Polyarylene ether-based separation membrane, method for producing same, and use thereof

Abstract

The application relates to the technical field of film materials, and discloses a polyarylene ether separation film, a preparation method and application. The separation film is prepared by hydrophilic modification of N-Bi2O2CO3 to obtain a modified substance, and the modified substance is loaded on the surface of a film material to obtain the separation film. The application is based on a film material as a substrate, and an anti-multiple pollution super-hydrophobic film material is prepared by combining a super-hydrophobic surface construction principle and surface functionalization technology. The film material is applied to the treatment of oily wastewater in a complex environment.

Description

Technical Field

[0001] This invention relates to the field of membrane materials technology, and more specifically, to polyarylether-based separation membranes, their preparation methods, and applications. Background Technology

[0002] Membrane separation technology has become the mainstream technology for oil-water separation applications due to its numerous advantages in practical oily wastewater treatment (such as high efficiency, low cost, and no secondary pollution). However, as the core material of membrane separation, polymer membranes with porous structures are prone to membrane fouling due to their inherent hydrophobicity, leading to increased energy consumption, decreased performance, and reduced service life. Therefore, to overcome these bottlenecks, developing advanced membrane materials with excellent antifouling capabilities, high chemical stability, and high separation efficiency is crucial.

[0003] Currently, membranes made from common polymers such as polyvinylidene fluoride (PVDF), polylactic acid (PLA), and polyacrylonitrile (PAN) often suffer from inherent defects, making them unsuitable for use in harsh environments and exhibiting poor mechanical properties. In contrast, polyarylene ether nitrile (PEN) membranes, due to the presence of benzene rings, cyano groups, and ether bonds in their molecular chains, offer unique advantages in the preparation of high-performance oil-water separation membrane materials. However, similar to the aforementioned polymer membrane materials, the inherent hydrophobicity of PEN membranes also easily leads to severe membrane fouling during oil-water separation, resulting in a reduction in membrane lifespan.

[0004] To address these issues, researchers have fabricated superwetting composite membranes by constructing micro / nano-rough structures and hydrophilic chemical compositions on the membrane surface. These membranes maintain high oil-water separation capabilities while extending membrane lifespan by reducing the adhesion of oil droplets to the membrane surface. However, real-world oily wastewater typically has a complex composition, containing soluble organic matter, colloidal substances, bacteria / microorganisms, and other multiple pollutants. The presence of these multiple pollutants creates more challenging membrane fouling problems, posing a greater challenge to the practical application of membrane materials. Therefore, the combination of photocatalytic degradation and membrane separation technologies, which offer advantages such as being green, sustainable, and energy-efficient, has become an effective method for solving complex membrane fouling problems in recent years. Summary of the Invention

[0005] <Technical Problem Solved by the Invention>

[0006] This technology aims to address the problem that existing membrane materials are easily contaminated when applied to oil-water separation, leading to a decrease in their service life.

[0007] <Technical Solution Adopted in This Invention>

[0008] To address the aforementioned technical problems, the present invention aims to provide polyarylether-based separation membranes, their preparation methods, and applications.

[0009] The details are as follows:

[0010] First, the present invention provides a polyarylether-based separation membrane, which is obtained by hydrophilically modifying N-Bi2O2CO3 to obtain a modified material, and then loading the modified material onto the surface of a membrane material to obtain a separation membrane.

[0011] Second, the present invention provides a method for preparing the aforementioned polyarylether-based separation membrane, comprising the following steps:

[0012] The modified material is filtered into the membrane material and dried to obtain the separation membrane.

[0013] Third, the present invention relates to the application of the aforementioned polyarylether-based separation membrane in oily wastewater.

[0014] <Beneficial effects achieved by the present invention>

[0015] This invention uses membrane materials as a substrate and combines the principle of superwetting surface construction with surface functionalization technology to prepare superwetting membrane materials resistant to multiple contaminants, which are then applied to the treatment of oily wastewater in complex environments. To this end, this invention combines surface hydrophilic modification with the construction of surface micro / nano rough structures, and stably loads N-Bi2O2CO3 onto the surface of the membrane material through loading, thus preparing a superwetting membrane with high-efficiency oil-water separation capability and resistance to multiple contaminants (anti-oil, photocatalytic self-cleaning, and antibacterial).

[0016] The polyarylene ether separation membrane obtained in this invention has an ultra-wet surface (WCA=0°, UOCA>150°), resulting in ultra-low oil viscosity. The polyarylene ether separation membrane exhibits excellent separation flux (632.79~762.81 L·m⁻¹) for various emulsions. -2 ·h -1 The composite membrane exhibits high separation efficiency (>99.16%). Even under high temperature and high salt conditions, it maintains its ultra-wet capability and excellent separation performance. More importantly, N-Bi₂O₂CO₃ endows the membrane with stronger photocatalytic self-cleaning ability, enabling the membrane material to effectively degrade various dyes (MO: 95.53%, MeB: 96.40%, CV: 96.45%, CR: 87.14%), achieving excellent synergistic antifouling capabilities. Attached Figure Description

[0017] Figure 1 (a) Water contact angle of the PEN membrane; (b) Water contact angle of M1-M5;

[0018] Figure 2 (a) Water contact angle and pure water flux of M1-M5; (b) Underwater oil contact angle of NB / ADP@PEN membrane for different types of oil droplets;

[0019] Figure 3 Dynamic adhesion experiment of NB / ADP@PEN composite film;

[0020] Figure 4 (a) Separation flux and efficiency of M1-M5 for petroleum ether SFE; (b) Oil-water separation flux and efficiency of M1-M5 for petroleum ether SSE.

[0021] Figure 5 The oil-water separation flux and efficiency of NB / ADP@PEN composite membrane for different types of (a) SFE; (b) SSE; (c) cyclic test of NB / ADP@PEN composite membrane.

[0022] Figure 6 (ab) Graph showing the relationship between immersion time of NB / ADP@PEN composite membrane in 90 ℃ and 2M NaCl solution and water contact angle and underwater oil contact angle; (cd) Graph showing the relationship between immersion time of NB / ADP@PEN composite membrane in 90 ℃ and 2M NaCl solution and emulsion separation flux and separation efficiency.

[0023] Figures 7-1 to 7-3 For the antifouling capabilities of B / ADP@PEN and NB / ADP@PEN composite membranes: Figure 7-1 In the figure, (a) photocatalytic degradation curves of B / ADP@PEN and NB / ADP@PEN composite membranes for different dyes; (b) absorbance curve of B / ADP@PEN for methyl orange; (c) absorbance curves of NB / ADP@PEN composite membrane for different dyes. Figure 7-2 In the figure, the absorbance curves of (df)NB / ADP@PEN composite film for different dyes are shown in Figures 2-4. Figure 7-3 In the middle, (g) are digital photographs of various dyes at different degradation times. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0025] <Technical Solution>

[0026] First, the present invention provides a polyarylether-based separation membrane, which is obtained by hydrophilically modifying N-Bi2O2CO3 to obtain a modified material, and then loading the modified material onto the surface of a membrane material to obtain a separation membrane.

[0027] In this invention, the hydrophilic modification step of N-Bi2O2CO3 is as follows: N-Bi2O2CO3 is dispersed to obtain a suspension; buffer solution, PEI and DA are mixed and then added to the suspension for reaction.

[0028] Furthermore, the mass ratio of N-Bi2O2CO3, PEI, and DA is 2~12:20~25:20~25.

[0029] Furthermore, the buffer solution comprises Tirs-HCl, APS, and a solvent. The mass ratio of Tirs-HCl to APS is 30-40:7-13. The pH of the buffer solution is 8.5.

[0030] In this invention, the membrane material is a PEN fiber membrane obtained by electrospinning PEN.

[0031] Specifically, in the PEN fiber membrane, the ratio of PEN to DMF is 10~20:70~80. The preparation method involves using electrospinning to prepare a porous PEN fiber membrane as the support layer of the composite membrane. First, a certain amount of PEN (polyarylene ether nitrile) (2.6 g) is dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a uniform spinning solution. Then, the spinning solution is placed in an electrospinning apparatus using a syringe. PEN fibers are collected using tin foil fixed to a cylinder (10 h). The operating parameters for electrospinning are: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers are placed between two glass plates and hot-pressed at 180°C for 2 h to obtain the base membrane.

[0032] In this invention, the preparation method of N-Bi2O2CO3 is as follows:

[0033] The bismuth source was dissolved to obtain solution A;

[0034] Sodium carbonate and CTAB are dissolved to obtain solution B;

[0035] Solution B was poured into solution A and stirred to obtain N-Bi₂O₂CO₃. After stirring, the product was repeatedly washed with isopropanol and water and then dried.

[0036] Furthermore, the mass ratio of bismuth source, sodium carbonate, and CTAB is 28~35:45~60:4~8. The bismuth source is bismuth nitrate pentahydrate (Bi(NO3)3·5H2O).

[0037] Furthermore, the solvent of solution A is H₂. + Acid solution with a concentration of 0.1~3 mol / L. Nitric acid is selected as the acid here.

[0038] Second, the present invention provides a method for preparing the aforementioned polyarylether-based separation membrane, comprising the following steps:

[0039] The modified material is filtered into the membrane material and dried to obtain the separation membrane.

[0040] Third, the present invention provides an application of the aforementioned polyarylether separation membrane in oily wastewater.

[0041] <Example>

[0042] Example 1

[0043] (1) Preparation of N-Bi2O2CO3

[0044] First, 4.85 g of bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) was fully dissolved in 10 mL of 1 mol / L nitric acid (HNO3) solution as solution A; simultaneously, 8.45 g of sodium carbonate (Na2CO3) and 1 g of hexadecyltrimethylammonium bromide (CTAB) were dissolved in 80 mL of water as solution B. Next, solution B was slowly poured into solution A with rapid stirring at room temperature for 30 min to obtain the product. Then, the product was repeatedly washed with isopropanol and pure water and dried at 60 °C for 24 h to obtain N-Bi2O2CO3.

[0045] (2) Preparation of PEN fiber membrane

[0046] First, a certain amount of PEN (2.6 g) was dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a homogeneous spinning solution. Then, the spinning solution was placed into an electrospinning apparatus using a syringe. PEN fibers were collected using tin foil fixed to a cylinder (10 h). The electrospinning operating parameters were as follows: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers were placed between two glass plates and hot-pressed at 180 °C for 2 h to obtain a base film.

[0047] (3) Preparation of NB / ADP@PEN composite membrane

[0048] First, 10 mg of N-Bi₂O₂CO₃ was added to 20 mL of pure water, and an N-Bi₂O₂CO₃ suspension was obtained by sonication. Next, 0.16 g of Tirs-HCl and 43.2 mg of APS were dissolved in 30 mL of pure water, and the pH was adjusted to 8.5 to obtain a buffer solution. Then, 0.1 g of PEI and 0.1 g of DA were added and dissolved completely. Next, the N-Bi₂O₂CO₃ suspension prepared above was added, and the reaction proceeded for 7 h. Finally, the hydrophilically modified N-Bi₂O₂CO₃ was filtered onto a PEN fiber membrane and dried at 40 °C to obtain an NB / ADP@PEN composite membrane.

[0049] Example 2

[0050] (1) Preparation of N-Bi2O2CO3

[0051] First, 4.85 g of bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) was fully dissolved in 10 mL of 1 mol / L nitric acid (HNO3) solution as solution A; simultaneously, 8.45 g of sodium carbonate (Na2CO3) and 1 g of hexadecyltrimethylammonium bromide (CTAB) were dissolved in 80 mL of water as solution B. Next, solution B was slowly poured into solution A with rapid stirring at room temperature for 30 min to obtain the product. Then, the product was repeatedly washed with isopropanol and pure water and dried at 60 °C for 24 h to obtain N-Bi2O2CO3.

[0052] (2) Preparation of PEN fiber membrane

[0053] First, a certain amount of PEN (2.6 g) was dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a homogeneous spinning solution. Then, the spinning solution was placed into an electrospinning apparatus using a syringe. PEN fibers were collected using tin foil fixed to a cylinder (10 h). The electrospinning operating parameters were as follows: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers were placed between two glass plates and hot-pressed at 180 °C for 2 h to obtain a base film.

[0054] (3) Preparation of NB / ADP@PEN composite membrane

[0055] First, 20 mg of N-Bi₂O₂CO₃ was added to 20 mL of pure water, and an N-Bi₂O₂CO₃ suspension was obtained by sonication. Next, 0.16 g of Tirs-HCl and 43.2 mg of APS were dissolved in 30 mL of pure water, and the pH was adjusted to 8.5 to obtain a buffer solution. Then, 0.1 g of PEI and 0.1 g of DA were added and dissolved completely. Next, the N-Bi₂O₂CO₃ suspension prepared above was added, and the reaction proceeded for 7 h. Finally, the hydrophilically modified N-Bi₂O₂CO₃ was filtered onto a PEN fiber membrane and dried at 40 °C to obtain an NB / ADP@PEN composite membrane.

[0056] Example 3

[0057] (1) Preparation of N-Bi2O2CO3

[0058] First, 4.85 g of bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) was fully dissolved in 10 mL of 1 mol / L nitric acid (HNO3) solution as solution A; simultaneously, 8.45 g of sodium carbonate (Na2CO3) and 1 g of hexadecyltrimethylammonium bromide (CTAB) were dissolved in 80 mL of water as solution B. Next, solution B was slowly poured into solution A with rapid stirring at room temperature for 30 min to obtain the product. Then, the product was repeatedly washed with isopropanol and pure water and dried at 60 °C for 24 h to obtain N-Bi2O2CO3.

[0059] (2) Preparation of PEN fiber membrane

[0060] First, a certain amount of PEN (2.6 g) was dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a homogeneous spinning solution. Then, the spinning solution was placed into an electrospinning apparatus using a syringe. PEN fibers were collected using tin foil fixed to a cylinder (10 h). The electrospinning operating parameters were as follows: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers were placed between two glass plates and hot-pressed at 180 °C for 2 h to obtain a base film.

[0061] (3) Preparation of NB / ADP@PEN composite membrane

[0062] First, 30 mg of N-Bi₂O₂CO₃ was added to 20 mL of pure water, and an N-Bi₂O₂CO₃ suspension was obtained by sonication. Next, 0.16 g of Tirs-HCl and 43.2 mg of APS were dissolved in 30 mL of pure water, and the pH was adjusted to 8.5 to obtain a buffer solution. Then, 0.1 g of PEI and 0.1 g of DA were added and dissolved completely. Next, the N-Bi₂O₂CO₃ suspension prepared above was added, and the reaction proceeded for 7 h. Finally, the hydrophilically modified N-Bi₂O₂CO₃ was filtered onto a PEN fiber membrane and dried at 40 °C to obtain an NB / ADP@PEN composite membrane.

[0063] Example 4

[0064] (1) Preparation of N-Bi2O2CO3

[0065] First, 4.85 g of bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) was fully dissolved in 10 mL of 1 mol / L nitric acid (HNO3) solution as solution A; simultaneously, 8.45 g of sodium carbonate (Na2CO3) and 1 g of hexadecyltrimethylammonium bromide (CTAB) were dissolved in 80 mL of water as solution B. Next, solution B was slowly poured into solution A with rapid stirring at room temperature for 30 min to obtain the product. Then, the product was repeatedly washed with isopropanol and pure water and dried at 60 °C for 24 h to obtain N-Bi2O2CO3.

[0066] (2) Preparation of PEN fiber membrane

[0067] First, a certain amount of PEN (2.6 g) was dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a homogeneous spinning solution. Then, the spinning solution was placed into an electrospinning apparatus using a syringe. PEN fibers were collected using tin foil fixed to a cylinder (10 h). The electrospinning operating parameters were as follows: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers were placed between two glass plates and hot-pressed at 180 °C for 2 h to obtain a base film.

[0068] (3) Preparation of NB / ADP@PEN composite membrane

[0069] First, 40 mg of N-Bi₂O₂CO₃ was added to 20 mL of pure water, and an N-Bi₂O₂CO₃ suspension was obtained by sonication. Next, 0.16 g of Tirs-HCl and 43.2 mg of APS were dissolved in 30 mL of pure water, and the pH was adjusted to 8.5 to obtain a buffer solution. Then, 0.1 g of PEI and 0.1 g of DA were added and dissolved completely. Next, the N-Bi₂O₂CO₃ suspension prepared above was added, and the reaction proceeded for 7 h. Finally, the hydrophilically modified N-Bi₂O₂CO₃ was filtered onto a PEN fiber membrane and dried at 40 °C to obtain an NB / ADP@PEN composite membrane.

[0070] Example 5

[0071] (1) Preparation of N-Bi2O2CO3

[0072] First, 4.85 g of bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) was fully dissolved in 10 mL of 1 mol / L nitric acid (HNO3) solution as solution A; simultaneously, 8.45 g of sodium carbonate (Na2CO3) and 1 g of hexadecyltrimethylammonium bromide (CTAB) were dissolved in 80 mL of water as solution B. Next, solution B was slowly poured into solution A with rapid stirring at room temperature for 30 min to obtain the product. Then, the product was repeatedly washed with isopropanol and pure water and dried at 60 °C for 24 h to obtain N-Bi2O2CO3.

[0073] (2) Preparation of PEN fiber membrane

[0074] First, a certain amount of PEN (2.6 g) was dissolved in N,N-dimethylformamide (DMF, 17.4 mL) to obtain a homogeneous spinning solution. Then, the spinning solution was placed into an electrospinning apparatus using a syringe. PEN fibers were collected using tin foil fixed to a cylinder (10 h). The electrospinning operating parameters were as follows: voltage: 19 kV; humidity: 25%; spinning distance: 20 cm. Finally, the PEN fibers were placed between two glass plates and hot-pressed at 180 °C for 2 h to obtain a base film.

[0075] (3) Preparation of NB / ADP@PEN composite membrane

[0076] First, 50 mg of N-Bi₂O₂CO₃ was added to 20 mL of pure water, and an N-Bi₂O₂CO₃ suspension was obtained by sonication. Next, 0.16 g of Tirs-HCl and 43.2 mg of APS were dissolved in 30 mL of pure water, and the pH was adjusted to 8.5 to obtain a buffer solution. Then, 0.1 g of PEI and 0.1 g of DA were added and dissolved completely. Next, the N-Bi₂O₂CO₃ suspension prepared above was added, and the reaction proceeded for 7 h. Finally, the hydrophilically modified N-Bi₂O₂CO₃ was filtered onto a PEN fiber membrane and dried at 40 °C to obtain an NB / ADP@PEN composite membrane.

[0077] <Experimental Example>

[0078] In the following figures, M1-M5 are mentioned, representing Examples 1-5 (the N-Bi2O2CO3 content was increased from 10 mg to 50 mg).

[0079] 1. Oil-water separation performance test method

[0080] (1) Preparation of oil-in-water emulsion

[0081] A series of oil-in-water emulsions (petroleum ether, mesitylene, n-heptane, n-hexane, and isooctane) were prepared by mixing oil and water at a volume ratio of 1:100 under ultrasonic conditions. SDS (0.2 mg / mL) was added to the above emulsions using the same method to prepare surfactant-stabilized oil-in-water emulsions.

[0082] (2) Evaluation indicators for oil-water separation

[0083] First, the composite membrane was thoroughly wetted by filtering with pure water for 20 minutes under a certain pressure. Then, under the same pressure, the prepared emulsion was separated using the composite membrane, and the separation time (5 minutes) and filtrate volume were recorded.

[0084] Test metric: Separation efficiency

[0085] The separation efficiency was tested using a carbon-nitrogen-water environment comprehensive measuring instrument. The concentration of the filtrate before and after the separation of the oil-in-water emulsion was analyzed by measuring the total organic carbon content (TOC).

[0086] The specific details of the test are as follows: the sample is placed in a container, and the carbon and nitrogen water environment comprehensive measuring instrument will oxidize the organic carbon in the sample into carbon dioxide (CO2), test the CO2 content, and finally calculate the CO2 content and record and analyze the data.

[0087] 2. Photocatalytic performance testing methods

[0088] To test the membrane's resistance to soluble organic fouling, its photocatalytic self-cleaning performance was also tested.

[0089] The photocatalytic self-cleaning performance was evaluated by degrading dyes with different characteristic wavelengths (methyl orange (MO): 350~550 nm, Congo red (CR): 400~600 nm, methylene blue (MeB): 550~750 nm, crystal violet (CV): 450~650 nm).

[0090] First, a dye solution with a concentration of 10 ppm was prepared. Then, the composite membrane was immersed in 50 mL of the dye solution with magnetic stirring and placed in the dark for 30 min. The composite membrane and solution were then transferred to a storage chamber equipped with a xenon lamp (500 W, 420 nm filter). Finally, during photodegradation, the illumination distance was set to 20 cm. At regular intervals, 3 mL of the dye solution was removed, and the dye concentration in the solution was measured using a UV-Vis spectrophotometer.

[0091] 3. Contact angle

[0092] like Figure 1 As shown in Figure a, the PEN membrane exhibits hydrophobic properties. Figure 1As shown in b, when the N-Bi2O2CO3 content increased from 10 mg to 50 mg, the hydrophilicity gradually increased, and the spreading time of water droplets on the membrane surface decreased from 4.6 s to 0.8 s.

[0093] like Figure 2 As shown in Figure a, the contact angle of the NB / ADP@PEN composite membrane decreases with increasing N-Bi₂O₂CO₃ content, decreasing from 33.4° in M1 to 7.9° in M5. The pure water flux increases from 5189.26 ± 59.14 L·m⁻¹. -2 ·h -1 Decreased to 3429.44±62.17 L·m -2 ·h -1 .like Figure 2 As shown in b, the contact angles of the composite membrane to the five oils are all greater than 150° (trimethylbenzene: 150.1±0.8°, petroleum ether: 154.3±0.8°, n-hexane: 160.4±0.9°, n-heptane: 151.2±1.3° and isooctane: 155.3±0.7°), indicating that the composite membrane has underwater superoleophobic properties.

[0094] The anti-oil adhesion performance of composite membranes is an important indicator of their ability to efficiently separate oil and water and their long-term use. Figure 3 Dynamic adhesion experiments show that even if isooctane droplets are severely bent and deformed when they contact the film surface, the droplets can still leave the film surface almost without deformation, and this is still the case even after the operation is repeated once.

[0095] 4. Oil-water separation performance

[0096] To obtain the optimal separation flux and efficiency, and to make the NB / ADP@PEN composite membrane more suitable for oil-water separation, the effect of N-Bi2O2CO3 addition on the membrane's oil-water separation performance was discussed.

[0097] like Figure 4 As shown in Figure a, with the increase of N-Bi₂O₂CO₃ content, the separation flux of the composite membrane for petroleum ether SFE increases from 1497.26 ± 42.89 L·m⁻¹. -2 ·h -1 Decreased to 951.28±28.13 L·m -2 ·h -1 The membrane separation efficiency increased from 99.01±0.18% to 99.59±0.16%. For petroleum ether SSE, the composite membrane also showed the same trend, such as... Figure 4 As shown in b, the flux of the composite membrane increased from 1156.18 ± 28.19 L·m -2 ·h -1 Decreased to 682.34 ± 29.74 L·m-2 ·h -1 The separation efficiency increased from 99.12±0.13% to 99.48±0.1%. Based on the above analysis, this invention selects the NB / ADP@PEN composite membrane (M4) with an N-Bi2O2CO3 dosage of 40 mg as the research object for subsequent oil-water separation and photocatalysis experiments.

[0098] like Figure 5 As shown in figure a, the separation flux of the composite membrane for all five SFE types is higher than 950 L·m⁻¹. -2 ·h -1 (Petroleum ether: 1105.66±29.13 L·m) -2 ·h -1 Trimethylbenzene: 968.14 ± 35.09 L·m -2 ·h -1 Isooctane: 1058.16±29.51 L·m -2 ·h -1 n-Hexane: 1165.73 ± 48.16 L·m -2 ·h -1 n-Heptane: 1004.34 ± 25.4 L·m -2 ·h -1 Furthermore, while maintaining good separation flux, the separation efficiency is also higher than 99% (petroleum ether: 99.61±0.18%, mesitylene: 99.32±0.16%, isooctane: 99.43±0.17%, n-hexane: 99.58±0.21%, n-heptane: 99.22±0.15%). Simultaneously, the composite membrane still exhibits good separation capability for SSE, such as... Figure 5 As shown in b, the separation flux of the composite membrane for SSE is higher than 850 L·m⁻¹. -2 ·h -1 (Petroleum ether: 928.61±31.02 L·m) -2 ·h -1 Trimethylbenzene: 868.14 ± 37.8 L·m -2 ·h -1 Isooctane: 873.54 ± 53.18 L·m -2 ·h -1 n-Hexane: 958.15 ± 45.95 L·m -2 ·h -1 n-Heptane: 881.97±31.29 L·m -2 ·h -1Furthermore, the separation efficiency remains above 99% (petroleum ether: 99.57±0.19%, mesitylene: 99.25±0.16%, isooctane: 99.34±0.16%, n-hexane: 99.47±0.13%, n-heptane: 99.16±0.15%). Figure 5 As shown in c, after 10 cycles, the composite membrane still maintains a SSE of 883.16 ± 30.36 L·m⁻¹ for n-hexane. -2 ·h -1 The separation flux and efficiency were 99.33±0.13%. This indicates that the good separation flux and efficiency are due to the excellent superwetting ability of the composite membrane and the low oil adhesion to the membrane surface.

[0099] The durability of the NB / ADP@PEN composite membrane under harsh conditions was tested by immersing it in a high-temperature (90 °C) and high-salt (2M NaCl) environment. The NB / ADP@PEN composite membrane maintained its superwetting ability after immersion in 90 °C and 2M NaCl solution for 10 h. Figure 6 ab). For example Figure 6 As shown in cd, the composite membrane still achieves a separation flux of over 700 L·m for various SSEs after immersion in a 90 °C environment for 10 h. -2 ·h -1 (Petroleum ether: 852.17±29.45 L·m) -2 ·h -1 Trimethylbenzene: 756.08 ± 31.09 L·m -2 ·h -1 Isooctane: 806.83±34.82 L·m -2 ·h -1 n-Hexane: 721.28 ± 33.17 L·m -2 ·h -1 n-Heptane: 721.28±33.19 L·m -2 ·h -1 Furthermore, the separation efficiency remains above 99% (petroleum ether: 99.42±0.17%, mesitylene: 99.34±0.13%, isooctane: 99.31±0.14%, n-hexane: 99.39±0.16%, n-heptane: 99.17±0.15%). Moreover, the composite membrane flux in 2M NaCl solution remains at 700 L·m⁻¹. -2 ·h -1 The above (petroleum ether: 807.63±34.18 L·m) -2 ·h -1 Trimethylbenzene: 825.83 ± 26.58 L·m -2 ·h -1Isooctane: 788.18 ± 37.16 L·m -2 ·h -1 n-Hexane: 869.52 ± 48.16 L·m -2 ·h -1 n-Heptane: 769.26 ± 27.19 L·m -2 ·h -1 Furthermore, the separation efficiency remains above 99% (petroleum ether: 99.49±0.17%, mesitylene: 99.2±0.16%, isooctane: 99.34±0.18%, n-hexane: 99.45±0.16%, n-heptane: 99.15±0.13%).

[0100] 5. Photocatalytic self-cleaning performance

[0101] Different dyes (MeB, CR, CV, and MO) were selected as soluble organic compounds to test the antifouling ability of the composite membrane.

[0102] like Figure 7-1 As shown in Figure a, the B / ADP@PEN composite membrane achieved a degradation rate of 71.13% for MO after 90 min, while the NB / ADP@PEN composite membrane achieved a degradation rate of 95.53% for MO within the same time period. This demonstrates that N-Bi₂O₂CO₃ can enhance the photocatalytic activity of the membrane. Furthermore, the NB / ADP@PEN composite membrane exhibited degradation efficiencies greater than 85% for various dyes (MO: 95.53%, MeB: 96.40%, CV: 96.45%, CR: 87.14%), with the strongest degradation capabilities observed for CV and MeB.

[0103] Figure 7-1 to Figure 7-3 In the figure, bf represents the wavelength of maximum absorbance for different dyes. The absorbance wavelengths of various dyes gradually decrease with increasing photocatalytic time, further verifying the good antifouling ability of the composite membrane. Furthermore, the change in the color of the dye solution with degradation time also demonstrates the good self-cleaning ability of the composite membrane. Figure 7-3 As shown in g, after 90 min of photocatalysis, all dyes became almost colorless. In summary, the NB / ADP@PEN composite membrane exhibits excellent photocatalytic degradation performance of dyes, providing a theoretical basis for treating membrane fouling caused by soluble organic matter in oily wastewater through photocatalytic self-cleaning.

[0104] In summary, the technical solution of this invention is applicable to various applications requiring efficient and stable oil-water separation, including industrial wastewater treatment, environmental sewage treatment, and domestic sewage treatment. Furthermore, this technology is also widely applicable to miniaturized, portable oil-water separation equipment with low requirements for processing equipment and site conditions.

[0105] In terms of operating environment, the oil-water separation method of this invention can adapt to various environments, including harsh environments such as high temperature, high salinity, and strong acids and alkalis. Furthermore, this method can be applied to various types of oil-water separation equipment both domestically and internationally, such as filter screens, filters, centrifuges, and sedimentation tanks. Its superior efficiency and stability can reduce equipment costs and subsequent maintenance costs, bringing new development prospects to the oil-water separation industry.

[0106] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A polyarylene ether-based separation membrane, characterized by, The N-Bi2O2CO3 is hydrophilically modified to obtain a modified substance, the modified substance is loaded on the surface of a membrane material to obtain a separation membrane.

2. The poly(arylene ether)-based separation membrane according to claim 1, wherein The hydrophilic modification step is that the N-Bi2O2CO3 is dispersed to obtain a suspension; the buffer, the polyethyleneimine and the dopamine are blended, and then the suspension is added and reacted to obtain.

3. The poly(arylene ether)-based separation membrane according to claim 2, wherein The mass ratio of the N-Bi2O2CO3, the polyethyleneimine and the dopamine is 2-12:20-25:20-25.

4. The poly(arylene ether)-based separation membrane according to claim 2, wherein The buffer comprises Tirs-HCl, APS and a solvent.

5. The poly(arylene ether)-based separation membrane according to claim 1, wherein The membrane material is a PEN fiber membrane obtained by electrospinning of a PEN.

6. The poly(arylene ether)-based separation membrane according to any one of claims 1 to 5, characterized in that, The preparation method of the N-Bi2O2CO3 is as follows: A bismuth source is dissolved to obtain a solution A; Sodium carbonate and CTAB are dissolved to obtain a solution B; The solution B is poured into the solution A, and stirred to obtain the N-Bi2O2CO3.

7. The poly(arylene ether)-based separation membrane according to claim 6, wherein The mass ratio of the bismuth source, the sodium carbonate and the CTAB is 28-35:45-60:4-8.

8. The poly(arylene ether)-based separation membrane according to claim 6, characterized by The solvent of solution A is H + 0.1-3 mol / L acid solution.

9. The method for producing a poly(arylene ether)-based separation membrane according to any one of claims 1 to 8, wherein The method comprises the following steps: The modified substance is suction filtered to the membrane material, and dried to obtain the separation membrane.

10. The polyarylether separation membrane according to any one of claims 1 to 8, or the polyarylether separation membrane obtained by the preparation method of claim 9 is applied to oil-containing wastewater.

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