CN111318181B - Durable underwater super-oleophobic composite membrane and preparation method and application thereof - Google Patents
Durable underwater super-oleophobic composite membrane and preparation method and application thereof Download PDFInfo
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- CN111318181B CN111318181B CN202010122750.1A CN202010122750A CN111318181B CN 111318181 B CN111318181 B CN 111318181B CN 202010122750 A CN202010122750 A CN 202010122750A CN 111318181 B CN111318181 B CN 111318181B
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention belongs to the technical field of preparation of environment functional materials, and particularly relates to a durable underwater super-oleophobic composite membrane and a preparation method and application thereof. According to the invention, polyvinylidene fluoride is used as a substrate material, and a surface graft polymerization method is utilized to enable the surface of the prepared composite membrane to contain a large number of covalent bonds, so that the stability and durability of the composite membrane are improved. The durable underwater super-oleophobic composite membrane provided by the invention has good chemical stability and durability, strong corrosion resistance, environmental friendliness and good recycling performance, is a low-price, high-efficiency and environment-friendly oil-water separation material, still has excellent characteristics of filtering and separating oil-containing emulsion in acid, alkali or salt environments, and has no remarkable reduction in flux and separation rate after repeated use. The prepared durable underwater super-oleophobic composite membrane is low in price, simple in membrane forming method, low in energy consumption and suitable for industrial application.
Description
Technical Field
The invention belongs to the technical field of preparation of environment functional materials, and particularly relates to a durable underwater super-oleophobic composite membrane and a preparation method and application thereof.
Background
With the rapid development of economy and the improvement of industrial level, a large amount of oily wastewater is generated in oil exploitation and transportation, chemical production, steel smelting, agriculture and the like. Oily wastewater has become a common pollution, and the large amount of discharge of the oily wastewater has great influence on environmental protection and ecological balance. Such as causing serious pollution to soil, water, atmosphere and the like, finally destroying the natural environment, influencing ecological balance and threatening human health. At present, the industrial method for separating oil-water mixture mainly uses the density difference of oil and water to carry out gravity separation, centrifugal separation, filtration and adsorption and the like, but the separation methods have relatively low efficiency and are easy to cause secondary pollution. While the common membrane material is widely used for oil-water separation, the common membrane material has poor selectivity, long time consumption and easy pollution, and the application of the common membrane material is limited by the pretreatment.
Due to low oil adhesion and high selectivity, the super-hydrophilic/underwater super-oleophobic membrane material is widely researched in oil-water separation. Research results show that the superhydrophilic membrane material indeed exhibits better stain resistance compared to conventional membrane materials. At present, a large number of ultra-wetting films construct a micro-nano structure by loading nano particles. For example, a polyvinylidene fluoride (PVDF) membrane modified by super-hydrophilic/underwater super-oleophobic HNTs has obvious emulsion separation efficiency and stain resistance, but in the long-term separation process, surface nanoparticles with weak adhesion are easy to fall off from the surface of the membrane, the recoverability is not high, secondary pollution is easy to cause, and the method is not suitable for oil-water emulsion separation in a complex environment. Therefore, the development of durable film materials is of great scientific interest.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a durable underwater super-oleophobic composite membrane and a preparation method and application thereof. The composite membrane provided by the invention enhances the durability of the membrane through surface cross-linking polymerization, and prolongs the service life of the membrane; the prepared membrane has super-hydrophilicity and underwater super-lipophobicity, can efficiently separate different oil-water emulsions, and has good reproducibility.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a durable underwater super-oleophobic composite membrane, which comprises the following steps:
(1) dissolving graphene oxide and polyvinylidene fluoride in N-methyl pyrrolidone, mechanically stirring, standing in a water bath to obtain a membrane casting solution, and scraping the membrane casting solution to obtain a hybrid membrane;
(2) dissolving KH-570 in a methanol solution, adding the hybrid membrane prepared in the step (1), magnetically stirring in a constant-temperature water bath, washing and drying the hybrid membrane;
(3) and (3) adding acrylic acid and ethylene glycol dimethacrylate into a methanol solution, adding the hybrid membrane dried in the step (2), adding azodiisobutyronitrile, carrying out water bath reaction under the protection of inert gas, cleaning, and drying to obtain the polyvinylidene fluoride underwater superoleophobic composite membrane.
The dosage ratio of the graphene oxide, the polyvinylidene fluoride and the N-methyl pyrrolidone in the step (1) is 0.2-0.4 g: 3g: 30 mL.
The temperature of the mechanical stirring in the step (1) is 40-60 ℃, and the time is 10-12 h; the standing temperature is 50-60 ℃, and the standing time is 10-12 hours.
In the step (2), the volume ratio of the KH-570 to the methanol solution is 1-2: 200 to 250 parts; the concentration of the methanol solution is 80%; the temperature of the water bath is 70-80 ℃, and the stirring time is 12-14 h.
In the step (3), the dosage ratio of the acrylic acid to the ethylene glycol dimethacrylate is 0.2-0.8 mL to 0.8 mL; the dosage ratio of the ethylene glycol dimethacrylate to the azobisisobutyronitrile is 0.8mL: 20-30 mg.
In the step (3), the water bath reaction temperature is 60-70 ℃, and the time is 10-12 h.
The invention also provides the durable underwater super-oleophobic composite membrane prepared by the preparation method, the composite membrane takes polyvinylidene fluoride as a substrate and is of a porous structure, imprinted polymer particles are embedded on the surface of the porous structure, and the composite membrane has super wettability.
The invention also provides application of the durable underwater super oleophobic composite membrane in the field of oil-water separation.
Further, the application of the invention is to separate an oil-water mixed system in an acid, alkali or salt environment.
The invention has the beneficial effects that:
the durable underwater super-oleophobic composite membrane provided by the invention has good chemical stability and durability, strong corrosion resistance, environmental friendliness and good recycling performance, is a low-price, high-efficiency and environment-friendly oil-water separation material, and has rapid and high-efficiency separation performance on toluene, petroleum ether, dichloroethane, n-hexane and the like. The preparation method provided by the invention uses polyvinylidene fluoride as a substrate material, and utilizes a surface graft polymerization method to enable the surface of the prepared composite membrane to contain a large number of covalent bonds, thereby increasing the stability and durability of the composite membrane. The oil-containing emulsion filtering and separating device has the advantages that the oil-containing emulsion filtering and separating device still has excellent oil-containing emulsion filtering and separating characteristics in acid, alkali or salt environments, and the flux and the separation rate are not remarkably reduced after the oil-containing emulsion filtering and separating device is repeatedly used. The durable underwater super-oleophobic composite membrane prepared by the composite membrane provided by the invention is low in price, simple in membrane forming method and low in energy consumption, and is suitable for industrial application.
Drawings
FIG. 1 is a scanning electron micrograph of a durable underwater superoleophobic composite membrane prepared in example 2; wherein, the picture a is a 2000-time scanning electron micrograph, and the picture a' is a 10000-time scanning electron micrograph;
FIG. 2 is a contact angle diagram of a durable underwater superoleophobic composite membrane made in example 2; wherein, the graph a is the contact angle of air and water, and the graph a' is the contact angle of underwater oil;
FIG. 3 is a graph of separation efficiency and flux for different organic solvents for the durable underwater superoleophobic composite membrane prepared in example 2;
FIG. 4 is a contact angle image of the durable underwater superoleophobic composite membrane prepared in example 2 in different solutions: wherein, panel a is in HCl, a ' is in NaOH, and a ' ' is in NaCl;
FIG. 5 is a graph of throughput and separation efficiency for separating petroleum ether/water emulsions in acidic, basic, and salt environments for durable underwater superoleophobic composite membranes prepared in example 2;
FIG. 6 is a graph of flux and separation efficiency for ten cycles of the durable underwater superoleophobic composite membrane prepared in example 2.
Detailed Description
The invention discloses a durable underwater super-oleophobic composite membrane and a preparation method and application thereof. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. The embodiments described below are only a part of the embodiments of the present invention, and not all of them. While the methods and products of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention. Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available.
Example 1:
(1) preparation of polyvinylidene fluoride/graphene oxide (PVDF/GO) hybrid membrane: dissolving 0.2g of Graphene Oxide (GO) and 3g of polyvinylidene fluoride (PVDF) powder in 30mL of N-methylpyrrolidone (NMP), mechanically stirring for 15h at 40 ℃, and standing in a water bath at 50 ℃ for 10h to obtain a casting solution; scraping the obtained casting solution on a glass plate, immersing the glass plate into deionized water for 12 hours to prepare a PVDF/GO hybrid membrane, and storing the prepared PVDF/GO hybrid membrane in the deionized water for later use;
(2) preparation of KH-570 modified PVDF/GO film (KH-570 @ PVDF/GO): dissolving 2mL of silane coupling agent KH-570 (gamma-methacryloxypropyl) in 400mL of methanol solution (with the concentration of 80%), adding the hybrid membrane prepared in the step (1), magnetically stirring in a constant-temperature water bath at 70 ℃ for 14h to obtain a KH-570@ PVDF/GO membrane, washing with ethanol and water, and airing for later use;
(3) adding 0.2mL of acrylic acid and 0.8mL of Ethylene Glycol Dimethacrylate (EGDMA) into 400mL of methanol solution, uniformly mixing, adding the KH-570@ PVDF/GO membrane prepared in the step 2, adding 30mg of Azobisisobutyronitrile (AIBN), reacting in a water bath at 60 ℃ under the nitrogen condition for 12 hours, washing with ethanol and water for multiple times, and airing to obtain the durable underwater super-oleophobic composite membrane.
Example 2:
(1) preparation of polyvinylidene fluoride/graphene oxide (PVDF/GO) hybrid membrane: dissolving 0.2g of GO and 3g of PVDF powder in 30mL of N-methylpyrrolidone (NMP), mechanically stirring for 12h at 50 ℃, standing for 12h in a water bath at 50 ℃, scraping the obtained casting solution on a glass plate, immersing the casting solution in deionized water for 12h to prepare a PVDF/GO hybrid membrane, and storing the prepared PVDF/GO hybrid membrane in the deionized water for later use;
(2) preparation of KH-570 modified PVDF/GO film (KH-570 @ PVDF/GO): dissolving 3mL of KH-570 in 500mL of methanol solution, adding the hybrid membrane prepared in the step (1), magnetically stirring in a water bath with constant temperature of 80 ℃ for 12h, taking out the KH-570@ PVDF/GO membrane, washing with ethanol and water, and then drying in the air;
(3) preparing an underwater super-oleophobic composite membrane: adding 0.4mL of acrylic acid and 0.8mL of Ethylene Glycol Dimethacrylate (EGDMA) into 500mL of methanol solution, uniformly mixing, adding the KH-570@ PVDF/GO membrane prepared in the step 2, adding 20mg of Azobisisobutyronitrile (AIBN), reacting in a water bath at 60 ℃ under the nitrogen condition for 12 hours, washing with ethanol and water for multiple times, and airing to obtain the durable underwater super-oleophobic composite membrane.
FIG. 1 is a scanning electron micrograph of a durable underwater superoleophobic composite membrane prepared in this example, wherein a is a 2000-fold scanning electron micrograph, and a' is a 10000-fold scanning electron micrograph; as can be seen from FIG. 1, the prepared durable underwater super-oleophobic composite membrane is in a porous structure, polymer particles can be clearly seen on the surface of the composite membrane, and the constructed composite membrane has super-wettability.
And (4) measuring and calculating the contact angle of the durable underwater super-oleophobic composite film prepared in the embodiment. FIG. 2 is a contact angle image of the durable underwater superoleophobic composite membrane prepared in the present example; wherein, the graph a is the contact angle of air and water, and the graph a' is the contact angle of underwater oil; as can be seen from FIG. 2, the water contact angle is about 0oUnderwater oil contact angle greater than 150oThe prepared composite membrane has super-hydrophilicity/underwater super-lipophobicity.
Toluene, petroleum ether, dichloroethane and n-hexane are respectively used as organic solvents for oil-water separation experiments, and the separation performance, the flux for separating petroleum ether/water emulsion and the separation efficiency of the prepared durable underwater super-oleophobic composite membrane are measured. FIG. 3 is a graph of separation efficiency and flux of the durable underwater superoleophobic composite membrane prepared according to the present example for different organic solvents; the dark bars represent separation efficiency and the light bars represent flux. As can be seen from figure 3, the separation performance of the composite membrane on different organic solvents is up to more than 99%, and the separation flux under the gravity condition is 133L m-2 h-1From the above, it is understood that the composite membrane has excellent separation performance for various oil-water emulsions.
Respectively at the same concentration (2 mol L)-1) The contact angles of the durable underwater super-oleophobic composite membrane prepared in the embodiment in acid, alkali and salt solutions are calculated by taking the HCl solution, the NaOH solution and the NaCl solution as examples, so that the underwater super-oleophobic performance of the composite membrane in a special environment is verified. FIG. 4 is a contact angle image of the durable underwater superoleophobic composite membrane prepared in this example in different solutions; where, panel a is the oil contact angle in HCl and a' is in NaOHOil contact angle, a' is the oil contact angle in NaCl; as can be seen from FIG. 4, the oil contact angles of the prepared durable underwater super-oleophobic composite membrane in HCl, NaOH or NaCl solutions are all larger than 150oIt can be known that the underwater super-oleophobic property of the composite membrane prepared in acid, alkali or salt environment is not damaged, and the composite membrane has good acid, alkali and salt resistance.
FIG. 5 is a graph of flux and separation efficiency for separating petroleum ether/water emulsion in acidic, basic and salt environments for a durable underwater superoleophobic composite membrane prepared in this example; as can be seen in FIG. 5, the separation performance in acidic, alkaline or salt environment is still as high as 97.2%, and the separation flux under gravity is 162L m-2 h-1Above, it was confirmed that the membrane has excellent separation performance in a complicated environment and has good durability.
FIG. 6 is a graph showing flux and separation efficiency of the durable polyvinylidene fluoride underwater superoleophobic composite membrane prepared in this example after 10 cycles; the dark plots represent separation efficiency and the light plots represent flux. As can be seen from fig. 6, the emulsion flux did not decrease significantly during 10 cycles, and the separation efficiency after 10 cycles still reached more than 98.5%, demonstrating good durability.
Example 3:
(1) preparation of polyvinylidene fluoride/graphene oxide (PVDF/GO) hybrid membrane: dissolving 0.4g of GO and 3g of PVDF powder in 30mL of NMP, mechanically stirring for 10h at 60 ℃, standing for 10h in a water bath at 60 ℃, scraping the obtained casting solution on a glass plate, immersing the glass plate in deionized water for 14h to prepare a PVDF/GO hybrid membrane, and storing the prepared PVDF/GO hybrid membrane in the deionized water for later use;
(2) preparation of KH-570 modified PVDF/GO film (KH-570 @ PVDF/GO): dissolving 4mL of KH-570 in 500mL of methanol solution, adding the hybrid membrane prepared in the step (1), magnetically stirring in a water bath with constant temperature of 80 ℃ for 12h, taking out the KH-570@ PVDF/GO membrane, washing with ethanol and water, and then drying in the air;
(3) preparing a durable underwater super-oleophobic composite membrane: adding 0.8mL of acrylic acid and 0.8mL of EGDMA into 500mL of methanol solution, uniformly mixing, adding the KH-570@ PVDF/GO membrane prepared in the step 2, adding 20mg of AIBN, reacting in a 70 ℃ water bath under argon conditions for 10h, washing with ethanol and water for multiple times, and airing to obtain the durable underwater super-oleophobic composite membrane.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. A preparation method of a durable underwater super-oleophobic composite membrane is characterized by comprising the following steps:
(1) dissolving graphene oxide and polyvinylidene fluoride in N-methyl pyrrolidone, mechanically stirring, standing in a water bath to obtain a membrane casting solution, and scraping the membrane casting solution to obtain a hybrid membrane;
(2) dissolving KH-570 in a methanol solution, adding the hybrid membrane prepared in the step (1), magnetically stirring in a constant-temperature water bath, washing the hybrid membrane, and drying in the air;
(3) adding acrylic acid and ethylene glycol dimethacrylate into a methanol solution, adding the hybrid membrane dried in the step (2), adding azodiisobutyronitrile, carrying out water bath reaction under the protection of inert gas, cleaning, and drying to obtain a polyvinylidene fluoride underwater superoleophobic composite membrane; the dosage ratio of the graphene oxide, the polyvinylidene fluoride and the N-methyl pyrrolidone in the step (1) is 0.2-0.4 g: 3g: 30 mL; in the step (3), the dosage ratio of the acrylic acid, the ethylene glycol dimethacrylate and the azobisisobutyronitrile is 0.2-0.8 mL: 20-30 mg.
2. The preparation method according to claim 1, wherein the temperature of the mechanical stirring in the step (1) is 40-60 ℃ and the time is 10-12 h; the standing temperature is 50-60 ℃, and the standing time is 10-12 hours.
3. The preparation method according to claim 1, wherein the volume ratio of the KH-570 to the methanol solution in the step (2) is 1-2: 200 to 250 parts; the concentration of the methanol solution was 80%.
4. The preparation method of claim 1, wherein the temperature of the water bath in the step (2) is 70-80 ℃, and the stirring time is 12-14 h.
5. The preparation method according to claim 1, wherein in the step (3), the water bath reaction temperature is 60-70 ℃ and the time is 10-12 h.
6. The durable underwater super-oleophobic composite membrane prepared by the preparation method of any one of claims 1-5, is characterized in that the composite membrane is a porous structure, and polymer particles are embedded in the surface of the structure.
7. Use of the durable underwater superoleophobic composite membrane of claim 6 for oil-water separation in an aqueous environment.
8. Use according to claim 7, for the separation of oil-water mixed systems in acid, alkaline, or salt environments.
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| CN112844339A (en) * | 2021-01-08 | 2021-05-28 | 北京科技大学 | Super-hydrophobic oil-water separation porous foam and preparation method thereof |
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