CN105233706A - Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof - Google Patents
Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and a preparation method thereof. According to the preparation method, anchoring of metal/metallic oxide nanoparticles on oxidized graphene is carried out; an obtained oxidized graphene dispersion liquid loaded with the metal/metallic oxide nanoparticles is added into a membrane material, and a membrane casting solution is obtained via mixing; the membrane casting solution is subjected to weaving so as to obtain the oxidized graphene metal/metallic oxide nanoparticle doped hollow fiber ultrafiltration membrane. Mechanical strength, water flux, retention rate, hydrophilic performance, pollution resistance, and service life of the hollow fiber ultrafiltration membrane are improved obviously; the preparation method is simple; operation is convenient; and repeatability is high.
Description
Technical field
The present invention relates to nanometer particle-modified hollow fiber ultrafiltration membrane of a kind of graphene oxide metal/metal oxide and preparation method thereof.
Background technology
Polymeric hollow fiber ultrafiltration membrane relies on its higher specific area, is easy to the advantages such as encapsulation, is widely used in drink water purifying, Industrial Waste Water Treatments, desalinization, municipal wastewater, middle Water Sproading, bio-medical numerous areas in recent years.At present, the high molecular polymer such as polysulfones, polyether sulfone, Kynoar relies on the features such as excellent mechanical strength, chemical stability, radiation hardness characteristic, heat resistance and workability to be chosen as the most frequently used ultrafiltration membrane material.But due to the hydrophobic property of these membrane materials itself, resistance tocrocking, the water flux of most of film are all undesirable, industrial demand cannot be met, in addition, because the preparation method of hollow fiber ultrafiltration membrane most on the market is at present all non-solvent phase inversion methods, obtained film comprises finger-like macroporous structure, pore-size distribution is uneven, easy fracture of wire, mechanical strength is poor, and membrane lifetime is short.Therefore, how improving hydrophily and the mechanical property of hollow fiber ultrafiltration membrane, is current study hotspot.
Nano particle refers to the fine particle of particle diameter between 1 ~ 100 nanometer.Metal and oxide nano-particles thereof rely on the physical and chemical performance of its excellence and obtain extensive concern with the peculiar property that other materials compound tense shows, and have broad application prospects in nano composite material.If add metal/metal oxide nano particle in hollow fiber ultrafiltration membrane material, the hydrophily of film, resistance tocrocking and mechanical property can be improved.But metal/metal oxide nano particle is easily reunited, can not be dispersed in membrane material well, and in the process of film Long-Time Service, metal/metal oxide nano particle easily comes off film body, contaminated filter water body, and shorten film service life, these are all problems to be solved.Also there is not a kind of method that can be combined in by metal/metal oxide nano particle well in hollow fiber ultrafiltration membrane temporarily at present.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide nanometer particle-modified hollow fiber ultrafiltration membrane of a kind of graphene oxide metal/metal oxide and preparation method thereof, the hollow fiber ultrafiltration membrane mechanical strength, water flux, rejection, hydrophily and the resistance tocrocking that obtain all are significantly improved, and method is implemented simple, easy operation, repeatable strong.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified, comprising:
1) by 1 part of graphene oxide, 0.001 ~ 3 part of metal/metal oxide nano particle, 10 ~ 200 part of first solvent mixing, ultrasonic disperse, obtains graphene oxide metal/metal oxide nanoparticle dispersion liquid;
2) by 10 ~ 30 parts of polymer membrane materials, 5 ~ 30 parts of pore-foaming agents, 30 ~ 70 part of second solvent, 0.1 ~ 15 part of graphene oxide metal/metal oxide nanoparticle dispersion liquid Homogeneous phase mixing, obtains casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 50 ~ 90 DEG C, casting solution enters coagulating bath with the speed of 0.5 ~ 5m/min in atmosphere after 5 ~ 100mm distance, in coagulating bath, stop 3 ~ 20s, obtain the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified.
Wherein, above-mentioned each component all according to the mass fraction.
In one embodiment: described step 2) in, polymer membrane material, pore-foaming agent, the second solvent, graphene oxide metal/metal oxide nanoparticle dispersion liquid totally 100 parts in casting solution.
In one embodiment: described step 1) in, the preparation method of graphene oxide comprises:
A) graphite, 93% concentrated sulfuric acid, catalyst ferrate are uniformly mixed, room temperature reaction 1h is to be oxidized exfoliated graphite layer; The formula rate of described graphite, 93% concentrated sulfuric acid, ferrate is 10g:400ml:60g;
B) by step a) in the reactant liquor that obtains remove the concentrated sulfuric acid, Separation of Solid and Liquid, obtains single-layer graphene oxide;
C) by step b) in the single-layer graphene oxide that obtains be placed in 60 DEG C at vacuum drying, obtain described graphene oxide.
In one embodiment: described step 1) in, metal/metal oxide nano particle is gold, silver, aluminium, copper, iron, zinc, zirconium, titanium, magnesium or its oxide nano-particles.
In one embodiment: described step 1) in, the first solvent is at least one in water, methyl alcohol, ethanol, acetone, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), ethylene glycol, diethylene glycol (DEG).
In one embodiment: described step 2) in, polymer membrane material is the one in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone, polyethylene, polypropylene, polyacrylonitrile or ethylene-vinyl alcohol copolymer.
In one embodiment: described step 2) in, pore-foaming agent is at least one in lithium nitrate, sodium chloride, calcium chloride, calcium nitrate, silica, alundum (Al2O3), calcium nitrate, kaolin, polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose.
In one embodiment: described step 2) in, the second solvent is at least one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO).
In one embodiment: described step 3) in, core liquid is the mixture of water or water and organic solvent.
In one embodiment: described step 3) in, stop after 3 ~ 20s in coagulating bath, the nanometer particle-modified hollow fiber ultrafiltration membrane of the graphene oxide metal/metal oxide obtained is placed in aqueous solution rinse 24h, finally soaks in glycerine water solution and preserves.。
The technical program is compared with background technology, and its tool has the following advantages:
The present invention carries out modification by graphene oxide and metal/metal oxide nano particle to hollow fiber ultrafiltration membrane, on graphene oxide after grappling metal/metal oxide nano particle, by grappling, the graphene oxide dispersion of metal/metal oxide nano particle adds in membrane material, be mixed to get casting solution, obtained casting solution be spun into the hollow fiber ultrafiltration membrane being doped with graphene oxide metal/metal oxide nano particle.Wherein, graphene oxide has excellent mechanical property, hydrophily is strong, can well be dispersed in polymeric film material, and surface of graphene oxide has the oxy radicals such as abundant carboxyl, carbonyl, epoxy-functional, by forming coordinate bond with metal ion, can metal nanoparticle be anchored on graphene oxide, solve metal nanoparticle well and easily reunite in casting solution and in use hold caducous problem; Simultaneously, by graphene oxide by after metal/metal oxide nanoparticle dispersion is in polymeric film material, environmental microbes, free volume and solution molecule transmission means can be changed, bring nontoxic, can sterilization, strongly hydrophilic, stablize under uv radiation, have the advantages such as many active anchor fixed points.By the synergistic function of graphene oxide and metal/metal oxide nano particle, make that the modification hollow fiber ultrafiltration membrane mechanical strength that obtains is high, good hydrophilic property, anti-pollution, water flux large, the hollow fiber composite membrane of long service life, and preparation method implements simply, easy operation, repeatable strong, there is very large realistic meaning.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is ESEM (SEM) the Electronic Speculum figure of the cross section of the nanometer particle-modified PES of graphene oxide alundum (Al2O3) prepared by embodiment 4;
Fig. 2 is the polyvinylidene fluoride hollow fiber ultrafiltration membrane surface SEM figure of graphene oxide Nano silver grain modification prepared by embodiment 1.
Detailed description of the invention
Content of the present invention is illustrated below by embodiment:
Embodiment 1
1) by 1 part of graphene oxide, 0.001 part of Nano silver grain, 200 part of first solvent volume mixes than for the water-methanol mixture of 1:1, and ultrasonic disperse, obtains graphene oxide silver nanoparticle dispersion liquid;
2) by 10 parts of polymer membrane material Kynoar, 30 parts of pore-foaming agent lithium nitrates, 59.9 part of second solvent dimethylformamide, 0.1 part of graphene oxide silver nanoparticle dispersion liquid Homogeneous phase mixing, obtains casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 50 DEG C, casting solution enters coagulating bath with the speed of 0.5m/min in atmosphere after 5mm distance, 3s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 1 of graphene oxide Nano silver grain modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide comprises:
A) 10g graphite, the 400ml93% concentrated sulfuric acid, 60g catalyst ferrate are uniformly mixed in reaction vessel, room temperature reaction 1h is to be oxidized exfoliated graphite layer;
B) by step a) in the reactant liquor centrifugal segregation concentrated sulfuric acid that obtains, repeatedly clean by deionized water, centrifugation, obtain single-layer graphene oxide;
C) by step b) in the single-layer graphene oxide that obtains be placed in vacuum drying at 60 DEG C in vacuum drying chamber, obtain described graphene oxide.
Another employing same method, the water-methanol mixture being 1:1 by the volume ratio of 0.1 part of graphene oxide silver nanoparticle dispersion liquid equal in quality substitutes, and the comparative film 1 of graphene oxide Nano silver grain is not added in preparation.
Embodiment 2
1) by 1 part of graphene oxide, 3 parts of copper nano-particles, 10 part of first etoh solvent mixing, ultrasonic disperse, obtains graphene oxide copper nano-particle dispersion liquid;
2) by 10 parts of polymer membrane material polyvinyl chloride, 5 parts of pore-foaming agent sodium chloride, 70 part of second solvent dimethylacetylamide, 15 parts of graphene oxide copper nano-particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 90 DEG C, casting solution enters coagulating bath with the speed of 3m/min in atmosphere after 5mm distance, 20s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 2 of graphene oxide copper nano-particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% dimethylformamide in water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the ethanol of 15 parts of graphene oxide copper nano-particle dispersion liquid equals in quality, and the comparative film 2 of graphene oxide copper nano-particle is not added in preparation.
Embodiment 3
1) by 1 part of graphene oxide, 3 parts of golden nanometer particles, 200 part of first solvent acetone mixing, ultrasonic disperse, obtains graphene oxide golden nanometer particle dispersion liquid;
2) by 30 parts of polymer membrane material polysulfones, pore-foaming agent 3 parts of calcium chloride and 2 parts of calcium nitrate, 55 part of second solvent dimethyl sulfoxide (DMSO), 10 parts of graphene oxide golden nanometer particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 90 DEG C, casting solution enters coagulating bath with the speed of 3m/min in atmosphere after 50mm distance, 15s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 3 of graphene oxide golden nanometer particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the acetone of 10 parts of graphene oxide golden nanometer particle dispersion liquid equals in quality, and the comparative film 3 of graphene oxide golden nanometer particle is not added in preparation.
Embodiment 4
1) by 1 part of graphene oxide, 2 parts of alundum (Al2O3) nano particles, 100 part of first solvent volume is than the dimethyl formamide-dimethylacetylamide mixed liquor mixing for 1:1, and ultrasonic disperse, obtains graphene oxide alundum (Al2O3) nanoparticle dispersion liquid;
2) by 20 parts of polymer membrane material polyethersulfone, pore-foaming agent 15 parts of silica and 15 parts of alundum (Al2O3)s, 40 part of second solvent dimethylacetylamide, 10 parts of graphene oxide alundum (Al2O3) nanoparticle dispersion liquid Homogeneous phase mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 75 DEG C, casting solution enters coagulating bath with the speed of 5m/min in atmosphere after 100mm distance, 3s is stopped in coagulating bath, take out, obtain the nanometer particle-modified hollow fiber ultrafiltration membrane of graphene oxide alundum (Al2O3) 4; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, dimethyl formamide-dimethylacetylamide the mixed liquor being 1:1 by the volume ratio of 10 parts of graphene oxide alundum (Al2O3) nanoparticle dispersion liquid equals in quality substitutes, ultrasonic disperse, the comparative film 4 of graphene oxide alundum (Al2O3) nano particle is not added in preparation.
Embodiment 5
1) by 1 part of graphene oxide, 0.5 part of ferriferrous oxide nano-particle, 100 part of first solvent dimethyl sulfoxide (DMSO) mixing, ultrasonic disperse, obtains graphene oxide ferriferrous oxide nano-particle dispersion liquid;
2) by 25 parts of polymer membrane material polyethylene, pore-foaming agent 12 parts of calcium nitrate and 18 parts of kaolin nano particles, 30 part of second solvent dimethylformamide, 15 parts of graphene oxide ferriferrous oxide nano-particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 75 DEG C, casting solution enters coagulating bath with the speed of 5m/min in atmosphere after 100mm distance, 3s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 5 of graphene oxide ferriferrous oxide nano-particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% dimethylformamide in water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the dimethyl sulfoxide (DMSO) of 15 parts of graphene oxide ferriferrous oxide nano-particle dispersion liquid equals in quality, and the comparative film 5 of graphene oxide ferriferrous oxide nano-particle is not added in preparation.
Embodiment 6
1) by 1 part of graphene oxide, 0.5 part of ferriferrous oxide nano-particle, 100 part of first solvent ethylene glycol mixing, ultrasonic disperse, obtains graphene oxide ferriferrous oxide nano-particle dispersion liquid;
2) by 27 parts of polymer membrane material polypropylene, 20 parts of pore-foaming agent polyethylene glycol, 40 part of second solvent dimethylformamide, 13 parts of graphene oxide ferriferrous oxide nano-particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 70 DEG C, casting solution enters coagulating bath with the speed of 3m/min in atmosphere after 50mm distance, 10s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 6 of graphene oxide ferriferrous oxide nano-particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% dimethylformamide in water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the ethylene glycol of 13 parts of graphene oxide ferriferrous oxide nano-particle dispersion liquid equals in quality, and the comparative film 6 of graphene oxide ferriferrous oxide nano-particle is not added in preparation.
Embodiment 7
1) by 1 part of graphene oxide, 0.5 part of zinc oxide nano-particle, 100 part of first solvent diethylene glycol (DEG), ultrasonic disperse, obtains graphene oxide zinc oxide nano-particle dispersion liquid;
2) by 27 parts of polymer membrane material polyacrylonitrile, pore-foaming agent 10 parts of polyoxyethylene and 10 parts of methylcellulose, 40 part of second solvent dimethylformamide, 13 parts of graphene oxide zinc oxide nano-particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 70 DEG C, casting solution enters coagulating bath with the speed of 3m/min in atmosphere after 50mm distance, in coagulating bath, stop 10s, obtain the hollow fiber ultrafiltration membrane 7 of graphene oxide zinc oxide nano-particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the diethylene glycol (DEG) of 13 parts of graphene oxide zinc oxide nano-particle dispersion liquid equals in quality, and the comparative film 7 of graphene oxide zinc oxide nano-particle is not added in preparation.
Embodiment 8
1) by 1 part of graphene oxide, 0.8 part of titanium dioxide nano-particle, 50 part of first solvent diethylene glycol (DEG), ultrasonic disperse, obtains graphene oxide titanium dioxide nano-particle dispersion liquid;
2) by 25 parts of polymer membrane material vinyl-ethenol copolymers, pore-foaming agent 20 parts of polyvinylpyrrolidones and 5 parts of hydroxypropyl celluloses, 40 part of second solvent dimethylformamide, 10 parts of graphene oxide titanium dioxide nano-particle homogeneous dispersion mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 70 DEG C, casting solution enters coagulating bath with the speed of 1m/min in atmosphere after 25mm distance, 6s is stopped in coagulating bath, take out, obtain the hollow fiber ultrafiltration membrane 8 of graphene oxide titanium dioxide nano-particle modification; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, substitutes the diethylene glycol (DEG) of 10 parts of graphene oxide titanium dioxide nano-particle dispersion liquid equals in quality, and the comparative film 8 of graphene oxide titanium dioxide nano-particle is not added in preparation.
Embodiment 9
1) by 1 part of graphene oxide, 0.8 part of bitter earth nano particle, 50 part of first solvent volume is than the water-methanol mixture for 1:1, and ultrasonic disperse, obtains graphene oxide bitter earth nano particle dispersion;
2) by 15 parts of polymer membrane material Kynoar, 25 parts of pore-foaming agent polyvinyl alcohol, 50 part of second solvent dimethylformamide, 10 parts of graphene oxide bitter earth nano particle dispersion Homogeneous phase mixing, obtain casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 50 DEG C, casting solution enters coagulating bath with the speed of 4m/min in atmosphere after 60mm distance, 15s is stopped in coagulating bath, take out, obtain the particle modified hollow fiber ultrafiltration membrane of graphene oxide bitter earth nano 9; Be placed in aqueous solution rinse 24h, finally soak in glycerine water solution and preserve; Described core liquid is 40% ethanol water, and described coagulating bath is water;
Wherein, above-mentioned each component all according to the mass fraction.
Described step 1) in, the preparation method of graphene oxide is with embodiment 1.
Another employing same method, the water-methanol mixture being 1:1 by the volume ratio of 10 parts of graphene oxide bitter earth nano particle dispersion equals in quality substitutes, and the comparative film 9 of graphene oxide bitter earth nano particle is not added in preparation.
Those skilled in the art are known, when technical parameter of the present invention changes in following scope, it is expected to obtain same as the previously described embodiments or close effect:
A preparation method for the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified, comprising:
1) by 1 part of graphene oxide, 0.001 ~ 3 part of metal/metal oxide nano particle, 10 ~ 200 part of first solvent mixing, ultrasonic disperse, obtains graphene oxide metal/metal oxide nanoparticle dispersion liquid;
2) by 10 ~ 30 parts of polymer membrane materials, 5 ~ 30 parts of pore-foaming agents, 30 ~ 70 part of second solvent, 0.1 ~ 15 part of graphene oxide metal/metal oxide nanoparticle dispersion liquid Homogeneous phase mixing, obtains casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 50 ~ 90 DEG C, casting solution enters coagulating bath with the speed of 0.5 ~ 5m/min in atmosphere after 5 ~ 100mm distance, in coagulating bath, stop 3 ~ 20s, obtain the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified.
Wherein, above-mentioned each component all according to the mass fraction.
Described step 2) in, polymer membrane material, pore-foaming agent, the second solvent, graphene oxide metal/metal oxide nanoparticle dispersion liquid totally 100 parts in casting solution.
Described step 1) in, the preparation method of graphene oxide comprises:
A) graphite, 93% concentrated sulfuric acid, catalyst ferrate are uniformly mixed, room temperature reaction 1h is to be oxidized exfoliated graphite layer; The formula rate of described graphite, 93% concentrated sulfuric acid, ferrate is 10g:400ml:60g;
B) by step a) in the reactant liquor that obtains remove the concentrated sulfuric acid, Separation of Solid and Liquid, obtains single-layer graphene oxide;
C) by step b) in the single-layer graphene oxide that obtains be placed in 60 DEG C at vacuum drying, obtain described graphene oxide.
Described step 1) in, metal/metal oxide nano particle is gold, silver, aluminium, copper, iron, zinc, zirconium, titanium, magnesium or its oxide nano-particles.
Described step 1) in, the first solvent is at least one in water, methyl alcohol, ethanol, acetone, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), ethylene glycol, diethylene glycol (DEG).
Described step 2) in, polymer membrane material is the one in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone, polyethylene, polypropylene, polyacrylonitrile or ethylene-vinyl alcohol copolymer.
Described step 2) in, pore-foaming agent is at least one in lithium nitrate, sodium chloride, calcium chloride, calcium nitrate, silica, alundum (Al2O3), calcium nitrate, kaolin, polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose.
Described step 2) in, the second solvent is at least one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO).
Described step 3) in, core liquid is the mixture of water or water and organic solvent.
Described step 3) in, stop after 3 ~ 20s in coagulating bath, the nanometer particle-modified hollow fiber ultrafiltration membrane of the graphene oxide metal/metal oxide obtained is placed in aqueous solution rinse 24h, finally soaks in glycerine water solution and preserves.
Above-described embodiment can realize the effect of following experimental example:
Experimental example
By hollow fiber ultrafiltration membrane nanometer particle-modified for each graphene oxide metal/metal oxide obtained in embodiment 1 ~ 9 and each comparative film, after the aqueous solution and the abundant rinse of glycerine water solution soak, dry, carry out the test of water flux, rejection, contact angle, hot strength and flux recovery rate respectively, result is as shown in table 1, hollow fiber ultrafiltration membrane after graphene oxide metal/metal oxide is nanometer particle-modified, its mechanical strength, water flux, rejection and hydrophily are all significantly improved.
The performance data that the modification of table 1 hollow fiber ultrafiltration membrane is forward and backward
The above, be only present pre-ferred embodiments, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (10)
1. a preparation method for the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified, is characterized in that: comprising:
1) by 1 part of graphene oxide, 0.001 ~ 3 part of metal/metal oxide nano particle, 10 ~ 200 part of first solvent mixing, ultrasonic disperse, obtains graphene oxide metal/metal oxide nanoparticle dispersion liquid;
2) by 10 ~ 30 parts of polymer membrane materials, 5 ~ 30 parts of pore-foaming agents, 30 ~ 70 part of second solvent, 0.1 ~ 15 part of graphene oxide metal/metal oxide nanoparticle dispersion liquid Homogeneous phase mixing, obtains casting solution;
3) casting solution standing and defoaming was extruded by spinning nozzle with core liquid after 24 hours simultaneously, spinning nozzle temperature is 50 ~ 90 DEG C, casting solution enters coagulating bath with the speed of 0.5 ~ 5m/min in atmosphere after 5 ~ 100mm distance, in coagulating bath, stop 3 ~ 20s, obtain the hollow fiber ultrafiltration membrane that graphene oxide metal/metal oxide is nanometer particle-modified.
Wherein, above-mentioned each component all according to the mass fraction.
2. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 2) in, polymer membrane material, pore-foaming agent, the second solvent, graphene oxide metal/metal oxide nanoparticle dispersion liquid totally 100 parts in casting solution.
3. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, is characterized in that: described step 1) in, the preparation method of graphene oxide comprises:
A) graphite, 93% concentrated sulfuric acid, catalyst ferrate are uniformly mixed, room temperature reaction 1h is to be oxidized exfoliated graphite layer; The formula rate of described graphite, 93% concentrated sulfuric acid, ferrate is 10g:400ml:60g;
B) by step a) in the reactant liquor that obtains remove the concentrated sulfuric acid, Separation of Solid and Liquid, obtains single-layer graphene oxide;
C) by step b) in the single-layer graphene oxide that obtains be placed in 60 DEG C at vacuum drying, obtain described graphene oxide.
4. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 1) in, metal/metal oxide nano particle is gold, silver, aluminium, copper, iron, zinc, zirconium, titanium, magnesium or its oxide nano-particles.
5. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 1) in, the first solvent is at least one in water, methyl alcohol, ethanol, acetone, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), ethylene glycol, diethylene glycol (DEG).
6. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 2) in, polymer membrane material is the one in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone, polyethylene, polypropylene, polyacrylonitrile or ethylene-vinyl alcohol copolymer.
7. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 2) in, pore-foaming agent is at least one in lithium nitrate, sodium chloride, calcium chloride, calcium nitrate, silica, alundum (Al2O3), calcium nitrate, kaolin, polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose.
8. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 2) in, the second solvent is at least one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO).
9. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, is characterized in that: described step 3) in, core liquid is the mixture of water or water and organic solvent.
10. the preparation method of the hollow fiber ultrafiltration membrane that a kind of graphene oxide metal/metal oxide according to claim 1 is nanometer particle-modified, it is characterized in that: described step 3) in, stop 3 ~ 20s in coagulating bath after, the nanometer particle-modified hollow fiber ultrafiltration membrane of the graphene oxide metal/metal oxide obtained is placed in aqueous solution rinse 24h, finally soaks in glycerine water solution and preserves.
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