CN111467973B - Zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane and preparation method thereof - Google Patents
Zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane and preparation method thereof Download PDFInfo
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01D69/10—Supported membranes; Membrane supports
Abstract
A silicon-titanium hybrid nanofiltration composite membrane modified by zwitterions and a preparation method thereof are disclosed, wherein the composite membrane comprises a supporting layer formed by a porous polyether sulfone high molecular structure, and a separation layer containing polyimide and silica-titanium dioxide gel modified by zwitterions is arranged on the supporting layer. According to the invention, an in-situ sol-gel method is adopted, inorganic silicon dioxide-titanium dioxide is introduced into an organic polymer in the form of a sol polymer, and by regulating and controlling film forming conditions, the agglomeration of inorganic components is avoided, so that an organic-inorganic hybrid interface is obviously optimized, and the film performance is obviously enhanced, thereby solving the problem of low flux of a nanofiltration membrane consisting of a porous polyether sulfone polymer structure and polyimide in the prior art. In addition, the invention grafts the zwitterion on the inorganic silicon dioxide-titanium dioxide by a chemical grafting method, the flux is obviously improved under the condition of keeping the salt rejection rate basically unchanged, and simultaneously, the pollution resistance of the membrane material is optimized.
Description
Technical Field
The invention belongs to the field of nanofiltration composite membranes, and particularly relates to a silicon-titanium hybrid nanofiltration composite membrane modified by zwitterions and a preparation method thereof.
Background
Nanofiltration membranes are a functional semipermeable membrane that allows the permeation of solvent molecules or certain low molecular weight solutes or low valent ions. It is a special and promising kind of separation membrane, which is named because of the size of the trapped matter is about nanometer, and the nanofiltration membrane is used to remove organic matter and chroma of surface water, remove hardness of underground water, partially remove soluble salt, concentrate fruit juice and separate useful matter in medicine.
At present, the low flux and the membrane pollution are the main bottlenecks limiting the development of the nanofiltration membrane. Aiming at low flux, researchers have developed various hybrid separation layers to solve the problem, for example, nanoparticles such as silica, graphene and MOFs are added in the interfacial polymerization process, but the hybrid method of direct physical blending adopted at present has the problem of poor compatibility of the organic polymer-inorganic nanoparticle interface, and the selectivity of the separation layer is greatly reduced while the flux is easily improved.
Disclosure of Invention
The invention provides a silicon-titanium hybrid nanofiltration composite membrane modified by zwitterions and a preparation method thereof, which are used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
a silicon-titanium hybrid nanofiltration composite membrane modified by zwitterions comprises a supporting layer formed by a porous polyether sulfone high-molecular structure, wherein a separation layer containing polyimide and silica-titanium dioxide gel modified by zwitterions is arranged on the supporting layer.
The thickness of the support layer of the zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane is 150-300 mu m.
The thickness of the separation layer is 100-500 nm.
According to the zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane, the mass ratio of the zwitterion-modified silicon dioxide-titanium dioxide gel to the polyimide filled in the separation layer is 0.02-0.1: 1.
According to the zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane, the molar ratio of silicon dioxide to titanium dioxide in the silicon dioxide-titanium dioxide gel is 1: 0.5-2.
A preparation method of a zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane comprises the following steps:
the method comprises the following steps: preparation of porous polyethersulfone structure supporting layer by non-solvent induced phase inversion method
Dissolving polyether sulfone polymer and polyethylene glycol in N, N-dimethylformamide, stirring for 4-6h at 60 ℃ to obtain a casting solution, standing and defoaming the casting solution, preparing the casting solution into a flat liquid film on a glass plate by using a scraper, immersing the liquid film into a water bath at room temperature, and carrying out a phase conversion process to realize curing and film forming;
step two: synthesis of functionalized silica-titania sol
Adding a silicon precursor into a hydrochloric acid aqueous solution with the mass concentration of 8-12%, hydrolyzing at the temperature of 40-50 ℃ for 2h to form a silica sol with the mass concentration of 5-10%, adding a titanium precursor into an N, N-dimethylformamide solution with the water content of 5-20% by mass, hydrolyzing at room temperature for 2h to form a titanium dioxide sol with the mass concentration of 5-10%, mixing the formed silica and the titanium dioxide sol, and stirring at room temperature; adding an acidic modifier, reacting at 30-60 ℃ for 1-5h, continuously adding an alkaline modifier, and reacting at 30-60 ℃ for 1-5h to obtain a functionalized silica-titanium dioxide sol;
step three: method for preparing zwitterion modified silicon-titanium nanofiltration composite membrane by using in-situ sol-gel method
Mixing the functionalized silica-titanium dioxide sol prepared in the step two with a piperazine water solution with the concentration of 1-5g/L to obtain a water phase medium; dissolving trimesoyl chloride in n-heptane to obtain an oil phase medium with the concentration of 1-5 g/L; firstly soaking the polyether sulfone porous support layer prepared in the step one in a water phase medium for 20-30min, removing excessive water on the surface of the membrane, then soaking the membrane in an oil phase medium for 0.5-2min, taking the membrane out of the oil phase medium, and standing for 10-60min at the temperature of 25-60 ℃ for in-situ sol-gelation; obtaining the zwitterion modified silicon-titanium nanofiltration composite membrane Z-Si-Ti/PE.
According to the preparation method of the zwitterion modified silicon-titanium hybrid nanofiltration composite membrane, the feeding mass ratio of the polyether sulfone to the polyethylene glycol is 1: 0.5-1.
In the second step, the silica sol and the titanium dioxide sol are mixed according to the molar ratio of 1:0.5-2, and are stirred and reacted for 4-5 hours at room temperature after being mixed.
In the second step, the silicon precursor is any one of methyl orthosilicate and ethyl orthosilicate or the mixture of the methyl orthosilicate and the ethyl orthosilicate in any proportion.
In the second step, the titanium precursor is one or a mixture of butyl titanate and titanium tetrachloride in any proportion.
In the second step, the acidic modifier is any one or mixture of 3-mercaptopropyltrimethoxysilane and 3, 4-dihydroxyphenylpropionic acid in any proportion.
According to the preparation method of the zwitterion modified silicon-titanium hybrid nanofiltration composite membrane, the alkaline modifier is any one or two of 3-aminopropyltriethoxysilane and 2- (3, 4-dihydroxyphenyl) ethylamine which are mixed in any proportion.
The invention has the advantages that: according to the invention, an in-situ sol-gel method is adopted, inorganic silicon dioxide-titanium dioxide is introduced into an organic polymer in the form of a sol polymer, and the problem of inorganic component agglomeration easily caused by a traditional physical blending method for preparing a hybrid membrane is avoided by regulating and controlling the membrane forming conditions, so that an organic-inorganic hybrid interface is obviously optimized, the membrane performance is obviously enhanced, and the problem of low flux of a nanofiltration membrane consisting of a porous polyether sulfone polymer structure and polyimide in the prior art is solved. In addition, the invention grafts the zwitterion on the inorganic silicon dioxide-titanium dioxide by a chemical grafting method, and synthesizes the zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane in one step while preparing the hybrid membrane, so that the grafting process is simple and convenient, the grafting amount is large, the chemical microenvironment in the membrane is adjusted, the flux is obviously improved under the condition of keeping the salt rejection rate basically unchanged, and the pollution resistance of the membrane material is optimized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a surface SEM image of a nanofiltration composite membrane prepared according to the present invention;
fig. 2 is a cross-sectional SEM picture of a nanofiltration composite membrane prepared according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. 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.
Example 1
Dissolving 50g of polyether sulfone polymer and 40g of polyethylene glycol in 100mL of N, N-dimethylformamide, stirring for 5h at 60 ℃ to obtain a membrane casting solution, standing and defoaming the membrane casting solution, preparing the membrane casting solution into a flat liquid membrane on a glass plate by using a scraper, immersing the liquid membrane into a water bath at room temperature, and carrying out a phase conversion process to realize curing and membrane forming;
step two: synthesis of functionalized silica-titania sol
Adding 2g of methyl orthosilicate and ethyl orthosilicate into 40mL of hydrochloric acid aqueous solution with the mass concentration of 10%, hydrolyzing at 45 ℃ for 2h to form silica sol with the mass concentration of 7%, adding 9g of butyl titanate and titanium tetrachloride into 40mL of N, N-dimethylformamide solution with the water content of 15% by mass, hydrolyzing at room temperature for 2h to form titanium dioxide sol with the mass concentration of 7%, mixing the silica sol and the titanium dioxide sol according to the molar ratio of 1:1.2, and stirring at room temperature to react for 4 h; adding 1g of 3-mercaptopropyltrimethoxysilane and 1g of 3, 4-dihydroxyphenylpropionic acid, reacting for 3.5 hours at the temperature of 45 ℃, continuously adding 1g of 3-aminopropyltriethoxysilane and 0.5g of 2- (3, 4-dihydroxyphenyl) ethylamine, and reacting for 4 hours at the temperature of 30-60 ℃ to obtain functionalized silica-titanium dioxide sol;
step three: method for preparing zwitterion modified silicon-titanium nanofiltration composite membrane by using in-situ sol-gel method
Mixing the functionalized silica-titanium dioxide sol prepared in the step two with a piperazine water solution with the concentration of 2g/L to obtain a water phase medium; dissolving trimesoyl chloride in n-heptane to obtain an oil phase medium with the concentration of 2 g/L; firstly soaking the polyether sulfone porous support layer prepared in the step one in a water phase medium for 25min, removing excessive water on the surface of the membrane, then soaking the membrane in an oil phase medium for 1min, taking the membrane out of the oil phase medium, standing for 50min at the temperature of 35 ℃ and carrying out in-situ sol-gelation; the zwitterion modified silicon-titanium nanofiltration composite membrane Z-Si-Ti/PE obtained is recorded as example 1.
Example 2
Dissolving 50g of polyether sulfone polymer and 25g of polyethylene glycol in 100mL of N, N-dimethylformamide, stirring for 4h at 60 ℃ to obtain a membrane casting solution, standing and defoaming the membrane casting solution, preparing the membrane casting solution into a flat liquid membrane on a glass plate by using a scraper, immersing the liquid membrane into a water bath at room temperature, and carrying out a phase conversion process to realize curing and membrane forming;
step two: synthesis of functionalized silica-titania sol
Adding 2g of methyl orthosilicate into 40mL of hydrochloric acid aqueous solution with the mass concentration of 11%, hydrolyzing at 45 ℃ for 2h to form silica sol with the mass concentration of 7%, adding 4.5g of butyl titanate into 40mL of N, N-dimethylformamide solution with the water mass fraction of 17%, hydrolyzing at room temperature for 2h to form titanium dioxide sol with the mass concentration of 8%, mixing the silica sol and the titanium dioxide sol according to the molar ratio of 1:0.8, and stirring at room temperature to react for 4-5 h; adding 1g of 3-mercaptopropyltrimethoxysilane and 1g of 3, 4-dihydroxyphenylpropionic acid, reacting at the temperature of 45 ℃ for 1-5h, continuously adding 1g of 3-aminopropyltriethoxysilane and 1g of 2- (3, 4-dihydroxyphenyl) ethylamine, and reacting at the temperature of 30-60 ℃ for 1-5h to obtain functionalized silica-titanium dioxide sol;
step three: method for preparing zwitterion modified silicon-titanium nanofiltration composite membrane by using in-situ sol-gel method
Mixing the functionalized silica-titanium dioxide sol prepared in the step two with piperazine water solution with the concentration of 3g/L to obtain a water phase medium; dissolving trimesoyl chloride in n-heptane to obtain an oil phase medium with the concentration of 4 g/L; firstly soaking the polyether sulfone porous support layer prepared in the step one in a water phase medium for 25min, removing excessive water on the surface of the membrane, then soaking the membrane in an oil phase medium for 2min, taking the membrane out of the oil phase medium, standing for 40min at the temperature of 40 ℃ and carrying out in-situ sol-gelation; the zwitterion modified silicon-titanium nanofiltration composite membrane Z-Si-Ti/PE obtained is recorded as example 2.
Example 3
Dissolving 50g of polyether sulfone polymer and 50g of polyethylene glycol in 100mL of N, N-dimethylformamide, stirring for 6h at 60 ℃ to obtain a membrane casting solution, standing and defoaming the membrane casting solution, preparing the membrane casting solution into a flat liquid membrane on a glass plate by using a scraper, immersing the liquid membrane into a water bath at room temperature, and carrying out a phase conversion process to realize curing and membrane forming;
step two: synthesis of functionalized silica-titania sol
Adding 2g of methyl orthosilicate and ethyl orthosilicate into 40mL of hydrochloric acid aqueous solution with the mass concentration of 12%, hydrolyzing at the temperature of 50 ℃ for 2h to form silica sol with the mass concentration of 8%, adding 2.3g of butyl titanate and titanium tetrachloride into 40mL of N, N-dimethylformamide solution with the water content of 14% by mass, hydrolyzing at room temperature for 2h to form titanium dioxide sol with the mass concentration of 7%, mixing the silica sol and the titanium dioxide sol according to the molar ratio of 1:2, and stirring at room temperature to react for 4.5 h; adding 1g of 3-mercaptopropyltrimethoxysilane and 0.5g of 3, 4-dihydroxyphenylpropionic acid, reacting for 4 hours at the temperature of 50 ℃, continuously adding 1g of 3-aminopropyltriethoxysilane and 1g of 2- (3, 4-dihydroxyphenyl) ethylamine, and reacting for 3 hours at the temperature of 45 ℃ to obtain functionalized silica-titanium dioxide sol;
step three: method for preparing zwitterion modified silicon-titanium nanofiltration composite membrane by using in-situ sol-gel method
Mixing the functionalized silica-titanium dioxide sol prepared in the step two with a piperazine water solution with the concentration of 4g/L to obtain a water phase medium; dissolving trimesoyl chloride in n-heptane to obtain an oil phase medium with the concentration of 3 g/L; firstly soaking the polyether sulfone porous support layer prepared in the step one in a water phase medium for 25min, removing excessive water on the surface of the membrane, then soaking the membrane in an oil phase medium for 1min, taking the membrane out of the oil phase medium, standing for 30min at the temperature of 40 ℃ and carrying out in-situ sol-gelation; the zwitterion modified silicon-titanium nanofiltration composite membrane Z-Si-Ti/PE obtained is recorded as example 3.
A nanofiltration membrane which is commercially available and consists of a porous polyether sulfone high-molecular structure and polyimide is selected as a comparison example.
The same sewage is treated by the nanofiltration membranes prepared in the examples 1-3 and the comparative example with the same size in the same method and for the same time, and the performances of the examples 1-3 and the comparative example are obtained by detecting and analyzing the sewage before and after treatment, and the performance results are shown in the table one.
The SNW-1/PA nanofiltration composite membrane prepared by the invention adopts a flat membrane performance evaluation device to evaluate the water flux, the salt rejection rate and the pollution resistance.
Water flux calculation formula: j ═ V/(a · t · Δ P), where J is the water flux (L/m) of the membrane2h.MP), V is the volume of water (L) permeating the membrane, A is the effective area of the membrane (m)2) T is the permeation time (h) and P is the operating pressure (Pa).
The salt is Na2SO4And the salt rejection rate calculation formula is as follows: r ═ 1-Cp/Cf) X 100% where CpIs the permeate mass concentration (g/L), CfThe mass concentration (g/L) of the stock solution is shown.
And (3) anti-pollution capability test: filtering 1g/L bovine serum albumin solution by using the prepared membrane, wherein the initial flux is J1And the flux after 2 hours of testing is recorded as J2Flux decline rate (J)1-J2)/J1To characterize the membrane's resistance to fouling.
Watch 1
In summary, the data in table one show that the membranes prepared in the examples not only maintain the salt rejection rate at a similar level to that of the control example, but also significantly improve the water flux, and significantly improve the anti-pollution capability, so that the comprehensive performance of the membranes prepared in the above 3 examples is enhanced.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A zwitterion-modified silicon-titanium hybrid nanofiltration composite membrane is characterized in that: the support layer is provided with a separation layer containing polyimide and silicon dioxide-titanium dioxide gel modified by zwitterions;
the preparation method comprises the following steps:
the method comprises the following steps: preparation of porous polyethersulfone structural support layer by non-solvent induced phase inversion method
Dissolving polyether sulfone polymer and polyethylene glycol in N, N-dimethylformamide, stirring for 4-6h at 60 ℃ to obtain a casting solution, standing and defoaming the casting solution, preparing the casting solution into a flat liquid film on a glass plate by using a scraper, immersing the liquid film into a water bath at room temperature, and carrying out a phase conversion process to realize curing and film forming;
step two: synthesis of functionalized silica-titania sol
Adding a silicon precursor into a hydrochloric acid aqueous solution with the mass concentration of 8-12%, hydrolyzing at the temperature of 40-50 ℃ for 2h to form a silica sol with the mass concentration of 5-10%, adding a titanium precursor into an N, N-dimethylformamide solution with the water content of 5-20% by mass, hydrolyzing at room temperature for 2h to form a titanium dioxide sol with the mass concentration of 5-10%, mixing the formed silica and the titanium dioxide sol, and stirring at room temperature; adding an acidic modifier, reacting at 30-60 ℃ for 1-5h, continuously adding an alkaline modifier, and reacting at 30-60 ℃ for 1-5h to obtain a functionalized silica-titanium dioxide sol;
step three: method for preparing zwitterion modified silicon-titanium nanofiltration composite membrane by using in-situ sol-gel method
Mixing the functionalized silica-titanium dioxide sol prepared in the step two with a piperazine water solution with the concentration of 1-5g/L to obtain a water phase medium; dissolving trimesoyl chloride in n-heptane to obtain an oil phase medium with the concentration of 1-5 g/L; firstly soaking the polyether sulfone porous support layer prepared in the first step in a water phase medium for 20-30min, removing excessive water on the surface of the membrane, then soaking the membrane in an oil phase medium for 0.5-2min, taking the membrane out of the oil phase medium, and standing for 10-60min at the temperature of 25-60 ℃ for in-situ sol-gelation; obtaining a zwitterion modified silicon-titanium nanofiltration composite membrane;
in the second step, the acidic modifier is any one or two of 3-mercaptopropyltrimethoxysilane and 3, 4-dihydroxyphenylpropionic acid which are mixed in any proportion;
the alkaline modifier is any one or mixture of 3-aminopropyl triethoxysilane and 2- (3, 4-dihydroxyphenyl) ethylamine in any proportion.
2. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: the thickness of the support layer is 150-300 μm.
3. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: the thickness of the separation layer is 100-500 nm.
4. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: the mass ratio of the zwitterion modified silicon dioxide-titanium dioxide gel and the polyimide filled into the separation layer is 0.02-0.1: 1.
5. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: the mol ratio of the silicon dioxide to the titanium dioxide in the silicon dioxide-titanium dioxide gel is 1: 0.5-2.
6. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: the mass ratio of the polyether sulfone to the polyethylene glycol is 1: 0.5-1.
7. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: and in the second step, the silica sol and the titanium dioxide sol are mixed according to the molar ratio of 1:0.5-2, and are stirred and react for 4-5 hours at room temperature after being mixed.
8. The zwitterionic-modified silicon-titanium hybrid nanofiltration composite membrane according to claim 1, wherein: in the second step, the silicon precursor is any one or two of methyl orthosilicate and ethyl orthosilicate which are mixed in any proportion;
and in the second step, the titanium precursor is any one or mixture of butyl titanate and titanium tetrachloride in any proportion.
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