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

Abstract

The invention discloses a textile-based oil absorption material and application thereof in heavy oil photo-thermal absorption in the field of oil absorption materials, and a preparation method of the textile-based oil absorption material comprises the following steps: taking multi-walled carbon nanotubes and modified Fe3O4 powder, adding a sodium dodecyl benzene sulfonate aqueous solution, and treating to obtain a suspension; polyacrylonitrile fibers are taken and added into N, N-dimethylformamide, then the suspension liquid is added, a hydrophobic modifier and a catalyst are dropwise added, an electrostatic spinning solution is obtained and spun into a net, and then modified thousand-foot insect shell powder is taken and sprayed to the surface of the fiber net and cured; and performing high-temperature treatment on the fiber net to obtain the textile-based oil absorption material. According to the oil absorption material, dual photo-thermal synergistic factors of the multi-walled carbon nanotubes and the modified Fe3O4 powder are adopted, so that the overall photo-thermal efficiency of the material is greatly improved, the problem that a conventional oil absorption material is low in oil absorption efficiency for heavy oil is solved, in addition, a porous textile base structure is adopted, the surface is subjected to hydrophobic modification treatment, excellent hydrophobic lipophilicity can be shown, and the oil absorption efficiency is improved. The efficient oil-water separation is favorably realized.

Description

Technical Field

[0001] The present invention relates to the field of oil absorbing materials, in particular to a textile-based oil absorbing material and application thereof in light and heat absorption of heavy oil. Background Art

[0002] In order to protect the ecosystem, there is an urgent need 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 may also cause secondary pollution to the environment. Physical adsorption is considered a good alternative for oil spill cleanup because it can effectively recover oil from water. A variety of porous oil-absorbing materials have been proposed for oil spill cleanup, such as modified commercial sponges, modified foams, aerogels and biomass materials. Rapid absorption of oil 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, these porous absorbent materials typically exhibit high absorption capacity for low-viscosity oils (typically less than 1000 mPa·s), but are inadequate for the higher viscosity oil spills (103-105 mPa·s at room temperature), which account for approximately 40% of oil spills in real life. High-viscosity oils, such as heavy oil, have difficulty effectively diffusing and penetrating the internal pores of porous absorbent materials, significantly reducing their absorption rate. Furthermore, excessively high viscosity can also disrupt the internal pore structure of the absorbent material, reducing its efficiency. Therefore, developing absorbent materials suitable for high-viscosity oil spills is of great practical and scientific significance.

[0004] It is well known that the viscosity of heavy oil generally decreases as the oil temperature increases. Photothermal material systems can directly convert sustainable solar energy into thermal energy, which can reduce the viscosity of heavy oil, thereby promoting its flow and improving its extraction efficiency. Currently, effective photothermal conversion can be achieved through the use of carbon-based materials such as graphene oxide and carbon nanotubes. Based on this technical direction, applying photothermal conversion materials to oil-absorbing materials can theoretically improve the adsorption effect of heavy oil. However, there is currently little research in this area, and there is a lack of similar oil-absorbing materials on the market. Summary of the Invention

[0005] The object of the present invention is to provide a textile-based oil-absorbing material and its application in heavy oil light and heat absorption, which solves the problem of low oil absorption efficiency of conventional oil-absorbing materials for heavy oil.

[0006] The present invention achieves the above-mentioned purpose through the following technical solutions: A textile-based oil-absorbing material is prepared by the following method: S1, taking multi-walled carbon nanotubes and modified Fe3O4 powder, mixing them, adding sodium dodecylbenzenesulfonate aqueous solution, and ultrasonically treating them in an ice bath to form a homogeneous suspension; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide, stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing to obtain an electrospinning solution; S3, electrospinning the electrospinning solution into a web to obtain a fiber web, then evenly spraying 4-8% of the modified millipede shell powder by weight of the fiber web onto the surface of the fiber web, heating the fiber web to 110-120° C. and maintaining the temperature for 6-8 seconds to soften the fiber web and combine it with the modified millipede shell powder; S4. Pre-oxidize the fiber web 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 it to 750-800° C. at a heating rate of 3-5° C. / min under inert gas protection, then keep it warm for 1-2 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing material.

[0007] A further improvement is that in step S1, the mass ratio of the multi-walled carbon nanotubes, modified Fe3O4 powder and sodium dodecylbenzenesulfonate aqueous solution is 1-3:0.5-1.5:50, and sodium dodecylbenzenesulfonate accounts for 0.3-0.5% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder.

[0008] A further improvement is that in step S1, the preparation method of the modified Fe3O4 powder is: Take cyclohexane, add nonylphenol polyoxyethylene ether (0.04-0.08% by volume of the cyclohexane), stir and disperse evenly to obtain an emulsion, then dropwise add ferric chloride hexahydrate (0.4-0.8 mol / L by volume of the cyclohexane) and ammonia (1.5-2.5 mol / L by volume of the cyclohexane) to the emulsion, and stir to react to obtain a Fe3O4 particle dispersion; To the Fe3O4 particle dispersion, 16-20% by volume of ethyl orthosilicate and 15-20% by volume of cyclohexane and 1.5-2.5 mol / L ammonia water were added dropwise, and the mixture was stirred to react to obtain Fe3O4 composite particles coated with silica. Separate the Fe3O4 composite particles and add them to ethanol at a ratio of 1g particles to 50-60mL ethanol. Heat to 55-60℃ and stir evenly. Then add hexamethyldisilazane (12-16% by volume of ethanol) and heat to 120-130℃, stirring and reacting for 1.5-2.5h. The Fe3O4 composite particles are separated, washed and dried to obtain modified Fe3O4 powder.

[0009] A further improvement is that 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.

[0010] A further improvement is 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.

[0011] A further improvement is that in step S2, the pressure of the vacuum degassing treatment is -0.1 MPa and the time is 2-3 hours.

[0012] A further improvement is that in step S3, the electrospinning voltage is 15-25 kV, the liquid supply rate 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 speed is 10-50 rpm.

[0013] A further improvement is that in step S3, the preparation method of the modified millipede shell powder is as follows: after washing and removing impurities from artificially cultured millipedes, the millipedes are soaked in a 0.3-0.5M HCl solution for 0.5-1.5 hours, taken out, freeze-dried and crushed to obtain shell powder, the shell powder is immersed in an ethanol solution containing 8-12wt% ethyl orthosilicate for 1.5-2 hours, the shell powder is taken out and solidified at 50-60°C for 8-12 hours, and then the shell powder is immersed in an acetic acid solution containing 1.5-2wt% chitosan and 0.8-1.2wt% boric acid, stirred at 50-60°C for 2-4 hours, and finally the shell powder is taken out, washed and dried to obtain the modified millipede shell powder.

[0014] A further improvement is that the shell powder has a particle size of 60-80 μm.

[0015] The present invention also provides an application of the textile-based oil-absorbing material in light and heat absorption of heavy oil.

[0016] The beneficial effects of the present invention are: (1) The oil-absorbing material adopts the dual photothermal synergistic factors of multi-walled carbon nanotubes and modified Fe3O4 powder. By utilizing the wide spectrum absorption characteristics of multi-walled carbon nanotubes and the near-infrared response characteristics of modified Fe3O4 powder, the overall photothermal efficiency of the material is greatly enhanced, thereby effectively solving the problem of low oil absorption efficiency of conventional oil-absorbing materials for heavy oil.

[0017] Among them, the modified Fe3O4 powder is coated with a thin layer of silicon dioxide and surface treated with hexamethyldisilazane, which greatly improves the dispersibility and compatibility of the powder without affecting the near-infrared response characteristics, thereby ensuring its compounding effect with multi-walled carbon nanotubes and avoiding sedimentation and agglomeration.

[0018] (2) The oil-absorbing material adopts a porous textile-based structure, and its surface is hydrophobically modified, which can show excellent hydrophobicity and lipophilicity, and helps to achieve efficient oil-water separation.

[0019] Specifically, the oil-absorbing material is loaded with modified millipede shell powder on the surface of the fiber mesh. After carbonization, the porous skeleton is further improved, and the hydrophobic oil-absorbing performance of the material is enhanced. The self-modification treatment 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 mesh, thereby ensuring that it exerts a hydrophobic oil-absorbing effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is the transmission electron microscopy image of the modified Fe3O4 powder; Figure 2 The digital images of each group of textile-based oil-absorbing materials when a water droplet contacts the surface; Figure 3 These are digital images of each group of textile-based oil-absorbing materials when an oil droplet contacts the surface. DETAILED DESCRIPTION

[0021] The present application is further described in detail below in conjunction with the accompanying drawings. It is necessary to point out here that the following specific implementation methods are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Technical personnel in this field can make some non-essential improvements and adjustments to the present application based on the above application content.

[0022] 1. Main Materials Multi-walled carbon nanotubes: purchased from Shanghai Yaotian New Materials Technology Co., Ltd. Ferric chloride hexahydrate: FeCl3·6H2O, purchased from Wuhan Xingzhongcheng Technology Co., Ltd.; Sodium dodecylbenzenesulfonate: purchased from Jinan Maoxin Chemical Co., Ltd. Polyacrylonitrile fiber: diameter of about 12 μm, purchased from Changzhou Bochao Engineering Materials Co., Ltd. N,N-dimethylformamide: purchased from Shandong Maofa Chemical Co., Ltd. Polydimethylsiloxane: molecular weight 15000, purchased from Guangzhou Huazhiwang Chemical Co., Ltd. Dibutyltin dilaurate: purchased from Shandong Yaotong Industrial Co., Ltd. Millipedes: purchased from Xunqiancao agricultural and sideline products purchasing and selling store in Qiaocheng District, Bozhou City.

[0023] 2. Implementation of the Experiment Example 1 A textile-based oil-absorbing material is prepared by the following method: 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: 35 kHz, power: 500 W, treatment time: 3 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 1:0.5:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.3% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder; The preparation method of the modified Fe3O4 powder is as follows: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.04% by volume of the cyclohexane, stirring and dispersing uniformly to obtain an emulsion, then dripping ferric chloride hexahydrate aqueous solution accounting for 3% by volume of the cyclohexane and having a concentration of 0.8 mol / L, and ammonia water accounting for 6% by volume of the cyclohexane and having a concentration of 2.5 mol / L into the emulsion, stirring and reacting to obtain a Fe3O4 particle dispersion; dripping ethyl orthosilicate accounting for 16% by volume of the cyclohexane into the Fe3O4 particle dispersion; , and 2.5 mol / L ammonia water accounting for 15% 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: 50mL of ethanol, heating to 55°C and stirring evenly, then adding hexamethyldisilazane accounting for 12% by volume of ethanol, heating to 120°C and stirring for 2.5h; separating the Fe3O4 composite particles, washing and drying them, and obtaining modified Fe3O4 powder; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (pressure of -0.1 MPa, time for 2 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 10:90:2:0.8:0.01; S3, electrospinning the electrospinning solution into a web, the electrospinning voltage is 15 kV, the liquid supply rate is 2 mL / h, the receiving distance is 12 cm, the inner diameter of the needle is 0.3 mm, and the speed of the dynamic receiving aluminum roller is 10 rpm to obtain a fiber web, and then taking 4% of the modified millipede shell powder of the fiber web mass and spraying it evenly onto the surface of the fiber web, heating the fiber web to 110 ° C and maintaining it for 8 s to soften the fiber web and combine it with the modified millipede shell powder; The modified millipede shell powder is prepared by washing and removing impurities from artificially cultured millipedes, soaking them in a 0.3M HCl solution for 1.5 hours, taking them out, freeze-drying them, and crushing them to obtain shell powder with a particle size of about 60 μm, taking the shell powder and soaking it in an ethanol solution containing 8wt% ethyl orthosilicate for 2 hours, taking the shell powder out and curing it at 50°C for 12 hours, then soaking the shell powder in an acetic acid solution containing 1.5wt% chitosan and 0.8wt% boric acid, stirring and reacting at 50°C for 4 hours, and finally taking out the shell powder, washing it with water, and drying it to obtain the modified millipede shell powder. S4. Pre-oxidize the fiber web in an air atmosphere at 270° C. for 2.5 h, then place it in a high-temperature tube furnace, and heat it to 750° C. at a heating rate of 3° C. / min under inert gas protection, then keep it warm for 2 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing material.

[0024] Example 2 A textile-based oil-absorbing material is prepared by the following method: 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: 38 kHz, power: 550 W, treatment time: 2.5 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 2:1:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder; The preparation method of the modified Fe3O4 powder is as follows: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.06% by volume of cyclohexane, stirring and dispersing uniformly to obtain an emulsion, then dripping ferric chloride hexahydrate aqueous solution accounting for 4% by volume of cyclohexane and with a concentration of 0.6 mol / L, and ammonia water accounting for 7% by volume of cyclohexane and with a concentration of 2 mol / L to the emulsion, stirring and reacting to obtain a Fe3O4 particle dispersion; dripping ethyl orthosilicate accounting for 18% by volume of cyclohexane, and 2 mol / L ammonia water accounting for 18% by volume of cyclohexane to the Fe3O4 particle dispersion. L of ammonia water, stirred and reacted to obtain Fe3O4 composite particles with silica coated on the surface; the Fe3O4 composite particles were separated and added to ethanol at a ratio of 1g particles: 55mL ethanol, heated to 58℃ and stirred evenly, and then hexamethyldisilazane accounting for 14% of the volume of ethanol was added, and the temperature was raised to 125℃ and stirred for 2h; the Fe3O4 composite particles were separated, washed and dried to obtain modified Fe3O4 powder; the morphology of the prepared modified Fe3O4 powder was characterized using a transmission electron microscope (JEM-1200EX), and the results are as follows Figure 1 As shown, it can be seen that the powder is spherical nanometer level, and there is no obvious agglomeration between the particles, and the dispersion is good.

[0025] S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (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; S3, electrospinning the electrospinning solution into a web, 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 6% of the modified millipede shell powder of the fiber web mass and spraying it evenly onto the surface of the fiber web, heating the fiber web to 115 ° C and maintaining it for 7 seconds to soften the fiber web and combine it with the modified millipede shell powder; 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. 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.

[0026] Example 3 A textile-based oil-absorbing material is prepared by the following method: 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; 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; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (pressure of -0.1 MPa, time for 3 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 12:100:2:0.9:0.015; S3, electrospinning the electrospinning solution into a web, the electrospinning voltage is 25 kV, the liquid supply rate is 4 mL / h, the receiving distance is 18 cm, the inner diameter of the needle is 0.5 mm, and the dynamic receiving aluminum roller speed is 50 rpm to obtain a fiber web, and then taking 8% of the modified millipede shell powder of the fiber web mass and spraying it evenly onto the surface of the fiber web, heating the fiber web to 120 ° C and maintaining it for 6 seconds to soften the fiber web and combine it with the modified millipede shell powder; The modified millipede shell powder is prepared by washing and removing impurities from artificially cultured millipedes, soaking them in a 0.5M HCl solution for 0.5 h, taking them out, freeze-drying them, and crushing them to obtain shell powder with a particle size of about 80 μm, taking the shell powder and immersing it in an ethanol solution containing 12 wt% ethyl orthosilicate for 1.5 h, taking the shell powder out and curing it at 60° C. for 8 h, then immersing the shell powder in an acetic acid solution containing 2 wt% chitosan and 1.2 wt% boric acid, stirring and reacting at 60° C. for 2 h, and finally taking out the shell powder, washing it with water, and drying it to obtain the modified millipede shell powder. S4. Pre-oxidize the fiber web in an air atmosphere at 280° C. for 1.5 h, then place it in a high-temperature tube furnace, and heat it to 800° C. at a heating rate of 5° C. / min under inert gas protection, then keep it warm for 1 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing material.

[0027] Comparative Example 1 A textile-based oil-absorbing material is prepared by the following method: S1. Mix multi-walled carbon nanotubes and Fe3O4 powder, add an aqueous solution of sodium dodecylbenzenesulfonate, and ultrasonically treat the mixture in an ice bath (frequency: 38 kHz, power: 550 W, treatment time: 2.5 h) to form a homogeneous suspension; the mass ratio of the multi-walled carbon nanotubes, Fe3O4 powder, and aqueous solution of sodium dodecylbenzenesulfonate is 2:1:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and Fe3O4 powder; The preparation method of the Fe3O4 powder comprises: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.06% by volume of the cyclohexane, stirring and dispersing the mixture uniformly to obtain an emulsion, then dropwise adding ferric chloride hexahydrate aqueous solution accounting for 4% by volume of the cyclohexane and having a concentration of 0.6 mol / L, and ammonia water accounting for 7% by volume of the cyclohexane and having a concentration of 2 mol / L, to the emulsion, stirring and reacting to obtain a Fe3O4 particle dispersion; separating the Fe3O4 particles, washing, and drying the particles to obtain Fe3O4 powder; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (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; S3, electrospinning the electrospinning solution into a web, 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 6% of the modified millipede shell powder of the fiber web mass and spraying it evenly onto the surface of the fiber web, heating the fiber web to 115 ° C and maintaining it for 7 seconds to soften the fiber web and combine it with the modified millipede shell powder; 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. 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.

[0028] Comparative Example 2 A textile-based oil-absorbing material is prepared by the following method: 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: 38 kHz, power: 550 W, treatment time: 2.5 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 2:1:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder; The preparation method of the modified Fe3O4 powder is as follows: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.06% of the volume of cyclohexane, stirring and dispersing uniformly to obtain an emulsion, then dripping ferric chloride hexahydrate aqueous solution accounting for 4% of the volume of cyclohexane and with a concentration of 0.6 mol / L, and ammonia water accounting for 7% of the volume of cyclohexane and with a concentration of 2 mol / L, stirring and reacting to obtain a Fe3O4 particle dispersion; dripping tetraethyl orthosilicate accounting for 18% of the volume of cyclohexane into the Fe3O4 particle dispersion; Ester, and 2 mol / L ammonia water accounting for 18% by volume of cyclohexane, stirred and reacted to obtain Fe3O4 composite particles with surface coating of silica; separated Fe3O4 composite particles were added to ethanol at a ratio of 1g particles: 55mL of ethanol, heated to 58°C and stirred evenly, and then hexamethyldisilazane accounting for 14% by volume of ethanol was added, heated to 125°C and stirred for 2h; separated Fe3O4 composite particles were washed and dried to obtain modified Fe3O4 powder; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (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; 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 dynamic receiving aluminum roller speed is 30 rpm to obtain a fiber web; 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.

[0029] Comparative Example 3 A textile-based oil-absorbing material is prepared by the following method: 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: 38 kHz, power: 550 W, treatment time: 2.5 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 2:1:50, and the sodium dodecylbenzenesulfonate in the aqueous solution of sodium dodecylbenzenesulfonate accounts for 0.4% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder; The preparation method of the modified Fe3O4 powder is as follows: taking cyclohexane, adding nonylphenol polyoxyethylene ether accounting for 0.06% by volume of cyclohexane, stirring and dispersing uniformly to obtain an emulsion, then dripping ferric chloride hexahydrate aqueous solution accounting for 4% by volume of cyclohexane and with a concentration of 0.6 mol / L, and ammonia water accounting for 7% by volume of cyclohexane and with a concentration of 2 mol / L to the emulsion, stirring and reacting to obtain a Fe3O4 particle dispersion; dripping ethyl orthosilicate accounting for 18% by volume of cyclohexane, and 2 mol / L ammonia water accounting for 18% by volume of cyclohexane to the Fe3O4 particle dispersion. L of ammonia water, stirred and reacted to obtain Fe3O4 composite particles with silica coated on the surface; the Fe3O4 composite particles were separated and added to ethanol at a ratio of 1g particles: 55mL ethanol, heated to 58℃ and stirred evenly, and then hexamethyldisilazane accounting for 14% of the volume of ethanol was added, and the temperature was raised to 125℃ and stirred for 2h; the Fe3O4 composite particles were separated, washed and dried to obtain modified Fe3O4 powder; the morphology of the prepared modified Fe3O4 powder was characterized using a transmission electron microscope (JEM-1200EX), and the results are as follows Figure 1 As shown, it can be seen that the powder is spherical nanometer level, and there is no obvious agglomeration between the particles, and the dispersion is good.

[0030] S2. Add polyacrylonitrile fiber to N,N-dimethylformamide and stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing (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; 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; 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; 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.

[0031] 3. Performance Testing (1) Surface wetting properties 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.

[0032] (2) Oil absorption performance 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.

[0033]

[0034] Where: m0 is the initial mass, unit is g; m1 is the mass after oil absorption, unit is g.

[0035] 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.

[0036] 4. Results Analysis (1) Surface wetting properties 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.

[0037] (2) Oil absorption performance 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: Table 1: Oil absorption ratio of each group of textile-based oil-absorbing materials at room temperature and light-heat absorption

[0038] As can be seen from Table 1 above, the textile-based oil-absorbing material prepared in the present invention has outstanding oil absorption performance, especially Example 2, whose room temperature oil absorption rate reaches 45.14 g / g and the photothermal oil absorption rate reaches 62.17 g / g. In Comparative Example 1, the Fe3O4 powder was not coated with a thin layer of silicon dioxide and surface treated with hexamethyldisilazane. Its oil absorption performance and room temperature oil absorption rate were slightly lower than those in Example 2, but the photothermal oil absorption rate was significantly lower. This shows that the modification of the Fe3O4 powder can significantly improve its photothermal performance. In Comparative Example 2, the modified millipede shell powder was not loaded on the surface of the fiber web. Its room temperature and photothermal oil absorption rates were significantly lowered, which were 21.6% and 18.7% lower than those in Example 2, respectively. In Comparative Example 3, the modified millipede shell powder was replaced with ordinary millipede shell powder. Its room temperature and photothermal oil absorption rates were also significantly lowered, which were 11.1% and 12.6% lower than those in Example 2, respectively. This further shows that the modified millipede shell powder plays an important role in promoting the oil absorption performance of the material.

[0039] The above-described embodiments merely illustrate several implementations of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, and all such variations and improvements fall within the scope of protection of the present invention.

Claims

1. A textile-based oil-absorbing material, characterized in that: It is prepared by the following method: S1, taking multi-walled carbon nanotubes and modified Fe3O4 powder, mixing them, adding sodium dodecylbenzenesulfonate aqueous solution, and ultrasonically treating them in an ice bath to form a homogeneous suspension; S2. Add polyacrylonitrile fiber to N,N-dimethylformamide, stir until completely dissolved, then add the suspension, continue stirring and dropwise add polydimethylsiloxane hydrophobic modifier and dibutyltin dilaurate catalyst, and perform vacuum degassing to obtain an electrospinning solution; S3, electrospinning the electrospinning solution into a web to obtain a fiber web, then evenly spraying 4-8% of the modified millipede shell powder by weight of the fiber web onto the surface of the fiber web, heating the fiber web to 110-120° C. and maintaining the temperature for 6-8 seconds to soften the fiber web and combine it with the modified millipede shell powder; S4. Pre-oxidize the fiber web 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 it to 750-800° C. at a heating rate of 3-5° C. / min under inert gas protection, then keep it warm for 1-2 h, and finally cool it naturally to room temperature to obtain the textile-based oil-absorbing 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 sodium dodecylbenzenesulfonate aqueous solution is 1-3:0.5-1.5:50, and sodium dodecylbenzenesulfonate accounts for 0.3-0.5% of the total mass of the multi-walled carbon nanotubes and modified Fe3O4 powder.

3. A textile-based oil-absorbing material according to claim 1, characterized in that: In step S1, the preparation method of the modified Fe3O4 powder is: Take cyclohexane, add nonylphenol polyoxyethylene ether (0.04-0.08% by volume of the cyclohexane), stir and disperse evenly to obtain an emulsion, then dropwise add ferric chloride hexahydrate (0.4-0.8 mol / L by volume of the cyclohexane) and ammonia (1.5-2.5 mol / L by volume of the cyclohexane) to the emulsion, and stir to react to obtain a Fe3O4 particle dispersion; To the Fe3O4 particle dispersion, 16-20% by volume of ethyl orthosilicate and 15-20% by volume of cyclohexane and 1.5-2.5 mol / L ammonia water were added dropwise, and the mixture was stirred to react to obtain Fe3O4 composite particles coated with silica. Separate the Fe3O4 composite particles and add them to ethanol at a ratio of 1g particles to 50-60mL ethanol. Heat to 55-60℃ and stir evenly. Then add hexamethyldisilazane (12-16% by volume of ethanol) and heat to 120-130℃, stirring and reacting for 1.5-2.5h. The Fe3O4 composite particles are separated, washed and dried to obtain modified Fe3O4 powder.

4. A textile-based oil-absorbing material according to claim 1, characterized in that: 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 hours.

5. A textile-based oil-absorbing material according to claim 1, characterized 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.

6. A textile-based oil-absorbing material according to claim 1, characterized in that: In step S2, the vacuum degassing treatment is performed at a pressure of -0.1 MPa for 2-3 hours.

7. A textile-based oil-absorbing material according to claim 1, characterized in that: In step S3, the voltage of the electrospinning is 15-25 kV, the liquid supply rate 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 speed of the dynamic receiving aluminum roller is 10-50 rpm.

8. The textile-based oil-absorbing material according to claim 1, characterized in that: In step S3, the preparation method of the modified millipede shell powder is as follows: after washing and removing impurities from artificially cultured millipedes, soaking them in a 0.3-0.5M HCl solution for 0.5-1.5h, taking them out, freeze-drying and crushing them to obtain shell powder, taking the shell powder and immersing it in an ethanol solution containing 8-12wt% ethyl orthosilicate for 1.5-2h, after taking out the shell powder, curing it at 50-60°C for 8-12h, and then immersing the shell powder in an acetic acid solution containing 1.5-2wt% chitosan and 0.8-1.2wt% boric acid, stirring and reacting at 50-60°C for 2-4h, and finally taking out the shell powder, washing and drying it to obtain the modified millipede shell powder.

9. A textile-based oil-absorbing material according to claim 8, characterized in that: The particle size of the shell powder is 60-80 μm.

10. Use of the textile-based oil-absorbing material according to any one of claims 1 to 9 in light and heat absorption of heavy oil.

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