action of a membrane under the action of external energy or chemical potential difference for the purposes of separation, purification and the like. Membrane separation technology has been widely used in various fields such as industrial production, municipal sewage treatment, and industrial wastewater treatment as a high-efficiency separation technology. Because the problems of environmental pollution, water resource shortage and the like are very serious in China at present, the state also sets up a stricter water quality discharge standard correspondingly, the problem of recycling after sewage treatment is more and more emphasized, and the sewage can be recycled by adopting a membrane separation technology. The membrane separation technology is combined with other technologies, so that the development direction of membrane water treatment is oriented. Nanofiltration is a new technology which is developed on the basis of reverse osmosis and is a new membrane separation process between ultrafiltration and reverse osmosis, so that the membrane technology is rapidly increased. The nanofiltration membrane is obviously improved in acid and alkali resistance, solvent resistance and oxidation stability, so that the nanofiltration application field is expanded, and the nanofiltration membrane is widely applied to separation and purification in the industrial fields of environmental protection, metallurgy, printing and dyeing, textile, papermaking, petroleum and the like. The preparation method of the nanofiltration membrane mainly comprises the methods of surface polymerization, in-situ polymerization, plasma polymerization and the like. The interfacial polymerization method is a mature method for industrially producing composite nanofiltration membranes with more applications at present. The nanofiltration membrane structure mainly comprises a support layer and a separation layer covered on the surface of the support layer, and the principle of the interfacial polymerization method is that two monomers are respectively dissolved in two mutually incompatible solvents, and an interfacial polymerization reaction is carried out on the monomers at the solvent interface, so that a polymerization layer with a separation effect is generated on the surface of the support layer. Polysulfone has the advantages of low price, easy availability, good thermal stability, chemical stability, acid corrosion resistance, mechanical property and the like, and is currently used as a nanofiltration membrane supporting layer material, but polysulfone has a hydrophobic property, so that solutes with hydrophobicity in water generate over-adsorption deposition on the surface and in membrane pores of a polysulfone membrane, so that membrane body pollution is caused, membrane performance is reduced, and service life is shortened.
Chinese patent publication No. CN108114616 discloses a polysulfone composite nanofiltration membrane for anhydrous treatment and a preparation method thereof, wherein the composite nanofiltration membrane comprises a hydrophilic polysulfone base membrane and a composite layer covered on the base membrane; chinese patent publication No. CN109745878 discloses a method for preparing polypiperazine amide/amphiphilic block polymer nanofiltration membrane, which comprises preparing polysulfone ultrafiltration basement membrane by liquid phase inversion method, and preparing separating layer on the basement membrane by interfacial polymerization method. In the patents, a polysulfone base membrane which is not subjected to modification treatment is used as a supporting layer of the nanofiltration membrane, and because polysulfone is a hydrophobic material, solutes with hydrophobicity in a water body generate over-adsorption deposition on the surface of the polysulfone membrane and in membrane pores, so that membrane body pollution is caused, and membrane performance is reduced.
Chinese patent publication No. CN108745008 discloses a method for preparing a polysulfone composite membrane, which comprises modifying a polysulfone membrane by adding nano titanium dioxide, and adding hydrophilic nano titanium dioxide into a polysulfone solution to improve the hydrophilic performance of the composite membrane and the anti-pollution performance of the composite membrane, but the nano titanium dioxide is easily agglomerated, so that the nano titanium dioxide is unevenly dispersed in the membrane, and the performance of the composite membrane is reduced.
Chinese patent publication No. CN105771704 discloses a preparation method of a novel anti-pollution high-selectivity sulfonated polysulfone nanofiltration membrane, sulfonated polysulfone and tetrabutyl titanate are dissolved in ethylene glycol monomethyl ether to prepare a membrane casting solution, the membrane casting solution is coated on the surface of a polysulfone ultrafiltration membrane to prepare a composite nanofiltration membrane by adopting a coating method, nano titanium dioxide colloid particles hydrolyzed by tetrabutyl titanate can be uniformly dispersed in the membrane casting solution, so that the hydrophilic anti-pollution performance of the membrane is improved, but tetrabutyl titanate is added into the polysulfone solution for hydrolysis, and the polysulfone membrane casting solution has certain viscosity, so that tetrabutyl titanate hydrolysis is slowly carried out, the hydrolysis is insufficient, raw materials are wasted, and redundant unhydrolyzed tetrabutyl titanate remains in a membrane to cause membrane pollution.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of an anti-pollution polysulfone composite nanofiltration membrane for water filtration.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of an anti-pollution polysulfone composite nanofiltration membrane for water body filtration comprises the following steps:
1) mixing N, N-dimethylacetamide and N-methylpyrrolidone to obtain a mixed solvent, adding polysulfone into the mixed solvent, stirring and dissolving, then adding a polyethylene glycol pore-forming agent and nano titanium dioxide composite particles, stirring and mixing uniformly, and standing and defoaming at room temperature to obtain a membrane casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in the air for 1-2min, then immersing the glass plate in a deionized water coagulation bath to form a film, washing the solvent on the surface of the film by using deionized water, and airing the film at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizing agent triethylamine, stirring and mixing uniformly to obtain an aqueous phase solution for later use; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 1-5min, taking out, wiping with a sponge to remove excess aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and performing interfacial polymerization reaction for 30-60s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for thermosetting crosslinking reaction, then soaking the nascent composite nanofiltration membrane in deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thereby obtaining the anti-pollution polysulfone composite nanofiltration membrane.
Preferably, the mass ratio of the polysulfone to the nano titanium dioxide composite particles in the step 1) is 1: 0.1-0.3.
Preferably, the film forming time of the coagulating bath in the step 2) is 10-20 h.
Preferably, the concentration of trimesoyl chloride in the organic phase solution in the step 3) is 0.2-1.5 wt%.
Preferably, the concentration of m-phenylenediamine in the aqueous solution in the step 3) is 2.0 to 5.0 wt%.
Preferably, the thermal curing and crosslinking temperature in the step 4) is 40-60 ℃, and the thermal curing and crosslinking time is 15-30 min.
Preferably, the method for preparing the nano titanium dioxide composite particles in the step 1) comprises the following steps:
adding an epoxy silane coupling agent and montmorillonite into deionized water, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution to adjust the pH of the system to 3-4, heating in a water bath to 45-60 ℃, stirring and reacting for 1-2h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite; adding silane coupling agent modified montmorillonite into tannic acid aqueous solution, adding a catalyst, heating in water bath to 80-90 ℃, stirring for reaction for 2-3h, filtering, washing, and drying to obtain tannic acid modified montmorillonite; adding glacial acetic acid and distilled water into absolute ethyl alcohol, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution to adjust the pH to 2-3, then adding tannic acid modified montmorillonite, and carrying out ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 50-60 ℃ after dripping, standing for 3-6h, filtering, separating, washing and drying to obtain the nano titanium dioxide composite particles.
Preferably, the mass ratio of the montmorillonite to the epoxy silane coupling agent is 1: 0.2-0.3.
Preferably, the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1: 0.3-0.5.
Preferably, the mass ratio of the tannic acid modified montmorillonite to tetrabutyl titanate is 1: 2-4.
The polysulfone membrane has the advantages of low cost, easy obtainment, good thermal stability, good chemical stability, good acid corrosion resistance, good mechanical property and the like, the polysulfone material is selected as the base membrane of the composite nanofiltration membrane, and the surface of the polysulfone base membrane (supporting layer) is subjected to interfacial polymerization reaction by utilizing trimesoyl chloride and m-phenylenediamine, so that the surface of the polysulfone base membrane is covered with a separation layer with the filtering and separating effects, as shown in figure 1, the cross-sectional microscopic scanning electron microscope image of the polysulfone composite nanofiltration membrane in embodiment 1 of the invention, and the surface of the polysulfone base membrane can be observed to be covered with a polyamide separation layer. Because the polysulfone is a hydrophobic material, the hydrophobic solute in the water generates over-adsorption deposition on the surface and in the pores of the polysulfone membrane, so that the membrane body is polluted, the membrane performance is reduced, and the service life is shortened. Therefore, the hydrophilic nano titanium dioxide composite particles are added into the polysulfone membrane casting solution, so that the hydrophilic performance of the polysulfone base membrane is improved, and the hydrophilic polysulfone base membrane is not easy to adsorb hydrophobic impurity particles in a water body, so that the anti-pollution performance of the polysulfone base membrane is improved.
In the prior art, in order to improve the anti-pollution performance of a hydrophobic polysulfone composite membrane, two methods are generally adopted: firstly, hydrophilic nano titanium dioxide is directly added into a polysulfone membrane casting solution, so that the hydrophilic property of the polysulfone base membrane is improved, and the anti-pollution property of the polysulfone base membrane is further improved, but the method has the problems that the nano titanium dioxide is easy to agglomerate, the nano titanium dioxide is not uniformly dispersed in the polysulfone membrane casting solution, and the prepared polysulfone composite membrane has poor anti-pollution property; secondly, tetrabutyl titanate solution is added into the polysulfone membrane casting solution, and after the tetrabutyl titanate solution and the polysulfone membrane casting solution are uniformly mixed, nanometer titanium dioxide is generated through hydrolysis of tetrabutyl titanate, so that the nanometer titanium dioxide is uniformly dispersed in the polysulfone membrane casting solution.
For the defects existing in the prior art method, the invention firstly carries out modification treatment on the montmorillonite, an epoxy silane coupling agent is grafted on the surface of the montmorillonite, so that the surface of the montmorillonite is loaded with epoxy functional groups, tannin molecules have a large amount of hydroxyl groups, the epoxy functional groups and the hydroxyl groups on the tannin molecules are subjected to ring-opening reaction, so that the tannin molecules are grafted on the surface of the montmorillonite, the surface of the montmorillonite is enriched with hydroxyl groups, then tetrabutyl titanate is used as a precursor, nano titanium dioxide colloid particles are prepared by hydrolysis, the nano titanium dioxide obtained by hydrolyzing the tetrabutyl titanate is deposited on the surface of the montmorillonite under the action of hydrogen bonding attraction by utilizing the hydrogen bonding force between the hydroxyl groups on the surface of the nano titanium dioxide colloid particles and the hydroxyl groups on the surface of the montmorillonite, and then the nano titanium dioxide loaded on the montmorillonite is obtained, and the particle size of the nano titanium dioxide loaded on the montmorillonite is far, the particles do not agglomerate, so that the dispersion uniformity of the nano titanium dioxide in the membrane casting solution is improved, and the anti-pollution performance of the polysulfone base membrane is greatly improved.
On the other hand, according to the invention, after montmorillonite-loaded nano titanium dioxide is added into a polysulfone membrane casting solution and is subjected to liquid phase curing to form a membrane, a part of montmorillonite-loaded nano titanium dioxide particles are naked and dispersed on the surface of a polysulfone base membrane, and the micron-nano structure formed by combining montmorillonite and nano titanium dioxide can obviously improve the roughness of the surface of the polysulfone base membrane, so that the roughness of the surface of the polysulfone base membrane is improved, and the polysulfone base membrane and a polyamide separation layer (the polyamide separation layer generated by interfacial polymerization reaction of trimesoyl chloride and m-phenylenediamine) on the surface of the polysulfone base membrane can form a rivet effect, thereby improving the binding force between the polysulfone base membrane and the polyamide separation layer, ensuring that the polyamide separation layer is not easy to separate from the surface of the polysulfone base membrane; in addition, a large number of hydroxyl active groups are arranged on tannin molecules grafted on the surface of montmorillonite, and in the process of interfacial polymerization reaction between trimesoyl chloride and m-phenylenediamine, active hydroxyl on the tannin molecules reacts with acyl chloride groups on trimesoyl chloride molecules, so that a polyamide separation layer is connected to the surface of a polysulfone base film under the action of chemical bonding, the binding acting force between the polyamide separation layer and the polysulfone base film is further improved, and the lasting stability of the performance of the polysulfone composite nanofiltration film is improved.
Drawings
FIG. 1 is a microscopic scanning electron microscope image of the cross section of the polysulfone composite nanofiltration membrane in example 1 of the present invention.
Detailed Description
In the present invention, unless otherwise specified, all the raw materials and equipment used in the present invention are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Epoxy silane coupling agent: model KH5-60, gamma-glycidoxypropyltrimethoxysilane, Jeccard chemical Co., Ltd, Hangzhou; montmorillonite: average particle size of 1.9-2.3 μm, swelling degree > 12.5, whiteness > 80, CEC80-100, Hubeixin run chemical Co., Ltd; polysulfone resin powder model SP-100, manufactured by Guangzhou Arisen Polymer materials Ltd.
Example 1
The preparation method of the nano titanium dioxide composite particles comprises the following steps:
adding an epoxy silane coupling agent KH-560 and montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the epoxy silane coupling agent KH-560 is 1:0.25, the mass-volume ratio of the montmorillonite to the deionized water is 1g/50mL, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH of the system to 4, heating in a water bath to 45 ℃, stirring and reacting for 1.5h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite;
adding tannic acid into deionized water, stirring and dissolving to prepare a tannic acid solution with the concentration of 2.5 wt%, adding silane coupling agent modified montmorillonite into the tannic acid solution, wherein the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1:0.4, then adding a stannic chloride catalyst, wherein the addition amount of the stannic chloride catalyst is 3.0 wt% of the tannic acid, heating in a water bath to 90 ℃, stirring and reacting for 2.5h, filtering, washing and drying to obtain tannic acid modified montmorillonite;
adding glacial acetic acid and distilled water into absolute ethyl alcohol, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1:3:8, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH value to 3, then adding tannic acid modified montmorillonite, wherein the mass-to-volume ratio of the tannic acid modified montmorillonite to the solution is 1g/60mL, and performing ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution with the mass concentration of 5.0%, slowly dropwise adding the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 60 ℃ after dropwise adding, standing for 5h, filtering, separating, washing and drying to obtain the nano titanium dioxide composite particles, wherein the mass ratio of the tannic acid modified montmorillonite to the tetrabutyl titanate is 1: 3.5.
The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration comprises the following steps:
1) uniformly mixing N, N-dimethylacetamide and N-methylpyrrolidone according to a volume ratio of 1:1 to obtain a mixed solvent, adding polysulfone resin powder into the mixed solvent according to a mass-volume ratio of 1g/50mL, stirring for dissolving, then adding a polyethylene glycol 6000 pore-forming agent and nano titanium dioxide composite particles, wherein the addition amount of the polyethylene glycol 6000 is 1.0 wt% of the polysulfone resin powder, the mass ratio of the polysulfone resin powder to the nano titanium dioxide composite particles is 1:0.25, stirring for uniformly mixing, and standing for defoaming for 24 hours at room temperature to obtain a casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in air for 2min, then immersing the glass plate in a deionized water coagulation bath for 10h to form a film, washing the solvent on the surface of the film by using deionized water, and airing at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution, wherein the concentration of the trimesoyl chloride in the organic phase solution is 1.0 wt% for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizer triethylamine, and stirring and mixing uniformly to obtain an aqueous phase solution, wherein the m-phenylenediamine accounts for 4.0 percent of the mass percentage concentration of the aqueous phase solution, the sodium dodecyl sulfate accounts for 0.5 percent of the mass percentage concentration of the aqueous phase solution, and the triethylamine accounts for 1.5 percent of the mass percentage concentration of the aqueous phase solution; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 4min, taking out, wiping with a sponge to remove the redundant aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and carrying out interfacial polymerization reaction for 50s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for carrying out thermosetting crosslinking reaction for 25min at 60 ℃, then immersing the membrane into deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thus obtaining the anti-pollution polysulfone composite nanofiltration membrane.
Example 2
The preparation method of the nano titanium dioxide composite particles comprises the following steps:
adding an epoxy silane coupling agent KH-560 and montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the epoxy silane coupling agent KH-560 is 1:0.25, the mass-volume ratio of the montmorillonite to the deionized water is 1g/50mL, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH of the system to 3, heating in a water bath to 60 ℃, stirring and reacting for 1.5h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite;
adding tannic acid into deionized water, stirring and dissolving to prepare a tannic acid solution with the concentration of 2.5 wt%, adding silane coupling agent modified montmorillonite into the tannic acid solution, wherein the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1:0.35, then adding a stannic chloride catalyst, wherein the addition amount of the stannic chloride catalyst is 3.0 wt% of the tannic acid, heating in a water bath to 80 ℃, stirring and reacting for 2.5h, filtering, washing and drying to obtain tannic acid modified montmorillonite;
adding glacial acetic acid and distilled water into absolute ethyl alcohol, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1:3:8, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH value to 2, then adding tannic acid modified montmorillonite, wherein the mass-to-volume ratio of the tannic acid modified montmorillonite to the solution is 1g/60mL, and performing ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution with the mass concentration of 5.0%, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 50 ℃ after dripping, standing for 4h, filtering and separating, washing, and drying to obtain the nano titanium dioxide composite particles.
The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration comprises the following steps:
1) uniformly mixing N, N-dimethylacetamide and N-methylpyrrolidone according to a volume ratio of 1:1 to obtain a mixed solvent, adding polysulfone resin powder into the mixed solvent according to a mass-volume ratio of 1g/50mL, stirring for dissolving, then adding a polyethylene glycol 6000 pore-forming agent and nano titanium dioxide composite particles, wherein the addition amount of the polyethylene glycol 6000 is 1.0 wt% of the polysulfone resin powder, the mass ratio of the polysulfone resin powder to the nano titanium dioxide composite particles is 1:0.15, stirring for uniformly mixing, and standing for defoaming for 24 hours at room temperature to obtain a casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in air for 1min, then immersing the glass plate in a deionized water coagulation bath for 20h to form a film, washing the solvent on the surface of the film by using deionized water, and airing the film at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution, wherein the concentration of the trimesoyl chloride in the organic phase solution is 0.6 wt% for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizer triethylamine, and stirring and mixing uniformly to obtain an aqueous phase solution, wherein the m-phenylenediamine accounts for 3.0 percent of the mass percentage concentration of the aqueous phase solution, the sodium dodecyl sulfate accounts for 0.5 percent of the mass percentage concentration of the aqueous phase solution, and the triethylamine accounts for 1.5 percent of the mass percentage concentration of the aqueous phase solution; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 2min, taking out, wiping with a sponge to remove the redundant aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and carrying out interfacial polymerization reaction for 40s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for carrying out thermosetting crosslinking reaction at 40 ℃ for 20min, then soaking the nascent composite nanofiltration membrane in deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thereby obtaining the anti-pollution polysulfone composite nanofiltration membrane.
Example 3
The preparation method of the nano titanium dioxide composite particles comprises the following steps:
adding an epoxy silane coupling agent KH-560 and montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the epoxy silane coupling agent KH-560 is 1:0.3, the mass-volume ratio of the montmorillonite to the deionized water is 1g/50mL, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH of the system to 3.5, heating in a water bath to 50 ℃, stirring and reacting for 2h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite;
adding tannic acid into deionized water, stirring and dissolving to prepare a tannic acid solution with the concentration of 2.5 wt%, adding silane coupling agent modified montmorillonite into the tannic acid solution, wherein the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1:0.5, then adding a stannic chloride catalyst, wherein the addition amount of the stannic chloride catalyst is 3.0 wt% of the tannic acid, heating in a water bath to 85 ℃, stirring and reacting for 3 hours, filtering, washing and drying to obtain tannic acid modified montmorillonite;
adding glacial acetic acid and distilled water into absolute ethyl alcohol, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1:3:8, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH value to 2.5, then adding tannic acid modified montmorillonite, wherein the mass-to-volume ratio of the tannic acid modified montmorillonite to the solution is 1g/60mL, and performing ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution with the mass concentration of 5.0%, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 55 ℃ after dripping, standing for 6h, filtering and separating, washing, and drying to obtain the nano titanium dioxide composite particles.
The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration comprises the following steps:
1) uniformly mixing N, N-dimethylacetamide and N-methylpyrrolidone according to a volume ratio of 1:1 to obtain a mixed solvent, adding polysulfone resin powder into the mixed solvent according to a mass-volume ratio of 1g/50mL, stirring for dissolving, then adding a polyethylene glycol 6000 pore-forming agent and nano titanium dioxide composite particles, wherein the addition amount of the polyethylene glycol 6000 is 1.0 wt% of the polysulfone resin powder, the mass ratio of the polysulfone resin powder to the nano titanium dioxide composite particles is 1:0.3, stirring for uniformly mixing, and standing for defoaming for 24 hours at room temperature to obtain a casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in the air for 1.5min, then immersing the glass plate in a deionized water coagulation bath for 15h to form a film, washing the solvent on the surface of the film by using deionized water, and airing the film at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution, wherein the concentration of the trimesoyl chloride in the organic phase solution is 1.5wt% for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizer triethylamine, and stirring and mixing uniformly to obtain an aqueous phase solution, wherein the m-phenylenediamine accounts for 5.0 percent of the mass percentage concentration of the aqueous phase solution, the sodium dodecyl sulfate accounts for 0.5 percent of the mass percentage concentration of the aqueous phase solution, and the triethylamine accounts for 1.5 percent of the mass percentage concentration of the aqueous phase solution; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 5min, taking out, wiping with a sponge to remove the redundant aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and carrying out interfacial polymerization reaction for 60s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for carrying out thermocuring crosslinking reaction for 30min at 50 ℃, then immersing the nascent composite nanofiltration membrane in deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thus obtaining the anti-pollution polysulfone composite nanofiltration membrane.
Example 4
The preparation method of the nano titanium dioxide composite particles comprises the following steps:
adding an epoxy silane coupling agent KH-560 and montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the epoxy silane coupling agent KH-560 is 1:0.2, the mass-volume ratio of the montmorillonite to the deionized water is 1g/50mL, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH of the system to 3.5, heating in a water bath to 50 ℃, stirring and reacting for 1h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite;
adding tannic acid into deionized water, stirring and dissolving to prepare a tannic acid solution with the concentration of 2.5 wt%, adding silane coupling agent modified montmorillonite into the tannic acid solution, wherein the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1:0.3, then adding a stannic chloride catalyst, wherein the addition amount of the stannic chloride catalyst is 3.0 wt% of the tannic acid, heating in a water bath to 85 ℃, stirring and reacting for 2 hours, filtering, washing and drying to obtain tannic acid modified montmorillonite;
adding glacial acetic acid and distilled water into absolute ethyl alcohol, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1:3:8, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH value to 2.5, then adding tannic acid modified montmorillonite, wherein the mass-to-volume ratio of the tannic acid modified montmorillonite to the solution is 1g/60mL, and performing ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution with the mass concentration of 5.0%, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 55 ℃ after dripping, standing for 3h, filtering and separating, washing, and drying to obtain the nano titanium dioxide composite particles.
The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration comprises the following steps:
1) uniformly mixing N, N-dimethylacetamide and N-methylpyrrolidone according to a volume ratio of 1:1 to obtain a mixed solvent, adding polysulfone resin powder into the mixed solvent according to a mass-volume ratio of 1g/50mL, stirring for dissolving, then adding a polyethylene glycol 6000 pore-forming agent and nano titanium dioxide composite particles, wherein the addition amount of the polyethylene glycol 6000 is 1.0 wt% of the polysulfone resin powder, the mass ratio of the polysulfone resin powder to the nano titanium dioxide composite particles is 1:0.1, stirring for uniformly mixing, and standing for defoaming for 24 hours at room temperature to obtain a casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in the air for 1.5min, then immersing the glass plate in a deionized water coagulation bath for 15h to form a film, washing the solvent on the surface of the film by using deionized water, and airing the film at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution, wherein the concentration of the trimesoyl chloride in the organic phase solution is 0.2 wt% for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizer triethylamine, and stirring and mixing uniformly to obtain an aqueous phase solution, wherein the m-phenylenediamine accounts for 2.0 percent of the mass percentage concentration of the aqueous phase solution, the sodium dodecyl sulfate accounts for 0.5 percent of the mass percentage concentration of the aqueous phase solution, and the triethylamine accounts for 1.5 percent of the mass percentage concentration of the aqueous phase solution; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 1min, taking out, wiping with a sponge to remove the redundant aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and carrying out interfacial polymerization reaction for 30s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for carrying out thermocuring crosslinking reaction for 15min at 50 ℃, then immersing the nascent composite nanofiltration membrane in deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thus obtaining the anti-pollution polysulfone composite nanofiltration membrane.
Comparative example 1:
the difference between the comparative example 1 and the example 1 is that the nano titanium dioxide composite particles are not added in the preparation step 1) of the polysulfone composite nanofiltration membrane.
Comparative example 2:
the difference between the comparative example 2 and the example 1 is that the nano titanium dioxide composite particles in the step 1) of preparing the polysulfone composite nanofiltration membrane are replaced by common nano titanium dioxide.
Comparative example 3:
comparative example 3 is different from example 1 in that the preparation method of the nano titanium dioxide composite particle comprises the following steps:
adding glacial acetic acid and distilled water into absolute ethyl alcohol, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1:3:8, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution with the concentration of 0.5mol/L to adjust the pH value to 3, then adding montmorillonite, wherein the mass volume ratio of the montmorillonite to the solution is 1g/60mL, and carrying out ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution with the mass concentration of 5.0%, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, wherein the mass ratio of montmorillonite to tetrabutyl titanate is 1:3.5, heating in a water bath to 60 ℃ after dripping, standing for 5h, filtering, separating, washing and drying to obtain the nano titanium dioxide composite particles.
And (3) testing the performance of the composite nanofiltration membrane:
1. and (3) testing the anti-pollution performance:
the attenuation of the membrane flux is mainly caused by a membrane pollution phenomenon, the membrane pollution refers to the phenomenon that colloid, particles or macromolecular solute contained in feed liquid generates adsorption, deposition and membrane pore blocking on the surface of a membrane, so that the water flux of the membrane is reduced, and the pressure difference between two sides of the membrane is increased, and the water flux recovery rate of the membrane is an important index for representing the anti-pollution performance of the composite nanofiltration membrane. The composite nanofiltration membranes of examples 1 to 4 and the composite nanofiltration membranes of comparative examples 1 to 3 are installed in a membrane performance evaluation device, and Na with the concentration of 2000mg/L is adopted2SO4The solution and 100mg/L BSA mixed solution were used as targets for evaluating the anti-fouling performance of the membrane. Adding 2000mg/L of Na2SO4Taking the solution as a feed solution, prepressing (0.2MPa) for 30min, and recording the water flux as J0Then, the loop filtration experiment was started, first with 2000mg/L Na2SO4The solution was filtered as feed for 4h, the water flux of the permeate was recorded every 1h, and 2000mg/L Na was added2SO4And 100mg/L BAS mixed solution as a feeding solution, performing filtration for 4h, recording the water flux of the permeate at intervals of 1h, then changing the filtrate into deionized water, and performing filtration and cleaning for 3 h. The water flux recovery rate was calculated according to the following formula:
Jr＝Jt/J0x 100%, wherein JrRepresents the water flux recovery,%; j. the design is a squaretRepresents a water flux per interval of 1h, L/m2h；J0Represents the initial flux of the membrane, L/m2h。
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| J0(L/m2h) | 15.56 | 15.37 | 15.83 | 15.19 | 5.68 | 11.25 | 13.51 |
| Jt(L/m2h) | 14.42 | 14.28 | 14.57 | 13.85 | 3.27 | 8.55 | 11.26 |
| Jr(％) | 92.7 | 92.9 | 92.0 | 91.2 | 57.6 | 76.0 | 83.3 |
The water flux sum of the composite nanofiltration membrane prepared in the embodiment 1-4 is higher than that of the comparative example 1-3, and the hydrophilic performance of the composite nanofiltration membrane in the embodiment is better than that of the composite nanofiltration membrane in the comparative example; the recovery rate of the water flux of the composite nanofiltration membrane prepared in the examples 1 to 4 is up to more than 90 percent and is much higher than that of the composite nanofiltration membrane prepared in the comparative examples 1 to 3, and the results prove that the composite nanofiltration membrane prepared in the examples 1 to 4 has excellent anti-pollution performance.
2. And (3) testing the stability of the composite nanofiltration membrane:
na with the concentration of 2000mg/L is prepared2SO4Solution, the composite nanofiltration membranes of examples 1 to 4 and the composite nanofiltration membranes of comparative examples 1 to 3 are arranged in a membrane performance evaluation device, and Na is adopted2SO4Performing a cross-flow filtration test on a solution serving as a filtrate, operating for 30min under the low pressure of 0.2MPa, recording the concentration of a penetrating fluid, operating for 24h under the high pressure of 0.5MPa, recording the concentration of the penetrating fluid, and calculating the rejection rate of the composite nanofiltration membrane on a sodium sulfate solution according to the concentration of the penetrating fluid, wherein the rejection rate calculation formula is as follows:
Q＝(P0-P)/POx 100%, wherein Q represents a rejection (%), PORepresents the concentration of the filtrate before filtration, PORepresents the concentration of the filtrate after filtration.
Compared with the comparative examples 1 to 3, the rejection rates of the composite nanofiltration membranes in the examples 1 to 4 have little change to the rejection rate of sodium sulfate when the composite nanofiltration membranes are operated at high pressure compared with the rejection rate of sodium sulfate when the composite nanofiltration membranes are operated at low pressure, and the rejection rate of the composite nanofiltration membranes in the comparative examples 1 to 3 has much reduction to the rejection rate of sodium sulfate when the composite nanofiltration membranes are operated at high pressure compared with the rejection rate of sodium sulfate when the composite nanofiltration membranes are operated at low pressure. The reason is that the micron-nanometer structure formed by combining the montmorillonite and the nanometer titanium dioxide in the preparation process of the composite nanofiltration membrane can obviously improve the roughness of the surface of the polysulfone base membrane, and the improvement of the roughness of the surface of the polysulfone base membrane is beneficial to forming a rivet effect between the polysulfone base membrane and the polyamide separation layer on the surface of the polysulfone base membrane, so that the binding force between the polysulfone base membrane and the polyamide separation layer is improved, the polyamide separation layer is not easy to separate from the surface of the polysulfone base membrane under the impact of water power, and the lasting stability of the performance of the polysulfone composite nanofiltration membrane is; on the other hand, in the invention, a large number of hydroxyl active groups are arranged on tannin molecules grafted on the surface of montmorillonite, and in the process of interfacial polymerization reaction between trimesoyl chloride and m-phenylenediamine, active hydroxyl on the tannin molecules reacts with acyl chloride groups on trimesoyl chloride molecules, so that a polyamide separation layer is connected to the surface of a polysulfone base film through the action of chemical bonding, the binding acting force between the polyamide separation layer and the polysulfone base film is further improved, and the lasting stability of the performance of the polysulfone composite nanofiltration film is improved.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of an anti-pollution polysulfone composite nanofiltration membrane for water body filtration is characterized by comprising the following steps:
1) mixing N, N-dimethylacetamide and N-methylpyrrolidone to obtain a mixed solvent, adding polysulfone resin powder into the mixed solvent, stirring for dissolving, then adding a polyethylene glycol pore-forming agent and nano titanium dioxide composite particles, stirring and mixing uniformly, and standing and defoaming at room temperature to obtain a membrane casting solution;
2) pouring the casting solution obtained in the step 1) on one side surface of a glass plate, uniformly coating the casting solution on the side surface of the glass plate by using a scraper, standing the glass plate in the air for 1-2min, then immersing the glass plate in a deionized water coagulation bath to form a film, washing the solvent on the surface of the film by using deionized water, and airing the film at room temperature to obtain a polysulfone base film;
3) adding trimesoyl chloride into a normal hexane solvent, stirring and dissolving to prepare an organic phase solution for later use; adding m-phenylenediamine into deionized water, stirring for dissolving, then adding surfactant sodium dodecyl sulfate and acid neutralizing agent triethylamine, stirring and mixing uniformly to obtain an aqueous phase solution for later use; soaking the polysulfone base membrane obtained in the step 2) in an aqueous phase solution for 1-5min, taking out, wiping with a sponge to remove excess aqueous phase solution on the surface of the polysulfone base membrane, immediately soaking in an organic phase solution, and performing interfacial polymerization reaction for 30-60s at room temperature to obtain a nascent-state polysulfone composite nanofiltration membrane;
4) and (3) placing the nascent composite nanofiltration membrane in the step 3) in an oven for thermosetting crosslinking reaction, then soaking the nascent composite nanofiltration membrane in deionized water to clean and remove monomers which do not participate in the reaction on the surface of the membrane, thereby obtaining the anti-pollution polysulfone composite nanofiltration membrane.
2. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the mass ratio of the polysulfone resin powder to the nano titanium dioxide composite particles in the step 1) is 1: 0.1-0.3.
3. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the coagulation bath film formation time in the step 2) is 10-20 h.
4. The method for preparing the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the concentration of trimesoyl chloride in the organic phase solution in the step 3) is 0.2-1.5 wt%.
5. The method for preparing the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the concentration of m-phenylenediamine in the aqueous solution in the step 3) is 2.0-5.0 wt%.
6. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the thermosetting crosslinking temperature in the step 4) is 40-60 ℃, and the thermosetting crosslinking time is 15-30 min.
7. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 1, wherein the step 1) of preparing the nano titanium dioxide composite particles comprises the following steps:
adding an epoxy silane coupling agent and montmorillonite into deionized water, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution to adjust the pH of the system to 3-4, heating in a water bath to 45-60 ℃, stirring and reacting for 1-2h, filtering, washing and drying to obtain silane coupling agent surface modified montmorillonite; adding silane coupling agent modified montmorillonite into tannic acid aqueous solution, adding a catalyst, heating in water bath to 80-90 ℃, stirring for reaction for 2-3h, filtering, washing, and drying to obtain tannic acid modified montmorillonite; adding glacial acetic acid and distilled water into absolute ethyl alcohol, stirring and mixing uniformly, dropwise adding a hydrochloric acid solution to adjust the pH to 2-3, then adding tannic acid modified montmorillonite, and carrying out ultrasonic oscillation to obtain a suspension for later use; adding tetrabutyl titanate into absolute ethyl alcohol, stirring and dissolving to obtain a tetrabutyl titanate solution, slowly dripping the tetrabutyl titanate solution into the suspension under the stirring condition, heating in a water bath to 50-60 ℃ after dripping, standing for 3-6h, filtering, separating, washing and drying to obtain the nano titanium dioxide composite particles.
8. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 7, wherein the mass ratio of montmorillonite to epoxy silane coupling agent is 1: 0.2-0.3.
9. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 7, wherein the mass ratio of the silane coupling agent surface modified montmorillonite to the tannic acid is 1: 0.3-0.5.
10. The preparation method of the anti-pollution polysulfone composite nanofiltration membrane for water body filtration according to claim 7, wherein the mass ratio of the tannic acid modified montmorillonite to tetrabutyl titanate is 1: 2-4.
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