CN110141975A - A kind of multi-walled carbon nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane and preparation method thereof - Google Patents
A kind of multi-walled carbon nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane and preparation method thereof Download PDFInfo
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- CN110141975A CN110141975A CN201910414032.9A CN201910414032A CN110141975A CN 110141975 A CN110141975 A CN 110141975A CN 201910414032 A CN201910414032 A CN 201910414032A CN 110141975 A CN110141975 A CN 110141975A
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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Abstract
The present invention relates to the preparation fields of modified ultrafiltration membrane, and in particular to a kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane and preparation method thereof；A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 14~17 parts of film base material, acidification multi-walled carbon nanotube/Fe3O4/SiO20.1~1.0 part, 72~75 parts of solvent, 12~15 parts of pore-foaming agent and negative 0.05~0.3 part of surfactant.Many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane produced by the present invention, the harmful heavy metal ions being not only able in water removal, such as Cr3+、Pb2+、Zn2+Deng also having many advantages, such as that mechanical performance is strong, antifouling property is excellent, water flux is high, rejection is excellent and service life is long.
Description
Technical field
The present invention relates to the preparation fields of modified ultrafiltration membrane, and in particular to a kind of many walls nanotube-polyacrylonitrile (MWCNT-
PAN) composite hyperfiltration membrane and preparation method thereof.
Background technique
Seperation film is a kind of membranous type material that ability is penetrated with selectivity.It can usually divide by separating mechanism and the scope of application
For microfiltration membranes, ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane and amberplex etc..Ultrafiltration membrane is that a kind of aperture specification is consistent and specified
Aperture is 0.01 μm of micropore filtering film below.Appropriate pressure is imposed in the side of film, the solute point less than membrane aperture can be sifted out
Son is greater than the particle of 10nm to separate molecular weight greater than 500 dalton, partial size；Ultrafiltration membrane is the macromolecule separation developed earliest
One of film.The structure of ultrafiltration membrane is divided into symmetrical and asymmetric: the former be it is isotropic, without cortex, on all directions
Hole is the same, and belongs to in-depth filtration；The latter has finer and close surface layer and the bottom based on finger, and surface layer is thick
Degree is 0.1 μm or smaller, and has orderly aligned micropore, and underlayer thickness is 200~250 μm, belongs to both surface filtration.
Polyacrylonitrile (polyacrylonitrile) is to be obtained by monomers acrylonitrile through Raolical polymerizable, big point
Acrylonitrile unit in subchain connects head-tail mode and is connected.Polyacrylonitrile (PAN) is a kind of common membrane material, due to it
Have many advantages, such as good solvent resistant, chemical stability, preferable film forming, hydrophily, easy processing, cheap therefore extensive
Apply to the fields such as water process and haemodialysis.Again due to the very strong cyano containing polarized in polyacrylonitrile molecule, so that high
Molecule interchain active force is big, flexible poor, and also mechanical strength is lower, wearability and fatigue resistance is poor and resistance tocrocking
The weakness such as poor limit it in the utilization in film field.
In order to enable the performance (mechanical strength, water-flowing amount, resistance tocrocking) of polyacrylonitrile membrane material is more in line with separation
Demand is widened application range of the polyacrylonitrile in membrane separation technique, is modified to polyacrylonitrile material, and grind in recent years
The hot spot studied carefully.
Summary of the invention
In view of the deficiencies of the prior art, it is compound super to provide a kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) by the present invention
Filter membrane and preparation method thereof, the ultrafiltration membrane are not only able to the harmful heavy metal ions in water removal, such as Cr3+、Pb2+、Zn2+Deng tool
Have the advantages that mechanical performance is strong, antifouling property is excellent, water flux is high, rejection is excellent and service life is long.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: film
14~17 parts of substrate, acidification multi-walled carbon nanotube/Fe3O4/SiO20.1~1.0 part, 72~75 parts of solvent, pore-foaming agent 12~15
Part and negative 0.05~0.3 part of surfactant.
Preferably, film base material is polyacrylonitrile；Polyacrylonitrile molecular weight is 100,000, and polyacrylonitrile purity >=93%.
Preferably, it is acidified multi-walled carbon nanotube/Fe3O4/SiO2In, purity >=95% of multi-walled carbon nanotube, multi wall carbon is received
10~20nm of diameter of mitron, and length is 5~20 μm, Fe3O4And SiO2Mass ratio be 2:1.
Preferably, solvent is one or more of dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone.
Preferably, pore-foaming agent is one in polyethylene glycol 400, Macrogol 600, polyvinylpyrrolidone and polyvinyl alcohol
Kind is several；Negative surfactant is one of lauryl sodium sulfate, sodium alkyl sulfonate and polymethylacrylic acid or several
Kind, pore-foaming agent and negative surfactant are that analysis is pure.
A kind of preparation method of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, comprising the following steps:
(1) preparation acidification multi-walled carbon nanotube/Fe3O4/SiO2,
1. flow back 14 h at 80 DEG C after the mixture S1 of multi-walled carbon nanotube and nitration mixture is vibrated 1 h；It is cooled to room temperature, uses
Hydrophilic film filtering, then being washed with deionized to the pH value of mixture S1 is 6.3~7.0, and acidification multi-walled carbon nanotube is made；
2. the mixture S2 of pure water, ferric chloride hexahydrate, green vitriol and above-mentioned acidification multi-walled carbon nanotube is first shaken
It swings 30 min, again under protection of argon gas after 50 DEG C of 30 min of oscillation, is warming up to 65 DEG C；The pH value of mixture S2 is adjusted to lye
12 or more, after persistent oscillation 60min, it is down to room temperature, then dilute, filter to neutrality；After being dried in vacuo 12 h at 80 DEG C, it is ground into
Acidification multi-walled carbon nanotube/Fe is made in powder3O4；
3. by pure water, nano silica and above-mentioned acidification carbon nanotube/Fe3O4Mixture S3 shake 30 min after, 120
It is dried in vacuo 12 h at DEG C, pulverizes, acidification multi-walled carbon nanotube/Fe is made3O4/SiO2；
(2) casting solution is prepared, by solvent, pore-foaming agent, negative surfactant and above-mentioned acidification multi-walled carbon nanotube/Fe3O4/
SiO2Mixture S4 ultrasound after, polyacrylonitrile is added, is stirred under heating to polyacrylonitrile and is completely dissolved, uniform casting film is made
Liquid；
(3) composite hyperfiltration membrane is prepared, after above-mentioned casting solution circulating filtration, vacuumizing and defoaming, static 24 h at 40 DEG C；40℃
It is lower to use gel phase inversion by casting solution spinning, the composite hyperfiltration membrane of hollow fiber is made；
(4) it post-processes, above-mentioned composite hyperfiltration membrane is impregnated in glycerol liquor.
Preferably, in step (1), nitration mixture is made of the sulfuric acid that volume ratio is 3:1 and nitric acid, and hydrophilic film is ePTFE/PP parent
Moisture film；The molar ratio of ferric chloride hexahydrate and green vitriol is (1.7~2): 1, lye is sodium hydroxide solution or hydrogen
Potassium oxide solution；The partial size of nano silica is 20~40nm.
Preferably, in step (2), before polyacrylonitrile is added, catalyst n, N- dicyclohexylcarbodiimide or 4- is first added
Dimethylamino naphthyridine.
Preferably, in step (3), the mass fraction for closing multi-walled carbon nanotube in ultrafiltration membrane is 0.3~0.7%.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention uses nitration mixture (sulfuric acid and nitric acid) to multi-walled carbon nanotube oxidation processes, so that the carbon nano tube surface produces
Raw hydroxy functional group, these hydroxyls have reactivity；Then with nano-oxide to hydroxyl multi-walled carbon nanotube into
Row is modified, then passes through multi-walled carbon nanotube/Fe3O4/SiO2On hydroxyl reacted with the carboxyl on polyacrylonitrile so that polypropylene
Nitrile is grafted to carbon nano tube surface；It is acidified multi-walled carbon nanotube/Fe3O4/SiO2So that the composite hyperfiltration membrane form it is finer and close
Sectional layer, there is good supporting role, and such microcellular structure, hydrophilicity and the pure water for improving the ultrafiltration membrane be logical
Amount.
(2) modified multiwalled carbon nanotube can provide stable and regular nanochannel in the composite hyperfiltration membrane, so that this is super
Filter membrane carries out quick Selective Separation to system, and also adds the antibiotic property and contamination resistance of the ultrafiltration membrane；Because
Fe3O4With magnetism, therefore Fe is loaded3O4Acidification multi-walled carbon nanotube/Fe3O4/SiO2Also it is provided with magnetism, imparts this
The good electromagnetic performance of ultrafiltration membrane and absorption property；Again due to SiO2With good stickiness, so that the anti-tensile of the ultrafiltration membrane is strong
Degree increases with elongation percentage；The introducing of additive (pore-foaming agent and negative surfactant) so that the composite hyperfiltration membrane without
By being hydrophilicity, surface roughness, porosity or its interception capacity to harmful substance, there is huge improvement.
(3) compared with virgin pp nitrile filter membrane, it is acidified multi-walled carbon nanotube/Fe3O4/SiO2Introducing so that the present invention is super
The pure water flux of filter membrane increases by 36%, swellbility raising 40%, permeance property and antifouling property and is also obviously improved；The ultrafiltration membrane exists
In alkaline environment, Cr can be adsorbed3+、Pb2+、Zn2+Equal harmful metal ions, and also have very to organic matter, bacterium, virus etc.
Good rejection effect.
(4) present invention is by modified multi-walled carbon nanotube, polypropylene nitrile, pore-foaming agent, negative surfactant and organic
Solvent is blended, and by the combination of heterogeneity material, defect of the homogenous material in performance and function is made up, thus by a variety of materials
The advantages of material, concentrates, to obtain the ideal ultrafiltration membrane of separating effect.
(5) in preparation process of the invention, casting solution is subjected to circulating filtration, the machinery on the one hand filtered out in casting solution is miscellaneous
Matter prevents blocking spinning head, on the other hand by circulating filtration, is uniformly mixed casting solution；By the ultrafiltration membrane of hollow fiber
It is immersed in glycerol liquor, is resided in film wire convenient for glycerol, using the fixedness and moisture pick-up properties of glycerol, protect the wet of biofilm silk
Profit state；Modified material need to be only evenly mixed in casting solution by the preparation method, easy to operate, be conducive to industrialized production.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 14
Part polyacrylonitrile, 0.1 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 72 parts of dimethylformamides, 12 parts of polyethylene glycol 400s and
0.05 part of lauryl sodium sulfate；Polyacrylonitrile molecular weight is 100,000, purity >=93%；Purity >=95% of multi-walled carbon nanotube,
10~20nm of diameter of multi-walled carbon nanotube, and length is 5~20 μm, Fe3O4And SiO2Mass ratio be 2:1；Pore-foaming agent and yin
Property surfactant be analysis it is pure.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
It is rapid: (1) preparation acidification multi-walled carbon nanotube/Fe3O4/SiO2,
1. by multi-walled carbon nanotube and nitration mixture (VSulfuric acid: VNitric acidAfter 1 h of mixture S1 oscillation of 3:1), flow back 14 h at 80 DEG C；
It is cooled to room temperature, is filtered with ePTFE/PP hydrophilic film, then being washed with deionized to the pH value of mixture S1 is 6.3, and acid is made
Multi-walled carbon nano-tube；
2. the mixture S2 of pure water, ferric chloride hexahydrate, green vitriol and above-mentioned acidification multi-walled carbon nanotube is vibrated
30 min, again under protection of argon gas after 50 DEG C of 30 min of oscillation, 65 DEG C are warming up to；With sodium hydroxide solution by the pH of mixture S2
Value is adjusted to 12 or more, after vibrating 60min, is down to room temperature, dilution is filtered to neutrality；After being dried in vacuo 12 h at 80 DEG C, it is ground into
Acidification multi-walled carbon nanotube/Fe is made in powder3O4；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.7:1；
3. by pure water, nano silica and above-mentioned acidification multi-walled carbon nanotube/Fe3O4Mixture S3 shake 30 min after,
It is dried in vacuo 12 h at 120 DEG C, pulverizes, acidification multi-walled carbon nanotube/Fe is made3O4/SiO2；The grain of nano silica
Diameter is 20~40nm；
(2) casting solution is prepared, by above-mentioned solvent, pore-foaming agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/
SiO2Mixture S4 ultrasonic disperse after, be added polyacrylonitrile, be stirred under heating to polyacrylonitrile and be completely dissolved, be made uniform
Casting solution；
(3) composite hyperfiltration membrane is prepared, after above-mentioned casting solution filter screen circulating filtration, is placed in spinning box, vacuumizing and defoaming,
Static 24 h at 40 DEG C；Then it uses casting solution spinning at 40 DEG C of gel phase inversion, hollow fiber and multi wall is made
The composite hyperfiltration membrane that carbon nanotube mass score is 0.1%；
(4) it post-processes, above-mentioned composite hyperfiltration membrane is impregnated in glycerol liquor, keeps the moisture state of the ultrafiltration membrane.
Embodiment 2
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 15
Part polyacrylonitrile, 0.3 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 72.5 parts of dimethylformamides, 13 parts of polyethylene glycol 400s
With 0.1 part of lauryl sodium sulfate.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.4, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.7:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition polyacrylonitrile simultaneously stirs, and casting film is made
Liquid；Deaeration after casting solution is filtered, static rear spinning, is made the composite hyperfiltration membrane that multi-walled carbon nanotube mass fraction is 0.3%.
Embodiment 3
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 16
Part polyacrylonitrile, 0.6 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 73 parts of dimethyl acetamides, 13.5 parts of polyvinyl pyrroles
Alkanone and 0.15 part of sodium alkyl sulfonate.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.5, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and upper multi-walled carbon nano-tube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.8:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition polyacrylonitrile simultaneously stirs, and casting film is made
Liquid；Deaeration after casting solution is filtered, static rear spinning, is made the composite hyperfiltration membrane that multi-walled carbon nanotube mass fraction is 0.58%.
Embodiment 4
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 17
Part polyacrylonitrile, 0.9 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 73.5 parts of dimethyl acetamides, 14 parts of Macrogol 600s
With 0.2 part of sodium alkyl sulfonate.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.6, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.8:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition polyacrylonitrile simultaneously stirs, and casting film is made
Liquid；Deaeration after casting solution is filtered, static rear spinning, is made the composite hyperfiltration membrane that multi-walled carbon nanotube mass fraction is 0.7%.
Embodiment 5
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 15
Part polyacrylonitrile, 0.5 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 74 parts of N-Methyl pyrrolidones, 14.5 parts of polyethylene glycol
600 and 0.25 parts of polymethylacrylic acid.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.7, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.9:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition polyacrylonitrile simultaneously stirs, and casting film is made
Liquid；By deaeration after the filtering of casting film ring, the composite hyperfiltration membrane that multi-walled carbon nanotube mass fraction is 0.48% is made in static rear spinning.
Embodiment 6
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: poly-
17 parts of acrylonitrile, acidification multi-walled carbon nanotube/Fe3O4/SiO21.0 parts, 75 parts of N-Methyl pyrrolidone, 15 parts of polyvinyl alcohol and
0.3 part of polymethylacrylic acid.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.8, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 2.0:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition polyacrylonitrile simultaneously stirs, and casting film is made
Liquid；Deaeration after casting solution is filtered, static rear spinning, is made the composite hyperfiltration membrane that multi-walled carbon nanotube mass fraction is 0.85%.
Embodiment 7
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: 15
Part polyacrylonitrile, 0.5 part of acidification multi-walled carbon nanotube/Fe3O4/SiO2, 74 parts of N-Methyl pyrrolidones, 14.5 parts of polyethylene glycol
400 and 0.25 parts of polymethylacrylic acid.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.7, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of ferric chloride hexahydrate and green vitriol is 1.9:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition catalyst n, N- dicyclohexyl carbon two are sub-
Amine；Polyacrylonitrile stirring is added, casting solution is made；Deaeration after casting solution is filtered, static rear spinning, is made Compound Ultrafiltration
Film.
Embodiment 8
A kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, the raw material including following weight: poly-
17 parts of acrylonitrile, acidification multi-walled carbon nanotube/Fe3O4/SiO21.0 parts, 75 parts of N-Methyl pyrrolidone, 15 parts of polyvinyl alcohol and
0.3 part of polymethylacrylic acid.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
Rapid: referring to embodiment 1, by multi-walled carbon nanotube and nitration mixture vibration reflux, filtering, then washing to pH value is 6.8, and it is more that acidification is made
Wall carbon nano tube；Acidification is made with pure water, ferric chloride hexahydrate, green vitriol, acidification multi-walled carbon nanotube and lye
Multi-walled carbon nanotube/Fe3O4；With pure water, nano silica and acidification multi-walled carbon nanotube/Fe3O4Acidification multi wall carbon is made to receive
Mitron/Fe3O4/SiO2；The molar ratio of six water and iron chloride and seven water and ferrous sulfate is 2.0:1；To the solvent after ultrasound, cause
Hole agent, negative surfactant and acidification multi-walled carbon nanotube/Fe3O4/SiO2Middle addition catalyst 4-dimethylaminopyridine；Again
Polyacrylonitrile stirring is added, casting solution is made；Deaeration after casting solution is filtered, static rear spinning, is made composite hyperfiltration membrane.
Blank example
A kind of polyacrylonitrile ultrafiltration film, the raw material including following weight: 15 parts of polyacrylonitrile, 74 parts of N- crassitudes
Ketone, 14.5 parts of Macrogol 600s and 0.25 part of polymethylacrylic acid.
A kind of preparation method of above-mentioned many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, including following step
It is rapid: to prepare casting solution, by solvent, pore-foaming agent, negative surfactant and polyacrylonitrile ultrasonic disperse, uniform casting film is made
Liquid；By vacuumizing and defoaming after above-mentioned casting solution circulating filtration, polyacrylonitrile ultrafiltration is made in the spinning after static 24 h at 40 DEG C
Film.
The Properties Testing of composite hyperfiltration membrane
(1) Mechanics Performance Testing
Using the tensile strength and tension fracture elongation rate of electronic tensile machine measurement composite hyperfiltration membrane, test temperature is room
Temperature, rate of extension are 2 mm/min.
The result shows that: compared with the polyacrylonitrile ultrafiltration film of blank example, composite hyperfiltration membrane made from Examples 1 to 6 resists
Zhang Qiangdu and elongation percentage all increase；This is because containing multi-walled carbon nanotube in composite hyperfiltration membrane produced by the present invention
Fe3O4/SiO2, SiO2With good stickiness, the elasticity of film is helped to improve.
(2) water flux is tested
At room temperature, composite hyperfiltration membrane is placed in cup type ultrafilter, 1 h of precompressed under 0 .1MPa pressure, collects certain time
The volume of interior permeate tests the pure water flux of composite hyperfiltration membrane.
The result shows that: compared with the polyacrylonitrile ultrafiltration film of blank example, composite hyperfiltration membrane made from Examples 1 to 6 it is pure
Water flux is significantly improved, and growth rate is up to 36%；This is because acidification multi-walled carbon nanotube/Fe3O4/SiO2So that this is compound
Ultrafiltration membrane film forms finer and close sectional layer, has good supporting role, and such microcellular structure, helps to improve
The energy and pure water flux of the ultrafiltration membrane.
(3) swellbility
Composite hyperfiltration membrane is cut into the diaphragm of 3cm × 3cm size, impregnates 48h in deionized water at room temperature, inhales diaphragm sufficiently
It is water-swellable；After composite hyperfiltration membrane is taken out, excess surface moisture is sucked with filter paper rapidly, is weighed, wet film sheet weight is obtained
(WW)；Wet film piece is placed in 60 DEG C of baking ovens dry 12h to constant weight, weighing obtains dry film weight (Wd).The swellbility of composite membrane
(WR) calculation formula it is as follows:
WR =×100%
The result shows that: the swellbility of composite hyperfiltration membrane made from Examples 1 to 6 improves 40% compared with polyacrylonitrile ultrafiltration film, swelling
Degree is the important indicator for measuring the porosity and average pore size of filter membrane；The result shows that: using acidification multi-walled carbon nanotube/Fe3O4/
SiO2To modified polyacrylonitrile, the filter efficiency of composite hyperfiltration membrane is helped to improve.
(4) rejection
At room temperature, a series of BSA standard solution for preparing concentration, measures through ultraviolet-uisible spectrophotometer, obtains corresponding
Absorbance A draws standard curve A-CBSA.Then certain density BSA solution is filtered into a period of time under a certain pressure again,
After stability of flow, a certain amount of filtrate is collected, measures the A of material liquid and filtrate, root respectively with ultraviolet-uisible spectrophotometer
Corresponding concentration can be calculated according to calibration curve equation, then calculates the rejection R of ultrafiltration membrane:
R=×100%
Wherein CfThe concentration of material liquid, CpThe concentration of permeate.
The result shows that: under equal conditions, polyacrylonitrile ultrafiltration film is to the rejection of bovine serum albumin (BSA)
51.26%, the rejection to bisphenol-A (BPA) is 42.83%；And composite hyperfiltration membrane made from embodiment 5 is to bovine serum albumin
(BSA) rejection is 78.37%, and the rejection to bisphenol-A (BPA) is 63.12%；Using raw material proportioning and preparation of the invention
Method, composite hyperfiltration membrane rejection obtained improve 30% or more compared with polyacrylonitrile ultrafiltration film.
(5) magnetic Fe has been loaded3O4Multi-walled carbon nanotube also there is magnetism so that composite hyperfiltration membrane of the invention has
Good electromagnetic performance and absorption property；Also, in the environment of pH > 7, which can be adsorbed such as Cr3+、Pb2+、
Zn2+Equal poisonous metals, and also have good rejection effect to organic matter, bacterium, virus, have in the ultrafiltration membrane alkaline environment
Good adsorption of metal ions ability.
(6) compared with the polyacrylonitrile ultrafiltration film of blank example, the permeance property of composite hyperfiltration membrane produced by the present invention and anti-
Pollutant performance is obviously improved, when the mass fraction of multi-walled carbon nanotube in composite hyperfiltration membrane is 0.5%, the infiltration of composite hyperfiltration membrane
Permeability can be best with antifouling property performance.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (9)
1. a kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane, which is characterized in that including following parts by weight
The raw material of proportion: 14~17 parts of film base material, acidification multi-walled carbon nanotube/Fe3O4/SiO20.1~1.0 part, 72~75 parts of solvent,
12~15 parts of pore-foaming agent and negative 0.05~0.3 part of surfactant.
2. many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 1, which is characterized in that
The film base material is polyacrylonitrile；The polyacrylonitrile molecular weight is 100,000, and polyacrylonitrile purity >=93%.
3. many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 2, which is characterized in that
Acidification multi-walled carbon nanotube/the Fe3O4/SiO2In, purity >=95% of the multi-walled carbon nanotube, multi-walled carbon nanotube it is straight
10~20nm of diameter, and length is 5~20 μm, the Fe3O4And SiO2Mass ratio be 2:1.
4. many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 2 or 3, feature exist
In the solvent is one or more of dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone.
5. many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 4, which is characterized in that
The pore-foaming agent is one or more of polyethylene glycol 400, Macrogol 600, polyvinylpyrrolidone and polyvinyl alcohol；Institute
Stating negative surfactant is one or more of lauryl sodium sulfate, sodium alkyl sulfonate and polymethylacrylic acid, described
Pore-foaming agent and negative surfactant are that analysis is pure.
6. a kind of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane as claimed in any one of claims 1 to 3
Preparation method, which comprises the following steps:
Preparation acidification multi-walled carbon nanotube/Fe3O4/SiO2,
1. flow back 14 h at 80 DEG C after the mixture S1 of multi-walled carbon nanotube and nitration mixture is vibrated 1 h；It is cooled to room temperature, uses
Hydrophilic film filtering, then being washed with deionized to the pH value of mixture S1 is 6.3~7.0, and acidification multi-walled carbon nanotube is made；
2. the mixture S2 of pure water, ferric chloride hexahydrate, green vitriol and above-mentioned acidification multi-walled carbon nanotube is first shaken
It swings 30 min, again under protection of argon gas after 50 DEG C of 30 min of oscillation, is warming up to 65 DEG C；The pH value of mixture S2 is adjusted to lye
12 or more, after persistent oscillation 60min, it is down to room temperature, then dilute, filter to neutrality；After being dried in vacuo 12 h at 80 DEG C, it is ground into
Acidification multi-walled carbon nanotube/Fe is made in powder3O4；
3. by pure water, nano silica and above-mentioned acidification carbon nanotube/Fe3O4Mixture S3 shake 30 min after, 120 DEG C
12 h of lower vacuum drying, pulverize, and acidification multi-walled carbon nanotube/Fe is made3O4/SiO2；
(2) casting solution is prepared, by solvent, pore-foaming agent, negative surfactant and above-mentioned acidification multi-walled carbon nanotube/Fe3O4/
SiO2Mixture S4 ultrasound after, polyacrylonitrile is added, is stirred under heating to polyacrylonitrile and is completely dissolved, uniform casting film is made
Liquid；
(3) composite hyperfiltration membrane is prepared, after above-mentioned casting solution circulating filtration, vacuumizing and defoaming, static 24 h at 40 DEG C；40℃
It is lower to use gel phase inversion by casting solution spinning, the composite hyperfiltration membrane of hollow fiber is made；
(4) it post-processes, above-mentioned composite hyperfiltration membrane is impregnated in glycerol liquor.
7. the preparation method of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 6,
It is characterized in that, the nitration mixture is made of the sulfuric acid that volume ratio is 3:1 and nitric acid in step (1), the hydrophilic film is ePTFE/
PP hydrophilic film；The molar ratio of the ferric chloride hexahydrate and green vitriol is (1.7~2): 1, the lye is hydrogen-oxygen
Change sodium solution or potassium hydroxide solution；The partial size of the nano silica is 20~40nm.
8. the preparation method of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 7,
It is characterized in that, before polyacrylonitrile is added, catalyst n, N- dicyclohexylcarbodiimide or 4- diformazan is first added in step (2)
Aminopyridine.
9. the preparation method of many walls nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane according to claim 6,
It is characterized in that, the mass fraction of multi-walled carbon nanotube is 0.3~0.7% in the composite hyperfiltration membrane in step (3).
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