Superhydrophobic superoleophilic renewable oil-water separation material, and preparation method and application thereof

Abstract

The application belongs to the technical field of oil-water separation, and particularly relates to a super-hydrophobic super-oil-wetting renewable oil-water separation material and a preparation method and application thereof. The preparation method of the super-hydrophobic super-oil-wetting renewable oil-water separation material comprises the following steps: (1) cleaning and plasma pretreating carbon fibers; (2) coating a Cu-TiO2 seed layer on the surface of the pretreated carbon fibers, and depositing Cu-TiO2 nanocrystals on the surface of the Cu-TiO2 seed layer; and (3) modifying the Cu-TiO2 nanocrystals in step (2) by using long-chain carboxylic acid to obtain the super-hydrophobic super-oil-wetting renewable oil-water separation material. The super-hydrophobic super-oil-wetting renewable oil-water separation material has excellent super-hydrophobic and super-oil-wetting properties, high separation efficiency for oil-water mixtures, and can be recycled and utilized by using the photocatalytic performance of Cu-TiO2. The preparation process of the separation material is simple, easy to industrialize, and has a good application prospect in the field of oil-water separation.

Description

Technical Field

[0001] This application belongs to the field of oil-water separation technology, specifically relating to a superhydrophobic and superoleophilic renewable oil-water separation material, its preparation method, and its application. Background Technology

[0002] As industrialization progresses, the amount of oily wastewater discharged from oilfield extraction, steel smelting, and many other sectors is increasing daily. If this polluted wastewater is not properly treated, it will cause serious economic losses and environmental pollution. To address the severe problem of oily wastewater pollution, gravity sedimentation, centrifugation, adsorption, chemical separation, and biological treatment have been applied in the field of oil-water separation. However, each of these separation technologies has its limitations. Gravity sedimentation cannot handle dissolved and emulsified oils; adsorption methods are costly and have low recovery rates; and biological treatment is inefficient. In contrast, membrane separation technology, with its advantages of energy saving, environmental protection, and high separation efficiency, shows a broader application prospect. Among them, superhydrophobic / superoleophilic membrane materials have the advantages of good oil-water separation selectivity and high separation flux, and are considered the most promising oil-water separation materials. However, superhydrophobic / superoleophilic membrane materials are susceptible to corrosion and contamination during use, leading to poor recyclability and decreased separation efficiency, thus failing to meet the actual needs of long-term operation. Summary of the Invention

[0003] This application provides a superhydrophobic and superoleophilic regenerable oil-water separation material, its preparation method, and its application, aiming to solve the problems of low separation efficiency, poor stability, and inability to regenerate and recycle existing oil-water separation materials.

[0004] The first aspect of this application provides a method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material, comprising the following steps: (1) Cleaning and plasma pretreatment of carbon fibers; (2) A Cu-TiO2 seed layer is coated on the surface of the pretreated carbon fiber, and Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer; (3) The Cu-TiO2 nanocrystals described in step (2) are modified with long-chain carboxylic acids to obtain the superhydrophobic and superoleophilic renewable oil-water separation material.

[0005] According to some embodiments of the preparation method of superhydrophobic and superoleophilic renewable oil-water separation material described in this application, in step (1), the cleaning pretreatment step includes: immersing the carbon fiber in sodium carbonate solution and nitric acid in sequence for cleaning treatment.

[0006] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the mass concentration of the sodium carbonate solution is 0.5%-2%, the immersion temperature of the carbon fiber in the sodium carbonate solution is 20-30℃, and the immersion time of the carbon fiber in the sodium carbonate solution is 1-4h.

[0007] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the mass concentration of the nitric acid is 10%-25%, the immersion temperature of the carbon fiber in the nitric acid is 20-30℃, and the immersion time of the carbon fiber in the nitric acid is 1-4h.

[0008] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the vacuum degree of the plasma pretreatment is 20-60 Pa, the power of the plasma pretreatment is 80-200 W, and the duration of the plasma pretreatment is 5-30 min.

[0009] According to some embodiments of the preparation method of superhydrophobic and superoleophilic renewable oil-water separation material described in this application, in step (2), the pretreated carbon fiber is immersed in Cu-TiO2 solution. After the immersion is completed, the immersed carbon fiber is subjected to vacuum plasma treatment and heat treatment in sequence to achieve the coating of Cu-TiO2 seed layer on the surface of carbon fiber.

[0010] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the raw materials for preparing the Cu-TiO2 solution include a titanium source, a chelating agent, a copper source, and a solvent.

[0011] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the titanium source includes tetrabutyl titanate.

[0012] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the chelating agent includes benzoyl acetone and / or acetylacetone.

[0013] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the copper source includes one or more of copper nitrate, copper sulfate, and copper acetate.

[0014] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the solvent includes one or more of methanol, ethanol, and propanol.

[0015] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the molar ratio of titanium source to copper source in the raw materials for preparing the Cu-TiO2 solution is 1:(0.01-0.1).

[0016] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the molar ratio of titanium source and chelating agent in the raw materials for preparing the Cu-TiO2 solution is 1:(0.8-1.2).

[0017] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the molar ratio of titanium source to solvent in the Cu-TiO2 solution is 1:(80-350). According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the pretreated carbon fiber is impregnated in Cu-TiO2 solution at a temperature of 20-30°C for a duration of 5-20 minutes.

[0018] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the vacuum degree of the impregnated carbon fiber is 20-60 Pa, the power is 80-200 W, and the treatment time is 5-30 min.

[0019] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the heat treatment temperature is 300-500℃ and the heat treatment time is 1-4h.

[0020] According to some embodiments of the preparation method of superhydrophobic and superoleophilic renewable oil-water separation material described in this application, carbon fibers coated with Cu-TiO2 seed layer are brought into contact with Cu-TiO2 solution for hydrothermal reaction to achieve the deposition of Cu-TiO2 nanocrystals on the surface of Cu-TiO2 seed layer.

[0021] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the temperature of the hydrothermal reaction is 80-120℃, and the time of the hydrothermal reaction is 6-12h.

[0022] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the carbon fibers with Cu-TiO2 nanocrystals deposited in step (2) are contacted with a long-chain carboxylic acid modifier solution to carry out a self-assembly reaction, thereby obtaining the superhydrophobic and superoleophilic renewable oil-water separation material.

[0023] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the long-chain carboxylic acid modifier solution includes long-chain carboxylic acids and organic solvents.

[0024] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the mass concentration of the long-chain carboxylic acid in the long-chain carboxylic acid modifier solution is 0.5%-5%.

[0025] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the long-chain carboxylic acid includes one or more of lauric acid, myristic acid, stearic acid, and oleic acid.

[0026] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the organic solvent includes one or more of methanol, ethanol, and isopropanol.

[0027] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the temperature of the self-assembly reaction is 50-80℃, and the time of the self-assembly reaction is 1-8h.

[0028] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic regenerable oil-water separation material described in this application, the method also includes a material regeneration operation: By using ultraviolet light to irradiate and separate superhydrophobic and superoleophilic regenerable oil-water separation materials whose performance has deteriorated, and then modifying them with long-chain carboxylic acids, the superhydrophobic and superoleophilic regenerable oil-water separation materials can be regenerated.

[0029] According to some embodiments of the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in this application, the main wavelength of ultraviolet light irradiation is 254-365nm, preferably 254nm, 300nm and 365nm; the duration of ultraviolet light irradiation is 40-80min.

[0030] The second aspect of this application provides a superhydrophobic and superoleophilic renewable oil-water separation material, which is prepared by the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in the first aspect of this application.

[0031] The third aspect of this application provides the application of a superhydrophobic and superoleophilic renewable oil-water separation material prepared by the method described in the first aspect of this application, or the superhydrophobic and superoleophilic renewable oil-water separation material described in the second aspect of this application, in the treatment of industrial oily wastewater and emergency response to marine oil spills.

[0032] The beneficial effects of this application include: First, a Cu-TiO2 seed layer is coated onto carbon fibers using plasma treatment and sol-gel impregnation methods. Then, Cu-TiO2 nanocrystals are further deposited on the seed layer using a hydrothermal process. This preparation process not only ensures the deposition efficiency of Cu-TiO2 crystals but also guarantees good adhesion between the functional coating and the substrate. This endows the Cu-TiO2-coated carbon fiber superhydrophobic / superoleophilic renewable oil-water separation material with excellent structural stability and durability, as well as highly efficient superwetting and separation performance. Furthermore, the process is simple, the parameters are controllable, and it is suitable for industrial production.

[0033] This application modifies Cu-TiO2 nanocrystals with long-chain carboxylic acids, and by controlling the surface chemical composition and surface energy, endows the material with superhydrophobic / superoleophilic superwetting properties. This enables rapid oil phase penetration and efficient water phase barrier, thus exhibiting excellent oil-water separation performance.

[0034] The Cu-TiO2-coated carbon fiber renewable oil-water separation material prepared in this application has Cu-TiO2 nanocrystals on its surface with excellent photocatalytic activity. When pollutants remain on the material surface, these Cu-TiO2 nanocrystals can exert photocatalytic activity to degrade the pollutants simply by irradiating them with ultraviolet light. Furthermore, by modifying the material with long-chain carboxylic acids again, the superhydrophobic / superoleophilic function of the material can be completely restored, thereby enabling the material to be recycled and reused multiple times. Attached Figure Description

[0035] Figure 1 The image shows the XRD pattern of the superhydrophobic and superoleophilic renewable oil-water separation material described in Example 1 of this application. Figure 2 This is a SEM image of the superhydrophobic and superoleophilic renewable oil-water separation material described in Example 1 of this application; Figure 3 This is a diagram showing the water contact angle and oil contact angle of the superhydrophobic and superoleophilic renewable oil-water separation material described in Embodiment 1 of this application; Figure 4 This is an oil-water separation flux diagram of the superhydrophobic and superoleophilic renewable oil-water separation material described in Examples 1-4 of this application. Detailed Implementation

[0036] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0037] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0038] This application provides a method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material, including the following steps: (1) Cleaning and plasma pretreatment of carbon fibers; (2) A Cu-TiO2 seed layer is coated on the surface of the pretreated carbon fiber, and Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer; (3) The Cu-TiO2 nanocrystals described in step (2) are modified with long-chain carboxylic acids to obtain the superhydrophobic and superoleophilic renewable oil-water separation material.

[0039] Carbon fiber (CF) possesses excellent physicochemical stability and good mechanical strength, making it an ideal substrate for preparing membrane separation materials. Titanium dioxide (TiO2) exhibits superior photocatalytic degradation performance; modifying the surface of carbon fiber with TiO2 can endow membrane materials with the ability to efficiently degrade organic pollutants adhering to their surface. This application uses carbon fiber as a substrate and employs processes such as plasma treatment, impregnation, and hydrothermal reaction, followed by a self-assembly reaction, to successfully prepare a superhydrophobic / superoleophilic regenerable oil-water separation material coated with Cu-TiO2 modified with long-chain carboxylic acids. In various oil-water systems, the material described in this application can achieve efficient and stable selective separation of oil and water. Furthermore, through photocatalytic degradation, it can effectively remove surface pollutants, thereby restoring its initial performance and enabling recycling. This material shows broad application prospects in the field of oil-water separation and is expected to effectively solve the problems faced by existing membrane materials in terms of recycling.

[0040] In some embodiments of this application, step (1) includes cleaning pretreatment step: immersing carbon fiber in sodium carbonate solution and nitric acid in sequence for cleaning treatment.

[0041] In some embodiments of this application, the mass concentration of the sodium carbonate solution is 0.5%-2%, the immersion temperature of the carbon fiber in the sodium carbonate solution is 20-30°C, and the immersion time of the carbon fiber in the sodium carbonate solution is 1-4 hours. After immersion, the carbon fiber is removed, rinsed with deionized water, dried at 40-100°C for 2-4 hours, and then immersed in nitric acid.

[0042] In some embodiments of this application, the mass concentration of the nitric acid is 10%-25%, the immersion temperature of the carbon fiber in the nitric acid is 20-30°C, and the immersion time of the carbon fiber in the nitric acid is 1-4 hours. After immersion, the carbon fiber is removed, rinsed with deionized water until the surface is neutral, and dried at a temperature of 40-100°C for 2-4 hours.

[0043] In some embodiments of this application, the vacuum degree of the plasma pretreatment is 20-60 Pa, the power of the plasma pretreatment is 80-200 W, and the duration of the plasma pretreatment is 5-30 min.

[0044] In some embodiments of this application, in step (2), the pretreated carbon fiber is immersed in a Cu-TiO2 solution. After immersion, the immersed carbon fiber is subjected to vacuum plasma treatment and heat treatment in sequence to achieve the coating of a Cu-TiO2 seed layer on the surface of the carbon fiber. The coating of the carbon fiber surface with a Cu-TiO2 seed layer ensures its good bonding force with the substrate, improves the deposition efficiency of Cu-TiO2 crystals, and makes the superhydrophobic and superoleophilic renewable oil-water separation material have excellent structural stability and durability.

[0045] In some embodiments of this application, the raw materials for preparing the Cu-TiO2 solution include a titanium source, a chelating agent, a copper source, and a solvent.

[0046] In some embodiments of this application, the titanium source includes tetrabutyl titanate.

[0047] In some embodiments of this application, the chelating agent includes benzoylacetone and / or acetylacetone.

[0048] In some embodiments of this application, the copper source includes one or more of copper nitrate, copper sulfate, and copper acetate.

[0049] In some embodiments of this application, the solvent includes one or more of methanol, ethanol, and propanol.

[0050] In some embodiments of this application, the molar ratio of titanium source to copper source in the raw materials for preparing the Cu-TiO2 solution is 1:(0.01-0.1), for example 1:0.01, 1:0.03, 1:0.05, 1:0.08, 1:0.1, etc.

[0051] In some embodiments of this application, the molar ratio of titanium source and chelating agent in the raw materials for preparing Cu-TiO2 solution is 1:(0.8-1.2), for example 1:0.8, 1:0.9, 1:1.0, 1:1.2, etc.

[0052] In some embodiments of this application, the molar ratio of titanium source to solvent in the Cu-TiO2 solution is 1:(80-350), such as 1:80, 1:100, 1:180, 1:210, 1:260, 1:300, 1:320, 1:350, etc.

[0053] In some embodiments of this application, the volume of the Cu-TiO2 solution is not specified; the solution is simply in excess and the carbon fiber is submerged.

[0054] In some embodiments of this application, the pretreated carbon fibers are impregnated in Cu-TiO2 solution at a temperature of 20-30°C for 5-20 minutes. After impregnation, they are removed, spun dry, and then dried at 50-120°C for 1-4 hours.

[0055] In some embodiments of this application, the vacuum degree of the impregnated carbon fiber is 20-60 Pa, the power is 80-200 W, and the treatment time is 5-30 min.

[0056] In some embodiments of this application, the temperature of the heat treatment is 300-500℃, such as 300℃, 350℃, 380℃, 430℃, 460℃, 500℃, etc., and the time of the heat treatment is 1-4h, such as 1h, 2h, 3h, 4h, etc.

[0057] In some embodiments of this application, carbon fibers coated with a Cu-TiO2 seed layer are brought into contact with a Cu-TiO2 solution for a hydrothermal reaction to deposit Cu-TiO2 nanocrystals on the surface of the Cu-TiO2 seed layer. After deposition, the product is removed and dried at 80-120°C for 12-24 hours.

[0058] In some embodiments of this application, the volume of the Cu-TiO2 solution is not specified; the solution is in excess and the carbon fiber is submerged in the solution. In some embodiments of this application, the temperature of the hydrothermal reaction is 80-120°C, such as 80°C, 90°C, 105°C, 110°C, 120°C, etc., and the time of the hydrothermal reaction is 6-12h, such as 6h, 8h, 10h, 12h, etc.

[0059] In some embodiments of this application, the carbon fibers deposited with Cu-TiO2 nanocrystals obtained in step (2) are contacted with a long-chain carboxylic acid modifier solution to perform a self-assembly reaction, thereby obtaining the superhydrophobic and superoleophilic renewable oil-water separation material. Because the long carbon chains are nonpolar groups, they can significantly reduce surface energy, making the material surface highly repellent to water. Water cannot wet the surface upon contact, and the resulting water droplets easily roll off and are difficult to spread. However, it has good affinity for oil, allowing oil to spread rapidly and be adsorbed.

[0060] In some embodiments of this application, the long-chain carboxylic acid modifier solution comprises a long-chain carboxylic acid and an organic solvent.

[0061] In some embodiments of this application, the mass concentration of the long-chain carboxylic acid in the long-chain carboxylic acid modifier solution is 0.5%-5%; for example, 0.5%, 1.2%, 1.8%, 2.3%, 3.6%, 4.1%, 5%, etc.

[0062] In some embodiments of this application, the long-chain carboxylic acid includes one or more of lauric acid, myristic acid, stearic acid, and oleic acid.

[0063] In some embodiments of this application, the organic solvent includes one or more of methanol, ethanol, and isopropanol.

[0064] In some embodiments of this application, the volume of the long-chain carboxylic acid modifier solution is not specified; the modifier solution is in excess and the carbon fiber is submerged in the solution. In some embodiments of this application, the temperature of the self-assembly reaction is 50-80°C, such as 50°C, 60°C, 68°C, 73°C, 80°C, etc., and the time of the self-assembly reaction is 1-8h, such as 1h, 3h, 4h, 5h, 8h, etc.

[0065] In some embodiments of this application, a material regeneration operation is also included: ultraviolet light is used to irradiate the superhydrophobic and superoleophilic regenerable oil-water separation material whose separation performance has deteriorated, and then long-chain carboxylic acids are used for modification to achieve the regeneration of the superhydrophobic and superoleophilic regenerable oil-water separation material.

[0066] In some embodiments of this application, the main wavelength of ultraviolet light irradiation is 254-365nm, preferably 254nm, 300nm and 365nm; the duration of ultraviolet light irradiation is 40-80min.

[0067] This application also provides a superhydrophobic and superoleophilic renewable oil-water separation material, which is prepared by the preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material described in the first aspect of this application.

[0068] The superhydrophobic and superoleophilic regenerable oil-water separation material described in this application is made by plasma treatment of carbon fibers, which activates the surface and facilitates subsequent coating adhesion. A Cu-TiO2 seed layer is coated onto the carbon fibers using a sol-gel impregnation method, followed by hydrothermal deposition of Cu-TiO2 nanocrystals on the seed layer, ensuring efficient deposition and good adhesion between the functional coating and the substrate. Through the self-assembly reaction of long-chain carboxylic acids and Cu-TiO2 nanocrystals, the long-chain hydrocarbon groups of the carboxylic acids are chemically bonded to the surface. Since the long-chain hydrocarbon groups are nonpolar, they significantly reduce surface energy, resulting in a strong water repellency; water cannot wet upon contact and forms droplets that easily roll off and are difficult to spread. However, it has good affinity for oil, allowing oil to spread and be adsorbed quickly. When the performance of the carbon fibers deteriorates after use, the photocatalytic properties of Cu-TiO2 oxidize and decompose the oil on the surface after irradiation, restoring the surface structure and activity, thus achieving regenerative recycling and efficient oil-water separation.

[0069] This application also provides an application of the superhydrophobic and superoleophilic renewable oil-water separation material prepared by the method described in the first aspect of this application, or the superhydrophobic and superoleophilic renewable oil-water separation material described in the second aspect of this application, in industrial oily wastewater treatment and marine oil spill emergency response.

[0070] The technical solution of this application will be further described below with reference to specific embodiments.

[0071] Example 1 A method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material includes the following steps: Step 1.1: Immerse the carbon fiber in a 0.5% sodium carbonate (Na2CO3) solution at 25°C for 4 hours. After immersion, rinse with deionized water and dry at 40°C for 4 hours. Step 1.2: Immerse the carbon fiber dried in step 1.1 in a 10% dilute nitric acid solution at 25°C for 4 hours. After immersion, rinse with deionized water until the surface is neutral and dry at 40°C for 4 hours. Step 1.3: The carbon fiber treated in step 1.2 is subjected to plasma treatment, wherein the vacuum degree of plasma treatment is 20 Pa, the power is 80 W, and the treatment time is 30 min.

[0072] Step 2: Weigh 3.2 mmol of tetrabutyl titanate and dissolve it in 262 mmol of anhydrous ethanol solution. Then add 3.84 mmol of benzoyl acetone to the mixed solution and stir well. Next, weigh 0.32 mmol of copper nitrate and dissolve it in 858 mmol of anhydrous ethanol and stir thoroughly. Then mix the two solutions to obtain Cu-TiO2 solution, wherein the molar ratio of titanium source to copper salt is 1:1. Step 3.1: Immerse the pretreated carbon fiber obtained in Step 1 in a Cu-TiO2 solution (the solution should completely submerge the carbon fiber) at a temperature of 25°C for 5 minutes. After immersion, remove the carbon fiber and spin it dry with tweezers. Then dry it at 50°C for 4 hours. Step 3.2: The dried material is subjected to vacuum plasma treatment for 30 min under a vacuum degree of 20 Pa and a plasma power of 80 W, and then placed in a heating furnace at a temperature of 300 °C for 4 h for heat treatment; to achieve the coating of Cu-TiO2 seed layer on the carbon fiber surface; Step 4: Place the carbon fiber coated with Cu-TiO2 seed layer into a reaction vessel containing Cu-TiO2 solution (the solution should immerse the carbon fiber), seal it, and heat it fully in an oven at 80°C for 12 hours. After the reaction vessel cools to room temperature, remove it and dry it at 90°C for 24 hours; thus, Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer.

[0073] Step 5: Weigh 0.5g of lauric acid and add it to 99.5g of methanol solution. Stir and dissolve thoroughly to obtain lauric acid modifier solution. Place the carbon fiber coated with Cu-TiO2 nanocrystals into the lauric acid modifier solution (the solution should just cover the carbon fiber) and perform a self-assembly reaction at 50℃ for 8h. After the reaction is complete, remove the carbon fiber, wash it three times with ethanol, and dry it at 80℃ for 14h to obtain the superhydrophobic and superoleophilic renewable oil-water separation material, denoted as Cu-TiO2@CF.

[0074] The XRD pattern of the superhydrophobic and superoleophilic renewable oil-water separation material prepared in Example 1 of this application is shown below. Figure 1 As shown.

[0075] from Figure 1 It can be seen that the diffraction peaks at 25.8°, 37.8°, 48.0°, 53.9°, 55.0°, 62.1°, and 70.3° correspond to the (101), (004), (200), (105), (211), (213), and (220) crystal planes of the anatase crystal form, respectively. The results show that the Cu-TiO2 coatings prepared by the sol-gel method are all anatase structures, indicating that Cu doping did not change the anatase structure of TiO2.

[0076] Scanning electron microscope image of the superhydrophobic and superoleophilic renewable oil-water separation material prepared in Example 1 of this application, as shown below. Figure 2 As shown ( Figure 2 a1 shows the microstructure of the superhydrophobic and superoleophilic renewable oil-water separation material at a scale bar of 5 μm. Figure 2 a2 is Figure 2 (Enlarged view of the area within the red box in a1).

[0077] from Figure 2 As can be seen, the surface coating of the superhydrophobic and superoleophilic renewable oil-water separation material is uniform and free of cracks and pores, indicating that the oxide coating grows well.

[0078] The water contact angle and oil contact angle of the superhydrophobic and superoleophilic renewable oil-water separation material prepared in Example 1 of this application are as follows: Figure 3 As shown ( Figure 3 a1 is a diagram showing the contact between oil droplets and the material surface. Figure 3 a2 shows the spread of oil droplets on the material surface (demonstrating superoleophilicity). Figure 3 Figure b shows the contact between a water droplet and the material surface (demonstrating superhydrophobicity).

[0079] from Figure 3 As can be seen from the above, the superhydrophobic and superoleophilic renewable oil-water separation material prepared in Example 1 of this application has an oil contact angle (OCA) of 0° and a water contact angle (WCA) of 161°. When water droplets come into contact with the material surface, they will form a spherical shape. Oil droplets are rapidly absorbed when they come into contact with the material, which shows that the material has superoleophilic and superhydrophobic properties.

[0080] Using a chromatography column as the oil-water separation device and the superhydrophobic / superoleophilic regenerable oil-water separation material prepared in Example 1 of this application as the separation membrane, oil-water separation was performed. An aqueous phase-chlorobenzene oil-water mixture (volume ratio 1:1) entered from the upper inlet and, under gravity, flowed downwards to contact the separation membrane. Due to the superhydrophobic / superoleophilic properties of the separation membrane, chlorobenzene was observed to pass through the separation membrane and flow into the receiving container below; while the aqueous phase was blocked by the separation membrane and remained in the separation tube, thus achieving oil-water separation.

[0081] Tests conducted using the aforementioned separation device showed that the superhydrophobic and superoleophilic regenerable oil-water separation membrane prepared in Example 1 of this application achieved an average separation flux of 118641.23 L / m³ for separating chlorobenzene from an aqueous-chlorobenzene oil-water mixture over one hour. 2 •h•bar.

[0082] After a 12-hour cycle experiment, the separation flux of chlorobenzene in the aqueous-chlorobenzene oil-water mixture was 115675.20 L / m³. 2The concentration of hydrostatic pressure (H·bar) decreased by 3.5%, indicating good durability of the material. After 48 hours of continuous separation, the water contact angle (WCA) decreased from 161° to 156°, and the separation flux decreased to 109775.76 L / m³. 2 •h•bar. At this point, the separation membrane was removed and dried, then irradiated with ultraviolet light at a main wavelength of 254nm for 40min. The water contact angle of the Cu-TiO2 nanocrystalline coated carbon fiber material was found to be 0°. Further modification with a long-chain carboxylic acid (using the same method as in Example 1) yielded a regenerated superhydrophobic and superoleophilic regenerable oil-water separation material. Testing with the aforementioned separation device showed that the WCA recovered to 161°, and the OCA was 0°. Continuing the oil-water separation performance test, the separation flux of chlorobenzene in the aqueous-chlorobenzene oil-water mixture recovered to 118590.09 L / m³. 2 •h•bar indicates that the superhydrophobic / superoleophilic regenerable oil-water separation material prepared in this embodiment can recover its superhydrophobic / superoleophilic properties after ultraviolet light irradiation and secondary carboxylic acid modification.

[0083] Example 2 A method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material includes the following steps: Step 1.1: Immerse the carbon fiber in a 1% sodium carbonate (Na2CO3) solution at 25°C for 3 hours. After immersion, rinse with deionized water and dry at 60°C for 3 hours. Step 1.2: Immerse the carbon fiber dried in step 1.1 in a 15% dilute nitric acid solution at 25°C for 3 hours. After immersion, rinse with deionized water until the surface is neutral and dry at 60°C for 3 hours. Step 1.3: The carbon fiber surface after step 1.2 is subjected to plasma treatment, wherein the vacuum degree of plasma treatment is 30 Pa, the power is 120 W, and the treatment time is 20 min.

[0084] Step 2: Weigh 2 mmol of tetrabutyl titanate and dissolve it in 250 mmol of methanol solution. Then add 2 mmol of acetylacetone to the mixed solution and stir well. Next, weigh 1 mmol of copper sulfate and dissolve it in 180 mmol of methanol and stir thoroughly. Then mix the two solutions to obtain Cu-TiO2 solution, wherein the molar ratio of titanium source to copper salt is 3:1. Step 3.1: Immerse the pretreated carbon fiber obtained in Step 1 in a Cu-TiO2 solution (the solution should completely submerge the carbon fiber) at a temperature of 25°C for 10 minutes. After immersion, remove the carbon fiber and spin it dry with tweezers. Then dry it at 70°C for 3 hours. Step 3.2: The dried material is subjected to vacuum plasma treatment for 20 min under a vacuum degree of 30 Pa and a plasma power of 120 W, and then placed in a heating furnace at a temperature of 375 °C for 3 h for heat treatment; to achieve the coating of Cu-TiO2 seed layer on the carbon fiber surface; Step 4: Place the carbon fiber coated with Cu-TiO2 seed layer into a reaction vessel containing Cu-TiO2 solution (the solution should immerse the carbon fiber), seal it, and heat it fully in an oven at 90°C for 10 hours. After the reaction vessel cools to room temperature, remove it and dry it at 100°C for 20 hours; thus, Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer.

[0085] Step 5: Weigh 1.5g of myristic acid and add it to 98.5g of ethanol solution. Stir and dissolve thoroughly to obtain a myristic acid modifier solution. Place the carbon fibers coated with Cu-TiO2 nanocrystals into the myristic acid modifier solution (the solution should just submerge the carbon fibers) and perform a self-assembly reaction at 60℃ for 6h. After the reaction is complete, remove the carbon fibers, wash them 4 times with ethanol, and dry them at 90℃ for 12h to obtain the superhydrophobic and superoleophilic renewable oil-water separation material, denoted as Cu-TiO2@CF.

[0086] Using a chromatography column as the oil-water separation device and the superhydrophobic / superoleophilic regenerable oil-water separation material prepared in Example 2 of this application as the separation membrane, a receiving container for the oil phase is placed at the bottom of the exchange column. An aqueous phase-bromobenzene oil-water mixture (volume ratio 1:1) enters from the upper inlet and flows downwards to contact the separation membrane under gravity. Due to the superhydrophobic / superoleophilic properties of the separation membrane, bromobenzene can pass through the separation membrane and flow into the receiving container below; while the aqueous phase is blocked by the separation membrane and remains in the separation tube, thus achieving oil-water separation.

[0087] Tests conducted using the aforementioned separation device showed that the superhydrophobic and superoleophilic regenerable oil-water separation material prepared in Example 2 of this application achieved an average separation flux of 95001.27 L / m³ for 1 hour in the aqueous-bromobenzene oil-water mixture system. 2 After a 12-hour cycle experiment, the separation flux decreased to 92331.73 L / m³. 2 •h•bar decreased by 2.81%, indicating that the material has good oil-water separation durability; after 48 hours of continuous separation, WCA decreased from 161° to 156°, and the separation flux decreased to 87418.12 L / m 2•h•bar. At this point, after removing and drying the separation membrane, it was irradiated with ultraviolet light at a main wavelength of 365nm for 80 minutes, resulting in a water contact angle of 0° for the Cu-TiO2 nanocrystalline coated carbon fiber material. Further modification with a long-chain carboxylic acid (using the same method as in Example 2) yielded a regenerated superhydrophobic and superoleophilic regenerable oil-water separation material. Testing with the aforementioned separation device showed that the WCA recovered to 159°, and the OCA was 0°. Continuing the oil-water separation performance test, the separation flux for bromobenzene recovered to 94826.36 L / m. 2 •h•bar indicates that the prepared material has strong ultraviolet light-driven regeneration performance.

[0088] Example 3 A method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material includes the following steps: Step 1.1: Immerse the carbon fiber in a 1.5% sodium carbonate (Na2CO3) solution at 25°C for 2 hours. After immersion, rinse with deionized water and dry at 80°C for 2 hours. Step 1.2: Immerse the carbon fiber dried in step 1.1 in a 20% dilute nitric acid solution at 25°C for 2 hours. After immersion, rinse with deionized water until the surface is neutral and then bake at 80°C for 2 hours. Step 1.3: The carbon fiber treated in step 1.2 is subjected to plasma treatment, wherein the vacuum degree of plasma treatment is 40 Pa, the power is 160 W, and the treatment time is 15 min.

[0089] Step 2: Weigh 4 mmol of tetrabutyl titanate and dissolve it in 200 mmol of propanol solution. Then add 4 mmol of benzoylacetone to the mixture and stir well. Next, weigh 0.004 mmol of copper acetate and dissolve it in 157 mmol of propanol and stir thoroughly. Then mix the two solutions to obtain a Cu-TiO2 solution with a concentration of 0.15 mol / L, wherein the molar ratio of titanium source to copper salt is 5:1. Step 3.1: Immerse the pretreated carbon fiber obtained in Step 1 in a Cu-TiO2 solution (the solution should completely submerge the carbon fiber) at a temperature of 25°C for 15 minutes. After immersion, remove the carbon fiber and spin it dry with tweezers. Then dry it at 90°C for 2 hours. Step 3.2: The dried material is subjected to vacuum plasma treatment for 15 minutes under a vacuum degree of 40 Pa and a plasma power of 160 W, and then placed in a heating furnace at a temperature of 450℃ for 2 hours to achieve the coating of Cu-TiO2 seed layer on the carbon fiber surface; Step 4: Place the carbon fiber coated with Cu-TiO2 seed layer into a reaction vessel containing Cu-TiO2 solution (the solution should immerse the carbon fiber), seal it, and heat it fully in an oven at 100°C for 8 hours. After the reaction vessel cools to room temperature, remove it and dry it at 110°C for 16 hours; thus, Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer.

[0090] Step 5: Weigh 5g of stearic acid and add it to 95g of isopropanol solution. Stir and dissolve thoroughly to obtain stearic acid modifier solution. Place the carbon fiber coated with Cu-TiO2 nanocrystals into the stearic acid modifier solution (the solution should just cover the carbon fiber) and perform a self-assembly reaction at 80℃ for 2h. After the reaction is complete, remove the carbon fiber, wash it 5 times with ethanol, and dry it at 95℃ for 10h to obtain the superhydrophobic and superoleophilic renewable oil-water separation material, denoted as Cu-TiO2@CF.

[0091] Using a chromatography column as the oil-water separation device and the superhydrophobic / superoleophilic regenerable oil-water separation material prepared in Example 3 of this application as the separation membrane, a receiving container for the oil phase is placed at the bottom of the exchange column. A water-nitrobenzene oil-water mixture (volume ratio 1:1) enters from the upper inlet and flows downwards to contact the separation membrane under gravity. Due to the superhydrophobic / superoleophilic properties of the separation membrane, nitrobenzene can be observed to pass through the separation membrane and flow into the receiving container below; while the water phase is blocked by the separation membrane and remains in the separation tube, thus achieving oil-water separation.

[0092] Tests conducted using the aforementioned separation device showed that the superhydrophobic and superoleophilic regenerable oil-water separation material prepared in Example 3 of this application achieved an average separation flux of 104052.79 L / m³ for 1 hour in the aqueous-nitrobenzene oil-water mixture system for separating nitrobenzene. 2 After a 12-hour cycle experiment, the separation flux was 101690.79 L / m³. 2 The concentration of hydrobar decreased by 2.27%, indicating that the material has good oil-water separation durability; after 48 hours of continuous separation, the separation flux decreased to 96606.25 L / m³. 2 •h•bar. At this point, after removing and drying the separation membrane, it was irradiated with ultraviolet light at a main wavelength of 365nm for 60min, resulting in a water contact angle of 0° for the Cu-TiO2 nanocrystal-coated carbon fiber material. Further modification with a long-chain carboxylic acid (using the same method as in Example 3) yielded a regenerated superhydrophobic and superoleophilic regenerable oil-water separation material. Testing with the aforementioned separation device revealed that WCA and OCA returned to their original values. Continuing oil-water separation performance testing, the separation flux of p-nitrobenzene recovered to 103827.13 L / m. 2 •h•bar indicates that the prepared material has strong UV-driven regeneration performance and maintains good separation flux after cyclic separation.

[0093] Example 4 A method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material includes the following steps: Step 1.1: Immerse the carbon fiber in a 2% sodium carbonate (Na2CO3) solution at 25°C for 1 hour, then rinse with deionized water and dry at 100°C for 1 hour. Step 1.2: Immerse the carbon fiber dried in step 1.1 in a 25% dilute nitric acid solution at 25°C for 1 hour. After immersion, rinse with deionized water until the surface is neutral and dry at 100°C for 1 hour. Step 1.3: The carbon fiber treated in step 1.2 is subjected to plasma treatment, wherein the vacuum degree of plasma treatment is 60 Pa, the power is 200 W, and the treatment time is 5 min.

[0094] Step 2: Weigh 5 mmol of tetrabutyl titanate and dissolve it in a mixed solution of 120 mmol methanol and 120 mmol ethanol (volume ratio 1:1). Then add 6 mmol benzoyl acetone to the mixed solution and stir until homogeneous. Separately weigh 0.125 mmol of a mixture of copper nitrate and 0.125 mmol of copper sulfate and dissolve it in a mixed solution of 80 mmol methanol and 80 mmol ethanol. Stir thoroughly. Then mix the two solutions thoroughly to obtain a Cu-TiO2 solution, wherein the molar ratio of titanium source to copper salt is 8:1. Step 3.1: Immerse the pretreated carbon fiber obtained in Step 1 in a Cu-TiO2 solution (the solution should completely submerge the carbon fiber) at a temperature of 25°C for 20 minutes. After immersion, remove the carbon fiber and spin it dry with tweezers. Then dry it at 120°C for 1 hour. Step 3.2: The dried material is subjected to vacuum plasma treatment for 5 minutes under a vacuum degree of 60 Pa and a plasma power of 200 W, and then placed in a heating furnace at a temperature of 500℃ for 1 hour; to achieve the coating of Cu-TiO2 seed layer on the carbon fiber surface. Step 4: Place the carbon fiber coated with Cu-TiO2 seed layer into a reaction vessel containing Cu-TiO2 solution (the solution should immerse the carbon fiber), seal it, and heat it fully in an oven at 120°C for 6 hours. After the reaction vessel cools to room temperature, remove it and dry it at 120°C for 12 hours; thus, Cu-TiO2 nanocrystals are deposited on the surface of the Cu-TiO2 seed layer.

[0095] Step 5: Weigh 2.5g of oleic acid and add it to 97.5g of a mixed solution of ethanol and isopropanol (volume ratio 1:1). Stir thoroughly to dissolve and obtain an oleic acid modifier solution. Place the carbon fibers coated with Cu-TiO2 nanocrystals into the oleic acid modifier solution (the solution should just submerge the carbon fibers) and allow them to self-assemble at 70°C for 4 hours. After the reaction is complete, wash with ethanol 4 times and dry at 100°C for 8 hours to obtain the superhydrophobic, superoleophilic, renewable oil-water separation material, denoted as Cu-TiO2@CF.

[0096] The superhydrophobic / superoleophilic Cu-TiO2@CF material obtained in Example 4 has a surface enriched with Ti and O elements, accompanied by a small amount of Cu elements. The elements are evenly distributed, indicating that the prepared Cu-TiO2 coating can uniformly and densely cover the CF surface.

[0097] Using a chromatography column as the oil-water separation device and the superhydrophobic / superoleophilic regenerable oil-water separation material prepared in Example 4 of this application as the separation membrane, a receiving container for the oil phase is placed at the bottom of the exchange column. A water-carbon tetrachloride oil-water mixture (volume ratio 1:1) enters from the upper inlet and flows downwards to contact the separation membrane under gravity. Due to the superhydrophobic / superoleophilic properties of the separation membrane, carbon tetrachloride can pass through the separation membrane and flow into the receiving container below; while the water phase is blocked by the separation membrane and remains in the separation tube, thus achieving oil-water separation.

[0098] Tests conducted using the aforementioned separation device showed that the superhydrophobic and superoleophilic renewable oil-water separation material prepared in Example 4 of this application achieved a separation flux of 88,000.43 L / m³ for gasoline separation in an aqueous-carbon tetrachloride oil-water mixture over one hour. 2 After a 12-hour cycle experiment (•h•bar), the gasoline separation flux in the aqueous-carbon tetrachloride oil-water mixture was 86073.22 L / m³. 2 The concentration of hydrobar decreased by 2.19%, indicating that the material has good oil-water separation durability; after 48 hours of continuous separation, the separation flux decreased to 81786.77 L / m³. 2 •h•bar. At this point, after removing and drying the separation membrane, it was irradiated with ultraviolet light at a main wavelength of 300nm for 50min, resulting in a water contact angle of 0° for the regenerated Cu-TiO2 nanocrystal-coated carbon fiber material. Further modification with a long-chain carboxylic acid (using the same method as in Example 1) yielded a regenerated superhydrophobic and superoleophilic regenerable oil-water separation material. Testing with the aforementioned separation device showed that the WCA returned to its original value. Further oil-water separation performance testing showed that the separation flux for carbon tetrachloride recovered to 87843.59 L / m³. 2 •h•bar indicates that the material can still maintain its original separation flux after photocatalytic regeneration.

[0099] Note: The results of the chlorobenzene separation flux described in Example 1, the bromobenzene separation flux described in Example 2, the nitrobenzene separation flux described in Example 3, and the carbon tetrachloride separation flux described in Example 4 of this application are as follows: Figure 4 As shown.

[0100] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.

Claims

1. A method for preparing a superhydrophobic and superoleophilic renewable oil-water separation material, characterized in that, Includes the following steps: (1) Cleaning and plasma pretreatment of carbon fibers; (2) The pretreated carbon fiber is immersed in Cu-TiO2 solution. After the immersion is completed, the immersed carbon fiber is subjected to vacuum plasma treatment and heat treatment in sequence to coat the surface of the carbon fiber with Cu-TiO2 seed layer. The carbon fiber coated with Cu-TiO2 seed layer is brought into contact with Cu-TiO2 solution for hydrothermal reaction to deposit Cu-TiO2 nanocrystals on the surface of Cu-TiO2 seed layer. (3) The Cu-TiO2 nanocrystals described in step (2) are modified with long-chain carboxylic acids to obtain the superhydrophobic and superoleophilic renewable oil-water separation material.

2. The preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, In step (1), the cleaning pretreatment step includes: immersing the carbon fiber in sodium carbonate solution and nitric acid in sequence for cleaning treatment.

3. The preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 2, characterized in that, The sodium carbonate solution has a mass concentration of 0.5%-2%, the carbon fiber is immersed in the sodium carbonate solution at a temperature of 20-30℃, and the carbon fiber is immersed in the sodium carbonate solution for 1-4 hours. And / or, the mass concentration of the nitric acid is 10%-25%, the immersion temperature of the carbon fiber in the nitric acid is 20-30℃, and the immersion time of the carbon fiber in the nitric acid is 1-4h; And / or, the vacuum degree of the plasma pretreatment is 20-60 Pa, the power of the plasma pretreatment is 80-200 W, and the duration of the plasma pretreatment is 5-30 min.

4. The preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, The raw materials for preparing the Cu-TiO2 solution include a titanium source, a chelating agent, a copper source, and a solvent; The titanium source includes tetrabutyl titanate; The chelating agent includes benzoyl acetone and / or acetylacetone; The copper source includes one or more of copper nitrate, copper sulfate, and copper acetate; The solvent includes one or more of methanol, ethanol, and propanol.

5. The preparation method of the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 4, characterized in that, The molar ratio of titanium source to copper source in the raw materials for preparing the Cu-TiO2 solution is 1:(0.01-0.1). And / or, the molar ratio of titanium source to chelating agent in the raw materials for preparing the Cu-TiO2 solution is 1:(0.8-1.2). And / or, the molar ratio of titanium source to solvent in the Cu-TiO2 solution is 1:(80-350).

6. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, The pretreated carbon fibers are impregnated in Cu-TiO2 solution at a temperature of 20-30℃ for a duration of 5-20 minutes. And / or, the vacuum degree of the impregnated carbon fiber is 20-60Pa, the power is 80-200W, and the treatment time is 5-30min. And / or, the heat treatment temperature is 300-500℃, and the heat treatment time is 1-4h.

7. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, The hydrothermal reaction temperature is 80-120℃, and the hydrothermal reaction time is 6-12h.

8. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, The carbon fibers with Cu-TiO2 nanocrystals deposited in step (2) are contacted with a long-chain carboxylic acid modifier solution to carry out a self-assembly reaction, thereby obtaining the superhydrophobic and superoleophilic renewable oil-water separation material. The long-chain carboxylic acid modifier solution comprises a long-chain carboxylic acid and an organic solvent; The long-chain carboxylic acid modifier solution has a mass concentration of 0.5%-5% for the long-chain carboxylic acid. The long-chain carboxylic acids include one or more of lauric acid, myristic acid, stearic acid, and oleic acid; The organic solvent includes one or more of methanol, ethanol, and isopropanol; The temperature of the self-assembly reaction is 50-80℃, and the time of the self-assembly reaction is 1-8h.

9. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 1, characterized in that, It also includes the regeneration of separated materials: By using ultraviolet light to irradiate and separate superhydrophobic and superoleophilic regenerable oil-water separation materials whose performance has deteriorated, and then modifying them with long-chain carboxylic acids, the superhydrophobic and superoleophilic regenerable oil-water separation materials can be regenerated.

10. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 9, characterized in that, The main wavelength of ultraviolet light irradiation is 254-365nm, and the duration of ultraviolet light irradiation is 40-80min.

11. The method for preparing the superhydrophobic and superoleophilic renewable oil-water separation material according to claim 9, characterized in that, The main wavelength of the ultraviolet light irradiation is 254nm, 300nm, or 365nm.

12. A superhydrophobic and superoleophilic renewable oil-water separation material, characterized in that, It is prepared by the method for preparing superhydrophobic and superoleophilic renewable oil-water separation material according to any one of claims 1-11.

13. The application of the superhydrophobic and superoleophilic renewable oil-water separation material of claim 12 in the treatment of industrial oily wastewater and emergency response to marine oil spills.

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