CN111266019A - Preparation method and application of vertically-oriented magnetic nanosheet/sodium alginate composite membrane - Google Patents
Preparation method and application of vertically-oriented magnetic nanosheet/sodium alginate composite membrane Download PDFInfo
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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Abstract
The invention discloses a preparation method of a vertical orientation magnetic nano-sheet/sodium alginate composite membrane, which utilizes the magnetic field responsiveness of magnetic nano-sheets to form a vertical orientation structure in a magnetic field so as to prepare a high-performance pervaporation composite membrane. The magnetic nano-plate comprises a nano-plate with intrinsic magnetic responsiveness or other nano-plates with magnetic responsiveness generated by loading magnetic response particles. The preparation method specifically comprises the steps of dispersing magnetic nanosheets uniformly, then physically blending the magnetic nanosheets with sodium alginate to form a membrane casting solution, standing, defoaming, then spin-coating the membrane casting solution on a polyacrylonitrile ultrafiltration membrane, placing the composite membrane in a magnetic field, drying at room temperature, and crosslinking to obtain the magnetic nanosheet/sodium alginate composite membrane with vertical orientation. The preparation process is simple and controllable, and the raw materials are cheap and easy to obtain. The obtained composite membrane is suitable for pervaporation ethanol dehydration, has high permeation flux and high selectivity to water molecules, and has good operation stability at high temperature.
Description
Technical Field
The invention relates to a preparation method and application of a vertically-oriented magnetic nanosheet/sodium alginate composite membrane, and belongs to the technical field of polymer-inorganic composite membranes.
Background
Energy safety and environmental pollution are the focus problems restricting sustainable development since the new century. China has limited reserves of fossil energy (such as coal, petroleum and natural gas), and in recent years, China has vigorously developed clean renewable energy sources to replace traditional energy sources. Bioethanol has the characteristics of cleanness and reproducibility, and research gradually becomes a hotspot. Among them, ethanol dehydration is an important stage for producing fuel ethanol, and the dehydration stage has high energy consumption, accounting for 20% of the total energy consumption. Common dehydration techniques are: special rectification method, adsorption method and pervaporation method. The pervaporation technology has the advantages of high single-stage separation degree, simple operation, cleanness, no pollution and the like, is particularly suitable for separating the azeotrope of ethanol-water, can be continuously operated, has 50 percent lower energy consumption than an adsorption method and about 65 percent lower energy consumption than special rectification, and has huge development potential.
At present, a polymer film is mainly adopted in the pervaporation process, but due to the restriction relationship between the chain rigidity and the chain spacing of the polymer, a Trade-off effect which is difficult to overcome exists between the permeability and the selectivity of a polymer material, and the introduction of an inorganic filler into a polymer matrix can simultaneously obtain high permeability, selectivity and stability by introducing an additional transfer channel and a screening function through regulating and controlling the structure of the inorganic filler and the appearance of a polymer-inorganic interface. The two-dimensional nano material has the characteristics of anisotropy, high specific surface area, high aspect ratio and ultrathin thickness, has good permeability and provides a channel for the rapid transmission of water molecules. The traditional two-dimensional material serving as a filler tends to be arranged in parallel in a polymer matrix, and at the moment, the mass transfer path is long, the flow resistance is large, and the permeability of the membrane cannot be obviously improved.
Disclosure of Invention
Aiming at the prior art, the invention provides a preparation method and application of a vertical orientation magnetic nano-sheet/sodium alginate composite membrane, the invention prepares the magnetic nano-sheet/sodium alginate composite membrane under the assistance of a magnetic field, wherein the magnetic nano-sheet comprises a nano-sheet with intrinsic magnetic responsiveness and other nano-sheets with magnetic responsiveness generated by loading magnetic response particles, and aims to utilize the magnetic responsiveness of the magnetic nano-sheet, and a filling agent, namely the magnetic nano-sheet, is rearranged under the action of the magnetic field to construct a vertical mass transfer channel, improve the hydrophilicity of the membrane surface and realize the great promotion of selectivity and flux. The preparation method is simple and universal, and the prepared composite membrane can be used for pervaporation ethanol-water system dehydration and has higher separation performance and operation stability. So far, no literature report is found for preparing the magnetic nano-sheet/polymer composite membrane for pervaporation ethanol dehydration through magnetic field assistance.
In order to solve the technical problem, the vertical orientation magnetic nanosheet/sodium alginate composite membrane provided by the invention comprises sodium alginate, and magnetic nanosheets are vertically distributed in the sodium alginate.
Furthermore, the mass ratio of the magnetic nanosheets to the sodium alginate is 0.1-10: 100.
The magnetic nano-sheet comprises a nano-sheet with intrinsic magnetic responsiveness or a nano-sheet with magnetic responsiveness generated by loading magnetic response particles.
Meanwhile, the invention also provides a preparation method of the vertical orientation magnetic nano-sheet/sodium alginate composite membrane, which comprises the steps of dispersing the magnetic nano-sheets uniformly, then physically blending the magnetic nano-sheets with sodium alginate to form a membrane casting solution, standing, defoaming, then spin-coating the membrane casting solution on a polyacrylonitrile ultrafiltration membrane, placing the composite membrane in a magnetic field, drying at room temperature, and crosslinking to obtain the vertical orientation magnetic nano-sheet/sodium alginate composite membrane. The method comprises the following steps:
dispersing magnetic nanosheets in water, wherein the concentration of a dispersion solution is 1-10 mg/ml;
step two, stirring the magnetic nanosheet dispersion liquid obtained in the step one with a certain amount of sodium alginate at 30 ℃ for 5 hours to obtain a membrane casting liquid, wherein the mass ratio of the sodium alginate to the magnetic nanosheets is 100: 0.1-10;
and step three, filtering the membrane casting solution obtained in the step two, standing for defoaming, and then uniformly spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 10-100 ten thousand to obtain the composite membrane, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s;
placing the composite film obtained in the step three in a permanent magnet with the magnetic induction intensity of 10-500 mT, constructing an intra-film mass transfer channel through magnetic field assistance, enabling the magnetic nanosheets to be vertically arranged in the sodium alginate, and drying at room temperature;
and step five, soaking the composite membrane processed in the step four in a calcium chloride solution with the molar concentration of 0.1-1.0 mol/L for crosslinking for 10min, and airing at room temperature to finally obtain the composite membrane, namely the vertical orientation magnetic nanosheet/sodium alginate composite membrane.
The vertical orientation magnetic nano-sheet/sodium alginate composite membrane prepared by the invention is used for pervaporation ethanol/water system dehydration, the membrane performance is evaluated under the condition that the raw material liquid is ethanol water solution with the mass fraction of 90% at 76 ℃, and the permeation flux is 1026-1783 g/m2h, the separation factor is 1410-2762.
Compared with the prior art, the invention has the beneficial effects that:
in the preparation method, the two-dimensional vertical mass transfer channel in the composite membrane is constructed by the aid of the magnetic field, so that the mass transfer distance can be greatly shortened, and the permeability of the membrane is improved; meanwhile, the magnetic field is assisted to regulate and control the distribution of the magnetic nanosheets, the hydrophilicity and hydrophobicity of the surface of the membrane are improved, and the selectivity of the membrane is improved. The preparation process provided by the invention is simple and convenient, strong in controllability, easy in raw material obtaining and universal. The prepared composite membrane is used for a pervaporation ethanol-water solution system, has high permeation flux and high selectivity to water molecules, and has good operation stability at high temperature.
Drawings
FIG. 1 is a schematic process diagram of the preparation method of the present invention;
FIG. 2 is a sectional electron micrograph of the film 2 produced in example 2;
FIG. 3 is a sectional electron micrograph of film 3 produced in example 3;
FIG. 4 is a sectional electron micrograph of a comparative film 1 produced in comparative example 1;
FIG. 5 is a sectional electron micrograph of comparative film 2 produced in comparative example 2.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
According to the preparation method of the vertically-oriented magnetic nanosheet/sodium alginate composite membrane, provided by the invention, a vertically-oriented structure is formed in a magnetic field by utilizing the magnetic field responsiveness of the magnetic nanosheets, namely the magnetic nanosheets are vertically arranged in the sodium alginate, so that the high-performance pervaporation composite membrane is obtained. The composite membrane is composed of magnetic nanosheets and sodium alginate according to a mass ratio of 0.1-10: 100, wherein the magnetic nanosheets comprise intrinsic magnetic-responsiveness nanosheets and nanosheets which generate magnetic-responsiveness through loading magnetic-response particles. The method specifically comprises the steps of dispersing magnetic nanosheets uniformly, then physically blending the magnetic nanosheets with sodium alginate to form a membrane casting solution, standing, defoaming, then spin-coating the membrane casting solution on a polyacrylonitrile ultrafiltration membrane, placing the composite membrane in a magnetic field, drying at room temperature, and constructing an intramembrane mass transfer channel (as shown in figure 1) in the airing process through the assistance of the magnetic field, so that the magnetic nanosheet/sodium alginate composite membrane with vertical orientation is obtained after crosslinking. The preparation process is simple and controllable, and the raw materials are cheap and easy to obtain. The obtained composite membrane is suitable for pervaporation ethanol dehydration, has high permeation flux and high selectivity to water molecules, and has good operation stability at high temperature.
Embodiment 1, a vertically-oriented ferroferric oxide-loaded graphene oxide/sodium alginate composite membrane is prepared, which includes the following steps:
and stirring and ultrasonically dispersing a 1mg/ml ferroferric oxide-loaded graphene oxide dispersion liquid uniformly, wherein the transverse size of the graphene oxide is 500-1000 nm, and the thickness of the graphene oxide is 1-2 nm. 380 mul of dispersion liquid is added into deionized water, so that the filler, namely the ferroferric oxide-loaded graphene oxide is dispersed in 24.6ml of deionized water.
And adding 0.38g of sodium alginate into the dispersion liquid, and stirring for 5 hours at 30 ℃ to obtain a casting solution with the mass ratio of the ferroferric oxide-loaded graphene oxide to the sodium alginate particles being 0.001: 1.
Filtering the membrane casting solution, standing for defoaming, and uniformly spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 100 ten thousand, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s; and (5) obtaining the composite membrane.
Placing the composite film between permanent magnets with the magnetic induction intensity of 500mT, and drying at room temperature; and then soaking the membrane in a calcium chloride solution with the molar concentration of 1.0mol/L for crosslinking for 10min, washing with a large amount of deionized water, and then drying at room temperature to finally obtain the vertically-oriented ferroferric oxide-loaded graphene oxide/sodium alginate composite membrane, which is marked as a membrane 1.
The membrane 1 is used for pervaporation ethanol dehydration, and the permeation flux is 1428g/m under the condition of 76 ℃ and 90/10 wt% (ethanol/water) of raw material solution concentration2h, separation factor 1983.
Embodiment 2, a composite membrane is prepared by preparing a vertically-oriented ferroferric oxide nanosheet/sodium alginate composite membrane, and the preparation method comprises the following steps:
dissolving 0.6g of ferric chloride hexahydrate in 30ml of diethylene glycol, magnetically stirring for 1 hour, adding 1.5g of sodium acetate, magnetically stirring for 0.5 hour to obtain a black solution, carrying out solvent thermal reaction for 15 hours at 200 ℃ to obtain a black precipitate, centrifuging and washing the precipitate by using ethanol and water in sequence to obtain a ferroferric oxide nanosheet with the size of 100-200 nm and the thickness of 5-10 nm, storing a product in deionized water, uniformly stirring and ultrasonically dispersing, drying a quantitative dispersion liquid, and weighing the precipitate mass, wherein the concentration of the dispersion liquid is 3 mg/ml. And stirring and ultrasonically dispersing the prepared ferroferric oxide dispersion liquid uniformly. 380. mu.l of dispersion liquid was added to deionized water to disperse the filler, i.e., the ferroferric oxide nanosheet, in 24.3ml of deionized water.
And then adding 0.38g of sodium alginate into the dispersion liquid, and stirring for 5 hours at 30 ℃ to obtain a membrane casting liquid with the mass ratio of the ferroferric oxide nano-sheets to the sodium alginate particles being 0.003: 1.
Filtering the membrane casting solution, standing for defoaming, and uniformly spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 10 ten thousand, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s; and (5) obtaining the composite membrane.
Placing the composite film between permanent magnets with the magnetic induction intensity of 10mT, and drying at room temperature; and then soaking the film in a calcium chloride solution with the molar concentration of 0.5mol/L for crosslinking for 10min, washing with a large amount of deionized water, and then drying at room temperature to finally obtain the vertically oriented ferroferric oxide nano-sheet/sodium alginate composite film, which is marked as a film 2. Homogeneous membranes were prepared for characterization in the same manner and the cross-sectional view is shown in FIG. 2.
The membrane 2 is used for pervaporation ethanol dehydration, and the permeation flux is 1742g/m under the conditions of 76 ℃ and 90/10 wt% (ethanol/water) of raw material solution concentration2h, separation factor 2071.
Embodiment 3, a vertically oriented ferroferric oxide nanosheet/sodium alginate composite membrane is prepared, including the following steps:
the preparation process is basically the same as that of the embodiment 2, except that in the film forming process, the volume of the dispersion liquid is 507 mu l, and the volume of the deionized water is 24.5ml, so as to obtain a casting solution with the mass ratio of the ferroferric oxide nano-sheets to the sodium alginate particles being 0.004: 1; and after spin coating, drying the film between permanent magnets with the magnetic induction intensity of 200mT to finally obtain a vertically oriented ferroferric oxide nanosheet/sodium alginate composite film, which is marked as a film 3, wherein the cross-sectional view of the film 3 is shown in figure 3.
The membrane 3 is used for pervaporation ethanol dehydration, and the permeation flux is 1783g/m under the conditions of 76 ℃ and 90/10 wt% (ethanol/water) of raw material solution concentration2h, separation factor 2762.
Embodiment 4, a vertically oriented ferroferric oxide nanosheet/sodium alginate composite membrane is prepared, including the following steps:
the preparation process is basically the same as that of the embodiment 2, except that in the film forming process, the volume of the dispersion liquid is 760 mul, and the volume of the deionized water is 24.2ml, so as to obtain a casting film liquid with the mass ratio of the ferroferric oxide nano-sheet to the sodium alginate particles being 0.006:1, and finally obtain a magnetic field assisted ferroferric oxide nano-sheet/sodium alginate composite film, which is marked as film 4.
The membrane 4 is used for pervaporation ethanol dehydration, and the permeation flux is 1732g/m under the condition of 76 ℃ and the concentration of raw material liquid is 90/10 wt% (ethanol/water)2h, separation factor 1410.
Example 5 preparation of vertically oriented γ -Fe2O3The nano-sheet/sodium alginate composite membrane comprises the following steps:
the procedure was essentially the same as in example 1 except that the dispersion was: will be commercially available gamma-Fe2O3The nanoplatelets are dispersed in deionized water, wherein gamma-Fe2O3The size of the nano-sheet is 200nm, and 10mg/ml of dispersion liquid is obtained; in the film forming process, the volume of the dispersion liquid is 266 mu l, and the volume of the deionized water is 24.7ml, so that the gamma-Fe is obtained2O3The mass ratio of the nano-sheets to the sodium alginate particles is 0.007:1, and finally the vertically oriented gamma-Fe is obtained2O3The nanosheet/sodium alginate composite membrane is denoted as membrane 5.
The membrane 5 is used for pervaporation ethanol dehydration, and the permeation flux is 1026g/m under the condition of 76 ℃ and 90/10 wt% (ethanol/water) of raw material liquid concentration2h, separation factor 2401.
Embodiment 6, a vertically oriented ferroferric oxide supported boron nitride nanosheet/sodium alginate composite membrane is prepared by the following steps:
the procedure was essentially the same as in example 1 except that the dispersion was: dispersing boron nitride nanosheets loaded with ferroferric oxide in deionized water, wherein the transverse size of the boron nitride nanosheets loaded with ferroferric oxide is 5000nm, and obtaining 3mg/ml of dispersion liquid; in the film forming process, the volume of the dispersion liquid is 12.6ml, the volume of the deionized water is 12.4ml, a casting film liquid with the mass ratio of the boron nitride nanosheet loaded with the ferroferric oxide to the sodium alginate particles being 0.1:1 is obtained, and finally the vertically-oriented boron nitride nanosheet/sodium alginate composite film loaded with the ferroferric oxide is obtained and is marked as a film 6.
The membrane 6 is used for pervaporation ethanol dehydration, and the permeation flux is 1681/m at 76 deg.C and 90/10 wt% (ethanol/water) of raw material solution concentration2h, separation factor 1630.
Comparative example 1 a pure sodium alginate membrane was prepared with the following steps:
dissolving 0.38g of sodium alginate in 25ml of deionized water, stirring for 5 hours at 30 ℃, filtering, standing and defoaming to obtain a uniform membrane casting solution; filtering the membrane casting solution, and spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 10 ten thousand, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s; obtaining a composite membrane, and drying at room temperature; and then soaking the film in a calcium chloride solution with the molar concentration of 0.1mol/L for crosslinking for 10min, washing with a large amount of deionized water, and drying at room temperature to finally obtain a pure sodium alginate film which is marked as a comparative film 1, preparing a homogeneous film for characterization by using the same method, wherein a section electron microscope image of the comparative film 1 is shown in figure 4.
The comparative membrane 1 was used for pervaporation ethanol dehydration with a permeate flux of 1451g/m at 76 ℃ and a feed solution concentration of 90/10 wt% (ethanol/water)2h, separation factor 296.
Comparative example 2, a magnetic field-free auxiliary ferroferric oxide nanosheet/sodium alginate composite membrane is prepared, and the steps are as follows:
and stirring and ultrasonically dispersing the prepared ferroferric oxide dispersion liquid uniformly. Adding 507 mu l of dispersion liquid into deionized water to disperse the ferroferric oxide nano-sheets in 24.5ml of deionized water, then adding 0.38g of sodium alginate into the dispersion liquid, and stirring for 5 hours at 30 ℃ to obtain a membrane casting liquid with the mass ratio of the ferroferric oxide nano-sheets to the sodium alginate particles being 0.004: 1; filtering the membrane casting solution, standing for defoaming, and uniformly spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 10 ten thousand, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s; obtaining a composite membrane, and drying at room temperature; and then soaking the film in a calcium chloride solution with the molar concentration of 0.5mol/L for crosslinking for 10min, washing with a large amount of deionized water, and then drying at room temperature to finally obtain a magnetic field-free assisted ferroferric oxide nanosheet/sodium alginate composite film, which is marked as a comparison film 2, and preparing a homogeneous film for characterization by using the same method, wherein a section electron microscope image of the comparison film 2 is shown in FIG. 5.
The comparative membrane 2 was used for pervaporation ethanol dehydration with a permeate flux of 1573g/m at 76 ℃ with a feed solution concentration of 90/10 wt% (ethanol/water)2h, separation factor 1206.
Test example 1, a method for testing ethanol/water separation performance of a composite membrane, comprising the steps of:
(1) cutting a composite membrane to be tested and evaluated into support plates with proper sizes, and installing a membrane chamber;
(2) adding 90 wt% ethanol water solution into a raw material tank, performing feed liquid circulation at a flow rate of 60L/h, and adjusting a heating device to ensure that the temperature of the raw material liquid is stabilized at 76 ℃;
(3) analyzing the concentration of the raw material liquid by using a gas chromatograph;
(4) recording the total mass of the dry cold trap and the sealing plug; after the temperature and the flow of the circulating raw material liquid are stable, connecting a cold trap, starting a vacuum pump to reduce the downstream pressure side to about 0.1kPa, immersing the cold trap in liquid nitrogen for cooling, and starting timing;
(5) the experiment was repeated by replacing the cold trap every 0.5 h. Sealing the cold trap filled with the permeation liquid with a sealing plug, placing the cold trap in normal temperature water, removing water drops on the outer wall after the internal permeation liquid is completely melted, weighing, recording data, taking a certain amount of permeation liquid, and analyzing the composition of the permeation liquid by gas chromatography.
(6) Repeating the two steps to obtain 3 groups of data, and averaging the results;
(7) and after the test is finished, the heating device, the circulating device and the vacuum cooling device are closed. The results of the membrane separation performance test are shown in table 1.
The ethanol/water separation performance test method of the composite membrane is utilized to respectively test the membranes 1 to 6 and the comparison membranes 1 and 2, and the result shows that: the vertically-oriented magnetic nanosheet/sodium alginate composite membranes (membranes 1-6) of the various embodiments obtained according to the preparation method provided by the present invention exhibit the highest permeability coefficient and separation factor.
TABLE 1 permeation coefficient and separation factor comparison of membranes 1-6 and comparative membranes 1-2 made in accordance with the examples of the invention
Permeate flux (g/m)2h) | Separation factor | |
Membrane 1 | 1428 | 1983 |
Membrane 2 | 1742 | 2071 |
Membrane 3 | 1783 | 2762 |
Membrane 4 | 1732 | 1410 |
Membrane 5 | 1026 | 2401 |
Membrane 6 | 1681 | 1630 |
Comparative film 1 | 1451 | 296 |
Comparative film 2 | 1573 | 1206 |
According to the data in table 1, the separation factor and the permeation flux of the composite membrane are obviously improved compared with those of a pure sodium alginate membrane by introducing the magnetic nanosheets in the preparation method, because the magnetic nanosheets adjust the chain rigidity of the polymer chain segments, the magnetic nanosheets/sodium alginate composite membrane with the vertical orientation prepared under the assistance of the magnetic field are rearranged in the polymer, the constructed vertical channel improves the hydrophilicity of the membrane surface, and simultaneously, the network structure of the polymer is optimized, so that the separation factor and the permeation flux of the composite membrane are further improved compared with those of the composite membrane prepared under the assistance of the non-magnetic field.
Although the present invention is described above with reference to the drawings, the present invention is not limited to the above-mentioned specific embodiments, and the above-mentioned specific embodiments are only illustrative and not restrictive, and although it is exemplified that the magnetic nanosheet/sodium alginate composite film is prepared by magnetic field assistance, since sodium alginate is one of polymers, the technical solution of the present invention is to prepare the magnetic nanosheet/polymer composite film by magnetic field assistance, rather than just the magnetic nanosheet/sodium alginate composite film and its preparation and application, that is, those skilled in the art can realize the preparation of the magnetic nanosheet/polymer composite film by magnetic field assistance without departing from the spirit of the present invention, and these are within the protection of the present invention.
Claims (6)
1. A vertical orientation magnetic nano-sheet/sodium alginate composite film is characterized by comprising sodium alginate, wherein magnetic nano-sheets are vertically distributed in the sodium alginate.
2. The vertically-oriented magnetic nanosheet/sodium alginate composite membrane of claim 1, wherein the mass ratio of the magnetic nanosheets to the sodium alginate is 0.1-10: 100.
3. The vertically-oriented magnetic nanosheet/sodium alginate composite membrane of claim 1 or 2, wherein the magnetic nanosheets comprise intrinsically magnetically-responsive nanosheets or nanosheets that are magnetically-responsive by being loaded with magnetically-responsive particles.
4. A preparation method of the vertically-oriented magnetic nanosheet/sodium alginate composite membrane according to claim 1, wherein the preparation method comprises: dispersing the magnetic nano-sheets uniformly, then physically blending the magnetic nano-sheets with sodium alginate to form a membrane casting solution, standing for defoaming, then spin-coating the membrane casting solution on a polyacrylonitrile ultrafiltration membrane, placing the composite membrane in a magnetic field, drying at room temperature, and crosslinking to obtain the magnetic nano-sheet/sodium alginate composite membrane with vertical orientation.
5. The preparation method of the vertically-oriented magnetic nanosheet/sodium alginate composite membrane according to claim 4, wherein the steps are as follows:
dispersing magnetic nanosheets in water, wherein the concentration of a dispersion solution is 1-10 mg/ml;
step two, stirring the magnetic nanosheet dispersion liquid obtained in the step one with a certain amount of sodium alginate at 30 ℃ for 5 hours to obtain a membrane casting liquid, wherein the mass ratio of the sodium alginate to the magnetic nanosheets is 100: 0.1-10;
and step three, filtering the membrane casting solution obtained in the step two, standing for defoaming, and then uniformly spin-coating on a polyacrylonitrile ultrafiltration membrane with the molecular weight cutoff of 10-100 ten thousand to obtain the composite membrane, wherein the spin-coating process conditions are as follows: spin-coating at 500rpm for 20s, and then spin-coating at 800rpm for 40 s;
placing the composite film obtained in the step three in a permanent magnet with the magnetic induction intensity of 10-500 mT, constructing an intra-film mass transfer channel through magnetic field assistance, enabling the magnetic nanosheets to be vertically arranged in the sodium alginate, and drying at room temperature;
and step five, soaking the composite membrane processed in the step four in a calcium chloride solution with the molar concentration of 0.1-1.0 mol/L for crosslinking for 10min, and airing at room temperature to finally obtain the composite membrane, namely the vertical orientation magnetic nanosheet/sodium alginate composite membrane.
6. The application of the vertically-oriented magnetic nanosheet/sodium alginate composite membrane is characterized in that the vertically-oriented magnetic nanosheet/sodium alginate composite membrane prepared by the preparation method of claim 4 or 5 is used for pervaporation ethanol dehydration, and the permeation flux is 1026-1783 g/m under the condition that the raw material solution is an ethanol aqueous solution with the mass fraction of 90% at 76 DEG C2h, the separation factor is 1410-2762.
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CN113289506A (en) * | 2021-06-15 | 2021-08-24 | 江南大学 | Asymmetric magnetic oxygen-nitrogen separation membrane and preparation method thereof |
CN115463556A (en) * | 2022-08-30 | 2022-12-13 | 石河子大学 | Mixed matrix membrane based on dual-functional modified GO nanosheets and preparation method and application thereof |
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CN115651451A (en) * | 2022-10-19 | 2023-01-31 | 南方科技大学 | Magnetic control micro-nano robot with biocompatibility and manufacturing method and application thereof |
CN115651451B (en) * | 2022-10-19 | 2023-12-05 | 南方科技大学 | Magnetic control micro-nano robot with biocompatibility and manufacturing method and application thereof |
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