A kind of all-weather fast recovery high viscosity crude oil fiber felt, preparation method and application thereof

Abstract

The application discloses a kind of fibrous felt that can be all-weather fast recovery high viscosity crude oil, preparation method and its application.The fibrous felt includes the fibrous substrate formed by profiled cross-section fiber, and the binder layer, functional layer and hydrophobic coating sequentially loaded on its surface;Functional layer is used to generate Joule heat when energized and generate photo-thermal effect under light;The water contact angle of fibrous felt is greater than 140°.The application also provides its preparation method and application.The application integrates photo-thermal and Joule heat effect in the same felt, realizes all-weather operation ability;Use C-shaped or Y-shaped profiled cross-section fiber, accelerate the penetration and absorption of high viscosity crude oil;Through the synergistic effect of polypyrrole layer and MXene layer, the resistance is significantly reduced and the oil absorption time is shortened.The fibrous felt of the application has simple preparation process, and is suitable for all-weather oil spill recovery in complex environment such as ocean oil spill.

Description

Technical Field

[0001] This invention belongs to the field of oil-water separation material preparation technology, specifically relating to a fiber felt that can rapidly recover high-viscosity crude oil in all weather conditions, its preparation method, and its application. Background Technology

[0002] With the rapid development of offshore oil production and transportation, oil spills and chemical leaks occur frequently worldwide. These accidents cause severe ecological disasters, and removing these organic pollutants from water sources is a major environmental problem that continues to attract significant attention. Currently, strategies for addressing these problems can generally be categorized into three main types: physical methods (e.g., adsorbents, skimmers, oil booms), chemical methods (e.g., in-situ combustion, solidification agents), and biological methods (e.g., bioremediation). Among these methods, adsorbents are considered an economical and effective countermeasure against oil spills.

[0003] Fiber-based polymer adsorbents are considered ideal materials for oil spill treatment due to their ease of manufacture, low cost, and scalability. However, existing fiber adsorbents still face many challenges in practical applications.

[0004] First, when dealing with high-viscosity crude oil (viscosity 10) 3 ~10 5 The high viscosity of oil (10 to 1000 times higher than that of conventional crude oil) severely hinders the permeability of the material's internal pores, causing the adsorbent to only adsorb a small amount of oil on the surface, while the internal pores cannot be fully utilized. This significantly reduces the adsorbent's oil absorption capacity and rate. Therefore, improving the adsorbent's ability to penetrate high-viscosity crude oil is one of the urgent technical problems to be solved in this field.

[0005] Secondly, research shows that crude oil viscosity decreases rapidly with increasing temperature. When the temperature rises from 20℃ to 90℃, its viscosity can decrease by two orders of magnitude, allowing it to flow like light oil. Based on this principle, developing thermally effective fiber materials for high-viscosity oil recovery has become a promising technological direction. Under the influence of sunlight or electricity, thermally effective felt can heat the surrounding crude oil, reducing its viscosity and thus achieving rapid absorption.

[0006] However, existing single-effect heating methods have significant drawbacks. While solar energy is energy-efficient and environmentally friendly, it cannot meet heating requirements under conditions of insufficient sunlight, such as at night or on cloudy days. On the other hand, simple Joule heating (electric heating), although not limited by sunlight conditions, consumes a lot of energy when continuously powered, and is difficult to implement in certain scenarios (such as remote sea areas without power supply). Therefore, neither single solar irradiation heating nor single electric heating methods can meet the complex and varied real-world application scenarios.

[0007] Therefore, how to organically combine the photothermal effect and the Joule heating effect, so that the adsorbent can be heated by solar energy on sunny days and by low voltage driving heating on cloudy days or at night, thereby achieving all-weather, low-energy consumption, and high-efficiency recovery of high-viscosity crude oil, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0008] The purpose of this invention is to overcome the shortcomings of the prior art and provide a fiber felt that can rapidly recover high-viscosity crude oil in all weather conditions, its preparation method and application, so as to solve the problems of slow absorption rate of high-viscosity crude oil by existing oil-absorbing materials and inability to work in all weather conditions.

[0009] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0010] A fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions. The fiber felt includes a fiber substrate composed of fibers with irregular cross-sections, and an adhesive layer, a functional layer, and a hydrophobic coating sequentially loaded on the surface of the fiber substrate. The functional layer is used to generate Joule heating when energized and to generate photothermal effects under light.

[0011] Furthermore, the cross-sectional shape of the irregularly shaped fiber is preferably C-shaped or Y-shaped to provide additional capillary driving force and accelerate the penetration and absorption of high-viscosity crude oil.

[0012] Furthermore, the functional layer consists of a conductive polymer layer and a nanosheet layer, wherein the conductive polymer layer is a polypyrrole layer and the nanosheet layer is an MXene nanosheet layer.

[0013] Furthermore, the hydrophobic coating is a silane coating.

[0014] Furthermore, the silane reagent used in the silane coating is selected from one of methyltrimethoxysilane, methyltriethoxysilane, or methyltrichlorosilane.

[0015] Furthermore, the conductive polymer layer and the nanosheet layer are combined to form a three-dimensional composite conductive network, which can significantly reduce the material resistance and shorten the oil absorption time under electrothermal assistance.

[0016] The present invention also provides a method for preparing the above-mentioned fiber felt, comprising the following steps:

[0017] S1: Provides a fiber substrate composed of irregularly shaped cross-section fibers, which has been pretreated. It can be washed with an aqueous ethanol solution and then dried.

[0018] S2: The pretreated fiber substrate is immersed in an adhesive solution, and after drying, an adhesive layer is formed on the fiber surface. The adhesive solution can be an aqueous solution of polyvinyl alcohol or polyethylene glycol, and the concentration is preferably 0.4 g / 200 mL to 1 g / 200 mL.

[0019] S3: A conductive polymer layer is formed on the surface of a fiber substrate having an adhesive layer. Specifically, pyrrole monomers can be polymerized in situ on the fiber surface using ferric chloride as an oxidant. The molar ratio of pyrrole monomers to ferric chloride is preferably 1:1 to 1:2, and the reaction time is preferably 2 to 4 hours, thereby forming a polypyrrole layer.

[0020] S4: Load the nanosheet layer onto the fiber substrate treated in step S3, and after drying, allow the conductive polymer layer and the nanosheet layer to together form a functional layer. The nanosheet layer is preferably an MXene nanosheet layer, and the concentration of the MXene nanosheet solution used during loading is preferably 2 mg / mL to 10 mg / mL.

[0021] S5: The surface of the fiber substrate treated in step S4 is hydrophobically modified to form a hydrophobic coating, thus obtaining the fiber felt. Hydrophobic modification is preferably performed using vapor deposition, with a deposition temperature preferably between 60°C and 80°C, and a deposition time preferably between 3 and 5 hours. The silane reagent used can be selected from one of methyltrimethoxysilane, methyltriethoxysilane, or methyltrichlorosilane.

[0022] The present invention also provides the application of the above-mentioned fiber felt in the adsorption and recovery of high-viscosity crude oil or in the treatment of oil spills on water surfaces containing high-viscosity crude oil.

[0023] The present invention, by adopting the above-described technical solution, has the following beneficial effects:

[0024] 1. This invention integrates photothermal and Joule heating effects into the same fiber felt, creating a complementary effect. Under sunny conditions, free solar energy can be used for photothermal heating, eliminating the need for electricity. On cloudy days or at night when sunlight is insufficient, Joule heating can be supplemented by applying a low voltage (e.g., 10V). Figure 5 As shown, the fiber felt of this invention can achieve high viscosity crude oil (viscosity 10 at room temperature 25℃) under three simulated scenarios: sunny day (1kW / m² light), cloudy day (0.5kW / m² light), and nighttime (10V voltage only). 5 Rapid absorption of (mPa·s). In contrast, existing single photothermal materials cannot work at all under no-light conditions (see Table 1, the original felt does not absorb crude oil under electric assistance), while single electrothermal materials suffer from high energy consumption and dependence on power facilities. This invention achieves true "all-weather" operation capability.

[0025] 2. Through silane vapor deposition modification, the water contact angle of the fiber felt of this invention is greater than 140° (see Table 2, the contact angles of Examples 1 to 7 are 140° to 152°), exhibiting excellent hydrophobic properties. This characteristic enables the felt to effectively repel water during oil absorption, achieving selective oil-water adsorption, making it particularly suitable for oil spill recovery in complex aquatic environments such as marine oil spills and oily wastewater. The higher water contact angle also helps reduce the adhesion of crude oil to the felt surface, facilitating desorption after oil absorption and material regeneration.

[0026] 3. This invention loads the conductive polymer polypyrrole and the two-dimensional nanomaterial MXene onto the fiber surface. As shown in Table 3, the composite exhibits a significant synergistic effect:

[0027] (1) Significantly reduced resistance: The resistance was 400Ω when the polypyrrole layer was loaded alone, and 300Ω when the MXene layer was loaded alone. However, the resistance dropped to 110Ω after the two were combined, representing reductions of 72.5% and 63.3%, respectively.

[0028] (2) The oil absorption time of the electric heating is greatly shortened: Under the assistance of 10V voltage, the oil absorption time of the composite material is 110s, while that of polypyrrole alone is 320s and that of MXene alone is 280s, which are shortened by 65.6% and 60.7% respectively;

[0029] (3) Enhanced coating adhesion: The coating peeling rate of the composite material is only 2%, which is better than that of polypyrrole alone (10%) and MXene alone (5%).

[0030] The mechanism of the above-mentioned synergistic effect is that polypyrrole and MXene are combined to form a three-dimensional composite conductive network. Polypyrrole forms a continuous conductive skeleton on the fiber surface, while MXene nanosheets fill the gaps in the network as highly conductive fillers. Together, they construct an efficient three-dimensional conductive pathway, thereby significantly improving the electrothermal conversion efficiency of the material.

[0031] 4. This invention uses C-shaped or Y-shaped irregular cross-section fibers as the substrate, which has significant advantages over conventional circular cross-section fibers. For example... Figure 4 As shown, under the same illumination conditions, high-viscosity oil droplets on circular fibers only appear as barrel-shaped droplets, making diffusion difficult; while on Y-shaped and C-shaped fibers, the oil droplets diffuse rapidly along the fiber axis, with C-shaped fibers exhibiting the fastest diffusion speed. Figure 6 As shown, using the same modified formulation, the oil absorption rate of C-shaped fiber felt is significantly faster than that of circular fiber felt and commercial polyurethane sponge. This is because the grooved structure on the surface of the irregular fibers provides additional capillary channels, generating a stronger capillary driving force, thereby overcoming the flow resistance of high-viscosity crude oil and accelerating the penetration and absorption of oil inside the felt.

[0032] 5. This invention is for high-viscosity crude oil (viscosity 10). 3 ~10 5 The design of the C-shaped felt (mPa·s) was optimized. Through photothermal or electrothermal heating, the felt can rapidly raise the temperature of the surrounding crude oil to above the threshold for a significant reduction in viscosity (the viscosity can decrease by two orders of magnitude when the temperature rises from 20℃ to 90℃). As shown in Table 1, under 1kW / m² light irradiation, the modified C-shaped felt of this invention completely absorbed a 0.5mL crude oil droplet in only 50±3s, while the original felt required 85±3s, representing a 41% increase in absorption rate. Under 10V electrothermal assistance, the original felt did not absorb anything, while the modified C-shaped felt completely absorbed it in only 110±4s. This demonstrates that this invention effectively solves the technical problem of high-viscosity crude oil being difficult for porous materials to absorb quickly.

[0033] 6. The fiber felt of this invention can be widely used in emergency response to marine oil spills, purification of oily industrial wastewater, and recovery of oil spills, and is especially suitable for complex marine environments with variable lighting conditions and limited power supply. Attached Figure Description

[0034] The present invention will be further described below with reference to the accompanying drawings:

[0035] Figure 1 The images are scanning electron microscope (SEM) images of the C-shaped felt before and after modification in Example 1.

[0036] Figure 2 The water contact angle test diagrams are for the C-shaped felt in Examples 1, 2, and 4.

[0037] Figure 3 The figure shows the effect of the coating on the photothermal heating rate and electrical conductivity of the C-shaped felt in Example 1.

[0038] Figure 4 This is a comparison of the diffusion rates of high-viscosity oil droplets by single fibers with different cross-sectional shapes.

[0039] Figure 5 The diagram shows the oil absorption rate of C-shaped cross-section fiber felt under different conditions (sunny day, insufficient light, and electric heating at night).

[0040] Figure 6 This is a comparison chart showing the oil absorption rates of oil-absorbing materials prepared using the formulation of Example 1, with C-shaped felt, R-shaped felt, and polyurethane sponge as substrates. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of this invention clearer, the embodiments of this invention will be described in further detail below with reference to the accompanying drawings. It should be noted that the following embodiments are only for a better understanding of this invention and do not constitute a limitation on the scope of protection of this invention.

[0042] The contact angle testing method of this invention: In this invention, the water contact angle of the fiber felt is tested using a contact angle measuring instrument at room temperature (25±2℃). During the test, 3.0 μL of deionized water is dropped onto the felt surface, and the measurement is performed using the seated drop method. At least 5 different locations are selected for testing for each sample, and the average value is taken as the final contact angle.

[0043] The oil absorption performance test method of this invention: The high-viscosity crude oil used in this invention has a viscosity of 105 mPa·s at room temperature (25℃). During the test, 0.5 mL of crude oil is dropped onto the surface of the felt, and the time required for the crude oil drop to be completely absorbed is recorded. The light-assisted test uses a simulated sunlight source with an illumination intensity of 1 kW / m²; the electric-assisted test applies a 10V DC voltage to both ends of the felt.

[0044] Example 1

[0045] 1. Preparation method

[0046] S1: Cut the raw material felt (C-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0047] S2: At room temperature, dissolve 1g of polyvinyl alcohol (PVA) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0048] S3: Dissolve 0.5g of pyrrole monomer in 40mL of ethanol to form solution A. Weigh 0.03g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 1.19g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 4 hours at a shaking frequency of 100r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0049] S4: Soak the above felt in a 10 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80 °C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0050] S5: Place the above felt in a container containing 1 mL of methyltrimethoxysilane (MTMS) and 1 mL of deionized water, and perform vapor deposition at 80°C for 5 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0051] 2. Performance Test Results

[0052] like Figure 1 As shown, in this embodiment, the fiber felt has polypyrrole particles, MXene nanosheets, and hydrophobic methyltrimethoxysilane particles uniformly distributed and fixed on the surface of the felt skeleton through PVA adhesion.

[0053] like Figure 2 As shown in Table 2 below, the fiber felt prepared in this embodiment has a 3.0 μL water contact angle of 152 ± 2°, achieving a good hydrophobic effect.

[0054] like Figure 3 As shown in Table 3 below, the felt prepared in this embodiment has excellent heating capacity, reaching a temperature of approximately 101°C under 1kW / m² sunlight intensity (compared to approximately 36°C for the original felt). Its resistivity is 110Ω, significantly lower than Comparative Example A (polypyrrole only, 400Ω) and Comparative Example B (MXene only, 300Ω). Figure 1 As shown, polypyrrole and MXene are composited on the fiber surface to form a three-dimensional composite conductive network, demonstrating their synergistic conductive effect.

[0055] The oil absorption performance test results are shown in Table 1: Under 1kW / m² light assisted, the complete absorption time of the modified C-shaped felt in this embodiment for 0.5mL crude oil droplets is 50±3s; under 10V electric heating assisted, the complete absorption time is 110±4s.

[0056] Table 1 compares the oil absorption time of the felt in Example 1 with that of the original felt.

[0057] Table 1:

[0058]

[0059] The above results demonstrate that the method and C-shaped structure of this invention can significantly improve the absorption rate of high-viscosity crude oil by the material.

[0060] Example 2

[0061] 1. Preparation method

[0062] S1: Cut the raw material felt (C-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0063] S2: At room temperature, dissolve 1g of polyethylene glycol (PEG) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0064] S3: Dissolve 0.4g of pyrrole monomer in 50mL of ethanol to form solution A. Weigh 0.02g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 1.14g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 4 hours at a shaking frequency of 100r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0065] S4: Immerse the above felt in an 8 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80°C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0066] S5: Place the above felt in a container containing 1 mL of methyltriethoxysilane (MTES) and 1 mL of deionized water, and perform vapor deposition at 80°C for 5 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0067] 2. Performance Test Results

[0068] Tests showed that the water contact angle of the fiber felt prepared in this embodiment was 145±1°, and the resistivity was 120Ω. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 55±3s; under 10V electric heating irradiation, the complete absorption time was 125±5s.

[0069] Example 3

[0070] 1. Preparation method

[0071] S1: Cut the raw material felt (C-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0072] S2: At room temperature, dissolve 0.6g of polyethylene glycol (PEG) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0073] S3: Dissolve 0.4g of pyrrole monomer in 40mL of ethanol to form solution A. Weigh 0.03g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 0.95g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 2 hours at a shaking frequency of 100r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0074] S4: Immerse the above felt in a 6 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80°C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0075] S5: Place the above felt in a container containing 1 mL of methyltrimethoxysilane (MTMS) and 1 mL of deionized water, and perform vapor deposition at 80°C for 4 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0076] 2. Performance Test Results

[0077] The water contact angle of the fiber felt prepared in this embodiment was 146±1° and the resistivity was 200Ω, as tested. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 54±3s; under 10V electric heating irradiation, the complete absorption time was 168±4s.

[0078] Example 4

[0079] 1. Preparation method

[0080] S1: Cut the raw material felt (Y-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0081] S2: At room temperature, dissolve 0.6g of polyethylene glycol (PEG) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0082] S3: Dissolve 0.3g of pyrrole monomer in 40mL of ethanol to form solution A. Weigh 0.02g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 1.065g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 4 hours at a shaking frequency of 80r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0083] S4: Immerse the above felt in a 10 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80 °C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0084] S5: Place the above felt in a container containing 1 mL of methyltriethoxysilane (MTES) and 1 mL of deionized water, and perform vapor deposition at 80°C for 5 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0085] 2. Performance Test Results

[0086] Tests showed that the water contact angle of the fiber felt prepared in this embodiment was 148±1°, and the resistivity was 150Ω. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 52±2s; under 10V electric heating irradiation, the complete absorption time was 152±4s.

[0087] Example 5

[0088] 1. Preparation method

[0089] S1: Cut the raw material felt (C-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0090] S2: At room temperature, dissolve 0.4g of polyvinyl alcohol (PVA) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0091] S3: Dissolve 0.3g of pyrrole monomer in 20mL of ethanol to form solution A. Weigh 0.02g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 0.95g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 2 hours at a shaking frequency of 60r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0092] S4: Immerse the above felt in a 5 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 60°C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0093] S5: Place the above felt in a container containing 1 mL of methyltrichlorosilane (MTCS) and 1 mL of deionized water, and perform vapor deposition at 80°C for 3 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0094] 2. Performance Test Results

[0095] Tests showed that the water contact angle of the fiber felt prepared in this embodiment was 140±1°, and the resistivity was 500Ω. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 54±3s; under 10V electric heating irradiation, the complete absorption time was 500±20s.

[0096] Example 6

[0097] 1. Preparation method

[0098] S1: Cut the raw material felt (C-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0099] S2: At room temperature, dissolve 0.4g of polyethylene glycol (PEG) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0100] S3: Dissolve 0.3g of pyrrole monomer in 20mL of ethanol to form solution A. Weigh 0.04g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 1.42g of ferric chloride to prepare 30mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 3 hours at a shaking frequency of 60r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0101] S4: Immerse the above felt in a 9 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80°C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0102] S5: Place the above felt in a container containing 1 mL of methyltrimethoxysilane (MTMS) and 1 mL of deionized water, and perform vapor deposition at 80°C for 4 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0103] 2. Performance Test Results

[0104] The water contact angle of the fiber felt prepared in this embodiment was 146±1° and the resistivity was 160Ω, as tested. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 52±3s; under 10V electric heating irradiation, the complete absorption time was 138±3s.

[0105] Example 7

[0106] 1. Preparation method

[0107] S1: Cut the raw material felt (Y-shaped cross section) into pieces with a side length of 5cm×5cm×0.4cm, immerse them in an aqueous solution containing 50% volume ethanol for 10 minutes, remove them, squeeze them dry and dry them at 80℃ to obtain the pretreated felt.

[0108] S2: At room temperature, dissolve 0.4g of polyvinyl alcohol (PVA) in 200mL of deionized water to obtain an adhesive solution. Immerse the dried felt in this solution, squeeze it out, and dry it at 80℃ to form an adhesive layer.

[0109] S3: Dissolve 0.4g of pyrrole monomer in 20mL of ethanol to form solution A. Weigh 0.04g of sodium dodecylbenzenesulfonate and dissolve it in 50mL of deionized water to form solution B. Pour solution B into solution A to form mixed solution C. Add the fiber felt with the binder layer to solution C. Using ferric chloride as an oxidant, weigh 0.955g of ferric chloride to prepare 50mL of aqueous solution, pour it into the above mixed solution C, seal it, and place it in a shaker to react for 2 hours at a shaking frequency of 80r / min. After the reaction is complete, wash and dry to form a polypyrrole layer.

[0110] S4: Immerse the above felt in a 6 mg / mL MXene nanosheet aqueous solution for 10 min, drain, and dry at 80°C to form an MXene nanosheet layer. The polypyrrole layer and the MXene nanosheet layer together constitute the functional layer.

[0111] S5: Place the above felt in a container containing 1 mL of methyltrichlorosilane (MTCS) and 1 mL of deionized water, and perform vapor deposition at 55°C for 5 hours to form a hydrophobic silane coating, thus obtaining fiber felt.

[0112] 2. Performance Test Results

[0113] The water contact angle of the fiber felt prepared in this embodiment was 143±2° and the resistivity was 320Ω, as tested. Under 1kW / m² light irradiation, the complete absorption time for a 0.5mL crude oil droplet was 54±3s; under 10V electric heating irradiation, the complete absorption time was 230±10s.

[0114] Comparative Example A

[0115] Comparative Example A is basically the same as Example 1, except that: in step S4, no MXene nanosheet layer is loaded, that is, only the polypyrrole layer is used as the functional layer, without containing MXene nanosheet layer. All other steps are the same as in Example 1.

[0116] Comparative Example B

[0117] Comparative Example B is basically the same as Example 1, except that a polypyrrole layer is not formed in step S3; that is, only the MXene nanosheet layer is used as the functional layer, without the polypyrrole layer. All other steps are the same as in Example 1.

[0118] Comparison of properties of irregularly shaped fibers

[0119] like Figure 4As shown, the diffusion ability of single fibers with different cross-sectional shapes for high-viscosity oil droplets was compared. Under illumination of 1 kW / m², oil droplets on R-shaped (circular) fibers appeared only as barrel-shaped droplets; while on Y-shaped and C-shaped fibers, the oil droplets diffused along the fiber axis, with the C-shaped fiber exhibiting the fastest diffusion rate. This indicates that shaped fibers have superior diffusion performance compared to ordinary circular fibers.

[0120] like Figure 6 As shown, different oil-absorbing materials were prepared using polyurethane sponge, C-shaped fiber felt, and R-shaped fiber felt as substrates, according to the formulation of Example 1, and their dynamic oil absorption rate curves under 1kW / m² light irradiation were tested. The results show that the oil absorption rate of C-shaped fiber felt is significantly faster than that of polyurethane sponge and R-shaped fiber felt.

[0121] All-weather oil absorption performance verification

[0122] like Figure 5 As shown, C-shaped felt reacts with high-viscosity oil (viscosity 10 at room temperature 25℃) under different conditions. 5 The absorption performance (mPa·s) indicates that the material's absorption effect is poor in the absence of light; however, the felt can effectively absorb crude oil under both sunlight (1kW / m², simulating a sunny day) and insufficient light (0.5kW / m², simulating a cloudy day); even under conditions of no sunlight at night, only a 10V voltage is required to achieve rapid absorption of crude oil. This demonstrates that the felt of this invention has the ability to recover high-viscosity oils in all weather conditions.

[0123] The performance parameters of each embodiment are summarized in Table 2.

[0124] Table 2:

[0125]

[0126] As shown in Table 2, the water contact angles of the fiber felts prepared in each embodiment of the present invention are all greater than 140°, exhibiting good hydrophobic properties; their resistivity values ​​are between 110Ω and 500Ω, demonstrating electrothermal response capabilities; and they can achieve rapid absorption of high-viscosity crude oil under both light-assisted and electric-assisted conditions, indicating that the technical solution of the present invention has broad applicability and feasibility. Among them, Example 1, which uses C-shaped cross-section fibers, PVA binder, and a 10 mg / mL MXene concentration, exhibits the best overall performance.

[0127] Table 3 summarizes the effects of different coating loads on felt performance.

[0128] Table 3:

[0129]

[0130] Compared to Comparative Example A (polypyrrole layer only) and Comparative Example B (MXene layer only), Example 1 (polypyrrole layer + MXene layer) exhibited the lowest resistance (110 Ω), the shortest electrothermal oil absorption time (110 s), and the best coating adhesion (with a peeling rate of only 2%). This indicates that polypyrrole and MXene are composited on the fiber surface, forming a three-dimensional composite conductive network and producing a significant synergistic effect. Specifically, polypyrrole forms a continuous conductive framework on the fiber surface, while MXene nanosheets, as highly conductive fillers, fill the gaps in the network. Together, they construct an efficient three-dimensional conductive pathway, thereby significantly improving the electrothermal conversion efficiency of the material.

[0131] The fiber felt and its preparation method provided by this invention are simple, operate under mild conditions, and use readily available raw materials. The resulting fiber felt possesses excellent hydrophobic properties and synergistic heating capabilities of photothermal and Joule heating, enabling rapid recovery of high-viscosity crude oil under all-weather conditions, including sunny days, cloudy days, and nighttime. This material is particularly suitable for marine oil spill treatment, oily industrial wastewater purification, and oil spill recovery, and has promising prospects for industrial application.

[0132] The above are merely specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions, or modifications made based on the present invention to solve essentially the same technical problems and achieve essentially the same technical effects are all covered within the protection scope of the present invention.

Claims

1. A fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, characterized in that, include: Fiber-based substrates composed of irregularly shaped cross-section fibers, and An adhesive layer, a functional layer, and a hydrophobic coating are sequentially loaded onto the surface of the fiber substrate; The functional layer is used to generate Joule heating when energized and to generate a photothermal effect under illumination.

2. The fiber felt for rapid, all-weather recovery of high-viscosity crude oil according to claim 1, characterized in that: The cross-sectional shape of the irregular cross-section fiber is C-shaped or Y-shaped.

3. The fiber felt for rapid, all-weather recovery of high-viscosity crude oil according to claim 1, characterized in that: The functional layer includes a conductive polymer layer and a nanosheet layer, wherein the conductive polymer layer is a polypyrrole layer and the nanosheet layer is an MXene nanosheet layer.

4. The fiber felt for rapid, all-weather recovery of high-viscosity crude oil according to claim 1, characterized in that: The hydrophobic coating is a silane coating.

5. The fiber felt for rapid, all-weather recovery of high-viscosity crude oil according to claim 4, characterized in that: The silane reagent used for the silane coating is selected from one of methyltrimethoxysilane, methyltriethoxysilane, or methyltrichlorosilane.

6. The fiber felt for rapid, all-weather recovery of high-viscosity crude oil according to claim 3, characterized in that: The conductive polymer layer and the nanosheet layer are combined to form a three-dimensional composite conductive network.

7. A method for preparing a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1: Provide a fiber substrate made of irregularly shaped cross-section fibers and pre-treat it; S2: Immerse the pretreated fiber substrate in the adhesive solution and dry it to form an adhesive layer on the surface of the pretreated fiber substrate; S3: A conductive polymer layer is formed on the surface of a fiber substrate having an adhesive layer; S4: Load the nanosheet layer onto the fiber substrate treated in step S3 and dry it; wherein, the conductive polymer layer and the nanosheet layer together constitute the functional layer; S5: The surface of the fiber substrate after step S4 is hydrophobically modified to form a hydrophobic coating, thereby obtaining the fiber felt.

8. The method for preparing a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in claim 7, is characterized in that: In step S2, the adhesive solution is an aqueous solution of polyvinyl alcohol or polyethylene glycol with a concentration of 0.4 g / 200 mL to 1 g / 200 mL.

9. The method for preparing a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in claim 7, is characterized in that: In step S3, the method for forming the conductive polymer layer is as follows: pyrrole monomer is subjected to in-situ polymerization on the surface of a fiber substrate with an adhesive layer using ferric chloride as an oxidant to form a polypyrrole layer; wherein the molar ratio of pyrrole monomer to ferric chloride is 1:1 to 1:2, and the reaction time is 2 to 4 hours.

10. The method for preparing a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in claim 7, is characterized in that: In step S4, the nanosheet layer is an MXene nanosheet layer, and the concentration of the MXene nanosheet solution used during loading is 2 mg / mL to 10 mg / mL.

11. The method for preparing a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in claim 7, is characterized in that: In step S5, hydrophobic modification is performed by vapor deposition at a temperature of 60°C to 80°C for 3 to 5 hours. The silane reagent used is selected from one of methyltrimethoxysilane, methyltriethoxysilane, or methyltrichlorosilane.

12. The application of a fiber felt capable of rapidly recovering high-viscosity crude oil in all weather conditions, as described in any one of claims 1 to 6, in the adsorption and recovery of high-viscosity crude oil or in the treatment of oil spills on water surfaces containing high-viscosity crude oil.

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