An anti-pollution hydrophilic hollow fiber membrane and its preparation method

Abstract

The present invention provides an anti-pollution hydrophilic hollow fiber membrane and a preparation method thereof. The method includes mixing, kneading, and extruding a thermoplastic polymer resin, an organic pore-forming agent, an inorganic pore-forming agent, and nano-titanium dioxide; extracting and separating the filamentous hollow fiber; immersing the base membrane in a titanium crystal growth solution, hydrolyzing it under acidic conditions to form a nano-level gel on the membrane surface, and then performing desolvation and dehydration to form an anti-pollution titanium crystal nano-layer; soaking the membrane in an aqueous solution of a polymer with hydrophilic groups, and forming a hydrophilic composite layer through a hydrogen bond reaction. In the preparation method of the anti-pollution hydrophilic hollow fiber membrane of the present invention, nano-titanium dioxide is pre-added to the base membrane to form nano-crystal seeds, further titanium crystals are generated on the membrane surface, and finally the combination of titanium crystals and hydrophilic polymers forms a complete layer with anti-pollution and hydrophilization functional layers on the surface of the base membrane. This membrane is suitable for applications in the field of sewage treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of membrane separation, and particularly relates to an anti-fouling hydrophilic hollow fiber membrane and a preparation method thereof. Background Technique

[0002] In recent years, the application of membrane separation technology has developed rapidly in the industrial and civilian fields. Especially in the face of the increasingly prominent water resource crisis, effective water treatment methods and the recycling of water resources have become even more important, and membrane separation technology provides an important solution.

[0003] Since the membrane is prone to fouling during long-term operation, which will lead to problems such as reduced treatment performance, increased energy consumption, and short service life, it greatly restricts its development in the water treatment field. Therefore, overcoming the deficiencies of the membrane itself and developing products with good permeability and excellent anti-fouling ability have become popular research goals in the industry.

[0004] The currently widely used hollow fiber filter membrane is generally made of some polymer organic materials, which usually have the advantages of chemical stability, weather resistance, radiation resistance, and easy film formation. However, the surface energy of the material is low, the hydrophobicity is strong, and it is prone to fouling in water treatment, which increases the transmembrane pressure and decreases the water flux, thus increasing the membrane cleaning frequency and membrane cost. Therefore, improving the anti-fouling and hydrophilic modification of the membrane has become an important research topic.

[0005] To improve the hydrophilicity of the membrane, the main modification methods include surface modification, chemical modification, and blending modification. However, the coating layer of surface modification is easy to fall off from the membrane surface and has poor persistence; chemical modification will reduce the membrane strength and the process is complex; blending modification is simple to operate and the reaction conditions are mild, so it has certain advantages compared with other methods. The common nanoparticles used for blending modification mainly include silica (SiO2), alumina (Al2O3), calcium carbonate (CaCO3), and titanium dioxide (TiO2), etc. Some existing studies have shown that appropriately mixing and dispersing inorganic nanoparticles can promote the improvement of the membrane performance of polymer materials.

[0006] Nano-titanium dioxide is a new type of functional material with advantages such as super hydrophilicity, chemical stability, thermal stability, non-toxicity, antibacterial property, excellent strength, large specific surface area and high activity. Some studies have improved the performance of the membrane by mixing nano-titanium dioxide into the membrane raw materials, and also improved the hydrophilicity and filtration performance of the membrane to a certain extent. However, with this technology, many particles only exist in the support of the membrane and do not reach the filtration surface of the membrane, so that the distribution of particles on the membrane surface in contact with the filtrate is small, and it plays its due role. However, in order to increase the concentration of titanium dioxide on the membrane surface, the amount of mixing must be increased. On the one hand, a large proportion of mixing will increase the cost, and on the other hand, the agglomeration of nanoparticles will occur, resulting in uneven distribution and reducing the porosity of the membrane, resulting in a decrease in some performance indicators of the membrane. Excessive addition of inorganic components also makes it difficult to form a film and loses the characteristics of high molecular polymers, so that the film cannot be formed at all. The truly effective anti-pollution and hydrophilic effects only require a functional nanolayer on the inner and outer surfaces of the entire membrane. Summary of the invention

[0007] In view of this, the present invention aims to overcome the defects in the prior art and proposes an anti-fouling hydrophilic hollow fiber membrane and a preparation method thereof.

[0008] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0009] The present invention provides a method for preparing an anti-fouling hydrophilic hollow fiber membrane, comprising the following steps:

[0010] (1) mixing a thermoplastic polymer resin, an organic pore-forming agent, an inorganic pore-forming agent and nano-titanium dioxide at high speed, and kneading and extruding the powdery mixture in an extruder through a thermoinduced phase film-making process to obtain a filamentous hollow fiber of the polymer;

[0011] (2) extracting the filamentous hollow fibers to obtain a high molecular weight polymer hollow fiber porous base membrane containing nano-titanium dioxide crystal seeds;

[0012] (3) immersing the high molecular weight polymer hollow fiber porous base membrane containing nano titanium dioxide crystal seeds into a titanium crystal growth solution, hydrolyzing it under acidic conditions to form a nano-scale gel on the membrane surface, and then desolventizing and dehydrating it to obtain a hollow fiber membrane with a primary titanium crystal nanolayer on the surface;

[0013] (4) The hollow fiber membrane with the primary titanium crystal nanolayer on the surface is immersed in an aqueous solution of a polymer having a hydrophilic group to form a hydrophilic composite layer through a hydrogen bonding reaction, thereby obtaining the anti-fouling hydrophilic hollow fiber membrane.

[0014] Further, the titanium crystal growth solution in step (3) is an ethanol solution containing tetrabutyl titanate, tetra-isobutyl titanate or tetraethyl titanate; the concentration of the titanium crystal growth solution is 0.5-2%.

[0015] Further, the hydrolysis step in step (3) is carried out using a titanium crystal growth device on the membrane surface for the reaction.

[0016] Preferably, the titanium crystal growth solution in step (3) is an ethanol solution of tetrabutyl titanate, wherein the weight percentage of tetrabutyl titanate is 0.5-2%, and the weight percentage of ethanol is 99-100%.

[0017] Further, the weight percentage of the polymer with hydrophilic groups in the aqueous solution of the polymer with hydrophilic groups in step (4) is 0.5-3%; the polymer with hydrophilic groups is at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) or polyethylene oxide (PEO).

[0018] Further, the particle size of the nano-titanium dioxide in step (1) is less than or equal to 20 nm; the mass ratio of the thermoplastic polymer resin, organic pore-forming agent, inorganic pore-forming agent and nano-titanium dioxide in step (1) is 30-50:20-40:20-50:1-5.

[0019] Further, the inorganic pore-forming agent in step (1) is a hydrophobic nano-oxide; the hydrophobic nano-oxide is at least one of active nano-oxide, nano-diatomite or nano-kaolin; the active nano-oxide is at least one of nano-zinc oxide, nano-calcium carbonate or nano-silicon dioxide; the specific surface area of the inorganic pore-forming agent in step (1) is 30-150 m 2 / g, and the average particle size is less than or equal to 100 nm. The activity in the active nano-oxide refers to the organic hydrophobic treatment of the surface of the substance, so that the substance can be well dispersed in the organic system.

[0020] Further, the thermoplastic polymer resin in step (1) is at least one of polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polyethersulfone (PES), polysulfone (PS), polypropylene (PP) or polyethylene (PE);

[0021] The organic pore-forming agent in step (1) is at least one of phthalate pore-forming agents, γ-butyrolactone pore-forming agents, benzoate pore-forming agents, sebacate pore-forming agents or adipate pore-forming agents; the phthalate pore-forming agents are at least one of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) or dioctyl phthalate (DOP).

[0022] The described preparation method first prepares a hollow fiber-based membrane containing titanium dioxide (TiO2) seeds through a thermally induced phase separation (TIPS) process. A small amount of nano-titanium dioxide is highly mixed into the membrane-forming raw materials as titanium seeds in the membrane to improve some properties of the membrane layer. Then, a special process is used on the surface of the base membrane to generate a new active nano-titanium dioxide (TiO2) and titanium hydroxide (TiO(OH)2) titanium crystal nano-layer on the seeds. This combines with the titanium dioxide (TiO2) that was previously mixed in and exists on the inner and outer surfaces of the membrane layer, just like "nails rooted in the membrane layer", greatly enhancing the binding firmness of inorganic nano-titanium dioxide on the surface of the organic base membrane and avoiding the incompatibility between general organic materials and inorganic materials, which may cause peeling during application. At the same time, the functional nano-titanium crystal layer only exists on the inner and outer surfaces of the membrane layer, greatly improving the effective anti-pollution effect. Since it is a nano-scale functional layer, it does not affect the size of the micron-scale membrane pores of the original base membrane.

[0023] Due to the presence of nano-titanium dioxide (TiO2) and titanium hydroxide (TiO(OH)2) in the titanium crystal nano-functional layer of the hollow fiber, the hydrophilicity of the membrane surface is also improved, as well as the inherent catalytic properties of TiO2. At the same time, the anti-pollution ability of the membrane is enhanced. During the application process of sewage treatment, especially for organic and biological sewage, nano-TiO2 particles can generate free radicals in the presence of H2O2, showing good decomposition and removal effects on organic substances and biomass.

[0024] At the same time, the hydrophilic layer formed by the hydrogen bonding of nano-titanium dioxide (TiO2) and titanium hydroxide (TiO(OH)2) with water-soluble polymers further greatly improves the surface hydrophilicity of the membrane, preventing the attachment and blockage of organic hydrophobic substances on the membrane surface and avoiding the decrease in water flux caused by organic pollutants. And the hydrogen bonding effect firmly combines the hydrophilic layer of the water-soluble polymer with the titanium crystal nano-layer, greatly reducing its loss during use.

[0025] This preparation method solves the problems of limited blending ratios in the simple blending method and only a small part of the surface particles playing a role, and also avoids the problem of easy peeling when only coating the functional layer on the surface of the membrane pores. It gives play to the synergistic advantages of the two methods while avoiding the negative impacts. Furthermore, the hydrophilic layer formed by the hydrogen bonding of the water-soluble polymer further enhances the anti-pollution and hydrophilic functions of this membrane.

[0026] The present invention also provides an anti-pollution hydrophilic hollow fiber membrane, and the hollow fiber membrane is prepared by the described preparation method.

[0027] An application of the anti-pollution hydrophilic hollow fiber membrane, and the application of the hollow fiber membrane in the field of sewage treatment.

[0028] Furthermore, the application of the hollow fiber membrane in treating industrial organic sewage and biological sewage.

[0029] The present invention also provides a titanium crystal growth device on the membrane surface, which includes a reaction tank. A membrane wire rack is arranged inside the reaction tank, and the polymer hollow fiber base membrane is placed in the reaction tank through the membrane wire rack. An air pipeline is connected to the bottom of the reaction tank.

[0030] Furthermore, an air vent, a pressure gauge, a vacuum port, a thermometer and an observation port are provided at the top of the reaction tank. A stock solution inlet and a regulating solution inlet are provided at the upper part of the reaction tank. A liquid discharge port is provided at the bottom of the reaction tank, and a liquid level gauge is arranged on the reaction tank.

[0031] Place the polymer hollow fiber base membrane in the reaction tank filled with titanium crystal growth solution through the membrane wire rack, introduce nitrogen to stir the solution in the tank by air flow. After reacting for a certain period of time, a nano gel body is formed on the membrane surface. After the reaction is completed, the remaining solution is collected through the bottom liquid discharge port for reuse. The reaction tank is connected to a vacuum system. Under vacuum conditions, the colloid formed on the membrane wire surface is desolvated and dehydrated to form titanium crystals, and a condensation system is connected to realize the condensation collection and reuse of the solvent gas.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] In the preparation method of the anti-pollution hydrophilic hollow fiber membrane of the present invention, nano titanium dioxide is pre-added to the base membrane to form nano crystal seeds; however, when an excessive amount of titanium dioxide (TiO2) is added, since titanium dioxide (TiO2) exists in the membrane as a very stable compound, it will greatly reduce the porosity of the membrane, resulting in a decrease in water flux, and it will also destroy the characteristics of the original "organic membrane" of the polymer membrane, and it is difficult to form a membrane during the preparation process; when the addition amount of titanium dioxide (TiO2) is too small, the anti-pollution and hydrophilic characteristics of nano titanium dioxide (TiO2) cannot be exerted; further, titanium crystals are formed on the membrane surface, and the composition of its ethanol solution is 0.5-2% by weight of tetrabutyl titanate (Ti(OBu)4). Finally, the combination of titanium crystals and hydrophilic polymer (0.5-3% aqueous solution by weight percentage) completely forms a layer of anti-pollution and hydrophilic functional layer on the surface of the hollow fiber membrane base membrane. This membrane is suitable for application in the field of sewage treatment, especially industrial organic and biological sewage.

[0034] The preparation method of the anti-pollution hydrophilic hollow fiber membrane described in the present invention adds a nano-layer of titanium crystal on the inner and outer surfaces of the entire membrane layer, including the membrane surface of the cross-section, and can fully and effectively exert the anti-pollution function of nano-titanium dioxide (TiO2). A small amount of nano-titanium dioxide (TiO2) as a seed crystal is added to the base membrane layer. Embedding the seed crystal like a "nail" significantly improves the bonding force of the newly formed titanium crystal series nano-layer compound covering the surface.

[0035] The titanium crystal growth device on the membrane surface described in the present invention uses gas stirring to fully stir the solution, avoiding the risk caused by mechanical stirring to the flammable solvent, and controlling the pressure of the system by adjusting the air outlet through the pressure control table during the reaction process; after the reaction is completed, the remaining solution is collected through the liquid discharge port at the bottom, and the external waste liquid recovery tank can be reused after distillation; the vacuum port is connected to the external vacuum system. Under a vacuum state of 0.05 MPa, the colloid generated on the surface of the membrane filament is desolvated and dehydrated to generate titanium crystals (TiO(OH)2 and TiO2), and then connected to the condensation system to realize the condensation collection and reuse of the solvent gas.

[0036] In the treatment of industrial sewage with particularly harsh environments in sewage treatment, the newly formed titanium crystal series compounds and the hydrophilic layer formed by the strengthened hydrophilic polymer hydrogen bonds have a degradation effect on highly polluted organic matter and biomass under the action of H2O2. At the same time, the synergistic effect of hydrophilicity reduces the adsorption of these pollutants on the membrane surface. These all greatly improve the anti-organic and biological pollution resistance of the overall membrane, well solve the weakness of poor anti-pollution resistance of the hollow fiber of the polymer prepared by the thermally induced phase separation process, and can well maintain the operation of the membrane equipment at high flux and reduce the energy consumption effect. Description of the Drawings

[0037] Figure 1 It is a schematic diagram of the titanium crystal growth device on the membrane surface described in the embodiment of the present invention;

[0038] Figure 2 It is an internal structure schematic diagram of the titanium crystal growth device on the membrane surface described in the embodiment of the present invention;

[0039] Figure 3 It is the Fourier transform attenuated total reflection infrared spectrum of the hollow fiber membrane described in the embodiment of the present invention;

[0040] Figure 4 It is a cross-sectional electron micrograph of the polyvinylidene fluoride hollow fiber membrane described in the embodiment of the present invention;

[0041] Figure 5 It is a schematic diagram of the component made of the polyvinylidene fluoride hollow fiber membrane described in the embodiment of the present invention applied in the simulated MBR wastewater filtration system device;

[0042] Figure 6 Variation diagram of transmembrane pressure (TMP) of the wastewater filtration system of the simulated MBR according to the embodiment of the present invention;

[0043] Figure 7 Schematic diagram of the anti-pollution ability test device according to the embodiment of the present invention;

[0044] Figure 8 Variation diagram of transmembrane pressure of the anti-pollution ability test according to the embodiment of the present invention.

[0045] Explanation of reference numerals:

[0046] 1, raw liquid inlet; 2, air vent; 3, pressure gauge; 4, vacuum port; 5, thermometer; 6, observation port; 7, membrane filament support; 8, regulating liquid inlet; 9, liquid level gauge; 10, liquid discharge port; 11, reaction tank; 12, air pipeline; 13, polymer hollow fiber base membrane. Specific implementation mode

[0047] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which the present invention belongs. The test reagents used in the following embodiments are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0048] The present invention will be described in detail below with reference to the embodiments.

[0049] Example 1 Preparation of anti-pollution hydrophilic hollow fiber membrane

[0050] A method for preparing an anti-pollution hydrophilic hollow fiber membrane includes the following steps:

[0051] Mix 40% of polyvinylidene fluoride, 20% of dioctyl phthalate, 38.5% of 50 - 60 m 2 / g of active nano calcium carbonate and 1.5% of nano titanium dioxide P25 in a high-speed mixer to obtain a uniform powdery mixture, then knead and melt-extrude it through a twin-screw extruder at a temperature of 240 °C, extrude hollow fiber filaments through a spinneret ring mold with air passing through, enter a cooling water tank for solidification and cooling, then stretch it online at a draw ratio of 1:2, and wind it on a winding wheel. After unloading the wheel, carry out organic extraction twice at room temperature with dichloromethane to remove the organic pore-forming agent, then carry out 5% hydrochloric acid reaction twice at room temperature to extract the inorganic pore-forming agent, and finally wash it clean with pure water, dry and shape it at 120 °C to obtain a polyvinylidene fluoride hollow fiber base membrane containing nano-TiO2 seeds;

[0052] The obtained polyvinylidene fluoride hollow fiber base membrane containing nano-TiO2 seeds is passed through a membrane surface titanium crystal growth device, such as Figure 1-2As shown, a new primary titanium crystal nano-layer is formed on its inner and outer surfaces:

[0053] Place the polyvinylidene fluoride hollow fiber base membrane on the membrane filament rack in the reaction tank. Introduce a 1% tetrabutyl titanate ethanol solution (ethanol 99.5%) into the reaction tank. Immerse the above hollow fiber base membrane in this solution at room temperature. Pass nitrogen through the connected air pipeline to stir the solution with gas. Adjust the pH value of the solution to about pH = 4 with acetic acid and ammonia water to make the titanium crystal growth process tend to be stable. The reaction time is 30 min, and the reaction is completed in the crystal growth reaction tank;

[0054] Then transfer the membrane filaments obtained to a vacuum box at room temperature. Under a vacuum degree of 0.05 MPa, remove ethanol and dehydrate to form a nano-titanium crystal series layer on the inner and outer surfaces of the membrane, as Figure 3 shown. Rinse with pure water to remove the adsorbed compounds on the free surface. Then immerse the obtained new titanium crystal membrane filaments in an aqueous solution of 2% polyvinylpyrrolidone (K-30). A hydrophilic layer is formed on the membrane surface through hydrogen bonds with the titanium crystal series. After soaking for 1 hour, air-dry to obtain an anti-pollution and hydrophilic polyvinylidene fluoride hollow fiber membrane, as Figure 4 shown. Outer diameter: 1.51 mm, inner diameter: 0.85 mm, bubble point: 0.21 MPa, breaking tensile strength: 18.2 MPa, breaking strength elongation rate: 60%, surface contact angle: 53°, critical wetting surface tension: 72 dyne / cm.

[0055] Preparation of the hollow fiber membrane in Comparative Example 1

[0056] The difference from Example 1 is only that: the hollow fiber membrane includes 40% polyvinylidene fluoride, 20% dioctyl phthalate and 40% of 50 - 60 m 2 / g active nano calcium carbonate.

[0057] Obtain a polyvinylidene fluoride hollow fiber dry membrane as Figure 3 shown. Outer diameter: 1.50 mm, inner diameter: 0.83 mm, bubble point: 0.20 MPa, breaking tensile strength: 18.5 MPa, breaking strength elongation rate: 56%, surface contact angle: 83°, critical wetting surface tension: 45 dyne / cm.

[0058] Anti-pollution performance of the hollow fiber membrane in Example 2

[0059] Filter the simulated wastewater with the polyvinylidene fluoride hollow fiber membrane obtained in Example 1 in the membrane bioreactor (MBR) system device, as Figure 5 shown. The sludge concentration (MLSS) is 8 g / L, the set membrane flux (Flux) is 20 LMH, and the F / M ratio is 0.4.

[0060] The diaphragm made of the hollow fiber membrane obtained in Example 1 and the diaphragm made of the hollow fiber membrane obtained in Comparative Example 1 were each subjected to 100 days of continuous operation. 0.03% sodium hypochlorite was used as MC every 7 days (maintenance cleaning). The change in transmembrane pressure difference over time during 100 days of operation of the nano-titanium crystal hollow fiber membrane and the hollow fiber membrane without titanium crystal was observed. After the TMP reaches the peak value, cleaning is required to maintain the membrane flux. Through Figure 6 The cleaning frequency of various membranes can be observed from the change in TMP in

[0061] The diaphragm of Example 1 and the diaphragm of Comparative Example 1 were used for a simulated anti-fouling test with bovine serum albumin (LBSA), as Figure 7 shown. The content of bovine serum albumin (LBSA) in the influent water was 0.5 g / L and the operation was continuous for 100 days. Chemical cleaning (MC) was carried out with 0.03% NaClO, as Figure 8 shown. It can be concluded that the transmembrane pressure difference of the membrane module of Example 1 is less than that of the membrane module of Comparative Example 1.

[0062] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing an anti-pollution hydrophilic hollow fiber membrane, characterized in that: It includes the following steps: (1) High-speed mixing, kneading, and extrusion of a thermoplastic polymer resin, an organic pore-forming agent, an inorganic pore-forming agent, and nano-titanium dioxide to obtain a filamentous hollow fiber of the polymer; (2) Extracting and obtaining a porous base membrane of a polymer hollow fiber containing nano-titanium dioxide crystal seeds from the filamentous hollow fiber; (3) Immersing the porous base membrane of the polymer hollow fiber containing nano-titanium dioxide crystal seeds in a titanium crystal growth solution, hydrolyzing under acidic conditions to form a nano-level gel on the membrane surface, and then performing desolvation and dehydration to obtain a hollow fiber membrane covered with a primary titanium crystal nano-layer on the surface; (4) Immersing the hollow fiber membrane covered with a primary titanium crystal nano-layer on the surface in an aqueous solution of a polymer with a hydrophilic group, and forming a hydrophilic composite layer through a hydrogen bond reaction to obtain the anti-pollution hydrophilic hollow fiber membrane; The particle size of the nano-titanium dioxide in step (1) is less than or equal to 20 nm; the mass ratio of the thermoplastic polymer resin, the organic pore-forming agent, the inorganic pore-forming agent, and the nano-titanium dioxide in step (1) is 30 - 50:20 - 40:20 - 50:1 - 5; The inorganic pore-forming agent in the step (1) is a hydrophobic nano-oxide; the hydrophobic nano-oxide is at least one of active nano-oxides, nano-diatomite or nano-kaolin; the active nano-oxide is at least one of nano-zinc oxide, nano-calcium carbonate or nano-silica; the specific surface area of the inorganic pore-forming agent in the step (1) is 30-150 m 2 / g, and the average particle size is less than or equal to 100 nm.

2. The preparation method of the anti-pollution hydrophilic hollow fiber membrane according to claim 1, characterized in that: The titanium crystal growth solution in step (3) is an ethanol solution containing tetrabutyl titanate, tetraisobutyl titanate, or tetraethyl titanate; the concentration of the titanium crystal growth solution is 0.5 - 2%; 3. The preparation method of the anti-pollution hydrophilic hollow fiber membrane according to claim 1, wherein: The hydrolysis step in step (3) uses a membrane surface titanium crystal growth device for the reaction; 4. The preparation method of the anti-pollution hydrophilic hollow fiber membrane according to claim 1, characterized in that: The weight percentage of the polymer with a hydrophilic group in the aqueous solution of the polymer with a hydrophilic group in step (4) is 0.5 - 3%; the polymer with a hydrophilic group is at least one of polyvinylpyrrolidone, polyethylene glycol, or polyethylene oxide; 5. The preparation method of the anti-pollution hydrophilic hollow fiber membrane according to claim 1, characterized in that: The thermoplastic polymer resin in step (1) is at least one of polyvinylidene fluoride, polyvinyl chloride, polyethersulfone, polysulfone, polypropylene, or polyethylene; The organic pore-forming agent in step (1) is at least one of phthalate pore-forming agents, γ-butyrolactone pore-forming agents, benzoate pore-forming agents, sebacate pore-forming agents, or adipate pore-forming agents; the phthalate pore-forming agents are at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, or dioctyl phthalate; 6. A pollution-resistant hydrophilic hollow fiber membrane, characterized in that: The hollow fiber membrane is prepared by the preparation method described in any one of claims 1 - 5.

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