Textile-based oil-absorbing material and its application in heavy oil photo-thermal absorption

Abstract

The application discloses a kind of textile-based oil-absorbing materials in the field of oil-absorbing material and its application in heavy oil light-heat absorption, and the material preparation method is as follows: take multi-walled carbon nanotube and modified Fe3O4 powder, add sodium dodecyl benzene sulfonate aqueous solution to obtain a suspension; take polyacrylonitrile fiber and add it to N, N-dimethylformamide, then add the suspension, and drop hydrophobic modifier and catalyst to obtain electrospinning solution, spin into a web, then take modified millipede shell powder and spray it onto the surface of the fiber web and solidify; take the fiber web and treat it at high temperature to obtain the textile-based oil-absorbing material. The oil-absorbing material uses multi-walled carbon nanotube and modified Fe3O4 powder as double light-heat synergistic factors, which greatly enhances the overall light-heat efficiency of the material, thereby solving the problem of low oil absorption efficiency of conventional oil-absorbing materials for heavy oil. In addition, the porous textile-based structure is used, and the surface is treated by hydrophobic modification, which can exhibit excellent hydrophobic and oleophilic properties, and is helpful to achieve efficient oil-water separation.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of oil absorption materials, in particular to a textile-based oil absorption material and its application in heavy oil light-heat absorption. BACKGROUND

[0002] In order to protect the ecological system, it is urgent to develop an efficient and environmentally friendly oil recovery method. Unfortunately, traditional oil spill recovery methods such as mechanical technology, chemical dispersion and bioremediation not only have low separation efficiency, but also can cause secondary pollution to the environment. Physical adsorption is considered to be a good alternative for oil spill cleanup because it can effectively recover oil from water. Various porous oil absorption materials have been proposed for oil spill cleanup, such as modified commercial sponges, modified foams, aerogels and biomass materials, etc. Rapid absorption of oil spills can effectively save oil spill cleanup time, reduce the spread of oil spills, thereby reducing the environmental damage caused by oil spills, and saving costs as much as possible.

[0003] However, the above-mentioned porous absorption materials generally show high absorption capacity for low viscosity oils (usually less than 1000 mPa·s), but are not suitable for higher viscosity oil spills (103-105 mPa·s at room temperature) which account for about 40% in reality. High viscosity oil such as heavy oil is difficult to effectively diffuse and penetrate into the internal pores of the porous absorption material, thereby significantly reducing the oil absorption rate. At the same time, too high viscosity can also destroy the internal pore structure of the absorption material, reducing its efficiency. Therefore, it is of great practical significance and scientific value to develop an absorption material suitable for high-viscosity oil spill treatment.

[0004] It is well known that the viscosity of heavy oil generally decreases with increasing oil temperature, and a light-heat material system can directly convert sustainable solar energy into heat energy, which can reduce the viscosity of heavy oil, thereby promoting the flow of heavy oil and improving the efficiency of heavy oil extraction. Currently effective light-heat conversion can be achieved by using carbon-based materials such as graphene oxide, carbon nanotubes, etc. Based on this technical direction, the application of light-heat conversion materials to oil absorption materials can theoretically improve the heavy oil absorption effect. However, there are few studies in this area, and there is a lack of similar oil absorption materials on the market. SUMMARY

[0005] The present application relates to the field of oil absorption materials, in particular to a textile-based oil absorption material and its application in heavy oil light-heat absorption.

[0006] The present application relates to the field of oil absorption materials, in particular to a textile-based oil absorption material and its application in heavy oil light-heat absorption.

[0007] A textile-based oil absorption material is prepared by the following method:

[0008] S1, take multi-walled carbon nanotubes and modified Fe3O4 powder, add sodium dodecyl benzene sulfonate aqueous solution, ultrasonic treatment under ice bath condition, form homogeneous suspension;

[0009] S2, take polyacrylonitrile fiber and add to N, N-dimethylformamide, stir until completely dissolved, then add the suspension, continue stirring and drop polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, vacuum degassing treatment to obtain electrospinning solution;

[0010] S3, electrospinning with the electrospinning solution to obtain fiber web, then take 4-8% of the mass of the fiber web of modified millipede shell powder and uniformly spray onto the surface of the fiber web, heat the fiber web to 110-120 DEG C and maintain for 6-8s, so that the fiber web softens and combines with the modified millipede shell powder;

[0011] S4, take the fiber web and place it in an air atmosphere of 270-280 DEG C for 1.5-2.5h, then place it in a high-temperature tube furnace and heat to 750-800 DEG C at a heating rate of 3-5 DEG C / min under inert gas protection, then maintain for 1-2h, and finally naturally cool to room temperature to obtain the textile-based oil absorption material.

[0012] Further improvement lies in that in step S1, the mass ratio of the multi-walled carbon nanotubes, the modified Fe3O4 powder and the sodium dodecyl benzene sulfonate aqueous solution is 1-3:0.5-1.5:50, and the sodium dodecyl benzene sulfonate accounts for 0.3-0.5% of the total mass of the multi-walled carbon nanotubes and the modified Fe3O4 powder.

[0013] Further improvement lies in that in step S1, the preparation method of the modified Fe3O4 powder is as follows:

[0014] Take cyclohexane, add 0.04-0.08% of nonylphenol polyoxyethylene ether based on the volume of cyclohexane, stir to disperse uniformly to obtain an emulsion, then drop 3-5% of iron chloride hexahydrate aqueous solution based on the volume of cyclohexane and 6-8% of ammonia water based on the volume of cyclohexane, and the concentration of the iron chloride hexahydrate aqueous solution is 0.4-0.8 mol / L and the concentration of the ammonia water is 1.5-2.5 mol / L, stir to obtain Fe3O4 particle dispersion liquid;

[0015] Drop 16-20% of tetraethyl orthosilicate based on the volume of cyclohexane and 15-20% of ammonia water based on the volume of cyclohexane into the Fe3O4 particle dispersion liquid, and the concentration of the ammonia water is 1.5-2.5 mol / L, stir to obtain Fe3O4 composite particles coated with silicon dioxide on the surface;

[0016] The Fe3O4 composite particles are separated, added into ethanol at a ratio of 1g particles: 50-60mL ethanol, uniformly stirred at 55-60℃, and then 12-16% of hexamethyl disilazane based on the volume of ethanol is added, and the stirring reaction is carried out at 120-130℃ for 1.5-2.5h;

[0017] The Fe3O4 composite particles are separated, washed and dried to obtain the modified Fe3O4 powder.

[0018] Further improvement lies in that, in step S1, the frequency of the ultrasonic treatment is 35-40kHz, the power is 500-600W, and the treatment time is 2-3h.

[0019] Further improvement lies in that, in step S2, the mass ratio of polyacrylonitrile fiber, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 10-12:90-100:2-3:0.8-0.9:0.01-0.015.

[0020] Further improvement lies in that, in step S2, the pressure of the vacuum defoaming treatment is -0.1MPa, and the time is 2-3h.

[0021] Further improvement lies in that, in step S3, the voltage of the electrospinning is 15-25kV, the liquid supply speed is 2-4mL / h, the receiving distance is 12-18cm, the inner diameter of the needle is 0.3-0.5mm, and the rotating speed of the dynamic receiving aluminum roller is 10-50rpm.

[0022] Further improvement lies in that, in step S3, the preparation method of the modified millipede shell powder is as follows: the artificially bred millipedes are cleaned and impurities are removed, then the millipedes are soaked in a 0.3-0.5M HCl solution for 0.5-1.5h, and then the millipedes are taken out and freeze-dried and crushed to obtain the shell powder; the shell powder is immersed in an ethanol solution containing 8-12wt% tetraethyl orthosilicate for 1.5-2h, and then the shell powder is taken out and solidified at 50-60℃ for 8-12h; then the shell powder is immersed in an acetic acid solution containing 1.5-2wt% chitosan and 0.8-1.2wt% boric acid, and the stirring reaction is carried out at 50-60℃ for 2-4h; finally, the shell powder is taken out, washed with water and dried to obtain the modified millipede shell powder.

[0023] Further improvement lies in that, the particle size of the shell powder is 60-80μm.

[0024] The application further provides an application of the textile-based oil absorption material in heavy oil light-heat absorption.

[0025] The application has the following beneficial effects:

[0026] (1) The oil absorption material adopts a double photothermal synergistic factor of multi-walled carbon nanotubes and modified Fe3O4 powder. The wide spectrum absorption characteristics of multi-walled carbon nanotubes and the near-infrared response characteristics of modified Fe3O4 powder make the overall photothermal efficiency of the material greatly enhanced, thereby effectively solving the problem of low oil absorption efficiency of conventional oil absorption materials for heavy oil.

[0027] The modified Fe3O4 powder is coated with a thin layer of silicon dioxide and treated with hexamethyldisilazane, which greatly improves the dispersibility and compatibility of the powder without affecting the near-infrared response characteristics, thereby ensuring the compounding effect with multi-walled carbon nanotubes and avoiding sedimentation and agglomeration.

[0028] (2) The oil absorption material adopts a porous textile-based structure, and the surface is treated with hydrophobic modification, which can exhibit excellent hydrophobic and oleophilic properties, helping to achieve efficient oil-water separation.

[0029] Specifically, the oil absorption material has modified millipede shell powder loaded on the surface of the fiber web, which further perfects the porous skeleton after carbonization and enhances the hydrophobic and oil absorption properties of the material. The modification of the modified millipede shell powder can reduce the ash content (CaO) after carbonization and improve the toughness, ensuring that it can be stably loaded on the surface of the fiber web, thereby ensuring the hydrophobic and oil absorption effect. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a transmission electron micrograph of modified Fe3O4 powder;

[0031] Figure 2 is a digital image of each group of textile-based oil absorption materials when water droplets contact the surface;

[0032] Figure 3 is a digital image of each group of textile-based oil absorption materials when oil droplets contact the surface. DETAILED DESCRIPTION

[0033] The following detailed description of the application in conjunction with the accompanying drawings is necessary to point out that the following detailed description is only used to further illustrate the application and cannot be understood as limiting the scope of protection of the application. Those skilled in the art can make some non-essential improvements and adjustments to the application based on the above application content.

[0034] I. Main materials

[0035] Multi-walled carbon nanotubes: purchased from Shanghai Xu Tian New Material Technology Co., Ltd.;

[0036] Iron chloride hexahydrate: FeCl3·6H2O, purchased from Wuhan Xingzhongcheng Technology Co., Ltd.;

[0037] Sodium dodecylbenzenesulfonate: purchased from Jinan Maoxin Chemical Co., Ltd.

[0038] Polyacrylonitrile fiber: diameter of about 12 μm, purchased from Changzhou Boxiao Engineering Material Co., Ltd.

[0039] N,N-dimethylformamide: purchased from Shandong Mao Fa Chemical Co., Ltd.

[0040] Polydimethylsiloxane: molecular weight of 15000, purchased from Guangzhou Huazhiwang Chemical Co., Ltd.

[0041] Dibutyltin dilaurate: purchased from Shandong Yaotong Industry Co., Ltd.

[0042] Millipede: purchased from Bozhou Qiancheng District Xunqian Grass Agricultural Products Store.

[0043] II. Experimental implementation

[0044] Example 1

[0045] A textile-based oil-absorbing material is prepared by the following method:

[0046] S1, mix multi-walled carbon nanotubes and modified Fe3O4 powder, add sodium dodecyl benzene sulfonate aqueous solution, and ultrasonically treat under ice bath conditions (frequency of 35 kHz, power of 500 W, and treatment time of 3 h) to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder, and sodium dodecyl benzene sulfonate aqueous solution is 1:0.5:50, and the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution accounts for 0.3% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder;

[0047] The preparation method of the modified Fe3O4 powder is as follows: take cyclohexane, add 0.04% nonylphenol polyoxyethylene ether by volume of the cyclohexane, stir and disperse uniformly to obtain an emulsion, then drop 3% iron chloride hexahydrate aqueous solution by volume of the cyclohexane and 6% ammonia water by volume of the cyclohexane into the emulsion, the concentration of the iron chloride hexahydrate aqueous solution is 0.8 mol / L, and the concentration of the ammonia water is 2.5 mol / L, and stir to obtain a Fe3O4 particle dispersion liquid; drop 16% tetraethyl orthosilicate by volume of the cyclohexane and 15% ammonia water by volume of the cyclohexane into the Fe3O4 particle dispersion liquid, the concentration of the ammonia water is 2.5 mol / L, and stir to obtain Fe3O4 composite particles coated with silicon dioxide; separate the Fe3O4 composite particles, add them into ethanol at a ratio of 1 g particles:50 mL ethanol, stir uniformly when heated to 55°C, then add 12% hexamethyldisilazane by volume of the ethanol, and stir to react at 120°C for 2.5 h; separate the Fe3O4 composite particles, wash and dry them, and the modified Fe3O4 powder is obtained;

[0048] S2, the polyacrylonitrile fiber is added into N, N-dimethylformamide, stirred until completely dissolved, then the suspension is added, stirring is continued and the polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst are added dropwise, after vacuum degassing treatment (pressure is -0.1 MPa, time is 2 h), an electrospinning solution is obtained; the mass ratio of the polyacrylonitrile fiber, N, N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 10:90:2:0.8:0.01;

[0049] S3, electrospinning is performed with the electrospinning solution, the voltage of electrospinning is 15 kV, the liquid supply speed is 2 mL / h, the receiving distance is 12 cm, the inner diameter of the needle is 0.3 mm, the rotating speed of the dynamic receiving aluminum roller is 10 rpm, a fiber web is obtained, then 4% of the modified millipede shell powder by mass of the fiber web is uniformly sprayed onto the surface of the fiber web, the fiber web is heated to 110℃ and maintained for 8 s, so that the fiber web is softened and combined with the modified millipede shell powder;

[0050] The preparation method of the modified millipede shell powder is as follows: after the artificially bred milliped is cleaned and impurities are removed, the milliped is soaked in a 0.3 M HCl solution for 1.5 h, then the milliped is taken out and freeze-dried and crushed to obtain shell powder with a particle size of about 60 μm, the shell powder is immersed in an ethanol solution containing 8 wt% tetraethyl orthosilicate for 2 h, then the shell powder is taken out and solidified at 50℃ for 12 h, then the shell powder is immersed in an acetic acid solution containing 1.5 wt% chitosan and 0.8 wt% boric acid, and stirred at 50℃ for 4 h, finally the shell powder is taken out, washed with water and dried, thereby obtaining the modified millipede shell powder;

[0051] S4, the fiber web is placed in an air atmosphere at 270℃ for pre-oxidation for 2.5 h, then the fiber web is placed in a high-temperature tube furnace and heated to 750℃ at a heating rate of 3℃ / min under the protection of inert gas, and then the fiber web is kept at 750℃ for 2 h, finally the fiber web is naturally cooled to room temperature, thereby obtaining the textile-based oil absorption material.

[0052] Example 2

[0053] A textile-based oil absorption material is prepared by the following method:

[0054] S1, the multi-walled carbon nanotubes and the modified Fe3O4 powder are mixed, and the sodium dodecylbenzenesulfonate aqueous solution is added, and ultrasonic treatment (frequency is 38 kHz, power is 550 W, treatment time is 2.5 h) is performed under ice bath conditions to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, the modified Fe3O4 powder and the sodium dodecylbenzenesulfonate aqueous solution is 2:1:50, and the sodium dodecylbenzenesulfonate in the sodium dodecylbenzenesulfonate aqueous solution accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and the modified Fe3O4 powder;

[0055] The preparation method of the modified Fe3O4 powder is as follows: cyclohexane is taken, 0.06% of nonylphenol polyoxyethylene ether based on the volume of the cyclohexane is added, and stirring is performed to uniformly disperse to obtain an emulsion, then 4% of an aqueous ferric chloride hexahydrate solution based on the volume of the cyclohexane and with a concentration of 0.6 mol / L and 7% of ammonia water based on the volume of the cyclohexane and with a concentration of 2 mol / L are added dropwise to the emulsion, and stirring is performed to obtain a Fe3O4 particle dispersion liquid; 18% of tetraethyl orthosilicate based on the volume of the cyclohexane and 18% of ammonia water based on the volume of the cyclohexane and with a concentration of 2 mol / L are added dropwise to the Fe3O4 particle dispersion liquid, and stirring is performed to obtain Fe3O4 composite particles coated with silicon dioxide; the Fe3O4 composite particles are separated, added to ethanol at a ratio of 1 g of particles:55 mL of ethanol, stirred uniformly while being heated to 58℃, then 14% of hexamethyldisilazane based on the volume of the ethanol is added, and stirring is performed while being heated to 125℃ for 2 h; the Fe3O4 composite particles are separated, washed and dried, and the modified Fe3O4 powder is obtained; the morphology of the prepared modified Fe3O4 powder is characterized by using a transmission electron microscope (JEM-1200EX), and the results are shown in Figure 1 It can be seen that the powder is spherical and nanoscale, and there is no obvious agglomeration phenomenon between the particles, and the dispersibility is good.

[0056] S2, polyacrylonitrile fibers are taken and added to N,N-dimethylformamide, and stirring is performed until the polyacrylonitrile fibers are completely dissolved, then the suspension is added, stirring is continued, and polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst are added dropwise, and vacuum degassing treatment (pressure: -0.1 MPa, time: 2.5 h) is performed to obtain an electrospinning solution; the mass ratio of the polyacrylonitrile fibers, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 11:95:2.5:0.8:0.012;

[0057] S3, electrospinning is performed on the electrospinning solution to form a fiber web, the voltage for electrospinning is 20 kV, the liquid supply speed is 3 mL / h, the receiving distance is 15 cm, the inner diameter of the needle is 0.4 mm, and the rotating speed of the dynamic receiving aluminum roller is 30 rpm, then 6% of the modified millipede shell powder based on the mass of the fiber web is uniformly sprayed onto the surface of the fiber web, the fiber web is heated to 115℃ and maintained for 7 s, so that the fiber web is softened and combined with the modified millipede shell powder;

[0058] The modified millipede shell powder is prepared by washing and removing impurities from artificially cultured millipedes, soaking them in a 0.4M HCl solution for 1 hour, taking them out, freeze-drying them, and crushing them to obtain shell powder with a particle size of about 70 μm, taking the shell powder and immersing it in an ethanol solution containing 10wt% ethyl orthosilicate for 1.8 hours, taking the shell powder out and curing it at 55°C for 10 hours, then immersing the shell powder in an acetic acid solution containing 1.8wt% chitosan and 1wt% boric acid, stirring and reacting at 55°C for 3 hours, and finally taking out the shell powder, washing it with water, and drying it to obtain the modified millipede shell powder.

[0059] S4. Pre-oxidize the fiber web in an air atmosphere at 275° C. for 2 h, then place it in a high-temperature tube furnace and heat it to 780° C. at a heating rate of 4° C. / min under inert gas protection, then keep the temperature for 1.5 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing material.

[0060] Example 3

[0061] A textile-based oil-absorbing material is prepared by the following method:

[0062] S1. Mix multi-walled carbon nanotubes and modified Fe3O4 powder, add an aqueous solution of sodium dodecylbenzenesulfonate, and ultrasonically treat in an ice bath (frequency of 40 kHz, power of 600 W, and treatment time of 2 h) to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder, and aqueous solution of sodium dodecylbenzenesulfonate is 3:1.5:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.5% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder;

[0063] The preparation method of the modified Fe3O4 powder is as follows: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.08% by volume of the cyclohexane, stirring and dispersing uniformly to obtain an emulsion, then dripping ferric chloride hexahydrate aqueous solution accounting for 5% by volume of the cyclohexane and having a concentration of 0.4 mol / L, and ammonia water accounting for 8% by volume of the cyclohexane and having a concentration of 1.5 mol / L into the emulsion, stirring and reacting to obtain a Fe3O4 particle dispersion; dripping ethyl orthosilicate accounting for 20% by volume of the cyclohexane into the Fe3O4 particle dispersion; , and 1.5 mol / L ammonia water accounting for 20% by volume of cyclohexane, stirring and reacting to obtain Fe3O4 composite particles with surface coating of silica; separating the Fe3O4 composite particles, adding them to ethanol at a ratio of 1g of particles: 60mL of ethanol, heating to 60°C and stirring evenly, then adding hexamethyldisilazane accounting for 16% by volume of ethanol, heating to 130°C and stirring to react for 1.5h; separating the Fe3O4 composite particles, washing and drying them, and obtaining modified Fe3O4 powder;

[0064] S2, the polyacrylonitrile fiber is added into N,N-dimethylformamide, stirred until completely dissolved, then the suspension is added, stirring is continued and the polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst are added dropwise, after vacuum degassing treatment (pressure is -0.1 MPa, time is 3 h), an electrospinning solution is obtained; the mass ratio of the polyacrylonitrile fiber, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 12:100:2:0.9:0.015;

[0065] S3, electrospinning is performed using the electrospinning solution, the voltage for electrospinning is 25 kV, the liquid supply speed is 4 mL / h, the receiving distance is 18 cm, the inner diameter of the needle is 0.5 mm, the rotating speed of the dynamic receiving aluminum roller is 50 rpm, a fiber web is obtained, then 8% of the modified millipede shell powder by mass of the fiber web is uniformly sprayed onto the surface of the fiber web, the fiber web is heated to 120℃ and maintained for 6 s, so that the fiber web is softened and combined with the modified millipede shell powder;

[0066] The preparation method of the modified millipede shell powder is as follows: after the artificially bred milliped is cleaned and impurities are removed, the milliped is soaked in a 0.5 M HCl solution for 0.5 h, then the milliped is taken out and freeze-dried and crushed to obtain shell powder with a particle size of about 80 μm, the shell powder is immersed in an ethanol solution containing 12 wt% tetraethyl orthosilicate for 1.5 h, then the shell powder is taken out and solidified at 60℃ for 8 h, then the shell powder is immersed in an acetic acid solution containing 2 wt% chitosan and 1.2 wt% boric acid, and stirred and reacted at 60℃ for 2 h, finally the shell powder is taken out, washed with water and dried, to obtain the modified millipede shell powder;

[0067] S4, the fiber web is placed in an air atmosphere at 280℃ for pre-oxidation for 1.5 h, then the fiber web is placed in a high-temperature tube furnace and heated to 800℃ at a heating rate of 5℃ / min under the protection of inert gas, then the fiber web is kept at 800℃ for 1 h, and finally the fiber web is naturally cooled to room temperature, to obtain the textile-based oil absorption material.

[0068] Comparative Example 1

[0069] A textile-based oil absorption material is prepared by the following method:

[0070] S1, multi-walled carbon nanotubes and Fe3O4 powder are mixed, a sodium dodecyl benzene sulfonate aqueous solution is added, and ultrasonic treatment (frequency is 38 kHz, power is 550 W, treatment time is 2.5 h) is performed under ice bath conditions to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, Fe3O4 powder and sodium dodecyl benzene sulfonate aqueous solution is 2:1:50, and the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and Fe3O4 powder;

[0071] The preparation method of the Fe3O4 powder is as follows: cyclohexane is taken, 0.06% of nonylphenol polyoxyethylene ether based on the volume of the cyclohexane is added, and stirring is performed to uniformly disperse to obtain an emulsion, then 4% of an aqueous solution of iron chloride hexahydrate based on the volume of the cyclohexane and having a concentration of 0.6 mol / L and 7% of ammonia water based on the volume of the cyclohexane and having a concentration of 2 mol / L are added dropwise into the emulsion, and stirring is performed to obtain a Fe3O4 particle dispersion liquid; Fe3O4 particles are separated, cleaned and dried, and thus the Fe3O4 powder is obtained;

[0072] S2, polyacrylonitrile fibers are taken and added into N,N-dimethylformamide, and stirring is performed until the polyacrylonitrile fibers are completely dissolved, then the suspension is added, and stirring and dropwise addition of a polydimethylsiloxane hydrophobic modifier and a dibutyltin dilaurate catalyst are continuously performed, and after vacuum degassing treatment (pressure: -0.1 MPa, time: 2.5 h), an electrospinning solution is obtained; the mass ratio of the polyacrylonitrile fibers, the N,N-dimethylformamide, the suspension, the polydimethylsiloxane hydrophobic modifier and the dibutyltin dilaurate catalyst in the electrospinning solution is 11:95:2.5:0.8:0.012;

[0073] S3, electrospinning is performed on the electrospinning solution to form a fiber web, the voltage for electrospinning is 20 kV, the liquid supply speed is 3 mL / h, the receiving distance is 15 cm, the inner diameter of the needle is 0.4 mm, and the rotating speed of the dynamic receiving aluminum roller is 30 rpm, and thus a fiber web is obtained, 6% of modified millipede shell powder based on the mass of the fiber web is uniformly sprayed onto the surface of the fiber web, the fiber web is heated to 115℃ and maintained for 7 s, and thus the fiber web is softened and combined with the modified millipede shell powder;

[0074] The preparation method of the modified millipede shell powder is as follows: after artificial breeding millipedes are cleaned and impurities are removed, the millipedes are soaked in an HCl solution with a concentration of 0.4 M for 1 h, and then the millipedes are taken out and subjected to freeze-drying and pulverization to obtain shell powder with a particle size of about 70 μm, the shell powder is taken and soaked in an ethanol solution containing 10 wt% of tetraethyl orthosilicate for 1.8 h, the shell powder is taken out and solidified at 55℃ for 10 h, then the shell powder is soaked in an acetic acid solution containing 1.8 wt% of chitosan and 1 wt% of boric acid, stirring is performed at 55℃ for 3 h, and finally the shell powder is taken out, washed with water and dried, and thus the modified millipede shell powder is obtained;

[0075] S4, the fiber web is placed in an air atmosphere at 275℃ for pre-oxidation for 2 h, then the fiber web is placed in a high-temperature tube furnace, and the temperature is raised to 780℃ at a raising rate of 4℃ / min under the protection of inert gas, and then the temperature is maintained for 1.5 h, and finally the fiber web is naturally cooled to room temperature, and thus the textile-based oil absorption material is obtained.

[0076] Comparative Example 2

[0077] A textile-based oil absorption material is prepared by the following method:

[0078] S1, take the multi-walled carbon nanotubes and modified Fe3O4 powder mixed, adding sodium dodecyl benzene sulfonate aqueous solution, ultrasonic treatment (frequency of 38 kHz, power of 550 W, processing time of 2.5 h) under ice bath conditions, form homogeneous suspension; The mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder and sodium dodecyl benzene sulfonate aqueous solution is 2:1:50, and the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and the modified Fe3O4 powder;

[0079] The preparation method of the modified Fe3O4 powder is: taking cyclohexane, adding 0.06% of the volume of cyclohexane nonylphenol polyoxyethylene ether, stirring and dispersing uniformly to obtain an emulsion, then adding 4% of the volume of cyclohexane and 0.6 mol / L of the concentration of iron chloride hexahydrate aqueous solution, and 7% of the volume of cyclohexane and 2 mol / L of the concentration of ammonia water, stirring to obtain a Fe3O4 particle dispersion; To the Fe3O4 particle dispersion, add 18% of the volume of cyclohexane and 2 mol / L of the concentration of tetraethyl orthosilicate, and 18% of the volume of cyclohexane and 2 mol / L of the concentration of ammonia water, and stir to obtain Fe3O4 composite particles coated with silicon dioxide; Separately take the Fe3O4 composite particles and add them to ethanol at a ratio of 1 g of particles to 55 mL of ethanol, stir uniformly at 58°C, then add 14% of the volume of ethanol hexamethyl disilazane, and stir to react at 125°C for 2 h; Separately take the Fe3O4 composite particles, wash and dry, and obtain the modified Fe3O4 powder;

[0080] S2, take the polyacrylonitrile fiber and add it to N,N-dimethylformamide, stir until completely dissolved, then add the suspension, continue to stir and add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, vacuum degassing treatment (pressure of-0.1 MPa, time of 2.5 h) to obtain an electrospinning solution; The mass ratio of polyacrylonitrile fiber, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 11:95:2.5:0.8:0.012;

[0081] S3, electrospinning with the electrospinning solution, the voltage of electrospinning is 20 kV, the liquid supply speed is 3 mL / h, the receiving distance is 15 cm, the inner diameter of the needle is 0.4 mm, and the dynamic receiving aluminum roller rotates at 30 rpm to obtain a fiber web;

[0082] S4, take the fiber web and place it in an air atmosphere at 275°C for 2 h, then place it in a high-temperature tube furnace and heat it to 780°C at a rate of 4°C / min under inert gas protection, then keep it at temperature for 1.5 h, and finally naturally cool to room temperature to obtain the textile-based oil absorption material.

[0083] Comparative Example 3

[0084] A textile-based oil-absorbing material is prepared by the following method:

[0085] S1, mix multi-walled carbon nanotubes and modified Fe3O4 powder, add sodium dodecyl benzene sulfonate aqueous solution, and ultrasonically treat (frequency 38 kHz, power 550 W, treatment time 2.5 h) under ice bath conditions to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder, and sodium dodecyl benzene sulfonate aqueous solution is 2:1:50, and the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder;

[0086] The preparation method of the modified Fe3O4 powder is as follows: take cyclohexane, add 0.06% nonylphenol polyoxyethylene ether by volume of the cyclohexane, stir and disperse uniformly to obtain an emulsion, then add 4% iron chloride hexahydrate aqueous solution by volume of the cyclohexane and 7% ammonia water by volume of the cyclohexane, and the concentration of the iron chloride hexahydrate aqueous solution is 0.6 mol / L and the concentration of the ammonia water is 2 mol / L, and stir and react to obtain a Fe3O4 particle dispersion liquid; add 18% ethyl silicate by volume of the cyclohexane and 18% ammonia water by volume of the cyclohexane to the Fe3O4 particle dispersion liquid, and the concentration of the ammonia water is 2 mol / L, and stir and react to obtain Fe3O4 composite particles coated with silicon dioxide; separate the Fe3O4 composite particles, add them to ethanol at a ratio of 1 g of particles to 55 mL of ethanol, stir uniformly while heating to 58°C, then add 14% hexamethyldisilazane by volume of the ethanol, and stir and react at 125°C for 2 h; separate the Fe3O4 composite particles, wash and dry them, and the modified Fe3O4 powder is obtained; the morphology of the prepared modified Fe3O4 powder is characterized using a transmission electron microscope (JEM-1200EX), and the results are shown in Figure 1 It can be seen that the powder is spherical at the nanometer level, and there is no obvious agglomeration between the particles, and the dispersibility is good.

[0087] S2, add polyacrylonitrile fibers to N,N-dimethylformamide, stir until completely dissolved, then add the suspension, continue to stir and add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and vacuum degassing treatment (pressure -0.1 MPa, time 2.5 h) to obtain an electrospinning solution; the mass ratio of polyacrylonitrile fibers, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier, and dibutyltin dilaurate catalyst in the electrospinning solution is 11:95:2.5:0.8:0.012;

[0088] S3, electrospinning the electrospinning solution into a web, wherein the electrospinning voltage is 20 kV, the liquid supply rate is 3 mL / h, the receiving distance is 15 cm, the inner diameter of the needle is 0.4 mm, and the speed of the dynamic receiving aluminum roller is 30 rpm to obtain a fiber web, and then taking millipede shell powder accounting for 6% of the mass of the fiber web and spraying it evenly onto the surface of the fiber web, and heating the fiber web to 115° C. and maintaining it for 7 seconds to soften the fiber web and combine it with the millipede shell powder;

[0089] The millipede shell powder is prepared by washing and removing impurities from artificially cultured millipedes, freeze-drying and pulverizing the millipedes to obtain shell powder with a particle size of about 70 μm, thus obtaining the millipede shell powder;

[0090] S4. Pre-oxidize the fiber web in an air atmosphere at 275° C. for 2 h, then place it in a high-temperature tube furnace and heat it to 780° C. at a heating rate of 4° C. / min under inert gas protection, then keep the temperature for 1.5 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing material.

[0091] 3. Performance Testing

[0092] (1) Surface wetting properties

[0093] The oil absorbing material samples prepared in Examples 1-3 and Comparative Examples 1-3 were taken using a video contact angle meter (DSA-20) to photograph droplets (5 μL deionized water droplets and 5 μL crude oil droplets taken by the instrument) as they contacted the surface of the oil absorbing material sample. The contact angles of the droplets in contact with the oil absorbing material sample were calculated using Image Pro software.

[0094] (2) Oil absorption performance

[0095] Room-Temperature Oil Absorption: Samples of the textile-based oil-absorbing materials prepared in Examples 1-3 and Comparative Examples 1-3 were weighed at their initial mass. The samples were then immersed in simulated viscous oil (seawater and crude oil in a 7:3 volume ratio) for static adsorption. After 5 minutes, the samples were removed and then held in the air for 30 seconds to allow excess crude oil to drip due to gravity. The adsorbed mass was then weighed and the oil absorption rate was calculated using the following formula. This step was repeated three times, and the average of the three results was used as the final oil absorption rate.

[0096]

[0097] Where: m0 is the initial mass, unit is g; m1 is the mass after oil absorption, unit is g.

[0098] Photothermal Oil Absorption: The textile-based oil-absorbing materials prepared in Examples 1-3 and Comparative Examples 1-3 were exposed to sunlight, and the temperature was recorded in real time using a contact thermocouple (TES-1384) to evaluate their photothermal performance. After 10 minutes of sunlight exposure, the oil absorption rate was tested again using the above method. The sunlight was provided by a simulated sunlight xenon lamp (CEL-PE300-4A, Beijing Zhongjiao Jinyuan Technology Co., Ltd.), combined with an optical power density meter, and the light intensity (1.0 sun standard sunlight intensity) was controlled by adjusting the voltage.

[0099] 4. Results Analysis

[0100] (1) Surface wetting properties

[0101] like Figure 2 As shown, these are photos of the textile-based oil-absorbing materials prepared in Examples 1-3 and Comparative Examples 1-3 when water droplets contact the surface; Figure 3 The following are photographs of the textile-based oil-absorbing materials prepared in Examples 1-3 and Comparative Examples 1-3, showing oil droplets contacting their surfaces. As can be seen, the textile-based oil-absorbing materials prepared in Examples 1-3 of the present invention exhibit excellent hydrophobic and oil-absorbing properties, with water contact angles exceeding 149.6° and oil contact angles of 0°. Comparative Examples 1-3 are all adjustments made on the basis of Example 2, wherein: Comparative Example 1 does not coat the Fe3O4 powder with a thin layer of silicon dioxide and does not perform surface treatment with hexamethyldisilazane, and its hydrophobicity and oil absorption performance are slightly reduced. The analysis shows that the reason may be that its sedimentation and agglomeration have a certain impact on the material; Comparative Example 2 does not load the modified millipede shell powder on the surface of the fiber web, and its hydrophobicity and oil absorption performance are significantly reduced, the water contact angle is reduced to 113.4°, and the oil contact angle is increased to 65.4°; Comparative Example 3 replaces the modified millipede shell powder with ordinary millipede shell powder, and its hydrophobicity and oil absorption performance are also significantly reduced, the water contact angle is reduced to 123.7°, and the oil contact angle is increased to 41.3°. This shows that the modified millipede shell powder plays an important role in promoting the hydrophobic and oil absorption properties of the material.

[0102] (2) Oil absorption performance

[0103] The oil absorption rates of the textile-based oil-absorbing materials prepared in Examples 1-3 and Comparative Examples 1-3 at room temperature and photothermal oil absorption are statistically reported in Table 1 below:

[0104] Table 1: Oil absorption ratio of each group of textile-based oil-absorbing materials at room temperature and light-heat absorption

[0105]

[0106] From the above table 1, it can be seen that the oil absorption performance of the textile-based oil absorption material prepared by the present application is outstanding, especially example 2, the oil absorption rate at room temperature reaches 45.14 g / g, and the light-heat oil absorption rate reaches 62.17 g / g. Comparative example 1 does not perform silica thin layer coating and hexamethyldisilazane surface treatment on Fe3O4 powder, and the oil absorption performance of the oil absorption rate at room temperature is slightly lower than that of example 2, but the light-heat oil absorption rate is significantly reduced, which shows that the modification treatment of Fe3O4 powder can significantly improve its light-heat performance; Comparative example 2 does not load modified millipede shell powder on the surface of the fiber web, and the oil absorption rate at room temperature and the light-heat oil absorption rate are significantly reduced, which are respectively reduced by 21.6% and 18.7% compared with example 2; Comparative example 3 replaces the modified millipede shell powder with ordinary millipede shell powder, and the oil absorption rate at room temperature and the light-heat oil absorption rate are also significantly reduced, which are respectively reduced by 11.1% and 12.6% compared with example 2; which further shows that the modified millipede shell powder plays an important role in promoting the oil absorption performance of the material.

[0107] The above examples only express several embodiments of the present application, which are described in detail and specifically, but cannot be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application.

Claims

1. A textile-based oil-absorbing material, characterized by, It is prepared by the following method: S1, take multi-walled carbon nanotubes and modified Fe3O4 powder, add sodium dodecyl benzene sulfonate aqueous solution, ultrasonic treatment under ice bath conditions, form homogeneous suspension; The preparation method of the modified Fe3O4 powder is: Take cyclohexane, add 0.04-0.08% nonylphenol polyoxyethylene ether based on the volume of cyclohexane, stir and disperse uniformly to obtain an emulsion, then add 3-5% iron chloride hexahydrate aqueous solution based on the volume of cyclohexane and with a concentration of 0.4-0.8 mol / L, and 6-8% ammonia water based on the volume of cyclohexane and with a concentration of 1.5-2.5 mol / L, stir and react to obtain Fe3O4 particle dispersion liquid; Add 16-20% tetraethyl orthosilicate based on the volume of cyclohexane to the Fe3O4 particle dispersion liquid, and 15-20% ammonia water based on the volume of cyclohexane and with a concentration of 1.5-2.5 mol / L, stir and react to obtain Fe3O4 composite particles coated with silicon dioxide on the surface; Separately take the Fe3O4 composite particles, add to ethanol at a ratio of 1 g of particles: 50-60 mL of ethanol, heat to 55-60°C and stir uniformly, then add 12-16% hexamethyldisilazane based on the volume of ethanol, heat to 120-130°C and stir and react for 1.5-2.5 h; Separately take the Fe3O4 composite particles, wash and dry to obtain the modified Fe3O4 powder; S2, take polyacrylonitrile fibers and add to N, N-dimethylformamide, stir until completely dissolved, then add the suspension, continue to stir and add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, vacuum degassing treatment to obtain electrospinning solution; S3, electrospinning with the electrospinning solution to obtain a fiber web, then take 4-8% modified millipede shell powder based on the mass of the fiber web and uniformly spray onto the surface of the fiber web, heat the fiber web to 110-120°C and maintain for 6-8 s, so that the fiber web softens and combines with the modified millipede shell powder; The preparation method of the modified millipede shell powder is: take artificially bred millipedes, clean and remove impurities, then soak in 0.3-0.5 M HCl solution for 0.5-1.5 h, take out and freeze-dry and crush to obtain shell powder, soak the shell powder in an ethanol solution containing 8-12 wt% tetraethyl orthosilicate for 1.5-2 h, take out the shell powder and solidify at 50-60°C for 8-12 h, then soak the shell powder in an acetic acid solution containing 1.5-2 wt% chitosan and 0.8-1.2 wt% boric acid, stir and react at 50-60°C for 2-4 h, and finally take out the shell powder, wash and dry to obtain the modified millipede shell powder; S4, take the fiber web and pre-oxidize in an air atmosphere at 270-280°C for 1.5-2.5 h, then place it in a high-temperature tube furnace and heat to 750-800°C at a heating rate of 3-5°C / min under the protection of inert gas, then maintain for 1-2 h, and finally naturally cool to room temperature to obtain the textile-based oil absorption material.

2. A textile-based oil-absorbing material according to claim 1, characterized in that, In step S1, the mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder and aqueous solution of sodium dodecylbenzenesulfonate is 1-3:0.5-1.5:50, and the sodium dodecylbenzenesulfonate accounts for 0.3-0.5% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder.

3. The textile-based oil-absorbing material according to claim 1, wherein In step S1, the frequency of the ultrasonic treatment is 35-40 kHz, the power is 500-600 W, and the treatment time is 2-3 h.

4. The textile-based oil-absorbing material according to claim 1, wherein In step S2, the mass ratio of the polyacrylonitrile fiber, N,N-dimethylformamide, suspension, polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst in the electrospinning solution is 10-12:90-100:2-3:0.8-0.9:0.01-0.

015.

5. The textile-based oil-absorbing material according to claim 1, wherein In step S2, the pressure of the vacuum defoaming treatment is -0.1 MPa, and the time is 2-3 h.

6. The textile-based oil-absorbing material according to claim 1, wherein In step S3, the voltage of the electrospinning is 15-25 kV, the liquid supply speed is 2-4 mL / h, the receiving distance is 12-18 cm, the inner diameter of the needle is 0.3-0.5 mm, and the dynamic receiving aluminum roller rotation speed is 10-50 rpm.

7. The textile-based oil-absorbing material according to claim 1, wherein The particle size of the shell powder is 60-80 µm.

8. Use of the textile-based oil-absorbing material according to any one of claims 1-7 in the photothermal absorption of heavy oil.

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