CN112409634A - Silanized boron nitride modified super-hydrophobic sponge for oil/water separation and preparation method thereof - Google Patents
Silanized boron nitride modified super-hydrophobic sponge for oil/water separation and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of oil-water separation, and particularly relates to a silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation and a preparation method thereof. And (3) dipping commercial melamine sponge in a suspending solution of octadecyl trimethoxy silane modified boron nitride, and drying to obtain the modified super-hydrophobic sponge. The silanized boron nitride modified super-hydrophobic sponge prepared by the method shows good super-hydrophobicity, the adsorption capacity to oil is 50-100 times that of commercial melamine sponge, and the absorption performance does not obviously decline after 20 continuous absorption cycles, which indicates that the silanized boron nitride modified sponge has obvious cyclability. The prepared modified super-hydrophobic sponge has excellent flame retardant property. Compared with the traditional method that the super-hydrophobic coating is physically attached to the sponge, the stability of the silanized boron nitride modified sponge is remarkably improved due to the covalent bonding of the alkyl silane and the surface of the skeleton.
Description
Technical Field
The invention belongs to the technical field of oil-water separation, and particularly relates to a silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation and a preparation method thereof.
Background
In recent years, oil spill at sea frequently occurs, and poses serious threats to marine environment and aquatic ecosystem. In addition, the development of the industries such as mining, food, textile, leather, metal processing, steel and automotive, etc., produces a large amount of oily wastewater, causing serious damage to the marine ecosystem and human health. Therefore, oil-water separation is a problem to be solved urgently in modern industrial pollution and marine environment. Traditional oil-water separation techniques include separation, filtration, centrifugation, flotation, electrochemical methods, and the like. Among the various oil removal methods developed at present, adsorption techniques have received much attention because of their characteristics of simplicity, high efficiency, relatively low cost, etc. Because oil-water separation is an interface problem, designing a functional material capable of efficiently realizing oil-water separation is an effective strategy. The three-dimensional porous commercial melamine sponge has the advantages of low cost, light weight, environmental friendliness, three-dimensional porous structure and the like, and has wide application prospect in large-scale oily sewage treatment. However, melamine sponges with hydrophilic and lipophilic properties tend to absorb both water and oil, which reduces the separation efficiency, making the sponge a secondary contaminant. Therefore, the premise for improving the separation efficiency of the sponge on oil-water mixture is to improve the selectivity of the sponge on oil and water, such as developing super-hydrophobic/lipophilic sponge.
The surface of the sponge is modified by coating the hydrophobic material on the surface of the sponge, so that the surface property of the sponge can be adjusted from hydrophilicity to superhydrophobicity, and the adsorption selectivity is greatly improved. At present, hydrophobic polymers, super-hydrophobic activated carbon, carbon nanotubes, graphene, and the like are mainly used to modify the surface properties of commercial sponges. However, the above-mentioned techniques have many problems, such as that the hydrophobic coating layer is easily separated from the sponge skeleton during the extrusion process due to weak adhesion between the coating layer and the skeleton. Therefore, the reproducibility of oil recovery by compression is still poor. For another example, because most of the grease is flammable, there may be a fire hazard and an explosion hazard when the sponge absorbs crude oil and organic solvents, and it is important that the sponge has flame retardant properties. In addition, most sponges with flexible segments are unstable in harsh environments, limiting their large-scale application.
Disclosure of Invention
The invention aims to provide a silanized boron nitride modified super-hydrophobic sponge for oil/water separation and a preparation method thereof, which are used for achieving certain improvement or improvements in super-hydrophobicity, flame retardance and chemical stability through modification of commercial melamine sponge.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a silanized boron nitride modified super-hydrophobic sponge for oil/water separation comprises the steps of dipping commercial melamine sponge in a suspension solution of octadecyl trimethoxy silane modified boron nitride at normal temperature, and drying to obtain the modified super-hydrophobic sponge.
The mass concentration of the suspension solution of the octadecyl trimethoxy silane modified boron nitride is 5-20wt%, and the dipping time is 20-40 min.
The drying is carried out at 60-90 ℃ for 1-5 hours.
Specifically, the unreacted boron nitride and silane on the surface of the sponge can be cleaned by acetone before drying after impregnation.
The commercial melamine sponge can also be replaced by other polymer matrix materials suitable for oil-water separation.
Preferably, the octadecyl trimethoxy silane modified boron nitride is obtained by the following method: performing silane coupling reaction on octadecyl trimethoxy siloxane and hydroxylated boron nitride in a mixture of solvent ethanol and water for 4-6h, preferably 5h at 80-100 ℃, centrifuging and drying after the reaction is finished to obtain the octadecyl trimethoxy silane modified boron nitride.
The mass ratio of the octadecyl trimethoxy siloxane to the hydroxylated boron nitride to the solvent is preferably 1-20:5-10: 100.
The solvent is a mixture of ethanol and water, and the ratio of the ethanol to the water is 19: 1-5.
The hydroxylated boron nitride is preferably obtained by: uniformly grinding a mixture of KOH (2.0600 parts), NaOH (2.7160 parts) and h-BN powder (1 part), transferring the mixture to a Polytetrafluoroethylene (PTFE) stainless steel autoclave and heating at 180 ℃ for 2 hours; taking out the mixture, cooling to room temperature, collecting a solid product, and repeatedly washing with ethanol and deionized water until the pH value of the filtrate is close to neutral; and finally, centrifuging the solution to obtain hydroxylated boron nitride powder.
The method comprises the steps of immersing commercial melamine sponge in a suspension solution of octadecyl trimethoxy silane modified boron nitride, introducing a silane modified boron nitride coating through the covalent bonding effect of the material and the surface of the sponge, and obtaining the silanization modified boron nitride sponge for high-efficiency oil/water separation.
The invention prepares the peeled hydroxylated boron nitride nanosheet by a melting method, and then prepares the silanized boron nitride nanosheet by a silane coupling reaction method. And finally, the melamine sponge is immersed in the silanized boron nitride solution to prepare the silanized modified super-hydrophobic sponge, the advantages of the two materials are ingeniously combined, the prepared sponge has excellent flame retardant property and compression resistance, the problem of interface compatibility of inorganic materials and polymers is solved through covalent bonding, and the sponge is selective to grease, organic solvents/water.
Compared with the prior art, the invention has the following advantages:
1) the silanized boron nitride modified super-hydrophobic sponge prepared by the method shows good super-hydrophobicity, the adsorption capacity to oil is 50-100 times that of commercial melamine sponge, and the absorption performance does not obviously decline after 20 continuous absorption cycles, which indicates that the silanized boron nitride modified sponge has obvious cyclability;
2) the prepared modified super-hydrophobic sponge has excellent flame retardant property;
3) compared with the traditional method that the super-hydrophobic coating is physically attached to the sponge, the stability of the silanized boron nitride modified sponge is remarkably improved due to the covalent bonding of the alkyl silane and the surface of the skeleton.
Drawings
FIG. 1 is a diagram of the adsorption process of n-hexane and chloroform in the silanized boron nitride modified super-hydrophobic sponge prepared in example 2;
FIG. 2 is a graph of the flame retardant properties of an original melamine sponge (corresponding to MS), a silanized boron nitride modified super-hydrophobic sponge (corresponding to Silane-grafted BN-MS) prepared in example 2, and a Silane modified melamine sponge (corresponding to Silane-MS) obtained in a control example;
fig. 3 is a stress-strain curve of the compressive test of the original melamine sponge, the silanized boron nitride modified super-hydrophobic sponge obtained in example 2, the silane modified melamine sponge obtained in the comparative example, and the modified super-hydrophobic sponge obtained in example 2 after being recycled for 500 times, wherein a bar chart is a stress value corresponding to the sponge when the strain is 55%.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
A silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation is prepared by the following specific steps:
1) preparing hydroxylated boron nitride: a mixture of KOH (2.0600g), NaOH (2.7160g) and h-BN powder (1g) was uniformly ground. After grinding, the mixture was further transferred to a Polytetrafluoroethylene (PTFE) stainless steel autoclave. Subsequently, the system was heated at 180 ℃ for 2 hours. The mixture was taken out and then cooled to room temperature. The solid product was collected and washed repeatedly with ethanol and deionized water until the pH of the filtrate was near neutral. Finally, centrifuging the solution to obtain hydroxylated boron nitride powder, and drying the hydroxylated boron nitride powder for use;
2) preparing silanized boron nitride: the silane coupling reaction was carried out at 90 ℃ in a mixture of octadecyl trimethoxy siloxane (0.5mL), hydroxylated boron nitride (0.05g), ethanol and water for 5 h. After the reaction is finished, obtaining silanized boron nitride powder through centrifugation, and drying the silanized boron nitride powder at 80 ℃ for use;
3) preparing a silanized boron nitride modified sponge: a commercial melamine sponge was immersed in a suspension solution containing 5 wt% of silanized modified boron nitride and reacted for half an hour. After the reaction is finished, the unreacted boron nitride and Silane on the surface of the sponge are cleaned by acetone solution and dried in an oven at 80 ℃ for 5 hours, and the prepared sponge is marked as Silane-BN @ 5%.
Example 2
A preparation method of a silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation comprises the steps 1) and 2) as in example 1.
Step 3) preparing a silanized boron nitride modified sponge, and immersing commercial melamine sponge into a suspension solution containing 10 wt% of silanized modified boron nitride, wherein the reaction time is half an hour. After the reaction is finished, the unreacted boron nitride and Silane on the surface of the sponge are cleaned by acetone solution and dried for 5 hours in an oven at 80 ℃, and the prepared sponge is marked as Silane-BN @ 10%.
Example 3
A preparation method of a silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation comprises the steps 1) and 2) as in example 1.
Step 3) preparing a silanized boron nitride modified sponge, and immersing commercial melamine sponge into a suspension solution containing 15 wt% of silanized modified boron nitride, wherein the reaction time is half an hour. After the reaction is finished, the unreacted boron nitride and Silane on the surface of the sponge are cleaned by acetone solution and dried for 5 hours in an oven at 80 ℃, and the prepared sponge is marked as Silane-BN @ 15%.
Example 4
A preparation method of a silanized boron nitride modified super-hydrophobic sponge for efficient oil/water separation comprises the steps 1) and 2) as in example 1.
Step 3) preparing a silanized boron nitride modified sponge, and immersing a commercial melamine sponge into a suspension solution containing 20wt% of silanized modified boron nitride, wherein the reaction time is half an hour. After the reaction is finished, the unreacted boron nitride and Silane on the surface of the sponge are cleaned by acetone solution and dried for 5 hours in an oven at 80 ℃, and the prepared sponge is marked as Silane-BN @ 20%.
Comparative example (Silane modified sponge (marked as Silane-BN @ 0%))
A process for the preparation of a silane-modified sponge for oil/water separation by immersing a commercial melamine sponge in a suspension containing 10% by weight of octadecyltrimethoxysiloxane for half an hour. After the reaction is finished, the unreacted Silane on the surface of the sponge is cleaned by acetone solution and dried for 5 hours in an oven at 80 ℃, and the prepared sponge is marked as Silane-BN @ 0%.
Table 1 lists the saturated adsorption capacities for n-hexane, chloroform, peanut oil and crude oil for the modified sponges obtained in examples 1-4 and the control, and each data was tested in 5 replicates with reasonable error.
TABLE 1
It can be seen from the table that after the octadecyl trimethoxy Silane modified boron nitride is introduced, the commercial sponge selectively adsorbs an organic solvent and grease, the oil-water separation performance is obviously improved, wherein the Silane-BN @ 10% sponge has the best performance, the adsorption capacity of the modified super-hydrophobic sponge is two times to four times that of the Silane modified sponge, and the separation efficiency of different organic solvents, grease and water is more than 99.9%.
Table 2 shows the adsorption performance data of the modified superhydrophobic sponge prepared in example 2 and part of the adsorbents reported in the literature.
TABLE 2
Claims (7)
1. A preparation method of a silanized boron nitride modified super-hydrophobic sponge for oil/water separation is characterized in that commercial melamine sponge is immersed in a suspension solution of octadecyl trimethoxy silane modified boron nitride at normal temperature, and then the modified super-hydrophobic sponge is obtained after drying.
2. The method for preparing the silanized boron nitride modified superhydrophobic sponge for oil/water separation according to claim 1, wherein the mass concentration of the suspension solution of the octadecyltrimethoxysilane modified boron nitride is 5-20wt%, and the dipping time is 20-40 min.
3. The method for preparing the silylated boron nitride-modified superhydrophobic sponge for oil/water separation of claim 2 wherein the octadecyltrimethoxysilane-modified boron nitride is obtained by: performing silane coupling reaction on octadecyl trimethoxy siloxane and hydroxylated boron nitride in a mixture of solvent ethanol and water for 4-6h at the temperature of 80-100 ℃, and centrifuging and drying after the reaction is finished to obtain the octadecyl trimethoxy silane modified boron nitride.
4. The method for preparing the silylated boron nitride-modified superhydrophobic sponge for oil/water separation according to claim 3 wherein the mass ratio of octadecyl trimethoxy siloxane, hydroxylated boron nitride and solvent is 1-20:5-10: 100.
5. The method for preparing the silylated boron nitride modified super-hydrophobic sponge for oil/water separation as claimed in claim 4 wherein the solvent is a mixture of ethanol and water in a ratio of 19: 1-5.
6. The method for preparing the silylated boron nitride modified superhydrophobic sponge for oil/water separation of claim 1 wherein the drying is carried out at 60-90 ℃ for 1-5 hours.
7. The silanized boron nitride modified superhydrophobic sponge for oil/water separation obtained by the preparation method of any one of claims 1-6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011250A (en) * | 2021-11-23 | 2022-02-08 | 合肥学院 | Dopamine modified boron nitride/carbon nanotube flexible composite membrane and preparation method and application thereof |
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| CN105999767A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of hexagonal boron nitride modified oil absorption sponge |
| CN107936776A (en) * | 2017-12-22 | 2018-04-20 | 江苏波迩德特种材料科技有限公司 | A kind of hexagonal boron nitride modified epoxy super-hydrophobic coating material and preparation method thereof |
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Patent Citations (4)
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| JPH08183906A (en) * | 1994-12-28 | 1996-07-16 | Shin Etsu Chem Co Ltd | Suspension of boron nitride |
| CN105999767A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of hexagonal boron nitride modified oil absorption sponge |
| CN107936776A (en) * | 2017-12-22 | 2018-04-20 | 江苏波迩德特种材料科技有限公司 | A kind of hexagonal boron nitride modified epoxy super-hydrophobic coating material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011250A (en) * | 2021-11-23 | 2022-02-08 | 合肥学院 | Dopamine modified boron nitride/carbon nanotube flexible composite membrane and preparation method and application thereof |
| CN114011250B (en) * | 2021-11-23 | 2023-08-15 | 合肥学院 | Dopamine modified boron nitride/carbon nanotube flexible composite membrane and preparation method and application thereof |
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Application publication date: 20210226 |