CN106310976A - Self-assembled super-molecular polymer nano-filtration membrane based on graphene and preparation method thereof - Google Patents
Self-assembled super-molecular polymer nano-filtration membrane based on graphene and preparation method thereof Download PDFInfo
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—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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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B01D71/06—Organic material
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Abstract
The invention provides a self-assembled super-molecular polymer nano-filtration membrane based on graphene and a preparation method thereof. The specific method comprises: taking a polyacrylonitrile super-filtration membrane or a sulfonated polyethersulfone super-filtration membrane which are subjected to alkali modification treatment as a base membrane and fixing the base membrane into a container with a porous supporting layer; putting a membrane surface upward; adding a covalent cationic polyelectrolyte solution and a super-molecular polymer solution into the container respectively; pressurizing and assembling; sufficiently washing with de-ionized water and repeating for a plurality of times; putting the membrane into a drying oven for carrying out heat treatment to obtain a multilayered super-molecular polymer nano-filtration membrane; finally, immersing the multilayered super-molecular polymer nano-filtration membrane into a graphene oxide solution; pressurizing and assembling; sufficiently washing with de-ionized water; putting the multilayered super-molecular polymer nano-filtration membrane into the drying oven for carrying out heat treatment to obtain the self-assembled super-molecular polymer nano-filtration membrane based on the graphene. The nano-filtration membrane prepared by the preparation method provided by the invention contains a super-molecular polymer so that the controllability of the nano-filtration membrane is improved and the separation effect is good; the preparation method is simple and efficient and does not utilize an organic solvent, so that the protection method is green and environment-friendly.
Description
Technical field
The invention belongs to separation membrane technical field, be specifically related to the polymerization of a kind of self-assembled supermolecular based on Graphene
Thing NF membrane and preparation method.
Background technology
Membrane material is the core of membrane separation technique, and the character of membrane material directly affects the stability of membrance separation and separates effect
Really, NF membrane has high selection separation property, high flux and preferable mechanical strength, chemically stable compared with traditional membrane material
Property, thermostability and anti-fouling performance.The material of NF membrane has that cellulose family, polyamide be tired, polysulfones and inorganic ceramic class etc., single
The NF membrane material of one material all has respective pluses and minuses, and the permeation flux of cellulose family NF membrane is relatively low, selects separation property
Poor, polyamide-based NF membrane not resistance to oxidation, antifouling property is poor, although the antifouling property of polysulfones NF membrane is due to polyamides
Amine, but antifouling property still has much room for improvement, and the preparation technology of Inorganic Nanofiltration Membranes is complex.Therefore, single in order to make up
Material NF membrane some shortcomings present in the separation process, prepare the material mixing of different materials and form composite nanometer filtering film,
To improve the combination property of NF membrane.
Supermolecule polymer is different from traditional polymer, and the repetitive of supermolecule polymer is reversible and directivity
Non-covalent interaction combine, supermolecule polymer can be divided into metallo-supramolecular polymers, π-π stacked, hydrogen bond
Type, ion-type and Combination, wherein metallo-supramolecular polymers is to have metal ion, organic or inorganic part and spacer units
Constitute, can improve electron transfer and transport process, the photosynthetic energy conversion etc. of polymer, at present physics, chemistry,
The field such as bio-medical, nanotechnology is commonly employed.Disclosed in Chinese patent CN 105032208A, one is based on metal
The novel blended gas separation membrane of supermolecule polymer, this separation film is with terpyridyl, polyethers triblock copolymer, slaine
It is primary raw material with polyether co-polyamide, first terpyridyl, catalyst, polyethers triblock copolymer is dissolved in dimethyl sulfoxide
In, under nitrogen atmosphere, add saturated aqueous common salt, be dried, add normal hexane, centrifugal drying obtains product, then with slaine, first
Alcohol reaction obtains metal supermolecular polymer, and metal supermolecular polymer and solvent, polyether co-polyamide are mixed to form formwork
Feed liquid, scrapes film forming through painting and is dried to obtain separation film.Metal supermolecular polymer is joined formation film material in preparation liquid by the method,
Preparation method is simple, but poor controllability.
LBL self-assembly is a kind of surface modification method simple, multi-functional, has been used to the preparation of NF membrane, preparation side
Method is divided into electrostatic method and dynamically sends out, and wherein dynamic method is under pressure, by oppositely charged by the way of filtration
Polyelectrolyte solution alternating deposit is in membrane surface, and compared with static method, the number of plies of NF membrane prepared by dynamic method is relatively low, preparation
Efficiency is high.But the most not yet there is research to be applied to by metal supermolecular polymer in the NF membrane of LBL self-assembly, the present invention
Applicant transition metal and double blank are bent metal supermolecular polymer self assembles prepared by oxalic acid in membrane surface, and at outermost
Layer one layer of graphene oxide of self assembly, prepares functional all good NF membrane.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene
And preparation method, alkali modification is processed polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafilter membrane is basement membrane, respectively by covalency sun from
In sub-polyelectrolyte solution and supermolecule polymer solution, pressurization is assembled in the surface of basement membrane, repeated several times, then is placed in baking oven
Middle heat treatment, obtains multilamellar supermolecule polymer NF membrane, finally molten for graphene oxide pressurization is assembled in outermost layer, obtains base
Self-assembled supermolecular polymer nano filter membrane in Graphene.NF membrane prepared by the present invention improves containing supermolecule polymer
The controllability of NF membrane, good separating effect, and preparation method are simply efficient, do not use organic solvent, environmental protection.
For solving above-mentioned technical problem, the technical scheme is that
A kind of self-assembled supermolecular polymer nano filter membrane based on Graphene, described self-assembled supermolecular based on Graphene
Polymer nano filter membrane includes basement membrane, supermolecule polymer composite bed and nano-particle outer layer, and described basement membrane is that alkali modification process is poly-
Acrylonitrile ultrafilter membrane or sulfonated polyether sulfone ultrafilter membrane, described supermolecule polymer composite bed is by supermolecule polymer layer and covalency sun
Cationic polyelectrolyte replaces self assembly and constitutes, and described nano-particle outer layer is made up of graphene oxide self assembly, described supermolecule
Polymer is bent oxalate ligand coordination and is constituted by transition metal ions and double blank.
Preferred as technique scheme, described transition metal ions be zinc ion, copper ion, cobalt ion, iron ion,
One or more in lanthanum ion and europium ion.
Preferred as technique scheme, described covalency cationic polyelectrolyte is polymine, polyvinylamine, poly-
Allyl ammonium chloride, poly-N, N-alkyl dimethyl ammonium chloride or chitosan.
The present invention also provides for the preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene, including with
Lower step:
(1) polymine, polyvinylamine, poly diallyldimethylammonium chloride, poly-N, N-alkyl dimethyl ammonium chloride or chitosan add
Enter in deionized water, be sufficiently stirred for, add sodium chloride, stir, obtain covalency cationic polyelectrolyte solution, wherein chlorination
The concentration of sodium is 0.5M, and pH value is 2.5-3.
(2) transition metal ion solution and double blank are bent oxalic acid solution mixing, with the pH value of buffer regulation mixed system
For 5-6, it is sufficiently stirred for obtaining supermolecule polymer solution；
(3) alkali modification is processed polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafilter membrane is basement membrane, basement membrane is fixed on one
In the individual container with porous support layer, face upward, then adds the poly-electricity of covalency cation prepared by step (1) in container
Electrolyte solution, pressurization assembling deionized water is fully washed, and obtains cation-modified film；
(4) cation-modified film prepared by step (3) is placed in supermolecule polymer solution prepared by step (2), adds
Pressure assembles, and fully washes with deionized water, is placed in heat treatment in baking oven, obtains bilayer modified film；
(5) bilayer modified film prepared by step (4) is placed in covalency cationic polyelectrolyte solution prepared by step (1),
Pressurization assembling deionized water is fully washed, then is placed in supermolecule polymer solution prepared by step (2), and pressurization assembles, and uses
Deionized water is fully washed, and repeats 1-4 time, obtains multilamellar supermolecule polymer NF membrane；
(6) multilamellar supermolecule polymer NF membrane step (5) prepared immerses in graphene oxide solution, pressurization group
Dress, fully washes with deionized water, is placed in heat treatment in baking oven, obtain self-assembled supermolecular polymer nanofiltration based on Graphene
Film.
Preferred as technique scheme, in described step (2), transition metal ions in transition metal ion solution
Concentration is 1-5mmol/L.
Preferred as technique scheme, in described step (2), in supermolecule polymer solution transition metal ions with
It is 1:1-2 that double blank bends the mol ratio of oxalic acid.
Preferred as technique scheme, in described step (3), the molecular cut off of basement membrane is 3-5 ten thousand.
Preferred as technique scheme, in described step (4), step (5) or step (6), the pressure that pressurization assembles
Strong is 0.1-0.8MPa, and the time that pressurization assembles is 5-30min, and the time of washing is 1-5min.
Preferred as technique scheme, in described step (4) or step (6), the temperature of heat treatment is 90-100
DEG C, the time is 1-5min.
Preferred as technique scheme, in described step (6), the concentration of graphene oxide solution is 0.01-
0.05mg/L。
Compared with prior art, the method have the advantages that
(1) method of self-assembled supermolecular polymer nano filter membrane based on the Graphene employing self assembly that prepared by the present invention will
Covalency cationic polyelectrolyte, supermolecule polymer and graphene oxide under the effect of static pressure by electrostatic force,
Hydrophobic force, the surface acting on basement membrane of hydrogen bond form supermolecule polymer composite bed and nano-particle outer layer, whole assemble
The solvent that journey uses is deionized water, does not use organic solvent, preparation process environmental protection, utilizes static self-assembly process
Preparation method is simple, and efficiency is high, and controllability is good, assembles the number of plies few, is suitable for actual production.
(2) self-assembled supermolecular polymer nano filter membrane transition metal ions based on Graphene prepared by the present invention is with double
The white supermolecule polymer bending oxalic acid coordination preparation replaces traditional anionic polyelectrolyte, expands the assembling material of NF membrane
Material, and supermolecule polymer has reversibility and the high degree of orientation compared with anionic polyelectrolyte, and due to supermolecule
Combining with weak secondary interaction between polymer, its structure and performance can change with the change of environmental stimuli, improve
The processability of NF membrane, response and self-healing properties, give the more added value of NF membrane, improve the economic valency of NF membrane
Value and range.
(3) outermost layer of self-assembled supermolecular polymer nano filter membrane based on Graphene prepared by the present invention is graphite oxide
Alkene nano-particle layer, graphene oxide has excellent mechanical performance, antibiotic property and permeability, is added to by graphene oxide and receive
In filter membrane, the flux of NF membrane can be improved, give NF membrane antibiotic property, improve the serviceability of NF membrane.
(4) graphene oxide and supermolecule polymer are applied in composite nanometer filtering film by the present invention, and utilize electrostatic from group
Installation prepares the composite nanometer filtering film that controllability is higher, preparation method simply, environmental protection, preparation based on Graphene
The separating property of self-assembled supermolecular polymer nano filter membrane and antifouling property are excellent, are suitable for plant produced and marketing.
Detailed description of the invention
The present invention is described in detail, in illustrative examples and the explanation of this present invention below in conjunction with specific embodiment
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1:
(1) during polymine adds deionized water, it is sufficiently stirred for, adds sodium chloride, stir, obtain mass fraction
Being the covalency cationic polyelectrolyte solution of 0.2%, wherein the concentration of sodium chloride is 0.5M, and pH value is 2.5.
(2) zinc ion transition metal ion solution and the double blank of 1mmol/L are bent oxalic acid solution mixing, wherein transition metal
It is 1:1 that ion and double blank bend the mol ratio of oxalic acid, is 5 with the pH value of buffer regulation mixed system, is sufficiently stirred for obtaining oversubscription
Sub-polymer solution.
(3) alkali modification that molecular cut off is 30,000 being processed polyacrylonitrile ultrafiltration film is basement membrane, and basement membrane is fixed on one
In container with porous support layer, face upward, then adds covalency cationic polyelectrolyte solution in container,
Under 0.1MPa, pressurization assembles 5min, fully washes 1min with deionized water, obtains cation-modified film.
(4) being placed in supermolecule polymer solution by cation-modified film, pressurization assembles 10min at 0.2 mpa, spends
Ionized water fully washes 2min, is placed in heat treatment 5min in the baking oven of 90 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, under 0.1MPa, pressurization assembles 5min, spends
Ionized water fully washes 1min, then is placed in supermolecule polymer solution, and pressurization assembles 10min at 0.2 mpa, uses deionization
Water fully washes 5min, is repeated 1 times, and obtains multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.01mg/L, under 0.4MPa
Pressurization assembles 5min, fully washes 1min with deionized water, is placed in heat treatment 1min in the baking oven of 90 DEG C, obtains based on Graphene
Self-assembled supermolecular polymer nano filter membrane.
Embodiment 2:
(1) during polyvinylamine adds deionized water, being sufficiently stirred for, add sodium chloride, stir, obtaining mass fraction is
The covalency cationic polyelectrolyte solution of 0.5%, wherein the concentration of sodium chloride is 0.5M, and pH value is 3.
(2) copper ion of 3mmol/L and cobalt ion transition metal ion solution and double blank are bent oxalic acid solution mixing, wherein
It is 1:2 that transition metal ions and double blank bend the mol ratio of oxalic acid, is 6 with the pH value of buffer regulation mixed system, is sufficiently stirred for
Obtain supermolecule polymer solution.
(3) it is basement membrane by the sulfonated polyether sulfone ultrafilter membrane that molecular cut off is 50,000, basement membrane is fixed on one with porous
In the container of supporting layer, face upward, then adds covalency cationic polyelectrolyte solution in container, pressurizes under 0.8MPa
Assemble 5min, fully wash 5min with deionized water, obtain cation-modified film.
(4) cation-modified film is placed in supermolecule polymer solution, under 0.4MPa pressurization assemble 5min, spend from
Sub-water fully washes 5min, is placed in heat treatment 1min in the baking oven of 100 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, under 0.8MPa, pressurization assembles 5min, spends
Ionized water fully washes 5min, then is placed in supermolecule polymer solution, and under 0.4MPa, pressurization assembles 5min, uses deionized water
Fully wash 5min, be repeated 2 times, obtain multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.05mg/L, at 0.2 mpa
Pressurization assembles 10min, fully washes 5min with deionized water, is placed in heat treatment 2min in the baking oven of 100 DEG C, obtains based on graphite
The self-assembled supermolecular polymer nano filter membrane of alkene.
Embodiment 3:
(1) during poly diallyldimethylammonium chloride adds deionized water, it is sufficiently stirred for, adds sodium chloride, stir, obtain quality
Mark is the covalency cationic polyelectrolyte solution of 0.3%, and wherein the concentration of sodium chloride is 0.5M, and pH value is 2.7.
(2) iron ion of 3.5mmol/L and lanthanum ion transition metal ion solution and double blank are bent oxalic acid solution mixing, its
It is 1:1.5 that middle transition metal ions and double blank bend the mol ratio of oxalic acid, is 5.4 with the pH value of buffer regulation mixed system, fills
Stirring is divided to obtain supermolecule polymer solution.
(3) alkali modification that molecular cut off is 40,000 being processed polyacrylonitrile ultrafiltration film is basement membrane, and basement membrane is fixed on one
In container with porous support layer, face upward, then adds covalency cationic polyelectrolyte solution in container,
Under 0.5MPa, pressurization assembles 10min, fully washes 3min with deionized water, obtains cation-modified film.
(4) being placed in supermolecule polymer solution by cation-modified film, under 0.3MPa, pressurization assembles 20min, spends
Ionized water fully washes 4min, is placed in heat treatment 5min in the baking oven of 90 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, pressurization assembles 30min at 0.2 mpa, uses
Deionized water fully washes 5min, then is placed in supermolecule polymer solution, under 0.4MPa pressurization assemble 10min, spend from
Sub-water fully washes 5min, is repeated 3 times, and obtains multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.02mg/L, under 0.3MPa
Pressurization assembles 5-30min, fully washes 4min with deionized water, is placed in heat treatment 2min in the baking oven of 90 DEG C, obtains based on stone
The self-assembled supermolecular polymer nano filter membrane of ink alkene.
Embodiment 4:
(1) poly-N, N-alkyl dimethyl ammonium chloride adds in deionized water, is sufficiently stirred for, and adds sodium chloride, stirs, obtain
Mass fraction is the covalency cationic polyelectrolyte solution of 0.4%, and wherein the concentration of sodium chloride is 0.5M, and pH value is 2.5.
(2) zinc ion of 4mmol/L and europium ion transition metal ion solution and double blank are bent oxalic acid solution mixing, wherein
It is 1:1 that transition metal ions and double blank bend the mol ratio of oxalic acid, is 6 with the pH value of buffer regulation mixed system, is sufficiently stirred for
Obtain supermolecule polymer solution.
(3) it is basement membrane by the sulfonated polyether sulfone ultrafilter membrane that molecular cut off is 50,000, basement membrane is fixed on one with porous
In the container of supporting layer, face upward, then adds covalency cationic polyelectrolyte solution in container, pressurizes under 0.3MPa
Assemble 15min, fully wash 5min with deionized water, obtain cation-modified film.
(4) being placed in supermolecule polymer solution by cation-modified film, under 0.3MPa, pressurization assembles 10min, spends
Ionized water fully washes 2min, is placed in heat treatment 2min in the baking oven of 100 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, under 0.3MPa, pressurization assembles 15min, uses
Deionized water fully washes 2min, then is placed in supermolecule polymer solution, under 0.3MPa pressurization assemble 10min, spend from
Sub-water fully washes 2min, is repeated 2 times, and obtains multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.03mg/L, under 0.3MPa
Pressurization assembles 10min, fully washes 4min with deionized water, is placed in heat treatment 2min in the baking oven of 100 DEG C, obtains based on graphite
The self-assembled supermolecular polymer nano filter membrane of alkene.
Embodiment 5:
(1) during chitosan adds deionized water, being sufficiently stirred for, add sodium chloride, stir, obtaining mass fraction is
The covalency cationic polyelectrolyte solution of 0.4%, wherein the concentration of sodium chloride is 0.5M, and pH value is 3.
(2) zinc ion of 4mmol/L and lanthanum ion transition metal ion solution and double blank are bent oxalic acid solution mixing, wherein
It is 1:2 that transition metal ions and double blank bend the mol ratio of oxalic acid, is 5 with the pH value of buffer regulation mixed system, is sufficiently stirred for
Obtain supermolecule polymer solution.
(3) alkali modification that molecular cut off is 30,000 being processed polyacrylonitrile ultrafiltration film is basement membrane, and basement membrane is fixed on one
In container with porous support layer, face upward, then adds covalency cationic polyelectrolyte solution in container,
Under 0.5MPa, pressurization assembles 20min, fully washes 5min with deionized water, obtains cation-modified film.
(4) being placed in supermolecule polymer solution by cation-modified film, under 0.5MPa, pressurization assembles 15min, spends
Ionized water fully washes 5min, is placed in heat treatment 3min in the baking oven of 95 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, under 0.7MPa, pressurization assembles 20min, uses
Deionized water fully washes 5min, then is placed in supermolecule polymer solution, under 0.5MPa pressurization assemble 10min, spend from
Sub-water fully washes 5min, is repeated 3 times, and obtains multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.05mg/L, under 0.3MPa
Pressurization assembles 10min, fully washes 5min with deionized water, is placed in heat treatment 5min in the baking oven of 100 DEG C, obtains based on graphite
The self-assembled supermolecular polymer nano filter membrane of alkene.
Embodiment 6:
(1) during polymine adds deionized water, it is sufficiently stirred for, adds sodium chloride, stir, obtain mass fraction
Being the covalency cationic polyelectrolyte solution of 0.3%, wherein the concentration of sodium chloride is 0.5M, and pH value is 3.
(2) cobalt ion of 3mmol/L and iron ion transition metal ion solution and double blank are bent oxalic acid solution mixing, wherein
It is 1:2 that transition metal ions and double blank bend the mol ratio of oxalic acid, is 6 with the pH value of buffer regulation mixed system, is sufficiently stirred for
Obtain supermolecule polymer solution.
(3) it is basement membrane by the sulfonated polyether sulfone ultrafilter membrane that molecular cut off is 3-5 ten thousand, basement membrane is fixed on one with many
In the container of hole supporting layer, face upward, then adds covalency cationic polyelectrolyte solution in container, adds under 0.4MPa
Pressure assembles 15min, fully washes 5min with deionized water, obtains cation-modified film.
(4) cation-modified film is placed in supermolecule polymer solution, under 0.4MPa pressurization assemble 5min, spend from
Sub-water fully washes 2min, is placed in heat treatment 5min in the baking oven of 100 DEG C, obtains bilayer modified film.
(5) bilayer modified film being placed in covalency cationic polyelectrolyte solution, under 0.6MPa, pressurization assembles 10min, uses
Deionized water fully washes 5min, then is placed in supermolecule polymer solution, under 0.5MPa pressurization assemble 20min, spend from
Sub-water fully washes 3min, is repeated 1 times, and obtains multilamellar supermolecule polymer NF membrane.
(6) multilamellar supermolecule polymer NF membrane is immersed in the graphene oxide solution of 0.04mg/L, under 0.1MPa
Pressurization assembles 30min, fully washes 2min with deionized water, is placed in heat treatment 1min in the baking oven of 100 DEG C, obtains based on graphite
The self-assembled supermolecular polymer nano filter membrane of alkene.
The separating property of self-assembled supermolecular polymer nano filter membrane based on Graphene prepared by embodiment 1-6 uses cross-flow
Formula film evaluates instrument and conductivity meter test, and test temperature is room temperature, and test pressure is 0.6MPa.
Self-assembled supermolecular polymer nano based on Graphene filter permeability of the membrane prepared by embodiment 1-6 is used under the conditions of being somebody's turn to do
Water flux or the saline solution flux of film characterize.
The selective penetrated property film of self-assembled supermolecular polymer nano filter membrane based on Graphene prepared by embodiment 1-6 divides
In the other sodium chloride to 1000mg/L, magnesium chloride, sodium sulfate and Adlerika, the removal efficiency of salt characterizes.
Antibiotic property, the separation property of self-assembled supermolecular polymer nano filter membrane based on Graphene prepared by embodiment 1-6, ooze
The result of property and selective penetrated property is as follows thoroughly:
As seen from the above table, the antibiotic property of self-assembled supermolecular polymer nano filter membrane based on Graphene prepared by the present invention
Good, more preferable to the removal efficiency of high valence ion, flux is good, and Selective Separation is effective.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause
This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art
All equivalences become are modified or change, and must be contained by the claim of the present invention.
Claims (10)
1. a self-assembled supermolecular polymer nano filter membrane based on Graphene, it is characterised in that: described based on Graphene from
Assembling supermolecule polymer NF membrane and include basement membrane, supermolecule polymer composite bed and nano-particle outer layer, described basement membrane is alkali
Modification polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafilter membrane, described supermolecule polymer composite bed is by supermolecule polymer
Layer and covalency cationic polyelectrolyte replace self assembly and constitute, and described nano-particle outer layer is made up of graphene oxide self assembly,
Described supermolecule polymer is bent oxalate ligand coordination and is constituted by transition metal ions and double blank.
A kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 1, it is characterised in that:
Described transition metal ions is one or more in zinc ion, copper ion, cobalt ion, iron ion, lanthanum ion and europium ion.
A kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 1, it is characterised in that:
Described covalency cationic polyelectrolyte is polymine, polyvinylamine, poly diallyldimethylammonium chloride, poly-N, N-alkyl dimethyl ammonium chloride
Or chitosan.
4. the preparation method of a self-assembled supermolecular polymer nano filter membrane based on Graphene, it is characterised in that include following
Step:
(1) polymine, polyvinylamine, poly diallyldimethylammonium chloride, poly-N, N-alkyl dimethyl ammonium chloride or chitosan addition are gone
In ionized water, it is sufficiently stirred for, adds sodium chloride, stir, obtain covalency cationic polyelectrolyte solution, wherein sodium chloride
Concentration is 0.5M, and pH value is 2.5-3；
(2) transition metal ion solution and double blank are bent oxalic acid solution mixing, is 5-with the pH value of buffer regulation mixed system
6, it is sufficiently stirred for obtaining supermolecule polymer solution；
(3) alkali modification is processed polyacrylonitrile ultrafiltration film or sulfonated polyether sulfone ultrafilter membrane is basement membrane, basement membrane is fixed on a band
Having in the container of porous support layer, face upward, then adds covalency cationic polyelectrolyte prepared by step (1) in container
Solution, pressurization assembling deionized water is fully washed, and obtains cation-modified film；
(4) cation-modified film prepared by step (3) is placed in supermolecule polymer solution prepared by step (2), pressurization group
Dress, fully washes with deionized water, is placed in heat treatment in baking oven, obtain bilayer modified film；
(5) bilayer modified film prepared by step (4) is placed in covalency cationic polyelectrolyte solution prepared by step (1), pressurization
Assembling deionized water is fully washed, then is placed in supermolecule polymer solution prepared by step (2), pressurization assemble, spend from
Sub-water is fully washed, and repeats 1-4 time, obtains multilamellar supermolecule polymer NF membrane；
(6) multilamellar supermolecule polymer NF membrane step (5) prepared immerses in graphene oxide solution, and pressurization assembles, and uses
Deionized water is fully washed, and is placed in heat treatment in baking oven, obtains self-assembled supermolecular polymer nano filter membrane based on Graphene.
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (2), in transition metal ion solution, the concentration of transition metal ions is 1-5mmol/L.
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (2), in supermolecule polymer solution, transition metal ions and double blank are bent the mol ratio of oxalic acid and are
1:1-2。
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (3), the molecular cut off of basement membrane is 3-5 ten thousand.
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (4), step (5) or step (6), the pressure that pressurization assembles is 0.1-0.8MPa, pressurization group
The time of dress is 5-30min, and the time of washing is 1-5min.
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (4) or step (6), the temperature of heat treatment is 90-100 DEG C, and the time is 1-5min.
The preparation method of a kind of self-assembled supermolecular polymer nano filter membrane based on Graphene the most according to claim 4,
It is characterized in that: in described step (6), the concentration of graphene oxide solution is 0.01-0.05mg/L.
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