CN113150369A - Preparation method of graphene oxide modification-based oil absorption sponge - Google Patents
Preparation method of graphene oxide modification-based oil absorption sponge Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- 230000004048 modification Effects 0.000 title claims abstract description 21
- 238000012986 modification Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 46
- 239000004814 polyurethane Substances 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 18
- -1 graphene peroxide Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005055 methyl trichlorosilane Substances 0.000 claims abstract description 12
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 4
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- 230000007246 mechanism Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 11
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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
- C08J9/40—Impregnation
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention discloses a preparation method of an oil absorption sponge based on graphene oxide modification, which comprises the following steps: firstly, cleaning polyurethane sponge with ethanol, soaking in 0.1 wt% of graphene oxide solution, and drying for later use; uniformly mixing n-hexane serving as a solvent and 1.0 wt% of methyltrichlorosilane serving as a functional material to obtain a modified solution; soaking the polyurethane sponge soaked with the graphene peroxide solution into the modified solution for more than or equal to 1 min; and thirdly, fishing out the sponge soaked in the step II, and drying to prepare the modified oil absorption sponge. Compared with the prior art, according to the application, the methyl trichlorosilane is used as a functional material to be dissolved in n-hexane, and the polyurethane sponge loaded with the graphene oxide is soaked in the functional material to generate polysiloxane to cover the surface of the sponge, so that the hydrophobic oil absorption effect of the sponge is greatly improved.
Description
Technical Field
The invention relates to the field of oil absorption sponges, and particularly relates to a preparation method of an oil absorption sponge based on graphene oxide modification.
Background
With the increase of the use amount of petroleum and petroleum products, the marine ecological environment and the fresh water ecological environment are greatly damaged by leakage and various oil wastes generated in the processes of petroleum exploitation, processing, refining, storage, transportation and use of the petroleum products. Oil spill and oil stain in water not only reduce the quality of marine and fresh water environments, influence the circulation of food chains, destroy ecological balance, but also threaten human health. The damage caused by the oil spill at sea has the characteristics of large harm degree, wide spread range, difficult clearing and the like. The prior common sea surface floating oil treatment method is a physical treatment method, adopts an oil fence, a vortex type sea surface cleaner and the like, and has huge project scale and high cost. The chemical treatment method uses spraying dispersant, detergent and other surfactants to disperse the floating oil on the sea surface into very tiny particles, so that the particles are emulsified, dispersed, dissolved or settled on the sea bottom in the sea water, and other pollutants are introduced into the sea water.
The graphene has the characteristics of large specific surface area, excellent adsorption performance and the like, has oleophylic and hydrophobic performance after modification, is loaded on the sponge to obtain the graphene oil absorption sponge, can conveniently and quickly absorb oil floating on the sea surface, and greatly reduces the cost. How to efficiently prepare the oil absorption sponge material with better oil absorption effect is a key scientific research direction of numerous scientific researchers.
In view of the above, the applicant has made an intensive study on the above-mentioned defects in the prior art, and has made this invention.
Disclosure of Invention
The invention mainly aims to provide a preparation method of an oil absorption sponge based on graphene oxide modification, and the sponge material prepared by the preparation method has the characteristics of good oil absorption effect and good reusability.
In order to achieve the above purpose, the solution of the invention is:
a preparation method of an oil absorption sponge based on graphene oxide modification comprises the following steps:
firstly, cleaning polyurethane sponge with ethanol, soaking in 0.1 wt% of graphene oxide solution, and drying for later use;
uniformly mixing n-hexane serving as a solvent and 1.0 wt% of methyltrichlorosilane serving as a functional material to obtain a modified solution; soaking the polyurethane sponge soaked with the graphene peroxide solution into the modified solution for more than or equal to 1 min;
and thirdly, fishing out the sponge soaked in the step II, and drying to prepare the modified oil absorption sponge.
And step three, before the sponge is fished out, the sponge soaked in the modified solution is centrifuged, and redundant solution is not recovered for recycling.
Further, the step (i) also comprises the following steps:
1) slowly adding 100ml of concentrated sulfuric acid (95%), 1g of expandable graphite and 3g of potassium permanganate in sequence in an ice-water bath, and continuously stirring for 30 min;
2) heating to 35 deg.C, and stirring for 30 min; then, slowly adding deionized water dropwise until no bubbles are discharged, wherein the generation of purple smoke is observed;
3) heating the reaction system to 95 ℃, continuing stirring for 15min, adding 300ml of deionized water to stop the reaction, and adding 10ml of hydrogen peroxide (30%) into the obtained tan mixture to change the color into golden yellow; naturally cooling the golden yellow mixture, filtering and washing, firstly washing with 10% hydrochloric acid, finally washing with deionized water until the pH value is 7, and vacuum-drying the obtained red brown colloidal substance at 35 ℃ to obtain graphite oxide;
4) weighing a certain amount of graphite oxide, and ultrasonically stripping in deionized water with a certain volume to prepare a graphene oxide solution; during ultrasonic stripping, 30 percent (about 200W) of the maximum power of an ultrasonic cell crusher is adopted for ultrasonic treatment for 2 hours; and centrifuging the graphene oxide dispersion liquid obtained by ultrasonic treatment in a high-speed centrifuge at the rotating speed of 8000r/min for 10min, and taking the supernatant, namely the graphene oxide solution for later use.
Further, the third step also comprises the step of carrying out oil absorption multiplying power test on the prepared oil absorption sponge:
weighing the polyurethane sponge before and after the modification of the small blocks, recording the original weight as m1, respectively placing the polyurethane sponge into oily liquid to absorb oil for 2 minutes, taking out the polyurethane sponge, naturally dripping for 30 seconds after the polyurethane sponge is taken out until oil drops do not drip, placing the polyurethane sponge into a measuring cup to be weighed with balance, and recording the weight as m2, then obtaining the weight of the polyurethane sponge
k＝(m2-m1)/m1
Wherein k is the oil absorption (g/g) of the sample, m1 is the mass (g) of the polyurethane sponge before oil absorption, and m2 is the mass (g) of the polyurethane sponge after oil absorption; the oil absorption capacity of the polyurethane sponge before and after modification is compared, so that the effect of improving the oil absorption multiplying power before and after modification can be obtained through comparison.
Furthermore, the soaking time t in the step II is within the range that t is more than or equal to 1min and less than or equal to 15 min.
And step three, drying the polyurethane sponge by using an oven, wherein the drying temperature T is more than or equal to 50 ℃ and less than or equal to 300 ℃, and the drying time is 2-12 hours.
Further, the oven comprises a box body, the box body comprises an inner cavity for placing polyurethane sponge, an air inlet mechanism is arranged on the box body below the inner cavity, and an air outlet mechanism is arranged on the box body above the inner cavity; a left placing cavity and a right placing cavity are transversely arranged in the inner cavity of the box body, and heating devices are arranged in the left placing cavity and the right placing cavity; a first air channel is arranged between the left placing cavity and the right placing cavity, and a second air channel and a third air channel are respectively arranged on one sides of the left placing cavity and the right placing cavity, which are far away from the first air channel; a plurality of vent holes communicated with the placing cavity are formed in the first air channel, the second air channel and the third air channel respectively, and the lower ends of the first air channel, the second air channel and the third air channel are connected with the air inlet mechanism; the upper ends of the left placing cavity and the right placing cavity are respectively communicated with the air outlet mechanism; the left placing cavity and the right placing cavity are provided with a plurality of trays used for placing sponges from top to bottom at intervals.
Further, the air inlet mechanism comprises a first fan, a second fan and a third fan; the first fan, the second fan and the third fan correspond to the first air duct, the second air duct and the third air duct respectively; and a first partition plate and a second partition plate are respectively arranged between the air outlet of the first fan and the air outlets of the second fan and the third fan for separation.
Further, the air outlet mechanism comprises an air outlet draught fan, a first air outlet and a second air outlet are respectively arranged at the upper ends of the left placing cavity and the right placing cavity, a mixing cavity is arranged in the box body above the first air outlet and the second air outlet, the air outlet draught fan is located in the mixing cavity, a third air outlet is arranged at the top of the box body, and the air outlet draught fan is connected with the third air outlet; and the air flow in the left placing cavity and the right placing cavity passes through the first air outlet and the second air outlet and then is discharged through the third air outlet.
Further, the honeycomb duct is connected to third air outlet upper end, be provided with first contact tube and second contact tube on the honeycomb duct, first contact tube and second contact tube are connected with tail gas treatment equipment respectively.
After the structure is adopted, the preparation method of the graphene oxide modification-based oil absorption sponge has at least the following beneficial effects:
firstly, the surface of a sponge matrix soaked in the graphene peroxide solution has rich hydroxyl groups, and the methyltrichlorosilane is hydrolyzed in the solution to separate chlorine elements, so that a trihydroxy compound is generated. The hydroxyl compounds can mutually generate condensation polymerization reaction to form cross-linked polysiloxane, and meanwhile, the hydroxyl compounds can also generate condensation reaction with the hydroxyl on the surface of the substrate, so that the generated polysiloxane covers the surface of the sponge. The methyl trichlorosilane directly forms polysiloxane with a porous structure in the hydrolysis and polycondensation processes, so that the composite material simultaneously meets two necessary conditions for preparing a hydrophobic surface, namely a micro-nano structure and low surface energy.
Secondly, the sponge prepared by the method has a larger contact angle, the hydrophobicity of the sponge is greatly higher than that of the unmodified sponge, and the hydrophobicity of the sponge is still higher after oil absorption.
Compared with the prior art, according to the application, the methyl trichlorosilane is used as a functional material to be dissolved in n-hexane, and the polyurethane sponge loaded with the graphene oxide is soaked in the functional material to generate polysiloxane to cover the surface of the sponge, so that the hydrophobic oil absorption effect of the sponge is greatly improved.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of an oil absorption sponge based on graphene oxide modification.
FIG. 2 is a schematic view of the preparation process of the present invention.
FIG. 3 is a diagram showing the oil-water separation process of the modified sponge (a) and the original sponge (b).
FIG. 4 is a scanning electron micrograph of unmodified polyurethane sponges (a, b) and modified polyurethane sponges (c, d).
FIG. 5 is a graph showing the comparison of the oil absorption capacity of the sponge.
FIG. 6 is a graph comparing the hydrophobic properties of two sponges, 1 and 2 unmodified sponges and 3 and 4 modified sponges.
Fig. 7 is a graph of the effect of oil absorption capacity at different repetition times.
Fig. 7A is a schematic flow chart of preparing a graphene oxide solution.
Fig. 8 and 9 are schematic perspective views of different angles of the oven.
Fig. 10 is a schematic sectional structure view of the oven.
Fig. 11 is an enlarged schematic view of a portion a in fig. 10.
Fig. 12 is an enlarged schematic view of B in fig. 10.
In the figure:
a box body 1; a left placement chamber 11; a door body 111; a control box 112; a right placement chamber 12; a tray 13; a first air duct 141; a second air duct 142; a third air duct 143; a vent 144;
an air inlet mechanism 2; a first fan 21; a second fan 22; a third fan 23; a first partition 241; a second separator 242;
an air outlet mechanism 3; an air outlet draught fan 31; a mixing chamber 32; a first air outlet 331; the second air outlet 332; a third outlet 333; a draft tube 34; a first delivery tube 341; a second delivery line 342.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
As shown in fig. 1 to 12, the preparation method of the graphene oxide modified oil absorption sponge according to the present invention includes the following steps: firstly, cleaning polyurethane sponge with ethanol, soaking in 0.1 wt% of graphene oxide solution, and drying for later use; uniformly mixing n-hexane serving as a solvent and 1.0 wt% of methyltrichlorosilane serving as a functional material to obtain a modified solution; soaking the polyurethane sponge soaked with the graphene peroxide solution into the modified solution for t, wherein t is more than or equal to 1 min; preferably, the soaking time t in the step (II) is more than or equal to 1min and less than or equal to 15 min. And thirdly, fishing out the sponge soaked in the step II, and drying to prepare the modified oil absorption sponge.
Therefore, according to the preparation method of the graphene oxide modified oil absorption sponge, the surface of the sponge matrix soaked in the graphene peroxide solution has rich hydroxyl groups, and the methyl trichlorosilane is hydrolyzed in the solution to separate chlorine elements, so that a trihydroxy compound is generated. The hydroxyl compounds can mutually generate condensation polymerization reaction to form cross-linked polysiloxane, and simultaneously, the hydroxyl compounds can also generate condensation reaction with the hydroxyl on the surface of the substrate, so that the generated polysiloxane covers the surface of the sponge. The methyl trichlorosilane directly forms polysiloxane with a porous structure in the hydrolysis and polycondensation processes, so that the composite material simultaneously meets two necessary conditions for preparing hydrophobic surfaces, namely a micro-nano structure and low surface energy. The sponge prepared by the method has a larger contact angle, the hydrophobicity of the sponge is greatly higher than that of an unmodified sponge, and the hydrophobicity of the sponge is still higher after oil absorption.
As shown in (a) of FIG. 4, the polyurethane sponge has a three-dimensional network structure, which is rich in certain elasticity, and the reticular cavities can be filled with and absorb materials with other properties, so that the properties of the sponge are enhanced. FIG. 4(b) shows that the surface appearance of the unmodified polyurethane sponge is smooth and flat. FIGS. 4(c) and (d) are scanning electron micrographs of the modified polyurethane sponge at different magnifications, respectively. From fig. 4(c), it can be seen that the modified polyurethane sponge still presents a three-dimensional network structure, which provides a basis for subsequent sustainable utilization, and a layer of polysiloxane is uniformly coated on the surface of each branch of the sponge, so that the modified sponge has hydrophobic and oleophilic properties, and the oil-water selectivity of the modified sponge can be improved while the elasticity of the polyurethane sponge is maintained. FIGS. 3 to 8(d) are enlarged views of the modified polyurethane sponge, showing that the polysiloxane is distributed in a flaky form and uniformly spread on the surface of the polyurethane sponge.
As shown in fig. 6, the unmodified sponge (shown as 1 and 2 in fig. 6) had a contact angle of 108 ° before oil absorption and a contact angle of 96 ° after oil absorption. The contact angle of the modified sponge (shown as 3 and 4 in figure 6) before oil absorption is 154 degrees, and the contact angle after oil absorption is 145 degrees, so that the hydrophobic property of the modified polyurethane sponge adopting the graphene oxide nanosheets and the methyltrichlorosilane is greatly higher than that of the unmodified sponge, and the hydrophobic property of the modified polyurethane sponge is still higher after oil absorption.
Placing the sponge in a beaker mixed with oil and water, simulating the actual environment by magnetic stirring, placing the sponge in the beaker, taking out the sponge after 2min, and testing the oil absorption multiple of the sponge, wherein the specific result is shown in figure 5. The oil absorption multiple of the original sponge is about 8 times, the oil absorption multiple of the modified sponge is about 19 times, and the oil absorption multiple of the modified sponge is improved by one time compared with that of the original sponge.
The reusability of the oil-water separation material was investigated by testing the oil absorption capacity change of the modified sponge at different cycle times, and the specific results are shown in fig. 7. After the modified sponge is subjected to oil absorption test, the sponge is fully cleaned and deoiled through absolute ethyl alcohol and then recycled, and through 10 regeneration experiments, the oil absorption capacity of the modified sponge is kept about 19 times, which indicates that the repeated use capacity is better.
Preferably, before the sponge is fished out in the third step, the sponge soaked in the modified solution is centrifuged, and redundant solution is not recovered for recycling. Thus, the modified solution can be fully utilized, and the production cost of the modified polyurethane sponge is greatly reduced.
Preferably, the step (i) further comprises preparing a graphene oxide solution: 1) slowly adding 100ml of concentrated sulfuric acid (95%), 1g of expandable graphite and 3g of potassium permanganate in the ice-water bath in sequence, and continuously stirring for 30 min; 2) heating to 35 deg.C, and stirring for 30 min; immediately thereafter, deionized water was slowly added dropwise until no bubbles were released, during which the generation of purple smoke was observed; 3) heating the reaction system to 95 ℃, continuing stirring for 15min, adding 300ml of deionized water to stop the reaction, and adding 10ml of hydrogen peroxide (30%) into the obtained tan mixture to change the color into golden yellow; naturally cooling the golden yellow mixture, filtering and washing, firstly washing with 10% hydrochloric acid, finally washing with deionized water until the pH value is 7, and vacuum-drying the obtained red brown colloidal substance at 35 ℃ to obtain graphite oxide; 4) weighing a certain amount of graphite oxide, and ultrasonically stripping in deionized water with a certain volume to prepare a graphene oxide solution; during ultrasonic stripping, 30 percent (about 200W) of the maximum power of an ultrasonic cell crusher is adopted for ultrasonic treatment for 2 hours; and centrifuging the oxidized graphene dispersion liquid obtained by ultrasonic treatment in a high-speed centrifuge at the rotating speed of 8000r/min for 10min, and taking the supernatant, namely the oxidized graphene solution for later use.
Preferably, the step three further comprises the step of carrying out oil absorption multiplying power test on the prepared oil absorption sponge: weighing the polyurethane sponge before and after the modification of the small blocks, wherein the original weight is m1, respectively placing the small blocks in oily liquid to absorb oil for 2 minutes, naturally dripping for 30 seconds after taking out until oil drops do not drip, placing the small blocks in a measuring cup to be weighed by balance, and if the weight is m2, then k is (m2-m1)/m 1;
wherein k is the oil absorption (g/g) of the sample, m1 is the mass (g) of the polyurethane sponge before oil absorption, and m2 is the mass (g) of the polyurethane sponge after oil absorption; the oil absorption capacity of the polyurethane sponge before and after modification is compared, so that the effect of improving the oil absorption multiplying power before and after modification can be obtained through comparison.
Preferably, in the step III, the polyurethane sponge is dried by using an oven, the drying temperature T is more than or equal to 50 ℃ and less than or equal to 300 ℃, and the drying time is 2-12 hours. Further, the drying temperature T preferably ranges from: t is more than or equal to 80 ℃ and less than or equal to 150 ℃.
Furthermore, the oven comprises a box body 1, the box body 1 comprises an inner cavity for placing polyurethane sponge, an air inlet mechanism 2 is arranged on the box body 1 below the inner cavity, and an air outlet mechanism 3 is arranged on the box body 1 above the inner cavity; a left placing cavity 11 and a right placing cavity 12 are transversely arranged in the inner cavity of the box body 1, and heating devices (not shown in the figure) are arranged in the left placing cavity 11 and the right placing cavity 12; a first air duct 141 is arranged between the left placing cavity 11 and the right placing cavity 12, and a second air duct 142 and a third air duct 143 are respectively arranged on one sides of the left placing cavity 11 and the right placing cavity 12 far away from the first air duct 141; a plurality of vent holes 144 communicated with the placing cavity are formed on the first air duct 141, the second air duct 142 and the third air duct 143 respectively, and the lower ends of the first air duct 141, the second air duct 142 and the third air duct 143 are connected with the air inlet mechanism 2; the upper ends of the left placing cavity 11 and the right placing cavity 12 are respectively communicated with the air outlet mechanism 3; a plurality of trays 13 for placing sponges are arranged in the left placing cavity 11 and the right placing cavity 12 at intervals from top to bottom.
Thus, the air intake mechanism 2 delivers dry air to the placing cavity through the vents 144 of the first air duct 141, the second air duct 142 and the third air duct 143, and further dries the sponges in the left placing cavity 11 and the right placing cavity 12. The vent holes 144 are uniformly arranged from top to bottom, so that the sponge in the placing cavity can be uniformly dried. The front and the back of the left placing cavity 11 and the right placing cavity 12 are both provided with openable door bodies 111.
Preferably, a control box 112 is arranged at the upper part of the front side of the oven to control the drying temperature and the drying time.
Preferably, the air intake mechanism 2 comprises a first fan 21, a second fan 22 and a third fan 23; the first fan 21, the second fan 22 and the third fan 23 respectively correspond to the first air duct 141, the second air duct 142 and the third air duct 143; a first partition board 241 and a second partition board 242 are respectively arranged between the air outlet of the first fan 21 and the air outlets of the second fan 22 and the third fan 23 for partitioning. By the separation action of the first partition 241 and the second partition 242, the first fan 21, the second fan 22, and the third fan 23 can push air into the first air duct 141, the second air duct 142, and the third air duct 143, respectively. Furthermore, an air inlet of the air inlet mechanism 2 is connected with an air drying device (not shown in the figure).
Preferably, the air outlet mechanism 3 includes an air outlet induced draft fan 31, the upper ends of the left placing cavity 11 and the right placing cavity 12 are respectively provided with a first air outlet 331 and a second air outlet 332, a mixing cavity 32 is arranged in the box body 1 above the first air outlet 331 and the second air outlet 332, the air outlet induced draft fan 31 is located in the mixing cavity 32, the top of the box body 1 is provided with a third air outlet 333, and the air outlet induced draft fan 31 is connected with the third air outlet 333; the air flows in the left placing cavity 11 and the right placing cavity 12 pass through the first air outlet 331 and the second air outlet 332 and then are discharged through the third air outlet 333. The air dried by the sponge is discharged into the mixing cavity 32 through the first air outlet 331 and the second air outlet 332, and the air is discharged upwards to the third air outlet 333 by the air outlet induced draft fan 31. Furthermore, the upper end of the third air outlet 333 is connected to the draft tube 34, the draft tube 34 is provided with a first delivery tube 341 and a second delivery tube 342, and the first delivery tube 341 and the second delivery tube 342 are respectively connected to a tail gas treatment device (not shown in the figure). Therefore, the residual solvent in the air is collected, and the pollution to the atmosphere is reduced.
Compared with the prior art, according to the application, the methyl trichlorosilane is used as a functional material to be dissolved in n-hexane, and the polyurethane sponge loaded with the graphene oxide is soaked in the functional material to generate polysiloxane to cover the surface of the sponge, so that the hydrophobic oil absorption effect of the sponge is greatly improved.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. A preparation method of an oil absorption sponge based on graphene oxide modification is characterized by comprising the following steps:
firstly, cleaning polyurethane sponge with ethanol, soaking in 0.1 wt% of graphene oxide solution, and drying for later use;
uniformly mixing n-hexane serving as a solvent and 1.0 wt% of methyltrichlorosilane serving as a functional material to obtain a modified solution; soaking the polyurethane sponge soaked with the graphene peroxide solution into the modified solution for more than or equal to 1 min;
and thirdly, fishing out the sponge soaked in the step II, and drying to prepare the modified oil absorption sponge.
2. The method for preparing the graphene oxide modified oil absorption sponge according to claim 1, wherein the step (iii) of centrifuging the sponge soaked in the modifying solution without recycling excess solution before fishing out the sponge is performed.
3. The preparation method of the graphene oxide modified oil absorption sponge as claimed in claim 1, wherein the step (r) further comprises the following steps:
1) slowly adding 100ml of concentrated sulfuric acid (95%), 1g of expandable graphite and 3g of potassium permanganate in sequence in an ice water bath, and continuously stirring for 30 min;
2) heating to 35 deg.C, and stirring for 30 min; then, slowly adding deionized water dropwise until no bubbles are discharged, wherein the generation of purple smoke is observed;
3) heating the reaction system to 95 ℃, continuing stirring for 15min, adding 300ml of deionized water to stop the reaction, and adding 10ml of hydrogen peroxide (30%) into the obtained tan mixture to change the color into golden yellow; naturally cooling the golden yellow mixture, filtering and washing, firstly washing with 10% hydrochloric acid, finally washing with deionized water until the pH value is 7, and vacuum-drying the obtained red brown colloidal substance at 35 ℃ to obtain graphite oxide;
4) weighing a certain amount of graphite oxide, and ultrasonically stripping in deionized water with a certain volume to prepare a graphene oxide solution; during ultrasonic stripping, 30 percent (about 200W) of the maximum power of an ultrasonic cell crusher is adopted for ultrasonic treatment for 2 hours; and centrifuging the graphene oxide dispersion liquid obtained by ultrasonic treatment in a high-speed centrifuge at the rotating speed of 8000r/min for 10min, and taking the supernatant, namely the graphene oxide solution for later use.
4. The preparation method of graphene oxide modified oil absorption sponge as claimed in claim 3, wherein the step (iii) further comprises the following oil absorption rate test of the prepared oil absorption sponge:
weighing the polyurethane sponge before and after the modification of the small blocks, recording the original weight as m1, respectively placing the small blocks into the oily liquid to absorb oil for 2 minutes, taking out the small blocks, naturally dripping for 30 seconds until the oil drops do not drip, placing the small blocks into a measuring cup to be weighed with balance, and recording the weight as m2, then obtaining the weight of the small blocks
k＝(m2-m1)/m1
Wherein k is the oil absorption (g/g) of the sample, m1 is the mass (g) of the polyurethane sponge before oil absorption, and m2 is the mass (g) of the polyurethane sponge after oil absorption; the oil absorption of the polyurethane sponge before and after modification is compared, so that the promotion effect of the oil absorption multiplying power before and after modification can be obtained through comparison.
5. The preparation method of the graphene oxide modified oil absorption sponge as claimed in claim 1, wherein the soaking time t in the step (II) is within a range of 1min to 15 min.
6. The preparation method of the graphene oxide modified oil absorption sponge as claimed in any one of claims 1 to 5, wherein the polyurethane sponge is dried by using an oven in the step (iii), wherein the drying temperature T is in a range of 50 ℃ to 300 ℃, and the drying time is 2-12 hours.
7. The preparation method of the graphene oxide modified oil absorption sponge as claimed in claim 6, wherein the oven comprises a box body, the box body comprises an inner cavity for placing the polyurethane sponge, an air inlet mechanism is arranged on the box body below the inner cavity, and an air outlet mechanism is arranged on the box body above the inner cavity; a left placing cavity and a right placing cavity are transversely arranged in the inner cavity of the box body, and heating devices are arranged in the left placing cavity and the right placing cavity; a first air channel is arranged between the left placing cavity and the right placing cavity, and a second air channel and a third air channel are respectively arranged on one sides of the left placing cavity and the right placing cavity, which are far away from the first air channel; a plurality of vent holes communicated with the placing cavity are formed in the first air duct, the second air duct and the third air duct respectively, and the lower ends of the first air duct, the second air duct and the third air duct are connected with the air inlet mechanism; the upper ends of the left placing cavity and the right placing cavity are respectively communicated with the air outlet mechanism; the left placing cavity and the right placing cavity are provided with a plurality of trays used for placing sponges from top to bottom at intervals.
8. The preparation method of the graphene oxide modified oil absorption sponge based on the claim 7, wherein the air inlet mechanism comprises a first fan, a second fan and a third fan; the first fan, the second fan and the third fan correspond to the first air duct, the second air duct and the third air duct respectively; and a first partition plate and a second partition plate are respectively arranged between the air outlet of the first fan and the air outlets of the second fan and the third fan for separation.
9. The preparation method of the graphene oxide modification-based oil absorption sponge according to claim 7, wherein the air outlet mechanism comprises an air outlet draught fan, a first air outlet and a second air outlet are respectively arranged at the upper ends of the left placing cavity and the right placing cavity, a mixing cavity is arranged in the box body above the first air outlet and the second air outlet, the air outlet draught fan is located in the mixing cavity, a third air outlet is arranged at the top of the box body, and the air outlet draught fan is connected with the third air outlet; and the air flow in the left placing cavity and the right placing cavity passes through the first air outlet and the second air outlet and then is discharged through the third air outlet.
10. The method for preparing the graphene oxide modified oil absorption sponge according to claim 9, wherein a flow guide pipe is connected to an upper end of the third air outlet, a first delivery pipe and a second delivery pipe are arranged on the flow guide pipe, and the first delivery pipe and the second delivery pipe are respectively connected to a tail gas treatment device.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987528A (en) * | 2015-06-29 | 2015-10-21 | 武汉工程大学 | Modification method of oleophylic and hydrophobic nano-sponge |
| WO2018113698A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Graphene polyurethane sponge, preparation method therefor and applications thereof |
| CN109608688A (en) * | 2019-02-18 | 2019-04-12 | 山东星火科学技术研究院 | A kind of preparation method of the graphene sponge of high efficiency oil-water separation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987528A (en) * | 2015-06-29 | 2015-10-21 | 武汉工程大学 | Modification method of oleophylic and hydrophobic nano-sponge |
| WO2018113698A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Graphene polyurethane sponge, preparation method therefor and applications thereof |
| CN109608688A (en) * | 2019-02-18 | 2019-04-12 | 山东星火科学技术研究院 | A kind of preparation method of the graphene sponge of high efficiency oil-water separation |
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