CN103736400A - Preparation method of graphene oxide composite nano filter membrane - Google Patents
Preparation method of graphene oxide composite nano filter membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphene oxide composite nano filter membrane, and belongs to the technical field of separation membrane preparation. The preparation method of the graphene oxide composite nano filter membrane comprises the following steps: (1) preparing a graphene oxide water liquid; (2) preparing a graphene oxide cross linking liquid; and (3) preparing the graphene oxide composite nano filter membrane. The graphene oxide composite nano filter membrane provided by the invention has the characteristics that the surface of the membrane has a great deal of free carboxyl and hydroxy, the hydrophilicity is high, the flux is high, meanwhile, the charge on the surface of the membrane is negative, the salt cutting ratio is effectively improved, the flux and a desalting effect of the nano filter membrane are remarkably improved, and the graphene oxide composite nano filter membrane has the good large-scale industrialized application prospects.
Description
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Technical field
The present invention relates to a kind of preparation method of graphene oxide composite nanometer filtering film, belong to diffusion barrier preparing technical field.
background technology
Nanofiltration is a kind of novel membrane separation technique, and between counter-infiltration and ultrafiltration, aperture, within the scope of nanoscale, is generally 0.5-2.0nm.The preparation method of NF membrane mainly contains composite algorithm, phase inversion, lotus electrochemical process and blending method etc. at present, and wherein composite algorithm comprises surperficial coating process and interfacial polymerization.Composite algorithm be use at most at present, the most effective NF membrane preparation method, be also the method that production commercialization NF membrane kind is maximum, output is maximum.The method is the ultrathin functional layer at ultrafiltration or the compound last layer of micro-filtration membrane surface with nanoscale aperture.The advantage of composite membrane is can choose different materials to produce basement membrane and composite bed, makes their performance reach respectively optimization, the selection permeability that wherein ultrathin functional layer can be realized ideal, and supporting layer can reach best intensity and pressure tightness.
CMC is formed with chloroacetate reaction under proper condition by shitosan, has good water-soluble, film forming, emulsibility, and due to contain in its molecule～OH ,～NH
2,～the groups such as COOH, the more effective chemical modification of carrying out of energy, is therefore widely used in the fields such as film separation, food, pharmacy, papermaking.
Graphene is the Two-dimensional Carbon atomic crystal of monatomic thickness, since 2004 are found, just with its unique chemical constitution and good electricity, optics, calorifics and mechanical performance, has attracted the extensive concern of scientific circles.Graphene oxide had both had the monolayer honeycomb shape hexaplanar structure of Graphene, contained again a large amount of functional groups, as-OH ,-COOH ,-O-, C=O etc., therefore there is good dispersiveness, hydrophily, with the compatibility of polymer etc.At present, graphene oxide has become preparation and the modification of a kind of novel interpolation material for separating of film.In the world graphene oxide is adopted to the conventional film material blend such as graphene oxide and polytetrafluoroethylene (PTFE), polysulfones as the research of separation membrane material more, by phase inversion, prepare milipore filter and milipore filter is carried out to hydrophily and antibiotic property study on the modification.But, because graphene oxide is easily reunited, and be difficult for being scattered in most of high molecular polymer, adopt phase inversion to prepare graphene oxide milipore filter and limited its application aspect preparing at diffusion barrier.Meanwhile, for the research of graphene oxide, only limit to milipore filter at present, the preparation and property research of NF membrane is seldom related to.Therefore; based on graphene oxide at polar solvent (as water, N; dinethylformamide etc.) in preferably dispersed; by composite algorithm, prepare the graphene oxide composite nanometer filtering film of a kind of high flux, high salt-stopping rate; thereby effectively improve performance and the service efficiency of film, significant for the scale application of NF membrane.
Summary of the invention
The object of the invention is to solve the deficiency that above-mentioned prior art exists, the preparation method of a kind of high flux, the high graphene oxide composite nanometer filtering film that cuts salt amount is provided.
The invention provides a kind of preparation method of graphene oxide composite nanometer filtering film, special character is to comprise the following steps: (one). the preparation of graphite oxide aqueous solution: take expansible graphite as raw material, add the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator, with the Hummmers legal system of modification, obtain graphite oxide aqueous solution;
(2). the preparation of graphene oxide crosslinker solution: add crosslinking agent in the graphite oxide aqueous solution making in step (), and regulate pH by alkaline solution, make graphene oxide crosslinker solution;
(3). the preparation of graphene oxide composite nanometer filtering film: take high molecular polymer milipore filter as basement membrane, adopt surperficial coating process on basement membrane, first to apply one deck carboxymethyl chitosan sugar aqueous solution, dip-coating one deck graphene oxide crosslinker solution, makes graphene oxide NF membrane again.
Further, preparation method's concrete steps of graphene oxide composite nanometer filtering film are as follows:
(1). in the ice-water bath of 0 ℃, the concentrated sulfuric acid that is 98% by mass fraction successively and potassium permanganate are added in expansible graphite, stir, and be placed in water bath with thermostatic control and be heated to 30～40 ℃ under lower than 20 ℃ of temperature conditions, keep 1～1.5h;
(2). in step (1), in gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keeps 30～40min, and solution is sepia;
(3). in step (2) gained solution, adding mass fraction is 30% hydrogenperoxide steam generator, is cooled to room temperature, and solution is khaki by brown stain;
(4). step (3) gained solution filter is obtained to brown pasty state colloid, through pickling, deionized water, wash to solution and be neutral, in ultra-pure water, ultrasonic dispersion obtains brown solution, is placed in the dry graphene oxide powder that makes of baking oven of 40～60 ℃;
(5). the graphene oxide powder making in step (4) is carried out to ultrasonic dispersion in ultra-pure water and obtain graphene oxide solution, it is 0.2-500mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration;
(6). in step (5) gained solution, add crosslinking agent and prepare to obtain graphene oxide crosslinker solution, and with alkaline solution regulator solution pH to 13-14;
(7). take the milipore filter of high molecular polymer as basement membrane, apply the carboxymethyl chitosan sugar aqueous solution that one deck 0.5～0.8mm is thick on basement membrane, the baking oven that is placed in 50～70 ℃ heats 1-3h;
(8). step (8) the gained graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again on the CMC aqueous layer of step (7), is placed in the crosslinked 0.5-3h of baking oven of 60～80 ℃;
(9). the NF membrane that step (8) is made is carried out acetone cleaning 3-4 time, then in deionized water, soaks 24h.
In described step (1), every 1g expansible graphite adds the concentrated sulfuric acid of 50-75ml, and the addition of potassium permanganate is 2-4 times of expansible graphite quality.
The concentrated sulfuric acid in described step (1), (2), (3): ultra-pure water: the volume ratio of hydrogenperoxide steam generator is 50:100～300:10～40.
Crosslinking agent comprises that mass fraction is the glutaraldehyde that 0.5～1.0% epoxychloropropane or the mass fraction formaldehyde that is 0.5～1.5% or the mass fraction acetaldehyde that is 0.5～1.5% or mass fraction are 0.5～1.5% in described step (6).
Described step (6) neutral and alkali solution is NaOH solution or KOH solution.
In described step (7), carboxymethyl chitosan sugar aqueous solution mass fraction is 1.0-5.0%.
The relative molecular weight of holding back of described high molecular polymer milipore filter is 6000-10000.
Described high molecular polymer milipore filter material is polysulfones, polyether sulfone, polyacrylonitrile, polypropylene, polyethylene, Kynoar, cellulose acetate class, Polyurethane, polyvinyl chloride, polycaprolactam or poly-furans alcohol.
The invention provides a kind of preparation method of graphene oxide composite nanometer filtering film, there are a large amount of free carboxyl and hydroxyls on film surface, there is high-hydrophilic, high-throughout feature, film surface bear electricity simultaneously, can effectively improve salt-stopping rate, thereby significantly improved flux and the desalting effect of NF membrane, there is good heavy industrialization application prospect.
Accompanying drawing explanation
Fig. 1: graphene oxide composite nanometer filtering film scanning electron microscope diagram of the present invention, (a) surface topography map; (b) cross-section morphology figure;
Fig. 2: the contact angle test result figure of graphene oxide NF membrane of the present invention.
The specific embodiment
Referring to accompanying drawing, provide the specific embodiment of the present invention, be used for the present invention to be further described.
Embodiment 1
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 50ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 2 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki, the wherein concentrated sulfuric acid by brown stain: ultra-pure water: the volume ratio of hydrogen peroxide is 50:100:10.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 0.5mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 0.5% epoxychloropropane, prepare to obtain graphene oxide crosslinker solution, and the NaOH solution that is 1% with mass fraction regulates crosslinker solution pH to 14.
(3). take polysulphone super-filter membrane as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take polysulphone super-filter membrane as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 2.0%, the baking oven that is placed in 50～70 ℃ heats 2h; The 0.5mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 3h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Embodiment 2
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 60ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 3 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:200:20.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 50mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 0.7% epoxychloropropane, prepare to obtain graphene oxide crosslinker solution, and the NaOH solution that is 1% with mass fraction regulates crosslinker solution pH to 13.5.
(3). take polysulphone super-filter membrane as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take polysulphone super-filter membrane as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 3.0%, the baking oven that is placed in 50～70 ℃ heats 2h; The 50mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 1.5h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Embodiment 3
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 75ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 4 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:300:40.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 500mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 1.0% epoxychloropropane, prepare to obtain graphene oxide crosslinker solution, and the NaOH solution that is 1% with mass fraction regulates crosslinker solution pH to 13.
(3). take polysulphone super-filter membrane as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take polysulphone super-filter membrane as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 3.0%, the baking oven that is placed in 50～70 ℃ heats 1h; The 500mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 0.5h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Comparative example
Take polysulphone super-filter membrane as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 4.0%, the baking oven that is placed in 50～70 ℃ heats 2.5h; The epoxychloropropane that the mass fraction that dip-coating one deck 0.3～0.5mm is thick is again 0.5%, is placed in the crosslinked 3h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required composite nanometer filtering film.
The composite nanometer filtering film that the graphene oxide composite nanometer filtering film that embodiment 1-3 is made and comparative example make carries out pure water flux, initial salt rejection rate and initial permeation flux performance measurement on NF membrane evaluation instrument.At 25 ℃, flow is 120L/h, and operating pressure is 1.5MPa, uses respectively the NaCl of pure water, 1000mg/L concentration and the Na of 1000mg/L concentration
2sO
4solution is tested, and measurement result is in following table:
Embodiment 4
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 50ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 2 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:100:10.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 0.5mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 0.8% formaldehyde, prepare to obtain graphene oxide crosslinker solution, and the KOH solution that is 1% with mass fraction regulates crosslinker solution pH to 14.
(3). take polysulphone super-filter membrane as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take polysulphone super-filter membrane as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 2.0%, the baking oven that is placed in 50～70 ℃ heats 1.5h; The 0.5mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 1.5h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Embodiment 5
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 70ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 4 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:300:40.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 500mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 1.2% acetaldehyde, prepare to obtain graphene oxide crosslinker solution crosslinker solution, and the NaOH solution that is 1% with mass fraction regulates crosslinker solution pH to 14.
(3). take Polyurethane milipore filter as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take Polyurethane milipore filter as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 4.0%, the baking oven that is placed in 50～70 ℃ heats 2.5h; The 500mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 2h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Embodiment 6
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 60ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 3 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:200:20.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 50mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 1.0% glutaraldehyde, prepare to obtain graphene oxide crosslinker solution, and the KOH solution that is 1% with mass fraction regulates crosslinker solution pH to 13.
(3). to gather furans alcohol milipore filter as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
To gather furans alcohol milipore filter as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 3.0%, the baking oven that is placed in 50～70 ℃ heats 2h; The 50mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 2h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
Embodiment 7
(1). the Hummmers legal system with modification obtains graphite oxide aqueous solution.
Take expansible graphite as raw material, be placed in container, to adding mass fraction in expansible graphite, it is 98% the concentrated sulfuric acid, in ice-water bath, keeping mixture temperature is 0 ℃, add again potassium permanganate, in temperature, stir under lower than 20 ℃ of conditions, wherein every 1g expansible graphite adds the 50ml concentrated sulfuric acid, the quality of potassium permanganate is expansible graphite 2 times.
In above-mentioned gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keep 30～40min, adding mass fraction is 30% hydrogenperoxide steam generator again, be cooled to room temperature, solution is khaki pasty state colloid by brown stain, the wherein concentrated sulfuric acid: ultra-pure water: the volume ratio of hydrogen peroxide is 50:100:10.
Above-mentioned solution filter is obtained to brown pasty state colloid, colloid is cleaned, through pickling and deionized water, repeatedly wash to solution and be neutral, again colloid is placed in to the ultrasonic dispersion of ultra-pure water and obtains brown solution, be put in dry 72h in the baking oven of 40～60 ℃ and make graphene oxide powder, graphene oxide powder is carried out in ultra-pure water to ultrasonic dispersion and obtain graphene oxide solution, it is 0.5mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration.
(2). prepare graphene oxide crosslinker solution.
In the above-mentioned graphene oxide solution making, add mass fraction and be 0.7% epoxychloropropane, prepare to obtain graphene oxide crosslinker solution, and the KOH solution that is 1% with mass fraction regulates crosslinker solution pH to 14.
(3). take polypropylene milipore filter as basement membrane, through surperficial coating process, make graphene oxide composite nanometer filtering film.
Take polypropylene milipore filter as basement membrane, the carboxymethyl chitosan sugar aqueous solution that to apply mass fraction that one deck 0.5～0.8mm is thick on basement membrane be 2.0%, the baking oven that is placed in 50～70 ℃ heats 1.5h; The 0.5mg/L graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again, is placed in the crosslinked 2h of baking oven of 60～80 ℃; NF membrane is carried out to acetone and clean 3-4 time, then in deionized water, soak 24h, obtain required graphene oxide composite nanometer filtering film.
The invention provides a kind of preparation method of graphene oxide composite nanometer filtering film, there are a large amount of free carboxyl and hydroxyls on film surface, there is high-hydrophilic, high-throughout feature, film surface bear electricity simultaneously, can effectively improve salt-stopping rate, thereby significantly improved flux and the desalting effect of NF membrane, there is good heavy industrialization application prospect.
Claims (9)
1. a preparation method for graphene oxide composite nanometer filtering film, is characterized in that comprising the following steps:
(1). the preparation of graphite oxide aqueous solution: take expansible graphite as raw material, add the concentrated sulfuric acid, potassium permanganate, hydrogenperoxide steam generator, obtain graphite oxide aqueous solution with the Hummmers legal system of modification;
(2). the preparation of graphene oxide crosslinker solution: add crosslinking agent in the graphite oxide aqueous solution making in step (), and regulate pH by alkaline solution, make graphene oxide crosslinker solution;
(3). the preparation of graphene oxide composite nanometer filtering film: take high molecular polymer milipore filter as basement membrane, adopt surperficial coating process on basement membrane, first to apply one deck carboxymethyl chitosan sugar aqueous solution, dip-coating one deck graphene oxide crosslinker solution, makes graphene oxide NF membrane again.
2. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 1, is characterized in that concrete steps are as follows:
(1). in the ice-water bath of 0 ℃, the concentrated sulfuric acid that is 98% by mass fraction successively and potassium permanganate are added in expansible graphite, stir, and be placed in water bath with thermostatic control and be heated to 30～40 ℃ under lower than 20 ℃ of temperature conditions, keep 1～1.5h;
(2). in step (1), in gained solution, add ultra-pure water dilution, water bath with thermostatic control is heated to 90～100 ℃, keeps 30～40min, and solution is sepia;
(3). in step (2) gained solution, adding mass fraction is 30% hydrogenperoxide steam generator, is cooled to room temperature, and solution is khaki by brown stain;
(4). step (3) gained solution filter is obtained to brown pasty state colloid, through pickling, deionized water, wash to solution and be neutral, in ultra-pure water, ultrasonic dispersion obtains brown solution, is placed in the dry graphene oxide powder that makes of baking oven of 40～60 ℃;
(5). the graphene oxide powder making in step (4) is carried out to ultrasonic dispersion in ultra-pure water and obtain graphene oxide solution, it is 0.2-500mg/L that interpolation ultra-pure water is diluted to graphene oxide solution concentration;
(6). in step (5) gained solution, add crosslinking agent and prepare to obtain graphene oxide crosslinker solution, and with alkaline solution regulator solution pH to 13-14;
(7). take the milipore filter of high molecular polymer as basement membrane, apply the carboxymethyl chitosan sugar aqueous solution that one deck 0.5～0.8mm is thick on basement membrane, the baking oven that is placed in 50～70 ℃ heats 1-3h;
(8). step (8) the gained graphene oxide crosslinker solution that dip-coating one deck 0.3～0.5mm is thick again on the CMC aqueous layer of step (7), is placed in the crosslinked 0.5-3h of baking oven of 60～80 ℃;
(9). the NF membrane that step (8) is made is carried out acetone cleaning 3-4 time, then in deionized water, soaks 24h.
3. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that every 1g expansible graphite in described step (1) adds the concentrated sulfuric acid of 50-75ml, the addition of potassium permanganate be expansible graphite quality 2-4 doubly.
4. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that the concentrated sulfuric acid in described step (1), (2), (3): ultra-pure water: the volume ratio of hydrogenperoxide steam generator is 50:100～300:10～40.
5. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that crosslinking agent in described step (6) comprises that mass fraction is the glutaraldehyde that 0.5～1.0% epoxychloropropane or the mass fraction formaldehyde that is 0.5～1.5% or the mass fraction acetaldehyde that is 0.5～1.5% or mass fraction are 0.5～1.5%.
6. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that described step (6) neutral and alkali solution is NaOH solution or KOH solution.
7. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that in described step (7), carboxymethyl chitosan sugar aqueous solution mass fraction is 1.0-5.0%.
8. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that it is 6000-10000 that described high molecular polymer milipore filter is held back relative molecular weight.
9. the preparation method of graphene oxide composite nanometer filtering film as claimed in claim 2, is characterized in that described high molecular polymer milipore filter material is polysulfones, polyether sulfone, polyacrylonitrile, polypropylene, polyethylene, Kynoar, cellulose acetate class, Polyurethane, polyvinyl chloride, polycaprolactam or poly-furans alcohol.
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