A method for preparing a ternary metal acidic catalyst

Abstract

This invention discloses a method for preparing a ternary metal acidic catalyst, the method comprising the following steps: doping cerium into a copper-manganese spinel catalyst to form a ternary metal catalyst, and then chelating sulfate ions to form SO4. 2‑ / Cu x Ce 1‑x The Mn₂O₄ type acid catalyst is the aforementioned ternary metal acid catalyst. This catalyst mainly utilizes Cu... 2+ and Mn 2+ The strong interaction between the two catalyzes the generation of highly oxidizing, non-selective free radicals from ozone. A small amount of Ce doping can increase surface defects, enhancing the adsorption capacity for pollutants, while also providing sites for chelation with sulfuric acid, forming Lewis and Bronsted acidic sites. When the ternary metal acidic catalyst comes into contact with ozone micro- and nano-bubbles in water, it promotes the quenching of the bubbles, generating hydroxyl radicals. Furthermore, the ozone released from inside the bubbles is also catalyzed by the catalyst to generate hydroxyl radicals.

Description

Technical Field

[0001] This invention relates to the field of deep treatment technology for refined and chemical concentrate, and specifically to a method for preparing a ternary metal acid catalyst. Background Technology

[0002] Wastewater from the refining and chemical industry is characterized by high salinity, high ammonia nitrogen, and high oil content. The concentrated wastewater produced after membrane treatment of refining and chemical wastewater is mainly polluted by petroleum-based organic compounds, including phenols, aldehydes, aromatic hydrocarbons, and sulfur- and nitrogen-containing compounds. Currently, the treatment of refining and chemical concentrated wastewater mainly employs ultrafiltration-reverse osmosis dual-membrane system circulation treatment, multiphase photocatalytic oxidation technology, ozone oxidation catalytic technology, electrocatalytic oxidation technology, and the Fenton reagent method. During photocatalytic oxidation, both oxidation and reduction reactions occur simultaneously. Photogenerated holes can not only oxidize OH groups adsorbed on the semiconductor surface... - Photocatalysis reacts with H2O to generate highly oxidizing ·OH, ultimately degrading organic matter into CO2 and H2O. However, photocatalysis is unstable and too expensive for large-scale applications. Applying advanced electrochemical oxidation to treat high-salinity refinery concentrate can leverage many advantages, such as improved conductivity, reduced reaction energy consumption, milder reaction conditions, and ease of integration with subsequent operational units.

[0003] However, some problems still exist in the large-scale industrial application of advanced electrochemical oxidation technology. First, efficient wastewater treatment using electrochemical oxidation technology requires a pH range of 2-4. Since most high-salinity refining wastewater is moderately alkaline, adjusting the pH by adding acid would increase costs. Second, when using anodic oxidation technology to treat wastewater containing high concentrations of chloride ions, the chloride ions are oxidized at the anode into chlorine-containing reactive substances such as Cl2 and HOCl. - These can be further converted into toxic and harmful chlorinated byproducts. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a ternary metal acid catalyst that can efficiently degrade phenol in water without additional pH adjustment and without producing chlorinated byproducts.

[0005] In one aspect of the invention, a method for preparing a ternary metal acidic catalyst is provided. According to an embodiment of the invention, based on the preparation of a CuMn₂O₄ spinel catalyst, cerium ions are added to dope the CuMn₂O₄ spinel catalyst, forming a ternary metal catalyst, and then sulfate ions are chelated to form SO₄²⁻. 2- / Cu x Ce 1-x The Mn2O4 type acid catalyst is the ternary metal acid catalyst.

[0006] In addition, the preparation method of the ternary metal acid catalyst according to the above embodiments of the present invention may also have the following additional technical features:

[0007] In some embodiments of the present invention, the method includes the following steps:

[0008] (1) Mix nitrates containing Cu, Mn and Ce thoroughly in an aqueous solution and heat to 40-50℃ to obtain a metal nitrate solution;

[0009] (2) Add citric acid solution dropwise to metal nitrate solution, adjust the pH of the mixed solution with ammonia solution, heat to 70-80℃ and stir to evaporate the aqueous solution until it becomes a colloid;

[0010] (3) Dry the colloid to form a fluffy solid, calcine it for the first time, grind the calcined powder thoroughly, and immerse it in sulfuric acid or ammonium sulfate solution;

[0011] (4) Dry the impregnated catalyst and calcine it for the second time to obtain the ternary metal acid catalyst.

[0012] In some embodiments of the present invention, in step (1), the molar ratio of Cu, Mn and Ce is 1-x:1.5:x, where x = 0.05 to 0.2.

[0013] In some embodiments of the present invention, in step (2): the molar ratio of metal ions to citric acid is 1.5 to 2:1; the ammonia solution is composed of deionized water and 25% ammonia water in a volume ratio of 1:1, and the pH of the mixed solution is adjusted to alkaline by adding the ammonia solution dropwise.

[0014] In some embodiments of the present invention, in step (3): the temperature for drying the colloid is 50-60°C and the drying time is 2-3 hours; the temperature for the first calcination is 600-800°C and the calcination time is 4-5 hours, with a heating rate of 1-5°C / min; the impregnation time is 1-2 hours and the solid-liquid ratio for impregnation is 1:15-20.

[0015] In some embodiments of the present invention, in step (4): the drying temperature of the catalyst after impregnation is 60-80°C and the drying time is 1-2h; the temperature of the second calcination is 500-600°C and the calcination time is 2-3h, and the heating rate is 1-2°C / min.

[0016] In another aspect of the present invention, the present invention provides a ternary metal acid catalyst prepared according to the preparation method of the ternary metal acid catalyst described above.

[0017] In another aspect of the invention, the present invention proposes the use of a ternary metal acidic catalyst. According to embodiments of the invention, the ternary metal acidic catalyst is used to catalyze the degradation of the pollutant phenol by ozone micro / nanobubbles.

[0018] In addition, the use of a ternary metal acid catalyst according to the above embodiments of the present invention may also have the following additional technical features:

[0019] In some embodiments of the present invention, the ozone concentration is maintained at 0.3–1 mg / L, the ozone gas flow rate is 0.16–1.2 L / min, the dosage of the ternary metal acid catalyst is 500–1000 mg of catalyst per liter of waste liquid, and the concentration of the pollutant phenol is 10–40 mg / L.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] 1) This invention utilizes the sol-gel method to prepare high-purity CuMn2O4 copper-manganese spinel. Under these preparation conditions, the amount of Cu ions added is appropriately reduced, while an equal amount of Ce ions are added simultaneously to dope CuMn2O4 with Ce, forming more oxygen vacancies and surface defects, thereby enhancing the catalyst's adsorption capacity for pollutants. Simultaneously, it provides sites for chelation with sulfuric acid to facilitate surface acidification, chelating sulfate ions to form SO4. 2- / Cu x Ce 1-x Mn2O4 type acid catalyst forms Lewis and Bronsted acidic sites to promote the quenching of ozone micro-nano bubbles and generate hydroxyl radicals. At the same time, the interaction of Cu, Mn and Ce ions can catalyze ozone to generate highly oxidizing hydroxyl radicals, thereby efficiently degrading phenol in water.

[0022] 2) The preparation process of copper-manganese-cerium ternary acid catalyst is simple and easy to operate, and the catalyst preparation cycle is relatively short, which has potential application prospects in the treatment of concentrate in the petroleum industry.

[0023] 3) When the ternary metal acid catalyst comes into contact with ozone micro-nano bubbles in water, it promotes the quenching of the bubbles and generates hydroxyl radicals. In addition, the ozone released from inside the bubbles will also be catalyzed by the catalyst to generate hydroxyl radicals ·OH, which has great application prospects for the treatment of wastewater containing organic matter.

[0024] 4) Most high-salt refining wastewater is moderately alkaline, while ozone micro-nano bubble technology can efficiently degrade pollutants in a wide range of pH environments. In particular, in alkaline environments, ozone micro-nano bubbles are more conducive to chain reactions catalyzed by catalysts, generating a large amount of ·OH in the system. This eliminates the cost increase caused by adding acid to adjust the pH required by other technologies.

[0025] 5) Using a copper-manganese-cerium ternary acidic catalyst to catalyze ozone micro-nano bubbles will not produce toxic or harmful byproducts such as Cl2 and HOCl. - The entire degradation process is safe and environmentally friendly, and will not cause secondary pollution or harm. Attached Figure Description

[0026] Figure 1 The X-ray diffraction patterns of CuMn2O4 prepared by the nitrate mixed solution in Example 1 of the present invention at pH = 6, 7, and 8, and with a molar ratio of Cu ions to Mn ions of 1:2.

[0027] Figure 2 The X-ray diffraction patterns of CuMn2O4 prepared by the nitrate mixed solution in Example 1 of the present invention at pH = 6, 7, and 8, and with a molar ratio of Cu ions to Mn ions of 1:1.5, are shown.

[0028] Figure 3 The X-ray diffraction patterns of CuMn2O4 prepared in Example 1 of this invention are shown at pH = 7 and 8, and the molar ratio of Cu ions to Mn ions is 1:1.5 and 1:1, respectively.

[0029] Figure 4 The images show the FTIR curves of the CuMn2O4 catalyst obtained after calcination at 700℃ for 4 hours with a metal ion molar ratio of Cu:Mn = 1:1.5 and pH = 8 in Example 1 of this invention, and the SO42- content after sulfation of CuMn2O4 in Example 2. 2- The FTIR curve of the CuMn2O4 catalyst; the Cu prepared by reducing the amount of Cu ions by x = 0.15 mol in Example 3 and correspondingly doping with an equal amount of Ce ions by x = 0.15 mol. 0.85 Ce 0.15 SO4 obtained by Mn2O4 catalyst followed by sulfation and calcination 2- / Cu 0.85 Ce 0.15 The FTIR curve of Mn2O4 catalyst, and similarly, by reducing the amount of Cu ions by x = 0.05–0.2 mol, the Cu prepared by doping with an equal amount of Ce ions (x = 0.05–0.2 mol) 1-x Ce x Mn₂O₄ catalyst, followed by sulfation to obtain the ternary acidic catalyst SO₄. 2- / Cu x Ce 1-x FTIR curve of Mn2O4;

[0030] Figure 5 The SO42-dimethylamine catalysts in Examples 3 and 4 of this invention, after being impregnated with sulfuric acid or ammonium sulfate, are used to produce SO42-dimethylamine. 2- / Cu 0.85Ce 0.15 pyridine infrared detection image of Mn2O4;

[0031] Figure 6 This invention provides an example of using NH3-TPD for quantitative analysis of SO4 in Example 5. 2- / Cu 0.85 Ce 0.15 Mn2O4 surface acidity;

[0032] Figure 7 Examples of embodiments of the present invention 6 include the use of air micro-nano bubbles to degrade phenol wastewater, the use of ozone micro-nano bubbles alone to degrade phenol wastewater, and the use of SO4. 2- / Cu 0.85 Ce 0.15 Energy efficiency diagram of Mn2O4 catalyst synergistically degrading phenol wastewater with ozone micro-nano bubbles. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1

[0035] The preparation method of CuMn2O4 includes the following steps:

[0036] (1) Cu according to the molar ratio 2+ :Mn 2+ Dissolve the contents in 50 mL of deionized water at ratios of 1:2, 1:1.5, 1:1, and 1.5:1, and stir thoroughly.

[0037] (2) The molar ratio of citric acid to metal ions is 1:1. Dissolve citric acid in 25 ml of water and then add it dropwise to the mixed solution of metal ions while keeping the mixture stirred at high speed.

[0038] (3) Adjust the pH of the mixed solution to 6, 7, and 8 using diluted (1:1) ammonia water, continue stirring with a constant temperature magnetic stirrer, heat to 80℃ and then evaporate the aqueous solution at a constant temperature until the precursor solution turns into a viscous green colloid.

[0039] (4) First, transfer the colloid to an oven to dry it, and then put it into a muffle furnace to calcine at a high temperature of 700°C for 4 hours.

[0040] Depend on Figures 1-3As shown, comparing the XRD patterns under different conditions, high-purity CuMn2O4 can be obtained from the sample calcined at 700℃ for 4 h with a metal ion molar ratio of Cu:Mn = 1:1.5, pH = 8, and without the presence of CuO and Mn2O3. Subsequent catalyst preparation will be based on these conditions.

[0041] Example 2

[0042] SO4 2- The preparation method of CuMn2O4 catalyst includes the following steps:

[0043] (1) Following the method of Example 1, the parameters and conditions are as follows: calcination at 700℃ for 4h with a metal ion molar ratio of Cu:Mn = 1:1.5 and pH = 8, to obtain a high-purity CuMn2O4 catalyst;

[0044] (2) The CuMn2O4 catalyst powder was impregnated in 1mol / L sulfuric acid with a solid-liquid ratio of 1:15 for 1 hour, and then dried in an 80℃ oven.

[0045] (3) The dried powder from step (2) is transferred to a muffle furnace for calcination at a concentration of 600°C for 3 hours. The heating rate of the muffle furnace is 2°C / min. After calcination, the powder is allowed to cool naturally to room temperature, thus completing the process of creating the acidic metal catalyst SO4. 2- Preparation of CuMn2O4.

[0046] Example 3

[0047] A method for preparing a copper-manganese-cerium ternary acidic catalyst includes the following steps:

[0048] (1) Weigh 2.054g Cu(NO3)2·3H2O, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0049] (2) Weigh 5.368g of Mn(NO3)250wt%, mix it with 25mL of deionized water and stir well to obtain a clear solution;

[0050] (3) Weigh 0.651g Ce(NO3)3·6H2O, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0051] (4) Weigh 3g of citric acid, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0052] (5) Mix the solutions from steps (1), (2), and (3), heat to 50°C, maintain for 30 minutes, and stir vigorously at 600 r / min.

[0053] (6) At a solution temperature of 50°C and 600 r / min, the citric acid solution from step (4) is added dropwise to the solution from step (5).

[0054] (7) Dilute 25% ammonia water (the volume ratio of ammonia water to deionized water is 1:1), add the diluted ammonia water dropwise to the solution in step (6), and adjust the pH of the solution to 8;

[0055] (8) Increase the temperature of the solution in step (7) to 80°C, maintain the constant temperature, and stir vigorously at 800r / min for 2 hours to form a viscous colloid with poor flowability.

[0056] (9) Transfer the viscous colloid to an oven at 60°C and dry for 2 hours to form a fluffy and porous solid.

[0057] (10) Grind the loose and porous solid into powder, transfer it to a muffle furnace for calcination at a temperature of 700°C for 4 hours, and raise the temperature of the muffle furnace at a rate of 2°C / min. Then cool it naturally to room temperature to complete the preparation of the copper-manganese-cerium ternary metal catalyst. The catalyst is rinsed with deionized water and then dried.

[0058] (11) The copper-manganese-cerium ternary metal catalyst powder from step (10) is impregnated in 1 mol / L sulfuric acid with a solid-liquid ratio of 1:15 for 1 h, and then placed in an 80°C oven to dry.

[0059] (12) Transfer the dried powder from step (11) to a muffle furnace for calcination. The calcination temperature is 600℃, the calcination time is 3 hours, and the heating rate of the muffle furnace is 2℃ / min. After that, allow it to cool naturally to room temperature. This completes the process of obtaining the copper-manganese-cerium ternary acidic metal catalyst SO4. 2- / Cu 0.85 Ce 0.15 Preparation of Mn2O4.

[0060] Similarly, preparation Figure 4 A series of SO4 2- / Cu 1-x Ce x Mn2O4 (x = 0.05, 0.1, 0.2) catalysts were first prepared by adding metal salts in a molar ratio of Cu:Ce:Mn = 1-x:x:1.5 according to steps (1) to (3), and then preparing SO4 in the corresponding proportions according to steps (4) to (12). 2- / Cu 1-x Ce x Mn2O4 catalyst.

[0061] like Figure 4 As shown, the modified spinel phase is well preserved and undamaged, and at 1244 cm⁻¹ -1The presence of S=O at the catalyst surface indicates that metal ions and sulfate ions are chelated, and that SO42- is present on the catalyst surface. 2- .

[0062] Example 4

[0063] A method for preparing a copper-manganese-cerium ternary acidic catalyst includes the following steps:

[0064] (1) Accurately weigh 2.054g Cu(NO3)2·3H2O, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0065] (2) Accurately weigh 5.368g of Mn(NO3)250wt%, and stir it with 25mL of deionized water to obtain a clear solution;

[0066] (3) Accurately weigh 0.651g Ce(NO3)3·6H2O, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0067] (4) Accurately weigh 3g of citric acid, dissolve it in 25mL of deionized water, and stir on a constant temperature magnetic stirrer until the solid is completely dissolved;

[0068] (5) Mix the solutions from steps (1), (2), and (3), heat to 50°C, maintain for 30 minutes, and stir vigorously at 600 r / min.

[0069] (6) At a solution temperature of 50°C and 600 r / min, the citric acid solution from step (4) is added dropwise to the solution from step (5).

[0070] (7) Dilute 25% ammonia water (the volume ratio of ammonia water to deionized water is 1:1), add the diluted ammonia water dropwise to the solution in step (6), and adjust the pH of the solution to 8;

[0071] (8) Raise the temperature of the solution in step (7) to 80°C, maintain the constant temperature, and stir vigorously at 800 r / min for 2 h to form a viscous colloid with poor flowability.

[0072] (9) Transfer the colloid to an oven at 60°C and dry for 2 hours to form a fluffy and porous solid.

[0073] (10) Grind the dried solid into powder, transfer it to a muffle furnace for calcination at 700℃ for 4 hours, and raise the temperature of the muffle furnace at 2℃ / min. Then, allow it to cool naturally to room temperature to complete the preparation of the copper-manganese-cerium ternary metal catalyst. Rinse the catalyst with deionized water and then dry it.

[0074] (11) The catalyst powder was impregnated in 1.5 mol / L ammonium sulfate. Each 1 g of catalyst was impregnated with 10 ml of ammonium sulfate solution for 2 h. After impregnation, it was dried in an 80 °C oven.

[0075] (12) Transfer the dried powder from (11) to a muffle furnace for calcination. The calcination temperature is 600℃, the calcination time is 3 hours, and the heating rate of the muffle furnace is 2℃ / min. After that, allow it to cool naturally to room temperature. This completes the process of obtaining the copper-manganese-cerium ternary acidic metal catalyst SO4. 2- / Cu 0.85 Ce 0.15 Preparation of Mn2O4.

[0076] like Figure 5 As shown, at 1490m -1 A characteristic peak was detected at the site, which is the common binding site for Lewis acid and Bronsted acid.

[0077] Example 5

[0078] like Figure 6 As shown, the ternary metal acid catalyst SO4 prepared in Example 3 is used. 2- / Cu 0.85 Ce 0.15 Mn2O4 exhibits desorption peaks of NH3 molecules in the temperature range of 100–700℃. These desorption regions are divided into peak I (100–200℃), peak II (400–500℃), and peak III (630–700℃), which are respectively attributed to the NH3 desorption peaks of physisorption, weak acid, and moderately strong acid sites.

[0079] Example 6

[0080] Using the ternary metal acid catalyst SO4 prepared in Example 3 2- / Cu 0.85 Ce 0.15 The degradation of pollutant phenol by Mn2O4-catalyzed ozone micro-nanobubbles includes the following steps:

[0081] Gas-liquid mixing pump liquid flow rate = 1m 3 / L, the inlet water pressure of the micro / nano bubble generator is 40 MPa, the gas flow rate is 120 mL / min, the ozone concentration is 0.4 mg / L, and the gas-liquid ratio is 1:17. SO4 is added. 2- / Cu 0.85 Ce 0.15 The Mn2O4 catalyst was 500 mg / L, and microwave ultrasound was used to uniformly disperse the catalyst in the solution.

[0082] Air micro-nano bubbles and ozone micro-nano bubbles were used as a control group. The generation condition for air micro-nano bubbles was that the liquid flow rate of the gas-liquid mixing pump was 1 m³ / s.3 The inlet water pressure of the micro / nano bubble generator is 40 MPa, the air flow rate is 120 mL / min, and the gas-liquid ratio is 1:17. The ozone micro / nano bubble generation conditions are: gas-liquid mixing pump liquid flow rate = 1 m³ / L. 3 / L, the inlet water pressure of the micro-nano bubble generator is 40Mpa, the gas flow rate is 120mL / min, the ozone concentration is 0.4mg / L, and the gas-liquid ratio is 1:17.

[0083] A phenol solution of 40 mg / L was prepared for the experiment. The reaction temperature was maintained at 25℃. Water samples were taken at set time points, and the phenol concentration was measured using a UV spectrophotometer.

[0084] from Figure 7 As can be seen, air micro-nano bubbles have no effect on degrading phenol. However, when ozone micro-nano bubbles are used alone to degrade phenol, the removal rate can reach 75%, and SO4 is also reduced. 2- / Cu 0.85 Ce 0.15 After the Mn2O4 catalyst is introduced into the system, the degradation rate can reach more than 90%, and the removal efficiency of phenol is improved by 15%.

[0085] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the present invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a ternary metal acidic catalyst, characterized in that: On the basis of preparing CuMn2O4 spinel catalyst, cerium ions are added, Ce is doped in CuMn2O4 spinel catalyst to form ternary metal catalyst, and then chelated with sulfate to form SO4 2- / Cu 1-x Ce x Mn2O4 type acid catalyst, that is, the ternary metal acidic catalyst, wherein the molar ratio of Cu, Mn and Ce is 1-x:1.5:x, wherein x=0.05~0.2; The method specifically includes the following steps: (1) Mix nitrates containing Cu, Mn and Ce thoroughly in an aqueous solution and heat to 40~50 °C to obtain a metal nitrate solution; (2) Add citric acid solution dropwise to metal nitrate solution, adjust the pH of the mixed solution with ammonia solution, heat to 70~80 ℃ and stir to evaporate the aqueous solution until it becomes a colloid; (3) Dry the colloid to form a fluffy solid, calcine it for the first time, grind the calcined powder thoroughly, and immerse it in sulfuric acid; (4) Dry the impregnated catalyst and calcine it for the second time to obtain the ternary metal acid catalyst.

2. The method for preparing a ternary metal acidic catalyst according to claim 1, characterized in that, In step (2): The molar ratio of metal ions to citric acid is 1.5~2:1; The ammonia solution is composed of deionized water and 25% ammonia water in a volume ratio of 1:

1. The pH of the mixed solution is adjusted to alkaline by adding the ammonia solution dropwise.

3. The method for preparing a ternary metal acidic catalyst according to claim 1, characterized in that, In step (3): The temperature for drying the colloid is 50~60 ℃, and the drying time is 2~3 h; The temperature of the first calcination is 600~800 ℃, the calcination time is 4~5 h, and the heating rate is 1~5 ℃ / min; The soaking time is 1-2 hours, and the solid-liquid ratio is 1:15-20.

4. The method for preparing a ternary metal acidic catalyst according to claim 1, characterized in that, In step (4): The catalyst after impregnation is dried at a temperature of 60~80 ℃ for 1~2 h. The second calcination temperature is 500~600 ℃, the calcination time is 2~3 h, and the heating rate is 1~2 ℃ / min.

5. A ternary metal acid catalyst prepared by the method according to any one of claims 1-4.

6. The use of the ternary metal acidic catalyst according to claim 5, characterized in that: The ternary metal acid catalyst is used to catalyze the degradation of pollutant phenol by ozone micro-nano bubbles.

7. The use of the ternary metal acidic catalyst according to claim 6, characterized in that: The ozone concentration is 0.3~1 mg / L, and the ozone gas flow rate is 0.16~1.2 L / min; The dosage of ternary metal acid catalyst is 500-1000 mg of catalyst per liter of wastewater; The concentration of the pollutant phenol is 20~40 mg / L.

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