Preparation method and application of Cu-Mn bimetallic catalyst
A Cu-Mn bimetallic catalyst was prepared by hydrothermal-ball milling and then used to generate Cu(III) active species by catalytic ozone oxidation. This solved the problem of insufficient removal efficiency of organic pollutants in high-salt wastewater and achieved a wastewater treatment effect with high efficiency and no secondary pollution.
Patent Information
- Application Number
- CN202511898641.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-16
- Publication Date
- 2026-02-13
AI Technical Summary
Existing heterogeneous catalytic ozone oxidation technology has limited effectiveness in removing pollutants from high-salinity wastewater, making it difficult to achieve efficient and selective removal, resulting in poor organic matter mineralization and the risk of secondary pollution.
A Cu-Mn bimetallic catalyst (CuxO/MnO2) was prepared by hydrothermal-ball milling. Cu(III) active species were generated in high-salt wastewater by catalytic ozone oxidation, thereby achieving efficient removal of organic pollutants.
It achieves efficient removal of organic pollutants from high-salinity wastewater, is easy to operate, low in cost, and produces no secondary pollution. It is suitable for treating high-salinity wastewater in industries such as coal chemical, petrochemical, pharmaceutical, and leather processing.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of water treatment technology and relates to the preparation of Cu-Mn bimetallic catalysts and their application in catalytic ozone oxidation for the removal of organic pollutants from wastewater. By directionally controlling the synthesis of Cu-Mn bimetallic catalysts with Cu(I) sites, Cu(III) active species are selectively generated in a heterogeneous catalytic ozone system, achieving efficient removal of organic pollutants from high-salinity wastewater. This invention is suitable for treating high-salinity wastewater in industries such as coal chemical, petrochemical, pharmaceutical, and leather tanning. Background Technology
[0002] High-salinity wastewater originates widely from various industrial sectors such as coal chemical, petrochemical, pharmaceutical, and leather tanning, characterized by high salt content (total dissolved solids > 1.0 wt%) and high organic matter concentration (COD can reach up to 200,000 mg / L). With global population growth, accelerated urbanization, and rapid industrialization, the discharge of high-salinity wastewater continues to rise, currently accounting for more than 5% of global wastewater volume. Conventional treatment processes for high-salinity wastewater mainly include three core steps: conventional biological treatment, alternating use of membrane separation and oxidation processes, and deep treatment through evaporation and crystallization. However, the high salt concentration in high-salinity wastewater significantly restricts the operational performance of existing oxidation treatment systems. It not only drastically inhibits the pollutant degradation efficiency of the oxidation process and reduces the purity of the final crystallized salt product, but also exacerbates membrane module fouling and clogging, shortens the lifespan of membrane materials, and ultimately leads to a significant increase in the operating costs of the entire treatment system and a substantial decline in economic benefits. Therefore, there is an urgent need to develop suitable oxidation treatment technologies to achieve efficient removal of organic matter from high-salinity wastewater.
[0003] Heterogeneous catalytic ozone oxidation combines green and high-efficiency characteristics, exhibiting excellent degradation performance on recalcitrant pollutants and showing broad application prospects in the oxidation treatment of high-salinity wastewater. Previous studies have mostly relied on heterogeneous catalysts to induce ozone decomposition and generate hydroxyl radicals (HO). • This leads to the mineralization and removal of organic pollutants. Environ. Sci. Technol .2025, 59, 29, 15547–15557.). However, in high-salt environments, HO • Easily affected by Cl – Background ion quenching significantly inhibits the removal efficiency and reaction rate of pollutants. Therefore, developing novel heterogeneous catalytic ozone oxidation technology with anti-interference properties to achieve efficient and selective removal of organic matter from high-salinity wastewater has significant scientific and practical application value in the field of water pollution control. Summary of the Invention
[0004] The application aims to overcome the defects of the prior art, provide a catalytic ozone oxidation catalyst which is easy to operate, low in cost and has reusable catalyst, realizes selective generation of Cu(III) active species, and realizes efficient removal of organic pollutants in high-salinity wastewater by using the prepared catalyst, and the method has the advantages of excellent treatment effect, scalable application, no secondary pollution and the like.
[0005] The application aims to achieve the above technical scheme by the following technical scheme. The application discloses a preparation method of a Cu-Mn bimetallic catalyst. Step 1: first, the composite material precursors CuO and MnO2 are synthesized by a hydrothermal method, 38.0-42.0 g / L Cu(NO3)2·3H2O is added to deionized water to be fully dissolved and then is moved into a reaction kettle to perform a hydrothermal reaction, after the reaction, the reaction kettle is washed with deionized water until the effluent is colorless, and the composite material precursor CuO is obtained by drying at 70-80 DEG C for 8-10 hours; 7.0-7.8 g / L MnSO4·H2O and 17.0-18.5 g / L KMnO4 are added to deionized water to be fully dissolved and then are moved into a reaction kettle to perform a hydrothermal reaction, after the reaction, the reaction kettle is washed with deionized water until the effluent is colorless, and the composite material precursor MnO2 is obtained by drying at 70-80 DEG C for 8-10 hours; Step 2: the composite material precursors CuO and MnO2 are mixed according to a mass ratio of 1:24-1:6; Step 3: the mixture obtained in step 2 is moved into a 50 mL ball mill tank, and is subjected to ball milling treatment by a planetary ball mill, the ball-to-material ratio is 20:1, the ball milling speed is 180-220 rpm, and the ball milling time is 1-3 hours; Step 4: the mixture obtained in step 3 is calcined at a high temperature of 160-180 DEG C for 2 hours to remove impurities, and the Cu-Mn bimetallic catalyst, namely Cu x O / MnO2 composite material, is obtained.
[0006] The Cu-Mn bimetallic catalyst (Cu x O / MnO2) prepared by the above method.
[0007] The application of the Cu-Mn bimetallic catalyst in treating organic pollutant wastewater is disclosed. The Cu-Mn bimetallic catalyst and ozone are added into the wastewater, and the organic pollutants in the wastewater can be efficiently removed after 60-120 minutes of reaction; wherein the catalyst dosage is 0.1-0.3 g / L of wastewater, and the ozone dosage is 0.01-0.05 g / L of wastewater.
[0008] Compared with the prior art, the present application has the following advantages: 1) The method for preparing the catalyst is unique and simple to operate: the present application adopts a hydrothermal-ball milling method to prepare a Cu-Mn bimetallic catalyst (Cu x O / MnO2) and can catalyze the removal of organic pollutants in high-salinity wastewater by ozone oxidation. First, CuO and MnO2 are synthesized by a hydrothermal method, respectively, then the obtained CuO and MnO2 are mixed according to a certain mass ratio and transferred to a ball milling tank for ball milling, and finally, impurities are removed by high-temperature calcination to obtain the Cu-Mn bimetallic catalyst (Cu x O / MnO2).
[0009] 2) The method for removing organic pollutants in high-salinity wastewater by catalytic ozone oxidation is innovative in mechanism: the present application utilizes the catalyst to catalyze ozone oxidation to achieve efficient removal of organic pollutants in high-salinity wastewater. The catalyst is added to high-salinity wastewater to achieve efficient removal of organic pollutants in high-salinity wastewater under the condition of ozone being introduced.
[0010] 3) Scalable application: the present application can be used on a large scale. The amount of catalyst synthesized at a time in a laboratory under the condition of the present application is more than 10 g, which has the potential for large-scale preparation.
[0011] 4) No secondary pollution: the catalyst prepared by the present application is stable in water and does not cause secondary pollution. BRIEF DESCRIPTION OF DRAWINGS
[0012] Figure 1 Figure 1 is a schematic diagram of the synthesis path of Cu x O / MnO2 catalyst of Example 1 of the present application; Figure 2 Figure 2 is a schematic diagram of the removal effect of oxalic acid in Cu x O / MnO2 / O3 system and ozone system; Figure 3 Figure 3 is a schematic diagram of the influence of different catalyst dosages on the removal effect of oxalic acid in Cu x O / MnO2 / O3 system; Figure 4 Figure 4 is a schematic diagram of the influence of different ozone concentrations on the removal effect of oxalic acid in Cu x O / MnO2 / O3 system; Figure 5 Figure 5 is a schematic diagram of the influence of different initial pH values on the removal effect of oxalic acid in Cu x O / MnO2 / O3 system; Figure 6 Figure 6 is a schematic diagram of the influence of different concentrations of Cl – on the removal effect of oxalic acid in Cu x O / MnO2 / O3 system; Figure 7Cu x The TOC removal of different pollutants, 2,4-dichlorophenol, phenol, p-nitrobenzoic acid, aniline (2,4-DCP, Phenol, NBA, AN) by the O / MnO2 / O3 system is shown in the schematic diagram. DETAILED DESCRIPTION
[0013] The application will be described in further detail in connection with the preferred embodiments. It is to be understood that the specific examples described herein are merely by way of illustration and are not intended to limit the application.
[0014] Example 1 A method for preparing a Cu-Mn bimetallic oxide catalytic ozone oxidation catalyst includes two main links of synthesizing a catalyst precursor by a hydrothermal method and synthesizing a composite material by a ball milling method, and the specific steps are as shown in the following formula: Figure 1 First, 40.0 g / L Cu(NO3)2·3H2O is added to deionized water to be fully dissolved and then moved into a reaction kettle to perform a hydrothermal reaction. After the reaction, the precipitate is washed with deionized water until the effluent is colorless, and then dried at 80 ℃ for 12 h to obtain a composite material precursor CuO. 7.6 g / L MnSO4·H2O and 17.9 g / L KMnO4 are added to deionized water to be fully dissolved and then moved into a reaction kettle to perform a hydrothermal reaction. After the reaction, the precipitate is washed with deionized water until the effluent is colorless, and then dried at 80 ℃ for 12 h to obtain a composite material precursor MnO2. Subsequently, the obtained CuO and MnO2 are mixed according to a mass ratio of 1:9 and then added to a 50 mL ball mill tank. A planetary ball mill is used to perform a ball milling treatment at a speed of 200 rpm for 2 h. Finally, the ball-milled mixture is calcined at a high temperature of 160 ℃ for 2 h to remove impurities, thereby obtaining a Cu-Mn bimetallic catalyst (Cu x O / MnO2).
[0015] Example 2 The removal effect of the Cu x O / MnO2 / O3 system on organic pollutants in wastewater is investigated. Specifically, the effect of the method is tested through the following experiments.
[0016] Experiment 1: The removal effect of the Cu x O / MnO2 / O3 system on oxalic acid is tested.
[0017] The influence of the introduction of Cu x O / MnO2 on the removal efficiency in the ozone system is investigated, and the following two groups of conditions are set for comparison: 1) A reaction solution containing 0.5 mM oxalic acid and having a pH of 0=7.0 is prepared in a 200 mL beaker, and 20 mg of Cu xO / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L was introduced into the bottom of the solution (flow rate was 120 mL / min), and the reaction was carried out for 1 h; 2) 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0=7.0 was prepared and placed in a 200 mL beaker and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L was introduced into the bottom of the solution (flow rate was 120 mL / min), and the reaction was carried out for 1 h.
[0018] Figure 2 The removal of oxalic acid in the ozone system and Cu x O / MnO2 / O3 system is shown. After 1 h of reaction, there was almost no removal of oxalic acid in the ozone system, while Cu x O / MnO2 / O3 system had a removal rate of 100% for oxalic acid.
[0019] Experiment 2: Removal effect test of oxalic acid under different catalyst dosages.
[0020] The removal efficiency of Cu x O / MnO2 / O3 system for oxalic acid under different catalyst dosages was investigated, and the following conditions were set for comparison: 1) 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0=7.0 was prepared and placed in a 200 mL beaker, and 10 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L was introduced into the bottom of the solution (flow rate was 120 mL / min), and the reaction was carried out for 1 h; 2) 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L was introduced into the bottom of the solution (flow rate was 120 mL / min), and the reaction was carried out for 1 h; 3) 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0=7.0 was prepared and placed in a 200 mL beaker, and 30 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L was introduced into the bottom of the solution (flow rate was 120 mL / min), and the reaction was carried out for 1 h; 4) 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0=7.0 was prepared and placed in a 200 mL beaker, and 40 mg of Cu xO / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 40 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h.
[0021] Figure 3 Cu x The removal effect of oxalic acid by the O / MnO2 / O3 system was investigated, and it was found that Cu x The optimal dosage of O / MnO2 was 200 mg / L.
[0022] Experiment 3: Removal effect of oxalic acid under different ozone dosages.
[0023] The removal effect of oxalic acid by the O / MnO2 / O3 system was investigated, and it was found that Cu x The removal effect of oxalic acid by the O / MnO2 / O3 system was investigated, and the following conditions were set for comparison: 1) 100 mL of reaction solution containing 0.5 mM oxalic acid and pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 10 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 2) 100 mL of reaction solution containing 0.5 mM oxalic acid and pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 20 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 3) 100 mL of reaction solution containing 0.5 mM oxalic acid and pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 4) 100 mL of reaction solution containing 0.5 mM oxalic acid and pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 40 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 5) 100 mL of reaction solution containing 0.5 mM oxalic acid and pH0=7.0 was prepared and placed in a 200 mL beaker, and 20 mg of Cu xO / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 50 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h.
[0024] Figure 4 Cu2+ removal efficiency under different ozone dosages is shown. x The higher the concentration of ozone introduced (in the range of 10-50 mg / L), the better the Cu2+ removal efficiency of the O / MnO2 / O3 system. x The higher the concentration of ozone introduced (in the range of 10-50 mg / L), the better the Cu2+ removal efficiency of the O / MnO2 / O3 system.
[0025] Experiment 4: Test of oxalic acid removal efficiency under different initial pH conditions.
[0026] Investigate Cu2+ removal efficiency under different initial pH conditions. x O / MnO2 / O3 system on oxalic acid removal effect, and set the following several groups of conditions for comparison: 1) Prepare 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0= 4.0, and place it in a 200 mL beaker. Add 20 mg of Cu2+ and O / MnO2 to the reaction solution and carry out magnetic stirring. At the same time, introduce ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and the reaction is carried out for 1 h. x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 2) Prepare 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0= 5.0, and place it in a 200 mL beaker. Add 20 mg of Cu2+ and O / MnO2 to the reaction solution and carry out magnetic stirring. At the same time, introduce ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and the reaction is carried out for 1 h. x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 3) Prepare 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0= 7.0, and place it in a 200 mL beaker. Add 20 mg of Cu2+ and O / MnO2 to the reaction solution and carry out magnetic stirring. At the same time, introduce ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and the reaction is carried out for 1 h. x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 4) Prepare 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0= 8.0, and place it in a 200 mL beaker. Add 20 mg of Cu2+ and O / MnO2 to the reaction solution and carry out magnetic stirring. At the same time, introduce ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and the reaction is carried out for 1 h. x O / MnO2 was added to the reaction solution and magnetic stirring was carried out, and at the same time, ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) was introduced into the bottom of the solution, and the reaction was carried out for 1 h. 5) Prepare 100 mL of reaction solution containing 0.5 mM oxalic acid, pH0= 9.0, in a 200 mL beaker, and add 20 mg of Cu x O / MnO2 to the reaction solution and perform magnetic stirring, while introducing ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and react for 1 h; Figure 5 The removal effect of Cu x O / MnO2 / O3 on oxalic acid under different initial pH conditions is shown. x The removal effect of oxalic acid in the Cu
[0027] Experiment 5: Removal effect of oxalic acid under different concentrations of Cl – under interference.
[0028] Investigation of the removal effect of oxalic acid under different concentrations of Cl – under interference. x The removal effect of oxalic acid in the Cu 1) Prepare 100 mL of reaction solution containing 100 mM Cl – , 0.5 mM oxalic acid, and pH0= 7.0, in a 200 mL beaker, and add 20 mg of Cu x O / MnO2 to the reaction solution and perform magnetic stirring, while introducing ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and react for 1 h; 2) Prepare 100 mL of reaction solution containing 200 mM Cl – , 0.5 mM oxalic acid, and pH0= 7.0, in a 200 mL beaker, and add 20 mg of Cu x O / MnO2 to the reaction solution and perform magnetic stirring, while introducing ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and react for 1 h; 3) Prepare 100 mL of reaction solution containing 300 mM Cl – , 0.5 mM oxalic acid, and pH0= 7.0, in a 200 mL beaker, and add 20 mg of Cu x O / MnO2 to the reaction solution and perform magnetic stirring, while introducing ozone with a concentration of 30 mg / L (flow rate of 120 mL / min) into the bottom of the solution, and react for 1 h; 4) Prepare 100 mL of reaction solution containing 400 mM Cl –, 0.5 mM oxalic acid and pH0= 7.0, placed in a 200 mL beaker, 20 mg of Cu x O / MnO2was added to the reaction solution and magnetic stirring was performed, while the solution was bubbled with ozone at a concentration of 30 mg / L (flow rate of 120 mL / min) at the bottom of the solution for 1 h. 5) 100 mL of reaction solution containing 500 mM Cl – , 0.5 mM oxalic acid and pH0= 7.0, placed in a 200 mL beaker, 20 mg of Cu x O / MnO2was added to the reaction solution and magnetic stirring was performed, while the solution was bubbled with ozone at a concentration of 30 mg / L (flow rate of 120 mL / min) at the bottom of the solution for 1 h. 6) 100 mL of reaction solution containing 1000 mM Cl – , 0.5 mM oxalic acid and pH0= 7.0, placed in a 200 mL beaker, 20 mg of Cu x O / MnO2was added to the reaction solution and magnetic stirring was performed, while the solution was bubbled with ozone at a concentration of 30 mg / L (flow rate of 120 mL / min) at the bottom of the solution for 1 h.
[0029] Figure 6 shows the removal efficiency of Cu – O / MnO2 / O3system on oxalic acid under the interference of different concentrations of Cl x . Under the interference of 1000 mM Cl – , the removal rate of oxalic acid still remained about 70%.
[0030] Example 3 A variety of pollutants were selected as model organic compounds, including 2,4-dichlorophenol (2,4-DCP), phenol, p-nitrobenzoic acid (NBA), aniline (AN), and the broad-spectrum removal of organic pollutants by the Cu x O / MnO2catalyst under the conditions of an ozone concentration of 30 mg / L (flow rate of 120 mL / min).
[0031] The specific steps are as follows: (1) 0.5 mM of pollutants were added to deionized water, and the pH was adjusted to 7.0; (2) 0.2 g / L of Cu x O / MnO2was added to the reaction solution in step (1) and magnetic stirring was performed; (3) the solution in step (2) was bubbled with ozone at a concentration of 30 mg / L (flow rate of 120 mL / min) at the bottom of the solution for 2 h.
[0032] Figure 7 Cu x TOC removal of different pollutants by O / MnO2 / O3 system. After 2h reaction, Cu x O / MnO2 / O3 system has obvious advantages in TOC removal of different pollutants.
Claims
1. A method for preparing a Cu-Mn bimetallic catalyst, characterized in that, The specific steps include the following: Step 1: First, the precursors CuO and MnO2 of the composite material were synthesized separately by hydrothermal method. 38.0~42.0 g / L Cu(NO3)2•3H2O was added to deionized water and fully dissolved, then transferred to a reactor for hydrothermal reaction. After the reaction, the mixture was washed with deionized water until the effluent was colorless, and dried at 70~80 ℃ for 8~10 h to obtain the composite material precursor CuO. 7.0~7.8 g / L MnSO4·H2O and 17.0~18.5 g / L KMnO4 were added to deionized water and fully dissolved, then transferred to a reactor for hydrothermal reaction. After the reaction, the mixture was washed with deionized water until the effluent was colorless, and dried at 70~80 ℃ for 8~10 h to obtain the composite material precursor MnO2. Step 2: Mix the composite material precursors CuO and MnO2 at a mass ratio of 1:24 to 1:6; Step 3: Transfer the mixture obtained in Step 2 to a 50 mL ball mill jar and ball mill it using a planetary ball mill. The ball-to-material ratio is 20:1, the ball milling speed is 180~220 rpm, and the ball milling time is 1~3 h. Step 4: Calcine the mixture obtained in Step 3 at 160~180 °C for 2 h to remove impurities, thereby obtaining the Cu-Mn bimetallic catalyst, i.e., Cu x O / MnO2 composite material.
2. A Cu-Mn bimetallic catalyst prepared by the method of claim 1.
3. The application of the Cu-Mn bimetallic catalyst according to claim 2 in the treatment of organic pollutant wastewater.
4. The application according to claim 3, characterized in that, Adding the Cu-Mn bimetallic catalyst and ozone to the wastewater and reacting for 60-120 minutes can achieve efficient removal of organic pollutants from the wastewater; wherein the catalyst dosage is 0.1-0.3 g / L wastewater and the ozone dosage is 0.01-0.05 g / L wastewater.