CN110075710A - A kind of preparation method of graphene oxide nanofiltration membrane - Google Patents
A kind of preparation method of graphene oxide nanofiltration membrane Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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Abstract
The invention discloses a kind of preparation methods of graphene oxide nanofiltration membrane；Graphene oxide water solution is prepared first；Amine monomers are added in graphene oxide water solution, and the aqueous casting solution of graphene oxide is made；Using high molecular polymer ultrafiltration membrane as basement membrane, using surface application methods on basement membrane one layer of aqueous casting solution of graphene oxide of dip-coating, one layer of dip-coating oily phase again, make the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, dry 5~10h can be prepared by graphene oxide nanofiltration membrane at 60~100 DEG C.In graphene oxide nanofiltration membrane produced by the present invention, the micron-sized lamella of graphene interlocks in parallel, form the hole that fine and close filter layer covers all support membrane, filtered fluid cross-flow filtration, impurity is deposited in surface, cleaning effect can be reached after parallel flushing, so that nanofiltration membrane has excellent filter capacity, durability against pollution, and then significantly improve service life.
Description
Technical field
The present invention relates to nanofiltration membrane preparation technical fields, and in particular to a kind of preparation method of graphene oxide nanofiltration membrane.
Background technique
Nanofiltration-membrane technique is as a kind of novel membrane separation technique in water treatment field, petroleum, chemical industry, food, biology and doctor
Separation, purifying and the concentration of medicine industry substance, the fields such as removing of Industry Waste Organic substance in water have a wide range of applications.It receives
The preparation method of filter membrane mainly has L-S phase inversion, blending method, lotus electrochemical process and composite algorithm, using most and effective preparation
The method of nanofiltration membrane is composite algorithm, and traditional interfacial polymerization is the method being most widely used in composite algorithm.Interfacial polymerization
Although method preparation nanofiltration membrane have many advantages, such as flux height, rejection it is high, due to film surface hydrophobicity, film surface roughness and
Basement membrane and functional layer interaction etc. reasons, make nanofiltration membrane antipollution and in terms of existing defects, lead to film properties
Sharp fall, also shortens the service life of composite membrane, seriously constrains the application and development of composite nanometer filtering film.
By the retrieval discovery to existing patent document, application No. is 201710134251.2 Chinese invention patent applications
Disclose a kind of quaternary ammoniated graphene oxide composite nano filter membrane and preparation method thereof.The following steps are included: (1) aminated oxidation stone
The preparation of black alkene solution: aminated reagent is dispersed in graphene oxide solution, and it is molten that aminated graphene oxide is made
Liquid；(2) pressure aided filter method prepares aminated graphene oxide composite nano filter membrane: using high molecular polymer ultrafiltration membrane as base
Film, by the filtering of aminated graphene oxide solution on ultrafiltration membranes, preparation functional layer is the compound of aminated graphene oxide
Nanofiltration membrane；(3) cross-linking method prepares quaternary ammoniated graphene oxide composite nano filter membrane: aminated graphene oxide composite nano filter membrane is soaked
Bubble reacts in cross-linking agent solution, adjusts reaction temperature, and quaternary ammoniated graphene oxide composite nano filter membrane is made in reaction in-situ.This is multiple
It closes nanofiltration membrane and is provided simultaneously with positive charge and negative electrical charge, have high throughput, improve the cutoff performance to high-valence cationic.However,
The micron-sized lamella distributing homogeneity of graphene is not good enough in the aminated graphene oxide composite nano filter membrane, miscellaneous after filtrate
Matter is easy to be deposited in uneven place, influences the permeability and filter capacity of film itself, and influences service life.
Summary of the invention
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, a kind of graphene oxide nanofiltration membrane is provided
Preparation method.Graphene oxide nanofiltration membrane produced by the present invention has excellent anti-pollution characteristic, and to chemical engineering sewages such as dyestuffs
With high rejection.
The purpose of the present invention is achieved through the following technical solutions:
The present invention relates to a kind of preparation methods of graphene oxide nanofiltration membrane, and described method includes following steps:
The preparation of S1, graphene oxide water solution: using expansible graphite as raw material, the concentrated sulfuric acid, potassium permanganate, peroxide are added
Change hydrogen solution, graphene oxide water solution is obtained with modified Hummmers legal system；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared；
The preparation of S3, graphene oxide composite nano filter membrane: it using high molecular polymer ultrafiltration membrane as basement membrane, is applied using surface
Method one layer of aqueous casting solution of graphene oxide of dip-coating on basement membrane, time of immersion are 1~5min；One layer of dip-coating oily phase again, dip-coating
Time is 1~30min, makes the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, at 60~100 DEG C
Dry 5~10h can be prepared by graphene oxide nanofiltration membrane.
Preferably, in step S1, graphene oxide water solution passes through low-temp reaction, three medium temperature reaction, pyroreaction ranks
Section is prepared；The preparation includes the following steps:
(1) low-temp reaction: in -5~0 DEG C of ice-water bath, the concentrated sulfuric acid and height that are successively 97~99% by mass fraction
Potassium manganate is added in expansible graphite and stirs evenly, and reaction keeps 1.6~2.5h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 30~40 DEG C, is added after temperature is stablized super
Pure water dilution, reacts 4~6h, and solution is in sepia；
(3) pyroreaction: being heated to 105~120 DEG C in step (2) acquired solution water bath with thermostatic control, keep 45~
Then hydrogenperoxide steam generator is added in 60min, be cooled to room temperature, and solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration golden yellow paste colloid to step (3) acquired solution, washes through pickling, deionization
It washs to solution and is in neutrality, ultrasonic disperse obtains golden solution in ultrapure water, is placed in 40~60 DEG C of baking oven dry be made
Graphene oxide powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 0.5~300mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,.
It is further preferred that graphene oxide water solution concentration is 30~300mg/L.
Preferably, in step S1, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be
1:0.8~1.2:2.8~3.2:2.5~3.5；The mass concentration of the hydrogenperoxide steam generator is 28~32%.
Preferably, in step S3, the high molecular polymer of the high molecular polymer ultrafiltration membrane is polysulfones, polyether sulfone, gathers
Acrylonitrile, polypropylene, polyethylene, Kynoar, cellulose acetate class, Polyurethane, polyvinyl chloride, polycaprolactam or poly- furan
It mutters alcohol.
Preferably, in step S2, the amine monomers are m-xylene diamine, anthranilamide, phenylenediamine, benzoyl
The compounding of one or more of amine, 2- aminobenzamide.
Preferably, in step S2, the mass fraction of graphene oxide is 1~10% in the aqueous casting solution of graphene oxide.
Preferably, in step S2, solvent is water or ethyl alcohol.
Preferably, in step S3, oil is mutually pyromellitic trimethylsilyl chloride/hexane solution, and the concentration of pyromellitic trimethylsilyl chloride is
0.07~0.15g/100mL.
Preferably, molar concentration of the amine monomers in the aqueous casting solution of graphene oxide is with pyromellitic trimethylsilyl chloride in oily phase
In the ratio between molar concentration be 0.5~1.3:1.The ratio is that the micron-sized lamella of graphene interlocks in parallel, forms fine and close mistake
One of key parameter of filtering layer.
Compared with prior art, beneficial effects of the present invention are as follows:
In graphene oxide nanofiltration membrane produced by the present invention, graphene oxide has good hydrophily, and graphene
Micron-sized lamella interlocks in parallel, forms the hole that fine and close filter layer covers all support membrane, and filtered fluid cross-flow filtration is miscellaneous
Matter is deposited in surface, can reach cleaning effect after parallel flushing, will not influence the permeability and filter capacity of film itself,
Reach resistant effect, prolong the service life, chemical industry, medicine, sea water desalination and regeneration effluent process field can be widely used in, had
Good application prospect.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to a kind of preparation method of graphene oxide nanofiltration membrane, specifically comprises the following steps:
The preparation of S1, graphene oxide water solution:
(1) low-temp reaction: in -2 DEG C of ice-water bath, successively mass fraction is added for 98% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 2h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 35 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 5h, and solution is in sepia；
(3) pyroreaction: being heated to 115 DEG C in step (2) acquired solution water bath with thermostatic control, keep 50min, then plus
Enter the hydrogenperoxide steam generator that mass concentration is 30%, be cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration brown pasty colloid to step (3) acquired solution, washs through pickling, deionized water
It is in neutrality to solution, ultrasonic disperse obtains brown solution in ultrapure water, is placed in 50 DEG C of baking oven dry obtained graphite oxide
Alkene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 150mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,；
In above-mentioned steps, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:1:
3:3；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared in (m-xylene diamine)；Graphene oxide in the aqueous casting solution of the graphene oxide
Mass fraction is 5%；Molar concentration of the amine monomers in the aqueous casting solution of graphene oxide is with pyromellitic trimethylsilyl chloride in oily phase
In the ratio between molar concentration be 1:1；
The preparation of S3, graphene oxide composite nano filter membrane: it using high molecular polymer (polyether sulfone) ultrafiltration membrane as basement membrane, uses
Surface application methods one layer of aqueous casting solution of graphene oxide of dip-coating, time of immersion 3min on basement membrane；One layer of dip-coating oily phase again
(pyromellitic trimethylsilyl chloride/hexane solution, wherein the concentration of pyromellitic trimethylsilyl chloride is 0.1g/100mL), time of immersion 15min,
Make the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, dry 8h can be prepared by oxidation stone at 80 DEG C
Black alkene nanofiltration membrane.
Embodiment 2
The present embodiment is related to a kind of preparation method of graphene oxide nanofiltration membrane, specifically comprises the following steps:
The preparation of S1, graphene oxide water solution:
(1) low-temp reaction: in -1 DEG C of ice-water bath, successively mass fraction is added for 98% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 1.8h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 38 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 4.5h, and solution is in sepia；
(3) pyroreaction: being heated to 110 DEG C in step (2) acquired solution water bath with thermostatic control, keep 55min, then plus
Enter the hydrogenperoxide steam generator that mass concentration is 30%, be cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration brown pasty colloid to step (3) acquired solution, washs through pickling, deionized water
It is in neutrality to solution, ultrasonic disperse obtains brown solution in ultrapure water, is placed in 52 DEG C of baking oven dry obtained graphite oxide
Alkene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 30mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,；
In above-mentioned steps, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:1:
3:3；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared in (anthranilamide)；Graphite oxide in the aqueous casting solution of the graphene oxide
The mass fraction of alkene is 6%；Molar concentration and pyromellitic trimethylsilyl chloride of the amine monomers in the aqueous casting solution of graphene oxide exist
The ratio between molar concentration in oily phase is 0.9:1；
The preparation of S3, graphene oxide composite nano filter membrane: using high molecular polymer (Kynoar) ultrafiltration membrane as basement membrane,
Using surface application methods on basement membrane one layer of aqueous casting solution of graphene oxide of dip-coating, time of immersion 2min；One layer of dip-coating again
Oily phase (pyromellitic trimethylsilyl chloride/hexane solution, wherein the concentration of pyromellitic trimethylsilyl chloride is 0.11g/100mL), time of immersion is
20min makes the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, and dry 8.5h can make at 85 DEG C
Obtain graphene oxide nanofiltration membrane.
Embodiment 3
The present embodiment is related to a kind of preparation method of graphene oxide nanofiltration membrane, specifically comprises the following steps:
The preparation of S1, graphene oxide water solution:
(1) low-temp reaction: in -5 DEG C of ice-water bath, successively mass fraction is added for 99% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 2.5h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 40 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 4h, and solution is in sepia；
(3) pyroreaction: being heated to 105 DEG C in step (2) acquired solution water bath with thermostatic control, keep 60min, then plus
Enter the hydrogenperoxide steam generator that mass concentration is 28%, be cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration brown pasty colloid to step (3) acquired solution, washs through pickling, deionized water
It is in neutrality to solution, ultrasonic disperse obtains brown solution in ultrapure water, is placed in 60 DEG C of baking oven dry obtained graphite oxide
Alkene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 0.5mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,；
In above-mentioned steps, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:
0.8:2.8:2.5；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared in (2- aminobenzamide)；Graphite oxide in the aqueous casting solution of the graphene oxide
The mass fraction of alkene is 1%；Molar concentration and pyromellitic trimethylsilyl chloride of the amine monomers in the aqueous casting solution of graphene oxide exist
The ratio between molar concentration in oily phase is 0.5:1；
The preparation of S3, graphene oxide composite nano filter membrane: it, as basement membrane, is adopted using high molecular polymer (poly- furan alcohol) ultrafiltration membrane
With surface application methods on basement membrane one layer of aqueous casting solution of graphene oxide of dip-coating, time of immersion 5min；One layer of oil of dip-coating again
Phase (pyromellitic trimethylsilyl chloride/hexane solution, wherein the concentration of pyromellitic trimethylsilyl chloride is 0.15g/100mL), time of immersion is
30min makes the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, and dry 10h can make at 60 DEG C
Obtain graphene oxide nanofiltration membrane.
Embodiment 4
The present embodiment is related to a kind of preparation method of graphene oxide nanofiltration membrane, specifically comprises the following steps:
The preparation of S1, graphene oxide water solution:
(1) low-temp reaction: in 0 DEG C of ice-water bath, successively mass fraction is added for 97% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 1.6h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 30 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 6h, and solution is in sepia；
(3) pyroreaction: being heated to 120 DEG C in step (2) acquired solution water bath with thermostatic control, keep 45min, then plus
Enter the hydrogenperoxide steam generator that mass concentration is 32%, be cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration brown pasty colloid to step (3) acquired solution, washs through pickling, deionized water
It is in neutrality to solution, ultrasonic disperse obtains brown solution in ultrapure water, is placed in 40 DEG C of baking oven dry obtained graphite oxide
Alkene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 300mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,；
In above-mentioned steps, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:
1.2:3.2:3.5；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared in (benzamide)；The matter of graphene oxide in the aqueous casting solution of the graphene oxide
Measuring score is 10%；Molar concentration of the amine monomers in the aqueous casting solution of graphene oxide is with pyromellitic trimethylsilyl chloride in oily phase
The ratio between molar concentration be 1.3:1；
The preparation of S3, graphene oxide composite nano filter membrane: it using high molecular polymer (polyvinyl chloride) ultrafiltration membrane as basement membrane, adopts
With surface application methods on basement membrane one layer of aqueous casting solution of graphene oxide of dip-coating, time of immersion 1min；One layer of oil of dip-coating again
Phase (pyromellitic trimethylsilyl chloride/hexane solution, wherein the concentration of pyromellitic trimethylsilyl chloride is 0.07g/100mL), time of immersion is
1min makes the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, and dry 5h can be prepared by 100 DEG C
Graphene oxide nanofiltration membrane.
Embodiment 5
The present embodiment is related to a kind of preparation method of graphene oxide nanofiltration membrane, specifically comprises the following steps:
The preparation of S1, graphene oxide water solution:
(1) low-temp reaction: in -2 DEG C of ice-water bath, successively mass fraction is added for 98% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 1.8；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 32 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 4.5h, and solution is in sepia；
(3) pyroreaction: being heated to 112 DEG C in step (2) acquired solution water bath with thermostatic control, keep 48min, then plus
Enter the hydrogenperoxide steam generator that mass concentration is 30%, be cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration brown pasty colloid to step (3) acquired solution, washs through pickling, deionized water
It is in neutrality to solution, ultrasonic disperse obtains brown solution in ultrapure water, is placed in 50 DEG C of baking oven dry obtained graphite oxide
Alkene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphite oxide
Aqueous solution, it is 200mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,；
In above-mentioned steps, the expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:
1.1:3.1:3.5；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers are added in Yu Suoshu graphene oxide water solution
The aqueous alkene casting solution of graphite oxide is prepared in (phenylenediamine)；The quality of graphene oxide in the aqueous casting solution of the graphene oxide
Score is 7%；Molar concentration of the amine monomers in the aqueous casting solution of graphene oxide is with pyromellitic trimethylsilyl chloride in oily phase
The ratio between molar concentration is 0.8:1；
The preparation of S3, graphene oxide composite nano filter membrane: using high molecular polymer (polycaprolactam) ultrafiltration membrane as basement membrane,
Using surface application methods on basement membrane one layer of aqueous casting solution of graphene oxide of dip-coating, time of immersion 2.5min；Dip-coating one again
The oily phase of layer (pyromellitic trimethylsilyl chloride/hexane solution, wherein the concentration of pyromellitic trimethylsilyl chloride is 0.1g/100mL), time of immersion is
18min makes the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, and dry 7h can be prepared by 85 DEG C
Graphene oxide nanofiltration membrane.
Comparative example 1
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
The amine monomers of addition are ethylenediamine.
Comparative example 2
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
The amine monomers of addition are N, N- dimethyl-ethylenediamine.
Comparative example 3
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
The amine monomers of addition are N, N- dibutyl ethylenediamine.
Comparative example 4
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
The oil of selection is mutually for two benzyl chlorides/hexane solution.
Comparative example 5
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
The oil of selection is mutually for two benzyl chlorides/n-heptane solution.
Comparative example 6
This comparative example is related to a kind of preparation method of graphene oxide nanofiltration membrane, and specific steps are substantially with embodiment 1, and institute is not
It is with place:
It is reacted in the preparation of graphene oxide water solution without medium temperature, it may be assumed that
(1) low-temp reaction: in -2 DEG C of ice-water bath, successively mass fraction is added for 98% concentrated sulfuric acid and potassium permanganate
It adds in expansible graphite and stirs evenly, reaction keeps 2h；
(2) pyroreaction: being heated to 115 DEG C for bath temperature in step (1), it is added after temperature is stablized ultrapure
Water dilution, reacts 5h, and solution is in sepia；
(3) hydrogenperoxide steam generator that mass concentration is 30% is then added, is cooled to room temperature, solution is gold by brown stain
Yellow.
Graphene oxide nanofiltration membrane made from the above various embodiments and comparative example is subjected to pure water on nanofiltration membrane evaluation instrument
Flux, desalting performance and service life test, test condition are as follows: feed velocity 5m/s, operating pressure 1MPa, respectively with pure
The Adlerika of water, the metabisulfite solution of 2000ppm and 2000ppm is tested；Also, using the sodium sulphate of 2000ppm
Solution retest is repeated to 60% that salt rejection rate is initial salt rejection rate, the as corresponding number of service life；As a result such as table 1
It is shown:
Table 1
As shown in Table 1, amine monomers are ethylenediamine, N, N- dimethyl-ethylenediamine, N, the comparative example of N- dibutyl ethylenediamine
1,2,3 filter capacity, service life are significantly lower than embodiment 1；It and is that preparation graphene oxide water solution is reacted using medium temperature
Filter capacity, the service life of comparative example 6 be also significantly lower than embodiment 1.In fact, graphene oxide is aqueous in the present invention
The preparation of casting solution is crucial；The present invention is by selecting specific low-temp reaction, medium temperature reaction, the preparation of pyroreaction three phases
Graphene oxide water solution is obtained, and adds m-xylene diamine, anthranilamide, phenylenediamine, benzamide, 2- wherein
The compounding monomer of one or more of aminobenzamide is modified, so that in final graphene oxide nanofiltration membrane obtained
The micron-sized lamella of graphene interlocks in parallel, and filtered fluid cross-flow filtration, impurity is deposited in surface, can reach after parallel flushing
Cleaning effect；So that graphene oxide nanofiltration membrane has excellent permeability and filter capacity, more for excellent use
Service life.In addition, the selection of oily phase be also in graphene oxide nanofiltration membrane the micron-sized lamella of graphene can be interspersed in parallel
Another key point；As oily mutually for two benzyl chlorides/hexane solution comparative example 4, oil is mutually for two benzyl chlorides/n-heptane solution
Comparative example 5, corresponding filter capacity, service life be significantly lower than each embodiment.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (8)
1. a kind of preparation method of graphene oxide nanofiltration membrane, which is characterized in that described method includes following steps:
The preparation of S1, graphene oxide water solution: using expansible graphite as raw material, the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide are added
Solution obtains graphene oxide water solution with modified Hummmers legal system；
The preparation of the aqueous Casting solution of S2, graphene oxide: amine monomers preparation is added in the graphene oxide water solution
Obtain the aqueous casting solution of graphene oxide；
The preparation of S3, graphene oxide composite nano filter membrane: using high molecular polymer ultrafiltration membrane as basement membrane, existed using surface application methods
One layer of aqueous casting solution of graphene oxide of dip-coating on basement membrane, time of immersion are 1~5min；One layer of dip-coating oily phase again, time of immersion
For 1~30min, make the aqueous casting solution of graphene oxide and oil phase monomer that interface polymerization reaction occur, it is dry at 60~100 DEG C
5~10h can be prepared by graphene oxide nanofiltration membrane.
2. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that in step S1, oxidation
Graphene aqueous solution is prepared by low-temp reaction, medium temperature reaction, pyroreaction three phases；Specifically comprise the following steps:
(1) low-temp reaction: in -5~0 DEG C of ice-water bath, the concentrated sulfuric acid and permanganic acid that are successively 97~99% by mass fraction
Potassium is added in expansible graphite and stirs evenly, and reaction keeps 1.6~2.5h；
(2) medium temperature is reacted: bath temperature in step (1) being heated to 30~40 DEG C, adds ultrapure water after temperature is stablized
Dilution, reacts 4~6h, and solution is in sepia；
(3) pyroreaction: being heated to 105~120 DEG C in step (2) acquired solution water bath with thermostatic control, keep 45~60min,
Then hydrogenperoxide steam generator is added, is cooled to room temperature, solution is golden yellow by brown stain；
(4) washing filtering: being obtained by filtration golden yellow paste colloid to step (3) acquired solution, through pickling, deionized water wash to
Solution is in neutrality, and ultrasonic disperse obtains golden solution in ultrapure water, is placed in 40~60 DEG C of baking oven dry be made and is aoxidized
Graphene powder；
(5) graphene oxide powder obtained in step (4) is subjected in ultrapure water ultrasonic disperse and obtains graphene oxide water
Solution, it is 0.5~300mg/L that addition ultrapure water, which is diluted to graphene oxide water solution concentration,.
3. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that described in step S1
Expansible graphite, the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator amount ratio be 1:0.8~1.2:2.8~3.2:2.5~
3.5；The mass concentration of the hydrogenperoxide steam generator is 28~32%.
4. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that described in step S3
The high molecular polymer of high molecular polymer ultrafiltration membrane is polysulfones, polyether sulfone, polyacrylonitrile, polypropylene, polyethylene, polyvinylidene fluoride
Alkene, cellulose acetate class, Polyurethane, polyvinyl chloride, polycaprolactam or poly- furan alcohol.
5. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that described in step S2
Amine monomers be one of m-xylene diamine, anthranilamide, phenylenediamine, benzamide, 2- aminobenzamide or
Several compoundings.
6. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that in step S2, oxidation
The mass fraction of graphene oxide is 1~10% in the aqueous casting solution of graphene.
7. the preparation method of graphene oxide nanofiltration membrane according to claim 1, which is characterized in that in step S3, oily phase
For pyromellitic trimethylsilyl chloride/hexane solution, the concentration of pyromellitic trimethylsilyl chloride is 0.07~0.15g/100mL.
8. the preparation method of graphene oxide nanofiltration membrane according to claim 7, which is characterized in that amine monomers are aoxidizing
The ratio between the molar concentration of molar concentration with pyromellitic trimethylsilyl chloride in oily phase in the aqueous casting solution of graphene is 0.5~1.3:1.
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Application publication date: 20190802 |