Aeration membrane and preparation method thereof and wastewater ozone catalytic oxidation treatment system

Abstract

The present invention belongs to the field of wastewater treatment technology, specifically an aeration membrane and its preparation method and a wastewater ozone catalytic oxidation treatment system. The aeration membrane is a modified ceramic membrane with a surface-loaded UiO-66(Zr)-NH2 material, which has photoelectron energy storage and release and ozone catalysis functions. The wastewater ozone catalytic oxidation treatment system realizes the generation of ozone microbubbles through the aeration membrane, and realizes ozone catalysis and free radical generation during the wastewater treatment process, thereby improving the oxidative degradation efficiency of pollutants in the wastewater. Compared with the bubble particle size produced by traditional membrane aeration, the present invention constructs a plant photosynthesis bionic system by modifying the ceramic membrane, realizing the functions of electron energy storage under visible light conditions and continuous release of electrons under dark conditions, so that the pollutants in the wastewater can be degraded by light and dark cycles, and finally realizing efficient degradation of pollutants in the wastewater.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment, and in particular relates to an aeration membrane and a preparation method thereof, and a wastewater ozone catalytic oxidation treatment system. Background Art

[0002] Wastewater has complex components and often contains a large number of difficult-to-degrade pollutants. Traditional biochemical treatment methods are difficult to effectively remove pollutants. If it is directly discharged without meeting the standards, it will pollute the receiving water body and even endanger the ecological environment and human health. This seriously hinders the protection of the ecological environment and the realization of the goal of "zero discharge" of wastewater.

[0003] As an advanced oxidation technology, ozone can mineralize organic matter in wastewater into non-toxic small molecules CO2 and H2O. Compared with other advanced oxidation technologies, ozone has the advantages of low cost, simple operation, and no by-products, and is widely used in the pretreatment and deep treatment of wastewater. In actual application, ozone has problems such as low mass transfer efficiency and short residence time, resulting in low ozone utilization efficiency and increased costs. At present, microbubble technology is widely used to improve the mass transfer efficiency of ozone, but the pressurized dissolved gas method has high requirements for the particulate matter in the wastewater, and the bubble size produced by conventional jet aeration and membrane separation is often large. In addition, the oxidation efficiency of ozone alone is low, and it is difficult to achieve deep mineralization of organic matter. The conventional heterogeneous catalyst addition method is often limited by the diffusion and distribution of ozone and pollutants, and the free radical yield and utilization rate are low. Therefore, how to achieve efficient utilization and catalysis of ozone in wastewater treatment is the key to the removal of difficult-to-degrade organic matter. Summary of the invention

[0004] In order to make up for the deficiencies of the prior art and solve at least one technical problem raised in the background technology, the present invention provides an air membrane and a preparation method thereof and a wastewater ozone catalytic oxidation treatment system.

[0005] The technical solution adopted by the present invention to solve the technical problem is: the aeration membrane described in the present invention is a modified ceramic membrane with UiO-66(Zr)-NH2 material loaded on the surface.

[0006] The method for preparing the aeration membrane of the present invention comprises the following steps:

[0007] Step 1, ZrCl4 powder and 2-aminoterephthalic acid solution are mixed and then added into N,N-dimethylformamide solution to fully dissolve to obtain a first clarified liquid, and then formic acid solution is added into the first clarified liquid to obtain solution I;

[0008] Step 2, completely immersing the annular ceramic membrane in the solution I and heating it at a temperature of 120 to 150° C. for 24 hours;

[0009] Step 3, taking a certain amount of ZrCl4 powder and 2-aminoterephthalic acid solution, mixing the ZrCl4 powder and the 2-aminoterephthalic acid solution, adding them to the methanol solution, and obtaining a second clarified liquid after fully dissolving them, and then adding the formic acid solution to the second clarified liquid to obtain solution II;

[0010] Step 4, completely immersing the annular ceramic membrane treated in step 2 into the solution II, and heating it at a temperature of 120 to 150° C. for 72 hours;

[0011] Step 5, after the reaction is completed, the annular ceramic membrane treated in step 4 is taken out, and vacuum dried to obtain the aeration membrane.

[0012] Preferably, in step 1, the molar ratio of ZrCl4, 2-aminoterephthalic acid, and N,N-dimethylformamide is 1:2:300;

[0013] The volume ratio of the formic acid solution to the N,N-dimethylformamide solution is 10:1 to 2:1.

[0014] Preferably, in step 3, the molar ratio of ZrCl4, 2-aminoterephthalic acid, and methanol is 1:2:300;

[0015] The volume ratio of the formic acid solution to the methanol solution is 10:1 to 2:1.

[0016] Preferably, in step 5, the vacuum drying temperature is 60-80°C.

[0017] The wastewater ozone catalytic oxidation treatment system of the present invention comprises a reactor body and an aeration module;

[0018] The reactor body comprises a reactor frame, a water inlet and a water outlet respectively arranged on both sides above the reactor frame, an overflow port arranged on the top of the reactor frame and a drain port arranged below the reactor frame;

[0019] The aeration module includes an ozone generator, a hollow threaded tube and an aeration membrane, the air outlet of the ozone generator is connected to an air supply pipe, one end of the air supply pipe extends into the reactor frame; the hollow threaded tube is arranged in the reactor frame, one end of the hollow threaded tube is connected to a motor, and the other end is connected to the ozone generator through a rotating air pipe joint and the air supply pipe in sequence, the motor is configured to drive the hollow spiral tube to rotate to pre-cut the ozone, and a plurality of air vents are arranged on the side wall of the hollow threaded tube; the aeration membrane is the aeration membrane according to claim 1, the aeration membrane is arranged on the hollow threaded tube, the aeration membrane is connected to the air vents to receive the pre-cut ozone, and the aeration membrane is used to perform secondary cutting on the pre-cut ozone to form microbubbles and catalyze the microbubbles.

[0020] Preferably, a spiral mixer is also provided in the hollow threaded tube.

[0021] Preferably, the diameter of the aeration membrane is 15 to 20 cm;

[0022] The aeration membranes include a plurality of aeration membranes, and the distance between two adjacent aeration membranes is 5 to 20 cm.

[0023] Preferably, the reactor body is also connected to a detection and control module;

[0024] The detection and control module includes an ozone concentration detector and a data analysis and control module connected to the ozone concentration detector. The ozone concentration detector includes an ozone gas phase concentration sensor and an ozone liquid phase concentration sensor. The ozone gas phase concentration sensor is arranged at the overflow port, and the ozone liquid phase concentration sensor extends into the reactor frame. The ozone concentration detector is used to record the data monitored by the ozone gas phase concentration sensor and the ozone liquid phase concentration sensor, and transmit the data to the data analysis and control module. The data analysis and control module is connected to the ozone generator and the motor.

[0025] Preferably, the detection and control module further includes an ozone destroyer, and the ozone destroyer is connected to the overflow port.

[0026] The beneficial effects of the present invention are as follows:

[0027] 1. The present invention provides an aeration membrane, which is a modified ceramic membrane with UiO-66(Zr)-NH2 material loaded on the surface, and has photoelectron energy storage and release and ozone catalysis functions. The aeration membrane is applied to a wastewater ozone catalytic oxidation treatment system to generate ozone microbubbles. In the wastewater treatment process, ozone catalysis and free radical generation can be achieved, effectively improving the oxidation and degradation efficiency of pollutants in the wastewater.

[0028] 2. The present invention provides a method for preparing an aeration membrane with a surface-loaded UiO-66(Zr)-NH2 material. The pore size of the membrane can be further reduced by modifying the ceramic membrane. At the same time, the aeration membrane also has the functions of photoelectron energy storage and release and ozone catalysis. When ozone molecules diffuse to the UiO-66(Zr)-NH2 material through interface transport, due to the enriched adsorption sites and extremely high porosity of UiO-66(Zr)-NH2, it can show a high adsorption rate for ozone, which is beneficial to the zirconium oxide in the UiO-66(Zr)-NH2 material to catalyze ozone to form free radicals such as hydroxyl and superoxide, and efficiently remove organic matter. As the treatment proceeds, the turbidity and chromaticity of the wastewater decrease, which can improve the visible light utilization of UiO-66(Zr)-NH2 on the membrane surface, realize the degradation of pollutants and electronic energy storage, and the stored electrons can continue to be released under the dark light conditions formed by the next round of high turbidity and high chromaticity wastewater to degrade organic matter.

[0029] 3. The present invention realizes efficient mass transfer utilization and catalysis of ozone microbubbles through the combination of an aeration membrane with a surface-loaded UiO-66(Zr)-NH2 material and ozone. During the treatment process, a hollow threaded tube is used to drive the aeration membrane to rotate, thereby further cutting the bubbles and reducing the bubble size. At the same time, the momentum of the microbubbles of ozone generated by rotation can increase the diffusion range of ozone, promote the mixing of organic matter in wastewater, prevent membrane surface pollution, and improve mass transfer efficiency.

[0030] 4. The present invention sets a spiral mixer inside the hollow threaded tube, which can further cut the bubbles, reduce the bubble size, further increase the diffusion range of ozone, promote the mixing of organic matter in wastewater, prevent contamination of the membrane surface, and improve mass transfer efficiency.

[0031] 5. The present invention constructs a plant photosynthesis bionic system by modifying the ceramic membrane, realizing the functions of electron energy storage under visible light conditions and continuous electron release under dark conditions, thereby enabling light-dark cycle degradation of pollutants in wastewater. Even under the condition of depletion of stored electrons, the zirconium oxide in the aeration membrane of the surface-loaded UiO-66(Zr)-NH2 material will combine with the ozone microbubbles generated on the membrane surface, thereby catalyzing ozone to generate free radicals such as hydroxyl and superoxide, thereby achieving efficient degradation of pollutants in wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present invention will be further described below in conjunction with the accompanying drawings.

[0033] Figure 1 It is a structural diagram of the wastewater ozone catalytic oxidation treatment system.

[0034] Figure 2This is a graph showing the degradation performance of tetracycline hydrochloride by aeration membrane with UiO-66(Zr)-NH2 material loaded on the surface and unmodified annular ceramic membrane under light conditions and dark conditions.

[0035] Figure 3 It is a graph showing the change in TOC concentration after the biogas slurry is treated for 3 hours in Example 2 and Comparative Example 1.

[0036] Figure 4 This is a graph showing the change in turbidity after the biogas slurry is treated for 3 hours in Example 2 and Comparative Example 1.

[0037] In the figure: 1. Motor; 2. Ozone generator; 3. Data analysis and control module; 4. Water inlet; 5. Ozone destroyer; 6. Overflow port; 7. Ozone gas phase concentration sensor; 8. Ozone concentration detector; 9. Reactor frame; 10. Water outlet; 11. Ozone liquid phase concentration sensor; 12. Hollow threaded pipe; 13. Rotating air pipe joint; 14. Aeration membrane; 15. Drain port. DETAILED DESCRIPTION

[0038] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.

[0039] The present invention first provides an aeration membrane, wherein the aeration membrane 14 is a modified ceramic membrane with a surface-loaded UiO-66(Zr)-NH2 material, and has photoelectron energy storage and release and ozone catalysis functions. The aeration membrane 14 is applied to a wastewater ozone catalytic oxidation treatment system to generate ozone microbubbles, and in the wastewater treatment process, ozone catalysis and free radical generation can be achieved, effectively improving the oxidation and degradation efficiency of pollutants in the wastewater.

[0040] The present invention also provides a method for preparing an aeration membrane, comprising the following steps: step 1, mixing ZrCl4 powder and 2-aminoterephthalic acid solution, adding the mixture to N,N-dimethylformamide solution, fully dissolving to obtain a first clarified liquid, and then adding a formic acid solution to the first clarified liquid to obtain a solution I; step 2, completely immersing the annular ceramic membrane in solution I, and heating it at a temperature of 120 to 150° C. for 24 hours; step 3, taking another certain amount of ZrCl4 powder and 2-aminoterephthalic acid solution, mixing the ZrCl4 powder and the 2-aminoterephthalic acid solution, adding the mixture to a methanol solution, and fully dissolving to obtain a second clarified liquid, and then adding the formic acid solution to the second clarified liquid to obtain a solution II; step 4, completely immersing the annular ceramic membrane treated in step 2 in solution II, and heating it at a temperature of 120 to 150° C. for 72 hours; step 5, after the reaction is completed, taking out the annular ceramic membrane treated in step 4, and vacuum drying it to obtain an aeration membrane 14. In this embodiment, formic acid is added as a regulator, and the membrane pore size can be further reduced by modifying the ceramic membrane. At the same time, the aeration membrane 14 also has the functions of photoelectron energy storage and release and ozone catalysis. When ozone molecules diffuse to the UiO-66 (Zr) -NH2 material through interface transport, due to the enriched adsorption sites and extremely high porosity of UiO-66 (Zr) -NH2, it can show a high adsorption rate for ozone, which is beneficial to the zirconium oxide in the UiO-66 (Zr) -NH2 material to catalyze ozone to form free radicals such as hydroxyl and superoxide, and efficiently remove organic matter. As the treatment proceeds, the turbidity and chromaticity of the wastewater decrease, which can improve the visible light utilization of UiO-66 (Zr) -NH2 on the membrane surface, realize the degradation of pollutants and electronic energy storage, and the stored electrons can continue to be released under the dark light conditions formed by the next round of high turbidity and high chromaticity wastewater to degrade organic matter.

[0041] More specifically, in step 1, the molar ratio of ZrCl4, 2-aminoterephthalic acid, and N,N-dimethylformamide is 1:2:300; the volume ratio of formic acid solution to N,N-dimethylformamide solution is 10:1 to 2:1. In step 3, the molar ratio of ZrCl4, 2-aminoterephthalic acid, and methanol is 1:2:300; the volume ratio of formic acid solution to methanol solution is 10:1 to 2:1. In step 5, the vacuum drying temperature is 60 to 80°C.

[0042] The present invention also provides a wastewater ozone catalytic oxidation treatment system, which includes a reactor body and an aeration module; the reactor body includes a reactor frame 9, a water inlet 4 and a water outlet 10 respectively arranged on both sides above the reactor frame 9, an overflow port 6 arranged at the top of the reactor frame 9 and a drain port 15 arranged below the reactor frame 9; the aeration module includes an ozone generator 2, a hollow threaded pipe 12 and an aeration membrane 14, the air outlet of the ozone generator 2 is connected to an air supply pipe, one end of the air supply pipe extends into the reactor frame 9; the hollow threaded pipe 12 is arranged at the reactor In the frame 9, one end of the hollow threaded tube 12 is connected to the motor 1, and the other end is connected to the ozone generator 2 through the rotating air pipe joint 13 and the air supply pipe in turn. The motor 1 is configured to drive the hollow spiral tube to rotate to pre-cut the ozone, and a plurality of vents are arranged on the side wall of the hollow threaded tube 12; the aeration membrane 14 is the above-mentioned aeration membrane 14, and the aeration membrane 14 is arranged on the hollow threaded tube 12, and the aeration membrane 14 is connected to the vent to receive the pre-cut ozone, and the aeration membrane 14 is used to perform secondary cutting of the pre-cut ozone to form microbubbles, and catalyze the microbubbles. The present invention realizes efficient mass transfer utilization and catalysis of ozone microbubbles through the combination of the aeration membrane 14 and ozone with surface-loaded modified UiO-66(Zr)-NH2 material. During the treatment process, the hollow threaded tube 12 is used to drive the aeration membrane 14 to rotate, so as to further cut the bubbles and reduce the bubble size. At the same time, the momentum of the microbubbles of ozone generated by rotation can increase the diffusion range of ozone, promote the mixing of organic matter in the wastewater, prevent contamination of the membrane surface, and improve the mass transfer efficiency.

[0043] As an embodiment of the present invention, a spiral mixer is also provided in the hollow threaded tube 12. By providing the spiral mixer inside the hollow threaded tube 12, the bubbles can be further cut, the bubble size can be reduced, the diffusion range of ozone can be further increased, the mixing of organic matter in the wastewater can be promoted, the membrane surface can be prevented from being contaminated, and the mass transfer efficiency can be improved. It is worth noting that the spiral mixer can be customized according to different working conditions and the optimization of aeration can be achieved through 3D printing technology according to simulation.

[0044] As an embodiment of the present invention, the diameter of the aeration membrane 14 is 15 to 20 cm; the aeration membrane 14 includes a plurality of aeration membranes, and the interval between two adjacent aeration membranes 14 is 5 to 20 cm.

[0045] As an embodiment of the present invention, the reactor body is also connected to a detection and control module; the detection and control module includes an ozone concentration detector 8 and a data analysis and control module 3 connected to the ozone concentration detector 8, the ozone concentration detector 8 includes an ozone gas phase concentration sensor 7 and an ozone liquid phase concentration sensor 11, the ozone gas phase concentration sensor 7 is arranged at the overflow port 6, the ozone liquid phase concentration sensor 11 extends into the reactor frame 9, the ozone concentration detector 8 is used to record the data monitored by the ozone gas phase concentration sensor 7 and the ozone liquid phase concentration sensor 11, and transmit it to the data analysis and control module 3, the data analysis and control module 3 is connected to the ozone generator 2 and the motor 1. After receiving the real-time data from the ozone concentration detector 8, the data analysis and control module 3 can control the flow rate, concentration of ozone in the ozone generator 2 and the speed of the stepper motor 1 according to the value of the gas-liquid ozone concentration to generate ozone microbubbles of different concentrations and particle sizes.

[0046] As an embodiment of the present invention, the detection and control module further includes an ozone destroyer 5, which is connected to the overflow port 6. The ozone destroyer 5 is used to remove ozone emitted from the reactor frame 9 to prevent ozone from being discharged into the air.

[0047] To further illustrate the technical means and effects adopted by the present invention, a detailed description is given below in conjunction with specific embodiments.

[0048] Example 1

[0049] A method for preparing an aeration membrane 14 with a surface-loaded UiO-66(Zr)-NH2 material comprises the following steps:

[0050] Step 1, fully dissolving ZrCl4 and 2-aminoterephthalic acid in an N,N-dimethylformamide solution, and then adding formic acid to obtain solution I, wherein the molar ratio of ZrCl4, 2-aminoterephthalic acid, and N,N-dimethylformamide is 1:2:300, and the volume ratio of the formic acid solution to the N,N-dimethylformamide solution is 5:1;

[0051] Step 2, completely immersing the annular ceramic membrane in solution I and heating it in a hot atmosphere at 140° C. for 24 hours;

[0052] Step 3, taking a certain amount of ZrCl4 and 2-aminoterephthalic acid and fully dissolving them in N,N-dimethylformamide solution, and then adding formic acid to obtain solution II, wherein the molar ratio of ZrCl4, 2-aminoterephthalic acid, and N,N-dimethylformamide is 1:2:300, and the volume ratio of formic acid solution to N,N-dimethylformamide solution is 5:1;

[0053] Step 4, completely immersing the annular ceramic membrane treated in step 2 into solution II, and heating it in an environment at a temperature of 120 to 150° C. for 72 hours;

[0054] Step 5, taking out the annular ceramic membrane treated in step 4, and vacuum drying it at 70°C to obtain an aeration membrane 14, and obtaining an aeration membrane 14 with a surface loaded with UiO-66(Zr)-NH2 material.

[0055] Under light conditions and dark conditions, the aeration membrane 14 with UiO-66(Zr)-NH2 material on the surface and the unmodified annular ceramic membrane were placed in a 10 mg / L tetracycline hydrochloride solution, and the degradation capacity of tetracycline hydrochloride under no aeration conditions was measured. The results are shown in Figure 2 As shown in the figure, the degradation ability of the modified ceramic membrane for tetracycline hydrochloride is significantly better than that of the unmodified ceramic membrane. The modified ceramic membrane under light conditions has the best degradation effect on tetracycline hydrochloride, indicating that the loaded UiO-66(Zr)-NH2 material fully absorbs photoelectrons and is used for pollutant degradation. Under dark conditions, due to the energy storage characteristics of the loaded UiO-66(Zr)-NH2 material, electrons can still be released to promote the degradation of tetracycline hydrochloride, which is also confirmed by the results in the figure.

[0056] Example 2

[0057] The wastewater ozone catalytic oxidation treatment system of the present invention treats the biogas slurry in the anaerobic digestion tank of the pig farm. The volume of the reactor frame 9 of the system is 5L, the ozone concentration provided by the ozone generator 2 is 10mg / L, and the ventilation rate is 100mL / min.

[0058] An aeration membrane 14 with surface-loaded modified UiO-66(Zr)-NH2 material obtained by the preparation method of the above-mentioned embodiment 1 is arranged on a hollow threaded tube 12, and the hollow threaded tube 12 is fixed to a motor 1. The motor 1 is preferably a stepper motor 1, which is used to drive the hollow threaded tube 12 to rotate. A rotating air pipe joint 13 and an air supply pipe are installed at the other end of the hollow threaded tube 12. The air supply pipe is connected to an ozone generator 2. A plurality of vents are provided on the side wall of the hollow threaded tube 12 at the contact position between the hollow threaded tube 12 and the aeration membrane 14. The vents are used to allow ozone to enter the aeration membrane 14 through the hollow threaded tube 12. During the aeration process, the ceramic membrane is driven to rotate by the stepper motor 1, and microbubbles generated on the membrane surface can be further cut to generate ozone microbubbles of different particle sizes and catalyze them. The diameter of the aeration membrane 14 is 15 cm, and the number of aeration membrane sheets is 1.

[0059] Comparative Example 1

[0060] The difference between this comparative example and Example 2 is that the aeration module does not include the hollow threaded tube 12 and the aeration membrane 14, and the biogas slurry is treated by an aeration method using common aeration stones on the market.

[0061] Comparing the treatment effects of the systems in Example 2 and Comparative Example 1 on TOC and turbidity of the biogas slurry, the results are as follows: Figure 3 and Figure 4 shown.

[0062] from Figure 3 It can be seen that the wastewater ozone catalytic oxidation treatment system using the aeration membrane of the embodiment of the present invention has a better degradation effect on the TOC of the biogas slurry than the system using ordinary aeration stones. After 180 minutes of treatment, the TOC concentration dropped to 282.64 mg / L and 362.35 mg / L respectively, and the effect was improved by 28.20%. This shows that the aeration membrane fully promotes the mass transfer of ozone in the system, catalyzes the ozone oxidation reaction, and improves the treatment effect of the system.

[0063] from Figure 4 It can be seen that the wastewater ozone catalytic oxidation treatment system using the aeration membrane of the embodiment of the present invention has a better effect on the removal of turbidity of the biogas slurry than the system with ordinary aeration stones. After 180 minutes of treatment, the turbidity of the system containing the aeration membrane and the system with ordinary aeration stones dropped to 13.41 and 50.11 NTU respectively. The system containing the aeration membrane improves the degradation and removal of particulate pollutants in the biogas slurry by ozone. At the same time, the reduction in turbidity helps the load material on the membrane to absorb more photoelectrons, further promoting the catalysis of ozone and the degradation of pollutants.

[0064] The above-mentioned front, back, left, right, top and bottom are all based on the figures in the specification. Figure 1 As a benchmark, according to the person's observation perspective, the side of the device facing the observer is defined as the front, the left side of the observer is defined as the left, and so on.

[0065] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the scope of protection of the present invention.

[0066] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. An aeration membrane, characterized in that: The aeration membrane (14) is a modified ceramic membrane with a UiO-66(Zr)-NH2 material loaded on the surface; the aeration membrane (14) is used to perform secondary cutting on the pre-cut ozone to form microbubbles, and to catalyze the microbubbles.

2. A method for preparing an aeration membrane according to claim 1, characterized in that: The following steps are involved: Step 1, ZrCl4 powder and 2-aminoterephthalic acid solution are mixed and added into N,N-dimethylformamide solution to dissolve to obtain a first clarified liquid, and then formic acid solution is added into the first clarified liquid to obtain solution I; Step 2, completely immersing the annular ceramic membrane in the solution I and heating it at a temperature of 120 to 150° C. for 24 hours; Step 3, taking a certain amount of ZrCl4 powder and 2-aminoterephthalic acid solution, mixing the ZrCl4 powder and the 2-aminoterephthalic acid solution, adding them to the methanol solution, and obtaining a second clarified liquid after fully dissolving them, and then adding the formic acid solution to the second clarified liquid to obtain solution II; Step 4, completely immersing the annular ceramic membrane treated in step 2 into the solution II, and heating it at a temperature of 120 to 150° C. for 72 hours; Step 5, after the reaction is completed, the annular ceramic membrane treated in step 4 is taken out, and vacuum dried to obtain the aeration membrane (14).

3. The preparation method according to claim 2, characterized in that: In the step 1, the molar ratio of ZrCl4, 2-aminoterephthalic acid and N,N-dimethylformamide is 1:2:300; and the volume ratio of formic acid solution to N,N-dimethylformamide solution is 10:1 to 2:

1.

4. The preparation method according to claim 2, characterized in that: In step 3, the molar ratio of ZrCl4, 2-aminoterephthalic acid and methanol is 1:2:300; the volume ratio of formic acid solution to methanol solution is 10:1 to 2:

1.

5. The preparation method according to claim 2, characterized in that: In the step 5, the vacuum drying temperature is 60-80°C.

6. A wastewater ozone catalytic oxidation treatment system, characterized in that: The invention comprises a reactor body and an aeration module; the reactor body comprises a reactor frame (9), a water inlet (4) and a water outlet (10) respectively arranged on both sides above the reactor frame (9), an overflow port (6) arranged at the top of the reactor frame (9) and a drain port (15) arranged below the reactor frame (9); the aeration module comprises an ozone generator (2), a hollow threaded pipe (12) and an aeration membrane (14); the air outlet of the ozone generator (2) is connected to an air supply pipe, one end of which extends into the reactor frame (9); the hollow threaded pipe (12) is arranged in the reactor frame (9), one end of which is connected to a water supply pipe (15) and a water supply pipe (16) extending into the reactor frame (9); the hollow threaded pipe (12) is arranged in the reactor frame (9), one end of which is connected to a water supply pipe (15) and a water supply pipe (16) extending into the reactor frame (9); the water supply pipe (12) is connected to a water supply pipe (16 ... The motor (1) is connected to a motor (1), and the other end is connected to the ozone generator (2) in sequence through a rotating air pipe joint (13) and the air supply pipe. The motor (1) is configured to drive the hollow threaded tube (12) to rotate so as to pre-cut the ozone. A plurality of air vents are arranged on the side wall of the hollow threaded tube (12). The aeration membrane (14) is an aeration membrane (14) according to claim 1. The aeration membrane (14) is arranged on the hollow threaded tube (12). The aeration membrane (14) is connected to the air vents to receive the pre-cut ozone. The aeration membrane (14) is used to perform a secondary cutting on the pre-cut ozone to form microbubbles, and catalyze the microbubbles.

7. The wastewater ozone catalytic oxidation treatment system according to claim 6, characterized in that: A spiral mixer is also arranged inside the hollow threaded tube (12).

8. The wastewater ozone catalytic oxidation treatment system according to claim 6, characterized in that: The diameter of the aeration membrane (14) is 15 to 20 cm; the aeration membrane (14) comprises a plurality of aeration membranes, and the distance between two adjacent aeration membranes (14) is 5 to 20 cm.

9. The wastewater ozone catalytic oxidation treatment system according to claim 6, characterized in that: The reactor body is also connected to a detection and control module; the detection and control module comprises an ozone concentration detector (8) and a data analysis and control module (3) connected to the ozone concentration detector (8); the ozone concentration detector (8) comprises an ozone gas phase concentration sensor (7) and an ozone liquid phase concentration sensor (11); the ozone gas phase concentration sensor (7) is arranged at the overflow port (6); the ozone liquid phase concentration sensor (11) extends into the reactor frame (9); the ozone concentration detector (8) is used to record the data monitored by the ozone gas phase concentration sensor (7) and the ozone liquid phase concentration sensor (11), and transmit the data to the data analysis and control module (3); the data analysis and control module (3) is connected to the ozone generator (2) and the motor (1).

10. The wastewater ozone catalytic oxidation treatment system according to claim 6, characterized in that: The detection and control module further comprises an ozone destroyer (5), and the ozone destroyer (5) is connected to the overflow port (6).

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