CN104801208B - 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, more particularly to a kind of sodium alginate-sheet ZIF-8 hybridization compounding film and system
Standby and application.
Background technology
It is environment-friendly type oil substitutes that ethanol/water is separated --- the important step of fuel ethanol production, using pervaporation
Membrane technology carries out alcohol-water separation, with not limited by VLE, green, efficiently, the advantage such as energy-conservation, towards Clean Fuel Production
The national great demand of equal energy source and environmental area.The fine and close membrane separating process of pervaporation category, separation component by size and its
The suitable passage of molecular motion free path is transmitted, and is interacted using each component and membrane material and its transmission row in passage
For difference realize separate.Polymeric membrane is extensively easy to get, and processing is simple, is the most frequently used pervaporation membrane material, but due to
Its stalling characteristic depends on the arrangement of film inner macromolecule chain and motility and free volume hole size and distribution, there is permeability
With selective shifting Trade-off effects.Koros and Jiang et al. in polymer matrix by introducing inorganic filling out
Fill agent and prepare macromolecular-inorganic hybrid membrane, it is proposed that hybridized film overcomes the method and theory of Trade-off effects restriction, and
It was found that the high efficiency of membrane separating process can be realized by modulation inorganic medium physical arrangement and chemical constitution.
In recent years, the metal-organic framework materials (MOF) being made up of metal ion and organic ligand become what is received much concern
Hybridized film inorganic filler.MOF has higher porosity, regular pore passage structure and controllable pore size, can be hydridization
Film provides additional transmission channels and sieve effect.Zeolite imidazole skeleton material (ZIF) as MOF one kind, with higher
Stability, its pore size is more within 0.5nm, and the window diameter in wherein ZIF-8 ducts is only 0.34nm, can allow small size
Hydrone (kinetic diameter is 0.26nm) pass freely through, and (molecular dynamics is a diameter of to stop large-sized ethanol molecule
0.45nm), so as to have sieving actoion to the separation of ethanol/water system, be conducive to improving hybridized film for the selection of hydrone
Property.But ZIF-8 prepared by conventional method is usually nanoscale or micron-sized particle, the characteristics of with isotropism.It is existing
Research shows, nonselective boundary defect is easily formed between the hydrophobic surface and hydrophilic high mol of ZIF-8, by graininess ZIF-
8 are introduced into the hybridized film prepared in macromolecule is used for the pervaporation dehydration of ethanol/water system, and permeability is improved but under selectivity
Drop, is presented typical Trade-off phenomenons.Two-dimentional filler because with higher aspect ratio and specific surface area, easily formed compared with
Spontaneously can arrange parallel to film surface in hybridized film for preferable hybridized film interface configuration, and two-dimentional filler, be conducive to
Make full use of the pore passage structure of filler.Therefore, it is contemplated that by sheet ZIF-8 for preparing two-dimensional structure, hydridization membrane interface is regulated and controled
Form, gives full play to the sieving actoion of ZIF-8 pore passage structures, so as to regulate and control the mass transfer behavior of hybridized film, overcomes Trade-off to imitate
Should restrict, prepare high performance pervaporation dewatering membrane.
The content of the invention
To solve above-mentioned technical problem, it is an object of the invention to provide a kind of sodium alginate-sheet ZIF-8 hybridization compounding
Film and prepare and apply, by controlling synthesis condition, water mutually prepares sheet ZIF-8, by sodium alginate and sheet ZIF-8
Physical blending prepares hybridization film material, is spun to ultrafiltration membrane surface and prepares hybridization compounding film.Using the two dimension knot of sheet ZIF-8
Structure, reduces the probability that permeable molecule is transmitted by boundary defect, while using the regular pore passage structure of sheet ZIF-8 and conjunction
Suitable pore size, strengthens the sieving actoion that permeable molecule is transmitted by ZIF-8 ducts, overcomes Trade-off effects
Restriction, improves the separating property of hybridization compounding film.Sodium alginate obtained in the method-sheet ZIF-8 hybridization compounding film is used for
The pervaporation dehydration of ethanol/water system, with higher permeation flux and separation factor.
A kind of sodium alginate-sheet ZIF-8 hybridization compounding film that the present invention is provided, the hybridization compounding film is with the height of porous
Molecule milipore filter as supporting layer, with sodium alginate-sheet ZIF-8 hybridized film as separating layer；The polymer ultrafiltration of the porous
The molecular cut off of film is 100,000.Its preparation is comprised the following steps：
Step one, sodium alginate is added in deionized water, at 30 DEG C 1-2h is stirred, be configured to mass concentration for 1-3%
Sodium alginate soln；
Step 2, in sodium alginate soln obtained in step one sheet ZIF-8 is added, wherein, sheet ZIF-8 and marine alga
The mass ratio of sour sodium is 2-10%, stirs at 30 DEG C and is poured in a container after 3-6h, is stored at room temperature deaeration 1-2h, obtains casting film
Liquid；
Step 3, by step 2 obtain casting solution be spun to porous polymer ultrafiltration membrane surface, drying at room temperature 24-
48h, obtains uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film；
Step 4, the uncrosslinked sodium alginate for obtaining step 3-sheet ZIF-8 hybridization compounding film immersion 0.5-1.0M's
In calcium chloride water, normal temperature crosslinked reaction 5-20min then takes out, with excessive deionized water rinsing film surface 3-5 time, most
Afterwards drying at room temperature 24-48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
Further, sheet ZIF-8 for being added in step 2 is with Zn (NO3)2Mutually make for raw water with 2-methylimidazole
Standby to draw, preparation process is as follows：
Step one, by Zn (NO3)2It is dissolved in the Zn (NO that deionized water compound concentration is 0.01-0.1mol/L3)2Solution, will
2-methylimidazole is dissolved in the 2-methylimidazole solution that compound concentration in deionized water is 0.1-0.8mol/L；
Step 2, by the Zn (NO3)2Solution and 2-methylimidazole solution are 1 according to volume ratio：(1-3) it is well mixed,
At 30 DEG C, 600-1000rpm magnetic agitations 2-6h obtain milk-white coloured suspension；
Step 3, by the cellulose acetate micro-filtrate membrane filtration that the suspension aperture is 0.2 μm, filter cake is disperseed again
It is cleaned by ultrasonic in deionized water, then filters again, repeat three times, obtain white filter cake, by filter cake acetone point
Dissipate cleaning, filter, repeat three times, last filter cake is vacuum dried at 30 DEG C, sheet ZIF-8 is obtained after grinding；Obtained
Sheet ZIF-8 two-dimensional slice pattern is presented, thickness is 120nm or so.
The pervaporation that the sodium alginate-sheet ZIF-8 hybridization compounding film of the present invention can be used for ethanol/water system is taken off
Water, permeation flux is 832-1218g/m2H, separation factor is 853-1840.
It is an advantage of the current invention that：
Sodium alginate of the present invention-sheet ZIF-8 hybridization compounding film, using the two-dimensional structure and loose structure of sheet ZIF-8,
The sieving actoion that reinforcing hybridized film is transmitted to molecule, so as to improve the separating property of hybridization compounding film；Preparation process is simple, raw material
It is easy to get, membrane structure property is controllable, membrane stability is high, is easy to scale to prepare and amplify, easy large-scale production；Alginic acid of the present invention
Sodium-sheet ZIF-8 hybridization compounding film has a good application prospect, and can be used for the pervaporation dehydration of ethanol/water system, tool
There are higher permeation flux and separation factor.
Description of the drawings
Fig. 1 is SEM (SEM) photo of sheet ZIF-8 prepared in embodiment 1.
Fig. 2 is the SEM surface pictures of the sodium alginate-sheet ZIF-8 hybridization compounding film prepared in embodiment 2.
Fig. 3 is the SEM photograph of graininess ZIF-8 prepared in comparative example 1.
Specific embodiment
Specific description is done to the present invention below by case is embodied as.
A kind of sodium alginate proposed by the present invention-sheet ZIF-8 hybridization compounding film is made with the polymer ultrafiltration membrane of porous
For supporting layer, with sodium alginate-sheet ZIF-8 hybridized film as separating layer；The retention molecule of the polymer ultrafiltration membrane of the porous
Measure as 100,000, the polymer ultrafiltration membrane of the porous can be polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, SPSF ultrafiltration
One kind in film, 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, by sodium alginate add deionized water in, stir 1h at 30 DEG C, be configured to the sea that mass concentration is 32%
Solution of sodium alginate, it is stand-by；
Step 2, with Zn (NO3)2It is raw material with 2-methylimidazole, water is mutually prepared into sheet ZIF-8, and detailed process is：Will
Zn(NO3)2It is dissolved in the Zn (NO that deionized water compound concentration is 0.05mol/L3)2Solution, by 2-methylimidazole deionized water is dissolved in
Middle compound concentration is the 2-methylimidazole solution of 0.4mol/L, by the Zn (NO3)2Solution and 2-methylimidazole solution are with volume
Than 1：1 is well mixed, and at 30 DEG C, 600rpm magnetic agitations 4h obtain milk-white coloured suspension；It is with aperture by the suspension
0.2 μm of cellulose acetate micro-filtrate membrane filtration, filter cake is re-dispersed in deionized water and is cleaned by ultrasonic, and is then filtered again,
Repeat three times, obtain white filter cake.By filter cake acetone dispersion cleaning, filter, repeat three times, finally by filter cake
It is vacuum dried at 30 DEG C, sheet ZIF-8 is obtained after grinding, its SEM photograph is as shown in Figure 1.
Step 3, will in sodium alginate soln obtained in step one add sheet ZIF-8, wherein, sheet ZIF-8 consumption is
The 2wt.% of sodium alginate, stirs at 30 DEG C and is poured in container after 4h, is stored at room temperature deaeration 2h, obtains casting solution；
Step 4, the polyacrylonitrile ultrafiltration film surface that the casting solution that step 3 is obtained is spun to porous, drying at room temperature
48h, obtains uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film；
Step 5, the uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film for obtaining step 4 immerse the chlorination of 0.5M
In the calcium aqueous solution, normal temperature crosslinked reaction 10min then takes out, and with excessive deionized water rinsing film surface 3 times, last room temperature is done
Dry 48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
The sodium alginate prepared with embodiment 1-sheet ZIF-8 hybridization compounding film carries out ethanol/water separating property survey
Examination.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out ethanol/water infiltration under conditions of 1 to steam
Separating property test is sent out, permeation flux is 922g/m2H, 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, different
It is only that, in step 3, the consumption of sheet ZIF-8 is changed to by the 2wt.% for accounting for sodium alginate to account for the 4wt.% of sodium alginate；
The SEM surface pictures of the sodium alginate for finally giving-sheet ZIF-8 hybridization compounding film are as shown in Figure 2.
The sodium alginate prepared with embodiment 2-sheet ZIF-8 hybridization compounding film carries out ethanol/water separating property survey
Examination.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out ethanol/water infiltration under conditions of 1 to steam
Separating property test is sent out, permeation flux is 1218g/m2H, 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, different
It is only that, in step 3, the consumption of sheet ZIF-8 is changed to by the 2wt.% for accounting for sodium alginate to account for the 6wt.% of sodium alginate.
The sodium alginate prepared with embodiment 3-sheet ZIF-8 hybridization compounding film carries out ethanol/water separating property survey
Examination.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out ethanol/water infiltration under conditions of 1 to steam
Separating property test is sent out, permeation flux is 1066g/m2H, 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, different
It is only that, in step 3, the consumption of sheet ZIF-8 is changed to by the 2wt.% for accounting for sodium alginate to account for the 8wt.% of sodium alginate.
The sodium alginate prepared with embodiment 4-sheet ZIF-8 hybridization compounding film carries out ethanol/water separating property survey
Examination.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Carry out ethanol/water infiltration under conditions of 1 to steam
Separating property test is sent out, permeation flux is 832g/m2H, 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 (NO3)2It is dissolved in the Zn (NO that compound concentration in methyl alcohol is 0.1mol/L3)2Solution, by 2- methyl miaows
Azoles is dissolved in the 2-methylimidazole solution that compound concentration in methyl alcohol is 0.8mol/L, by the Zn (NO3)2Solution and 2-methylimidazole
Solution is with volume ratio 1：1 is well mixed, and at 30 DEG C, 600rpm magnetic agitations 1h, obtains milk-white coloured suspension.By the suspension
With the cellulose acetate micro-filtrate membrane filtration that aperture is 0.2 μm, filter cake is re-dispersed in deionized water and is cleaned by ultrasonic, Ran Houzai
Secondary filtration, repeats three times, obtains white filter cake.By filter cake acetone dispersion cleaning, filter, repeat three times, most
Filter cake is vacuum dried at 30 DEG C afterwards, graininess ZIF-8 is obtained after grinding, its SEM photograph is as shown in Figure 3；
Step 2, sodium alginate is added in deionized water and stirs 1h at 30 DEG C, be configured to the marine alga that concentration is 2wt.%
Acid sodium solution.Graininess ZIF-8 is added in the sodium alginate soln, wherein, graininess ZIF-8 consumption is sodium alginate
4wt.%, stirs at 30 DEG C and is poured in container after 4h, is stored at room temperature deaeration 2h, obtains casting solution；
Step 3, the polyacrylonitrile ultrafiltration film surface that the casting solution is spun to porous, drying at room temperature 48h is obtained not
Crossslinked sodium alginate-graininess ZIF-8 hybridization compounding film.By the uncrosslinked sodium alginate-graininess ZIF-8 hybridization compounding film
In the calcium chloride water of immersion 0.5M, normal temperature crosslinked reaction 10min then takes out, with excessive deionized water rinsing film surface 3
It is secondary, finally in drying at room temperature 48h, obtain sodium alginate-graininess ZIF-8 hybridization compounding film.
The sodium alginate prepared with comparative example 1-graininess ZIF-8 hybridization compounding film carries out ethanol/water separating property
Test.Using membrane separation plant, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:Ethanol/water infiltration is carried out under conditions of 1
Evaporation separating property test, permeation flux is 879g/m2H, separation factor is 678.
Comparative example 2, sodium alginate composite membrane, its preparation process is as follows：
Step one, sodium alginate is added in deionized water and stirs 1h at 30 DEG C, be configured to the marine alga that concentration is 2wt.%
Acid sodium solution.Then proceed to be poured in container after stirring 4h at 30 DEG C, be stored at room temperature 2h deaerations, obtain sodium alginate casting film
Liquid；
Step 2, the polyacrylonitrile ultrafiltration film surface that casting solution obtained in step one is spun to porous, drying at room temperature
48h, obtains uncrosslinked sodium alginate composite membrane.The uncrosslinked sodium alginate composite membrane is immersed into the calcium chloride water of 0.5M
In, normal temperature crosslinked reaction 10min then takes out, with excessive deionized water rinsing film surface 3 times, finally in drying at room temperature 48h,
Obtain sodium alginate composite membrane.
The sodium alginate composite membrane prepared with comparative example 2 carries out ethanol/water separating property test.Set using UF membrane
Standby, at 76 DEG C, ethanol/water mass ratio is 9 in material liquid:The test of ethanol/water pervaporation separating property is carried out under conditions of 1,
Permeation flux is 889g/m2H, separation factor is 533.
To sum up, the present invention prepares sodium alginate-sheet ZIF-8 hybridization compounding membrane process simplicity, and raw material is easy to get, and structure can
Control, obtained sodium alginate-sheet ZIF-8 hybridization compounding film is dehydrated for ethanol/water mixture pervaporation, with higher
Separating property.Sodium alginate-sheet ZIF-8 hybridization compounding the film properties prepared in embodiment 2 are optimal, especially have to hydrone
Higher selectivity, its separation factor improves 171% compared with 1 sodium alginate of comparative example-sheet ZIF-8 hybridization compounding film, more right
Sodium alginate composite membrane improves 245% in ratio 2.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned specific embodiment is only schematic, rather than restricted, and one of ordinary skill in the art is at this
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (5)
1. the preparation method of a kind of sodium alginate-sheet ZIF-8 hybridization compounding film, the hybridization compounding film is with the macromolecule of porous
Milipore filter as supporting layer, with sodium alginate-sheet ZIF-8 hybridized film as separating layer；The polymer ultrafiltration membrane of the porous
Molecular cut off is 100,000；Characterized in that, preparing according to following steps：
Step one, by sodium alginate add deionized water in, stir 1-2h at 30 DEG C, be configured to mass concentration be 1-3% sea
Solution of sodium alginate；
Step 2, in sodium alginate soln obtained in step one sheet ZIF-8 is added, wherein, sheet ZIF-8 and sodium alginate
Mass ratio be 2-10%, stir at 30 DEG C and poured in a container after 3-6h, be stored at room temperature deaeration 1-2h, obtain casting solution；
Step 3, by step 2 obtain casting solution be spun to porous polymer ultrafiltration membrane surface, drying at room temperature 24-48h,
Obtain uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film；
Step 4, the uncrosslinked sodium alginate-sheet ZIF-8 hybridization compounding film for obtaining step 3 immerse the chlorination of 0.5-1.0M
In the calcium aqueous solution, normal temperature crosslinked reaction 5-20min then takes out, with excessive deionized water rinsing film surface 3-5 time, most rear chamber
Temperature is dried 24-48h, obtains sodium alginate-sheet ZIF-8 hybridization compounding film.
2. the preparation method of sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 1, it is characterised in that described
The polymer ultrafiltration membrane of porous is polyacrylonitrile ultrafiltration film, polysulphone super-filter membrane, Sulfonated Polysulfone UF Membranes, poly (ether-sulfone) ultrafiltration membrane and gathers
One kind in acid imide milipore filter.
3. the preparation method of sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 1, wherein, institute in step 2
Sheet ZIF-8 of addition is with Zn (NO3)2Mutually prepare for raw water with 2-methylimidazole and draw, preparation process is as follows：
Step one, by Zn (NO3)2It is dissolved in the Zn (NO that deionized water compound concentration is 0.01-0.1mol/L3)2Solution, by 2- methyl
Imidazoles is dissolved in the 2-methylimidazole solution that compound concentration in deionized water is 0.1-0.8mol/L；
Step 2, by the Zn (NO3)2Solution and 2-methylimidazole solution are 1 according to volume ratio：(1-3) it is well mixed, 30 DEG C
Under, 600-1000rpm magnetic agitations 2-6h obtain milk-white coloured suspension；
Step 3, by the cellulose acetate micro-filtrate membrane filtration that the suspension aperture is 0.2 μm, filter cake is re-dispersed into
It is cleaned by ultrasonic in ionized water, then filters again, repeat three times, obtains white filter cake, the filter cake is clear with acetone dispersion
Wash, filter, repeat three times, last filter cake is vacuum dried at 30 DEG C, sheet ZIF-8 is obtained after grinding.
4. the preparation method of the sodium alginate-sheet ZIF-8 hybridization compounding film according to claim 3, wherein, described
Shape ZIF-8 is presented two-dimensional slice pattern, and thickness is 120nm.
5. the marine alga that a kind of preparation method of sodium alginate as claimed in claim 1-sheet ZIF-8 hybridization compounding film is prepared
Application of the sour sodium-sheet ZIF-8 hybridization compounding film in the dehydration of ethanol/water system pervaporation.
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| CN107551830A (en) * | 2017-08-04 | 2018-01-09 | 天津大学 | Sulfonated gilsonite/sodium alginate hybridized film and preparation and application |
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