CN104941466B - A kind of preparation method for being used to remove the hepatotoxic mesoporous carbon organic hybrid films of macromolecular in water removal - Google Patents

A kind of preparation method for being used to remove the hepatotoxic mesoporous carbon organic hybrid films of macromolecular in water removal Download PDF

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CN104941466B
CN104941466B CN201510310565.4A CN201510310565A CN104941466B CN 104941466 B CN104941466 B CN 104941466B CN 201510310565 A CN201510310565 A CN 201510310565A CN 104941466 B CN104941466 B CN 104941466B
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mesoporous carbon
pvdf
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mesoporous
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CN104941466A (en
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张伟贤
滕玮
范建伟
冉献强
杨建平
张颖纯
白楠
陈旺源
王晓敏
勾晓
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Tongji University
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Abstract

The present invention relates to a kind of preparation method of high content mesoporous carbon organic composite substratd film.Concretely comprise the following steps:Synthesize the order mesoporous carbon powder material of high-ratio surface;Using polyvinylpyrrolidone as additive, dimethylacetylamide is solvent, with Kynoar(PVDF)Mixing obtains pure casting solution;Mesoporous carbon dust is added, by being sufficiently stirred for, standing and defoaming obtains mesoporous carbon PVDF mixing casting solutions;Using film applicator, using glass as substrate, by the mixing casting solution striking film forming of deaeration, through prevapourising, coagulating bath is put into;Film is peeled off from glass, and continues to soak 1~3 day in solidification liquid;Soak stand-by in deionized water after flushing.The preparation method technique is simple, cost is relatively low, obtained mesoporous carbon PVDF mixed substrate membrane containing nano-grade molecular sieves in depth-averaged model can effectively quick adsorption and retention macromolecule contaminant such as blue algae hepatotoxin, organic dyestuff etc., adsorption capacity is big, clearance is up to 100%, while the features such as having high stability, high flux as simple, the easy-operating device of one kind.

Description

A kind of preparation for being used to remove the hepatotoxic mesoporous carbon organic hybrid films of macromolecular in water removal Method
Technical field
The invention belongs to macromolecule contaminant control in water process with removing field, and in particular to one kind is used to handle in water The preparation method of the mesoporous carbon organic hybrid films of macromolecular hepatotoxin pollutant.
Background technology
Waste water treating and reutilizing be solve shortage of water resources and water pollution it is increasingly serious between contradiction one of effective countermeasure.Mesh Before, the technique of most of municipal sewage plant can only all handle conventional organic pollution and nutrient salts etc., and trace is poisonous Macromolecular organic pollution such as Microcystin, organic dyestuff etc. if cannot effectively remove.Microcystin is used as blue-green algae A kind of hepatotoxin discharged after cell rupture, is frequency of occurrences height, the class poison for the most serious that causes harm in eutrophication water Plain pollutant.The nm of the hepatotoxic molecular size of blue algae about 2 is non-in water due to the presence of its cyclic structure and interval double bond It is often stable, still cannot preferably it be removed after conventional water treatment.Sewage produced by dyestuff manufacture is because it is containing a large amount of different Aromatic group material, and colourity is big, is still difficult to qualified discharge through materialization and biochemical treatment, it is more difficult to reach reuse standard. As can be seen here, how effectively to control and remove this kind of poisonous larger molecular organicses pollution has turned into that water purification field is urgently to be resolved hurrily to ask Topic.
The method that depth-averaged model removes pollutant has many kinds, and wherein ordered mesoporous carbon material is used as the new suction of a class Attached dose obtained researcher extensive concern.Ordered mesoporous carbon material is material of the class aperture in 2~50 nm, because it has Larger specific surface area and pore volume, pore-size distribution is homogeneous and the continuously adjustabe on nanoscale, and pore passage structure is from one-dimensional to three Tie up adjustable and regular, morphology controllable, the advantages of skeleton structure is stable so that it is to water pollutant, especially larger point The Adsorption of sub- pollutant has unrivaled superiority and wide application prospect.But, because mesoporous carbon is powder , there is the problem of being difficult to use and reclaim in actual application in the form of shape.
Membrane technology due to its separating effect stabilization, good, simple to operate reproducibility, non-secondary pollution the advantages of in depth More concern is obtained in water process.According to the purposes of film, it can substantially be divided into microfiltration membranes, milipore filter, reverse osmosis membrane, dialysis Film, infiltrating and vaporizing membrane, gas separation membrane and ion separation membrane etc..By material, organic milipore filter and Inorganic Ultrafiltration Membrane can be divided into.Mesh Before, the machine film of common are has cellulose acetate film(CA), PS membrane(PS), poly (ether sulfone) film(PES), polyacrylonitrile film(PAN), it is poly- Tetrafluoroethylene(PTFE)And polyvinylidene fluoride film(PVDF)Deng.Wherein PVDF is a kind of crystalline polymer, there is excellent resist Corrosion and ageing-resistant performance, its film-forming process is using extensively, and intensity is high after film forming, and permeability is good.But, pvdf membrane is to pollutant Selectivity it is poor, during exclusive use, its strainability is poor.
By the way that inorganic powder material and organic film material are combined and device, it can not only solve inorganic powder material and exist The problem of being difficult to operate continuously and recycle in actual water body, it can also realize that organic film material is inhaled to the high-performance of pollutant It is attached to remove.The preparation method of existing inorganic-organic mixed substrate membrane containing nano-grade molecular sieve has:It is sol-gel process, organic polymer thermal decomposition method, poly- Polymer solution sedimentation and phase inversion etc..Wherein immersion precipitation phase inversion process is because its is simple to operation, as a kind of more wide The general film-forming method used.Can by coating inorganic matter is scattered in a solvent or by film, come prepare on a large scale it is inorganic-have Machine mixed substrate membrane containing nano-grade molecular sieve.Many researchers are by different inorganic particles such as Al2O3, SiO2, TiO2, ZrO2Deng as additive to film The property of material, which changes, to be studied.Also there is the report of a small amount of mesoporous silicon/organic mixed-matrix membrane material at present.Shen etc. is respectively It is prepared for non-porous SiO2, mesoporous silicon MCM-41 and 4A molecular sieve/PVDF mixed substrate membrane containing nano-grade molecular sieves, and applied to gas absorption.It was found that adding Plus after inorganic matter, the increase of its flux, but not influence of the research inorganic matter property for absorption.Liao etc. reports one kind SBA-15/PVDF composite membranes, have studied its change to fenestra road and property.For carbon-based material, carbon nanometer is concentrated mainly on Pipe/organic film, the report for also having a small amount of graphene oxide/organic film.But how to make full use of organic each with inorganic material From advantage, using simple process, be made easy to operate, high stability, high-throughout composite membrane, in depth-averaged model Specific aim, which removes larger molecular organicses this problems, still huge research and application potential.
The content of the invention
Simple and easy to apply, environment-friendly it is used to handle macromolecular toxic contaminants in water it is an object of the invention to provide a kind of The preparation method of the mesoporous carbon organic hybrid films of thing.
The mesoporous carbon organic hybrid films of preparation proposed by the invention, make use of the huge absorption property of inorganic material with it is organic The advantage of the film forming stability of material, inorganic mesoporous carbon mass content accounts for the 0.1~80% of obtained composite membrane.
The preparation method of the present invention for being used to handle the mesoporous carbon organic hybrid films of macromolecule contaminant in water, specifically Step is as follows:
(1)Soft mode is used as using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent It polymerize obtained silicon in plate, tetraethyl orthosilicate as hard template, phenolic resin is volatilized using solvent and induced as carbon matrix precursor Self-assembly method synthesizes the order mesoporous carbon powder material of high-ratio surface;
(2)Configure Kynoar(PVDF)Casting solution, polyvinylpyrrolidone(PVP)For additive, dimethylacetamide Amine(DMAC)For solvent, PVDF is controlled:DMAC:PVP mass ratio is 1:(3~5):(0.1~0.3);Stirred at 40~80 DEG C Mix until PVDF fully dissolves, obtain pure PVDF casting solutions;
(3)By step(1)Obtained mesoporous carbon powder material and step(2)Obtained pure PVDF casting solutions mixing, DMAC For solvent, DMAC is controlled:PVDF casting solutions:The mass ratio of mesoporous carbon is 1:(1~4):(0.5~10), is passed through at 40~80 DEG C Spend 12~36 hours to stir, obtain mesoporous carbon PVDF mixing casting solutions;
(4)By step(3)Obtained mesoporous carbon PVDF mixing casting solution standing and defoamings;
(5)Using glass as substrate, by step(4)The obtained mesoporous carbon PVDF mixing casting solutions through deaeration use film applicator Film, pre-evaporation is 20~100 seconds;
(6)By step(5)Obtained film is put into coagulating bath, controls deionized water and the volume ratio of ethanol in coagulating bath to be 1:(1~5);After film is voluntarily peeled off from glass, continue to soak 1~3 day in coagulating bath;With deionized water rinsing and soak or Person's hang airing at room temperature.
Mesoporous carbon powder material in the present invention can synthesize high by the use solvent evaporation induced self-assembly method Order mesoporous carbon powder material than surface is one or more of in FDU-14, FDU-15, FDU-16, FDU-18 or CMK-3, or One or several kinds in other carbon-based powder materials such as activated carbon, CNT, graphene or graphene oxide.
In the present invention, mesoporous carbon PVDF mixing casting solution is in 20~60 DEG C of standing and defoamings 1~3 day or 20~60 DEG C of vacuum Deaeration 6~24 hours.
The preparation method of the present invention can make the addition quality of mesoporous carbon account for the 0.1~80% of composite membrane.
The composite membrane being made using the inventive method has two sets of primary apertures, and a set of micron order aperture 1 for PVDF~ 20 μm, a set of mesoporous nm of level aperture 2~7 for mesoporous material, specific surface area is 100~700 m2/g.Obtained composite membrane Belong to new construction, high-performance organic/inorganic composite film.
The present invention has the advantages that:
The invention provides a kind of preparation method of mesoporous carbon/PVDF Inorganic whisker films.Preparation method technique letter Single, cost is relatively low, and obtained mesoporous carbon PVDF composite membranes can effectively quick adsorption macromolecule contaminant be such as in depth-averaged model Blue algae hepatotoxin and dyestuff etc., clearance is up to 100%, the mg/g of adsorption capacity 20~100, while as a kind of simple, easy The features such as device of operation has high stability, high flux.
Brief description of the drawings
Fig. 1 has the transmission electron microscope of the ordered mesoporous carbon material of high-ratio surface(TEM)Photo, is made by embodiment 2.
Fig. 2 carbon contents are the cross-sectional scans Electronic Speculum of 25 wt% mesoporous carbon organic hybrid films(SEM)Photo, by implementing Example 3 is made.
Fig. 3 carbon contents are the cross-sectional scans Electronic Speculum of 40 wt% mesoporous carbon organic hybrid films(SEM)Photo, by implementing Example 4 is made.
Fig. 4 filter element optical photographs as made from composite membrane, are made by the material of embodiment 3.
Recycling performance when Fig. 5 composite membranes are removed to blue algae hepatotoxin in water body, is obtained using the material of embodiment 3 Arrive.
Embodiment
Embodiment 1
The preparation of organic polymer phenolic resin:24.0 g phenol are melted in 40~42 DEG C of water-baths, 5.04 g are added Mass percentage concentration is the 20% NaOH aqueous solution, is stirred 10 minutes, adds 40.8 g formalins(37 wt%), 70~75 Back flow reaction 1 hour, is cooled to room temperature at DEG C.It is neutral with 0.6 M HCl regulation pH value of solution.Reaction system is placed in 45 DEG C of water Vacuum distillation 1~2 hour in bath, obtains 28.7 g organic polymer phenolic resin(Molecular weight 200~500).By phenolic resin It is dissolved into 103.1 g absolute ethyl alcohols, centrifugation removes NaCl crystal, obtains light brown phenolic resin performed polymer ethanol solution standby With.
Embodiment 2
The synthesis of high-ratio surface ordered mesoporous carbon material:1.6 g nonionic surfactants PEOs-polycyclic oxygen Propane-PEO triblock copolymer(Pluronic F127)It is added to the M HCl of 1.0 g 0.2 in 8.0 g ethanol, Stirring obtains settled solution in l hours at 40 DEG C.Add 2.08 g tetraethyl orthosilicates and the wt% of 5.0 g 20 phenolic aldehyde tree Fat performed polymer ethanol solution, and continue stirring 2 hours.Resulting solution is transferred in glass culture dish, volatilization is placed at room temperature After 8 hours, in 100 DEG C of dryings in baking oven.After cooling, obtained orange-yellow thin-film material is scraped from culture dish, suitably ground After mill, it is heated to 900 DEG C with 2 DEG C/min in a nitrogen atmosphere and is kept for 2 hours.Finally gained black powder was immersed in In 10 wt% of amount HF solution, removing silica component is stirred overnight, high-ratio surface Jie is obtained after being filtered, washed and dried Hole carbon material.To be fully ground carry out by 300~500 mesh sieve and sieve the particle for obtaining homogeneous grain diameter.Its property such as institute of table 1 Show, transmission electron microscope picture is shown in Fig. 1.
Embodiment 3
Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, It polymerize obtained silicon in tetraethyl orthosilicate as hard template, the phenolic resin obtained using embodiment 1 is used as carbon matrix precursor Solvent evaporation induced self-assembly method synthesizes the order mesoporous carbon powder material of high-ratio surface;
The preparation of mesoporous carbon organic hybrid films(25 wt% carbon contents):By 4.25 g Kynoar(PVDF)With 1.0 g Polyvinylpyrrolidone(PVP)It is dissolved in 21.1 g dimethylacetylamides(DMAC)In, stirred at 70 DEG C until PVDF is fully molten Solution, obtains pure PVDF casting solutions.8.24 g casting solutions and 0.48 g meso-porous carbon materials is taken to be added in 4 g DMAC, at 70 DEG C Stirring one day, obtains mesoporous carbon/PVDF casting solutions.Standing and defoaming 2 days at room temperature.Glass does substrate, will be mixed using film applicator Casting solution coats film forming, and prevapourising 40 seconds is put into water:Ethanol is 1:In 1 coagulating bath.Film is peeled off from glass, and continued Soaked 1 day in solidification liquid;With deionized water rinsing and soak two days, at room temperature hang airing obtain mesoporous carbon/PVDF be combined Film.Its property is as shown in table 1.Composite membrane cross-sectional scans electron microscopic picture is shown in Fig. 2.
Embodiment 4
Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, It polymerize obtained silicon in tetraethyl orthosilicate as hard template, the phenolic resin obtained using embodiment 1 is used as carbon matrix precursor Solvent evaporation induced self-assembly method synthesizes the order mesoporous carbon powder material of high-ratio surface;
Mesoporous carbon organic hybrid films(40 wt% carbon contents)Preparation:4.25 g PVDF and 1.0 g PVP are dissolved in 21.1 In g DMAC, stirred at 70 DEG C until PVDF fully dissolves, obtain pure PVDF casting solutions.Take 8.24 g casting solutions and 0.96 g Meso-porous carbon material is added in 4 g DMAC, is stirred one day at 70 DEG C, is obtained mesoporous carbon/PVDF casting solutions.Under room temperature in vacuo Deaeration 6 hours.Glass does substrate, and using film applicator by the mixing casting solution striking film forming, prevapourising 60 seconds is put into water:Ethanol Volume ratio is 1:In 1 coagulating bath.Film is peeled off from glass, and continues to soak 1 day in solidification liquid;Use deionized water rinsing And soak two days, at room temperature hang airing obtain mesoporous carbon/PVDF composite membranes.Its property is as shown in table 1.Sweep composite membrane cross section Face electron microscopic picture is shown in Fig. 3.
Embodiment 5
Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, It polymerize obtained silicon in tetraethyl orthosilicate as hard template, the phenolic resin obtained using embodiment 1 is used as carbon matrix precursor Solvent evaporation induced self-assembly method synthesizes the order mesoporous carbon powder material of high-ratio surface;
The preparation of activated carbon organic hybrid films(25 wt% carbon contents):8.5 g PVDF and 2.0 g PVP are dissolved in 42.2 In g DMAC, stirred at 60 DEG C until PVDF fully dissolves, obtain pure PVDF casting solutions.Take 10.3 g casting solutions and 0.75 g The active carbon powder that grinding is sieved and dried is added in 5 g DMAC, is stirred 36 hours at 60 DEG C, is obtained carbon/PVDF casting films Liquid.Deaeration 12 hours under room temperature in vacuo.Glass does substrate, using film applicator by the mixing casting solution striking film forming, prevapourising 60 Second, it is put into water:Ethanol volume ratio is 1:In 1.5 coagulating bath.Film is peeled off from glass, and continues to soak 1 in solidification liquid My god;With deionized water rinsing and soak two days, at room temperature hang airing obtain activated carbon/PVDF composite membranes.Its property such as institute of table 1 Show.
Embodiment 6
Laboratory room small-sized blue-green algae hepatotoxin is carried out to the mesoporous carbon/PVDF organic/inorganic composite films prepared in embodiment, had The experiment that engine dyeing material is removed from water body.By the overlapping filter element for loading a diameter of 2.5cm of 4~10 layers of composite membrane.Use flexible pipe Filter element is connected with constant flow peristaltic pump, contaminant water is pumped into by peristaltic pump with constant flow rate, pass through water outlet after composite membrane. The initial concentration of macromolecule contaminant is respectively:Blue-green algae hepatotoxin 1mg/L, rhodamine B 1mg/L;Flow velocity 1mL/min, is adopted respectively Aqueous concentration is detected with efficient liquid phase instrument and Ultraviolet Detector.The composite membrane prepared in embodiment is to macromolecular in water body The removal ability of pollutant is as shown in table 2.Filter element optical photograph is shown in Fig. 4.
Embodiment 7
Laboratory room small-sized blue-green algae hepatotoxin is carried out from water to the mesoporous carbon/PVDF organic/inorganic composite films prepared in embodiment The regeneration removed in body uses experiment.Composite membrane is by the mg/L blue-green algae hepatotoxin solution of 10 mL 1, then with 5~10 mL first Alcoholic solution is eluted, then the methanol solution remained with 10 mL deionized water rinsings, detects the concentration of toxin.Circulating repetition six times with On.The recycling performance that the composite membrane prepared in embodiment is removed to macromolecule contaminant in water body is as shown in Figure 5.
Table 1 is the structural parameters and property of obtained mesoporous carbon and carbon-based/PVDF composite membranes in embodiment 2 to 5.
Table 1
Embodiment Aperture (nm) Pore volume (cm3/g) Specific surface area (m2/g)
Embodiment 2 2.1, 5.6 1.7 1600
Embodiment 3 2.0, 5.6 0.34 413
Embodiment 4 2.0, 5.6 0.44 550
Embodiment 5 < 2 0.11 130
Table 2 is blue in embodiment 6 to 7, to use mesoporous carbon made from embodiment 3 to 4/PVDF composite membranes to remove macromolecular Algae hepatotoxin and the effect of organic dyestuff rhodamine B
Table 2
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to implementation here Example, those skilled in the art do not depart from improvement that scope made and change all should be according to the announcement of the present invention Within protection scope of the present invention.

Claims (2)

1. a kind of preparation method for being used to handle the mesoporous carbon organic hybrid films of macromolecule contaminant in water, it is characterised in that specific Step is as follows:
(1)Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, It polymerize obtained silicon in tetraethyl orthosilicate as hard template, phenolic resin is induced certainly as carbon matrix precursor using solvent volatilization Construction from part synthesizes the order mesoporous carbon powder material of high-ratio surface;The use solvent evaporation induced self-assembly method synthesizes Gao Bibiao The order mesoporous carbon powder material in face is one or several kinds in FDU-14, FDU-15, FDU-16, FDU-18 or CMK-3;
(2)Configure Kynoar(PVDF)Casting solution, polyvinylpyrrolidone(PVP)For additive, dimethylacetylamide (DMAC)For solvent, PVDF is controlled:DMAC:PVP mass ratio is 1:(3~5):(0.1~0.3);Stirred at 40~80 DEG C Until PVDF fully dissolves, pure PVDF casting solutions are obtained;
(3)By step(1)Obtained order mesoporous carbon powder material and step(2)Obtained pure PVDF casting solutions mixing, DMAC For solvent, DMAC is controlled:PVDF casting solutions:The mass ratio of mesoporous carbon is 1:(1~4):(0.5~10), is passed through at 40~80 DEG C Spend 12~36 hours to stir, obtain mesoporous carbon PVDF mixing casting solutions;
(4)By step(3)Obtained mesoporous carbon PVDF mixing casting solution standing and defoamings;
(5)Using glass as substrate, by step(4)The obtained mesoporous carbon PVDF mixing casting solutions through deaeration are applied using film applicator Film, pre-evaporation is 20~100 seconds;
(6)By step(5)Obtained film is put into coagulating bath, and it is 1 to control deionized water and the volume ratio of ethanol in coagulating bath:(1 ~5);After film is voluntarily peeled off from glass, continue to soak 1~3 day in coagulating bath;With deionized water rinsing and immersion or room The lower hang airing of temperature, obtains mesoporous carbon/polytetrafluoroethylcomposite composite film;
The addition of described preparation method intermediary hole carbon accounts for the 0.1~80% of final compound film quality;
The composite membrane that the preparation method is obtained has two sets of primary apertures, a set of 1~20 μm of micron order aperture for pvdf membrane, A set of mesoporous nm of level aperture 2~7 for mesoporous material, specific surface area is 100~700 m2/g。
2. preparation method according to claim 1, it is characterised in that:Step(4)In, mesoporous carbon PVDF mixing casting solutions exist 20~60 DEG C of standing and defoamings 1~3 day or 20~60 DEG C of vacuum defoamations 6~24 hours.
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