CN109012238B - Preparation method of high-strength high-flux oil-water separation membrane and oil-water separation membrane - Google Patents
Preparation method of high-strength high-flux oil-water separation membrane and oil-water separation membrane Download PDFInfo
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- CN109012238B CN109012238B CN201810917116.XA CN201810917116A CN109012238B CN 109012238 B CN109012238 B CN 109012238B CN 201810917116 A CN201810917116 A CN 201810917116A CN 109012238 B CN109012238 B CN 109012238B
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- 239000012528 membrane Substances 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000926 separation method Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920001690 polydopamine Polymers 0.000 claims abstract description 33
- 229920001721 polyimide Polymers 0.000 claims abstract description 31
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 28
- 239000002121 nanofiber Substances 0.000 claims abstract description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000004642 Polyimide Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 5
- 230000005686 electrostatic field Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims 1
- 230000004907 flux Effects 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 21
- 235000019476 oil-water mixture Nutrition 0.000 abstract description 8
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
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- 238000002474 experimental method Methods 0.000 description 3
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- 239000011521 glass Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BCRQVSRWRCLQRV-UHFFFAOYSA-N 1,2-dichloroethane;hydrate Chemical compound O.ClCCCl BCRQVSRWRCLQRV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000002791 soaking Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LLDLZZVYXXUTJN-UHFFFAOYSA-N bromobenzene hydrate Chemical compound O.Brc1ccccc1 LLDLZZVYXXUTJN-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013267 controlled drug release Methods 0.000 description 1
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 238000001612 separation test Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PRDUHXPVDHDGKN-UHFFFAOYSA-N tetrachloromethane;hydrate Chemical compound O.ClC(Cl)(Cl)Cl PRDUHXPVDHDGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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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
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- B01D71/60—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
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- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种高强度高通量的油水分离膜的制备方法及油水分离膜，其包括，聚酰胺酸合成；电纺聚酰胺酸膜的制备；聚酰胺酸膜的亚胺化；聚多巴胺‑聚酰亚胺膜的制备；聚多巴胺/聚四氟乙烯‑聚酰亚胺膜的制备。本发明制备的具有高灵活性高机械强度的超疏水超亲油纳米纤维膜，所得到的纤维膜同时具有聚亚酰胺的高机械强度和聚多巴胺复合聚四氟乙烯分散液的亲油疏水的特性。改性的纤维膜能够有效的分离各种油水混合物，分离流量高达6000L·m‑ 2h‑1，分离效率可达到99％以上。此外纤维膜可以在各种极端条件下依然保持较高的稳定性，制备纤维膜的方法简单，在油水分离领域将会有很好的应用前景。
The invention discloses a preparation method of a high-strength and high-flux oil-water separation membrane and an oil-water separation membrane, which include: polyamic acid synthesis; preparation of electrospun polyamic acid membrane; imidization of polyamic acid membrane; Preparation of dopamine-polyimide film; preparation of polydopamine/polytetrafluoroethylene-polyimide film. The super-hydrophobic and super-oleophilic nanofiber membrane with high flexibility and high mechanical strength prepared by the invention has both the high mechanical strength of polyimide and the lipophilic and hydrophobic properties of polydopamine composite polytetrafluoroethylene dispersion. characteristic. The modified fiber membrane can effectively separate various oil-water mixtures, the separation flow rate is as high as 6000L·m ‑ 2 h ‑1 , and the separation efficiency can reach over 99%. In addition, the fiber membrane can still maintain high stability under various extreme conditions, and the method for preparing the fiber membrane is simple, which will have a good application prospect in the field of oil-water separation.
Description
Technical Field
The invention belongs to the technical field of oil-water separation membrane preparation, and particularly relates to a preparation method of a high-strength high-flux oil-water separation membrane and the oil-water separation membrane.
Background
In recent years, there has been a rapidly increasing demand for materials capable of efficiently and rapidly separating oil-water mixtures and oil-water emulsions. The existing oil-water separation technologies can be classified into the following categories: such as suspended gravity, centrifugal sedimentation, biological treatment, and electrodeposition. However, these techniques have more or less disadvantages such as low separation efficiency, high separation cost, easy generation of secondary pollution problem, etc., which greatly limit their applications. Research in recent years shows that the oil-water separation material taking the membrane as the substrate is proved to have good application prospect when being used for oil-water separation.
Inspired by the phenomenon that lotus leaves show hydrophobicity, researchers found that these materials with specific wettability to water can be applied to selective separation of oil or water. When the water contact angle of the surface of the material is more than 150 degrees, the material is super-hydrophobic, and simultaneously, the oil contact angle is less than 10 degrees, so that the material is super-oleophilic; on the contrary, the materials with the specific wettability are the materials which we want to obtain and the research direction is that the water contact angle is less than 10 degrees and the oil contact angle is more than 150 degrees and the materials are super-hydrophilic and super-oleophobic. In addition, the scholars also find that when the material shows a dimension result of micron or nanometer, namely larger roughness, the material has a good effect of improving the affinity and the hydrophobicity of the material.
Electrospinning is an efficient method for producing fibrous membranes composed of fibers of micro-nanometer size. Electrospun fibers have been demonstrated to be widely used in the fields of controlled drug release, air filtration, wound management, and the like. The electrostatic spinning fiber membrane has the characteristics of high specific surface area, which is very needed in oil-water separation application, and in addition, the electrostatic spinning fiber has a porous structure. The electrospun fiber membrane is a very suitable material for oil-water separation based on the advantages described above. However, electrospun membranes generally have a disadvantage of poor mechanical properties.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a preparation method of a high-strength and high-flux oil-water separation membrane.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a high-strength high-flux oil-water separation membrane comprises the following steps,
and (3) synthesis of polyamic acid: reacting 2.5-3 g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 1-1.2 g of p-phenylenediamine and 30-50 mL of N, N-dimethylacetamide for 12-24 h at-6-0 ℃ in an inert gas atmosphere to obtain polyamic acid;
preparation of electrospun polyamic acid membrane: spinning in a high-voltage electrostatic field by using an N, N-dimethylacetamide solution of 1-5 mass% of polyamic acid to obtain an electrospun polyamic acid membrane;
imidization of polyamic acid film: heating the polyamic acid nanofiber membrane by stages to perform imidization to obtain a polyimide membrane;
preparation of polydopamine-polyimide film: ammonia water, water and ethanol are mixed according to the volume ratio of 0.1-1 mL: 50-80 mL: 20-50 mL of the mixture is mixed according to the mass-volume ratio of 1-2: adding 500 parts of dopamine hydrochloride, adding the dopamine hydrochloride into the polyimide film, soaking for 10-14 hours, taking out, and drying to obtain the polydopamine-polyimide film;
preparing a polydopamine/polytetrafluoroethylene-polyimide film: and immersing the polydopamine-polyimide film into polytetrafluoroethylene dispersion liquid, stirring and drying to obtain the polydopamine/polytetrafluoroethylene-polyimide film.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the synthesis of the polyamic acid comprises the steps of mixing 0.01mol of 3,3 ', 4, 4' biphenyl tetracarboxylic dianhydride, 0.01mol of p-phenylenediamine and 40mLN, N-dimethylacetamide, and reacting for 24 hours in an atmosphere of inert gas at-five ℃.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the inert gas comprises nitrogen.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the preparation method of the electrospun polyamic acid membrane comprises the steps of enabling the voltage of a high-voltage electrostatic field to be 30kV, enabling the receiving distance to be 10-15cm, enabling the rotating speed of a flywheel of a receiving device to be 2000-3000 r/min, and enabling the electrospinning speed to be 0.5-1.0 mL/h.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: in the imidization of the polyamic acid film, the temperature is raised in stages, wherein the temperature is raised in sequence at 150 ℃/1h, 200 ℃/1h, 250 ℃/1h, 300 ℃/1h, 350 ℃/3h and 380 ℃/30 min.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the preparation method of the polydopamine-polyimide film comprises the steps of adding 0.40mL of 28% ammonia water into 100mL of a water/ethanol mixture, then adding 0.2 g of dopamine hydrochloride into the mixture and stirring to obtain a polydopamine solution, soaking the polyimide film into the polydopamine solution, stirring for 12 hours, taking out the polyimide film, drying for 1 hour at room temperature, and putting the polyimide film into a vacuum oven at 60 ℃ for 30 minutes to obtain the polydopamine-polyimide film.
As a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the volume ratio of the water to the ethanol is 7: 3.
as a preferred scheme of the preparation method of the high-strength high-flux oil-water separation membrane, the preparation method comprises the following steps: the preparation method of the polydopamine/polytetrafluoroethylene-polyimide film comprises the steps of immersing the polydopamine-polyimide film into polytetrafluoroethylene dispersion liquid, stirring for 4 hours, and placing the polydopamine-polyimide film in a vacuum oven to dry at 60 ℃.
As another aspect of the invention, the invention overcomes the defects in the prior art and provides the high-strength and high-flux oil-water separation membrane prepared by the preparation method.
In order to solve the technical problems, the invention provides the following technical scheme: the high-strength high-flux oil-water separation membrane prepared by the preparation method comprises the following steps: the high-strength high-flux oil-water separation membraneThe flow rate reaches 6000 L.m- 2h-1And the separation efficiency reaches more than 99 percent.
The invention has the beneficial effects that: the super-hydrophobic super-oleophylic nanofiber membrane with high flexibility and high mechanical strength, prepared by the method, has the characteristics of high mechanical strength of polyimide and oleophylic and hydrophobic properties of polydopamine composite polytetrafluoroethylene dispersion liquid. The modified fiber membrane can effectively separate various oil-water mixtures, and the separation flow is up to 6000 L.m-2h-1The separation efficiency reaches more than 99 percent, and the compressive strength reaches more than 300 MPa. In addition, the fiber membrane can still keep high stability under various extreme conditions, the method for preparing the fiber membrane is simple, and the fiber membrane has good application prospect in the field of oil-water separation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a flow chart of an experiment according to the present invention.
FIG. 2 is an electron microscope image before and after the nanofiber membrane of the present invention is modified.
FIG. 3 is a wetting performance test of nanofiber membranes of the present invention.
FIG. 4 is a diagram of an oil-water separation experiment according to the present invention.
FIG. 5 is a graph of the separation flow rate (a) and separation efficiency (b) of different oils according to the present invention.
FIG. 6 shows the flow (a) and separation efficiency (b) of a 1, 2-dichloroethane-water system of the present invention after ten cycles.
Fig. 7 shows pH stability (a) and temperature stability (b) of nanofiber membranes of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
experimental materials:
p-phenylenediamine, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), N-Dimethylacetamide (DMAC), Dichloromethane (DCM), chloroform, carbon tetrachloride and other solvent solutions, cetyltrimethylammonium bromide (CTAB) and dopamine hydrochloride (PDA) and aqueous Polytetrafluoroethylene (PTFE) dispersion (60% solids content).
The preparation process of the oil-water separation membrane comprises the following steps:
and (3) synthesis of polyamic acid:
preparation of polyamic acid (PAA) by low temperature ring opening addition polymerization: BPDA (2.9422g, 0.01mol), p-phenylenediamine (1.0814 g, 0.01mol) and 40mLDMAc were simultaneously added to a three-neck flask, and the reaction was terminated after 24 hours of reaction at-five degrees Celsius under a nitrogen atmosphere, and the molecular weight distribution of polyamic acid was measured by gel permeation chromatography.
Electro-spinning PAA film and imidizing process:
spinning with 1-5% (wt) PAA DMAc solution in 30kV high voltage electrostatic field with receiving distance of 10-15cm, flywheel rotation speed of 2000-3000 rpm, spinning speed of 0.5-1.0mL/h, and device as shown in FIG. 1. And imidizing the electrospun PAA nanofiber membrane in a tubular furnace according to the programmed temperature rise method of 150 ℃/1h, 200 ℃/1h, 250 ℃/1h, 300 ℃/1h, 350 ℃/3h and 380 ℃/30min to obtain the PI membrane.
Preparation of PDA/PTFE-PI film:
first, 0.40mL of 28% ammonia was added to 100mL of a water/ethanol mixture (7: 3, V/V). 0.2 g dopamine hydrochloride was then added to the mixture and stirred to give a PDA solution. Before modifying the PI film, the PI film is washed by acetone and distilled water for three times respectively and then soaked into a PDA solution. After stirring for 12h, taking out the PI film, drying the PI film for one hour at room temperature, putting the PI film into a vacuum oven at 60 ℃ for 30 minutes to obtain a PDA-PI film, immersing the PDA-PI film into the PTFE dispersion liquid, stirring for 4h, and drying the PI film in the vacuum oven at 60 ℃ to finally obtain the PDA/PTFE-PI nanofiber film.
Example 2:
oil-water separation test:
(1) 10mL portions of methylene chloride and water were measured, wherein the methylene chloride was stained with oil red and the water was stained blue with methyl blue. Standing the oil-water mixed solution for 1min, and separating oil from water. Water dyed blue was on the top layer, red oil was on the bottom layer, and PDA/PTFE-PI nanofiber membrane was fixed between two glass tubes. Then pouring the layered mixed solution into the upper glass tube for oil-water separation. The red color quickly permeated through the PDA/PTFE-PI nanofiber membrane and flowed into the beaker below, while the blue water remained in the glass tube above and the time to complete separation of the oil from the water was recorded and the volume of water before and after separation was measured, as shown in figure 4.
(2) Different oil-water mixtures (dichloromethane-water, bromobenzene-water, carbon tetrachloride-water, trichloromethane-water and 1,2 dichloroethane-water according to 1) are respectively selected for oil-water separation experiments.
Measurement of separation efficiency:
the liquid flow rate is calculated according to the following formula:
where V is the volume of liquid filtered, A is the effective membrane area, and Δ t is the time required for the liquid to pass through the membrane. The separation efficiency was calculated by the following formula:
wherein, V0Volume of water before filtration, V1Is the volume of water filtered.
The experimental results are as follows:
characterization of the membrane:
the average fiber diameter was about 300 nm. After treatment with the PDA solution, the surface of the PI nanofiber is covered by a layer of PDA, and a coarse micro-nano level hierarchical structure is formed. After treatment with the polytetrafluoroethylene dispersion, the presence of PTFE nanoparticles was clearly seen.
Wetting Performance testing of PDA/PTFE-PI membranes
The contact angle of the oil and water of the PI film before and after modification is tested by using a contact angle experimental instrument, and fig. 2a shows that the contact angle of the PDA/PTFE-PI nanofiber film to water is about 151 °, which indicates that the surface of the PDA/PTFE-PI nanofiber film is superhydrophobic and can completely repel water, and meanwhile, the state can be stable for more than 30 minutes, which means that the superhydrophobic performance is relatively stable. Contact angle of the oil was measured underwater using 1, 2-Dichloroethane (DCE) and it can be seen that DCM penetrates completely into the membrane in less than 1s, the contact angle being 0 °, as shown in fig. 2b and 2 c.
Oil-water separation and determination:
as a result, as shown in FIG. 5, the maximum flow rate of the PDA/PTFE-PI nanofiber membrane was 6000 L.m-2h-1(FIG. 5a), which far exceeds the commercial use of filtration membranes (20-200 L.m) reported so far-2h-1). In addition, in fig. 5b, the membrane has excellent separation capability for various oil-water mixture systems, and the separation efficiency can reach more than 99%. The result shows that the prepared PDA/PTFE-PI nanofiber membrane can be used for treating oil-water mixtures in large batch and is suitable for industrial production.
Stability testing of the membranes:
in the practical application process of oil-water separation, the stability of the wettability of the fiber membrane is a very important parameter. Fig. 6 shows that the PDA/PTFE-PI nanofiber membranes showed little change in flow rate (fig. 6a) and separation efficiency (fig. 6b) for the DCM-water mixed system after 10 cycles. In addition, we also tested the temperature performance of the PDA/PTFE-PI nanofiber membranes in high temperature environments as well as harsh environments. Chemical stability is achieved by changing the pH of the environment, from 1 to 13 inclusive (fig. 7 a). And the membrane is placed at different temperatures of 20 ℃ to 140 ℃, the water contact angle of the fiber membrane is measured (figure 7b), and the results prove that the water contact angle of the fiber membrane can be stably maintained above 150 ℃ under two environments, and the fiber membrane can still be used for separating oil-water mixtures under extremely severe conditions.
The PDA/PTFE-PI nanofiber membrane is prepared by modifying a PI membrane by adopting PDA and PTFE, and the research of the inventor finds that the PDA, the PTFE and the PI membrane of the invention have synergistic effect, and if the PTFE is replaced by SiO2The oil-water separation effect and the mechanical property are obviously reduced, and the hydrophilic and hydrophobic properties are obviously reduced only by adopting the PTFE modified PI film.
The super-hydrophobic super-oleophylic nanofiber membrane with high flexibility and high mechanical strength, prepared by the method, has the characteristics of high mechanical strength of polyimide and oleophylic and hydrophobic properties of polydopamine composite polytetrafluoroethylene dispersion liquid. The modified fiber membrane can effectively separate various oil-water mixtures, and the separation flow is up to 6000 L.m-2h-1The separation efficiency can reach more than 99 percent, and the compressive strength reaches more than 300 MPa. In addition, the fiber membrane can still maintain higher stability under various extreme conditions, the method for preparing the fiber membrane is simple, and the fiber membrane has good application prospect in the field of oil-water separation.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
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