CN104801208A - Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof - Google Patents
Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a sodium alginate-flaky ZIF-8 hybrid composite membrane, and belongs to the field of membrane separation. At first, Zn(NO3)2 and 2-methylimidazole are used as raw materials, and flaky ZIF-8 is prepared in a water phase form through control of synthesis conditions; then, the prepared platy ZIF-8 is dispersed in a sodium alginate water solution to prepare a casting solution, after standing and defoaming, the casting solution spirally coats the surface of a porous polymer ultrafiltration membrane, after drying, the porous polymer ultrafiltration membrane is crosslinked with a calcium chloride solution, and after drying again, the sodium alginate- flaky ZIF-8 hybrid composite membrane is obtained. The hybrid composite membrane can be used for dehydration through pervaporation of an ethanol/water system. Through utilization of the second-dimensional structure and the porous structure of the flaky ZIF-8, the screening effect of the hybrid composite membrane on molecular transport is enhanced, so that the separation performance of the hybrid composite membrane is improved. The preparation process is simple, raw materials are easy to obtain, the structure is controllable, the large-scale preparation and amplification are convenient, and the sodium alginate-flaky ZIF-8 hybrid composite membrane has a good application prospect.
Description
Technical field
The present invention relates to a kind of UF membrane field, particularly relate to a kind of sodium alginate-sheet ZIF-8 hybridization compounding film and Synthesis and applications.
Background technology
It is environment-friendly type oil substitutes that ethanol/water is separated---the important step of fuel ethanol production, pervaporation membrane technology is utilized to carry out alcohol-water separation, have by VLE restriction, the advantage such as green, efficient, energy-conservation, towards the great demand of country of Clean Fuel Production equal energy source and environmental area.Pervaporation belongs to dense film separation process, and separation component is transmitted by the passage that size is suitable with its molecular motion free path, utilizes each component to interact with membrane material and the difference of transfer behavior realizes being separated in passage.Polymeric membrane is extensively easy to get, processing is simple, be the most frequently used pervaporation membrane material, but depend on the arrangement of film inner macromolecule chain and motility and free volume hole size and distribution due to its stalling characteristic, there is permeability and selective shifting Trade-off effect.The people such as Koros and Jiang prepare macromolecular-inorganic hybrid membrane by introducing inorganic filler in polymer matrix, propose method and theory that hybridized film overcomes the restriction of Trade-off effect, and find the high efficiency realizing membrane separating process by modulation inorganic medium physical arrangement and chemical constitution.
In recent years, the metal-organic framework materials (MOF) be made up of metal ion and organic ligand becomes the hybridized film inorganic filler received much concern.MOF has higher porosity, regular pore passage structure and controlled pore size, can be hybridized film and provides additional transmission channels and sieve effect.Zeolite imidazole skeleton material (ZIF) is as the one of MOF, there is higher stability, its pore size is many within 0.5nm, wherein the window diameter in ZIF-8 duct is only 0.34nm, undersized hydrone (kinetic diameter is 0.26nm) can be allowed freely to pass through, and stop large-sized ethanol molecule (molecular dynamics diameter is 0.45nm), thus to the separation of ethanol/water system, there is sieving actoion, be conducive to improving selective for hydrone of hybridized film.But ZIF-8 prepared by conventional method is generally nanoscale or micron-sized particle, has isotropic feature.Now there are some researches show, easily nonselective boundary defect is formed between the hydrophobic surface of ZIF-8 and hydrophilic high mol, graininess ZIF-8 is introduced the pervaporation dehydration that the hybridized film prepared in macromolecule is used for ethanol/water system, permeability improves but selective decline, presents typical Trade-off phenomenon.Two dimension filler, because having higher aspect ratio and specific area, easily forms ideal hybridized film interface configuration, and two-dimentional filler spontaneously can be parallel to the arrangement of film surface in hybridized film, is conducive to the pore passage structure making full use of filler.Therefore, expect sheet ZIF-8 by preparing two-dimensional structure, regulation and control hybridized film interface configuration, give full play to the sieving actoion of ZIF-8 pore passage structure, thus the mass transfer behavior of regulation and control hybridized film, overcome the restriction of Trade-off effect, prepare high performance pervaporation dewatering membrane.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of sodium alginate-sheet ZIF-8 hybridization compounding film and Synthesis and applications, by controlling synthesis condition, aqueous phase prepares sheet ZIF-8, prepare hybridization film material by the physical blending of sodium alginate and sheet ZIF-8, be spun to ultrafiltration membrane surface and prepare hybridization compounding film.Utilize the two-dimensional structure of sheet ZIF-8, reduce the probability that permeable molecule is undertaken by boundary defect transmitting, the pore passage structure simultaneously utilizing sheet ZIF-8 regular and suitable pore size, strengthening permeable molecule carries out the sieving actoion of transmitting by ZIF-8 duct, overcome the restriction of Trade-off effect, improve the separating property of hybridization compounding film.Sodium alginate the method obtained-sheet ZIF-8 hybridization compounding film is used for the pervaporation dehydration of ethanol/water system, has higher permeation flux and separation factor.
A kind of sodium alginate provided by the invention-sheet ZIF-8 hybridization compounding film, this hybridization compounding film is using the polymer ultrafiltration membrane of porous as supporting layer, with sodium alginate-sheet ZIF-8 hybridized film for separating layer; The molecular cut off of the polymer ultrafiltration membrane of described porous is 100,000.Its preparation comprises the following steps:
Step one, sodium alginate is added in deionized water, stir 1-2h at 30 DEG C, be mixed with the sodium alginate soln that mass concentration is 1-3%;
Step 2, in the obtained sodium alginate soln of step one, add sheet ZIF-8, wherein, the mass ratio of sheet ZIF-8 and sodium alginate is 2-10%, pours in a container, room temperature standing and defoaming 1-2h at 30 DEG C after stirring 3-6h, acquisition casting solution;
Step 3, the casting solution that step 2 obtains is spun to the surface of the polymer ultrafiltration membrane of porous, drying at room temperature 24-48h, obtains uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film;
Step 4, uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film step 3 obtained immerse in the calcium chloride water of 0.5-1.0M, normal temperature crosslinked reaction 5-20min, then take out, with excessive deionized water rinsing film surface 3-5 time, last drying at room temperature 24-48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
Further, the sheet ZIF-8 added in step 2 is with Zn (NO
3)
2be that raw material aqueous phase is prepared into out with glyoxal ethyline, preparation process is as follows:
Step one, by Zn (NO
3)
2be dissolved in the Zn (NO that deionized water compound concentration is 0.01-0.1mol/L
3)
2solution, is dissolved in the glyoxal ethyline solution that compound concentration in deionized water is 0.1-0.8mol/L by glyoxal ethyline;
Step 2, by described Zn (NO
3)
2solution and glyoxal ethyline solution are 1:(1-3 according to volume ratio) mix, at 30 DEG C, 600-1000rpm magnetic agitation 2-6h, obtains milk-white coloured suspension;
Step 3, be the cellulose acetate micro-filtrate membrane filtration of 0.2 μm by described suspension aperture, filter cake is re-dispersed into deionized water for ultrasonic cleaning, and then filter, repeat three times, obtain white filter cake, by the acetone dispersion cleaning of this filter cake, filter, repeat three times, the vacuum drying at 30 DEG C of last filter cake, obtains sheet ZIF-8 after grinding; The sheet ZIF-8 obtained presents two-dimentional lamella pattern, and thickness is about 120nm.
Sodium alginate of the present invention-sheet ZIF-8 hybridization compounding film be may be used for the pervaporation dehydration of ethanol/water system, permeation flux is 832-1218g/m
2h, separation factor is 853-1840.
The invention has the advantages that:
Sodium alginate of the present invention-sheet ZIF-8 hybridization compounding film, utilizes two-dimensional structure and the loose structure of sheet ZIF-8, the sieving actoion that strengthening hybridized film is transmitted molecule, thus improves the separating property of hybridization compounding film; Preparation process is simple, and raw material is easy to get, and membrane structure character is controlled, and membrane stability is high, is convenient to scale preparation and amplifies, easy large-scale production; Sodium alginate of the present invention-sheet ZIF-8 hybridization compounding film has a good application prospect, and may be used for the pervaporation dehydration of ethanol/water system, has higher permeation flux and separation factor.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) photo of the sheet ZIF-8 of preparation in embodiment 1.
Fig. 2 is the SEM surface picture of the sodium alginate-sheet ZIF-8 hybridization compounding film of preparation in embodiment 2.
Fig. 3 is the SEM photo of the graininess ZIF-8 of preparation in comparative example 1.
Detailed description of the invention
Below by concrete case study on implementation, specific description is done to the present invention.
A kind of sodium alginate-sheet ZIF-8 hybridization compounding film that the present invention proposes is using the polymer ultrafiltration membrane of porous as supporting layer, with sodium alginate-sheet ZIF-8 hybridized film for separating layer; The molecular cut off of the polymer ultrafiltration membrane of described porous is 100,000, and the polymer ultrafiltration membrane of described porous can be the one in polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and polyimides milipore filter.
Embodiment 1, sodium alginate-sheet ZIF-8 hybridization compounding film, its preparation process is as follows:
Step one, sodium alginate is added in deionized water, stir 1h at 30 DEG C, be mixed with the sodium alginate soln that mass concentration is 32%, stand-by;
Step 2, with Zn (NO
3)
2be raw material with glyoxal ethyline, aqueous phase is prepared into sheet ZIF-8, and detailed process is: by Zn (NO
3)
2be dissolved in the Zn (NO that deionized water compound concentration is 0.05mol/L
3)
2solution, is dissolved in the glyoxal ethyline solution that compound concentration in deionized water is 0.4mol/L, by described Zn (NO by glyoxal ethyline
3)
2solution and glyoxal ethyline solution mix with volume ratio 1:1, and at 30 DEG C, 600rpm magnetic agitation 4h, obtains milk-white coloured suspension; By the cellulose acetate micro-filtrate membrane filtration that described suspension aperture is 0.2 μm, filter cake is re-dispersed into deionized water for ultrasonic cleaning, and then filters, repeat three times, obtain white filter cake.By the acetone dispersion cleaning of this filter cake, filter, repeat three times, finally by filter cake vacuum drying at 30 DEG C, obtain sheet ZIF-8 after grinding, its SEM photo as shown in Figure 1.
Step 3, add sheet ZIF-8 by sodium alginate soln obtained for step one, wherein, sheet ZIF-8 consumption is the 2wt.% of sodium alginate, pours in container at 30 DEG C after stirring 4h, room temperature standing and defoaming 2h, obtains casting solution;
Step 4, by step 3 obtain casting solution be spun to porous polyacrylonitrile ultrafiltration film surface, drying at room temperature 48h, obtains uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film;
Step 5, uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film step 4 obtained immerse in the calcium chloride water of 0.5M, normal temperature crosslinked reaction 10min, then take out, with excessive deionized water rinsing film surface 3 times, last drying at room temperature 48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
The sodium alginate prepared by embodiment 1-sheet ZIF-8 hybridization compounding film carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 922g/m
2h, separation factor is 1251.
Embodiment 2, sodium alginate-sheet ZIF-8 hybridization compounding film, its preparation process is substantially the same manner as Example 1, and difference is only, in step 3, the consumption of sheet ZIF-8 is changed into the 4wt.% accounting for sodium alginate by the 2wt.% accounting for sodium alginate; The SEM surface picture of the sodium alginate finally obtained-sheet ZIF-8 hybridization compounding film as shown in Figure 2.
The sodium alginate prepared by embodiment 2-sheet ZIF-8 hybridization compounding film carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 1218g/m
2h, separation factor is 1840.
Embodiment 3, sodium alginate-sheet ZIF-8 hybridization compounding film, its preparation process is substantially the same manner as Example 1, and difference is only, in step 3, the consumption of sheet ZIF-8 is changed into the 6wt.% accounting for sodium alginate by the 2wt.% accounting for sodium alginate.
The sodium alginate prepared by embodiment 3-sheet ZIF-8 hybridization compounding film carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 1066g/m
2h, separation factor is 1222.
Embodiment 4, sodium alginate-sheet ZIF-8 hybridization compounding film, its preparation process is substantially the same manner as Example 1, and difference is only, in step 3, the consumption of sheet ZIF-8 is changed into the 8wt.% accounting for sodium alginate by the 2wt.% accounting for sodium alginate.
The sodium alginate prepared by embodiment 4-sheet ZIF-8 hybridization compounding film carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 832g/m
2h, separation factor is 1105.
Comparative example 1, sodium alginate-graininess ZIF-8 hybridization compounding film, its preparation process is as follows:
Step one, by Zn (NO
3)
2be dissolved in the Zn (NO that compound concentration in methyl alcohol is 0.1mol/L
3)
2solution, is dissolved in the glyoxal ethyline solution that compound concentration in methyl alcohol is 0.8mol/L, by described Zn (NO by glyoxal ethyline
3)
2solution and glyoxal ethyline solution mix with volume ratio 1:1, at 30 DEG C, 600rpm magnetic agitation 1h, obtain milk-white coloured suspension.By the cellulose acetate micro-filtrate membrane filtration that described suspension aperture is 0.2 μm, filter cake is re-dispersed into deionized water for ultrasonic cleaning, and then filters, repeat three times, obtain white filter cake.By the acetone dispersion cleaning of this filter cake, filter, repeat three times, finally by filter cake vacuum drying at 30 DEG C, obtain graininess ZIF-8 after grinding, its SEM photo as shown in Figure 3;
Step 2, sodium alginate added in deionized water and at 30 DEG C, stirs 1h, be mixed with the sodium alginate soln that concentration is 2wt.%.In described sodium alginate soln, add graininess ZIF-8, wherein, graininess ZIF-8 consumption is the 4wt.% of sodium alginate, pours in container at 30 DEG C after stirring 4h, room temperature standing and defoaming 2h, obtains casting solution;
Step 3, described casting solution is spun to porous polyacrylonitrile ultrafiltration film surface, drying at room temperature 48h, obtains uncrosslinked sodium alginate-graininess ZIF-8 hybridization compounding film.Described uncrosslinked sodium alginate-graininess ZIF-8 hybridization compounding film is immersed in the calcium chloride water of 0.5M, normal temperature crosslinked reaction 10min, then takes out, with excessive deionized water rinsing film surface 3 times, last at drying at room temperature 48h, obtain sodium alginate-graininess ZIF-8 hybridization compounding film.
The sodium alginate prepared by comparative example 1-graininess ZIF-8 hybridization compounding film carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 879g/m
2h, separation factor is 678.
Comparative example 2, sodium alginate composite membrane, its preparation process is as follows:
Step one, sodium alginate added in deionized water and at 30 DEG C, stirs 1h, be mixed with the sodium alginate soln that concentration is 2wt.%.Then pour in container after continuing to stir 4h at 30 DEG C, room temperature leaves standstill 2h deaeration, obtains sodium alginate casting solution;
Step 2, casting solution obtained for step one is spun to the polyacrylonitrile ultrafiltration film surface of porous, drying at room temperature 48h, obtains uncrosslinked sodium alginate composite membrane.Immersed by described uncrosslinked sodium alginate composite membrane in the calcium chloride water of 0.5M, normal temperature crosslinked reaction 10min, then takes out, with excessive deionized water rinsing film surface 3 times, finally at drying at room temperature 48h, and acquisition sodium alginate composite membrane.
The sodium alginate composite membrane prepared by comparative example 2 carries out the test of ethanol/water separating property.Adopt membrane separation plant, at 76 DEG C, in material liquid, ethanol/water mass ratio is carry out the test of ethanol/water pervaporation separating property under the condition of 9:1, and permeation flux is 889g/m
2h, separation factor is 533.
To sum up, the present invention prepares that sodium alginate-sheet ZIF-8 hybridization compounding membrane process is easy, and raw material is easy to get, structure-controllable, and obtained sodium alginate-sheet ZIF-8 hybridization compounding film is used for the dehydration of ethanol/water mixture pervaporation, has higher separating property.Sodium alginate-sheet ZIF-8 hybridization compounding the film properties of preparation in embodiment 2 is best, especially have higher selective to hydrone, its separation factor comparatively comparative example 1 sodium alginate-sheet ZIF-8 hybridization compounding film improves 171%, and comparatively in comparative example 2, sodium alginate composite membrane improves 245%.
Although invention has been described for composition graphs above; but the present invention is not limited to above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.
Claims (7)
1. sodium alginate-sheet ZIF-8 hybridization compounding film, is characterized in that: this hybridization compounding film is using the polymer ultrafiltration membrane of porous as supporting layer, with sodium alginate-sheet ZIF-8 hybridized film for separating layer; The molecular cut off of the polymer ultrafiltration membrane of described porous is 100,000.
2. sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 1, it is characterized in that, the polymer ultrafiltration membrane of described porous is the one in polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and polyimides milipore filter.
3. a preparation method for sodium alginate-sheet ZIF-8 hybridization compounding film as claimed in claim 1, is characterized in that, comprise the following steps:
Step one, sodium alginate is added in deionized water, stir 1-2h at 30 DEG C, be mixed with the sodium alginate soln that mass concentration is 1-3%;
Step 2, in the obtained sodium alginate soln of step one, add sheet ZIF-8, wherein, the mass ratio of sheet ZIF-8 and sodium alginate is 2-10%, pours in a container, room temperature standing and defoaming 1-2h at 30 DEG C after stirring 3-6h, acquisition casting solution;
Step 3, the casting solution that step 2 obtains is spun to the surface of the polymer ultrafiltration membrane of porous, drying at room temperature 24-48h, obtains uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film;
Step 4, uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film step 3 obtained immerse in the calcium chloride water of 0.5-1.0M, normal temperature crosslinked reaction 5-20min, then take out, with excessive deionized water rinsing film surface 3-5 time, last drying at room temperature 24-48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
4. the preparation method of sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 3, wherein, the sheet ZIF-8 added in step 2 is with Zn (NO
3)
2be that raw material aqueous phase is prepared into out with glyoxal ethyline, preparation process is as follows:
Step one, by Zn (NO
3)
2be dissolved in the Zn (NO that deionized water compound concentration is 0.01-0.1mol/L
3)
2solution, is dissolved in the glyoxal ethyline solution that compound concentration in deionized water is 0.1-0.8mol/L by glyoxal ethyline;
Step 2, by described Zn (NO
3)
2solution and glyoxal ethyline solution are 1:(1-3 according to volume ratio) mix, at 30 DEG C, 600-1000rpm magnetic agitation 2-6h, obtains milk-white coloured suspension;
Step 3, be the cellulose acetate micro-filtrate membrane filtration of 0.2 μm by described suspension aperture, filter cake is re-dispersed into deionized water for ultrasonic cleaning, and then filter, repeat three times, obtain white filter cake, by the acetone dispersion cleaning of this filter cake, filter, repeat three times, the vacuum drying at 30 DEG C of last filter cake, obtains sheet ZIF-8 after grinding.
5. the preparation method of described sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 4, wherein, described sheet ZIF-8 presents two-dimentional lamella pattern, and thickness is about 120nm.
6. the preparation method of sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 3, wherein, in step 3, the polymer ultrafiltration membrane of described porous is the one in polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and polyimides milipore filter.
7. the application of sodium alginate-sheet ZIF-8 hybridization compounding film in the dehydration of ethanol/water system pervaporation as claimed in claim 1.
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