CN-116943441-B - Preparation method of nanofiber tubular membrane based on separable magnetic particle anti-fouling function

Abstract

The invention discloses a preparation method of a magnetic nanofiber tubular membrane based on a separable magnetic particle anti-fouling function, which comprises the following steps of 1) fully mixing an equal volume of ferric salt solution and fumaric acid solution, carrying out hydrothermal reaction after ultrasonic treatment, 2) fully mixing a solid product obtained in the step 1) with a vulcanizing agent-ethanol solution according to a certain mass ratio, continuing the hydrothermal reaction to obtain Fe 3 S 4 magnetic catalytic particles, 3) braiding polyester fibers into a braided tube, nesting the braided tube on an axially stacked magnetic tube to form the magnetic braided tube, 4) adding a fiber-forming polymer into a solvent to dissolve the fiber-forming polymer to obtain uniform and stable spinning solution, using the magnetic braided tube obtained in the step 3) as a receiver, spinning the spinning solution obtained in the step 4) by using an electrostatic spinning technology to obtain the magnetic nanofiber tubular membrane, and 6) loading the magnetic catalytic particles obtained in the step 2) on the surface of the membrane obtained in the step 5) to obtain the Fe 3 S 4 /magnetic nanofiber tubular membrane.

Inventors

• ZHAO JIAN
• PU HONGWEI
• QUAN QUAN
• ZHANG SHUJIE
• XIAO CHANGFA

Assignees

• 天津工业大学

Dates

Publication Date

20260505

Application Date

20230904

Claims (4)

1. 1. The preparation method of the magnetic nanofiber tubular membrane based on the separable magnetic particle anti-fouling function is characterized by comprising the following steps of: 1) Fully mixing an equal volume of ferric salt solution and fumaric acid solution, performing ultrasonic treatment, transferring into a hydrothermal reaction kettle, performing reaction at a certain temperature, centrifuging, washing and drying the obtained solid product after a period of time; 2) Synthesizing Fe 3 S 4 particles, namely fully and uniformly mixing the solid product obtained in the step 1) with a vulcanizing agent-ethanol solution according to a certain mass ratio, transferring the mixture into a hydrothermal reaction kettle for reaction at a certain temperature, centrifuging, washing and drying the obtained solid product after a period of time to obtain Fe 3 S 4 magnetic catalytic particles; 3) Preparing a magnetic braided tube matrix, namely braiding polyester fibers into a polyester fiber braided tube with a regular mesh structure through a braiding machine, and nesting the polyester fibers on the stacked magnetic tubes to form the magnetic braided tube matrix; 4) Preparing spinning solution, namely fully drying fiber-forming polymer powder with certain mass, adding the fiber-forming polymer powder into a corresponding solvent, and stirring the mixture for 12 hours at a certain temperature to obtain uniform and stable spinning solution; 5) Spinning, namely placing the spinning solution obtained in the step 4) into a syringe after standing or vacuum defoamation, taking the magnetic braided tube matrix obtained in the step 3) as a receiver, carrying out electrostatic spinning, and placing the obtained nanofiber tubular membrane nested with the stacked magnetic tubes into a vacuum oven for full drying after a period of time to obtain the nanofiber tubular membrane with magnetism; 6) And (3) loading the Fe 3 S 4 magnetic catalytic particles obtained in the step (2) on the surface of the magnetic nanofiber tubular membrane obtained in the step (5), so as to obtain the Fe 3 S 4 /magnetic nanofiber tubular membrane.
2. 2. The preparation method of the magnetic nanofiber tubular membrane based on the separable magnetic particle anti-fouling function is characterized in that in the step 1), the ferric salt solution is one of ferric trichloride hexahydrate (FeCl 3 ·6H 2 O) solution or ferric nitrate nonahydrate (Fe (NO 3 ) 3 ·9H 2 O) solution, the mass fraction of the ferric nitrate solution is 5-15wt%, the mass fraction of the fumaric acid solution is 1-10wt%, the ultrasonic treatment time is 10-30 min, the ultrasonic frequency is 20-40 kHz, the reaction temperature is 100-150 ℃, and the reaction time is 5-20 h.
3. 3. The preparation method of the magnetic nanofiber tubular membrane based on the separable magnetic particle anti-fouling function is characterized in that the vulcanizing agent-ethanol solution in the step 2) is 1-10wt% of Thioacetamide (TAA) ethanol solution, the mass ratio of the solid product to the vulcanizing agent-ethanol solution is 1:200-1:1000, the reaction temperature is 100-150 ℃, and the reaction time is 5-15 h.
4. 4. The preparation method of the magnetic nanofiber tubular membrane based on the separable magnetic particle anti-fouling function is characterized in that the fiber-forming polymer powder in the step 4) comprises one of polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyether sulfone (PES), poly-m-phenylene isophthalamide (PMIA) and Polyimide (PI), the mass concentration of spinning solution is 10-20wt%, the solvent is one or more solvents of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and acetone, the drying temperature of a vacuum oven is 60-100 ℃, and the vacuum pressure is-50 to-30 Pa.

Description

Preparation method of nanofiber tubular membrane based on separable magnetic particle anti-fouling function Technical Field The invention relates to the technical field of membrane separation, in particular to a preparation method of a nanofiber tubular membrane based on a separable magnetic particle anti-fouling function. Background Membrane separation technology is one of the effective ways to efficiently treat complex wastewater, but membrane pollution problems severely limit the performance and application cost of membrane materials. The actual wastewater has high concentration, complex components and strong chemical stability, and often contains a large amount of soluble components (dyes, antibiotics, sugar, proteins, phenols, aldehydes and the like) and insoluble components (humus, microorganisms, oil, dust, sand grains and other inorganic impurities). The wastewater is difficult to degrade, and a stable pollution layer is easily formed on the surface of the membrane by accumulation, so that the flux and separation efficiency of the membrane material are reduced, the service life of the membrane material is seriously shortened, and the economic cost of membrane washing and membrane replacement is obviously increased. The chemical cleaning is a widely used mode for cleaning membrane pollution at present, and can be classified into alkaline cleaning, acid cleaning, enzyme cleaning, disinfection cleaning, compound cleaning and the like according to different cleaning agents. Wherein, sodium hypochlorite is a common membrane pollution cleaning agent, has the characteristics of strong oxidizing property, strong deactivation and the like, and can rapidly remove organic pollutants deposited on the surface of a membrane and in a membrane hole. However, the high-concentration sodium hypochlorite can react with organic matters to generate disinfection byproducts with toxicity of three causes (mutation, canceration and distortion), so that the quality of effluent water is seriously influenced, the metabolism of aquatic organisms is influenced, and the safety of biological chains is threatened. In view of this, some work has been devoted to membrane contaminant cleaning using oxidants such as ozone, hydrogen peroxide (H 2O2) and the like instead of sodium hypochlorite. Although the oxidant can achieve better cleaning effect, disinfection byproducts with higher toxicity can be generated in the cleaning process, and irreversible chemical damage is caused to the membrane material, and the oxidant has no removal effect on most inorganic pollutants. In recent years, a great deal of researches show that the catalyst coupling film has good treatment effect on multiple types of complex waste water under the action of physical fields such as light, electricity, sound and the like. Wherein the catalyst can generate hydroxyl free radicals, superoxide anions, singlet oxygen and other Reactive Oxygen Species (ROS) as an oxidant body under proper conditions. The ROS can not only oxidize and degrade various organic pollutants, but also inhibit the generation of membrane pollution, and can effectively prolong the service life of the membrane material. The Chinese patent CN 202310381227.4 discloses a method for controlling membrane pollution by using ferrous particles (Fe 2+) to induce H 2O2 in-situ acid production of organic pollutants, which mainly aims at resisting pollution by using organic pollutants on the surface of a hydroxyl radical oxide membrane generated by Fenton (Fenton) reaction between Fe 2+ and H 2O2. Although Fenton reaction has strong oxidizing property and simple operation, a large amount of ferric salt, H 2O2 and the like are needed to be added in the reaction process, a large amount of iron mud can be generated, and the problem of exceeding of iron element in effluent water can be caused. Chinese patent No. CN202010218286.6 discloses an electrochemical system for membrane pollution control of a Membrane Bioreactor (MBR), which combines an electrochemical advanced oxidation method with an MBR process, accelerates degradation of organic pollutants by using a strong electric field effect of electrochemical oxidation, promotes a metabolic process of microorganisms, and inhibits occurrence of membrane pollution to a certain extent. The electrochemical-Membrane Bioreactor (MBR) coupling system can directly embed the electrochemical module into the MBR system, avoiding the problem of additional devices, but the practical application of the electrochemical module is severely limited by the process parameters and maintenance costs of the electrochemical module. The photocatalytic coupling film system is a multi-physical field (optical field) coupling film system which has been rapidly developed in recent years. The characteristics of environmental protection, energy conservation and high efficiency are widely paid attention to the fields of textile wastewater treatment and the like. The photocatalysis coupling membra