CN109248570B - Preparation method of PAN/PAMS/ZnO oil-water separation membrane - Google Patents
Preparation method of PAN/PAMS/ZnO oil-water separation membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 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 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 148
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 108
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 99
- 239000011787 zinc oxide Substances 0.000 claims description 74
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 42
- 238000009987 spinning Methods 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- 239000011324 bead Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 18
- 238000010041 electrostatic spinning Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008117 stearic acid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- HCHKCACWOHOZIP-OUBTZVSYSA-N zinc-66 atom Chemical group [66Zn] HCHKCACWOHOZIP-OUBTZVSYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 15
- 230000003075 superhydrophobic effect Effects 0.000 description 13
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007799 cork Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HCHKCACWOHOZIP-RKEGKUSMSA-N zinc-72 Chemical group [72Zn] HCHKCACWOHOZIP-RKEGKUSMSA-N 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
-
- 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
-
- 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
- B01D69/12—Composite membranes; Ultra-thin 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
- B01D71/28—Polymers of vinyl aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/26—Spraying processes
-
- 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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- Physics & Mathematics (AREA)
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- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of oil-water separation materials, and provides a preparation method of a PAN/PAMS/ZnO oil-water separation membrane. The method comprises the steps of casting a PAMS solution containing a poor solvent on the surface of a PAN nanofiber membrane to enable the PAMS to be curled on the outer wall of a PAN fiber to form a bead-shaped structure, then depositing by adopting a ZnO dispersion liquid to further form a multilayer coarse structure, and obtaining the PAN/PAMS/ZnO oil-water separation membrane. Compared with the traditional method, the oil-water separation membrane prepared by the invention has the advantages of large water contact angle, high separation efficiency when being used for oil-water separation, no need of complex equipment, simple preparation process, low energy consumption, lower comprehensive cost and suitability for large-scale production.
Description
Technical Field
The invention belongs to the technical field of oil-water separation materials, and provides a preparation method of a PAN/PAMS/ZnO oil-water separation membrane.
Background
Oily sewage is widely available, such as petrochemical, oil extraction, transportation, mechanical processing, leather, textile, food, medicine, and the like. Every year, 500-1000 million tons of oil in the world flows into the ocean through various ways. Because the oily sewage has high Chemical Oxygen Demand (COD), large oil content and serious environmental pollution, the oily sewage is required to be effectively separated no matter environment treatment, oil recovery and water reuse, and the research and application of an oil-water separation technology and materials thereof become a hot topic.
Conventional methods for treating oily sewage generally include gravity separation, skimming, flotation, demulsification, flocculation, and the like. Some of the traditional treatment methods have low separation efficiency, and some of the traditional treatment methods add too much chemical agents to cause secondary pollution, and also have too high energy consumption and high cost. In recent years, the membrane separation technology is mainly used for separating stable emulsified oil, and has a wide application range. In the separation process, although the change of the material flow can affect the yield, the separation quality is not affected, no chemical agent or only a few chemical agents are added, and the oil is relatively easy to recover. The separation process is carried out at normal temperature without phase change, the device is small, the energy consumption is low, and the separation process can be highly automated, so the method is popular.
The oil-water separation membrane is divided into two types according to the hydrophobic degree of the membrane surface: conventional hydrophobic separation membranes, highly hydrophobic/super-oleophilic separation (i.e. super-hydrophobic separation membranes). The super-hydrophobic separation membrane is widely applied, except for the special condition of extremely low surface energy, most of hydrophobic surfaces in an oil-water system present super-oleophylic characteristics, and can effectively realize oil-water separation. The preparation method for the super-hydrophobic oil-water separation membrane at present mainly comprises the following steps: template technology, etching technology, layer-by-layer assembly technology, sol-gel method, electrostatic spinning method and the like, and the research of a novel preparation technology method is widely regarded.
Chinese patent application No. 201610232770.8 discloses a super-hydrophobic porous membrane for oil-water separation and a preparation method and application thereof. Firstly, grinding the surface of a clean low-density polyethylene sheet by using sand paper to obtain a super-hydrophobic low-density polyethylene sheet; and then fixing the polyethylene sheet, and performing arrayed punching on the polyethylene sheet by using a stainless steel needle to obtain the super-hydrophobic porous membrane for oil-water separation in a concentrated acid, concentrated alkali and high-salt environment. The contact angle of the super-hydrophobic surface to water is more than 150 degrees, the contact angle to oil is less than 10 degrees, and the pore size and the spacing in the porous array structure are all in the scale of hundred micrometers. The invention has the defects of complex preparation process and high cost.
The Chinese patent application number 201710565096.X discloses a preparation method and application of a super-hydrophobic and super-oleophylic oil-water separation cork filter membrane, which comprises the steps of drying raw materials, oxidizing the surface and modifying the surface, wherein the contact angle between the prepared cork filter membrane and water is more than 150 degrees, the contact angle between the prepared cork filter membrane and oil is 0 degree, the rolling angle of water is less than 10 degrees, the prepared cork filter membrane is used for separating oil-water mixtures, the cork raw materials are convenient to obtain and can be regenerated, and the prepared filter membrane has the advantage of high separation efficiency. Although the materials are convenient to obtain, the preparation process is complex, and the oil-water separation efficiency of the obtained filter membrane needs to be improved.
In summary, the method for preparing the oil-water separation membrane material with excellent hydrophobic property in the prior art usually needs complicated mechanical equipment, has complicated preparation process and high energy consumption, and leads to high comprehensive cost of the super-hydrophobic membrane, so that the development of the super-hydrophobic oil-water separation membrane with low cost and high efficiency has important significance.
Disclosure of Invention
Therefore, in the prior art, in order to prepare the oil-water separation membrane material with excellent hydrophobic property, complicated mechanical equipment is usually required, the preparation process is complicated, the energy consumption is high, and the comprehensive cost of the super-hydrophobic membrane is high. Aiming at the situation, the invention provides a preparation method of a PAN/PAMS/ZnO oil-water separation membrane, which can effectively reduce the preparation cost, and has good super-hydrophobic property and high oil-water separation efficiency.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of a PAN/PAMS/ZnO oil-water separation membrane comprises the following specific steps:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane;
(4) and (3) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane.
Preferably, in the spinning solution in the step (1), 4-8 parts by weight of polyacrylonitrile and 92-96 parts by weight of N, N-dimethylformamide are added.
Preferably, the spinning voltage of the electrostatic spinning in the step (1) is 10-15 kV, the receiving distance is 10-15 cm, and the aperture of the spinning hole is 300-500 nm.
Preferably, in the casting solution in the step (3), 10 to 20 parts by weight of poly-alpha-methylstyrene, 40 to 60 parts by weight of N, N-dimethylformamide, and 30 to 40 parts by weight of a poor solvent are used.
Preferably, the poor solvent in step (3) is one of distilled water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and sec-butanol.
Preferably, in the dispersion liquid in the step (4), 2-4 parts by weight of stearic acid, 20-30 parts by weight of zinc oxide and 66-78 parts by weight of tetrahydrofuran are added.
Preferably, the heating temperature in the step (4) is 70-80 ℃, and the time is 60-90 min.
Preferably, in the PAN/PAMS/ZnO oil-water separation membrane, 40-60 parts by weight of polyacrylonitrile, 30-40 parts by weight of poly-alpha-methylstyrene and 10-20 parts by weight of zinc oxide are used.
The invention makes PAMS curl on the outer wall of PAN fiber to form beads by casting PAMS solution containing poor solvent on the surface of PAN nanofiber membrane, and the main process and principle are as follows: when no poor solvent is added, the molecular chain of PAMS is in a stretched state in the solution; after adding the poor solvent, gradually curling the molecular chain of the PAMS to achieve new balance, and coating the molecular chain on the outer wall of the PAN fiber to form a random coil; with the addition of the poor solvent and the volatilization of the solvent, the phase separation degree of the solution is increased, the cluster shrinkage degree of the coil is tighter and bigger, and finally a bead-shaped structure is formed on the PAN fiber. The structure can endow the fiber membrane with a rough surface, so that the hydrophobic property is obviously improved.
Furthermore, ZnO dispersion liquid is coated on the surface of the PAN/PAMS composite membrane, ZnO is deposited on the surface of PAMS beads, the roughness of the surface of the membrane is further increased, and the obtained PAN/PAMS/ZnO composite membrane has stronger super-hydrophobic performance.
The invention provides a preparation method of a PAN/PAMS/ZnO oil-water separation membrane, which has the outstanding characteristics and excellent effects compared with the prior art:
1. the oil-water separation membrane prepared by the invention has a multilayer coarse structure, a large water contact angle and high separation efficiency when used for oil-water separation.
2. The preparation method provided by the invention does not need to adopt complex equipment, is simple in preparation process, low in energy consumption and low in comprehensive cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic structural diagram of a PAN/PAMS/ZnO oil-water separation membrane prepared by the method.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 13kV, the receiving distance is 13cm, and the aperture of a spinning hole is 380 nm; in the spinning solution, 5 parts by weight of polyacrylonitrile and 95 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is distilled water; in the casting solution, 12 parts by weight of poly-alpha-methylstyrene, 33 parts by weight of N, N-dimethylformamide and 33 parts by weight of poor solvent;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 74 ℃ and the time is 70 min; in the dispersion, 3 parts by weight of stearic acid, 24 parts by weight of zinc oxide and 73 parts by weight of tetrahydrofuran;
in the PAN/PAMS/ZnO oil-water separation membrane, 52 parts by weight of polyacrylonitrile, 34 parts by weight of poly-alpha-methyl styrene and 14 parts by weight of zinc oxide.
Example 2
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 11kV, the receiving distance is 11cm, and the aperture of a spinning hole is 450 nm; in the spinning solution, 5 parts by weight of polyacrylonitrile and 95 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is methanol; in the casting solution, 12 parts by weight of poly-alpha-methylstyrene, 56 parts by weight of N, N-dimethylformamide and 32 parts by weight of poor solvent are added;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 72 ℃ and the time is 80 min; in the dispersion, 2 parts by weight of stearic acid, 23 parts by weight of zinc oxide and 75 parts by weight of tetrahydrofuran;
in the PAN/PAMS/ZnO oil-water separation membrane, 56 parts by weight of polyacrylonitrile, 32 parts by weight of poly-alpha-methyl styrene and 12 parts by weight of zinc oxide are used.
Example 3
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 14kV, the receiving distance is 14cm, and the aperture of a spinning hole is 450 nm; in the spinning solution, 7 parts by weight of polyacrylonitrile and 93 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is ethanol; in the casting solution, 17 parts by weight of poly-alpha-methylstyrene, 46 parts by weight of N, N-dimethylformamide and 37 parts by weight of poor solvent are added;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 78 ℃ and the time is 70 min; 4 parts by weight of stearic acid, 26 parts by weight of zinc oxide and 70 parts by weight of tetrahydrofuran in the dispersion liquid;
in the PAN/PAMS/ZnO oil-water separation membrane, 44 parts by weight of polyacrylonitrile, 38 parts by weight of poly-alpha-methyl styrene and 18 parts by weight of zinc oxide.
Example 4
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 10kV, the receiving distance is 10cm, and the aperture of a spinning hole is 300 nm; in the spinning solution, 4 parts by weight of polyacrylonitrile and 96 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is n-propanol; 10 parts of poly alpha-methyl styrene, 60 parts of N, N-dimethyl formamide and 30 parts of poor solvent in the casting solution;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 70 ℃ and the time is 90 min; in the dispersion, 2 parts by weight of stearic acid, 20 parts by weight of zinc oxide and 78 parts by weight of tetrahydrofuran;
in the PAN/PAMS/ZnO oil-water separation membrane, 60 parts by weight of polyacrylonitrile, 30 parts by weight of poly-alpha-methyl styrene and 10 parts by weight of zinc oxide.
Example 5
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 15kV, the receiving distance is 15cm, and the aperture of a spinning hole is 500 nm; in the spinning solution, 8 parts by weight of polyacrylonitrile and 92 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is isopropanol; in the casting solution, 20 parts by weight of poly-alpha-methylstyrene, 40 parts by weight of N, N-dimethylformamide and 40 parts by weight of poor solvent are added;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 80 ℃ and the time is 60 min; 4 parts by weight of stearic acid, 30 parts by weight of zinc oxide and 66 parts by weight of tetrahydrofuran in the dispersion liquid;
in the PAN/PAMS/ZnO oil-water separation membrane, 40 parts by weight of polyacrylonitrile, 40 parts by weight of poly-alpha-methyl styrene and 20 parts by weight of zinc oxide.
Example 6
(1) Dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane; the spinning voltage of electrostatic spinning is 12kV, the receiving distance is 12cm, and the aperture of a spinning hole is 400 nm; in the spinning solution, 6 parts by weight of polyacrylonitrile and 94 parts by weight of N, N-dimethylformamide;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane; the poor solvent is n-butyl alcohol; in the casting solution, 15 parts by weight of poly-alpha-methylstyrene, 50 parts by weight of N, N-dimethylformamide and 35 parts by weight of poor solvent are added;
(4) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly-alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane, wherein the heating temperature is 75 ℃ and the time is 75 min; in the dispersion, 3 parts by weight of stearic acid, 25 parts by weight of zinc oxide and 72 parts by weight of tetrahydrofuran;
in the PAN/PAMS/ZnO oil-water separation membrane, 50 parts by weight of polyacrylonitrile, 35 parts by weight of poly-alpha-methyl styrene and 15 parts by weight of zinc oxide are adopted.
Comparative example 1
During the preparation, poly-alpha-methylstyrene was not used to form a beaded structure, and the other preparation conditions were the same as in example 6.
Comparative example 2
During the preparation, no zinc oxide was used for the deposition, and the other preparation conditions were the same as in example 6.
And (3) performance testing:
(1) contact angle: taking the oil-water separation membrane prepared by the invention in any shape, adopting OCA20 video optical contact angle measurement instrument surface hydrophobic performance test, carrying out the test at room temperature, wherein the size of the used water drop is 5 mu L, and respectively measuring and calculating the average value at more than 5 different positions;
(2) oil removal rate: the oil-water separation membrane prepared by the invention is assembled into an oil-water separator, diesel oil is used as simulation oil to be mixed with water to obtain an oil-water mixed liquid sample, n-hexane is used as an extracting agent to extract the diesel oil in the water, a UV1101 type ultraviolet spectrophotometer is used to detect the absorbance of an extraction liquid, the concentration of the diesel oil is obtained according to a standard curve of different concentrations of the diesel oil in the n-hexane corresponding to the absorbance, the oil content of the oil-water mixed liquid sample before and after passing through the oil-water separation membrane is respectively tested, and the oil removal rate is calculated when the initial oil content is 500mg/L and is separated by: eta = (C)0-Cn）/C0X 100% where C0To an initial oil content, CnThe oil content after the oil-water separation membrane is separated by n grades;
the data obtained are shown in Table 1.
Table 1:
Claims (8)
1. a preparation method of a PAN/PAMS/ZnO oil-water separation membrane is characterized by comprising the following specific steps:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide to prepare spinning solution, and then performing electrostatic spinning to prepare a polyacrylonitrile nanofiber membrane;
(2) flatly paving the polyacrylonitrile nano-fiber membrane prepared in the step (1) on a glass substrate for later use;
(3) dissolving poly-alpha-methyl styrene in N, N-dimethyl formamide, stirring to form a uniform solution, then dropwise adding a poor solvent, casting the solution on the surface of a polyacrylonitrile nanofiber membrane on a substrate, gradually splitting the phase of the solution, curling molecular chains of the poly-alpha-methyl styrene into random coils on the outer wall of the polyacrylonitrile fiber, gradually enlarging the random coils to form beads, and drying to form a membrane to prepare the PAN/PAMS composite membrane;
(4) and (3) performing surface treatment on zinc oxide by using stearic acid, adding the zinc oxide into tetrahydrofuran, stirring to obtain uniform dispersion liquid, coating the uniform dispersion liquid on the surface of the PAN/PAMS composite membrane prepared in the step (3), heating to remove the tetrahydrofuran, and simultaneously depositing the zinc oxide on the surface of poly alpha-methylstyrene beads to prepare the PAN/PAMS/ZnO oil-water separation membrane.
2. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: in the spinning solution in the step (1), 4-8 parts by weight of polyacrylonitrile and 92-96 parts by weight of N, N-dimethylformamide are added.
3. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: the electrostatic spinning in the step (1) has the spinning voltage of 10-15 kV, the receiving distance of 10-15 cm and the aperture of a spinning hole of 300-500 nm.
4. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: in the step (3), in the solution formed by the poly-alpha-methylstyrene, the N, N-dimethylformamide and the poor solvent, 10 to 20 parts by weight of the poly-alpha-methylstyrene, 40 to 60 parts by weight of the N, N-dimethylformamide and 30 to 40 parts by weight of the poor solvent are added.
5. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: the poor solvent in the step (3) is one of distilled water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and sec-butanol.
6. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: in the dispersion liquid in the step (4), 2-4 parts by weight of stearic acid, 20-30 parts by weight of zinc oxide and 66-78 parts by weight of tetrahydrofuran.
7. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: and (4) heating to remove tetrahydrofuran at the heating temperature of 70-80 ℃ for 60-90 min.
8. The method for preparing a PAN/PAMS/ZnO oil-water separation membrane according to claim 1, which is characterized in that: in the PAN/PAMS/ZnO oil-water separation membrane, 40-60 parts by weight of polyacrylonitrile, 30-40 parts by weight of poly-alpha-methylstyrene and 10-20 parts by weight of zinc oxide.
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