A supported red mud-based prussian blue analogue catalyst, its preparation method and application

Abstract

The application discloses a supported red mud-based Prussian blue analogue catalyst and a preparation method and application thereof. The preparation method of the catalyst is as follows: red mud raw materials are subjected to acid dissolution to obtain an iron-containing liquid, a reducing agent and a potassium cobalt cyanide solution are sequentially added into the iron-containing liquid to perform reduction and precipitation reactions, and a solid is obtained through solid-liquid separation of a reaction product, and the catalyst is obtained. The catalyst obtained by the application has excellent catalytic performance, high stability and recycling utilization, and has good degradation effect on antibiotics in catalyzing H2O2 degradation. The preparation method is simple, low in cost and suitable for industrial application.

Description

Technical Field

[0001] This invention relates to a Prussian blue analog catalyst, specifically a supported red mud-based Prussian blue analog catalyst, as well as its preparation method and application, belonging to the field of iron-based MOF catalyst technology. Background Technology

[0002] The environmental pollution and ecotoxicity caused by antibiotic emissions have attracted great attention in recent years. To effectively purify antibiotic wastewater, researchers have successively constructed treatment systems with different functions. Compared with traditional physical, chemical, and biological treatment processes, advanced oxidation processes (AOPs) have the advantages of mild reaction, short process length, and rapid reaction. However, there is still a need to develop more low-cost, high-performance, environmentally friendly, highly reusable, and easily recyclable catalysts to meet practical applications.

[0003] Prussian blue analogues (PBAs) are a common class of iron-based MOF materials that can be easily synthesized at room temperature. They possess advantages such as tunable composition / structure, large specific surface area and porosity, and abundant active sites, making them promising candidates for advanced oxidation processes. However, due to the rapid reaction between metal ions and ligands during synthesis, PBAs often tend to grow irregularly and aggregate. This results in the covering of numerous active sites, thereby affecting the catalytic activity and mass utilization of PBAs.

[0004] Red mud is a large-scale solid waste product composed of oxides of elements such as Fe, Al, Si, and Ca, and has been extensively studied as a supporting matrix. Furthermore, red mud typically contains a high content of iron oxide, leading to the development of a series of red mud-based iron-based catalysts. These catalysts not only improve the resource utilization rate of red mud but also achieve low-cost and efficient purification of organic wastewater, representing a valuable "waste-to-waste" approach.

[0005] However, existing red mud-based catalysts (including publicly available red mud-based Prussian blue, etc.) have drawbacks such as limited activity, high preparation cost, and complex preparation process.

[0006] Therefore, developing a red mud-based Prussian blue analog catalyst is of great significance for the efficient utilization of red mud and the improvement of the purification and treatment capacity of antibiotic wastewater. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the first objective of this invention is to provide a supported red mud-based Prussian blue analog catalyst. This catalyst exhibits excellent catalytic performance, high stability, and recyclability.

[0008] A second objective of this invention is to provide a method for preparing a supported red mud-based Prussian blue analog catalyst. This method is simple, low-cost, and suitable for industrial production.

[0009] A third objective of this invention is to provide an application of a supported red mud-based Prussian blue analog catalyst. Based on the excellent catalytic performance of this catalyst, the degradation and purification efficiency of antibiotic wastewater can be significantly improved.

[0010] To achieve the above-mentioned technical objectives, the present invention provides a method for preparing a supported red mud-based Prussian blue analog catalyst. The method involves acid dissolving red mud raw material to obtain an iron-containing liquid, then sequentially adding a reducing agent and a potassium cobalt cyanide solution to the iron-containing liquid for reduction and precipitation reactions. The resulting reaction product is then separated into a solid to obtain the catalyst.

[0011] This invention firstly achieves dealkalization and dissolves iron from red mud raw materials through an acid dissolution process; secondly, it utilizes a reducing agent to dissolve the iron dissolved by the acid. 3+ Reduced to Fe 2+ Finally, through potassium cobalt cyanide and Fe 2+ The reaction produces PBA.

[0012] As a preferred embodiment, the solid obtained from the solid-liquid separation is dried. The drying temperature is 50–80°C.

[0013] As a preferred embodiment, the acid dissolution process is conducted under the following conditions: using at least one of hydrochloric acid, sulfuric acid, and nitric acid as the acid dissolution solution; a liquid-to-solid ratio of 20–200 mL: 1–10 g; a temperature of 85–95 °C; and a time of 1.5–4.5 h. Hydrochloric acid is a further preferred acid dissolution solution. Because hydrochloric acid is volatile, it will not affect the composition or properties of the material in the later stages.

[0014] As a preferred embodiment, the concentration of the acid solution is 1–5 mol / L.

[0015] As a preferred embodiment, the reducing agent includes at least one of ascorbic acid, formic acid, and oxalic acid.

[0016] As a preferred embodiment, the molar mass ratio of the reducing agent to the red mud raw material is 0.0016–0.016 mol: 1–10 g.

[0017] As a preferred embodiment, the conditions for the reduction reaction are: temperature of 20–40°C and time of 10–30 min.

[0018] As a preferred embodiment, the molar mass ratio of potassium cobalt cyanide to red mud raw material in the potassium cobalt cyanide solution is 0.0002-0.02 mol: 1-10 g.

[0019] As a preferred embodiment, the concentration of the potassium cobalt cyanide solution is 1–10 mM.

[0020] As a preferred embodiment, the potassium cobalt cyanide solution is added at a rate of 5–10 min / mL. Controlling the addition rate of the potassium cobalt cyanide solution is beneficial for improving the overall performance of the catalyst. Adding it too quickly may lead to rapid agglomeration of PBA particles, resulting in PBA agglomerates being loaded on the red mud matrix, thus failing to achieve the purpose of carrier dispersion.

[0021] This invention also provides a supported red mud-based Prussian blue analog catalyst, which is prepared by the above method. This catalyst exhibits excellent catalytic performance, solving problems such as low red mud utilization, high cost of catalysts for advanced oxidation processes, easy agglomeration of PBA catalysts, and difficulty in treating antibiotic wastewater.

[0022] This invention also provides an application of a supported red mud-based Prussian blue analog catalyst for catalyzing the degradation of antibiotics by H2O2. When this catalyst is used to catalyze the degradation of antibiotics by H2O2, it exhibits high catalytic efficiency and good degradation effect.

[0023] As a preferred method, it is used to catalyze the degradation of antibiotics in a solution system by H2O2.

[0024] As a preferred option, the antibiotic is ciprofloxacin.

[0025] As a preferred embodiment, the concentration of the supported red mud-based Prussian blue analog catalyst in the solution system is not less than 0.5 g / L.

[0026] As a preferred embodiment, the concentration of H2O2 in the solution system is not less than 48.9 mM.

[0027] As a preferred embodiment, the concentration of the antibiotic in the solution system is 5–30 ppm.

[0028] As a preferred embodiment, the initial pH of the solution system is 3 to 11, the solution system temperature is 20 to 40°C, and the shaking speed is 150 to 200 rpm.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The catalyst has excellent catalytic performance, does not have the strong alkalinity of red mud, and has good dispersibility and catalytic stability, and can be reused.

[0031] (2) The present invention uses red mud as an iron source and support and Prussian blue analogues as active ingredients to form a supported catalyst, which improves the availability of red mud and makes up for the defect of easy aggregation of Prussian blue analogues.

[0032] (3) It can be used to catalyze the degradation of antibiotics by hydrogen peroxide. It has high catalytic degradation efficiency and good purification effect on antibiotic wastewater. It has good application prospects in the field of advanced oxidation and is conducive to the large-scale application of red mud and the effective treatment of antibiotic wastewater.

[0033] (4) The catalyst preparation method is simple and low in cost, making it suitable for industrial production. Attached Figure Description

[0034] Figure 1 The X-ray diffraction (XRD) patterns of RM-CoPBA and RM raw materials prepared in Example 1, ARM prepared in Comparative Example 1, and Fe-CoPBA prepared in Comparative Example 2 are shown.

[0035] Figure 2 Scanning electron microscope (SEM) images of RM-CoPBA (c) and RM raw material (a) prepared in Example 1, ARM (b) prepared in Comparative Example 1, and Fe-Co PBA (d) prepared in Comparative Example 2.

[0036] Figure 3 The following describes the degradation of ciprofloxacin by Fe-CoPBA catalytic activation of H2O2, as prepared in Example 1, RM prepared in Comparative Example 1, and Fe-CoPBA prepared in Comparative Example 2.

[0037] Figure 4 The following describes the degradation of ciprofloxacin by RM-CoPBA catalytic activation with different concentrations of H2O2, as prepared in Example 1.

[0038] Figure 5 The degradation of different concentrations of ciprofloxacin by H2O2 catalytic activation using RM-CoPBA prepared in Example 1.

[0039] Figure 6 The following describes the catalytic activation of H2O2 to degrade ciprofloxacin using RM-CoPBA prepared in Example 1 at different pH values.

[0040] Figure 7 The RM-CoPBA prepared in Example 1 was recycled and reused for catalytic activation of H2O2 to degrade ciprofloxacin.

[0041] Figure 8 This refers to the degradation of ciprofloxacin by H2O2 catalyzed by RM-CoPBA prepared using hydrochloric acid solutions of different concentrations, as described in Example 7. Detailed Implementation

[0042] The following specific embodiments or implementation methods are intended to further illustrate the present invention, and are not intended to limit the present invention.

[0043] The red mud raw material used in this invention was purchased from Guangxi Branch of Aluminum Corporation of China Limited. It belongs to Bayer red mud and mainly contains phases such as hematite, gibbsite, boehmite, nepheline, hydrogarnet, and calcite. The contents of Fe, Ca, Al, Na, Si, and Ti are 18.06%, 11.61%, 9.72%, 7.37%, 7.13%, and 3.97%, respectively.

[0044] Example 1

[0045] The following is a supported red mud-based Prussian blue analog catalyst, comprising the following steps:

[0046] (1) Weigh 5g of red mud and pour it into an Erlenmeyer flask containing 100mL of 2.4mol / L hydrochloric acid solution;

[0047] (2) Place it in a water bath and stir magnetically at 90°C for 2 hours;

[0048] (3) After the temperature reaches room temperature, add 8 mmol of ascorbic acid and stir continuously for 30 min;

[0049] (4) Add 50 mL of a 0.04 mol / L potassium cobalt cyanide solution dropwise while stirring continuously at a rate of 4 mL / min.

[0050] (5) Stir continuously for 2 hours, then let stand for 12 hours;

[0051] (6) Centrifuge, wash and collect the solid product, and then put it into an 80℃ oven to dry, thus obtaining the supported red mud-based Prussian blue analog catalyst, denoted as RM-Co PBA.

[0052] Comparative Example 1

[0053] The following are the steps for acid-soluble red mud materials:

[0054] (1) Weigh 5g of red mud and pour it into an Erlenmeyer flask containing 100mL of 2.4mol / L hydrochloric acid solution;

[0055] (2) Place it in a water bath and stir magnetically at 90°C for 2 hours;

[0056] (3) After the temperature reaches room temperature, add 8 mmol of ascorbic acid and stir continuously for 30 min;

[0057] (4) Keep stirring for 2 hours, then let stand for 12 hours;

[0058] (5) Centrifuge, wash and collect the solid product, and then put it into an 80℃ oven to dry, thus obtaining acid-soluble red mud, denoted as ARM.

[0059] Comparative Example 2

[0060] The following are Prussian blue analogue catalysts, including the following steps:

[0061] (1) Prepare 100 mL of FeSO4·7H2O solution with a concentration of 0.06 mol / L, and denote it as solution A;

[0062] (2) Prepare 50 mL of FeSO4·7H2O solution with a concentration of 0.06 mol / L, and denote it as solution B;

[0063] (3) Add solution B dropwise to solution A while stirring continuously. The dropping rate is 4 mL / min.

[0064] (4) Stir continuously for 2 hours, then let stand for 12 hours;

[0065] (5) Centrifuge, wash and collect the solid product, and then put it into an 80℃ oven to dry, thus obtaining the Prussian blue analog catalyst, denoted as Fe-Co PBA.

[0066] like Figure 1 As shown, the red mud raw material is mainly composed of hematite, gibbsite, boehmite, nepheline, hydrogarnet, and calcite. After dissolution with hydrochloric acid, the peaks of nepheline, hydrogarnet, and calcite basically disappeared. The peaks at 17.3°, 24.6°, 35.1°, 39.4°, and 43.5° in RM-Co PBA match well with the spectrum of Fe-Co PBA, corresponding to the (200), (220), (400), (420), and (422) crystal planes of Prussian blue, respectively. This indicates that Prussian blue analog particles were successfully loaded into the RM-Co PBA catalyst.

[0067] like Figure 2 As shown, the red mud raw material consists of irregular large and small particles. In ARM, the number of small particles is relatively reduced, and pores appear on the surface, providing ample sites for the dispersion of Prussian blue analog particles. In the RM-Co PBA catalyst, the Prussian blue analogs are in regular hexahedral shapes, and they are well dispersed around and within the pores of the red mud support. The surrounding scattered red mud components also play a certain dispersing role. In contrast, the Fe-Co PBA catalyst exhibits more severe agglomeration and irregular particle shapes.

[0068] Example 2

[0069] The following describes the process of activating H2O2 with different materials to degrade ciprofloxacin, including the following steps:

[0070] (1) Use 0.1 mol / L sulfuric acid and sodium hydroxide to adjust the pH of the 20 ppm ciprofloxacin solution to 5.0, and then measure 100 mL of the solution and pour it into a 250 mL conical flask;

[0071] (2) Take 0.05g of red mud raw material, RM-Co PBA prepared in Example 1, ARM prepared in Comparative Example 1 and Fe-Co PBA prepared in Comparative Example 2 respectively into ciprofloxacin solution and carry out adsorption test in a shaker at 30℃ and 200rpm.

[0072] (3) After 30 min, add 0.5 mL of H2O2 solution with a concentration of 9790 mmol / L to make the concentration of H2O2 in the whole solution system 48.9 mM for catalytic degradation reaction, and the reaction time is 60 min;

[0073] (4) Take 0.5 mL of the reaction solution every 5–30 min, and immediately add 0.2 mL of tert-butanol for quenching. Then, use a UV-Vis spectrophotometer to measure the concentration of the remaining ciprofloxacin at a wavelength of 269 nm, and calculate the degradation rate (%) by the formula: [(C0-C...] t Calculate the degradation efficiency using [) / C0]×100.

[0074] like Figure 3 As shown, within 60 min, the degradation rates of ciprofloxacin catalyzed by RM, ARM, RM-Co PBA, and Fe-Co PBA in H2O2 activation were 5.54%, 17.47%, 83.76%, and 73.29%, respectively. The higher degradation rate of the RM-Co PBA / H2O2 system is mainly due to the improved dispersibility, which exposes a large number of active sites.

[0075] Example 3

[0076] The following describes the process of RM-Co PBA activating different concentrations of H2O2 to degrade ciprofloxacin, including the following steps:

[0077] (1) Use 0.1 mol / L sulfuric acid and sodium hydroxide to adjust the pH of the 20 ppm ciprofloxacin solution to 5.0, and then measure 100 mL of the solution into 5 250 mL conical flasks.

[0078] (2) Take 5 portions of 0.05g RM-Co PBA into the ciprofloxacin solution in (1) and conduct an adsorption test in a shaker at 30℃ and 200rpm.

[0079] (3) After 30 min, 0 mL, 0.2 mL, 0.5 mL, 0.7 mL and 1.0 mL of H2O2 solution with a concentration of 9790 mmol / L were added to the five conical flasks respectively, so that the concentrations of H2O2 in the whole solution system were 0 mM, 19.6 mM, 48.9 mM, 68.5 mM and 97.9 mM respectively for catalytic degradation reaction, and the reaction time was 60 min;

[0080] (4) Take 0.5 mL of the reaction solution every 5–30 min, and immediately add 0.2 mL of tert-butanol for quenching. Then, use a UV-Vis spectrophotometer to measure the concentration of the remaining ciprofloxacin at a wavelength of 269 nm, and calculate the degradation rate (%) by the formula: [(C0-C...] t Calculate the degradation efficiency using [) / C0]×100.

[0081] like Figure 4 As shown, the degradation rate of the RM-Co PBA / H2O2 system increases with increasing H2O2 concentration. However, the increase becomes less significant when the H2O2 concentration exceeds 48.9 mM, which is due to the self-quenching of excessive reactive oxygen species.

[0082] Example 4

[0083] The following describes the degradation process of ciprofloxacin at different concentrations using the RM-Co PBA / H2O2 system, including the following steps:

[0084] (1) Prepare ciprofloxacin solutions with concentrations of 5 mg / L, 10 mg / L, 20 mg / L and 30 mg / L, and adjust the pH of the solutions to 5.0 using 0.1 mol / L sulfuric acid and sodium hydroxide;

[0085] (2) Measure 100 mL of ciprofloxacin solution of different concentrations and pour it into different 250 mL conical flasks;

[0086] (3) Take 0.05g of RM-Co PBA into the ciprofloxacin solution in (2) and conduct an adsorption test in a shaker at 30℃ and 200rpm.

[0087] (4) After 30 min, add 0.5 mL of H2O2 solution with a concentration of 9790 mmol / L to each conical flask, so that the concentration of H2O2 in the whole solution system is 48.9 mM for catalytic degradation reaction, and the reaction time is 60 min;

[0088] (5) Take 0.5 mL of the reaction solution every 5–30 min, and immediately add 0.2 mL of tert-butanol for quenching. Then, use a UV-Vis spectrophotometer to measure the concentration of the remaining ciprofloxacin at a wavelength of 269 nm, and calculate the degradation rate (%) by the formula: [(C0-C...]]. t Calculate the degradation efficiency using [) / C0]×100.

[0089] like Figure 5 As shown, the degradation rate of the RM-Co PBA / H2O2 system gradually increases with decreasing ciprofloxacin concentration, reaching over 90% when the concentration is below 10 mg / L. This indicates that the RM-Co PBA / H2O2 system has better catalytic degradation efficiency for low-concentration ciprofloxacin in water.

[0090] Example 5

[0091] The following describes the degradation process of ciprofloxacin in the RM-Co PBA / H2O2 system under different pH conditions, including the following steps:

[0092] (1) Use 0.1 mol / L sulfuric acid and sodium hydroxide to adjust the pH of 20 ppm ciprofloxacin solution to 3.0, 5.0, 7.0, 9.0 and 11.0 respectively, and then measure 100 mL of the solution of the corresponding pH and pour it into a 250 mL conical flask.

[0093] (2) 0.05 g of RM-Co PBA was placed in ciprofloxacin solutions of different pH values ​​and adsorption tests were conducted in a shaker at 30 °C and 200 rpm.

[0094] (3) After 30 min, add 0.5 mL of H2O2 solution with a concentration of 9790 mmol / L to each conical flask, so that the concentration of H2O2 in the whole solution system is 48.9 mM for catalytic degradation reaction, and the reaction time is 60 min;

[0095] (4) Take 0.5 mL of the reaction solution every 5–30 min, and immediately add 0.2 mL of tert-butanol for quenching. Then, use a UV-Vis spectrophotometer to measure the concentration of the remaining ciprofloxacin at a wavelength of 269 nm, and calculate the degradation rate (%) by the formula: [(C0-C...] t Calculate the degradation efficiency using [) / C0]×100.

[0096] like Figure 6 As shown, the degradation process of ciprofloxacin by the RM-Co PBA / H2O2 system is less affected by pH changes, and a degradation efficiency of over 80% can be obtained in solution conditions with pH = 3 to 11. This indicates that the catalyst of the present invention has strong adaptability and excellent catalytic effect in a wide range of pH systems.

[0097] Example 6

[0098] The following is the process of RM-Co PBA recycling and activated H2O2 degradation of ciprofloxacin, including the following steps:

[0099] (1) Use 0.1 mol / L sulfuric acid and sodium hydroxide to adjust the pH of the 20 ppm ciprofloxacin solution to 5.0, and then measure 100 mL of the solution and pour it into a 250 mL conical flask;

[0100] (2) Take 0.05g of RM-Co PBA in ciprofloxacin solution and conduct an adsorption test in a shaker at 30℃ and 200rpm.

[0101] (3) After 30 min, add 0.5 mL of H2O2 solution with a concentration of 9790 mmol / L to make the concentration of H2O2 in the whole solution system 48.9 mM for catalytic degradation reaction, and the reaction time is 60 min;

[0102] (4) Take 0.5 mL of the reaction solution every 5–30 min, and immediately add 0.2 mL of tert-butanol for quenching. Then, use a UV-Vis spectrophotometer to measure the concentration of the remaining ciprofloxacin at a wavelength of 269 nm, and calculate the degradation rate (%) by the formula: [(C0-C...] t Calculate the degradation efficiency using [) / C0]×100.

[0103] (5) After degradation, RM-Co PBA is collected by filtration, dried and then used to activate H2O2 to degrade ciprofloxacin. This process is repeated 5 times.

[0104] like Figure 7 As shown, after 5 cycles, the degradation rate of ciprofloxacin in the system remained above 80%, indicating that the RM-Co PBA structure is relatively stable and can be reused.

[0105] Example 7

[0106] The following describes the process of preparing supported red mud-based Prussian blue analog catalysts and their degradation of ciprofloxacin using hydrochloric acid solutions of different concentrations, including the following steps:

[0107] (1) Weigh 5g of red mud and pour it into conical flasks containing 100mL of hydrochloric acid solutions with concentrations of 1.2mol / L, 2.4mol / L, 3.6mol / L, and 4.8mol / L, respectively;

[0108] (2) Place it in a water bath and stir magnetically at 90°C for 2 hours;

[0109] (3) After the temperature reaches room temperature, add 8 mmol of ascorbic acid and stir continuously for 30 min;

[0110] (4) Add 50 mL of a 0.04 mol / L potassium cobalt cyanide solution dropwise while stirring continuously at a rate of 4 mL / min.

[0111] (5) Stir continuously for 2 hours, then let stand for 12 hours;

[0112] (6) Centrifuge, wash and collect the solid product, and then put it into an 80℃ oven to dry, thus obtaining the supported red mud-based Prussian blue analog catalyst prepared by adding hydrochloric acid solutions of different concentrations.

[0113] (7) The obtained material was subjected to a ciprofloxacin degradation test under the conditions in Example 3.

[0114] like Figure 8 As shown, RM-Co PBA prepared with hydrochloric acid solutions of different concentrations exhibited certain differences in catalytic performance, with the RM-Co PBA prepared at 2.4 mol / L showing the best performance. This is because lower hydrochloric acid concentrations result in fewer Fe ions being generated, leading to insufficient active components in the prepared RM-Co PBA; while when the hydrochloric acid concentration is too high, the excessive dissolved Fe ions react relatively quickly, resulting in poor dispersion and less exposure of active sites.

Claims

1. A method for preparing a supported red mud-based Prussian blue analog catalyst, characterized in that: Red mud raw material is acid-dissolved to obtain iron-containing liquid. Then, a reducing agent and potassium cobalt cyanide solution are added to the iron-containing liquid in sequence to carry out reduction and precipitation reactions. The resulting reaction product is separated into solid and then obtained as a solid. Among them, at least one of hydrochloric acid, sulfuric acid, and nitric acid is used as the acid solution, and the liquid-to-solid ratio is 20-200 mL: 1-10 g. The reducing agent includes at least one of ascorbic acid, formic acid, and oxalic acid, and the molar mass ratio of the reducing agent to the red mud raw material is 0.0016~0.016mol:1~10g; The molar mass ratio of potassium cobalt cyanide to red mud raw material in the potassium cobalt cyanide solution is 0.0002~0.02mol:1~10g; the dropping rate of the potassium cobalt cyanide solution is 5~10min / mL.

2. The method for preparing a supported red mud-based Prussian blue analog catalyst according to claim 1, characterized in that: The acid dissolution conditions are: temperature 85~95℃, time 1.5~4.5h.

3. The method for preparing a supported red mud-based Prussian blue analog catalyst according to claim 1, characterized in that: The conditions for the reduction reaction are: temperature 20~40℃, time 10~30min.

4. The method for preparing a supported red mud-based Prussian blue analog catalyst according to claim 1, characterized in that: The concentration of the potassium cobalt cyanide solution is 1~10mM.

5. A supported red mud-based Prussian blue analog catalyst, characterized in that: It is prepared by the method described in any one of claims 1 to 4.

6. The application of the supported red mud-based Prussian blue analog catalyst according to claim 5, characterized in that: Used to catalyze the degradation of antibiotics by H2O2.

7. The application of the supported red mud-based Prussian blue analog catalyst according to claim 6, characterized in that: This catalyst is used to catalyze the degradation of antibiotics in a solution system using H2O2; the antibiotic is ciprofloxacin; the concentration of the supported red mud-based Prussian blue analog catalyst in the solution system is not less than 0.5 g / L; the concentration of H2O2 in the solution system is not less than 48.9 mM; the concentration of the antibiotic in the solution system is 5~30 ppm; the initial pH of the solution system is 3~11, and the temperature of the solution system is 20~40℃.

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