CN104941466A - Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water - Google Patents
Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water Download PDFInfo
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Abstract
The invention relates to a preparation method of a mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water. The preparation method particularly comprises the following steps: synthesizing an ordered mesoporous carbon powder material of a high specific surface area; mxing polyvinylpyrrolidone serving as an additive and dimethylacetamide serving as a solvent with polyvinylidene fluoride (PVDF), and stirring to obtain a pure casting solution; adding mesoporous carbon powder, fully stirring, leaving to stand and defoaming to obtain a mesoporous carbon and PVDF mixed casting solution; scraping the defoamed mixed casting solution to prepare a film through a film coating machine by use of glass as the substrate, conducting pre-evaporation, and placing the film in a coagulating bath; stripping the film off glass, and continually soaking the film in a coagulating bath for 1-3 days; after flushing, soaking the film in deionized water for later use. The preparation method is simple in process and relatively low in cost; the prepared mesoporous carbon and PVDF mixed substrate film can effectively and quickly adsorb and hold back macromolecular pollutants such as blue algae hepatotoxins and organic dyes during deep water treatment, has large adsorption capacity, and can reach the removal rate of 100%, and the mesoporous carbon organic composite film, as a simple and easy-to-operate device, has the characteristics of high stability and flux and the like.
Description
Technical field
The invention belongs to macromolecule contaminant in water treatment to control and removal field, be specifically related to a kind of preparation method of the mesoporous carbon organic hybrid films for the treatment of molecule hepatotoxin pollutant large in water.
Background technology
Waste water treating and reutilizing be solve shortage of water resources and water pollutions day by day serious between one of the effective countermeasure of contradiction.At present, the technique of most of municipal sewage plant all can only process conventional organic pollution and nutrient salts etc., and large molecular organic pollutants such as Microcystin, organic dyestuff etc. that trace is poisonous then can not get effective removal.A kind of hepatotoxin of release after Microcystin breaks as Cells of Blue-green Algae is that in eutrophication water, the frequency of occurrences is high, work the mischief a most serious toxoid pollutant.The hepatotoxic molecular size of blue algae about 2 nm, due to the existence of its circulus and interval double bond, highly stable in water, after conventional water treatment, still can not get good removal.The sewage that dyestuff manufacture produces is because it is containing aromatic group materials different in a large number, and colourity is large, is still difficult to qualified discharge, is more difficult to reach reuse standard through materialization and biochemical treatment.As can be seen here, how effectively to control and remove this kind of poisonous larger molecular organics and pollute and become water purification field problem demanding prompt solution.
The method that depth-averaged model removes pollutant has a variety of, and wherein ordered mesoporous carbon material obtains the extensive concern of researcher as the adsorbent that a class is novel.Ordered mesoporous carbon material is the material of a class aperture at 2 ~ 50 nm, because it has larger specific area and pore volume, pore-size distribution homogeneous and on nanoscale continuously adjustabe, pore passage structure is adjustable and regular from one dimension to three-dimensional, morphology controllable, the advantages such as skeleton structure is stable, make it to water pollutant, especially have unrivaled superiority and wide application prospect compared with the Adsorption of macromolecule contaminant.But, because mesoporous carbon is pulverous form, in actual application, there is the problem being difficult to use and reclaim.
Membrane technology due to its separating effect stablize, the advantage such as reproducibility is good, simple to operate, non-secondary pollution obtains more concern in depth-averaged model.According to the purposes of film, roughly microfiltration membranes, milipore filter, reverse osmosis membrane, dialyser, infiltrating and vaporizing membrane, gas separation membrane and ion separation membrane etc. can be divided into.By material, organic milipore filter and Inorganic Ultrafiltration Membrane can be divided into.At present, common are machine film and have CAM (CA), PS membrane (PS), poly (ether sulfone) film (PES), polyacrylonitrile film (PAN), poly tetrafluoroethylene (PTFE) and polyvinylidene fluoride film (PVDF) etc.Wherein PVDF is a kind of crystalline polymer, has excellent anticorrosive and ageing-resistant performance, and its film-forming process uses extensively, and after film forming, intensity is high, and permeability is good.But selective poor to pollutant of pvdf membrane, when being used alone, its strainability is poor.
By inorganic powder material and organic film material are combined and device, not only can solve the problem that inorganic powder material is difficult to continued operation and recycles in actual water body, also can realize the high-performance Adsorption of organic film material to pollutant.The preparation method of existing inorganic-organic mixed substrate membrane containing nano-grade molecular sieve has: sol-gel process, organic polymer thermal decomposition method, polymer solution sedimentation and phase inversion etc.Wherein immersion precipitation phase inversion process is simple to operation because of it, becomes the comparatively widely used film-forming method of one.By inorganic matter dispersion being applied in a solvent or by film, inorganic-organic mixed substrate membrane containing nano-grade molecular sieve can be prepared on a large scale.Many researchers by different inorganic particles as Al
2o
3, SiO
2, TiO
2, ZrO
2studied Deng as the character change of additive to membrane material.Also the report of a small amount of mesoporous silicon/organic mixed-matrix membrane material is had at present.Shen etc. have prepared atresia SiO respectively
2, mesoporous silicon MCM-41 and 4A molecular sieve/PVDF mixed substrate membrane containing nano-grade molecular sieve, and be applied to gas absorption.After finding to add inorganic matter, its flux increases, but research inorganic matter character is not for the impact of absorption.Liao etc. report a kind of SBA-15/PVDF composite membrane, have studied its change to fenestra road and character.For carbon-based material, mainly concentrate on CNT/organic film, also have the report of a small amount of graphene oxide/organic film.But how to make full use of organic with inorganic material advantage separately, use simple process, obtained easy to operate, high stability, high-throughout composite membrane, in depth-averaged model, specific aim removes this problem of larger molecular organics still huge investigation and application potentiality.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple, the eco-friendly mesoporous carbon organic hybrid films for the treatment of molecule toxic pollutant large in water.
The mesoporous carbon organic hybrid films of preparation proposed by the invention, make use of the advantage of the film forming stability of the huge absorption property of inorganic material and organic material, and inorganic mesoporous carbon mass content accounts for 0.1 ~ 80% of obtained composite membrane.
The preparation method of the mesoporous carbon organic hybrid films for the treatment of macromolecule contaminant in water of the present invention, concrete steps are as follows:
(1) using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, the silicon that obtains is polymerized as hard template in tetraethyl orthosilicate, phenolic resins, as carbon matrix precursor, uses the order mesoporous carbon powder material of solvent evaporation induced self-assembly method synthesis high-ratio surface;
(2) configure Kynoar (PVDF) casting solution, polyvinylpyrrolidone (PVP) is additive, and dimethylacetylamide (DMAC) is solvent, and the mass ratio of control PVDF:DMAC:PVP is 1:(3 ~ 5): (0.1 ~ 0.3); Stir until PVDF fully dissolves at 40 ~ 80 DEG C, obtain pure PVDF casting solution;
(3) the pure PVDF casting solution mixing that mesoporous carbon dusty material step (1) obtained and step (2) obtain, DMAC is solvent, control DMAC:PVDF casting solution: the mass ratio of mesoporous carbon is 1:(1 ~ 4): (0.5 ~ 10), stirred through 12 ~ 36 hours at 40 ~ 80 DEG C, obtain mesoporous carbon PVDF mixing casting solution;
(4) mesoporous carbon PVDF mixing casting solution standing and defoaming step (3) obtained;
(5) take glass as substrate, the mesoporous carbon PVDF mixing casting solution through deaeration step (4) obtained uses film applicator film, and pre-evaporation is 20 ~ 100 seconds;
(6) film that step (5) obtains is put into coagulating bath, in control solidi fication bath, the volume ratio of deionized water and ethanol is 1:(1 ~ 5); After film is peeled off voluntarily from glass, continue to soak 1 ~ 3 day in coagulating bath; Also soak or hang airing under room temperature with deionized water rinsing.
Mesoporous carbon dusty material in the present invention can be by the order mesoporous carbon powder material of described use solvent evaporation induced self-assembly method synthesis high-ratio surface in FDU-14, FDU-15, FDU-16, FDU-18 or CMK-3 one or more, or other carbon-based powder material is as one or several in active 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 defoaming 1 ~ 3 day or 20 ~ 60 DEG C of vacuum defoamations 6 ~ 24 hours.
Preparation method of the present invention can make the interpolation quality of mesoporous carbon account for 0.1 ~ 80% of composite membrane.
The composite membrane utilizing the inventive method to obtain has two cover primary aperture, and a set of is 1 ~ 20 μm, the micron order aperture of PVDF, and a set of is mesoporous level aperture 2 ~ 7 nm of mesoporous material, and specific area is 100 ~ 700 m
2/ g.Obtained composite membrane belongs to new construction, high-performance organic/inorganic composite film.
The present invention has following beneficial effect:
The invention provides the preparation method of a kind of mesoporous carbon/PVDF Inorganic whisker film.This preparation method's technique is simple, cost is lower, obtained mesoporous carbon PVDF composite membrane in depth-averaged model can effectively quick adsorption macromolecule contaminant as blue algae hepatotoxin and dyestuff etc., clearance can reach 100%, adsorption capacity 20 ~ 100 mg/g, simple as one, easy-operating device has the feature such as high stability, high flux simultaneously.
Accompanying drawing explanation
Fig. 1 has transmission electron microscope (TEM) photo of the ordered mesoporous carbon material of high-ratio surface, is obtained by embodiment 2.
Fig. 2 carbon content is cross-sectional scans Electronic Speculum (SEM) photo of the mesoporous carbon organic hybrid films of 25 wt%, is obtained by embodiment 3.
Fig. 3 carbon content is cross-sectional scans Electronic Speculum (SEM) photo of the mesoporous carbon organic hybrid films of 40 wt%, is obtained by embodiment 4.
The filter element optical photograph that Fig. 4 is obtained by composite membrane, is obtained by embodiment 3 material.
Recycle performance when Fig. 5 composite membrane is removed blue algae hepatotoxin in water body, use embodiment 3 material to obtain.
Detailed description of the invention
Embodiment 1
The preparation of organic polymer phenolic resins: by 24.0 g phenol meltings in 40 ~ 42 DEG C of water-baths, add the NaOH aqueous solution that 5.04 g mass percentage concentration are 20%, stir 10 minutes, add 40.8 g formalins (37 wt%), back flow reaction 1 hour at 70 ~ 75 DEG C, cool to room temperature.PH value of solution is regulated to be neutral with 0.6 M HCl.Reaction system is placed in 45 DEG C of water-bath decompression distillation 1 ~ 2 hour, obtains 28.7 g organic polymer phenolic resins (molecular weight 200 ~ 500).By phenol formaldehyde resin dissolves in 103.1 g absolute ethyl alcohols, centrifugal segregation NaCl crystal, obtains light brown phenolic resins performed polymer ethanolic solution for subsequent use.
Embodiment 2
The synthesis of high-ratio surface ordered mesoporous carbon material: 1.6 g non-ionic surface active agent PEO-PPOX-PEO triblock copolymers (Pluronic F127) and 1.0 g 0.2 M HCl join in 8.0 g ethanol, stir and obtain settled solution in l hour at 40 DEG C.Add the phenolic resins performed polymer ethanolic solution of 2.08 g tetraethyl orthosilicates and 5.0 g 20 wt%, and continue stirring 2 hours.Transfer in glass culture dish by gained solution, ambient temperatare put volatilization after 8 hours, 100 DEG C of dryings in baking oven.After cooling, the orange-yellow thin-film material obtained is scraped from culture dish, suitably after grinding, be heated to 900 DEG C with 2 DEG C/min in a nitrogen atmosphere and keep 2 hours.Finally gained black powder be immersed in the HF solution of 10 excessive wt%, stir removing silica component of spending the night, filter, wash and obtain high-specific-surface mesoporous material with carbon element after drying.Abundant grinding is undertaken by 300 ~ 500 mesh sieve sieving the particle obtaining homogeneous grain diameter.Its character is as shown in table 1, and Fig. 1 is shown in by transmission electron microscope picture.
Embodiment 3
Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, the silicon that obtains is polymerized as hard template in tetraethyl orthosilicate, the phenolic resins obtained using embodiment 1, as carbon matrix precursor, uses the order mesoporous carbon powder material of solvent evaporation induced self-assembly method synthesis high-ratio surface;
The preparation (25 wt% carbon content) of mesoporous carbon organic hybrid films: 4.25 g Kynoar (PVDF) and 1.0 g polyvinylpyrrolidones (PVP) are dissolved in 21.1 g dimethylacetylamides (DMAC), stir until PVDF fully dissolves at 70 DEG C, obtain pure PVDF casting solution.Get 8.24 g casting solutions and 0.48 g meso-porous carbon material joins in 4 g DMAC, stir one day at 70 DEG C, obtain mesoporous carbon/PVDF casting solution.Left at room temperature deaeration 2 days.Glass does substrate, uses film applicator mixing casting solution to be coated film forming, prevapourising 40 seconds, puts into water: ethanol is the coagulating bath of 1:1.Film is peeled off from glass, and continues to soak 1 day in solidification liquid; Soak two days with deionized water rinsing, under room temperature, hang airing obtains mesoporous carbon/PVDF composite membrane.Its character 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, the silicon that obtains is polymerized as hard template in tetraethyl orthosilicate, the phenolic resins obtained using embodiment 1, as carbon matrix precursor, uses the order mesoporous carbon powder material of solvent evaporation induced self-assembly method synthesis high-ratio surface;
The preparation of mesoporous carbon organic hybrid films (40 wt% carbon content): be dissolved in 21.1 g DMAC by 4.25 g PVDF and 1.0 g PVP, stirs until PVDF fully dissolves, obtains pure PVDF casting solution at 70 DEG C.Get 8.24 g casting solutions and 0.96 g meso-porous carbon material joins in 4 g DMAC, stir one day at 70 DEG C, obtain mesoporous carbon/PVDF casting solution.Deaeration 6 hours under room temperature in vacuo.Glass does substrate, uses film applicator by this mixing casting solution striking film forming, prevapourising 60 seconds, puts into water: ethanol contend is than the coagulating bath for 1:1.Film is peeled off from glass, and continues to soak 1 day in solidification liquid; Soak two days with deionized water rinsing, under room temperature, hang airing obtains mesoporous carbon/PVDF composite membrane.Its character is as shown in table 1.Composite membrane cross section surface sweeping electron microscopic picture is shown in Fig. 3.
Embodiment 5
Using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, the silicon that obtains is polymerized as hard template in tetraethyl orthosilicate, the phenolic resins obtained using embodiment 1, as carbon matrix precursor, uses the order mesoporous carbon powder material of solvent evaporation induced self-assembly method synthesis high-ratio surface;
The preparation (25 wt% carbon content) of active carbon organic hybrid films: be dissolved in 42.2 g DMAC by 8.5 g PVDF and 2.0 g PVP, stirs until PVDF fully dissolves, obtains pure PVDF casting solution at 60 DEG C.Get 10.3 g casting solutions and 0.75 g grinding is sieved and dry active carbon powder joins in 5 g DMAC, stir 36 hours at 60 DEG C, obtain carbon/PVDF casting solution.Deaeration 12 hours under room temperature in vacuo.Glass does substrate, uses film applicator by this mixing casting solution striking film forming, prevapourising 60 seconds, puts into water: ethanol contend is than the coagulating bath for 1:1.5.Film is peeled off from glass, and continues to soak 1 day in solidification liquid; Soak two days with deionized water rinsing, under room temperature, hang airing obtains active carbon/PVDF composite membrane.Its character is as shown in table 1.
Embodiment 6
Laboratory room small-sized blue-green algae hepatotoxin is carried out to the mesoporous carbon prepared in embodiment/PVDF organic/inorganic composite film, experiment that organic dyestuff is removed from water body.It is the filter element of 2.5cm that 4 ~ 10 layers of composite membrane overlap are loaded diameter.Filter element and constant flow peristaltic pump are coupled together with flexible pipe, contaminant water is pumped into constant flow rate by peristaltic pump, by 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, adopts efficient liquid phase instrument and Ultraviolet Detector to detect aqueous concentration respectively.The composite membrane prepared in embodiment is as shown in table 2 to the removal ability of macromolecule contaminant in water body.Filter element optical photograph is shown in Fig. 4.
Embodiment 7
The regeneration that laboratory room small-sized blue-green algae hepatotoxin removes from water body is carried out to the mesoporous carbon prepared in embodiment/PVDF organic/inorganic composite film and uses experiment.Composite membrane, by 10 mL 1 mg/L blue-green algae hepatotoxin solution, then uses 5 ~ 10 mL methanol solution wash-outs, then with the methanol solution that 10 mL deionized water rinsings remain, detects the concentration of toxin.Be cycled to repeat more than six times.What the composite membrane prepared in embodiment was removed macromolecule contaminant in water body recycles performance as shown in Figure 5.
Table 1 is structural parameters and the character of obtained mesoporous carbon and carbon back/PVDF composite membrane in embodiment 2 to 5.
Table 1
| Embodiment | Aperture (nm) | Pore volume (cm 3/g) | Specific area (m 2/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 in embodiment 6 to 7, uses 3 to the 4 mesoporous carbon/PVDF composite membranes obtained in embodiment to remove the effect of large molecule blue-green algae hepatotoxin and organic dyestuff rhodamine B
Table 2
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (5)
1., for the treatment of a preparation method for the mesoporous carbon organic hybrid films of macromolecule contaminant in water, it is characterized in that concrete steps are as follows:
(1) using polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer nonionic surface active agent as soft template, the silicon that obtains is polymerized as hard template in tetraethyl orthosilicate, phenolic resins, as carbon matrix precursor, uses the order mesoporous carbon powder material of solvent evaporation induced self-assembly method synthesis high-ratio surface;
(2) configure Kynoar (PVDF) casting solution, polyvinylpyrrolidone (PVP) is additive, and dimethylacetylamide (DMAC) is solvent, and the mass ratio of control PVDF:DMAC:PVP is 1:(3 ~ 5): (0.1 ~ 0.3); Stir until PVDF fully dissolves at 40 ~ 80 DEG C, obtain pure PVDF casting solution;
(3) the pure PVDF casting solution mixing that order mesoporous carbon powder material step (1) obtained and step (2) obtain, DMAC is solvent, control DMAC:PVDF casting solution: the mass ratio of mesoporous carbon is 1:(1 ~ 4): (0.5 ~ 10), stirred through 12 ~ 36 hours at 40 ~ 80 DEG C, obtain mesoporous carbon PVDF mixing casting solution;
(4) mesoporous carbon PVDF mixing casting solution standing and defoaming step (3) obtained;
(5) take glass as substrate, the mesoporous carbon PVDF mixing casting solution through deaeration step (4) obtained uses film applicator film, and pre-evaporation is 20 ~ 100 seconds;
(6) film that step (5) obtains is put into coagulating bath, in control solidi fication bath, the volume ratio of deionized water and ethanol is 1:(1 ~ 5); After film is peeled off voluntarily from glass, continue to soak 1 ~ 3 day in coagulating bath; Also soak or hang airing under room temperature with deionized water rinsing.
2. preparation method according to claim 1, it is characterized in that: the order mesoporous carbon powder material using solvent evaporation induced self-assembly method to synthesize high-ratio surface described in step (1) in FDU-14, FDU-15, FDU-16, FDU-18 or CMK-3 one or several, or one or several in active carbon, CNT, Graphene or graphene oxide.
3. preparation method according to claim 1, is characterized in that: in step (4), and mesoporous carbon PVDF mixing casting solution is in 20 ~ 60 DEG C of standing and defoaming 1 ~ 3 day or 20 ~ 60 DEG C of vacuum defoamations 6 ~ 24 hours.
4. preparation method according to claim 1, is characterized in that: the addition of described preparation method's intermediary hole carbon can account for 0.1 ~ 80% of final composite membrane quality.
5. preparation method according to claim 1, it is characterized in that: the composite membrane that described preparation method obtains has two cover primary aperture, a set of is 1 ~ 20 μm, the micron order aperture of pvdf membrane, and a set of is mesoporous level aperture 2 ~ 7 nm of mesoporous material, and specific area is 100 ~ 700 m
2/ g.
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