CN113754922A - Hydrophobic sponge loaded with carbon nanotubes, preparation method thereof and application thereof in oil-water separation - Google Patents
Hydrophobic sponge loaded with carbon nanotubes, preparation method thereof and application thereof in oil-water separation Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- 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
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention provides a hydrophobic sponge loaded with carbon nanotubes and a preparation method and application thereof, belonging to the technical field of oil-water separation. The invention firstly utilizes H2O2/H2SO4The mixed solution oxidizes the polyurethane sponge, so that the number of hydroxyl groups of the polyurethane sponge is increased, and modification is facilitated; the combination of the polyurethane sponge and the hydroxylated carbon nanotube is realized by utilizing the silane coupling agent, specifically, the hydroxyl of the polyurethane sponge and the hydroxyl of the hydroxylated carbon nanotube react with the silane coupling agent to obtain the hydrophobic sponge loaded with the carbon nanotube.On one hand, the carbon nano tube can increase the roughness of the surface of the polyurethane sponge and improve the hydrophobicity of the polyurethane sponge, thereby being beneficial to improving the oil-water separation efficiency; meanwhile, the carbon nano tube can also improve the oil absorption rate of the polyurethane sponge, so that the oil absorption efficiency is improved; in addition, the long-chain alkyl of the silane coupling agent is grafted to the polyurethane sponge, so that the hydrophobicity of the polyurethane sponge can be further improved, and the oil-water separation efficiency is further improved.
Description
Technical Field
The invention relates to the technical field of oil-water separation, in particular to a hydrophobic sponge loaded with carbon nanotubes, a preparation method thereof and application thereof in oil-water separation.
Background
With economic growth and development of the oil industry and marine transportation, marine oil spills present a serious environmental challenge. After the spilled oil is accumulated in the cultured fishes and shellfishes, the spilled oil can be eaten by human beings finally, and the spilled oil poses a great threat to the health of the human beings and the aquatic environment. Therefore, efficient oil-water separation is urgently needed.
Several conventional methods have been used to treat spilled oil, such as surface skimming, in situ combustion, dispersants and absorption. Since the absorption method is simple in operation and easy to separate, the absorption method is generally used for oil-water separation. Conventional absorbent materials, such as cellulose, activated carbon and zeolites, are mostly microporous materials. These materials have a low adsorption capacity, resulting in unsatisfactory oil-water separation efficiency. Therefore, researchers have tried to find an inexpensive and efficient oil-water separation material. The three-dimensional adsorption material has the characteristics of porosity and large specific surface area, and can adsorb oil stains on the surface of the material to realize oil-water separation. In addition, they are not only inexpensive, but also have a large absorption capacity. The polyurethane sponge is a three-dimensional porous material and has the excellent characteristics of low density, low price, excellent elasticity, high absorption rate and the like. However, since the sponge surface contains hydroxyl and carboxyl, which are usually hydrophilic, the sponge has an undesirable effect of absorbing hydrophobic oil, which is manifested by low oil absorption efficiency and oil-water separation efficiency.
Disclosure of Invention
The invention aims to provide a hydrophobic sponge loaded with carbon nanotubes, a preparation method thereof and application thereof in oil-water separation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hydrophobic sponge loaded with carbon nanotubes, which comprises the following steps:
impregnating polyurethane sponge into H2O2/H2SO4Carrying out oxidation reaction in the mixed solution to obtain polyurethane sponge rich in hydroxyl;
mixing a silane coupling agent, a hydroxylated carbon nanotube and a benzene solvent to obtain a modified liquid; the silane coupling agent is a C16-C26 silane coupling agent;
and (3) immersing the polyurethane sponge rich in hydroxyl into the modification liquid for coupling modification to obtain the hydrophobic sponge loaded with the carbon nano tube.
Preferably, said H2O2/H2SO4The mixed solution is prepared from H2O2Solution and H2SO4Mixing the solutions to obtain a mixture; said H2O2The mass fraction of the solution is 70 percent, and the content of the H is2SO4The mass fraction of the solution is 49%; said H2O2Solution and H2SO4The volume ratio of the solution was 7: 3.
Preferably, the time of the oxidation reaction is 4 h.
Preferably, the concentration of the silane coupling agent in the modifying liquid is 0.05 mol/L.
Preferably, the hydroxylated carbon nanotube has an inner diameter of 3-5 nm, an outer diameter of 8-15 nm and a length of 30-60 μm.
Preferably, the concentration of the hydroxylated carbon nanotube in the modification solution is 1 mg/mL.
Preferably, the coupling modification time is 6h or more.
Preferably, after the coupling modification, the method further comprises sequentially performing ultrasonic treatment and standing on the obtained modified system.
The invention provides the hydrophobic sponge loaded with the carbon nano tubes, which is prepared by the preparation method in the scheme, and comprises a polyurethane sponge and the carbon nano tubes loaded on the polyurethane sponge; the polyurethane sponge and the carbon nano tube are combined through a silane coupling agent.
The invention provides application of the carbon nanotube-loaded hydrophobic sponge in oil-water separation.
The invention provides a preparation method of a hydrophobic sponge loaded with carbon nanotubes, which comprises the following steps: impregnating polyurethane sponge into H2O2/H2SO4Carrying out oxidation reaction in the mixed solution to obtain polyurethane sponge rich in hydroxyl; mixing a silane coupling agent, a hydroxylated carbon nanotube and a benzene solvent to obtain a modified liquid; the silane coupling agent is a C16-C26 silane coupling agent; and (3) immersing the polyurethane sponge rich in hydroxyl into a modification solution for coupling modification to obtain the hydrophobic sponge loaded with the carbon nano tube.
The invention firstly utilizes H2O2/H2SO4The mixed solution oxidizes the polyurethane sponge, so that the number of hydroxyl groups of the polyurethane sponge is increased, and subsequent modification is facilitated; according to the invention, the combination of the polyurethane sponge and the hydroxylated carbon nanotube is realized by using the silane coupling agent, and specifically, the hydroxyl of the polyurethane sponge and the hydroxyl of the hydroxylated carbon nanotube react with the silane coupling agent to obtain the hydrophobic sponge loaded with the carbon nanotube. On one hand, the carbon nano tube can increase the roughness of the surface of the polyurethane sponge and improve the hydrophobicity of the polyurethane sponge, thereby being beneficial to improving the oil-water separation efficiency; on the other hand, the carbon nano tube can also improve the oil absorption rate of the polyurethane sponge, so that the oil absorption efficiency is improved; in addition, the long-chain alkyl of the silane coupling agent is grafted to the polyurethane sponge, so that the hydrophobicity of the polyurethane sponge can be further improved, and the oil-water separation efficiency is further improved.
Drawings
FIG. 1 is the contact angle of the hydroxyl-rich PU sponge of example 1 and the hydroxyl-rich PU sponge of comparative example 1 and the original PU sponge with water;
FIG. 2 is an infrared spectrum of the carbon nanotube-loaded hydrophobic sponge prepared in example 1;
FIG. 3 is the contact angle of the hydroxyl-rich PU sponge of example 1 and the carbon nanotube-loaded hydrophobic sponges prepared in examples 1-3 with water;
FIG. 4 is an SEM image of the hydroxyl-rich PU sponge of example 1 and the carbon nanotube-loaded hydrophobic sponges prepared in examples 1-3;
fig. 5 is a graph showing the hydrophobic properties of the carbon nanotube-loaded hydrophobic sponges prepared in examples 1 and 4 to 6.
Detailed Description
The invention provides a preparation method of a hydrophobic sponge loaded with carbon nanotubes, which comprises the following steps:
impregnating polyurethane sponge into H2O2/H2SO4Carrying out oxidation reaction in the mixed solution to obtain polyurethane sponge rich in hydroxyl;
mixing a coupling agent, a hydroxylated carbon nanotube and a benzene solvent to obtain a modified solution; the silane coupling agent is a C16-C26 silane coupling agent;
and (3) immersing the polyurethane sponge rich in hydroxyl into the modification liquid for coupling modification to obtain the hydrophobic sponge loaded with the carbon nano tube.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention impregnates the polyurethane sponge into H2O2/H2SO4And carrying out oxidation reaction in the mixed solution to obtain the polyurethane sponge rich in hydroxyl.
Before the oxidation reaction, the polyurethane sponge is preferably cleaned to remove dirt on the polyurethane sponge. In the present invention, the washing preferably includes: the polyurethane sponge is subjected to ultrasonic cleaning by using acetone, absolute ethyl alcohol and distilled water in sequence, and the cleaning time of each reagent is preferably 20 min.
After the cleaning is finished, the polyurethane sponge obtained by the invention is dried in vacuum and then is soaked in H2O2/H2SO4Carrying out oxidation reaction in the mixed solution; the temperature of the vacuum drying is preferably 80 ℃, and the time is preferably 24 hours.
In the present invention, said H2O2/H2SO4The mixed solution is preferably prepared from H2O2Solution and H2SO4Mixing the solutions to obtain a mixture; said H2O2The mass fraction of the solution is 70 percent, and the content of the H is2SO4Mass fraction of solutionIs 49 percent; said H2O2Solution and H2SO4The volume ratio of the solution was 7: 3. The invention adopts the mass fraction H2O2Solution and H2SO4Solution preparation H2O2/H2SO4The mixed solution has the best modification effect on the polyurethane sponge.
The invention is directed to the polyurethane sponges and H2O2/H2SO4The dosage of the mixed solution has no special requirement, and the polyurethane sponge can be completely immersed. In the present invention, the oxidation reaction is preferably performed at room temperature, and the time for the oxidation reaction is preferably 4 hours. In the oxidation reaction process, the surface of the polyurethane sponge is rich in a large amount of hydroxyl groups, so that subsequent modification is facilitated.
After the oxidation reaction is completed, the reacted polyurethane sponge is preferably washed by distilled water and then dried in vacuum at 80 ℃ for 24 hours to obtain the polyurethane sponge rich in hydroxyl groups.
According to the invention, a silane coupling agent, a hydroxylated carbon nanotube and a benzene solvent are mixed to obtain a modified solution.
In the present invention, the silane coupling agent is a C16-C26 silane coupling agent, preferably dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, hexadecyltrimethoxysilane or octadecyltrichlorosilane, more preferably octadecyltrichlorosilane.
In the invention, the hydroxylated carbon nanotube preferably has an inner diameter of 3 to 5nm, an outer diameter of 8 to 15nm and a length of 30 to 60 μm.
In the present invention, the benzene solvent is preferably toluene.
In the present invention, the mixing of the silane coupling agent, the hydroxylated carbon nanotube, and the benzene solvent preferably includes: adding a benzene solvent into a container, then adding a hydroxylated carbon nanotube, and performing ultrasonic dispersion for 20 min; adding a silane coupling agent into the obtained dispersion liquid, and dissolving the silane coupling agent to obtain a modified liquid.
In the present invention, the concentration of the silane coupling agent in the modification solution is preferably 0.05 mol/L.
In the present invention, the concentration of the hydroxylated carbon nanotube in the modification solution is preferably 1 mg/mL.
After the modification liquid is obtained, the polyurethane sponge rich in hydroxyl is immersed into the modification liquid for coupling modification, and the hydrophobic sponge loaded with the carbon nano tube is obtained.
In the invention, the coupling modification time is preferably 6 hours or more, more preferably 6 to 48 hours, further preferably 12 to 48 hours, and most preferably 24 hours. In the present invention, the coupling modification is preferably carried out at room temperature under stirring conditions; the rotation speed of the stirring is preferably 300 rpm. In the coupling modification reaction process, hydroxyl of the polyurethane sponge and hydroxyl of the hydroxylated carbon nano tube react with the silane coupling agent to load the carbon nano tube on the polyurethane sponge, and particularly, the sponge is combined with the silane coupling agent and the hydroxylated carbon nano tube through covalent bonds and hydrogen bonds.
After the coupling modification reaction is completed, the invention preferably carries out ultrasonic treatment and standing on the modified reaction system in sequence. In the present invention, the time of the ultrasonic treatment is preferably 20min, and the time of the standing is preferably 2 h. The invention has no special requirement on the power of the ultrasound, and the ultrasound power which is well known in the field can be adopted. The invention utilizes the ultrasound and the standing to fully disperse and load the carbon nano tube on the polyurethane sponge.
After standing, the polyurethane sponge is taken out for drying. In the present invention, the temperature of the drying is preferably 80 ℃, and the time of the drying is preferably 24 hours.
The invention provides the hydrophobic sponge loaded with the carbon nano tubes, which is prepared by the preparation method in the scheme, and comprises a polyurethane sponge and the carbon nano tubes loaded on the polyurethane sponge; in the present invention, the polyurethane sponge and the carbon nanotube are bonded to each other by a silane coupling agent.
The invention provides application of the carbon nanotube-loaded hydrophobic sponge in oil-water separation. The method for applying the invention has no special requirements, and the application method well known in the field can be adopted. The invention has no special requirement on the type of oil products in oil-water separation, and the oil products well known in the field can be used, and in the embodiment of the invention, the oil products are specifically chloroform, crude oil or kerosene. In the invention, the hydrophobic sponge loaded with the carbon nanotubes is suitable for removing floating oil on the water surface.
The hydrophobic sponge provided by the invention has no special requirement on the viscosity of oil, and is suitable for absorption and separation of oil with various viscosities. In an embodiment of the present invention, the oil has a viscosity of 1.671 to 11.78 mPas.
The carbon nanotube-loaded hydrophobic sponge, the preparation method thereof, and the application thereof in oil-water separation are described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The specifications of the hydroxylated carbon nanotubes used in the following examples are: an inner diameter of 3 to 5nm, an outer diameter of 8 to 15nm, and a length of 40 to 50 μm.
Example 1
Sequentially ultrasonic cleaning an original Polyurethane (PU) sponge with acetone, anhydrous ethanol and distilled water for 20min to remove dirt on bone, placing in a vacuum drying oven at 80 deg.C for 24 hr, and soaking the cleaned sponge in H2O2/H2SO4Mixed solution (70% H)2O2Solution with 49% H2SO4The volume ratio of the solution is 7: 3) carrying out oxidation reaction in the process, soaking for 4h, washing with distilled water, and drying the washed sponge in a vacuum drying furnace at 80 ℃ for 24h to obtain hydroxyl-rich PU sponge;
adding 50mL of toluene into a beaker, adding 50mg of hydroxylated carbon nanotubes (MWCNT) into the beaker, and performing ultrasonic treatment for 20min to disperse the carbon nanotubes to obtain a carbon nanotube dispersion solution; adding octadecyl trichlorosilane serving as a coupling agent into the carbon nano tube to prepare a modified liquid with the coupling agent concentration of 0.05 mol/L; immersing the PU sponge rich in hydroxyl into the modification liquid, magnetically stirring at 300rpm for coupling modification for 24h, then carrying out ultrasonic treatment for 20min, standing for 2h, taking out the sponge at 80 ℃, drying for 24h, obtaining the hydrophobic sponge loaded with the carbon nano tubes, and recording as: octadecyl trichlorosilane-CNTs/PU sponge.
Example 2
The difference from example 1 is that hexadecyltrimethoxysilane was used as the silane coupling agent, and the product obtained was noted as: hexadecyl trimethoxy silane-CNTs/PU sponge.
Example 3
The difference from example 1 is that dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride was used as coupling agent and the product obtained was reported as: dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride-CNTs/PU sponge.
Example 4
The difference from example 1 is that the coupling modification time is 6 h.
Example 5
The difference from example 1 is that the coupling modification time is 12 h.
Example 6
The difference from example 1 is that the coupling modification time is 48 h.
Comparative example 1
Hydroxyl-rich PU sponges were prepared according to the method of example 1, differing from example 1 only in that H was used2SO4The mass fraction of the solution was 33%.
Comparative example 2
The difference from example 1 is that H was used2SO4The mass fraction of the solution was 98%, with the result that the PU sponge was completely corroded.
And (3) structural and performance characterization:
1. the hydroxyl group-rich PU sponge of example 1 and the hydroxyl group-rich PU sponge of comparative example 1, as well as the original PU sponge, were subjected to water contact angle tests, and the results are shown in fig. 1. In FIG. 1, (a) example 1, (b) is comparative example 1, and (c) is the original PU sponge. As can be seen from FIG. 1, when the original PU sponge is treated with 49% by weight of sulfuric acid (i.e., example 1), the water contact angle is reduced, which indicates that more hydroxyl groups are obtained on the surface of the PU sponge, and is favorable for subsequent coupling modification. When the original PU sponge is treated by adopting the sulfuric acid with the mass fraction of 33% (namely the comparative example 1), compared with the original PU sponge, the water contact angle is increased, which shows that the number of hydroxyl groups is reduced, and the subsequent coupling modification is not facilitated.
2. Infrared spectroscopic characterization of the octadecyl trichlorosilane-CNTs/PU sponge prepared in example 1 was performed, and the results are shown in FIG. 2. As can be seen from FIG. 2, the FT-IR spectrum of the OTS-CNTs/PU sponge was 2923cm-1、2849cm-1、1470cm-1And 719cm-1The absorption peaks at (a) correspond to the tensile vibration and the bending vibration of the long-chain alkylmethylene group. Furthermore, 1112cm-1And 1057cm-1The absorption peaks at (A) are assigned to Si-O-Si and Si-O-C, respectively, indicating that the coupling agent has been coupled to the sponge.
3. The hydroxyl-rich PU sponge of example 1 and the carbon nanotube-loaded hydrophobic sponges prepared in examples 1 to 3 were subjected to hydrophobicity tests, and the results are shown in FIG. 3. In FIG. 3, (a) hydroxyl-rich PU sponge, (b) dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride-CNTs/PU sponge, (c) hexadecyltrimethoxysilane-CNTs/PU sponge, and (d) octadecyltrichlorosilane-CNTs/PU sponge.
As can be seen from FIG. 3, the hydrophobic sponges prepared by the method have different degrees of increase in hydrophobicity compared with hydroxyl-rich PU sponges, wherein the hydrophobic sponges prepared by using octadecyltrichlorosilane as a coupling agent have the best hydrophobicity, and the contact angle with water is 151.3 +/-1.2 degrees, which shows super-hydrophobicity. The higher the hydrophobicity, the higher the oil-water separation efficiency.
4. Scanning electron microscope observation is carried out on the hydroxyl-rich PU sponge in example 1 and the carbon nanotube-loaded hydrophobic sponges prepared in examples 1-3, and the results are shown in FIG. 4. In FIG. 4, (a) hydroxyl-rich PU sponge, (b) dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride-CNTs/PU sponge, (c) hexadecyltrimethoxysilane-CNTs/PU sponge, and (d) octadecyltrichlorosilane-CNTs/PU sponge.
As can be seen from fig. 4, compared with the PU sponge rich in hydroxyl groups, the hydrophobic sponge prepared by the present invention has increased surface roughness due to the carbon nanotubes loaded on the surface. Particularly, the surface roughness of the hydrophobic sponge obtained by using the octadecyl trichlorosilane as the coupling agent is increased most obviously, the hydrophobicity of the polyurethane sponge can be obviously improved, and the oil-water separation efficiency is further improved.
5. The results of the hydrophobicity tests performed on the hydrophobic sponges prepared in example 1 and examples 4-6 are shown in fig. 5, and the data corresponding to fig. 5 are shown in table 1.
As can be seen from fig. 5 and table 1, the coupling time 24h was selected because the hydrophobicity gradually increased with the increase of the coupling time using octadecyltrichlorosilane as the coupling agent, and the hydrophobicity was stronger but less changed when the coupling time was 24h and 48 h.
TABLE 1 hydrophobic Properties of the hydrophobic sponges prepared in example 1 and examples 4-6
| Coupling time | 6h | 12h | 24h | 48h |
| Water contact angle | 123.6° | 130.3° | 151.3° | 151.4° |
6. Chloroform, crude oil and kerosene were selected, and the influence of temperature on the oil absorption performance of the hydrophobic sponge prepared in example 1 was examined, specifically, chloroform, crude oil and kerosene were heated to corresponding temperatures, and then the hydrophobic sponge was immersed, and the results were measured as shown in table 2, and 20 ℃, 40 ℃, 60 ℃ andoil absorption of the sponge at 80 ℃ and a shear rate of 1s was measured-1The oil viscosity at different temperatures (see table 2).
TABLE 2 Effect of viscosity on oil-water separation of hydrophobic sponges
Note: chloroform boils at 80 deg.C, so there is no annual and absorption data.
From the results of Table 2, it is understood that the viscosity of various oils and organic solvents decreases with increasing temperature. For high viscosity oils, the reduction in viscosity makes the oil more readily absorbed by the sponge. For lower viscosity oils, the lower the viscosity, the less adhesion it will have to the sponge skeleton. However, the hydrophobic sponge of the present invention has a better absorption capacity for the oil with the viscosity, which indicates that the hydrophobic sponge of the present invention still has a higher oil absorption efficiency for the oil with the low viscosity.
7. The surface wettability of a hydrophobic sponge is affected by ionic strength, which in turn affects the oil absorption capacity. Adding electrolyte (such as NaCl and CaCl)2) The ionic strength can be varied. The hydrophobic sponge prepared in example 1 was soaked in NaCl or CaCl at 0.002mol/L, 0.004mol/L, 0.006mol/L and 0.008mol/L, respectively2After 24h in solution, the Water Contact Angle (WCA) was measured after drying. Subsequently, their absorption capacity for different oils was measured. The results are shown in Table 3.
TABLE 3 Effect of ionic strength on hydrophobic sponge hydrophobicity and oil absorption Capacity
As can be seen from table 3, the WCA of the hydrophobic sponge decreased with increasing ionic strength, indicating a decrease in hydrophobicity. In addition, the oil absorption of the sponge composite is also reduced. This is because the wettability of the sponge changes from superhydrophobic to hydrophobic, resulting in a decrease in the hydrophobic force between the sponge and the oil droplets.
ComparisonThe influence of the two salts on the sponge composite material is shown, and CaCl with the same concentration is found2The effect on the hydrophobicity and oil absorption properties of the hydrophobic sponge is greater than that of NaCl. The zeta potential of the hydrophobic sponge was-20.78 mV. Ca2+And Na+The surface of the sponge can be adsorbed on the surface of the sponge by electrostatic interaction, and they are easily combined with water molecules in the air through hydrogen bonds, resulting in a decrease in water contact angle, and the surface wettability changes from superhydrophobic to hydrophobic, which in turn affects the absorption efficiency. Ca2+Interaction with water molecules greater than Na+Interaction with water molecules. Therefore, when the hydrophobic sponge is used for oil-water separation, the soaking in saline wastewater is reduced as much as possible.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a hydrophobic sponge loaded with carbon nanotubes comprises the following steps:
impregnating polyurethane sponge into H2O2/H2SO4Carrying out oxidation reaction in the mixed solution to obtain polyurethane sponge rich in hydroxyl;
mixing a silane coupling agent, a hydroxylated carbon nanotube and a benzene solvent to obtain a modified liquid; the silane coupling agent is a C16-C26 silane coupling agent;
and (3) immersing the polyurethane sponge rich in hydroxyl into the modification liquid for coupling modification to obtain the hydrophobic sponge loaded with the carbon nano tube.
2. The method of claim 1, wherein the H is2O2/H2SO4The mixed solution is prepared from H2O2Solution and H2SO4Mixing the solutions to obtain a mixture; said H2O2The mass fraction of the solution is 70 percent, and the content of the H is2SO4The mass fraction of the solution is 49%; said H2O2Solution and H2SO4The volume ratio of the solution was 7: 3.
3. The method according to claim 1, wherein the oxidation reaction time is 4 hours.
4. The production method according to claim 1, wherein the concentration of the silane coupling agent in the modification liquid is 0.05 mol/L.
5. The method according to claim 1, wherein the hydroxylated carbon nanotube has an inner diameter of 3 to 5nm, an outer diameter of 8 to 15nm, and a length of 30 to 60 μm.
6. The method according to claim 1, wherein the concentration of the hydroxylated carbon nanotube in the modification solution is 1 mg/mL.
7. The method according to claim 1, wherein the coupling modification time is 6 hours or more.
8. The preparation method of claim 1, wherein after the coupling modification, the method further comprises sequentially performing ultrasonic treatment and standing on the obtained modified system.
9. The carbon nanotube-loaded hydrophobic sponge prepared by the preparation method of any one of claims 1 to 8, which comprises a polyurethane sponge and carbon nanotubes loaded on the polyurethane sponge; the polyurethane sponge and the carbon nano tube are combined through a silane coupling agent.
10. Use of the carbon nanotube-loaded hydrophobic sponge of claim 9 in oil-water separation.
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| Title |
|---|
| FEI QIANG: "Facile synthesis of super-hydrophobic, electrically conductive and mechanically flexible functionalized graphene nanoribbon/polyurethane sponge for efficient oil/water separation at static and dynamic states", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736347A (en) * | 2022-03-14 | 2022-07-12 | 中国神华煤制油化工有限公司 | Polyurethane sponge and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN113754922B (en) | 2022-07-26 |
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