A catalytic ultrafiltration membrane and preparation method thereof

Abstract

The present invention relates to the field of water treatment technology, specifically, to a catalytic ultrafiltration membrane and a preparation method thereof; the catalytic ultrafiltration membrane prepared by the method of the present invention consists of a hollow fiber tube and a separation precision layer, wherein the hollow fiber tube is made of a skin-core type composite catalytic fiber, and the skin layer of the composite catalytic fiber contains catalyst particles with a catalytic decomposition effect of a strong oxidant; when the catalytic ultrafiltration membrane is applied to a double-membrane wastewater reuse process, the separation precision layer can be used to filter out large molecular organic matter, and the catalyst particles loaded in the hollow fiber tube can catalytically decompose the strong oxidant in the effluent water on the clear liquid side of the ultrafiltration membrane, thereby avoiding the strong oxidant remaining in the front-end pretreatment process from damaging the RO membrane, without changing the original process design, adding equipment and reagent investment.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment, and in particular to a catalytic ultrafiltration membrane and a preparation method thereof. Background Art

[0002] With the continuous increase in industrial water consumption and total wastewater discharge, in order to save water resources and reduce environmental pollution, wastewater recycling has become the only way for industrial enterprises to save water and improve efficiency. At present, it is common to use double membrane method for wastewater recycling. In the double membrane wastewater reuse process, the effluent from the secondary sedimentation tank is pre-treated by sand filtration and multi-media filter, and then purified and filtered by ultrafiltration + reverse osmosis double membrane process, and the produced water enters the production water system. For application scenarios where raw water contains difficult-to-degrade organic matter, it is often necessary to combine ultraviolet photocatalysis, catalytic ozone oxidation, Fenton / Fenton-like oxidation, electrochemical oxidation and other front-end treatment measures to open the ring and break the chain of difficult-to-degrade organic matter, so as to reduce the operating load of the membrane system and improve the operating efficiency of the process. The front-end pretreatment process generally promotes the decomposition of strong oxidants to produce active oxygen species (hydroxyl radicals, superoxide radicals, sulfate radicals, etc.) through catalysis / activation. The active oxygen species degrade the difficult-to-degrade organic matter, so that a small amount of ozone, hydrogen peroxide and other strong oxidants will remain in the pretreated water. These strong oxidants will damage the post-reverse osmosis membrane (RO membrane) system when entering it. In order to protect the normal operation of the RO membrane system, it is necessary to configure online instruments to monitor the water quality entering the RO membrane system, and add reducing agents such as sodium sulfite to neutralize the strong oxidants, resulting in increased reagent consumption, which in turn results in higher wastewater reuse costs. Summary of the invention

[0003] The technical problem solved by the present invention is that in the double-membrane wastewater reuse process, in order to prevent the strong oxidant remaining in the front-end pretreatment process from damaging the RO membrane, it is necessary to increase the investment in special equipment and reagents to neutralize the strong oxidant, which in turn causes a high cost for wastewater reuse.

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0005] A method for preparing a catalytic ultrafiltration membrane, comprising:

[0006] Step S1, drying and melt-extruding the polymer slice A to obtain a melt A; mixing the polymer slice B with catalyst particles, drying and melt-extruding the mixture to obtain a melt B; the catalyst particles include metal oxide particles having a strong oxidant catalytic decomposition effect;

[0007] Step S2, spinning the melt A and the melt B as raw materials to obtain a core-skin composite catalytic fiber; the core layer of the composite catalytic fiber is formed by the melt A, and the skin layer of the composite catalytic fiber is formed by the melt B;

[0008] Step S3, using the composite catalytic fiber to obtain a hollow fiber tube by weaving or knitting;

[0009] Step S4, preparing a casting liquid, and using the casting liquid to form a separation precision layer on the outer wall of the hollow fiber tube to obtain a catalytic ultrafiltration membrane; the separation precision layer is used to filter macromolecular organic matter.

[0010] Preferably, in step S1, the catalyst particles include at least one of manganese dioxide particles, iron oxide particles and copper oxide particles.

[0011] Preferably, in the step S1, the particle size of the catalyst particles is 0.1-50 μm.

[0012] Preferably, in step S1, the polymer slice A and the polymer slice B are both made of one or more of polyamide, polyester, polyolefin, polyvinyl alcohol and polyurethane.

[0013] Preferably, in the step S2, spinning is carried out using the melt A and the melt B as raw materials to obtain a sheath-core type composite catalytic fiber, including: the melt A and the melt B are respectively fed into a composite spinning machine through metering pumps, sprayed out through a spinneret to form a filament bundle, and then subjected to air cooling, oiling, heat drawing and winding to obtain the composite catalytic fiber.

[0014] Preferably, in the step S1, the mass ratio of the polymer slice B to the catalyst particles is (60-99):(1-40).

[0015] Preferably, in step S2, the mass ratio of melt A to melt B is (30-70): (30-70).

[0016] Preferably, in step S4, the casting solution is prepared by a first polymer, an additive and an organic solvent in a mass ratio of (15-20): (15-20): (60-70), the first polymer is selected from polyvinylidene fluoride, polyether sulfone, polysulfone and polyvinyl chloride, the additive includes at least one of polyvinyl pyrrolidone, polyethylene glycol and a surfactant, and the organic solvent includes at least one of N,N-dimethylacetamide and N-methylpyrrolidone; the viscosity of the casting solution at 70°C is 5000-20000 mPa·s.

[0017] Preferably, in step S4, the use of the casting liquid to form a separation precision layer on the outer wall of the hollow fiber tube to obtain a catalytic ultrafiltration membrane includes: uniformly coating the casting liquid on the outer wall of the hollow fiber tube, gelling, washing and drying to form the separation precision layer on the outer wall of the hollow fiber tube, thereby obtaining the catalytic ultrafiltration membrane.

[0018] The present invention also provides a catalytic ultrafiltration membrane, which is prepared by the above-mentioned preparation method of the catalytic ultrafiltration membrane.

[0019] Compared with the prior art, the ultrafiltration membrane prepared by the method of the present invention is composed of a hollow fiber tube and a separation precision layer, wherein the hollow fiber tube is made of a skin-core composite catalytic fiber, and the skin layer of the composite catalytic fiber contains catalyst particles with oxidant catalytic decomposition effect; when the ultrafiltration membrane is applied to the double membrane method wastewater reuse process, the separation precision layer can be used to filter out macromolecular organic matter, and the catalyst particles with oxidant catalytic decomposition effect loaded in the hollow fiber tube can catalytically decompose the strong oxidant in the effluent water on the clear liquid side of the ultrafiltration membrane, and have no effect on the antibacterial effect of the residual oxidant on the concentrated liquid side of the ultrafiltration membrane, which can avoid the strong oxidant residual in the front-end pretreatment process from damaging the RO membrane, without changing the original process design, adding equipment and reagent input. In addition, in the present invention, the catalyst particles are loaded in the composite fiber during the manufacturing process of the composite catalytic fiber through the spinning process, and the process is simpler and more reliable, and no additional auxiliary reagents are required. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Schematic diagram of the process of preparing the catalytic ultrafiltration membrane in an embodiment of the present invention;

[0021] Figure 2 This is a comparison chart of the treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 on an aqueous solution containing an ozone concentration of 5 mg / L;

[0022] Figure 3 This is a comparison chart of the treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 on an aqueous solution containing an ozone concentration of 2 mg / L;

[0023] Figure 4 The figure is a comparison of the treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 on an aqueous solution containing 10 mg / L hydrogen peroxide. DETAILED DESCRIPTION

[0024] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0025] It should be noted that, in the absence of conflict, the features in the embodiments of the present invention can be combined with each other. The meanings of the terms "comprising", "including", "containing", and "having" are non-restrictive, that is, other steps and other ingredients that do not affect the results can be added. The above terms cover the terms "consisting of" and "essentially consisting of". Unless otherwise specified, materials, equipment, and reagents are all commercially available. It should be noted that the polymer chips in the present invention generally refer to polymer raw materials obtained by polymerization production, which are generally processed into flaky particles.

[0026] like Figure 1 As shown, an embodiment of the present invention provides a method for preparing a catalytic ultrafiltration membrane, comprising:

[0027] Step S1, drying and melt-extruding the polymer slice A to obtain a melt A; mixing the polymer slice B with catalyst particles, drying and melt-extruding the mixture to obtain a melt B; the catalyst particles include metal oxide particles having a strong oxidant catalytic decomposition effect;

[0028] Step S2, spinning the melt A and the melt B as raw materials to obtain a core-skin composite catalytic fiber; the core layer of the composite catalytic fiber is formed by the melt A, and the skin layer of the composite catalytic fiber is formed by the melt B;

[0029] Step S3, using the composite catalytic fiber to obtain a hollow fiber tube by weaving or knitting;

[0030] Step S4, preparing a casting liquid, and using the casting liquid to form a separation precision layer on the outer wall of the hollow fiber tube to obtain a catalytic ultrafiltration membrane; the separation precision layer is used to filter macromolecular organic matter.

[0031] Compared with the prior art, the ultrafiltration membrane prepared by the method of this embodiment is composed of a hollow fiber tube and a separation precision layer, wherein the hollow fiber tube is made of a skin-core composite catalytic fiber, and the skin layer of the composite catalytic fiber contains catalyst particles with oxidant catalytic decomposition effect; when the ultrafiltration membrane is applied to the double membrane wastewater reuse process, the separation precision layer can be used to filter out macromolecular organic matter, and the catalyst particles with oxidant catalytic decomposition effect loaded in the hollow fiber tube can catalytically decompose the strong oxidant in the effluent water on the clear liquid side of the ultrafiltration membrane, and have no effect on the antibacterial effect of the residual oxidant on the concentrated liquid side of the ultrafiltration membrane, which can avoid the strong oxidant residual in the front-end pretreatment process from damaging the RO membrane, without changing the original process design, adding equipment and reagent input. In addition, in this embodiment, the catalyst particles are loaded in the composite fiber during the manufacturing process of the composite catalytic fiber through the spinning process, and the process is simpler and more reliable, and no additional auxiliary reagents are required.

[0032] In some embodiments of the present invention, in step S1, the catalyst particles include at least one of manganese dioxide particles, iron oxide particles and copper oxide particles.

[0033] Illustratively, in some embodiments of the present invention, the method for preparing the catalyst particles comprises:

[0034] preparing a metal salt solution, wherein the metal salt solution contains at least one of iron, manganese and copper;

[0035] Adding ammonia water dropwise to the metal salt solution, adjusting the pH value of the system to 7-12, and filtering to obtain a metal hydroxide precipitate;

[0036] The metal hydroxide precipitate is washed, dried and calcined to obtain metal oxide particles;

[0037] The metal oxide particles are crushed by a jet mill, and then classified by a precision jet classifier to obtain catalyst particles with a specific particle size.

[0038] In some embodiments of the present invention, in the step S1, the particle size of the catalyst particles is 0.1-50 μm; preferably, the particle size of the catalyst particles is 0.1-5 μm. Small-sized catalyst particles with uniform particle size distribution can not only enhance the surface catalytic activity of the composite catalytic fiber, but also are easy to process and will not clog the spinneret during melt spinning. If the particle size of the catalyst particles is too large, the catalyst particles are easy to peel off during use, and due to the limitations of the spinning process, the addition ratio of the catalyst particles is not high. If the particle size of the catalyst particles is larger, the addition ratio is lower, and the catalytic active sites in contact with the feed liquid during use are fewer, and a longer contact reaction time is required to completely catalytically decompose the oxidant. If the particle size of the catalyst particles is too small, the catalyst particles are easily wrapped inside the cortex, and the catalyst particles cannot contact the feed liquid and cannot play a role in catalytically decomposing the oxidant.

[0039] In some embodiments of the present invention, in step S3, the outer diameter of the hollow braided tube is 1.0-3.0 mm, and the inner diameter is 0.5-2.5 mm.

[0040] In some embodiments of the present invention, in step S1, the polymer slice A and the polymer slice B are both made of one or more of polyamide, polyester, polyolefin, polyvinyl alcohol and polyurethane.

[0041] In some embodiments of the present invention, in step S2, spinning is performed using the melt A and the melt B as raw materials to obtain a sheath-core type composite catalytic fiber, including: the melt A and the melt B are respectively introduced into a composite spinning machine through a metering pump, sprayed out through a spinneret to form a filament bundle, and then subjected to air cooling, oiling, heat drawing and winding to obtain the composite catalytic fiber.

[0042] In some embodiments of the present invention, in step S1, the mass ratio of the polymer slice B to the catalyst particles is (60-99): (1-40).

[0043] In some embodiments of the present invention, in step S2, the mass ratio of melt A to melt B is (30-70): (30-70); preferably, the mass ratio of melt A to melt B is (45-50): (45-55). In step S2, if the mass ratio of melt A to melt B is too large, the cortex of the composite catalytic fiber will become thinner, the amount of loaded catalyst will be reduced, and the catalytic decomposition effect of the oxidant will be reduced. In addition, if the cortex of the composite catalytic fiber is too thin, the core-skin composite catalytic fiber will easily slip and peel under the action of external force, affecting the normal use of the ultrafiltration membrane; if the mass ratio of melt A to melt B is too small, the strength of the single filament of the composite catalytic fiber will decrease, the filament will be easily broken during processing, and the processing difficulty will increase.

[0044] In some embodiments of the present invention, in step S4, the casting solution is prepared by a first polymer, an additive and an organic solvent in a mass ratio of (15-20): (15-20): (60-70), the first polymer is selected from polyvinylidene fluoride, polyethersulfone, polysulfone and polyvinyl chloride, the additive includes at least one of polyvinyl pyrrolidone, polyethylene glycol and a surfactant, and the organic solvent includes at least one of N,N-dimethylacetamide and N-methylpyrrolidone; the viscosity of the casting solution at 70°C is 5000-20000mPa·s. If the viscosity of the casting solution is too high, the fluidity will be poor, and it will be difficult to immerse in the hollow fiber tube to form an effective adhesion strength; if the viscosity of the casting solution is too low, the separation precision layer formed will have poor strength, and it will be more easily damaged by impact and friction during production and use.

[0045] In some embodiments of the present invention, in step S4, the ultrafiltration membrane is obtained by using the casting liquid to form a separation precision layer on the outer wall of the hollow fiber tube, including: uniformly coating the casting liquid on the outer wall of the hollow fiber tube, gelling, washing and drying to form the separation precision layer on the outer wall of the hollow fiber tube, thereby obtaining the ultrafiltration membrane.

[0046] The embodiment of the present invention further provides a catalytic ultrafiltration membrane, which is prepared by the preparation method of the catalytic ultrafiltration membrane as described above.

[0047] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0048] Example 1

[0049] A1. Preparation of catalyst particles:

[0050] preparing a metal salt solution, wherein the metal salt solution contains hexadecyltrimethylammonium bromide, ferrous sulfate and manganese sulfate, wherein the molar ratio of ferrous sulfate to manganese sulfate is 1:1;

[0051] Adding ammonia water dropwise to the metal salt solution, adjusting the pH value of the system to 12, and filtering to obtain a metal hydroxide precipitate;

[0052] The metal hydroxide precipitate is washed with alcohol, washed with ultrasonic water, vacuum dried, and calcined to obtain metal oxide particles; wherein the calcination temperature is 550° C. and the time is 2 hours;

[0053] The metal oxide particles are crushed by a jet mill and then classified by a precision jet classifier to obtain catalyst particles; the particle size distribution range of the catalyst particles is 0.5-3 μm.

[0054] A2. After drying the polymer slice A, melt-extrude it at a screw extruder temperature of 280-294° C. to obtain melt A; after mixing the polymer slice B with the catalyst particles in a mass ratio of 99:1, dry it, and melt-extrude it at a screw extruder temperature of 280-294° C. to obtain melt B; wherein the materials of polymer slice A and polymer slice B are both PET.

[0055] A3. The melt A and the melt B are respectively introduced into a two-component composite melt spinning machine through a melt gear metering pump in a mass ratio of 1:1, and a thin stream of the melt is ejected through a porous composite spinneret. The melt is quickly condensed and solidified by air cooling to form a tow fiber, and then the composite catalytic fiber is obtained by oiling, hot drawing and winding. The core layer of the composite catalytic fiber is formed by the melt A, and the skin layer of the composite catalytic fiber is formed by the melt B; wherein the spinning process conditions are: spinning assembly temperature 291°C, spinneret aperture 0.32mm, spinning speed 600m / min; the process conditions of hot drawing are: hot roller temperature 80°C, hot plate temperature 160°C, traction multiple 3.5 times, and drawing speed 800m / min.

[0056] A4. The composite catalytic fiber is used to obtain a hollow fiber tube by weaving; the outer diameter of the hollow fiber tube is 3 mm and the inner diameter is 2 mm.

[0057] A5. Mix polyvinylidene fluoride, polyvinyl pyrrolidone K30, polyethylene glycol 400 and N,N-dimethylacetamide at a mass ratio of 15:6:9:70 at 80° C. to obtain a casting solution; wherein the casting solution has a viscosity of 6000 mPa·s at 70° C., and the molecular weight of polyvinylidene fluoride is 240000.

[0058] A6. Pass the hollow fiber tube vertically through a spinneret, inject the casting liquid into the spinneret, and evenly coat the casting liquid on the outer wall of the hollow fiber tube. After gelation, water washing and air-drying, the separation precision layer is formed on the outer wall of the hollow fiber tube, thereby obtaining the ultrafiltration membrane.

[0059] Comparative Example 1

[0060] The difference from Example 1 is that in step A2, melt B is made of polymer chips B, and melt B does not contain catalyst particles.

[0061] Experimental example

[0062] The ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were used to treat an aqueous solution containing an ozone concentration of 5 mg / L. The treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were compared. Figure 2 As shown, Figure 2 The figure shows the change of ozone concentration in the aqueous solution with the treatment time during the treatment of the aqueous solution (ozone concentration is 5 mg / L) by the ultrafiltration membrane prepared in Example 1 and Comparative Example 1. Figure 2 It can be seen that the ultrafiltration membrane prepared in Comparative Example 1 has no obvious effect on removing ozone in aqueous solution, while the ultrafiltration membrane prepared in Example 1 has obvious effect on removing ozone in aqueous solution, which can make the ozone concentration in the aqueous solution less than 0.5 mg / L, and the ozone removal rate is greater than 90%. It should be noted that Figure 2 The horizontal axis time represents the treatment time, and the vertical axis ozone concentration represents the concentration of dissolved ozone in the aqueous solution.

[0063] The ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were used to treat an aqueous solution containing an ozone concentration of 2 mg / L. The treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were compared. Figure 3 As shown, Figure 3 The figure shows the change of ozone concentration in the aqueous solution with the treatment time during the treatment of the aqueous solution (ozone concentration is 2 mg / L) by the ultrafiltration membrane prepared in Example 1 and Comparative Example 1. Figure 3 It can be seen that the ultrafiltration membrane prepared in Comparative Example 1 has no obvious effect on removing ozone in aqueous solution, while the ultrafiltration membrane prepared in Example 1 has obvious effect on removing ozone in aqueous solution, which can make the ozone concentration in the aqueous solution less than 0.3 mg / L, and the ozone removal rate is greater than 86%. It should be noted that Figure 3 The horizontal axis time represents the treatment time, and the vertical axis ozone concentration represents the concentration of dissolved ozone in the aqueous solution.

[0064] The ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were used to treat an aqueous solution containing 10 mg / L of hydrogen peroxide. The treatment effects of the ultrafiltration membranes prepared in Example 1 and Comparative Example 1 were compared. Figure 4 As shown, Figure 4 The figure shows the change of the concentration of hydrogen peroxide in the aqueous solution with the treatment time during the treatment of the aqueous solution (hydrogen peroxide concentration is 10 mg / L) by the ultrafiltration membrane prepared in Example 1 and Comparative Example 1. Figure 4 It can be seen that the ultrafiltration membrane prepared in Comparative Example 1 has no obvious removal effect on hydrogen peroxide in aqueous solution, while the ultrafiltration membrane prepared in Example 1 has obvious removal effect on hydrogen peroxide in aqueous solution, which can make the concentration of hydrogen peroxide in aqueous solution less than 0.5 mg / L, and the hydrogen peroxide removal rate is greater than 95%. It should be noted that Figure 3 The horizontal axis time represents the treatment time, and the vertical axis hydrogen peroxide concentration represents the hydrogen peroxide concentration in the aqueous solution.

[0065] In addition, it should be noted that, although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A method for preparing a catalytic ultrafiltration membrane, characterized in that: include: Step S1, drying and melt-extruding the polymer slice A to obtain a melt A; The polymer slice B is mixed with catalyst particles, dried, and melt-extruded to obtain a melt B; the catalyst particles include metal oxide particles having a strong oxidant catalytic decomposition effect; wherein the polymer slice A and the polymer slice B are both made of one or more of polyamide, polyester, polyolefin, polyvinyl alcohol and polyurethane; Step S2, spinning the melt A and the melt B as raw materials to obtain a core-skin composite catalytic fiber; the core layer of the composite catalytic fiber is formed by the melt A, and the skin layer of the composite catalytic fiber is formed by the melt B; Step S3, using the composite catalytic fiber to obtain a hollow fiber tube by weaving or knitting; Step S4, preparing a casting liquid, and using the casting liquid to form a separation accuracy layer on the outer wall of the hollow fiber tube to obtain a catalytic ultrafiltration membrane; the separation accuracy layer is used to filter macromolecular organic matter; wherein the casting liquid is prepared by a first polymer, an additive and an organic solvent in a mass ratio of (15-20): (15-20): (60-70), the first polymer is selected from polyvinylidene fluoride, polyether sulfone, polysulfone and polyvinyl chloride, the additive includes at least one of polyvinyl pyrrolidone, polyethylene glycol and a surfactant, and the organic solvent includes at least one of N,N-dimethylacetamide and N-methylpyrrolidone; the viscosity of the casting liquid at 70°C is 5000-20000 mPa·s.

2. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S1, the catalyst particles include at least one of manganese dioxide particles, iron oxide particles and copper oxide particles.

3. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S1, the particle size of the catalyst particles is 0.1-50 μm.

4. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S2, spinning is performed using the melt A and the melt B as raw materials to obtain a sheath-core type composite catalytic fiber, including: the melt A and the melt B are respectively fed into a composite spinning machine through metering pumps, sprayed out through a spinneret to form a filament bundle, and then subjected to air cooling, oiling, heat drawing and winding to obtain the composite catalytic fiber.

5. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S1, the mass ratio of the polymer slice B to the catalyst particles is (60-99):(1-40).

6. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S2, the mass ratio of the melt A to the melt B is (30-70): (30-70).

7. The method for preparing a catalytic ultrafiltration membrane according to claim 1, characterized in that: In the step S4, the separation precision layer is formed on the outer wall of the hollow fiber tube by using the casting liquid to obtain a catalytic ultrafiltration membrane, including: uniformly coating the casting liquid on the outer wall of the hollow fiber tube, gelling, washing and drying to form the separation precision layer on the outer wall of the hollow fiber tube, thereby obtaining the catalytic ultrafiltration membrane.

8. A catalytic ultrafiltration membrane, characterized in that: The catalytic ultrafiltration membrane is prepared by the preparation method of the catalytic ultrafiltration membrane according to any one of claims 1 to 7.

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