CN108543426B - Preparation method and application of magnetic field induced infiltration and gasification hybrid membrane - Google Patents
Preparation method and application of magnetic field induced infiltration and gasification hybrid membrane Download PDFInfo
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- CN108543426B CN108543426B CN201810354325.8A CN201810354325A CN108543426B CN 108543426 B CN108543426 B CN 108543426B CN 201810354325 A CN201810354325 A CN 201810354325A CN 108543426 B CN108543426 B CN 108543426B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/46—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a preparation method and application of a magnetic field induced infiltration and vaporization hybrid membrane, and belongs to the technical field of infiltration and vaporization membrane separation. Adding a polyether copolyamide solution into a magnetic nano material dispersion solution in two steps, and performing ultrasonic dispersion and vacuum defoaming to obtain a membrane casting solution; casting the casting solution on a glass plate, scraping the film by using a scraper, and horizontally placing the glass plate in a blast drying oven with a vertical magnetic field for drying; finally, vacuum drying and uncovering the membrane to obtain the pervaporation membrane. The pervaporation hybrid membrane prepared by the method has a controllable structure, the introduced magnetic nanoparticles can be enriched on the surface of the membrane, the adsorption selectivity of the membrane material to phenol and nitrophenol is improved, meanwhile, the magnetic nanoparticles in a polymer phase can be orderly arranged under the action of a magnetic field, a diffusion channel of phenol and nitrophenol tends to be formed, and the pervaporation hybrid membrane has a good effect on removing trace volatile organic matters such as phenol, nitrophenol and the like in water.
Description
Technical Field
The invention relates to a preparation method and application of a magnetic field induced infiltration and vaporization hybrid membrane, belonging to the technical field of infiltration and vaporization membrane separation.
Background
The pervaporation technology is used for separating liquid mixture, and has the outstanding advantage that separation tasks which are difficult to be completed by traditional methods such as distillation, extraction, absorption and the like can be realized with lower energy consumption. It is particularly suitable for the separation of near-boiling point and constant-boiling point mixtures and isomers which are difficult to separate or cannot be separated by distillation; has obvious technical and economic advantages for removing trace water in organic solvent and mixed solvent and separating a small amount of organic pollutants in waste water. Therefore, the PV technology has wide application prospect and market in the industrial fields of petrochemical industry, medicine, food, environmental protection and the like. Experts in the international academia refer to one of the most promising high technologies in the twenty-first century.
The industrial application of pervaporation technology depends mainly on the material of the pervaporation membrane. Among membrane materials, hybrid membrane (MMMs) is an important one. MMMs are obtained by incorporating nanoscale inorganic fillers into macromolecules. The MMMs have both high selectivity of inorganic fillers and controllability of polymer membranes. Commonly used inorganic fillers include mainly molecular sieves, metals and metal oxides, silica, carbon nanotubes, and the like. However, there are still several problems that limit the application of MMMs. Wherein the compatibility between the inorganic filler and the polymer is the most critical, and the film preparation process is easy to have defects, so that the separation selectivity of the film is not high. In addition, MMMs membranes generally have a trade-off effect, i.e. the better the selectivity, the lower the flux. In recent years, metal-organic frameworks (MOFs) have attracted more and more attention as a new type of filler. MOFs have controllable pore sizes, high porosity and selective adsorption (Liu X L, Li Y S, Zhu GQ, et al, organic peroxide decomposition membrane derivatives from metal to organic frame work nanoparticles for effective recovery of bio-alcohols [ J ]. Angew.chem. int. Ed., 2011, 50: 10636-. Meanwhile, MOFs are formed by linking transition metals through different organic ligands. Due to the existence of organic ligands, the problem of poor compatibility of fillers and polymers can be solved well (Kang C H, Lin Y F, Huang Y S, et al. Synthesis of ZIF-7/chitosan mixed-matrix membranes with improved separation performance of water/ethanol mixtures [ J ] J. Membrane. Sci., 2013, 438: 105-111).
However, the method for preparing the pervaporation membrane in the above document enables the introduced MOFs to be uniformly dispersed in the polymer phase only, and especially when the doping amount of the MOFs reaches the upper limit, the amount of the MOFs on the surface of the membrane of the pervaporation membrane contacting with the feed liquid to be separated does not increase continuously.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a permeable and gasified hybrid membrane under the induction of a magnetic field, wherein a ferroferric oxide loaded MOFs material (magnetic nano material) is introduced into a high molecular phase, and the magnetic field is introduced in the membrane preparation process. Under the action of a magnetic field, the magnetic nano material can be enriched on the surface of the membrane, so that the aims of regulating and controlling the microstructure and the separation performance of the pervaporation membrane are fulfilled. The pervaporation membrane prepared by the method has controllable microstructure, can be used for removing volatile organic matters such as nitrophenol, phenol and the like in water, and has high permeability and good separation selectivity.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a magnetic field induced lower permeation gasification hybrid membrane comprises the following steps:
(1) ultrasonically dispersing a magnetic nano material in an organic solvent at room temperature to obtain a magnetic nano material dispersion liquid, and then preparing a polyether copolyamide solution with the same mass fraction as that of the magnetic nano material dispersion liquid by using the same organic solvent;
(2) adding a small amount of polyether copolyamide solution into the magnetic nano-material dispersion liquid to obtain a premixed solution, carrying out ultrasonic treatment for a period of time, adding all the rest of polyether copolyamide solution into the magnetic nano-material dispersion liquid to obtain a mixed solution, carrying out ultrasonic treatment for a period of time, and then carrying out vacuum defoaming to obtain a membrane casting solution;
(3) casting the casting solution on a glass plate, scraping the film by a scraper, horizontally placing the glass plate in a blast drying box with a vertical magnetic field, drying for 10 hours at a certain temperature, vacuum-drying for 4 hours at 60 ℃, and then uncovering the film.
The magnetic nano material in the step (1) includes but is not limited to Fe3O4@Uio-66、Fe3O4@ MIL-53 (Al); the organic solvent is dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.
The mass fraction of the magnetic nano material dispersion liquid in the step (1) is 2-5%.
The mass ratio of the magnetic nano material dispersion liquid to the polyether copolyamide solution in the step (2) is 1: 100-30: 100.
And (3) carrying out ultrasonic treatment on the premixed liquid in the step (2) for 0.5-1 h, and carrying out ultrasonic treatment on the mixed liquid for 1-2 h.
The vertical magnetic field in the step (3) is composed of two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm multiplied by 50mm multiplied by 20mm, the two permanent magnets are placed up and down, the south poles face up, the distance is 4cm, and the magnetic field intensity is 2000 Gs-3800 Gs.
And (4) in the step (3), the drying temperature of the air-blast drying box is lower than the upper limit of the working temperature of the neodymium iron boron permanent magnet.
The drying temperature of the forced air drying oven in the step (3) is 80-100 ℃.
The pervaporation hybrid membrane obtained by the preparation method has an asymmetric structure and can be used for removing trace volatile organic compounds in water.
The trace volatile organic compounds include but are not limited to phenol and nitrophenol, and the concentration is 100 ppm-10000 ppm.
The invention has the beneficial effects that: the pervaporation hybrid membrane prepared by the method has a controllable structure, the introduced magnetic nanoparticles can be enriched on the surface of the membrane, the adsorption selectivity of the membrane material to phenol and nitrophenol is improved, and meanwhile, the magnetic nanoparticles in a polymer phase can be orderly arranged under the action of a magnetic field and tend to form a diffusion channel of phenol and nitrophenol. Compared with the polymer membrane, the flux of the obtained pervaporation hybrid membrane is improved by 1.8 times, and the separation factor is increased to more than 70.
Drawings
FIG. 1 is a SEM picture of the hybrid film obtained in example 1 with no magnetic field applied and with a magnetic field applied.
FIG. 2 shows AFM pictures of the hybrid films obtained in example 1 without (left) and with (right) applied magnetic field.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the permeable and vaporized hybrid membrane under the induction of the magnetic field of the embodiment comprises the following steps:
(1) 3g of Fe at room temperature3O4Ultrasonically dispersing the @ MIL-53 (Al) in dimethylformamide to obtain Fe with the mass fraction of 3%3O4@ MIL-53 (Al) 100g, then, 3g of polyether copolyamide is dissolved in dimethylformamide to obtain 100g of polyether copolyamide solution with the same mass fraction as 3%;
(2) 8g of polyether copolyamide solution was added to 1g of Fe3O4@ MIL-53 (Al) dispersion to obtain a premixed solution, ultrasonically treating for 0.5h, and adding 12g of polyether copolyamide solution into Fe3O4The preparation method comprises the following steps of (1) obtaining mixed liquor in @ MIL-53 (Al) dispersion liquid, carrying out ultrasonic treatment for 2 hours, and then carrying out vacuum defoaming to obtain membrane casting liquid;
(3) casting the casting solution on a glass plate, scraping the film by using a scraper, and then horizontally placing the glass plate in a blast drying box with a vertical magnetic field, wherein the vertical magnetic field is formed by two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm multiplied by 50mm multiplied by 20mm, the two permanent magnets are placed at the upper and lower positions, the south poles face upwards, the distance is 4cm, and the magnetic field intensity is 3000 Gs; drying at 80 deg.C for 10 hr, and vacuum drying at 60 deg.C for 4 hr.
Comparative example: 3g of Fe at room temperature3O4@ MIL-53 (Al) was ultrasonically dispersed in dimethylformamide to give 100g of a 3% mass dispersion, and then 3g of a polyether copolyamide was dissolved in dimethylformamide to give 100g of a 3% mass solution. 8g of polyether copolyamide solution was added to 1g of Fe3O4@ MIL-53 (Al) dispersion to obtain a premixed solution, ultrasonically treating for 0.5h, and adding 12g of polyether copolyamide solution into Fe3O4@ MIL-53 (Al) dispersion to obtain a mixed solution, performing ultrasonic treatment for 2 hours, and performing vacuum defoaming to obtain a casting solution. Casting the casting solution on a glass plate, scraping the film by a scraper, horizontally placing the glass plate in a forced air drying oven, drying at 80 ℃ for 10h, and removing the film after vacuum drying at 60 ℃ for 4 h. Hybrid membranes without magnetic field induction were prepared as a comparison according to the above preparation method.
Fig. 1 and fig. 2 are SEM and AFM pictures of the hybrid film obtained without and with magnetic field, respectively, and it can be seen that the magnetic nanomaterial is enriched on the surface of the film.
Example 2
The preparation method of the permeable and vaporized hybrid membrane under the induction of the magnetic field of the embodiment comprises the following steps:
(1) 4g of Fe at room temperature3O4@ Uio-66 ultrasonically dispersing in dimethylformamide to obtain Fe with the mass fraction of 4%3O4@ Uio-66 dispersion 100g, then, 4g of polyether copolyamide is dissolved in dimethylformamide to obtain 100g of polyether copolyamide solution with the same mass fraction as 4%;
(2) 8g of polyether copolyamide solution was added to 2g of Fe3O4@ Uio-66 to obtain a pre-mixed solution, ultrasonically treating for 1h, and adding 12g of polyether copolyamide solution into Fe3O4The @ Uio-66 dispersion liquid is subjected to ultrasonic treatment for 2 hours, and then vacuum defoaming is carried out to obtain casting solution;
(3) casting the casting solution on a glass plate, scraping the film by using a scraper, and then horizontally placing the glass plate in a blast drying box with a vertical magnetic field, wherein the vertical magnetic field is formed by two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm multiplied by 50mm multiplied by 20mm, the two permanent magnets are placed at the upper and lower positions, the south poles face upwards, the distance is 4cm, and the magnetic field intensity is 3000 Gs; drying at 80 deg.C for 10 hr, and vacuum drying at 60 deg.C for 4 hr.
The pervaporation hybrid membrane obtained in the embodiment can separate 8000ppm of aqueous solution containing phenol, and the permeation flux reaches 1400 g.m-2·h-1The separation factor is 75; for aqueous solution containing 8000ppm nitrophenol, the permeation flux reaches 1100 g.m-2·h-1The separation factor was 86.
Example 3
The preparation method of the permeable and vaporized hybrid membrane under the induction of the magnetic field of the embodiment comprises the following steps:
(1) 2g of Fe at room temperature3O4@ MIL-53 (Al) is ultrasonically dispersed in dimethylformamide to obtain 100g of dispersion liquid with the mass fraction of 2%, and then 2g of polyether copolyamide is dissolved in dimethylformamide to obtain 100g of solution with the mass fraction of 2%;
(2) 20g of the polyether copolyamide solution was added to 1g of Fe by mass3O4@ MIL-53 (Al) dispersion to obtain a premixed solution, ultrasonically treating for 0.5h, and adding 80g of polyether copolyamide solution into Fe3O4The preparation method comprises the following steps of (1) obtaining mixed liquor in @ MIL-53 (Al) dispersion liquid, carrying out ultrasonic treatment for 1h, and then carrying out vacuum defoaming to obtain a membrane casting liquid;
(3) casting the casting solution on a glass plate, scraping the film by using a scraper, and then horizontally placing the glass plate in a blast drying box with a vertical magnetic field, wherein the vertical magnetic field is formed by two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm multiplied by 50mm multiplied by 20mm, the two permanent magnets are placed at the upper and lower positions, the south poles face upwards, the distance is 4cm, and the magnetic field intensity is 3000 Gs; drying at 90 deg.C for 10h, and vacuum drying at 60 deg.C for 4h, and peeling off the film.
The pervaporation hybrid membrane obtained in this example was used to separate a mixture containing phenol 8000ppm aqueous solution, the permeation flux reaches 1100 g.m-2·h-1The separation factor is 68; for aqueous solution containing 8000ppm nitrophenol, the permeation flux reaches 900 g.m-2·h-1The separation factor was 75.
Example 4
The preparation method of the permeable and vaporized hybrid membrane under the induction of the magnetic field of the embodiment comprises the following steps:
(1) at room temperature, 5g of Fe3O4Ultrasonically dispersing the @ MIL-53 (Al) in dimethylformamide to obtain 5 mass percent of Fe3O4@ MIL-53 (Al) 100g, then, 5g of polyether copolyamide was dissolved in dimethylformamide to obtain 100g of polyether copolyamide solution with a mass fraction of 5%;
(2) 10g of the polyether copolyamide solution was added to 15g of Fe by mass3O4@ MIL-53 (Al) dispersion to obtain a premixed solution, ultrasonically treating for 0.5h, and adding 40g of polyether copolyamide solution into Fe3O4The preparation method comprises the following steps of (1) obtaining mixed liquor in @ MIL-53 (Al) dispersion liquid, carrying out ultrasonic treatment for 2 hours, and then carrying out vacuum defoaming to obtain membrane casting liquid;
(3) casting the casting solution on a glass plate, scraping the film by using a scraper, and then horizontally placing the glass plate in a blast drying box with a vertical magnetic field, wherein the vertical magnetic field is formed by two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm multiplied by 50mm multiplied by 20mm, the two permanent magnets are placed at the upper and lower positions, the south poles face upwards, the distance is 4cm, and the magnetic field intensity is 3000 Gs; drying at 100 deg.C for 10 hr, and vacuum drying at 60 deg.C for 4 hr.
The pervaporation hybrid membrane obtained in the embodiment separates an aqueous solution containing 8000ppm of phenol, and the permeation flux reaches 1800 g.m-2·h-1The separation factor is 81; 8000ppm of water solution containing nitrophenol, the permeation flux reaches 1650 g.m-2·h-1The separation factor is 92.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of a magnetic field induced infiltration gasification hybrid membrane for removing phenol/nitrophenol in water is characterized by comprising the following steps:
(1) ultrasonically dispersing a magnetic nano material in an organic solvent at room temperature to obtain a magnetic nano material dispersion liquid, and then preparing a polyether copolyamide solution with the same mass fraction as that of the magnetic nano material dispersion liquid by using the same organic solvent;
(2) adding a small amount of polyether copolyamide solution into the magnetic nano-material dispersion liquid to obtain a premixed solution, carrying out ultrasonic treatment for a period of time, adding all the rest of polyether copolyamide solution into the magnetic nano-material dispersion liquid to obtain a mixed solution, carrying out ultrasonic treatment for a period of time, and then carrying out vacuum defoaming to obtain a membrane casting solution;
(3) casting the casting solution on a glass plate, scraping the film by using a scraper, horizontally placing the glass plate in a blast drying box with a vertical magnetic field, drying for 10 hours at a certain temperature, vacuum-drying for 4 hours at 60 ℃, and then uncovering the film;
the pervaporation hybrid membrane has an asymmetric structure;
the magnetic nano material in the step (1) is Fe3O4@ Uio-66 or Fe3O4@ MIL-53 (Al); the organic solvent is dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide;
the concentration of phenol/nitrophenol in the water is between 100ppm and 10000 ppm.
2. The preparation method according to claim 1, wherein the mass fraction of the magnetic nanomaterial dispersion liquid in the step (1) is 2% to 5%.
3. The preparation method according to claim 1, wherein the mass ratio of the magnetic nanomaterial dispersion liquid to the polyether copolyamide solution in the step (2) is 1:100 to 30: 100.
4. The preparation method according to claim 1, wherein the ultrasonic treatment time of the premixed solution in the step (2) is 0.5 to 1 hour, and the ultrasonic treatment time of the mixed solution is 1 to 2 hours.
5. The preparation method according to claim 1, wherein the vertical magnetic field in step (3) is composed of two cuboid neodymium iron boron permanent magnets with the working temperature of 120 ℃ and the size of 100mm x 50mm x 20mm, the two permanent magnets are placed in an up-and-down position with south poles facing upwards and being 4cm away, and the magnetic field intensity is 2000 Gs-3800 Gs.
6. The preparation method according to claim 1, wherein the drying temperature of the forced air drying oven in the step (3) is lower than the upper working temperature limit of the neodymium-iron-boron permanent magnet.
7. The manufacturing method according to claim 6, wherein the drying temperature of the forced air drying oven in the step (3) is 80 ℃ to 100 ℃.
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| CN109316984A (en) * | 2018-10-26 | 2019-02-12 | 中国石油大学(华东) | A kind of gas separation membrane coating UiO-66- polyether block amide based on silver nano-grain/poly-dopamine |
| CN111266019A (en) * | 2020-01-23 | 2020-06-12 | 天津大学 | Preparation method and application of vertically-oriented magnetic nanosheet/sodium alginate composite membrane |
| US20220105470A1 (en) * | 2020-10-06 | 2022-04-07 | New Jersey Institute Of Technology | Electromagnetic Induction Pervaporation Membrane |
| CN114653209B (en) * | 2022-03-21 | 2023-04-25 | 东南大学 | Preparation method and application of magnetic conductive microfiltration membrane |
| CN114797472A (en) * | 2022-05-20 | 2022-07-29 | 北京赛诺膜技术有限公司 | Forward osmosis composite membrane prepared by magnetic field assisted thermally induced phase separation method and preparation method thereof |
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| JPH06262042A (en) * | 1993-03-11 | 1994-09-20 | Mitsubishi Kasei Eng Co | Apparatus for purification of liquid |
| CN103585899A (en) * | 2013-11-08 | 2014-02-19 | 江南大学 | Polyether copolyamide pervaporation membrane as well as preparation method and application thereof |
| CN104117292A (en) * | 2014-08-01 | 2014-10-29 | 天津工业大学 | Preparation method of polymer/inorganic nano-material composite ultrafiltration membrane |
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| JPH06262042A (en) * | 1993-03-11 | 1994-09-20 | Mitsubishi Kasei Eng Co | Apparatus for purification of liquid |
| CN103585899A (en) * | 2013-11-08 | 2014-02-19 | 江南大学 | Polyether copolyamide pervaporation membrane as well as preparation method and application thereof |
| CN104117292A (en) * | 2014-08-01 | 2014-10-29 | 天津工业大学 | Preparation method of polymer/inorganic nano-material composite ultrafiltration membrane |
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