CN112642292A - Super-hydrophilic graphene flat microporous filter membrane and preparation method thereof - Google Patents
Super-hydrophilic graphene flat microporous filter membrane and preparation method thereof Download PDFInfo
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- CN112642292A CN112642292A CN202011001698.0A CN202011001698A CN112642292A CN 112642292 A CN112642292 A CN 112642292A CN 202011001698 A CN202011001698 A CN 202011001698A CN 112642292 A CN112642292 A CN 112642292A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- 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
- B01D69/06—Flat membranes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/36—Hydrophilic membranes
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Abstract
The invention discloses a preparation method of a super-hydrophilic graphene flat microporous filter membrane, which comprises the following steps: blending the raw materials of the hydrophilic microporous filter membrane according to the proportion, stirring, dissolving to a uniform state, adding a certain amount of graphene, stirring uniformly again, and preparing to obtain a membrane casting solution; preparing the casting solution into a nascent state membrane in an environment with air humidity of 40-80%; and curing the nascent-state membrane into a membrane through a coagulating bath. According to the invention, raw materials of the hydrophilic microporous membrane are blended according to a ratio, stirred and dissolved to a uniform state, a casting solution is obtained after a certain amount of graphene is added, the casting solution is prepared into a nascent-state membrane in an environment with air humidity of 40-80%, the nascent-state membrane is solidified into a membrane in water, and then the membrane is sequentially subjected to washing and alcohol washing treatment to obtain the super-hydrophilic microporous membrane material.
Description
Technical Field
The invention relates to the technical field of microporous filter membranes, in particular to a super-hydrophilic graphene flat microporous filter membrane and a preparation method thereof.
Background
The microporous filter membrane is prepared by using a high-molecular chemical material and a pore-forming additive, and coating the porous filter membrane on a supporting layer after special treatment. In the application of the membrane separation technology, the microporous filter membrane is a membrane variety with the widest application range, is simple and quick to use, and is widely applied to the fields of scientific research, food detection, chemical industry, nanotechnology, energy, environmental protection and the like. The microporous filter membrane is mainly made of refined nitrocotton and proper amount of cellulose acetate, acetone, n-butanol and ethyl alcohol, etc. and is hydrophilic, non-toxic and sanitary, and is a porous membrane filter material, and its pore size distribution is uniform and its permeable micropores are distributed, and its micropore rate is up to 80% of absolute pore size. It is mainly used for filtering aqueous solutions, and is also called an aqueous membrane.
The microporous filter membrane is a very thin filter membrane with a porous sponge structure. Typical pore sizes range from 0.1 micron to 10 microns. The manufacturers of microporous filter membranes classify them into the following categories according to their morphological differences:
flat sheet tissue type filter membranes, hollow fiber type filter membranes, and tubular type filter membranes. Wherein, the flat-plate thin-paper type filter membrane can be further divided into two types of "flat-plate thin-paper type filter membrane without support" and "flat-plate thin-paper type filter membrane with support" according to the structural difference. According to the requirements of both technologies, the production process of the unsupported flat sheet membrane filter is more precise and complicated than the production process of the supported flat sheet membrane filter.
The micro-filtration is a screening process, and belongs to the field of precise filtration. Microfiltration refers to a filtration technique for filtering out particles of 0.1 μm to 10 μm, and generally speaking, a filtration mechanism is classified into a surface type and a deep type. The micro-filtration is a screening process, and belongs to the field of precise filtration. The filtration mechanism of MF membranes manufactured via advanced technology is surface type filtration. Because the filtering aperture is fixed, the filtering precision and reliability can be ensured. The deep filtration is divided into non-fixed irregular pore size and fixed irregular pore size, and the former is like chemical fiber wound filter core, which is generally only used as a coarser prefilter.
The flat plate microfiltration membranes can be used in various shapes including a disk shape and a cylindrical shape. The preparation of flat sheet microporous filter membranes is well known in the art and generally employs a phase transition method. The phase transition method is generally classified into the following methods: 1) evaporation of organic or non-organic solvents (dry process); 2) exposure to vapors of non-organic solvents, which are adsorbed on bare surfaces (vapor phase induced precipitation); 3) hardening in a non-organic solvent liquid, usually water (wet process); 4) quenching the hot film greatly reduces the solubility of the polymer (thermal process).
At present, hydrophobic polyolefins are generally adopted as raw materials of microporous filter membranes, but the hydrophobic membranes have lower surface energy and are not easy to wet by water, and membrane pollution is easy to occur due to the adsorption of pollutants, so that the hydrophilicity of membrane materials is improved by adding hydrophilic components. In the existing research reports and production, more hydrophilic components are generally polyethylene glycol, polyvinylpyrrolidone and the like. The hydrophilicity of the microfiltration membrane can be improved by adjusting the content of the hydrophilic component, but the strength and the toughness of the microfiltration membrane are sacrificed to a certain extent. Graphene is used as a novel raw material, is gradually applied to a filtering material, is generally selected as a supporting layer, forms a graphene functional layer on the surface of the supporting layer, and is connected with the microporous filtering layer and the graphene functional layer through drying. The process is complex in operation, the graphene consumption is large, the connection firmness between the two layers cannot be guaranteed, and the functional layer is easy to separate.
Disclosure of Invention
The invention aims to: in order to solve the problems, the super-hydrophilic graphene flat microporous filter membrane and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the super-hydrophilic graphene flat microporous filter membrane comprises the following components in parts by weight:
as a further description of the above technical solution:
the homopolymer is one or more of polyether sulfone, polysulfone, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polyimide, sulfonated polyether ether ketone and cellulose acetate.
As a further description of the above technical solution:
the additive is a non-solvent for hydrophilic polymers and homopolymers.
As a further description of the above technical solution:
the organic solvent is one or more of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, phenol or a water/isopropanol mixture.
As a further description of the above technical solution:
a preparation method of a super-hydrophilic graphene flat microporous filter membrane comprises the following steps:
a. mixing solid high molecular homopolymer, organic solvent, hydrophilic polymer and non-organic solvent additive, stirring, and dissolving at 40-120 deg.C in water bath to obtain uniform solution;
b. adding a certain amount of graphene into the solution obtained in the step a, and further stirring to obtain a membrane casting solution;
c. preparing the casting solution prepared in the step b into a nascent state membrane in a 40-80% water vapor environment;
d. c, placing the nascent membrane obtained in the step c in water of 20-70 ℃ for solidification to form a membrane;
e. and d, sequentially washing the membrane solidified in the step d with water and alcohol, and drying to obtain the super-hydrophilic graphene flat microporous filter membrane.
As a further description of the above technical solution:
the preparation method of the nascent membrane in the step c comprises the following steps: and spreading the casting film liquid on a roller or a conveying belt which continuously rotates, and exposing the film on the roller or the conveying belt to a water vapor environment with the humidity of 40-80% for 10s-3min to prepare the nascent state film.
As a further description of the above technical solution:
and e, the average flow pore size of the super-hydrophilic graphene flat microporous filter membrane prepared in the step e is 0.05-10 microns.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, raw materials of the hydrophilic microporous membrane are blended according to a ratio, stirred and dissolved to a uniform state, a casting solution is obtained after a certain amount of graphene is added, the casting solution is prepared into a nascent-state membrane in an environment with air humidity of 40-80%, the nascent-state membrane is solidified into a membrane in water, and then the membrane is sequentially subjected to washing and alcohol washing treatment to obtain the super-hydrophilic microporous membrane material.
Drawings
FIG. 1 is a schematic view of a contact angle structure of a super-hydrophilic graphene flat microporous filter membrane and a preparation method thereof 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. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the 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.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The super-hydrophilic graphene flat microporous filter membrane comprises the following components in parts by weight:
wherein the homopolymer is one or more of polyethersulfone, polysulfone, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polyimide, sulfonated polyether ether ketone and cellulose acetate.
Wherein the additive is a non-solvent of hydrophilic polymer and homopolymer, and the additive is polyethylene glycol, polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene or polyhydroxyethyl methacrylate, diethylene glycol, alcohol, water, etc.
Wherein the organic solvent is one or more of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, phenol or a water/isopropanol mixture.
A preparation method of a super-hydrophilic graphene flat microporous filter membrane comprises the following steps:
a. mixing solid high molecular homopolymer, organic solvent, hydrophilic polymer and non-organic solvent additive, stirring, and dissolving at 40-120 deg.C in water bath to obtain uniform solution;
b. adding a certain amount of graphene into the solution obtained in the step a, and further stirring to obtain a membrane casting solution;
c. preparing the casting solution prepared in the step b into a nascent state membrane in a 40-80% water vapor environment;
d. c, placing the nascent membrane obtained in the step c in water of 20-70 ℃ for solidification to form a membrane;
e. and d, sequentially washing the membrane solidified in the step d with water and alcohol, and drying to obtain the super-hydrophilic graphene flat microporous filter membrane.
Example 1
Referring to fig. 1, 12g of polyethersulfone, 5g of polyvinylpyrrolidone, 20g of dissolved polyethylene glycol and 63g of N-methylpyrrolidone are mixed, heated and stirred at 60 ℃ for 8h until the mixture is uniformly and thoroughly clear, and then sealed, stored and kept stand for 24 h. And preparing the obtained homogeneous casting film liquid on a release film by adopting a scraper with the diameter of 300 mu m, slowly passing through a steam box with the humidity of about 70% to obtain a nascent state film, solidifying the nascent state film into a film by using pure water with the temperature of 30 ℃, and obtaining a finished film through water washing, alcohol washing and drying treatment. The pure water flux of the prepared membrane is 20ml/min/cm 2-10 ps, the left contact angle is 45.49 degrees, and the right contact angle is 45.26 degrees.
Example 2
Referring to fig. 1, 12g of polyethersulfone, 5g of polyvinylpyrrolidone, 20g of dissolved polyethylene glycol and 63g of N-methylpyrrolidone are mixed, heated and stirred at 60 ℃ for 8 hours until the mixture is uniformly and thoroughly clear, 0.2g of graphene is added, the mixture is continuously stirred uniformly, and the mixture is sealed, stored and kept stand for 24 hours. And preparing the obtained homogeneous casting film liquid on a release film by adopting a scraper with the diameter of 300 mu m, slowly passing through a steam box with the humidity of about 70% to obtain a nascent state film, solidifying the nascent state film into a film by using pure water with the temperature of 30 ℃, and obtaining a finished film through water washing, alcohol washing and drying treatment. The pure water flux of the prepared membrane is 25ml/min/cm 2-10 ps, the left contact angle is 34.49 degrees, and the right contact angle is 34.26 degrees.
Example 3
Referring to fig. 1, 12g of polyethersulfone, 5g of polyvinylpyrrolidone, 20g of dissolved polyethylene glycol and 63g of N-methylpyrrolidone are mixed, heated and stirred at 60 ℃ for 8 hours until the mixture is uniformly and thoroughly clear, 0.5g of graphene is added, the mixture is continuously stirred uniformly, and the mixture is sealed, stored and kept stand for 24 hours. And preparing the obtained homogeneous casting film liquid on a release film by adopting a scraper with the diameter of 300 mu m, slowly passing through a steam box with the humidity of about 70% to obtain a nascent state film, solidifying the nascent state film into a film by using pure water with the temperature of 30 ℃, and obtaining a finished film through water washing, alcohol washing and drying treatment. The pure water flux of the prepared membrane is 30ml/min/cm 2-10 ps, the left contact angle is 27.33 degrees, and the right contact angle is 27.05 degrees.
Example 4
Referring to fig. 1, 20g of polyethersulfone, 10g of polyvinylpyrrolidone, 20g of dissolved polyethylene glycol and 50g of N-methylpyrrolidone are mixed, heated and stirred at 60 ℃ for 8 hours until the mixture is uniformly and thoroughly clear, 0.5g of graphene is added, the mixture is continuously stirred uniformly, and the mixture is sealed, stored and kept stand for 24 hours. And preparing the obtained homogeneous casting film liquid on a release film by adopting a scraper with the diameter of 300 mu m, slowly passing through a steam box with the humidity of about 70% to obtain a nascent state film, solidifying the nascent state film into a film by using pure water with the temperature of 30 ℃, and obtaining a finished film through water washing, alcohol washing and drying treatment. The pure water flux of the prepared membrane is 8ml/min/cm 2-10 ps, the left contact angle is 28.54 degrees, and the right contact angle is 28.19 degrees.
The hydrophilic property of the flat microporous filter membrane is reflected by measuring the contact angle of pure water on the surface of the flat microporous filter membrane. The tangent of the liquid surface and the tangent of the solid surface are made at the junction of the liquid/solid/gas three phases, and the two tangents form an included angle theta through the inside of the liquid, namely the contact angle. When θ is an acute angle, the liquid spreads on the surface of the solid, i.e., the liquid wets the solid. When θ is 0, it is called complete wetting. When theta is an obtuse angle, the liquid surface contracts but does not expand, and the liquid does not wet the solid, referred to as non-wetting. When θ is 180 °, it is said to be completely non-wetting.
| Pure water flux | Left contact angle | Right contact angle | |
| Example 1 | 20ml/min/cm2.-10ps | 45.49° | 45.26° |
| Example 2 | 25ml/min/cm2.-10ps | 34.49° | 34.26° |
| Example 3 | 30ml/min/cm2.-10ps | 27.33° | 27.05° |
| Example 4 | 8ml/min/cm2.-10ps | 28.54° | 28.19° |
The embodiment can obviously find that after the graphene is added, the contact angle of the microfiltration membrane is obviously reduced, which indicates that the hydrophilicity of the microfiltration membrane is enhanced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The super-hydrophilic graphene flat microporous filter membrane is characterized by comprising the following components in parts by weight:
2. the ultra-hydrophilic graphene flat microporous membrane according to claim 1, wherein the homopolymer is one or more of polyethersulfone, polysulfone, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polyimide, sulfonated polyether ether ketone, and cellulose acetate.
3. The ultra-hydrophilic graphene flat plate microfiltration membrane according to claim 1, wherein the additive is a non-solvent for hydrophilic polymers and homopolymers.
4. The ultra-hydrophilic graphene flat plate microfiltration membrane according to claim 1, wherein the organic solvent is one or more of dimethylsulfoxide, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, phenol or a water/isopropanol mixture.
5. The preparation method of the ultra-hydrophilic graphene flat microporous filter membrane according to claim 1, characterized by comprising the following steps:
a. mixing solid high molecular homopolymer, organic solvent, hydrophilic polymer and non-organic solvent additive, stirring, and dissolving at 40-120 deg.C in water bath to obtain uniform solution;
b. adding a certain amount of graphene into the solution obtained in the step a, and further stirring to obtain a membrane casting solution;
c. preparing the casting solution prepared in the step b into a nascent state membrane in a 40-80% water vapor environment;
d. c, placing the nascent membrane obtained in the step c in water of 20-70 ℃ for solidification to form a membrane;
e. and d, sequentially washing the membrane solidified in the step d with water and alcohol, and drying to obtain the super-hydrophilic graphene flat microporous filter membrane.
6. The method for preparing a superhydrophilic graphene flat microporous membrane according to claim 5, wherein the preparation method of the nascent membrane in the step c comprises: and spreading the casting film liquid on a roller or a conveying belt which continuously rotates, and exposing the film on the roller or the conveying belt to a water vapor environment with the humidity of 40-80% for 10s-3min to prepare the nascent state film.
7. The method as claimed in claim 5, wherein the average flow pore size of the ultra-hydrophilic graphene flat microporous membrane prepared in step e is 0.05 μm to 10 μm.
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| CN110141981A (en) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术（南通）有限公司 | A kind of preparation method of hydrophilic ethylene-chlorotrifluoroethylene hollow membrane |
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2020
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| CN101219350A (en) * | 2007-10-11 | 2008-07-16 | 亚美滤膜（南通）有限公司 | Method for producing hydrophilic polyethersulfone millipore filter |
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Application publication date: 20210413 |