CN117771984B - Pervaporation membrane based on electrostatic spinning process and preparation method and application thereof - Google Patents
Pervaporation membrane based on electrostatic spinning process and preparation method and application thereof Download PDFInfo
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- CN117771984B CN117771984B CN202311839379.0A CN202311839379A CN117771984B CN 117771984 B CN117771984 B CN 117771984B CN 202311839379 A CN202311839379 A CN 202311839379A CN 117771984 B CN117771984 B CN 117771984B
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- 239000012528 membrane Substances 0.000 title claims abstract description 125
- 238000005373 pervaporation Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002121 nanofiber Substances 0.000 claims abstract description 90
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims description 50
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- 238000011068 loading method Methods 0.000 claims description 23
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 23
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 20
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- 238000001723 curing Methods 0.000 claims description 14
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- 230000010355 oscillation Effects 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000855 fermentation Methods 0.000 claims description 5
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 claims description 4
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- 239000003054 catalyst Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 102100029880 Glycodelin Human genes 0.000 claims description 2
- 101000585553 Homo sapiens Glycodelin Proteins 0.000 claims description 2
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
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- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 65
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 56
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 17
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 17
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 17
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 17
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012527 feed solution Substances 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
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- 238000011065 in-situ storage Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- QAJJXHRQPLATMK-UHFFFAOYSA-N 4,5-dichloro-1h-imidazole Chemical compound ClC=1N=CNC=1Cl QAJJXHRQPLATMK-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- ZJLKZLGZJOXUSX-UHFFFAOYSA-N CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] ZJLKZLGZJOXUSX-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a pervaporation membrane based on an electrostatic spinning process, and a preparation method and application thereof, and belongs to the technical field of membrane separation. The preparation method comprises the following steps: firstly, preparing a polymer-based nanofiber film by using an electrostatic spinning process; adding a precursor, uniformly and continuously growing MOFs nano particles on a nanofiber skeleton to obtain a nanofiber/MOFs composite fiber membrane with uniformly dispersed MOFs; and backfilling the polymer solution into the fiber membrane system in a vacuum auxiliary mode, and then crosslinking and curing to obtain the nanofiber/MOFs-based pervaporation priority alcohol-permeable membrane with MOFs continuously distributed in the membrane. Compared with the hydrogel nanofiber membrane prepared by the sol-gel method, the interpenetrating network structure nanofiber membrane is prepared by using the electrostatic spinning process, the formed nanofiber membrane has higher mechanical strength, the requirements on the preparation method are reduced, the nanofibers are more uniform, the pore diameters of the nanofiber membrane are more uniform, the finally prepared separation channel is more uniform, and the selection range of the nanofibers is widened.
Description
Technical Field
The invention belongs to the technical field of pervaporation membrane separation, and particularly relates to a preparation method of an electrostatic spinning nanofiber/MOFs-based pervaporation membrane, wherein the pervaporation membrane is used for separating and purifying alcohol substances in fermentation liquor.
Background
The biological butanol is used as a novel biological fuel, has excellent physicochemical properties (the advantages of high heat value, low volatility, capability of being mixed with gasoline in any proportion and the like), and becomes a typical representative of the novel biological fuel capable of replacing the traditional fossil energy. However, when biological butanol is produced by a biological fermentation method, the inhibition effect of butanol products can lead to the problems of low product concentration and yield, excessively high energy consumption in the subsequent separation process, and the like; in order to solve the problem, alcohols are separated from fermentation liquor in a more energy-saving mode, so that the energy consumption is reduced, and the separation efficiency and the yield are improved. Pervaporation (Pervaporation, abbreviated as PV) is a novel high efficiency membrane separation technology that can economically and efficiently separate azeotropic mixtures, volatile aromatic compounds, and organic-organic mixtures, as well as remove and recover diluted organic compounds from aqueous solutions. Compared with the traditional separation mode, the PV separation process has the advantages of obvious low energy consumption, high efficiency, environmental protection and the like. The separation membrane is used as a key component in the PV separation technology, and the successful design and preparation of the high-efficiency alcohol-permselective pervaporation membrane are important.
In recent years, mixed matrix membranes with organic-inorganic filler synergism have become typical representatives of pervaporation membranes with preferential alcohol permeation, and have received extensive attention from the academia and engineering community. Metal-organic framework Materials (MOFs), which are novel multifunctional materials, have unique physicochemical properties (e.g., molecular sieving effect, preferential adsorption of target molecular compounds, good thermal and chemical stability). Therefore, it is widely used as an inorganic porous filler in mixed matrix membranes, becoming an important component of high performance pervaporation membranes. However, the MOFs-based mixed matrix membrane separation effect prepared by the traditional blending mode has larger deviation from the ideal expected effect. When the loading of MOFs in the polymer matrix reaches a certain high level (> 30%), the filler particles are very susceptible to agglomeration in the polymer matrix, resulting in poor compatibility and dispersibility of the filler with the polymer matrix, and a large number of defects are generated in the mixed matrix film, resulting in reduced pervaporation performance.
In view of the above problems, researchers have recently explored from various aspects such as MOFs crystal functionalization modification and mixed matrix membrane preparation process improvement, so as to achieve uniform dispersion of MOFs nanoparticles at high loading in a polymer, thereby achieving an important goal of improving the performance of mixed matrix membranes. The patent with publication number CN112717699A discloses a nanofiber/MOFs group preferential osmosis alcohol type osmotic gasification membrane and a preparation method thereof, which comprises the steps of firstly preparing a nanofiber hydrogel membrane, then loading MOFs particles on the hydrogel membrane nanofiber skeleton in situ, removing the solvent in the membrane pores, and then filling a polymer matrix back into the membrane pores to obtain the osmotic gasification membrane. The method can greatly improve the loading capacity of MOFs nano-particles, and the loading capacity of the MOFs nano-particles can be up to 63%. However, it still has the following problems: (1) The method is limited by the aperture of the nanofiber hydrogel film, so that the difficulty in continuously increasing the load is high; (2) Aramid nanofibers (such as Kevlar nanofibers) adopted in the hydrogel film are required to be dissociated from the aramid fibers to obtain the aramid nanofibers, and the preparation method is complicated; (3) The types of the nano fibers which can be adopted are limited, so that popularization and application of the preparation method are limited; (4) The hydrogel film has low mechanical strength, is fragile, has harsh operation steps (such as vacuum drying to remove the solvent), is easy to collapse and deform, and loses the original structural form. For this reason, the invention provides another preparation method of nanofiber/MOFs-based alcohol-based osmotic gasifying membrane with preferential permeation.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a nanofiber/MOFs-based pervaporation membrane based on an electrostatic spinning process and a preparation method thereof, and the problems that the mechanical strength is poor, the nanofiber uniformity is poor, the pore diameter is small and the like of a hydrogel nanofiber membrane prepared by a sol-gel method are solved by utilizing the strong bonding effect between a three-dimensional nanofiber interpenetrating network skeleton prepared by the electrostatic spinning technology and MOFs, so that the key problems that MOFs nanoparticles are easy to agglomerate in a polymer matrix and have low utilization rate to obviously inhibit the promotion of the pervaporation performance and the like in the prior art are solved.
The invention prepares the nanofiber membrane with high length-diameter ratio, high specific surface area and high porosity and mutually penetrating and communicating fiber structures in advance by means of a simple electrostatic spinning process technology, takes a nanofiber membrane skeleton network as a three-dimensional communicating template, obtains MOFs/nanofiber composite membranes with MOFs nano particles continuously and uniformly distributed on the nanofiber skeleton by means of two strategies of 'sowing' or subsequent deposition of metal ions in advance in the fiber skeleton, and then infiltrates and backfills a polymer matrix into the gaps of the composite membrane network and solidifies and forms to obtain the novel mixed matrix membrane with high content of MOFs uniformly and uniformly dispersed in the membrane, thereby being effectively applied to the high-efficiency low-energy separation process of biological butanol/biological ethanol.
The technical scheme adopted by the invention is as follows:
the preparation method of the pervaporation membrane based on the electrostatic spinning process comprises the following steps:
(101) Preparing an electrostatic spinning precursor solution, wherein the precursor solution comprises a spinning polymer and an organic solvent;
(102) Preparing a corresponding nanofiber membrane by using an electrostatic spinning process;
(103) Immersing the prepared nanofiber membrane in a metal ion solution and an organic ligand solution respectively, and uniformly growing and loading MOFs nano particles generated by the reaction of the organic ligand and the metal compound on a nanofiber skeleton to obtain MOFs@nanofiber composite membranes with MOFs nano particles continuously distributed;
(104) And backfilling a polymer matrix solution in the MOFs@nanofiber composite membrane network, and obtaining the continuous and uniform-distribution pervaporation membrane of the high MOFs filler after crosslinking and curing.
The preparation step of the precursor solution in the step (101) comprises the steps of mixing a certain amount of spinning polymer with an organic solvent, and fully dissolving the spinning polymer under magnetic stirring; magnetic stirring conditions are 20-1000 rpm/0.2-48 h/5-90 ℃; the mass fraction of the spinning polymer is 1-30wt%.
Preferably, in step (103), the nanofiber membrane is immersed in the metal ion solution and the organic ligand solution respectively under the oscillation condition, and the oscillation condition enables MOFs nano-particles generated in situ to be more uniformly loaded on the nanofiber, and simultaneously improves the loading capacity of the MOFs nano-particles. The oscillation condition is 0-90 ℃/10-300 rpm/2-48 h, and the oscillation conditions in the two immersion processes can be independently set.
The preparation method of the pervaporation membrane based on the electrostatic spinning process comprises the following steps:
(201) Preparing an electrostatic spinning precursor solution, wherein the precursor solution comprises a spinning polymer, an organic solvent and a metal compound;
(202) Preparing a corresponding nanofiber membrane by using an electrostatic spinning process;
(203) Immersing the prepared nanofiber membrane in an organic ligand solution, and uniformly growing and loading MOFs nano particles generated by the reaction of the organic ligand and the metal compound on a nanofiber skeleton to obtain MOFs@nanofiber composite membrane with MOFs nano particles continuously distributed;
(204) And backfilling a polymer matrix solution in the MOFs@nanofiber composite membrane network, and obtaining the alcohol-penetrating type pervaporation membrane with high MOFs filler continuously and uniformly distributed after crosslinking and curing.
The preparation step of the precursor solution in the step (201) comprises the steps of fully dissolving the spinning polymer in an organic solvent under magnetic stirring, then adding a metal compound, and continuing magnetic stirring to fully dissolve the metal compound; dissolution conditions: the magnetic stirring condition is 20-1000 rpm/0.2-48 h/5-80 ℃, and the two dissolving conditions can be independently set; the mass fraction of the spinning polymer is 2-25 wt%, and the mass fraction of the metal compound is 0.1-20 wt%.
Preferably, in step (203), the nanofiber membrane is immersed in the organic ligand solution under shaking conditions of 0 to 90 ℃/10 to 300rpm/2 to 48 hours.
The spinning polymer is one or more of polyacrylonitrile, polyvinylidene fluoride, carboxylated cellulose, cellulose acetate, chitosan and aramid, and the organic solvent is one or more of N-hexane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid, acetone, dichloromethane and dichloroethane.
The electrospinning process operating parameters in steps (102) and (202): the positive voltage is 0.1-40 kV, the negative voltage is-0.1 to-40 kV, the advancing rate of the electrostatic spinning precursor solution is 0.1-5.0L/h, and the spinning time is 0.5-24 h; the receiving distance is 5-50 cm; the spinning temperature is 0-80 ℃, and the spinning humidity is 1-85% RH.
The MOFs loaded in the steps (103) and (203) are one or more of ZIF-1, ZIF-8, ZIF-67, ZIF-90, ZIF-91 and the like.
The polymer matrix solution in the steps (104) and (204) is polysiloxane solution, which comprises polysiloxane, catalyst and organic solvent, wherein the mass fraction of the polysiloxane is 2-60 wt%; the polysiloxane curing mode is one or a combination of a plurality of thermal crosslinking curing, moisture curing and ultraviolet curing. Wherein the thermal crosslinking curing and the ultraviolet curing are respectively the thermal crosslinking curing and the ultraviolet induced crosslinking curing mentioned in the patent with publication number CN 112717699A.
The pervaporation membrane prepared by the preparation method is provided.
The pervaporation membrane is applied to separation and purification of alcohol substances in fermentation liquor.
Compared with the prior art, the application has the following beneficial effects: 1) Compared with the hydrogel nanofiber membrane prepared by a sol-gel method, the interpenetrating network structure nanofiber membrane is prepared by an electrostatic spinning process, the formed nanofiber membrane has higher mechanical strength, the requirements on the preparation method are reduced, the nanofibers are more uniform, the aperture of the nanofiber membrane is more uniform, and finally the prepared separation channel is more uniform, so that the separation channel of the membrane material can be conveniently regulated and controlled according to the separation requirements, and polymers which can be subjected to electrostatic spinning and have a certain binding force with MOFs can be used as the polymers in the application, so that the selection range of the nanofibers is widened; 2) The high specific surface area of the nanofiber network skeleton provides a large number of active sites for nucleation of MOFs nanoparticles, and the MOFs nanoparticles and the fiber skeleton are combined with strong bonding action (such as hydrogen bond and electrostatic force), so that continuous uniform growth load of the MOFs nanoparticles on the communicated network skeleton can be promoted, and the serious aggregation phenomenon of fillers generated by the traditional blending process is avoided; 3) The MOFs nano particles have stable growth mechanism on the nanofiber skeleton, and the loading capacity of the filler particles can be simply and conveniently regulated by means of regulating the concentration of the precursor raw materials; 4) The excellent anchoring synergistic uniform deposition effect and larger pore diameter of the nanofiber skeleton on MOFs nano particles can obviously improve the loading capacity of MOFs fillers, the highest loading capacity can reach more than 80wt%, and the adjustable range of the loading capacity is enlarged; 5) Due to the stable mechanical characteristics of the MOFs/nanofiber composite network, the distribution and the structural morphology of MOFs nano particles on a fiber framework are not damaged in the backfill and solidification process of a polymer matrix, and an ideal mixed matrix film is obtained; 6) The MOFs nano particles stably loaded along the interpenetrating nanofiber skeletons form a plurality of interconnected MOFs networks in the mixed membrane, so that a plurality of alcohol molecule selective transmission channels are provided, and the mixed membrane shows excellent pervaporation separation performance when alcohol-water mixed solution is separated.
Drawings
Fig. 1 is a digital photograph of PAN nanofiber spinning solution in example 1.
Fig. 2 is an SEM image of PAN nanofiber membrane at different magnifications in example 1.
Fig. 3 is SEM images of mofs@pan hybrid nanofiber membranes at different magnifications in example 1.
FIG. 4 is an SEM image (section) of a MOFs@PAN/PDMS pervaporation membrane according to example 1.
Detailed Description
The invention provides a preferential alcohol permeation vaporization membrane based on an electrostatic spinning process and a preparation method thereof, and the invention is further described in detail below for the purpose and the technical scheme effect of the invention to be clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
(1) Adding 1g of polyacrylonitrile PAN and 15ml of N, N-dimethylformamide into a 50ml beaker, and magnetically stirring (300 rpm) at 25 ℃ for 8 hours to completely dissolve the PAN to obtain a precursor spinning solution;
(2) Injecting the prepared precursor spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +20kV, the negative voltage is-5 kV, the syringe propulsion rate is 0.02ml/min, the receiving distance is 20cm, the rotating speed of the receiving device is 100rpm, the temperature is 30 ℃, the humidity is 20%, and the spinning time is 2h. After spinning is completed, the PAN nanofiber membrane is transferred to a forced air oven (60 ℃) and dried for 50min.
(3) Immersing the dried PAN nanofiber membrane into a methanol solution, and carrying out solvent exchange for 30min under the vacuum auxiliary condition. And then carrying out in-situ loading of ZIF-8 on the PAN nanofiber membrane at 25 ℃ (oscillating in 30mg/ml of 30-mg/ml of zinc nitrate hexahydrate methanol solution and 66mg/ml of 2-methylimidazole methanol solution in sequence at 25 ℃/100rpm/24 h) to obtain the ZIF-8@PAN hybrid nanofiber membrane, flushing with methanol three times after oscillation is finished, and drying in a vacuum environment at 60 ℃ for 12h to obtain the ZIF-8@PAN composite membrane, wherein the ZIF-8 loading is 51wt% through a weighing method.
(4) Immersing the ZIF-8@PAN composite membrane in vinyl-terminated polysiloxane n-hexane solution (30 wt%) for 10min at room temperature, and adsorbing excessive polysiloxane solution on the surface after full immersion; and (3) thermally crosslinking and curing for 2 hours at 40 ℃ to obtain the ZIF-8@PAN/PDMS mixed matrix membrane.
As shown in Table 1, the concentrations of the methanol solution of zinc nitrate hexahydrate and the methanol solution of 2-methylimidazole in the step (3) are adjusted in the experimental process to obtain ZIF-8@PAN composite films with different loadings.
The ZIF-8@PAN/PDMS mixed matrix membrane prepared in Table 1 is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on butanol aqueous solution is measured, and when the temperature of a feed solution is 45 ℃, and the butanol concentration is 2.0wt%, the separation factor and the permeation flux are shown in Table 1.
Example 2:
(1) Adding 3g of polyvinylidene fluoride (PVDF) and 20mL of N, N-dimethylacetamide into a 50ml beaker, magnetically stirring (800 rpm) at 75 ℃ for 10 hours to completely dissolve the polyvinylidene fluoride, and then adding 1g of zinc chloride to prepare a precursor spinning solution;
(2) Injecting the prepared precursor spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +15kV, the negative voltage is-2 kV, the syringe propulsion rate is 0.01ml/min, the receiving distance is 15cm, the rotating speed of the receiving device is 100rpm, the temperature is 30 ℃, the humidity is 40%, and the spinning time is 2h. After spinning is completed, the PVDF composite nanofiber membrane is transferred to a blast oven (60 ℃) and dried for 50 minutes.
(3) Immersing the dried PVDF composite nanofiber membrane into a methanol solution, and carrying out solvent exchange for 30min under the vacuum auxiliary condition. And then performing induction growth of the PVDF composite nanofiber membrane (shaking in a methanol solution of 2-methylimidazole with the concentration of 25mg/ml at 30 ℃/80rpm/18 h) at 35 ℃ to obtain the ZIF-8@PVDF hybrid nanofiber membrane, flushing with methanol three times after shaking, and drying in a vacuum environment at 60 ℃ for 12h to obtain the ZIF-8@PVDF composite membrane with the ZIF-8 loading capacity of 36wt%.
(4) The ZIF-8@PVDF composite film is immersed in a moisture-curable polysiloxane n-hexane solution (20 wt%) for 12min at room temperature, and is subjected to moisture curing for 12h, so that the ZIF-8@PVDF/PDMS mixed matrix film is obtained.
The prepared ZIF-8@PVDF/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 45 ℃, the butanol concentration is 2.0wt%, the separation factor is 27, and the permeation flux is 1955g/m 2 h.
Example 3:
(1) Adding 6.6g of Chitosan (CS) and 20ml of acetic acid solution into a 50ml beaker, and magnetically stirring (400 rpm) for 2 hours at 25 ℃ to fully dissolve the chitosan to obtain chitosan spinning solution;
(2) Injecting the prepared chitosan spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +20kV, the negative voltage is-5 kV, the syringe propulsion rate is 0.02ml/min, the receiving distance is 20cm, the rotating speed of the receiving device is 120rpm, the temperature is 30 ℃, the humidity is 45%, and the spinning time is 3h. After spinning is completed, the chitosan nanofiber membrane is transferred to a blast oven (60 ℃) and dried for 50 minutes.
(3) Immersing the dried CS nanofiber membrane into a methanol solution, and carrying out solvent exchange for 30min under the vacuum auxiliary condition. Subsequently, the CS nanofiber membrane is subjected to in-situ loading of ZIF-91 (shaking in a 10mg/ml methanol solution of Zn (Ac) 2·2H2 O and a 16mg/ml methanol solution of 4, 5-dichloroimidazole at a vibration condition of 40 ℃/120rpm/8h and 30 ℃/100rpm/12h respectively) at 25 ℃ to obtain a ZIF-91@CS hybrid nanofiber membrane, the ZIF-91@CS hybrid nanofiber membrane is washed three times by methanol after shaking, and the ZIF-91@CS hybrid nanofiber membrane is dried for 12h in a vacuum environment at 60 ℃ to obtain the ZIF-91@CS fiber membrane, wherein the ZIF-91 loading amount is 26wt%.
(4) 3% Of free radical photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone is added into the acrylic ester functionalized siloxane solution, and the mixed solution of acrylic ester functionalized polysiloxane is obtained after uniform stirring. Immersing the ZIF-91@CS nanofiber membrane into the acrylic ester functionalized polysiloxane solution (20wt%) for 30min at room temperature, and adsorbing excessive polysiloxane solution on the surface after full immersion; and polymerizing for 20s under irradiation of ultraviolet light with the power of 220W and the wavelength of 365nm to obtain the ZIF-91@CS/PDMS mixed matrix film.
The prepared ZIF-91@CS/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 50 ℃, the butanol concentration is 2.0wt%, the separation factor is 19, and the permeation flux is 1530g/m 2 h.
Example 4:
(1) 1g of CTA (cellulose triacetate) powder was dissolved in 9g of DMSO: CH 2Cl2 (v: v) =3: 1, magnetically stirring (500 rpm) the mixed solvent at 55 ℃ for 36 hours to fully dissolve the solute, thereby obtaining CTA spinning solution;
(2) Injecting the prepared CTA spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +17kV, the negative voltage is-2 kV, the syringe propulsion rate is 0.007ml/min, the receiving distance is 17cm, the rotating speed of the receiving device is 100rpm, the temperature is 30 ℃, the humidity is 50%, and the spinning time is 2.5h. After spinning is completed, the CTA nanofiber membrane is transferred to a forced air oven (60 ℃) and dried for 50 minutes.
(3) Immersing the dried CTA nanofiber membrane into a methanol solution, carrying out solvent exchange for 30min under a vacuum auxiliary condition, then carrying out in-situ loading of ZIF-8 (oscillating in a methanol solution of zinc nitrate hexahydrate with the concentration of 50mg/ml and a methanol solution of 2-methylimidazole with the concentration of 110mg/ml in sequence, wherein the oscillating condition is 30 ℃/120rpm/24 h), obtaining the ZIF-8@CTA hybrid nanofiber membrane, flushing with methanol for three times after oscillation is finished, and drying for 12h under a vacuum environment at 60 ℃ to obtain the ZIF-8@CTA nanofiber membrane with the ZIF-8 loading of 58wt%.
(4) Immersing a ZIF-8@CTA nanofiber membrane into a vinyl-terminated siloxane acetone solution (25 wt%) for 10min at room temperature, and adsorbing excessive polysiloxane solution on the surface after full immersion; and (3) thermally crosslinking and curing for 2 hours at 40 ℃ to obtain the ZIF-8@CTA/PDMS mixed matrix membrane.
The prepared ZIF-8@CTA/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 55 ℃, the butanol concentration is 1.5wt%, the separation factor is 47, and the permeation flux is 2946g/m 2 h.
Example 5:
(1) Adding 4g of PAN and 20ml of N, N-dimethylacetamide into a 50ml beaker, magnetically stirring (500 rpm) at 35 ℃ for 8 hours to completely dissolve the PAN, and then adding 2g of cobalt nitrate hexahydrate to prepare PAN spinning solution;
(2) Injecting the prepared PAN spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +15kV, the negative voltage is-2 kV, the syringe propulsion rate is 0.01ml/min, the receiving distance is 15cm, the rotating speed of the receiving device is 120rpm, the temperature is 30 ℃, the humidity is 30%, and the spinning time is 4 hours. After spinning is completed, the PAN nanofiber membrane is transferred to a forced air oven (60 ℃) and dried for 50min.
(3) Immersing the dried PAN nanofiber membrane into a methanol solution, carrying out solvent exchange for 30min under the assistance of vacuum, then carrying out induced growth of ZIF-67 (oscillation in the methanol solution of 2-methylimidazole with the concentration of 5.5mg/ml at 25 ℃/80rpm/16 h) on the PAN nanofiber membrane at 25 ℃ to obtain a ZIF-67@PAN hybrid nanofiber membrane, flushing three times with methanol after oscillation, and drying for 12h at 60 ℃ under the vacuum environment to obtain the ZIF-67@PAN nanofiber membrane with the ZIF-67 load of 30wt%.
(4) 3% Of free radical photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone is added into the acrylic ester functionalized polysiloxane solution, and the mixture solution of polysiloxane is obtained after uniform stirring. Immersing the ZIF-67@PAN nanofiber membrane into a siloxane solution (25 wt%) for 30min at room temperature, and adsorbing excessive polysiloxane solution on the surface after full immersion; and polymerizing for 30s under irradiation of ultraviolet light with the power of 220W and the wavelength of 365nm to obtain the ZIF-67@PAN/PDMS mixed matrix film.
The prepared ZIF-67@PAN/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 55 ℃, the butanol concentration is 1.5wt%, the separation factor is 22, and the permeation flux is 1813g/m 2 h.
Example 6:
(1) 1.5g CTA (cellulose triacetate) powder was dissolved in 10g DMSO: CH 2Cl2 (v: v) =3: 1, magnetically stirring (600 rpm) for 36 hours at 75 ℃ to completely dissolve the solute, then adding 2.5g of zinc acetate, and continuously stirring for 8 hours to prepare CTA spinning solution;
(2) Injecting the prepared CTA spinning solution into an injector for electrostatic spinning, wherein the spinning process parameters are as follows: the positive voltage is +17kV, the negative voltage is-2 kV, the syringe propulsion rate is 0.01ml/min, the receiving distance is 17cm, the rotating speed of the receiving device is 100rpm, the temperature is 35 ℃, the humidity is 30%, and the spinning time is 3h. After spinning is completed, the CTA nanofiber membrane is transferred to a forced air oven (60 ℃) and dried for 50 minutes.
(3) The dried CTA nanofiber membrane (nanofiber membrane B) was immersed in a methanol solution, and subjected to solvent exchange under vacuum assistance for 30min. And then performing induction growth of ZIF-91 on the CTA nanofiber membrane at 25 ℃ (oscillating 25 ℃/80rpm/24h in a methanol solution of 4, 5-dichloroimidazole with the concentration of 48 mg/ml) to obtain a ZIF-91@CTA hybrid nanofiber membrane, flushing three times with methanol after oscillation, and drying for 12h in a vacuum environment at 60 ℃ to obtain the ZIF-91@CTA fiber membrane with the ZIF-91 loading amount of 42wt%.
(4) The ZIF-91@CTA nanofiber membrane is immersed in a moisture-curable siloxane n-hexane solution (20 wt%) for 30min at room temperature, and is subjected to moisture curing for 3h, so that the ZIF-91@PAN/PDMS mixed matrix membrane is obtained.
The prepared ZIF-91@CTA/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 50 ℃, the butanol concentration is 2.0wt%, the separation factor is 31, and the permeation flux is 2350g/m 2 h.
Comparative example 1:
(1) As in example 1.
(2) Immersing the PAN nanofiber membrane into vinyl-terminated polysiloxane solution (30 wt%) for 10min at room temperature, and adsorbing excessive polysiloxane solution on the surface after full immersion; and (3) carrying out thermal crosslinking and curing for 2 hours at 40 ℃ to obtain the PAN/PDMS mixed matrix membrane.
The prepared PAN/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 45 ℃, the butanol concentration is 2.0wt%, the separation factor is 5, and the permeation flux is 95g/m 2 h.
Comparative example 2:
(1) As in example 1.
(2) The PVDF composite film was immersed in a moisture curable polysiloxane solution (20 wt%) at room temperature for 12min and moisture cured for 12h to give a PVDF/PDMS mixed matrix film.
The prepared PVDF/PDMS mixed matrix membrane is used for pervaporation separation of butanol aqueous solution, the separation performance of the membrane on the butanol aqueous solution is measured, when the temperature of a feed solution is 45 ℃, the butanol concentration is 2.0wt%, the separation factor is 7, and the permeation flux is 98g/m 2 h.
Finally, it is to be understood that the above preferred embodiments are merely illustrative of the technical solution of the present invention and not restrictive, and that although the invention has been described in detail with reference to the above preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the pervaporation membrane based on the electrostatic spinning process is characterized by comprising the following steps of:
(101) Preparing an electrostatic spinning precursor solution, wherein the precursor solution comprises a spinning polymer and an organic solvent;
(102) Preparing a corresponding nanofiber membrane by using an electrostatic spinning process;
(103) Immersing the prepared nanofiber membrane in a metal ion solution and an organic ligand solution respectively under an oscillation condition, uniformly growing MOFs nano particles generated by the reaction of the organic ligand and the metal compound and loading the MOFs nano particles on a nanofiber skeleton to obtain MOFs@nanofiber composite membranes with MOFs nano particles continuously distributed, wherein the oscillation condition is 0-90 ℃ and 10-300 rpm;
(104) And backfilling a polymer matrix solution in the MOFs@nanofiber composite membrane network, and obtaining the continuous uniform distribution pervaporation membrane of the high MOFs filler after crosslinking and curing, wherein the polymer matrix solution is a polysiloxane solution and comprises polysiloxane, a catalyst and an organic solvent.
2. The method for preparing a pervaporation membrane based on an electrostatic spinning process according to claim 1, wherein the mass fraction of the spinning polymer in the step (101) is 1-30 wt%.
3. The preparation method of the pervaporation membrane based on the electrostatic spinning process is characterized by comprising the following steps of:
(201) Preparing an electrostatic spinning precursor solution, wherein the precursor solution comprises a spinning polymer, an organic solvent and a metal compound, the mass fraction of the spinning polymer is 2-25 wt%, and the mass fraction of the metal compound is 0.1-20 wt%;
(202) Preparing a corresponding nanofiber membrane by using an electrostatic spinning process;
(203) Immersing the prepared nanofiber membrane in an organic ligand solution, and uniformly growing and loading MOFs nano particles generated by the reaction of the organic ligand and the metal compound on a nanofiber skeleton to obtain MOFs@nanofiber composite membrane with MOFs nano particles continuously distributed;
(204) And backfilling a polymer matrix solution in the MOFs@nanofiber composite membrane network, and obtaining the alcohol-penetrating type pervaporation membrane with high MOFs filler continuously and uniformly distributed after crosslinking and curing, wherein the polymer matrix solution is a polysiloxane solution and comprises polysiloxane, a catalyst and an organic solvent.
4. The method for preparing a pervaporation membrane based on an electrostatic spinning process according to claim 1 or 3, wherein the spinning polymer is one or more of polyacrylonitrile, polyvinylidene fluoride, carboxylated cellulose, cellulose acetate, chitosan and aramid, and the organic solvent is one or more of N-hexane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid, acetone, dichloromethane and dichloroethane.
5. A method of preparing a pervaporation membrane based on an electrospinning process according to claim 1 or 3, wherein the electrospinning process operating parameters in steps (102) and (202): the positive voltage is 0.1-40 kV, the negative voltage is-0.1 to-40 kV, the advancing rate of the electrostatic spinning precursor solution is 0.1-5.0L/h, and the spinning time is 0.5-24 h; the receiving distance is 5-50 cm; the spinning temperature is 0-80 ℃, and the spinning humidity is 1-85% RH.
6. The method for preparing a pervaporation membrane based on an electrospinning process according to claim 1 or 3, wherein the MOFs loaded in the steps (103) and (203) are one or more of the mixed types of ZIF-1, ZIF-8, ZIF-67, ZIF-90, ZIF-91.
7. A pervaporation membrane prepared by the method of preparation of claim 1 or 3.
8. Use of the pervaporation membrane according to claim 7 for the separation and purification of alcohols in fermentation broths.
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