Preparation method of high-crease antibacterial chemical fiber film and application thereof
High-pleat antibacterial synthetic fiber membranes were prepared by electrospinning and chemical modification, which solved the problems of poor separation performance and lack of antibacterial properties of kitchen waste wastewater, and achieved efficient oil-water separation and antifouling performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-10
- Publication Date
- 2026-04-10
AI Technical Summary
Existing separation membrane materials have poor separation performance when treating high-viscosity kitchen waste wastewater and lack antibacterial properties, leading to oil droplet deposition and bacterial adsorption, which affects separation efficiency and stability.
High-wrinkle antibacterial chemical fiber membranes were prepared using electrospinning technology. Through electrospinning, emulsification, and chemical modification, porous fiber membranes with nanoscale wrinkles were formed. Combined with treatment with 2-methylimidazole and dopamine, the membrane's anti-oil adhesion and antibacterial properties were enhanced.
It achieves an oil-water separation efficiency of over 99%, and maintains a separation efficiency of 97% even after 10 cycles of use, thus improving the membrane's antifouling performance and stability.
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Figure CN118835390B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of separation membrane materials, and relates to a fiber membrane, in particular to a preparation method of a high-crease antibacterial chemical fiber membrane and application thereof. BACKGROUND
[0002] Kitchen waste oily leachate is a kind of high-concentration organic wastewater, which contains not only water-soluble ammonia nitrogen, salt, amino acid and protein, but also a large amount of oil and bacteria. The oil layer accumulated on the aeration tank formed by the oil in the kitchen waste wastewater can significantly affect the efficiency of wastewater treatment. When the kitchen wastewater without oil separation is discharged into rivers or oceans, the oil film formed on the water surface can reduce the dissolved oxygen level, causing harm to aquatic organisms and fish death. More importantly, the edible oil in the oily leachate can be used as energy to produce valuable products, including biodiesel produced by ester exchange and bio-oil produced by pyrolysis.
[0003] Based on the "size screening" effect, developing superhydrophobic and superhydrophilic separation membrane materials is the main method to realize oil-water separation. Traditional superhydrophilic membrane materials can allow water to pass through their internal structure and trap oil droplets on the surface, thereby realizing oil-water separation. However, the deposition and clogging of oil droplets on the membrane surface can limit the application of superoleophobic membrane materials. Therefore, an ideal superhydrophilic separation membrane material should also have strong oil resistance.
[0004] Inspired by the underwater low oil adhesion of clams and fish scales, people began to make efforts to manufacture underwater superoleophobic separation membranes to solve the problem of oil fouling, including hydrogel coating membranes, polymer membranes and surface modified membranes, which make use of the layered structure of the surface and hydrated materials. However, the hydrophilic layer of these superhydrophilic membranes has poor stability, and is more suitable for the separation of non-polar solvents / low viscosity oils and water. In addition, these separation materials lack antibacterial properties, and bacteria in kitchen wastewater can be adsorbed on the membrane surface to form irreversible biofouling, which can exacerbate separation failure. SUMMARY
[0005] In view of the poor separation performance of high-viscosity kitchen waste wastewater and the lack of antibacterial properties in existing separation membranes, the present application discloses a preparation method of a high-crease antibacterial chemical fiber membrane.
[0006] The purpose of the method is achieved by the following technical solutions:
[0007] A preparation method of a high-crease antibacterial chemical fiber membrane, comprising the following steps:
[0008] a) Dissolve 2-8 g of chemical fiber per 100 mL of solvent to obtain a chemical fiber spinning solution, and prepare a chemical fiber membrane by electrospinning technology;
[0009] b) ultrasonic emulsification for 10-60 min to obtain an emulsion, according to 2-40 mL of organic solvent, 0.1-5 g of surfactant per 100 mL of water;
[0010] c) soaking for 10-60 min at 20-50 DEG C, taking out, washing with anhydrous ethanol for 1-3 times, washing with distilled water for 1-3 times, and drying at 30-100 DEG C for 3-24 h, to obtain the high-pleated chemical fiber membrane;
[0011] d) adding 1-5 mL of 2-methylimidazole, 20-100 mL of glycerol, 0.1-2 g of dopamine per 100 mL of anhydrous ethanol to obtain a mixed solution;
[0012] e) stirring for 24-72 h at 60-80 DEG C, taking out, washing with anhydrous ethanol for 3-6 times, washing with distilled water for 1-3 times, and drying at 30-100 DEG C for 5-12 h, to obtain the high-pleated antibacterial fiber membrane.
[0013] In the preferred disclosure of the application, in step a), the solvent is a combination of one or more of trifluoroacetic acid, N, N-dimethylformamide, dichloromethane, dimethyl sulfoxide, etc.
[0014] In the preferred disclosure of the application, in step a), the chemical fiber is any one or a combination of aramid, spandex, acrylic, polypropylene or chlorofiber, etc.
[0015] In the preferred disclosure of the application, in step a), the electrospinning process parameters are an electrostatic voltage of 5-25 kV, a spinning flow of 0.02-5 ml / h, and a receiving distance of 10-30 cm.
[0016] In the preferred disclosure of the application, in step b), the organic solvent is a combination of one or more of n-hexane, dichloromethane, ethyl acetate, toluene, etc.
[0017] In the preferred disclosure of the application, in step b), the surfactant is any one of cetyltrimethylammonium bromide, sodium laurate, ammonium lauryl sulfate, Span 80, etc.
[0018] The high-pleated antibacterial chemical fiber membrane prepared by the method of the application is formed by mechanically entangling fibers with a diameter of 0.2-20 μm, wherein the chemical fiber has a length of not less than 10 μm, the surface is covered with nano-level pleats, and the membrane pore size is 50-3000 nm.
[0019] Another object of the present application is to disclose the application of the prepared high-pleated antibacterial chemical fiber membrane as oil-water separation material, especially oily leachate separation material in food waste. The separation efficiency of water-in-oil emulsion is as high as 99% or more, and the separation efficiency is still higher than 97% after 10 cycles.
[0020] The pleat forming mechanism in the present application is as follows: the fiber membrane is oleophilic and hydrophobic, so it can absorb organic solvents in the emulsion. As the organic solvents continuously penetrate into the fiber, the volume of the fiber increases and swelling occurs. However, due to the uneven dispersion of organic solvents in the emulsion, the fiber surface stimulated by the organic solvents produces uneven swelling, that is, different tangential stresses are generated during the swelling process, which induces the fiber to form a nano-scale high-pleated morphology. Separation mechanism: in the water-in-oil separation process, due to the hydrophilicity of the fiber membrane, the water phase can be infiltrated and pass through the fiber membrane smoothly. The pleats on the surface of the fiber increase the contact area between the fiber and the liquid, and when the water phase wets the gap between the pleats, the steric hindrance effect generated can reduce the adhesion of oil droplets on the surface of the fiber, which is beneficial to maintaining the anti-fouling performance and separation stability of the membrane. At the same time, the oil droplets are isolated on the surface of the membrane by the "pore size screening" effect of the fiber membrane.
[0021] Advantages
[0022] The present application adopts electrospinning technology, which is simple in method, and the structural parameters such as membrane pore size and fiber aspect ratio are adjustable and have good repeatability. The high-pleated structure is directly constructed on the surface of the chemical fiber, realizing the unity of the flexibility and mechanical properties of the fiber membrane. The prepared high-pleated chemical fiber membrane has the characteristics of anti-oil fouling adhesion and antibacterial properties, and the required raw materials are cheap and easy to obtain. The separation efficiency of oily leachate is as high as 99% or more, and the separation efficiency is still higher than 97% after 10 cycles, which has broad application prospects in food waste treatment. BRIEF DESCRIPTION OF DRAWINGS
[0023] Figure 1 . SEM image of high-pleated PET fiber membrane. DETAILED DESCRIPTION
[0024] The present application will be described in detail below with reference to examples, so that those skilled in the art can better understand the present application, but the present application is not limited to the following examples.
[0025] Example 1
[0026] A preparation method of a high-pleated antibacterial chemical fiber membrane, comprising the following steps:
[0027] a) Based on the calculation of 4g of polyester dissolved in 100mL of trifluoroacetic acid, a polyester spinning solution was obtained after mechanical stirring; a No. 17 flat needle was used to prepare a polyester fiber membrane by electrospinning under the conditions of 15kV voltage, 15cm receiving distance and 2mL / h spinning flow rate.
[0028] b) Add 20 mL of n-hexane and 0.2 g of cetyltrimethylammonium bromide per 100 mL of water, and ultrasonically emulsify for 50 min to obtain an emulsion;
[0029] c) Add 2 mL of the emulsion prepared in step b) per square centimeter of chemical fiber membrane, and soak continuously at 20°C for 30 min; take out the chemical fiber membrane, wash twice with anhydrous ethanol, wash twice with distilled water, and dry at 60°C for 12 h to obtain a high-pleated polyester fiber membrane.
[0030] d) Add 3 mL of 2-methylimidazole, 40 mL of glycerol, and 1 g of dopamine to every 100 mL of anhydrous ethanol to obtain a mixed solution;
[0031] e) Add 10 mL of mixed solution per square centimeter of high-pleated chemical fiber membrane, stir at 80°C for 24 h, remove, wash 6 times with anhydrous ethanol, wash 2 times with distilled water, and dry at 80°C for 7 h to obtain high-pleated antibacterial polyester fiber membrane.
[0032] The 2mm thick high-pleated antibacterial polyester fiber membrane was sandwiched between two vertical glass tubes, and oily filtrate was poured in, achieving a separation efficiency of 99.3%.
[0033] The wrinkles that form on the surface of the swollen fibers are shown in the attached image. Figure 1 As shown, the fiber membrane, composed of intersecting and disordered fibers, possesses a porous structure with an average pore size of 1-3 μm and a single fiber diameter between 260 nm and 860 nm. This porous structure promotes the permeation of the oil phase. After undergoing a non-uniform swelling-shrinkage process in the emulsion, nanoscale wrinkles are formed on the fiber surface, achieving the preparation of a highly wrinkled fiber membrane.
[0034] Example 2
[0035] A method for preparing a highly wrinkled antibacterial synthetic fiber membrane includes the following steps:
[0036] a) Based on the calculation of 3g of spandex dissolved in 100mL of dichloromethane, a polyester spinning solution was obtained after mechanical stirring; a No. 17 flat needle was selected, and a spandex fiber membrane was prepared by electrospinning under the conditions of 12kV voltage, 17cm receiving distance and 3mL / h spinning flow rate.
[0037] b) Add 10 mL of dichloromethane and 0.1 g of sodium laurate per 100 mL of water, and ultrasonically emulsify for 60 min to obtain an emulsion;
[0038] c) Add 5 mL of the emulsion prepared in step b) per square centimeter of spandex fiber membrane, and soak continuously at 30°C for 60 min; take out the spandex fiber membrane, wash twice with anhydrous ethanol, wash twice with distilled water, and dry at 100°C for 3 h to obtain a high-wrinkle spandex fiber membrane.
[0039] d) Add 4 mL of 2-methylimidazole, 50 mL of glycerol, and 1.5 g of dopamine to every 100 mL of anhydrous ethanol to obtain a mixed solution;
[0040] e) Add 10 mL of mixed solution per square centimeter of high-pleated chemical fiber membrane, stir at 60°C for 48 h, remove, wash 5 times with anhydrous ethanol, wash 3 times with distilled water, and dry at 100°C for 5 h to obtain high-pleated antibacterial spandex fiber membrane.
[0041] The 2mm thick high-pleated antibacterial spandex fiber membrane was sandwiched between two vertical glass tubes, and oily permeate was poured in, achieving a separation efficiency of 99.0%.
[0042] Example 3
[0043] A method for preparing a highly wrinkled antibacterial synthetic fiber membrane includes the following steps:
[0044] a) An acrylic spinning solution was prepared by mechanical stirring, based on the principle of dissolving 4g of acrylic fiber per 100mL of dimethyl sulfoxide; a No. 17 flat-tipped needle was used, with a voltage of 18kV, a receiving distance of 12cm, and a spinning flow rate of 4...
[0045] Acrylic fiber membranes were prepared by electrospinning under conditions of mL / h.
[0046] b) Add 5 mL of n-hexane and 1 g of Span 80 per 100 mL of water, and ultrasonically emulsify for 50 min to obtain an emulsion;
[0047] c) Add 10 mL of the emulsion prepared in step b) per square centimeter of acrylic fiber membrane, and soak continuously at 50°C for 10 min; take out the acrylic fiber membrane, wash twice with anhydrous ethanol, wash twice with distilled water, and dry at 30°C for 24 h to obtain a high-wrinkle acrylic fiber membrane.
[0048] d) Add 5 mL of 2-methylimidazole, 100 mL of glycerol, and 2 g of dopamine to every 100 mL of anhydrous ethanol to obtain a mixed solution;
[0049] e) Add 5 mL of mixed solution per square centimeter of high-pleated chemical fiber membrane, stir at 80°C for 24 h, remove, wash 5 times with anhydrous ethanol, wash 3 times with distilled water, and dry at 30°C for 12 h to obtain high-pleated antibacterial acrylic fiber membrane.
[0050] The high-pleated antibacterial acrylic fiber membrane with a thickness of 2 mm is clamped between two vertical glass tubes, and the oil infiltration solution is poured in, and the separation efficiency reaches 99.4%.
[0051] Example 4
[0052] A method for preparing a high-pleated antibacterial chemical fiber membrane, comprising the following steps:
[0053] a) Dissolve 4 g of chlorofiber per 100 mL of N,N-dimethylformamide, and obtain chlorofiber spinning solution after mechanical stirring; select a 17-gauge flat needle, and prepare chlorofiber membrane by electrospinning under the conditions of a voltage of 20 kV, a receiving distance of 20 cm, and a spinning flow rate of 3 mL / h.
[0054] b) Add 10 mL of toluene and 0.5 g of sodium laurate per 100 mL of water, and ultrasonic emulsify for 30 min to obtain an emulsion;
[0055] c) Add 20 mL of the emulsion prepared in step b) per square centimeter of chlorofiber membrane, and continuously soak at 30°C for 60 min; take out the chlorofiber membrane, wash it with anhydrous ethanol for 2 times, wash it with distilled water for 2 times, and dry it at 80°C for 16 h to obtain a high-pleated chlorofiber membrane;
[0056] d) Add 3 mL of 2-methylimidazole, 80 mL of glycerol, and 0.1 g of dopamine per 100 mL of anhydrous ethanol to obtain a mixed solution;
[0057] e) Add 20 mL of the mixed solution per square centimeter of high-pleated chemical fiber membrane, stir at 80°C for 72 h, take out, wash it with anhydrous ethanol for 3 times, wash it with distilled water for 3 times, and dry it at 60°C for 8 h to obtain a high-pleated antibacterial chlorofiber membrane.
[0058] The high-pleated antibacterial chlorofiber membrane with a thickness of 2 mm is clamped between two vertical glass tubes, and the oil infiltration solution is poured in, and the separation efficiency reaches 99.2%.
[0059] Example 5
[0060] A method for preparing a high-pleated antibacterial chemical fiber membrane, comprising the following steps:
[0061] a) Dissolve 6 g of chlorofiber per 100 mL of dichloromethane, and obtain spandex spinning solution after mechanical stirring; select a 17-gauge flat needle, and prepare chlorofiber membrane by electrospinning under the conditions of a voltage of 20 kV, a receiving distance of 15 cm, and a spinning flow rate of 3
[0062] mL / h.
[0063] b) Add 10 mL of dichloromethane and 1.5 g of ammonium lauryl sulfate per 100 mL of water, and ultrasonic emulsify for 20 min to obtain an emulsion;
[0064] c) 5 mL of the emulsion prepared in step b) per square centimeter of the chlorofiber membrane, and soaking for 50 min at 20°C; taking out the chlorofiber membrane, washing twice with anhydrous ethanol, washing twice with distilled water, and drying at 50°C for 12 h to obtain the high-crease chlorofiber membrane;
[0065] d) 1 mL of 2-methylimidazole, 40 mL of glycerol, and 1 g of dopamine per 100 mL of anhydrous ethanol to obtain a mixed solution;
[0066] e) 8 mL of the mixed solution per square centimeter of the high-crease chlorofiber membrane, stirring at 70°C for 48 h, taking out, washing three times with anhydrous ethanol, washing three times with distilled water, and drying at 60°C for 10 h to obtain the high-crease antibacterial chlorofiber membrane.
[0067] The high-crease antibacterial chlorofiber membrane prepared above has a thickness of 2 mm, and is clamped between two vertical glass tubes, and poured with the oily percolate, and the separation efficiency reaches 99.7%.
[0068] The above description is only an embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation, or direct or indirect application in other related technical fields, is also included in the patent protection scope of the present application.
Claims
1. A method for preparing a high-pleated antibacterial synthetic fiber membrane, comprising the following steps: a) preparing a synthetic fiber membrane by electrospinning technology according to the following formula: 2-8 g of synthetic fiber per 100 mL of solvent; b) preparing an emulsion by ultrasonic emulsification for 10-60 min according to the following formula: 2-40 mL of organic solvent and 0.1-5 g of surfactant per 100 mL of water; c) soaking the synthetic fiber membrane in the emulsion for 10-60 min at 20-50 ℃, then washing it with anhydrous ethanol for 1-3 times, washing it with distilled water for 1-3 times, and drying it at 30-100 ℃ for 3-24 h to obtain a high-pleated synthetic fiber membrane; d) preparing a mixed solution according to the following formula: 1-5 mL of 2-methylimidazole, 20-100 mL of glycerol, and 0.1-2 g of dopamine per 100 mL of anhydrous ethanol; e) stirring the high-pleated synthetic fiber membrane in the mixed solution at 60-80 ℃ for 24-72 h, then washing it with anhydrous ethanol for 3-6 times, washing it with distilled water for 1-3 times, and drying it at 30-100 ℃ for 5-12 h to obtain a high-pleated antibacterial fiber membrane. In step a), the solvent is a combination of one or more of trifluoroacetic acid, N, N-dimethylformamide, dichloromethane, and dimethyl sulfoxide. In step a), the synthetic fiber is any one or a combination of aramid fiber, spandex, acrylic fiber, polypropylene fiber, or chlorofiber. In step a), the electrospinning process parameters are an electrostatic voltage of 5-25 kV, a spinning flow rate of 0.02-5 mL / h, and a receiving distance of 10-30 cm. In step b), the organic solvent is a combination of one or more of n-hexane, dichloromethane, ethyl acetate, and toluene. In step b), the surfactant is any one of cetyltrimethylammonium bromide, sodium laurate, ammonium lauryl sulfate, and Span 80.
7. The high-pleated antibacterial synthetic fiber membrane prepared by the method of any one of claims 1-6. The high-pleated antibacterial synthetic fiber membrane is formed by mechanically entangling fibers with a diameter of 0.2-20 μm, wherein the length of the synthetic fiber is not less than 10 μm, the surface is covered with nano-scale pleats, and the membrane pore size is 50-3000 nm. The high-pleated antibacterial synthetic fiber membrane can be used as an oil-water separation material. The high-pleated antibacterial synthetic fiber membrane can be used for separating oily leachate from food waste. 2. The method for preparing the high-wrinkle antibacterial chemical fiber membrane according to claim 1, characterized in that: 3. The method for preparing the high-wrinkle antibacterial chemical fiber membrane according to claim 1, characterized in that: 4. The method for preparing the high-wrinkle antibacterial chemical fiber membrane according to claim 1, characterized in that: 5. The method for preparing the high-wrinkle antibacterial chemical fiber membrane according to claim 1, characterized in that: 6. The method for preparing the high-wrinkle antibacterial synthetic fiber membrane according to claim 1, characterized in that: 8. The high-creping antibacterial chemical fiber membrane according to claim 7, characterized in that: 9. Use of the high-creped antibacterial fiber film according to claim 7 or 8, characterized in that: 10. The use of the high-crease antibacterial chemical fiber film according to claim 9, characterized by:
Citation Information
Patent Citations
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