Preparation method of photo-thermal super-hydrophobic material and continuous recovery device and method for high-viscosity spilled oil on water surface

Abstract

The invention discloses a preparation method of a photo-thermal super-hydrophobic material and a continuous recovery device and method for high-viscosity spilled oil on a water surface, and belongs to the technical field of spilled oil adsorption. The preparation method of the photo-thermal super-hydrophobic material comprises the following steps: selecting a waste textile fabric with compression-recovery performance as a raw material, firstly putting the waste textile fabric in an ethanol solution for ultrasonic treatment, then soaking the waste textile fabric in an aqueous solution containing Tris-HCl and dopamine hydrochloride, and oscillating at a constant temperature; the preparation method comprises the following steps of: soaking in a pyrrole aqueous solution, adding anhydrous FeCl3, oscillating at room temperature, and soaking in an aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine after pyrrole is completely polymerized; and finally, soaking in an ethyl acetate solution containing polydimethylsiloxane and a curing agent, and heating and curing after soaking to obtain the photo-thermal super-hydrophobic material. The material not only realizes efficient cyclic utilization of textile wastes, but also has excellent photo-thermal performance and compressible recovery performance under a high-viscosity-wet condition.

Description

Technical Field

[0001] This invention relates to the field of oil spill adsorption technology, specifically to a method for preparing a photothermal superhydrophobic material, and a device and method for continuous recovery of high-viscosity oil spills on the water surface using the photothermal superhydrophobic material prepared by this method. Background Technology

[0002] Oil pollution problems caused by oil transportation, processing, storage, and the discharge of oily wastewater are becoming increasingly serious, attracting widespread attention from all sectors of society, especially the frequent oil spills during crude oil extraction and transportation. These oil spills not only cause huge energy waste but also cause serious environmental pollution, threatening the marine ecosystem and human health. Currently, commonly used methods for handling marine oil spills include combustion, biodegradation, chemical dispersion, and physical adsorption. Compared with other methods, physical adsorption can collect and reuse spilled oil while adsorbing it, and it does not cause secondary pollution to the environment, making it considered the most ideal method for treating marine oil spills and oily wastewater. Some traditional oil-absorbing materials include biomass-based oil-absorbing materials such as straw, cotton, corn cobs, and bagasse; and inorganic oil-absorbing materials such as perlite, silica, zeolite, and graphite. These traditional oil-absorbing materials have advantages such as abundant natural resources, low cost, biodegradability, and no secondary pollution to the environment. However, they have problems such as low separation efficiency, adsorption of water while adsorbing crude oil, and poor recyclability, which seriously limit their development and application.

[0003] In the field of oil-water separation, materials with special wettability, such as superhydrophobic and superoleophilic separation materials, have been widely studied and applied. These materials typically possess a rough surface microstructure and low surface energy, resulting in high selectivity for oil or water. Their surfaces can selectively filter or adsorb oily substances floating on the sea surface while repelling water, thus achieving the adsorption of leaked crude oil. Common three-dimensional oil-absorbing materials, such as aerogels, are considered ideal crude oil recovery adsorbents due to their advantages of low cost, high porosity, and high separation efficiency. In recent years, researchers have developed various aerogels for the cleanup and recovery of leaked crude oil, mainly including carbon-based aerogels, modified commercial sponges, and biomass-based aerogels. Carbon-based aerogels rely on expensive raw materials such as carbon nanotubes and graphene, leading to high costs and low reusability, which limits their widespread application. Modified commercial sponges have advantages such as low cost, good compression resilience, and simple modification processes; however, their hydrophobic groups are only distributed on the surface, and once cut or damaged, the superhydrophobic-superoleophilic properties are difficult to maintain. The preparation of biomass-based aerogels largely relies on chemical vapor deposition, which hinders large-scale production and limits their widespread application. Furthermore, most aerogel materials currently exhibit low mechanical strength in the wet state, especially after adsorbing high-viscosity crude oil, resulting in severe internal structural collapse and near-complete destruction of the structure after extrusion and adsorption of spilled oil. Current published aerogel materials focus on the adsorption and extrusion recovery of low-viscosity oil droplets and organic solvents, failing to achieve continuous adsorption and extrusion recovery of high-viscosity crude oil. Therefore, aerogel materials cannot be combined with effective oil-water separation devices to achieve large-scale continuous crude oil recovery.

[0004] my country is the world's largest producer and consumer of textiles, processing over 50% of the global total of textile fibers. However, the country has a massive stockpile of waste textiles, and their potential for resource utilization has not been fully exploited. Reports indicate that my country generates over 6 million tons of waste textiles annually, but the recycling rate is only around 20%, highlighting the urgent need to build a resource-recycling industrial system and a waste material recycling system. Summary of the Invention

[0005] To address the aforementioned technical problems, one objective of this invention is to propose a method for preparing a photothermal superhydrophobic material. This method utilizes textiles with compression-recovery properties, such as waste mops, as raw materials to prepare a photothermal superhydrophobic material. This material possesses excellent photothermal properties and compressibility-recovery properties under high viscosity-wet conditions, enabling in-situ heating of high-viscosity crude oil and rapid alteration of its rheological properties to achieve rapid adsorption of floating oil.

[0006] The technical solution adopted in this invention is as follows:

[0007] A method for preparing a photothermal superhydrophobic material includes the following steps:

[0008] (1) Select waste textiles with compression-recovery properties as raw materials, place them in an ethanol solution for ultrasonic treatment, and then dry them for later use.

[0009] (2) The dried waste textile obtained in step (1) is soaked in an aqueous solution containing Tris-HCl and dopamine hydrochloride, shaken at a constant temperature, then washed with deionized water and dried to obtain polydopamine textile.

[0010] (3) The polydopamine textile obtained in step (2) is soaked in pyrrole aqueous solution, anhydrous FeCl3 is added, and the mixture is shaken at room temperature. After the pyrrole is completely polymerized, it is taken out and washed with deionized water. After drying, the photothermal composite textile is obtained.

[0011] (4) Dissolve dopamine hydrochloride and polyethyleneimine in Tris-HCl buffer to obtain an aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine; wet the photothermal composite textile obtained in step (3) with alcohol and soak it in the aqueous solution, shake at room temperature, then wash with deionized water and dry to obtain a photothermal enhanced composite textile.

[0012] (5) The photothermal enhanced composite textile obtained in step (4) is immersed in an ethyl acetate solution containing polydimethylsiloxane and curing agent. After immersion, it is heated and cured to obtain a photothermal superhydrophobic material.

[0013] The second objective of this invention is to provide a continuous recovery device for high-viscosity oil spills on the water surface, which uses a photothermal superhydrophobic material prepared by the method described above.

[0014] The device also includes a frame, on which a conveying mechanism is provided; a heating zone is provided at the end of the frame, and a heating mechanism is provided at the heating zone; an oil spill absorption zone is provided below the heating zone; and a squeezing recovery zone is provided in the middle of the frame, and a squeezing mechanism is provided in the squeezing recovery zone.

[0015] The conveying mechanism includes a motor, a drive wheel, a transmission wheel assembly, and a rotary conveyor belt. The rotary conveyor belt is wound around the drive wheel and the transmission wheel assembly. The motor drives the drive wheel to rotate via a synchronous belt, and the drive wheel drives the transmission wheel assembly to rotate via the rotary conveyor belt. The photothermal superhydrophobic material is disposed on the outer side of the rotary conveyor belt.

[0016] The heating mechanism includes a light source simulator and / or an electric heating plate for heating the photothermal superhydrophobic material;

[0017] The extrusion mechanism includes an extrusion roller assembly, which includes two cooperating extrusion rollers. The distance between the two extrusion rollers allows the photothermal superhydrophobic material to pass through and extrudes the photothermal superhydrophobic material.

[0018] An oil collection tank is provided below the extrusion mechanism.

[0019] The third objective of this invention is to propose a method for continuous recovery of high-viscosity oil spills on water surfaces. This method employs the aforementioned continuous recovery device for high-viscosity oil spills on water surfaces, comprising the following steps: A photothermal superhydrophobic material is used as the oil-absorbing material and moves along a rotary conveyor belt. First, it passes through a heating zone where the material is preheated by a heating mechanism. Then, it enters an oil spill adsorption zone for oil adsorption. Next, the oil-adsorbed material is conveyed to a compression recovery zone where a compression mechanism squeezes out the oil, which then falls into an oil collection tank below for recovery. The compressed oil-absorbing material returns along the rotary conveyor belt to the next working cycle, thus continuously recovering high-viscosity crude oil.

[0020] The beneficial technical effects of the present invention are as follows:

[0021] (1) This invention utilizes waste textiles with compression-recovery properties, such as waste mops, as raw materials. The waste mops are preferably adhesive flat mops, which include a sponge layer and a fiber adsorption layer on one side of the sponge layer. Combined with corresponding superhydrophobic treatment processes, the prepared photothermal superhydrophobic material has excellent photothermal properties and compressible recovery properties under high viscosity-wet conditions. It can heat high viscosity crude oil in situ after preheating treatment, quickly change the rheological properties of high viscosity crude oil to achieve rapid adsorption of floating oil. Moreover, after the high viscosity crude oil is recovered by extrusion, the photothermal superhydrophobic material can quickly recover to its original form.

[0022] (2) The waste adhesive flat mop used in this invention is a composite fabric adsorption material that can be purchased directly from the market. It consists of a porous polyurethane sponge layer and a surface adsorption layer on its surface. The surface adsorption layer is made of fiber material, such as an array of fiber tentacles or a coil arrangement of several fiber yarns. The unique structural design gives it excellent adsorption performance. The surface adsorption layer adopts a composite fiber yarn winding structure to form a three-dimensional array structure similar to "tentacles". It achieves instantaneous capture by increasing the contact area with oil and realizes rapid directional transport of oil through capillary channels between fibers. Under wet conditions, the material exhibits excellent recoverability. When compressed, its "tentacle" structure will collapse, but this deformation is reversible. When the external force is removed, it can quickly restore the initial configuration and maintain structural integrity. The porous sponge layer has the structural characteristics of high specific surface area and high porosity, which not only provides sufficient oil storage space, but also enhances capillary force, thereby significantly improving the adsorption capacity of the material and exhibiting excellent oil absorption performance. Furthermore, the three-dimensional porous structure provides elastic support, improving the compressibility of the mop and ensuring structural stability even after repeated compressions. This characteristic effectively solves the problems of low mechanical strength of traditional aerogel materials in a wet state, limitations in the adsorption-extrusion-recovery of low-viscosity oils, severe structural collapse during the adsorption of high-viscosity oils, and difficulty in reuse after extrusion and recovery.

[0023] (3) This invention uses polydopamine (PDA) to connect polypyrrole (PPy) and mops, etc., to attach photothermal chemically chained polypyrrole to the surface of the oil-absorbing material. In the preparation of PDA-PPy, Fe... 3+ PDA-PPy nanoparticles were synthesized by inducing copolymerization of DA and Py monomers, with non-covalent bond interactions (π-π stacking and hydrogen bonding) between polydopamine and polypyrrole chains. This enhanced the uniformity of the oil-absorbing material and provided stable photothermal conversion performance. Through efficient photothermal conversion, the viscosity of high-viscosity oils was effectively reduced, oil flowability was improved, and the adsorption capacity of the oil-absorbing material for high-viscosity oils was enhanced.

[0024] (4) This invention uses polydopamine (PDA) to copolymerize with polyethyleneimine (PEI) to form a more stable and uniform network structure. The catechol groups in PDA can interact with various substrates, and the molecules can also form non-covalent cross-linked structures through π-π stacking and hydrogen bonding. The addition of PEI will cause a Michael addition reaction with DA, which not only shortens the deposition time of PDA on the material surface, but also forms a more uniform and stable network structure. The PEI-PDA coating can also interact with various substrates. In the PEI-PDA coating, PDA can still exist as a "reaction platform" to provide interaction, while the presence of PEI disrupts the non-covalent interaction in the PDA aggregates, improving the stability of the coating. This step effectively encapsulates PPy between the material and the PEI-PDA layer, forming a layered sandwich structure (PEI-PDA / PPy / PDA@Mop).

[0025] (5) This invention utilizes polydimethylsiloxane as a hydrophobic agent to modify oil-absorbing materials for hydrophobic modification. A simple impregnation coating process is used to deposit PDMS onto the surface of PEI-PDA / PPy / PDA@Mop, transforming the hydrophilic groups on the surface of the oil-absorbing material into hydrophobic groups, thereby improving the oil-water selectivity of the oil-absorbing material and preparing a superhydrophobic coating with high surface roughness and low surface energy. Furthermore, PDMS has high transparency and will not affect the photothermal properties of the material. After high-temperature curing, a photothermal superhydrophobic oil-water separation material with excellent compression recovery, efficient photothermal conversion capability, excellent oil-water selectivity, and the ability to rapidly capture and transport oil was successfully prepared.

[0026] (6) The photothermal superhydrophobic material prepared by this invention has excellent cyclic compression performance and stable oil absorption ratio. During 100 adsorption-desorption cycles, its adsorption capacity did not decrease significantly, and the adsorption capacity for dichloromethane and n-hexane was 99.1% and 95.2% of the initial adsorption capacity, respectively. After 100 compression absorption cycles in n-hexane and crude oil, the basic shape of PDMS / PEI-PDA / PPy / PDA@Mop hardly changed, and its adsorption capacity did not decrease significantly.

[0027] (7) The photothermal superhydrophobic material prepared by this invention has excellent photothermal conversion ability, at 0.10 W / cm 2 Under certain light intensity, the oil-absorbing material rapidly increased in temperature to approximately 99.6℃ within 140 seconds and remained stable at 0.20 W / cm². 2Under the specified light intensity, the oil-absorbing material rapidly increased in temperature to approximately 143.2℃ within 140 seconds and remained stable. Furthermore, the modified oil-absorbing material exhibited excellent temperature response and higher photosensitivity. After five repeated on / off cycles, the modified oil-absorbing material reached the same steady-state temperature, demonstrating its rapid light response and stable photothermal conversion. This implies that the addition of PDA and PPy significantly improved the photothermal conversion efficiency.

[0028] (8) During the oil adsorption process, the photothermal superhydrophobic oil-absorbing material of the present invention exhibits excellent adsorption performance for various organic solvents and oils of different viscosities, and can still maintain good absorption and separation capabilities and mechanical properties after repeated adsorption-desorption multiple times.

[0029] (9) The photothermal superhydrophobic material (PDMS / PEI-PDA / PPy / PDA@Mop) prepared by this invention has excellent mechanical stability, photothermal conversion capability, and stable oil-water separation performance, and can widely adsorb various oils and organic solvents. In addition, under light-assisted heating, the PDMS / PEI-PDA / PPy / PDA@Mop material can significantly improve the adsorption efficiency of high-viscosity crude oil through in-situ heating, thus providing an innovative solution for developing efficient oil-absorbing materials for leaking high-viscosity crude oil.

[0030] (10) This invention also provides a device and method for continuous recovery of high-viscosity oil spills on water surfaces. The recovery device has a simple structure and is easy to operate. It can simulate the continuous recovery of high-viscosity oil spills on water surfaces. The oil-absorbing material is preheated by a heating mechanism and then enters the oil spill adsorption area for oil adsorption. The oil-absorbing material with adsorbed oil is then conveyed to the compression recovery area, where the oil is squeezed out by a compression mechanism and falls into the oil collection tank below for recovery. The oil-absorbing material then returns to its pre-compression state and enters the next working cycle to continuously recover high-viscosity crude oil. This invention can achieve continuous recovery of high-viscosity crude oil in crude oil spill cleanup and recovery. Attached Figure Description

[0031] Figure 1 The images show the microstructure of the photothermal superhydrophobic material prepared in this invention using SEM images; where a1-e1 are SEM images of the material surface structure; and a2-e2 and a3-e3 are SEM images of the polyurethane sponge structure, respectively.

[0032] Figure 2 The static water contact angle image of PDMS / PEI-PDA / PPy / PDA@Mop obtained by this invention;

[0033] Figure 3 The WCA of the PDMS / PEI-PDA / PPy / PDA@Mop prepared according to the present invention is shown under various conditions;

[0034] Figure 4 The photothermal properties of PDMS / PEI-PDA / PPy / PDA@Mop prepared according to the present invention are shown.

[0035] Figure 5 The wetting properties of PDMS / PEI-PDA / PPy / PDA@Mop prepared according to the present invention are shown.

[0036] Figure 6 This invention demonstrates the oil adsorption performance of PDMS / PEI-PDA / PPy / PDA@Mop prepared according to the present invention;

[0037] Figure 7 The image shows a comparison of the above-water and underwater adsorption rates of oil droplets of different viscosities by PDMS / PEI-PDA / PPy / PDA@Mop prepared in this invention under light and dark conditions.

[0038] Figure 8 A comparison of the penetration rates of high-viscosity crude oil on different material surfaces under conditions of light and darkness;

[0039] Figure 9 A comparison of the penetration rates of high-viscosity crude oil on the PDMS / PEI-PDA / PPy / PDA@Mop surface prepared in this invention under different light intensities;

[0040] Figure 10 This is a schematic diagram illustrating the principle of oil absorption and desorption circulation using waste adhesive flat mops in this invention.

[0041] Figure 11 This is a schematic diagram illustrating the structural principle of the continuous oil spill recovery device for high viscosity water surface provided in an embodiment of the present invention.

[0042] Figure 12 This is a three-dimensional structural diagram of a continuous oil spill recovery device for high viscosity water surface provided in an embodiment of the present invention.

[0043] In the diagram: 1-Drive wheel end, 2-Light source simulator, 3-Drive wheel, 4-First transmission wheel, 5-Second transmission wheel, 6-Third transmission wheel, 7-Heating plate, 8-Oil-water tank; 9-First extrusion roller, 10-Second extrusion roller, 11-Pressure regulator, 12-Pressure sensor, 13-Retractable bracket, 14-Oil collection tank, 15-Pressure gauge, 16-Thermometer, 17-Motor, 18-Motor tachometer, 19-Motor speed regulator, 20-Emergency stop button, 21-Steel plate, 22-Side support plate, 23-Frame, 24-Rotary conveyor belt, 25-Polyurethane foam layer, 26-Tent structure. Detailed Implementation

[0044] This invention proposes a method for preparing a photothermal superhydrophobic material and a device and method for continuous recovery of high-viscosity oil spills from water surfaces. The photothermal superhydrophobic material prepared by this invention exhibits excellent adsorption and photothermal properties, compressibility recovery performance under high-viscosity-wet conditions, and a stable oil absorption ratio. Its efficient photothermal conversion capability creates conditions for rapid adsorption of high-viscosity oil; it can heat high-viscosity crude oil in situ, rapidly changing the rheological properties of the high-viscosity crude oil to achieve rapid adsorption of floating oil. Moreover, the photothermal superhydrophobic material prepared by this invention has excellent compressibility and repeated oil absorption characteristics. After repeated adsorption and compression recovery of high-viscosity crude oil, it still maintains good compressibility recovery, and the adsorption capacity is basically unaffected.

[0045] Based on the photothermal superhydrophobic material prepared in this invention, a continuous oil spill recovery device for high-viscosity oil spills on the water surface was also designed. This device comprises four parts: a photo-electric heating zone, an oil spill adsorption zone, a compression recovery zone, and a conveying mechanism. The photothermal superhydrophobic material can be fixed to the rotary conveyor belt of the recovery device using adhesive materials, enabling continuous transport. This design ensures transport stability and supports rapid replacement of different oil-absorbing materials. The specific workflow of the recovery device is as follows: first, the material is preheated in the photo-electric heating zone, then enters the oil spill adsorption zone for oil adsorption, and then is conveyed to the compression recovery zone for compression recovery. Finally, the material returns to the oil adsorption zone via the rotary conveyor belt to enter the next working cycle. Through continuous adsorption and compression cycles, this device achieves efficient and continuous recovery of high-viscosity crude oil, providing a reliable technical solution for marine oil spill treatment.

[0046] This invention transforms waste textile materials such as adhesive flat mops into oil-absorbing materials, which not only achieves efficient recycling of textile waste, but also effectively removes oil spills at sea, thus achieving the dual benefits of environmental protection and resource regeneration.

[0047] Specifically, a method for preparing a photothermal superhydrophobic material includes the following steps:

[0048] (1) Select waste textiles with compression-recovery properties as raw materials, place them in an ethanol solution for ultrasonic treatment to remove surface impurities and oligomers, and then dry them for later use.

[0049] (2) The dried waste textile obtained in step (1) is soaked in an aqueous solution containing Tris-HCl and dopamine hydrochloride, shaken at a constant temperature, then washed with deionized water and dried to obtain polydopamine textile.

[0050] (3) The polydopamine textile obtained in step (2) is soaked in pyrrole aqueous solution, anhydrous FeCl3 is added, and the mixture is shaken at room temperature. After the pyrrole is completely polymerized, it is taken out and washed with deionized water. After drying, the photothermal composite textile is obtained.

[0051] (4) Dissolve dopamine hydrochloride and polyethyleneimine (PEI) in Tris-HCl buffer to obtain an aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine. Wet the photothermal composite textile obtained in step (3) with alcohol and soak it in the aqueous solution. Shake at room temperature, then wash with deionized water and dry to obtain the photothermal enhanced composite textile.

[0052] (5) The photothermal reinforced composite textile obtained in step (4) is immersed in an ethyl acetate solution containing polydimethylsiloxane and curing agent. The strong adhesive force of PDMS is used to firmly fix it on the fiber felt mop. After immersion, the fabric is heated and cured to obtain a photothermal superhydrophobic material.

[0053] In step (1) above: the waste textiles are preferably waste fiber felt and / or waste mops. Further, the waste mop is preferably an adhesive flat mop, which includes a polyurethane sponge layer 25, a fiber adsorption layer 26 on one side of the polyurethane sponge layer 25, and an adhesive layer on the other side of the polyurethane sponge layer 25. The fiber adsorption layer 26 can be an array of fiber tentacles or composed of coils of several fiber yarns wound together. Figure 10 As shown, the fiber adsorption layer 26 achieves instantaneous capture of oil by increasing the contact area with the oil, and realizes rapid directional transport of oil through capillary channels between fibers. Under wet conditions, this material exhibits excellent recoverability; its tentacle structure may collapse under pressure, but this deformation is reversible, and it can quickly recover its initial configuration and maintain structural integrity after the external force is removed. The porous polyurethane sponge layer has the structural characteristics of high specific surface area and high porosity, which not only provides sufficient oil storage space, but also enhances capillary force, thereby significantly improving the material's adsorption capacity and exhibiting excellent oil absorption performance. In addition, the three-dimensional pore structure can also provide elastic support, improve the compressibility of the oil-absorbing material, and ensure that the material maintains structural stability after multiple compressions. Based on this, the oil-absorbing material exhibits superior compressibility recovery performance under high viscosity-wet conditions.

[0054] Preferably, in step (1): the ultrasonic treatment time is 1-2 hours to remove surface impurities and oligomers, and the product is dried for later use. In step (2): the concentration of Tris-HCl in the aqueous solution containing Tris-HCl and dopamine hydrochloride is 1-2 wt%, and the concentration of dopamine hydrochloride is 0.2-0.3 wt%; the product is oscillated in a constant temperature and dark environment at 38-40℃ for 12-14 hours.

[0055] Preferably, in step (3): the concentration of the pyrrole aqueous solution is 3-4 mg / ml, the molar ratio of anhydrous FeCl3 to pyrrole in the pyrrole aqueous solution is 1:1, and the room temperature shaking time is controlled to be 1-2 h.

[0056] Preferably, in step (3), sodium dodecylbenzenesulfonate, a dispersant, is added to the pyrrole aqueous solution, and its concentration is controlled at 0.1-0.2 wt%.

[0057] Preferably, in step (4): the concentration of Tris-HCl in the aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine is 1-2 wt%, the concentration of dopamine hydrochloride is 0.2-0.3 wt%, and the concentration of polyethyleneimine is 1:1 with the concentration of dopamine hydrochloride; the solution is shaken in an aerobic environment at room temperature for 3-4 hours.

[0058] Preferably, in step (5), the ethyl acetate solution containing polydimethylsiloxane and curing agent is prepared by the following steps: dispersing polydimethylsiloxane and curing agent in ethyl acetate solution and sonicating, wherein the mass ratio of polydimethylsiloxane and curing agent is 10:1 and the concentration of polydimethylsiloxane is 7-10 mg / ml; controlling the soaking time of photothermal reinforced composite textile to be 10-20 min, and after taking it out, curing it at 80-85℃ for 4-5 h, and then naturally cooling to room temperature.

[0059] More specifically, the hydrophobic agent used is polydimethylsiloxane (PDMS), a fluorine-free hydrophobic finishing agent. The PDMS coating not only imparts excellent hydrophobic properties to the adsorbent material but also provides superior hydrophobic stability. The hydrophobic modification steps are as follows: PDMS and the matching curing agent are dispersed in an ethyl acetate solution and sonicated for 0.5 h, wherein the mass ratio of PDMS to curing agent is 10:1, and the concentration of PDMS is 7 mg / ml. The photothermal reinforced composite textile is immersed in the sonicated ethyl acetate solution for 10-20 min, then cured at 80℃ for 4 h, and subsequently cooled to room temperature to obtain the photothermal superhydrophobic material, namely PDMS / PEI-PDA / PPy / PDA@Mop.

[0060] This invention investigates the superhydrophobic properties and oil-water identification characteristics of the composite fiber felt mop prepared by the above method.

[0061] Specifically, this material can rapidly adsorb soybean oil from an incompatible system where soybean oil encapsulates water droplets while keeping the water out, and it can also rapidly adsorb high-viscosity crude oil from an incompatible system where water droplets encapsulate high-viscosity oil droplets while keeping the water out. Furthermore, this material can effectively adsorb both light oil on the water surface and heavy oil underwater without leaving any residue. When PDMS / PEI-PDA / PPy / PDA@Mop comes into contact with n-hexane floating on the water surface, the n-hexane is rapidly adsorbed by the material without leaving any residue. For underwater heavy oil, PDMS / PEI-PDA / PPy / PDA@Mop can adsorb dichloromethane that has sunk to the bottom, and no obvious water marks were observed on the material, demonstrating its excellent oil-water identification properties.

[0062] This invention investigates the repetitive oil absorption performance of photothermal superhydrophobic materials prepared by the above method.

[0063] After repeated use with oils and organic solvents of varying viscosities, the adsorption capacity did not decrease significantly, demonstrating excellent oil absorption capacity and good reusability. Specifically, when the photothermal superhydrophobic material prepared by the above method was immersed in hexane solution and crude oils of different viscosities, the oil-absorbing material exhibited good organic solvent adsorption performance and superoleophilic properties. Furthermore, after 100 cycles of adsorption-desorption, the structural integrity of PDMS / PEI-PDA / PPy / PDA@Mop remained almost unchanged, maintaining good re-adsorption performance and mechanical properties.

[0064] This invention investigates the durability of the superhydrophobic surface of the photothermal superhydrophobic material prepared by the above method, and explores the material's resistance to washing, extrusion, solvent, light, and salt.

[0065] Specifically, the material underwent 60 minutes of ultrasonic cleaning, and the results showed that the water contact angle of all samples remained at approximately 150°, demonstrating excellent water wash resistance. After 200 cycles of extrusion testing, the material still exhibited excellent superhydrophobic properties (WCA > 150°). To test the stability of the material's superhydrophobic properties under different environments, the material was immersed in various organic solvents (acetone, dimethyl sulfoxide, dichloromethane, ethyl acetate, isopropanol, and n-hexane) for 24 hours. After the solvents completely evaporated, the water contact angle was measured. The results showed that the material surface maintained superhydrophobicity (WCA > 150°) after treatment, indicating excellent solvent resistance. Irradiation of the material with a xenon lamp for different durations showed that the WCA remained above 150° after 12 hours of irradiation, indicating excellent light resistance. Furthermore, after immersing the material in seawater for 24 hours, the water contact angle remained stable at approximately 150°, indicating significant salt resistance and stability.

[0066] The photothermal superhydrophobic material prepared by the above method can be applied to the adsorption of high-viscosity oil spills and the recovery of oil spills on water surfaces.

[0067] Crude oil has a low viscosity that varies greatly with temperature. As the temperature rises (20℃, >45000mPa·s), the viscosity of crude oil gradually decreases (90℃, ~0mPa·s), and its fluidity is significantly enhanced, which will be beneficial for crude oil recovery.

[0068] Specifically, a drop of high-viscosity crude oil is placed on the surface of a photothermal superhydrophobic material, and crude oils of varying viscosities are adsorbed under photothermal driving strategies with different light intensities. The aforementioned light intensities can be 0.05-0.20 W / cm². 2 Combined with photothermal drive, the adsorption rate of high-viscosity oil is increased by more than 5 times, at a light intensity of 0.20 W / cm². 2 It can adsorb high-viscosity crude oil in as little as 80 seconds.

[0069] Specifically, crude oil was added to the surface of seawater samples to simulate an oil spill environment. A piece of photothermal superhydrophobic fiber felt was placed on top of the high-viscosity crude oil. The light intensity of the simulated solar xenon lamp source was adjusted to standard sunlight for the oil spill recovery experiment. A no-light condition was set up as a control group to compare and demonstrate the oil removal performance of the photothermal superhydrophobic fiber felt on water.

[0070] like Figure 11 , Figure 12 As shown, a continuous oil spill recovery device for high-viscosity water surfaces uses a photothermal superhydrophobic material prepared by the method described above as the adsorbent. The device also includes a frame 23, on which a conveying mechanism is mounted. A heating zone is located at the end of the frame, and a heating mechanism is located within the heating zone. Below the heating zone is an oil spill adsorption zone, or oil adsorption zone. A compression recovery zone is located in the middle of the frame, and a compression mechanism is located within the compression recovery zone. The conveying mechanism includes a motor 17, a drive wheel 3, a transmission wheel assembly, and a rotary conveyor belt 24, which is wound around the drive wheel 3 and the transmission wheel assembly. The transmission wheel assembly includes at least a first transmission wheel 4, a second transmission wheel 5, and a third transmission wheel 6. The shaft of the motor 17 is connected to the end 1 of the drive wheel via a synchronous belt drive. The motor 17 drives the drive wheel 3 to rotate via the synchronous belt, and the drive wheel 3 drives the transmission wheel assembly to rotate via the rotary conveyor belt 24. The photothermal superhydrophobic material is disposed on the outer side of the rotary conveyor belt. The heating mechanism includes a light source simulator 2 and an electric heating plate 7, used to heat the photothermal superhydrophobic material, i.e., to perform preheating treatment. Accordingly, the heating area is a photo-electric heating area.

[0071] When the sunlight intensity is sufficient to provide the required heating, the light source simulator 2 simulates sunlight irradiation, causing the surface temperature of the adsorbent material to rise rapidly. If the light intensity is insufficient, the heating plate 7 can provide auxiliary heating to the adsorbent material through thermal radiation, raising its temperature and thus achieving in-situ heating of the crude oil, accelerating the adsorption of the spilled oil. Of course, a temperature sensor can be further added to monitor the surface temperature of the material in real time, achieving precise temperature control.

[0072] An oil-water tank 8 is installed in the oil adsorption area. Located below the conveying mechanism, the tank contains a mixture of high-viscosity crude oil and water to simulate an oil spill environment at sea. When the conveying mechanism carries the adsorption material through the oil spill adsorption area and it comes into contact with the high-viscosity crude oil, the heat from the material's surface heats the oil in situ, altering the rheological properties of the surrounding high-viscosity crude oil. This effectively reduces the crude oil viscosity, thereby quickly removing the diffused oil film and high-viscosity crude oil.

[0073] The extrusion mechanism includes an extrusion roller assembly, which comprises two cooperating extrusion rollers, namely a first extrusion roller 9 and a second extrusion roller 10. The distance between the first extrusion roller 9 and the second extrusion roller 10 allows the photothermal superhydrophobic material to pass through and extrudes the material. An oil collection tank 14 is provided below the extrusion mechanism.

[0074] Furthermore, the extrusion mechanism also includes a pressure regulator 11, a pressure sensor 12, a telescopic bracket 13, and a pressure gauge 15. The second extrusion roller 10 is connected to the telescopic bracket 13 and moves via the telescopic bracket 13, thereby adjusting the distance between it and the first extrusion roller 9. The telescopic bracket 13 can be a slider and a slide rail that move telescopically relative to the frame 23. Furthermore, when the extrusion rollers are working, the pressure sensor 12 can detect the extrusion pressure between the extrusion rollers in real time and display the digital feedback on the pressure gauge 15, realizing adjustable and controllable pressure of the extrusion rollers, thereby improving the oil extrusion efficiency. The pressure regulator 11 is located to the right of the pressure sensor 12 and is directly connected to it. By manually rotating the pressure regulator 11, the telescopic bracket 13 moves horizontally, thereby changing the distance between the first extrusion roller 9 and the second extrusion roller 10, realizing the adjustment of the extrusion pressure between the two rollers. Under optimized pressure, the oil is fully extruded from the material and falls into the oil collection tank 14 below for collection.

[0075] Furthermore, the present invention also includes an emergency stop button 20, which controls the start and stop of the motor 17, and can quickly respond to unexpected situations during continuous oil suction operations, effectively ensuring operational safety.

[0076] The aforementioned rotary conveyor belt 24 uses an adhesive material to fix the adsorbent material, placing the adsorbent material above the entire rotary conveyor belt and allowing it to be continuously transported as the conveyor belt moves. This design ensures both transmission stability and supports quick replacement of different adsorbent materials.

[0077] The frame 23 of this invention has a lateral support plate 22 on one side and a steel plate 21 on the other side. The lateral support plate 22 is located at the front of the device and is made of transparent acrylic sheet, which facilitates observation of the device's operation and continuous oil suction process.

[0078] The device of this invention also includes a power supply mechanism, comprising a motor tachometer 18 and a motor speed regulator 19. The motor, located on the steel plate 21, provides power to the entire device to drive the belt movement and maintain the device's operation. The motor tachometer and motor speed regulator are located on a side support plate; the motor speed regulator adjusts the motor speed to control the conveying speed of the recycling device. The motor tachometer is located above the motor speed regulator and provides real-time digital feedback.

[0079] After completing one oil adsorption-desorption cycle, the recovery device of this invention can be transferred back to the oil spill adsorption area for continuous oil suction. Through continuous adsorption and compression cycles, this device achieves efficient and continuous recovery of crude oil, thereby significantly improving the recovery efficiency of high-viscosity crude oil.

[0080] This invention also provides a method for continuous recovery of high-viscosity oil spills on water surfaces, using the aforementioned continuous recovery device for high-viscosity oil spills on water surfaces, comprising the following steps: a photothermal superhydrophobic material is used as an oil-absorbing material and moves along a rotary conveyor belt. First, it passes through a heating zone where the oil-absorbing material is preheated by a heating mechanism. Then, it enters an oil spill adsorption zone for oil adsorption. Next, the oil-absorbing material with adsorbed oil is conveyed to a compression recovery zone where the oil is squeezed out by a compression mechanism and then falls into an oil collection tank below for recovery. The oil-absorbing material after compression returns along the rotary conveyor belt to enter the next working cycle, thereby continuously recovering high-viscosity crude oil.

[0081] The preparation method of the photothermal superhydrophobic material of the present invention will be described in more detail below with reference to specific embodiments.

[0082] Example 1

[0083] (1) Commercial waste fiber felt mops were ultrasonically treated in an ethanol solution for 1 hour to remove surface impurities and oligomers, and then dried for later use.

[0084] (2) The dried fiber felt mop was soaked in 200 ml of deionized water containing 2 ml of Tris-HCl (pH = 7.4) buffer solution, and 0.4 g of dopamine hydrochloride was added. The mop was then shaken at a constant temperature (40°C) for 14 h in the dark. The resulting fiber felt mop was washed several times with deionized water and dried in an oven to obtain polydopamine composite fiber felt mop.

[0085] (3) The dried polydopamine composite fiber felt mop was soaked in a pyrrole aqueous solution (200 ml, 4.0 mg / ml) containing SDBS (0.2 mg / ml), and anhydrous FeCl3 (FeCl3 to pyrrole molar ratio of 1:1) was added. After shaking at room temperature for 2 hours, it was taken out and washed, and then put into the oven to dry again to finally obtain the photothermal composite fiber felt mop.

[0086] (4) The photothermal composite fiber felt mop was moistened with alcohol and soaked in 200 ml of deionized water containing 2 ml of Tris-HCl (pH=8.5) buffer. 0.4 g of dopamine hydrochloride and 0.4 g of polyethyleneimine were added. The mop was shaken at room temperature for 4 h in an aerobic environment. Then it was washed with deionized water and dried to obtain the photothermal enhanced composite fiber felt mop.

[0087] (5) Immerse the photothermal reinforced composite fiber felt mop in 100 ml of ethyl acetate solution containing 7 mg / ml polydimethylsiloxane (10:1 with curing agent) for 10-20 min. After immersion, cure at 80°C for 4 h and then allow to cool naturally to room temperature to obtain the photothermal superhydrophobic composite fiber felt mop, namely (PDMS / PEI-PDA / PPy / PDA@Mop).

[0088] The photothermal superhydrophobic composite fiber felt mop prepared in Example 1, namely (PDMS / PEI-PDA / PPy / PDA@Mop), was subjected to microstructure observation, elemental composition analysis, compression performance testing, water contact angle testing, and photothermal performance testing. The oil absorption ratio and oil-water separation efficiency of the sample were evaluated. The methods and results are as follows:

[0089] (1) Material structure and surface water contact angle;

[0090] Figure 1 The images shown are scanning electron microscope (SEM) images of the composite fiber felt mop prepared in Example 1 before and after modification (e.g., Figure 1As shown in the image, SEM images of different parts of the composite fiber felt mop were used to observe its various structural morphologies. The SEM images reveal that after photothermal and hydrophobic modification, the fiber felt mop exhibits a large accumulation of PDA-PPy nanoparticles and a dense nano-coating, significantly increasing surface roughness and enhancing its strength and toughness, thus improving its compressibility. Furthermore, the presence of a large amount of silica nano-coating on the surface of the composite fiber felt mop further improves surface roughness and demonstrates excellent hydrophobic properties. Measurements show that the contact angle of water droplets on the PDMS / PEI-PDA / PPy / PDA@Mop surface is approximately 151° (e.g., ...). Figure 2 (As shown).

[0091] The surface stability and durability of materials play a crucial role in practical applications. The mechanical stability of the superhydrophobic surface of the PDMS / PEI-PDA / PPy / PDA@Mop material was tested through ultrasonic cleaning and cyclic pressing. The material underwent 60 minutes of ultrasonic cleaning. Figure 3 As shown in Figure a, the water contact angle of all samples remained at approximately 150°, demonstrating excellent water wash resistance. Figure 3 As shown in b, its mechanical properties were evaluated through a 200-cycle extrusion test. With increasing extrusion cycles, the contact angle of the material surface showed a slow decreasing trend, but it still exhibited excellent superhydrophobic properties (WCA > 150°), indicating stable durability and robustness under mechanical stress. Therefore, in normal use, PDMS / PEI-PDA / PPy / PDA@Mop can withstand most mechanical forces while maintaining excellent hydrophobic properties. Furthermore, to evaluate the suitability of PDMS / PEI-PDA / PPy / PDA@Mop material in marine environments, the material was immersed in seawater for 24 hours. Figure 3 As shown in Figure c, the water contact angle of the material remains stable at around 150°, indicating that the material has significant salt resistance and reliability. To test the stability of the material's superhydrophobic properties under different environments, PDMS- / PEI-PDA / PPy / PDA@Mop was immersed in various organic solvents (acetone, dimethyl sulfoxide, dichloromethane, ethyl acetate, isopropanol, n-hexane) for 24 hours. After the solvents had completely evaporated, its water contact angle was measured. Figure 3 As shown in d, the treated material surface still retains superhydrophobicity (WCA > 150°), indicating its excellent solvent resistance. The material's durability was also evaluated using xenon lamp irradiation (e.g., Figure 3 As shown in Figure e), with the extension of irradiation time, the WCA of PDMS / PEI-PDA / PPy / PDA@Mop decreased slightly, but after 12 hours of irradiation, the WCA remained above 150°, indicating that the material has excellent light resistance. Figure 3As shown in f, the water contact angle (WCA) of water droplets was also tested after continuous heating at different temperatures (40℃, 60℃, and 80℃) on the surface of PDMS / PEI-PDA / PPy / PDA@Mop for 20 min. The results show that after continuous heating at high temperature for 20 min, the water droplets still have a high water contact angle (WCA > 140°), indicating that the superhydrophobic surface of this material has a certain degree of thermal stability.

[0092] (2) Photothermal properties;

[0093] The original fiber felt mop surface equilibrium temperature was low, at 0.10 W / cm². 2 The equilibrium temperature under light is only 62.9℃, indicating poor photothermal conversion ability. With the increase of photothermal material layers, the photothermal conversion performance gradually improves. In contrast, PDMS / PEI-PDA / PPy / PDA@Mop exhibits excellent photothermal conversion performance, even when 0.10 W / cm² is applied. 2 After exposure to intense light, the surface temperature of the material can reach up to 99.6℃ (e.g., Figure 4 (as shown in a). The photothermal reactivity of PDMS / PEI-PDA / PPy / PDA@Mop under different light intensities was further analyzed (e.g., ...). Figure 4 As shown in b), the results show that the surface temperature of the material has a linear relationship with the simulated light intensity; as the light intensity increases, the surface temperature of the material also increases. Compared with the original material and the gradually modified fiber mat, PDMS / PEI-PDA / PPy / PDA@Mop exhibits excellent temperature response and higher photosensitivity. The highest surface temperature of PDMS / PEI-PDA / PPy / PDA@Mop can reach 0.05 W / cm². 2 The temperature reached 67.8℃ under light intensity; at 0.1 W / cm² 2 Under light intensity, it rapidly heats to 80.7℃ within 140s and tends to stabilize; and at 0.15W / cm 2 The temperature reached 106℃ under light intensity; when the light intensity increased to 0.2 W / cm²... 2 Under certain light intensity, the highest temperature can reach a steady-state temperature of 137.9℃ within 200 seconds (e.g., Figure 4 (As shown in c). Furthermore, the PDMS layer has high transparency and excellent light transmittance, which has little impact on the photothermal properties of the material. This means that the incorporation of PDA and PPy significantly improves the photothermal conversion capability. Under repeated on / off cycles, PDMS / PEI-PDA / PPy / PDA@Mop accurately reaches the same steady-state temperature (e.g., ...). Figure 4 As shown in d and 4e), this indicates its rapid photoresponse and photothermal conversion stability.

[0094] (3) Oil wetting properties and adsorption properties;

[0095] To selectively clean up oil leaks, the adsorbent material requires specific wettability. This invention conducted oil / water adsorption tests to investigate the wetting properties of the fiber felt. The unmodified sample did not selectively adsorb oil and water; both oil and water could penetrate into the material (e.g., ...). Figure 5 (As shown in a). Due to the presence of the PDMS coating on the surface of the fiber felt mop, the modified material endows the fiber felt mop with excellent hydrophobicity. Water forms spherical shapes on the surface of PDMS / PEI-PDA / PPy / PDA@Mop and no penetration occurs (e.g., Figure 5 (As shown in b). Due to its superhydrophobicity, when PDMS / PEI-PDA / PPy / PDA@Mop is completely immersed in water under external force, a large number of bubbles are observed on its surface, and there is obvious specular reflection (e.g., Figure 5 (as shown in c). Figure 5 Figure d illustrates the wetting behavior of water and oil droplets on the PDMS / PEI-PDA / PPy / PDA@Mop surface. Water droplets adhere to the material surface and are spherical, while oil droplets rapidly penetrate into the material's interior. These results reveal the superhydrophobic-superoleophilic properties of the PDMS / PEI-PDA / PPy / PDA@Mop surface. The material also exhibits strong repulsion against impinging water jets. Analysis of the wetting behavior of water droplets on the PDMS / PEI-PDA / PPy / PDA@Mop surface shows that when a high-pressure water jet contacts the cross-section of the material, an instantaneous contact point is immediately formed. The water droplets rapidly spread across the surface, forming a uniform liquid film. After spreading to a certain extent, the droplets gradually shrink and lose contact with the surface, eventually bouncing off at a certain speed (e.g., ...). Figure 5 As shown in e), this directly illustrates the low adhesion of PDMS / PEI-PDA / PPy / PDA@Mop to water droplets. Furthermore, the adhesion between the fiber mat and water droplets was investigated using a contact-separation test. Figure 5 As shown in f, when the needle tip is moved toward the surface of the fiber felt, the water droplet is compressed; when the needle tip is retracted, no water droplet adheres to the PDMS / PEI-PDA / PPy / PDA@Mop surface, indicating that the fiber felt has extremely low adhesion to water droplets and exhibits excellent superhydrophobic properties. Figure 5 g demonstrates the excellent superhydrophobic-superoleophilic properties and oil-water recognition characteristics of the PDMS / PEI-PDA / PPy / PDA@Mop material. This material can be used to rapidly adsorb soybean oil from incompatible systems while keeping water out (e.g., ...). Figure 5 g1) can also quickly adsorb high-viscosity crude oil while keeping water out (e.g. Figure 5 g2). When PDMS / PEI-PDA / PPy / PDA@Mop is placed in an oil / water mixture, the material can absorb n-hexane (e.g., g2) floating on the water surface. Figure 6 As shown in a), and dichloromethane that settles at the bottom (as shown in a). Figure 6 As shown in b), and no obvious water marks were observed on the material, this phenomenon reveals the material's selective absorption behavior of oil.

[0096] Furthermore, PDMS / PEI-PDA / PPy / PDA@Mop exhibits excellent adsorption performance for various oils (such as soybean oil and pump oil) and organic solvents (including isopropanol, ethanol, n-hexane, ethyl acetate, dichloromethane, and methanol). Although there are some differences in adsorption capacity for different oils, the test results show that its adsorption capacity can reach 4.36–10.99 g / g (e.g., ...). Figure 6 (As shown in c). Additionally, by compressing the fiber felt mop downwards with flat-tipped tweezers, the material can quickly return to its original shape. Therefore, oil can be recovered and reused for the next oil absorption by manually squeezing the oil-soaked fiber felt mop. (See diagram c). Figure 6 As shown in d, during 100 adsorption-desorption cycles for dichloromethane and n-hexane, the adsorption capacity did not decrease significantly. The adsorption capacity for n-hexane (e.g., after 100 cycles of adsorption-desorption) was [not specified]. Figure 6 The adsorption capacity after (e1) is 95.2% of the initial capacity; after 100 cycles of adsorption of dichloromethane (e.g.) Figure 6 The adsorption capacity after e2) was 99.1% of the initial capacity. After 100 compression absorption cycles in crude oil using the same method, the basic shape of PDMS / PEI-PDA / PPy / PDA@Mop remained almost unchanged, and its adsorption capacity did not decrease significantly (e.g., Figure 6 As shown in f), it exhibits satisfactory oil absorption capacity and good reusability.

[0097] Due to the multi-scale interwoven network structure of PDMS / PEI-PDA / PPy / PDA@Mop and the presence of -CH3-terminated methylsiloxane, the material exhibits significant oleophilic properties. Under conditions of no light exposure in air, such as... Figure 7 As shown in a1, b1, c1, and d1, the device can rapidly absorb oil drops of different types (specifically, 20W-50 and 20W-40) onto the surface within 16s, 8s, 1.65s, and 90s, respectively (test volume: 50μL). The device operates at a concentration of 0.1W / cm². 2 Under light intensity, the adsorption rate can be increased to 3s, 2s, 0.5s, and 35s respectively (e.g., Figure 7 (As shown in a2, b2, c2, and d2). Furthermore, to more intuitively demonstrate the promoting effect of light on the underwater oil adsorption of the material, this invention also compared the underwater oil droplet adsorption rates of PDMS / PEI-PDA / PPy / PDA@Mop under both illuminated and dark conditions (e.g., ...). Figure 7(As shown in e, f, g, h). Under conditions of no light, such as... Figure 7 As shown in e1, f1, g1, and h1, this material can rapidly adsorb oil drops of different types (specifically, different types of oil, corresponding to 20w-50 and 20w-40) onto water within 40s, 16s, 3s, and 73min, respectively (test volume: 50μL); at 0.1W / cm²... 2 Under light intensity, the adsorption rate can be increased to 20s, 5s, 2s, and 10min respectively (e.g., Figure 7 (As shown in e2, f2, g2, and h2). It can be seen that under light conditions, whether in air or underwater, the material promotes the adsorption of oils of different viscosities to varying degrees.

[0098] (4) Adsorption of high-viscosity crude oil;

[0099] Crude oil has high viscosity (10) 3 -10 5 The high viscosity of crude oil (10-1000 times higher than conventional crude oil) and its low fluidity hinder the penetration and flow of crude oil within the material's internal pores, making it extremely difficult for oleophilic materials to adsorb, thus exacerbating the difficulty of recovering high-viscosity oil spills. However, high-viscosity crude oil is very sensitive to temperature; its viscosity decreases as temperature increases. Based on this characteristic, under simulated sunlight irradiation using a light source simulator, the surface temperature of PDMS / PEI-PDA / PPy / PDA@Mop rises rapidly. This photothermal effect can effectively reduce the viscosity of high-viscosity crude oil, thereby improving its fluidity and further promoting crude oil adsorption.

[0100] To more intuitively demonstrate the material's promoting effect on the adsorption of high-viscosity crude oil, this invention also compared the permeation rate of high-viscosity crude oil (approximately 1 g) on ​​the surface of the original sample and the gradually modified sample under both light and dark conditions (e.g., ...). Figure 8 (As shown). The results indicate that, in the absence of light, the adsorption efficiency of both the original material and the gradually modified material for high-viscosity crude oil is limited, and viscous oil requires tens of minutes to be completely adsorbed. However, at 0.1 W / cm², the adsorption efficiency is significantly improved. 2 Under intense light irradiation, high-viscosity oil can completely penetrate into the original material within 80 seconds, and the penetration time gradually shortens with further modification. For PDMS / PEI-PDA / PPy / PDA@Mop materials with excellent photothermal conversion properties, the penetration time is shortened to within 36 seconds, and the penetration rate is significantly enhanced. Furthermore, light intensity also affects the adsorption capacity of crude oil, such as... Figure 9 As shown, as the light intensity increases from 0.05 W / cm², 2 Increased to 0.2 W / cm 2The penetration rate of high-viscosity oil on the surface of PDMS / PEI-PDA / PPy / PDA@Mop material was significantly improved, reaching 0.2 W / cm². 2 Under light conditions, high-viscosity oil can completely penetrate into the material in just 80 seconds, with a viscosity of 0.05 W / cm². 2 The permeation rate increased by 4.5 times under high light intensity, which fully demonstrates the great application potential of this material in separating high-viscosity crude oil.

[0101] Crude oil was added to the surface of a seawater sample to simulate a marine oil spill environment. A piece of photothermal superhydrophobic fiber felt was placed on top of the high-viscosity crude oil. The light intensity of a simulated solar xenon lamp source was adjusted to standard sunlight for an oil spill recovery experiment. A no-light condition was set up as a control group to compare and illustrate the oil removal performance of the photothermal superhydrophobic fiber felt on water. Figure 7 As shown, under 1 sun illumination, PDMS / PEI-PDA / PPy / PDA@Mop achieved in-situ adsorption and removal of crude oil from the seawater surface within 10 minutes. Conversely, under no-light conditions, the crude oil on the seawater surface remained almost solid, and in-situ adsorption of the crude oil was achieved after 72 minutes, greatly improving the oil absorption efficiency.

[0102] This invention uses composite fiber felt mop as the main material. Through photothermal modification with dopamine hydrochloride and pyrrole polymerization, and superhydrophobic modification with polydimethylsiloxane, a photothermal superhydrophobic composite fiber felt mop (PDMS / PEI-PDA / PPy / PDA@Mop) with high compression recovery, efficient photothermal conversion, rapid capture, adsorption, and conduction, and reusable oil absorption is prepared. This mop maintains its superhydrophobic properties even in harsh environments and can adsorb high-viscosity crude oil. The presence of coils and an elastic porous sponge structure endows this oil-absorbing material with excellent compression recovery and oil adsorption performance. The PDA-PPy nanoparticles polymerized on the surface of the composite fiber felt mop give it high photothermal conversion performance. Under simulated sunlight irradiation, the surface temperature can rapidly rise from room temperature to 99.6℃ and conduct heat downwards. Under repeated on / off cycles, PDMS / PEI-PDA / PPy / PDA@Mop accurately reaches the same steady-state temperature, demonstrating its rapid photoresponse and stable photothermal conversion. This characteristic enables the composite fiber felt mop to heat crude oil in situ, reducing its viscosity and accelerating its adsorption. Due to its excellent selectivity for oil / water mixtures and superior mechanical properties, the composite fiber felt mop can selectively adsorb light oil, heavy oil, and high-viscosity crude oil. It can also adsorb various oils and organic solvents, maintaining a relatively stable adsorption capacity after 100 cycles, demonstrating satisfactory oil absorption capacity and good reusability. Furthermore, a continuous collection device was designed using the PDMS / PEI-PDA / PPy / PDA@Mop composite fiber felt mop prepared using this invention. By simulating a light source, the surface temperature of the photothermal superhydrophobic composite fiber felt mop rapidly increases, altering the rheological properties of high-viscosity crude oil and effectively reducing its viscosity. This enables the adsorption of high-viscosity crude oil, and through dynamic mechanical assistance and continuous collection, continuous crude oil leak repair can be achieved, demonstrating high practical application potential in crude oil leak repair.

[0103] The above description of the embodiments is provided to enable those skilled in the art to understand and use the present invention. Of course, the above description is not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions, or substitutions made by those skilled in the art within the scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A method for preparing a photothermal superhydrophobic material, characterized in that... Includes the following steps: (1) Select waste textiles with compression-recovery properties as raw materials, place them in an ethanol solution for ultrasonic treatment, and then dry them for later use. (2) The dried waste textile obtained in step (1) is soaked in an aqueous solution containing Tris-HCl and dopamine hydrochloride, shaken at a constant temperature, then washed with deionized water and dried to obtain polydopamine textile. (3) The polydopamine textile obtained in step (2) is soaked in pyrrole aqueous solution, anhydrous FeCl3 is added, and the mixture is shaken at room temperature. After the pyrrole is completely polymerized, it is taken out and washed with deionized water. After drying, the photothermal composite textile is obtained. (4) Dissolve dopamine hydrochloride and polyethyleneimine in Tris-HCl buffer to obtain an aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine; wet the photothermal composite textile obtained in step (3) with alcohol and soak it in the aqueous solution, shake at room temperature, then wash with deionized water and dry to obtain a photothermal enhanced composite textile. (5) The photothermal enhanced composite textile obtained in step (4) is immersed in an ethyl acetate solution containing polydimethylsiloxane and curing agent. After immersion, it is heated and cured to obtain a photothermal superhydrophobic material.

2. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (1): the waste textiles are waste fiber felt and / or waste mops.

3. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that: The discarded mop is an adhesive flat mop, which includes a sponge layer, a fiber adsorption layer on one side of the sponge layer, and an adhesive layer on the other side of the sponge layer.

4. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (1): the ultrasonic treatment time is 1-2h; in step (2): the concentration of Tris-HCl in the aqueous solution containing Tris-HCl and dopamine hydrochloride is 1-2wt%, and the concentration of dopamine hydrochloride is 0.2-0.3wt%; the oscillation is controlled in a constant temperature and dark environment of 38-40℃ for 12-14h.

5. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (3): the concentration of the pyrrole aqueous solution is 3-4 mg / ml, the molar ratio of anhydrous FeCl3 to pyrrole in the pyrrole aqueous solution is 1:1, and the shaking time at room temperature is controlled to be 1-2 h.

6. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (3): sodium dodecylbenzenesulfonate, a dispersant, is added to the pyrrole aqueous solution, and its concentration is controlled at 0.1-0.2 wt%.

7. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (4): the concentration of Tris-HCl in the aqueous solution containing Tris-HCl, dopamine hydrochloride and polyethyleneimine is 1-2wt%, the concentration of dopamine hydrochloride is 0.2-0.3wt%, and the concentration of polyethyleneimine is 1:1 with the concentration of dopamine hydrochloride; shake at room temperature in an aerobic environment for 3-4 hours.

8. The method for preparing a photothermal superhydrophobic material according to claim 1, characterized in that, In step (5), the ethyl acetate solution containing polydimethylsiloxane and curing agent is prepared by the following steps: dispersing polydimethylsiloxane and curing agent in ethyl acetate solution and sonicating, wherein the mass ratio of polydimethylsiloxane and curing agent is 10:1 and the concentration of polydimethylsiloxane is 7-10 mg / ml; controlling the soaking time of photothermal reinforced composite textile to be 10-20 min, and after taking it out, curing it at 80-85℃ for 4-5 h, and then naturally cooling to room temperature.

9. A continuous oil spill recovery device for high viscosity water surface, characterized in that: Photothermal superhydrophobic materials prepared by any one of the methods described in claims 1-8; The device also includes a frame, on which a conveying mechanism is provided; a heating zone is provided at the end of the frame, and a heating mechanism is provided at the heating zone; an oil spill absorption zone is provided below the heating zone; and a squeezing recovery zone is provided in the middle of the frame, and a squeezing mechanism is provided in the squeezing recovery zone. The conveying mechanism includes a motor, a drive wheel, a transmission wheel assembly, and a rotary conveyor belt. The rotary conveyor belt is wound around the drive wheel and the transmission wheel assembly. The motor drives the drive wheel to rotate via a synchronous belt, and the drive wheel drives the transmission wheel assembly to rotate via the rotary conveyor belt. The photothermal superhydrophobic material is disposed on the outer side of the rotary conveyor belt. The heating mechanism includes a light source simulator and / or an electric heating plate for heating the photothermal superhydrophobic material; The extrusion mechanism includes an extrusion roller assembly, which includes two cooperating extrusion rollers. The distance between the two extrusion rollers allows the photothermal superhydrophobic material to pass through and extrudes the photothermal superhydrophobic material. An oil collection tank is provided below the extrusion mechanism.

10. A method for continuous recovery of high-viscosity oil spills from water surfaces, employing the continuous recovery device for high-viscosity oil spills from water surfaces as described in claim 9, characterized in that... Includes the following steps: The photothermal superhydrophobic material is used as an oil-absorbing material and moves along the rotary conveyor belt. First, it passes through the heating zone, where the oil-absorbing material is preheated by the heating mechanism. Then, it enters the oil overflow adsorption zone to adsorb the oil. Next, the oil-absorbing material with adsorbed oil is conveyed to the extrusion and recycling zone, where the oil is extruded by the extrusion mechanism and then falls into the oil collection tank below for recycling. The compressed oil-absorbing material is returned via a rotary conveyor belt to the next working cycle, in order to continuously recover high-viscosity crude oil.

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