CN107281941B - Magnetic graphene mixed matrix membrane and preparation method thereof - Google Patents
Magnetic graphene mixed matrix membrane and preparation method thereof Download PDFInfo
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- CN107281941B CN107281941B CN201710487144.8A CN201710487144A CN107281941B CN 107281941 B CN107281941 B CN 107281941B CN 201710487144 A CN201710487144 A CN 201710487144A CN 107281941 B CN107281941 B CN 107281941B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- 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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- 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
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/46—Magnetic properties
Abstract
The invention belongs to the technical field of membrane separation, and particularly relates to a magnetic graphene mixed matrix membrane and a preparation method thereof. The main characteristics are that: uniformly dispersing the prepared magnetic graphene into trichloromethane, adding microporous organic polymer powder, stirring uniformly, blade-coating the mixture on a polytetrafluoroethylene plate to form a film, and preparing a magnetic graphene mixed matrix film by a solvent volatilization method for separating oxygen and nitrogen. Compared with other magnetic films, the magnetic graphene in the magnetic film has the special two-dimensional lamellar structure of graphene and the magnetic performance of ferroferric oxide, is not easy to agglomerate in the magnetic film, has good dispersibility, has the characteristics of improving gas permeability and selectivity, and has important application prospect in the field of separating oxygen and nitrogen by the magnetic film.
Description
Technical Field
The invention belongs to the field of high and new technologies and preparation of gas separation membranes, and particularly relates to a magnetic graphene mixed matrix membrane and a preparation method thereof.
Background
The oxygen-enriched air is air with the integral number of oxygen more than 21%, has important functions of combustion supporting, breathing, industrial oxidation and the like of common air, and is widely applied to the fields of energy conservation, environmental protection, medical treatment, biological products and the like. The traditional preparation method of oxygen-enriched air mainly adopts a cryogenic separation method and a pressure swing adsorption method, and both have the defects of high energy consumption, complex equipment and the like. Compared with the method, the membrane technology has the advantages of compact structure, simple operation, high efficiency, energy conservation and the like, and is widely used for gas separation research. At present, commercial oxygen-enriched membranes have strong competitiveness in the field of preparation of low-concentration oxygen-enriched air (oxygen volume fraction is 28-40%), but are often uneconomical when high-concentration oxygen-enriched air with oxygen concentration exceeding 40% is prepared. Therefore, how to obtain the high-selectivity oxygen-enriched membrane by the design of the membrane physicochemical structure and the optimization of the membrane production process is always a research hotspot in the field of gas separation membrane preparation.
The magnetic oxygen-enriched film is a novel gas separation film which strengthens the oxygen-nitrogen separation process by means of the difference of the magnetization force of an external magnetic field on oxygen-nitrogen molecules. The magnetic oxygen-rich film is mainly composed of a mixed matrix film, a non-magnetic polymer and magnetic particles dispersed in the non-magnetic polymer. The non-magnetic polymer adopted at present is compact polymer of ethyl cellulose and poly (2, 6-dimethyl-1, 4-phenylate), and the magnetic particles are neodymium and Fe3O4、γ-Fe2O3Mainly comprises the following steps. The existing magnetic oxygen-enriched film has the problems that magnetic particles are easy to agglomerate in the film, the oxygen-nitrogen separation selectivity is low and the like, so that the application of a magnetic mixed matrix film in the field of oxygen-nitrogen separation is limited. Graphene is a typical two-dimensional sheet carbon material, has the advantages of simple synthesis, high specific surface area, excellent mechanical properties and thermal stability, surface functionalization and the like, and is widely applied to the fields of gas separation, ion separation, seawater desalination and the like. At present, researchers use graphene as a carrier, load a metal organic framework material ZIF-8 on the surface of a graphene sheet layer, and deposit the metal organic framework material ZIF-8 on Al2O3Support or adding into polymer to prepare gas separation membrane.
Disclosure of Invention
The invention aims to provide a magnetic graphene mixed matrix membrane and a preparation method thereof, so as to overcome the defects of the prior art.
The invention provides a preparation method of a magnetic graphene-based mixed matrix membrane, which is characterized by comprising the following steps of:
a, dissolving 1-5 parts of microporous organic polymer powder in 40-50 parts of a solvent, and magnetically stirring for 3-6 hours to form a uniform solution;
b, filtering the solution by using a 0.2-0.8 mu m needle filter, adding 0.0005-0.02 part of magnetic graphene powder, ultrasonically stirring for 6-12 hours, and then blade-coating a tetrafluoroethylene plate to form a film, wherein the thickness of the film is 80 mu m;
and C, drying the film at room temperature for 24 hours to remove part of the solvent, and drying the film in a vacuum drying oven to constant weight to obtain the magnetic graphene mixed matrix film product.
Preferably, the microporous organic polymer is one of poly-schiff base, polybenzothiazole, polybenzoxazole or polypyrrole.
Preferably, the molecular weight of the microporous organic polymer is 5-6 ten thousand.
Preferably, the solvent is any one or a mixture of several of N, N-dimethylformamide, chloroform and tetrahydrofuran.
Preferably, the magnetic graphene is ferroferric oxide nanoparticles loaded on the surface of a graphene sheet layer, the particle size of the ferroferric oxide is 30-50nm, and the loading amount is 85wt% -90 wt%.
The invention also provides a magnetic graphene mixed matrix film, which is characterized by comprising the following components in parts by weight: 1-5 parts of microporous organic polymer, 0.005-0.02 part of magnetic graphene and 40-50 parts of solvent.
Preferably, the microporous organic polymer is one of poly-schiff base, polybenzothiazole, polybenzoxazole or polypyrrole.
Preferably, the molecular weight of the microporous organic polymer is 5-6 ten thousand.
Preferably, the solvent is any one or a mixture of several of N, N-dimethylformamide, chloroform and tetrahydrofuran.
Preferably, the magnetic graphene is ferroferric oxide nanoparticles loaded on the surface of a graphene sheet layer, the particle size of the ferroferric oxide is 30-50nm, and the loading amount is 85wt% -90 wt%.
According to the magnetic graphene mixed matrix membrane provided by the invention, the polymer matrix is a microporous organic polymer, is connected by covalent bonds and takes micropores as main structural characteristics, so that the membrane has high gas permeation flux; the magnetic graphene dispersed inside has a special two-dimensional lamellar structure of graphene and the magnetic property of ferroferric oxide. In the separation process, ferroferric oxide on the surface of the graphene sheet layer generates an induction magnetic field under the action of an external magnetic field, and attracts oxygen molecules and repels nitrogen molecules, so that the selectivity of the magnetic graphene mixed matrix membrane to oxygen is obviously improved; meanwhile, a semi-cylindrical pore passage formed by a random fold structure of the magnetic graphene, pores among layers of the graphene sheets and nano micropores caused by the structural defects of the graphene provide additional channels for the transmission of gas separation, so that the permeability of gas molecules in the membrane is obviously improved; in addition, the addition of the magnetic graphene can also enlarge the molecular chain spacing of the polymer film, reduce the diffusion resistance of gas molecules in the magnetic mixed matrix film and improve the gas permeability.
In summary, the preparation method of the magnetic graphene mixed matrix film provided by the invention has the following advantages:
1. the magnetic graphene mixed matrix membrane is prepared by using a direct blending method, and the membrane preparation process is simple, convenient to operate and good in production repeatability;
2. the magnetic graphene formed by loading ferroferric oxide nanoparticles on the surface of the graphene sheet layer is used as a magnetic element, so that the magnetic graphene has the characteristics of small ferroferric oxide particle size, good dispersibility and difficult agglomeration, the defects of a magnetic mixed matrix film can be effectively reduced, and the selectivity of gas is improved;
3. the magnetic graphene mixed matrix membrane prepared by the method has good permeability to oxygen and high separation selectivity to oxygen/nitrogen due to the synergistic effect of the microporous structure and the magnetic elements of the membrane polymer matrix.
Detailed Description
The following are examples of magnetic graphene mixed matrix films and methods of making the same, but the examples do not limit the invention.
Example 1
A preparation method of a magnetic graphene mixed matrix membrane comprises the following steps:
(1) dissolving 1 part of poly-Schiff base with molecular weight of 5 ten thousand in 40 parts of N, N-dimethylformamide, and magnetically stirring for 3 hours to form a uniform solution; (2) filtering the solution by using a 0.2-micrometer needle filter, adding 0.005 part of magnetic graphene powder, wherein the particle size of ferroferric oxide is 30nm, the loading capacity is 85wt%, ultrasonically stirring for 6 hours, then blade-coating the solution on a tetrafluoroethylene plate to form a film, drying the film at the room temperature for 24 hours to remove part of the solvent, and drying the film in a vacuum drying oven to constant weight to obtain the magnetic graphene mixed matrix film product, wherein the thickness of the film is 80 micrometers (3).
The magnetic graphene-based mixed matrix membrane is applied to oxygen-nitrogen separation, oxygen permeates through the magnetic membrane preferentially, the separation factor is measured to be 2.90, and the oxygen permeation flux is measured to be 469 Barrer.
Example 2
The preparation method of the magnetic graphene mixed matrix film comprises the following steps of:
(1) dissolving 1 part of polybenzothiazole powder with the molecular weight of 6 ten thousand in 40 parts of trichloromethane, and magnetically stirring for 5 hours to form a uniform solution; (2) filtering the solution by using a 0.45-micrometer needle filter, adding 0.01 part of magnetic graphene powder, wherein the particle size of ferroferric oxide is 40nm, the loading capacity is 87wt%, ultrasonically stirring for 12 hours, then blade-coating the solution on a tetrafluoroethylene plate to form a film, drying the film at the room temperature for 24 hours to remove part of the solvent, and drying the film in a vacuum drying oven to constant weight to obtain the magnetic graphene mixed matrix film product, wherein the thickness of the film is 80 micrometers (3).
The magnetic graphene-based mixed matrix membrane is applied to oxygen-nitrogen separation, oxygen permeates the magnetic membrane preferentially, the separation factor is measured to be 2.73, and the oxygen permeation flux is measured to be 617 Barrer.
Example 3
The preparation method of the magnetic graphene mixed matrix film comprises the following steps of:
(1) dissolving 3 parts of polybenzoxazole powder with the molecular weight of 5.5 ten thousand in 50 parts of tetrahydrofuran, and magnetically stirring for 6 hours to form a uniform solution; (2) filtering the solution by using a 0.8-micron needle filter, adding 0.015 part of magnetic graphene powder, wherein the particle size of ferroferric oxide is 50nm, the loading capacity is 89wt%, ultrasonically stirring for 6 hours, then blade-coating the solution on a tetrafluoroethylene plate to form a film, drying the film at the room temperature for 24 hours to remove part of the solvent, and drying the film in a vacuum drying oven to constant weight to obtain the magnetic graphene mixed matrix film product, wherein the thickness of the film is 80 microns (3).
The magnetic graphene-based mixed matrix membrane is applied to oxygen-nitrogen separation, oxygen permeates the magnetic membrane preferentially, the separation factor is 7.07, and the oxygen permeation flux is 89 Barrer.
Example 4
The preparation method of the magnetic graphene mixed matrix film comprises the following steps of:
(1) dissolving 3 parts of polypyrrole powder with the molecular weight of 5 ten thousand in 50 parts of mixed solvent of trichloromethane and tetrahydrofuran, and magnetically stirring for 4 hours to form uniform solution; (2) filtering the solution by using a 0.4-micrometer needle filter, adding 0.02 part of magnetic graphene powder, wherein the particle size of ferroferric oxide is 40nm, the loading capacity is 90wt%, ultrasonically stirring for 12 hours, then blade-coating the solution on a tetrafluoroethylene plate to form a film, drying the film at the room temperature for 24 hours to remove part of the solvent, and drying the film in a vacuum drying oven to constant weight to obtain the magnetic graphene mixed matrix film product, wherein the thickness of the film is 80 micrometers (3).
The magnetic graphene mixed matrix membrane is applied to oxygen-nitrogen separation, oxygen permeates the magnetic membrane preferentially, the permeation flux is 361Barrer, and the separation factor of oxygen/nitrogen is 3.35.
Comparative example 1
The preparation method of the microporous polymer membrane comprises the following steps of:
(1) dissolving 5 parts of polybenzoxazole powder with the molecular weight of 5.5 ten thousand in 40 parts of trichloromethane, and magnetically stirring for 6 hours to form a uniform solution; (2) filtering the solution by using a 0.6 mu m needle filter, blade-coating the solution on a tetrafluoroethylene plate to form a film, drying the film at room temperature for 24 hours to remove part of the solvent with the film thickness of 80 mu m (3), and drying the film in a vacuum drying oven to constant weight to obtain a magnetic graphene mixed matrix film product.
One of the microporous polymer-based membranes described above was used for oxygen-nitrogen separation, with oxygen permeating preferentially through the magnetic membrane, and the separation factor was found to be 3.39, and the oxygen permeation flux was found to be 342 Barrer.
The above description of embodiments should be taken as illustrative, and it will be readily understood that many variations and combinations of the features set forth above may be made without departing from the spirit and scope of the invention as set forth in the claims, and that such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such variations are intended to be included within the scope of the following claims.
Claims (1)
1. A preparation method of a magnetic graphene mixed matrix film is characterized by comprising the following steps: the method comprises the following steps:
A. dissolving 1-5 parts of microporous organic polymer powder in 40-50 parts of solvent, and magnetically stirring for 3-6 hours to form a uniform solution;
B. filtering the solution by using a 0.2-0.8 mu m needle filter, adding 0.005-0.02 part of magnetic graphene powder, ultrasonically stirring for 6-12 hours, and then blade-coating a tetrafluoroethylene plate to form a film, wherein the thickness of the film is 80 mu m;
C. drying the film at room temperature for 24 hours to remove part of the solvent, and then drying the film in a vacuum drying oven to constant weight to obtain a magnetic graphene mixed matrix film product; the magnetic graphene mixed matrix membrane is applied to oxygen/nitrogen separation, and ferroferric oxide on the surface of a graphene sheet layer generates an induction magnetic field under the action of an external magnetic field in the separation process, so that oxygen molecules are attracted and nitrogen molecules are repelled, and the selectivity of the magnetic graphene mixed matrix membrane to oxygen is remarkably improved;
the microporous organic polymer is one of poly Schiff base, polybenzothiazole, polybenzoxazole or polypyrrole;
the solvent is any one or a mixture of more of N, N-dimethylformamide, trichloromethane and tetrahydrofuran;
the magnetic graphene is prepared by loading ferroferric oxide nanoparticles on the surface of a graphene sheet layer, wherein the particle size of the ferroferric oxide is 30-50nm, and the loading capacity is 85-90 wt%;
the molecular weight of the microporous organic polymer is 5-6 ten thousand.
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| CN112316754A (en) * | 2020-09-24 | 2021-02-05 | 宁波方太厨具有限公司 | Anti-pollution hollow fiber ultrafiltration membrane and preparation method thereof |
| CN113289506B (en) * | 2021-06-15 | 2023-02-28 | 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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| DE102006061292A1 (en) * | 2006-12-22 | 2008-06-26 | Evonik Degussa Gmbh | Superparamaggnetic ceramic gas isolating membrane for separating gas mixtures containing paramagnetic and diamagnetic gas has fixed superparamagnetic particles, minimum thickness of 1 mm and pore width of 50 to 100 mm |
| CN105396432A (en) * | 2015-10-30 | 2016-03-16 | 郑州大学 | Graphene oxide/Pebax hollow fiber membrane and preparation method thereof |
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| US9636631B1 (en) * | 2015-04-13 | 2017-05-02 | U.S. Department Of Energy | Mechanical membrane for the separation of a paramagnetic constituent from a fluid |
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| SG184918A1 (en) * | 2010-04-22 | 2012-11-29 | Univ Nanyang Tech | Method of preparing a nanocomposite membrane and nanocomposite membranes prepared thereof |
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| DE102006061292A1 (en) * | 2006-12-22 | 2008-06-26 | Evonik Degussa Gmbh | Superparamaggnetic ceramic gas isolating membrane for separating gas mixtures containing paramagnetic and diamagnetic gas has fixed superparamagnetic particles, minimum thickness of 1 mm and pore width of 50 to 100 mm |
| US9636631B1 (en) * | 2015-04-13 | 2017-05-02 | U.S. Department Of Energy | Mechanical membrane for the separation of a paramagnetic constituent from a fluid |
| CN105396432A (en) * | 2015-10-30 | 2016-03-16 | 郑州大学 | Graphene oxide/Pebax hollow fiber membrane and preparation method thereof |
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