CN113856487A - Preparation method of super-hydrophilic/underwater super-oleophobic separation membrane - Google Patents
Preparation method of super-hydrophilic/underwater super-oleophobic separation membrane Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical group CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 7
- -1 methoxy, ethoxy Chemical group 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000012756 surface treatment agent Substances 0.000 claims 2
- 230000004907 flux Effects 0.000 abstract description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 229920001477 hydrophilic polymer Polymers 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical compound N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Images
Classifications
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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
- B01D69/12—Composite membranes; Ultra-thin 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane. The preparation method comprises the steps of firstly depositing a layer of rough titanium dioxide on a base membrane, then introducing a reaction functional group on the surface of the base membrane by using a surfactant, and finally grafting a hydrophilic polymer on the surface of the base membrane by using a solution polymerization method to obtain the super-hydrophilic/underwater super-oleophobic separation membrane. The super-hydrophilic/underwater super-oleophobic separation membrane can be applied to oil-water separation. The super-hydrophilic/underwater super-oleophobic separation membrane has the properties of super-hydrophilicity in air and super-oleophobic underwater, oil can be trapped on the membrane after the membrane is wetted by water, and the water rapidly passes through meshes, so that the flux is large and the efficiency is high.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials and oil-water separation, and particularly relates to a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane.
Background
In recent years, a large amount of oily wastewater is generated in the industrial fields of mining industry, textile industry, food industry, petrochemical industry, metal smelting and the like, and the frequent leakage of crude oil causes serious environmental pollution and damage to an ecosystem. In order to protect limited water resources and recover oil, efficient oil-water separation of oil-containing wastewater is required. The oil-water separation membrane with special wettability has the advantages of environmental friendliness, economy, high efficiency, simple preparation and the like, and is a scheme for solving the problems. The separation membrane in the oil-water separation material with special wettability can be divided into a super-hydrophilic membrane and a super-hydrophilic membrane according to the difference of surface wettability.
However, due to the chemical instability, poor mechanical properties, short service life, low flux and the like of organic materials such as polymer membranes and cotton fabrics, the long-term application of the organic materials to oil-water separation is difficult, and the problems of low mechanical strength, complex preparation process, high cost, low water flux and the like of membrane materials of the composite membrane for oil-water separation in the prior art exist, so that the development of an oil-water separation membrane with mechanical stability and high flux is required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane, and the membrane has the advantages of good mechanical stability, large water flux, high oil-water separation efficiency and the like.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
1. a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane comprises the following steps:
(1) sequentially ultrasonically cleaning the metal mesh for 20min by using acetone, ethanol and deionized water, and drying to obtain a first substrate mesh film;
(2) immersing the first substrate mesh membrane in a solution of ammonium fluotitanate and boric acid, reacting for 10 hours in a water bath, taking out, washing with deionized water, and drying in the air to obtain a second substrate mesh membrane;
(3) placing the second substrate net film into a muffle furnace for calcining to obtain a third substrate net film loaded with titanium dioxide;
(4) pretreating the third substrate net film by using a surface treating agent to obtain a fourth substrate net film;
(5) and immersing the fourth substrate net film into the prepolymerization solution, stirring in a water bath for reaction, taking out, washing with a large amount of ionic water, and drying in the air to obtain the super-hydrophilic/underwater super-oleophobic separation membrane.
Further, the metal mesh in the step (1) is one of a stainless steel mesh or a copper mesh.
Further, in the step (2), the molar concentration ratio of the ammonium fluotitanate to the boric acid is 1: 2-3, and the water bath temperature is set to be 30-40 ℃.
Further, in the step (3), the calcining condition in the muffle furnace is that the heating rate is 2 ℃/min, the terminal temperature is 400-500 ℃, and the heat preservation time is 2 h.
Furthermore, the structural formula of the surface treating agent used in the step (4) is Y (CH2) nSiX3, X can be one of methoxy, ethoxy and methoxyethoxy, Y can be one of vinyl, amino, epoxy and methacryloxy, and the concentration of the surface treating agent is 1-3 vol%.
Further, in the pre-polymerization solution in the step (5), the monomer is N-isopropylacrylamide, the initiator is one of potassium persulfate, ammonium persulfate and azobisisobutylamidine hydrochloride, the crosslinking agent is N, N-methylenebisacrylamide, and the solvent is water.
Further, in the prepolymerization solution in the step (5), the parts of the substances in the same mass unit are 50-100 parts of N-isopropylacrylamide, 1-2 parts of an initiator, 1-2 parts of a cross-linking agent and 1000 parts of water 700-one.
Further, the water bath stirring temperature in the step (5) is 55-65 ℃, and the time is 6-8 hours.
As a preferred scheme of the invention, the ultrasonic washing process in the step (1) is beneficial to the implementation of the subsequent steps; in the step (2), ammonium fluotitanate and boric acid solution are selected to react, and titanium dioxide is deposited on the surface of the metal net; in the step (3), the titanium dioxide is calcined and sintered in a muffle furnace, so that the bonding force between the titanium dioxide and the base film is enhanced, and a rough structure is formed on the surface of the metal mesh, so that the special wettability is constructed; in the step (4), the surface of the metal mesh is modified by adopting a surface treating agent, so that a functional group can be introduced to the surface of the base membrane, and the subsequent graft polymerization reaction is facilitated; soaking the net membrane obtained in the last step into a prepolymerization solution by adopting a solution polymerization method, and polymerizing for 6-8 hours to obtain the hydrophilic/underwater super-oleophobic separation membrane; the monomer concentration, initiator amount, reaction temperature and time all play a key role in the preparation of the final product.
The invention has the beneficial effects that: the super-hydrophilic/underwater super-oleophobic separation membrane prepared by the invention has special wettability: the contact angle of the water drop in the air is 0 degree, the contact angle of the oil drop under water is more than 150 degrees, and the oil drop under water has good oil resistance. Because the net film has opposite wettability to oil and water, when an oil-water mixture is wetted before water extraction, water can pass through the net film, and oil is retained above the net film and cannot pass through, so that effective oil-water separation is realized, extremely high separation efficiency is shown for various oil-water mixtures such as normal hexane, vegetable oil, isooctane, petroleum ether and the like, the separation efficiency is more than 99%, and the flux reaches over 200000Lm-2h < -1 >.
In addition, the preparation method provided by the invention has the advantages of cheap and easily-obtained raw materials, simple process, easy operation, no toxic and harmful substances and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a diagram of the preparation steps of a separation membrane in the preparation method of the super-hydrophilic/underwater super-oleophobic separation membrane of the invention;
FIG. 2 is a SEM image of the stainless steel net in step (1) in the first embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of the titania-loaded mesh film obtained in step (3) in the first example of the present invention;
FIG. 4 is a scanning electron microscope image of the super-hydrophilic/underwater super-oleophobic separation membrane prepared in step (5) in the first embodiment of the invention;
FIG. 5 shows the contact angles of the super-hydrophilic/underwater super-oleophobic separation membrane prepared in step (5) of the first embodiment of the present invention with respect to oil drops in air and various oil drops in water, and optical photographs;
FIG. 6 is a diagram of the separation process of the super-hydrophilic/underwater super-oleophobic separation membrane prepared in step (5) in the first embodiment of the invention after being wetted by water.
FIG. 7 is a schematic diagram of the oil-water separation efficiency and flux of the super-hydrophilic/underwater super-oleophobic separation membrane prepared in step (5) in the first embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: as shown in fig. 1-4, a method for preparing a super-hydrophilic/underwater super-oleophobic separation membrane comprises the following steps:
(1) sequentially ultrasonically cleaning a 300-mesh stainless steel net for 20min by using acetone, ethanol and deionized water, and then drying to obtain a first substrate net film;
(2) immersing the first base mesh membrane in an aqueous solution (40ml) of ammonium fluotitanate (0.9892g) and boric acid (0.617g), reacting for 10 hours at a constant temperature of 30 ℃ in a water bath kettle, taking out and washing with deionized water, and drying in the air to obtain a second base mesh membrane;
(3) and (3) putting the second substrate net film into a muffle furnace for heating and calcining, wherein the heating speed is 2 ℃/min, the terminal temperature is 400 ℃, and the heat preservation time is 2 h. Taking out the titanium dioxide loaded third substrate net film after the calcination is finished;
(4) soaking the third substrate net film in 20ml of ethanol water solution (V ethanol: V water: 9:1) of 3 vol% gamma-methacryloxypropyltrimethoxysilane (KH570), stirring for reaction for 30min, taking out, and drying in a constant-temperature oven at 80 ℃ for 2h to obtain a fourth substrate net film;
(5) immersing the fourth substrate net film into a prepolymerization solution (0.71 g of N-isopropyl acrylamide, 0.01g of potassium persulfate, 0.02g of N, N-methylene bisacrylamide and 7.2g of water), bubbling for 15min by introducing N2, stirring and reacting for 8h in a water bath at 80 ℃, taking out after the reaction is finished, washing by using a large amount of water to remove unreacted monomers, and drying to obtain the super-hydrophilic/underwater super-oleophobic separation membrane.
Example two: a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane comprises the following steps:
(1) sequentially ultrasonically cleaning a 300-mesh stainless steel net for 20min by using acetone, ethanol and deionized water, and then drying to obtain a first substrate net film;
(2) immersing the first substrate net film into an aqueous solution (40ml) of ammonium fluotitanate (0.988g) and boric acid (0.625g), reacting for 10 hours at a constant temperature of 30 ℃ in a water bath kettle, taking out and washing with deionized water, and drying in the air to obtain a second substrate net film;
(3) and (3) placing the second substrate net film into a muffle furnace for calcining, wherein the temperature rise speed is set to be 2 ℃/min, the terminal temperature is 400 ℃, and the heat preservation time is 2 h. Taking out the titanium dioxide loaded third substrate net film after the calcination is finished;
(4) soaking the third substrate net film in 20ml of ethanol water solution (V ethanol: V water: 9:1) of 3 vol% gamma-methacryloxypropyltrimethoxysilane (KH570), stirring for reaction for 30min, taking out, and drying in a constant-temperature oven at 80 ℃ for 2h to obtain a fourth substrate net film;
(5) immersing the fourth substrate net film into a prepolymerization solution (0.72 g of N-isopropyl acrylamide, 0.01g of ammonium persulfate, 0.15g of N, N-methylene bisacrylamide and 7.2g of water), bubbling for 15min by introducing N2, stirring and reacting for 8h in a water bath at 80 ℃, taking out after the reaction is finished, washing with a large amount of water to remove unreacted monomers, and drying to obtain the super-hydrophilic/underwater super-oleophobic separation membrane;
example three: a preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane comprises the following steps:
(1) sequentially ultrasonically cleaning a 200-mesh stainless steel net for 20min by using acetone, ethanol and deionized water, and drying to obtain a first substrate net film;
(2) immersing the first substrate net film into an aqueous solution (40ml) of ammonium fluotitanate (0.9895g) and boric acid (0.613g), reacting for 10 hours at a constant temperature of 30 ℃ in a water bath kettle, taking out and washing with deionized water, and drying in the air to obtain a second substrate net film;
(3) and (3) placing the second substrate net film into a muffle furnace for calcining, wherein the temperature rise speed is set to be 2 ℃/min, the terminal temperature is 400 ℃, and the heat preservation time is 2 h. Taking out the titanium dioxide loaded third substrate net film after the calcination is finished;
(4) soaking the third substrate net film in 20ml of ethanol water solution (V ethanol V water V9: 1) of 3 vol% gamma-methacryloxypropyltrimethoxysilane (KH570), stirring for reaction for 30min, taking out, and drying in a constant-temperature oven at 80 ℃ for 2h to obtain a fourth substrate net film;
(5) immersing the fourth substrate net film into a prepolymerization solution (0.8 g of N-isopropyl acrylamide, 0.012g of potassium ammonium persulfate, 0.18g of N, N-methylene bisacrylamide and 8g of water), bubbling for 15min through N2, stirring and reacting for 8h in a water bath at 80 ℃, taking out after the reaction is finished, washing with a large amount of water to remove unreacted monomers, and drying to obtain a super-hydrophilic/underwater super-oleophobic separation net film;
experimental example: as shown in fig. 5-7, oil-water separation test:
respectively selecting 10ml of n-hexane, vegetable oil, isooctane, petroleum ether and 10ml of water to mix to form an oil-water mixture. The superhydrophilic/underwater superoleophobic separation membrane prepared in example 1 was fixed between glass containers for oil-water separation, and the volumes of oil before and after separation were recorded, respectively.
The oil-water separation efficiency is calculated by the following formula:
separation efficiency n ═ Vt/Vo 100%
Where Vo is the volume of the initial oil before separation and Vt is the volume of the oil after separation.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Furthermore, the terms "first", "second", "third", "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, whereby the features defined as "first", "second", "third", "fourth" may explicitly or implicitly include at least one such feature.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a super-hydrophilic/underwater super-oleophobic separation membrane comprises the following steps:
(1) sequentially ultrasonically cleaning the metal mesh for 20min by using acetone, ethanol and deionized water, and drying to obtain a first substrate mesh film;
(2) immersing the first substrate mesh membrane in a solution of ammonium fluotitanate and boric acid, reacting for 10 hours in a water bath, taking out, washing with deionized water, and drying in the air to obtain a second substrate mesh membrane;
(3) placing the second substrate net film into a muffle furnace for calcining to obtain a third substrate net film loaded with titanium dioxide;
(4) pretreating the third substrate net film by using a surface treating agent to obtain a fourth substrate net film;
(5) and immersing the fourth substrate net film into the prepolymerization solution, stirring in a water bath for reaction, taking out, washing with a large amount of ionic water, and drying in the air to obtain the super-hydrophilic/underwater super-oleophobic separation membrane.
2. The method for preparing the super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, wherein the metal mesh in step (1) is one of a stainless steel mesh or a copper mesh.
3. The preparation method of the super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, characterized in that the molar concentration ratio of ammonium fluotitanate to boric acid in step (2) is 1: 2-3, and the water bath temperature is set to 30-40 ℃.
4. The preparation method of the super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, characterized in that in step (3), the calcination condition in a muffle furnace is that the temperature rise rate is 2 ℃/min, the terminal temperature is 400-500 ℃, and the holding time is 2 h.
5. The method for preparing the super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, characterized in that the structural formula of the surface treatment agent used in step (4) is Y (CH2) nSiX3, X can be one of methoxy, ethoxy and methoxyethoxy, Y can be one of vinyl, amino, epoxy and methacryloxy, and the concentration of the surface treatment agent is 1-3 vol%.
6. The method for preparing a super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, wherein in the pre-polymerization solution in step (5), the monomer is N-isopropylacrylamide, the initiator is one of potassium persulfate, ammonium persulfate and azobisisobutylamidine hydrochloride, the cross-linking agent is N, N-methylenebisacrylamide, and the solvent is water.
7. The method for preparing a super-hydrophilic/underwater super-oleophobic separation membrane according to claims 1 and 6, characterized in that in the pre-polymerization solution in step (5), the parts of each substance in terms of the same mass unit are 50-100 parts of N-isopropylacrylamide, 1-2 parts of initiator, 1-2 parts of cross-linking agent and 1000 parts of water 700-.
8. The preparation method of the super-hydrophilic/underwater super-oleophobic separation membrane according to claim 1, characterized in that in step (5), the water bath stirring temperature is 55-65 ℃ and the time is 6-8 h.
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| CN101760737A (en) * | 2009-12-29 | 2010-06-30 | 天津大学 | Method for preparing enhanced heat-transfer and scale prevention coating of micron/nanometer titanium dioxide on stainless steel substrate |
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| CN101760737A (en) * | 2009-12-29 | 2010-06-30 | 天津大学 | Method for preparing enhanced heat-transfer and scale prevention coating of micron/nanometer titanium dioxide on stainless steel substrate |
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