Preparation method and application of cof reinforced pps immobilized ternary mn-based catalyst

Abstract

The application discloses a preparation method and application of a COF reinforced PPS solidified ternary Mn-based catalyst, and mainly comprises the following steps. A cleaned PPS filter material is reacted with trimethylchlorosilane to obtain a chloromethylated PPS filter material, and then the chloromethylated PPS filter material is reacted with ammonia water to introduce an amino group into the PPS filter material. A ternary Mn-based catalyst is solidified on the PPS filter material by an in-situ synthesis method. Finally, an amino group is used as an anchor point, and a COF fixing layer is formed in-situ on the PPS filter material, so that a COF reinforced PPS-based low-temperature denitration catalyst is obtained. The catalyst has good denitration capacity at low temperature, can meet the integration requirement of denitration and dust removal, and greatly solves the problem that a catalyst prepared by a traditional method is easy to fall off.

Description

Technical Field

[0001] This invention belongs to the field of green catalytic low-temperature denitrification, and relates to the preparation and application of a COF-enhanced PPS-supported ternary Mn-based catalyst. Background Technology

[0002] The exhaust gas released from coal combustion contains large amounts of NOx (x=1,2) and particulate matter, causing a series of environmental and human health problems. Therefore, selective catalytic reduction (SCR) technology for NOx removal and baghouse dust collection technology for controlling particulate matter emissions have been widely researched and applied. Commercially available V₂O₅ + WO₃(MoO₃) / TiO₂ catalysts suffer from a high operating window (300-400℃) and the toxicity of V-based catalysts. Furthermore, current SCR catalysts still have limitations such as a high activity temperature window (200-300℃) and complex preparation methods (high-temperature calcination and high-temperature high-pressure hydrothermal methods), making them unsuitable for simple and effective denitrification of low-temperature exhaust gas (<200℃) after dust removal and desulfurization.

[0003] Baghouse dust collection, as one of the most competitive dust removal technologies, has been widely used in stationary source dust collection. Denitrification filter bags combining baghouse dust collection with low-temperature SCR technology can simultaneously remove NOx and particulate matter from coal-fired flue gas. The preparation process of denitrification filter bags typically involves catalyst preparation and catalyst immobilization, which presents challenges such as an insufficiently simple preparation process, uneven dispersion of active components, and poor bonding strength between the active components and the filter media.

[0004] Polyphenylene sulfide (PPS) filter media, as a chemically synthesized filter medium, possesses high thermal stability, high strength, good heat resistance, and chemical corrosion resistance. This invention uses PPS filter media as a carrier to prepare a series of COF-reinforced PPS-supported ternary Mn-based low-temperature denitrification catalysts. These catalysts not only overcome the problems of insufficient low-temperature activity below 200℃ and complex preparation methods of existing low-temperature SCR catalysts, but also endow them with better low-temperature denitrification activity and SO2 resistance, enabling them to effectively denitrify low-temperature exhaust gases after dust removal and desulfurization. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention proposes a method for preparing and applying a COF-enhanced PPS-supported ternary Mn-based low-temperature denitrification catalyst; specifically, it is a manganese-based ternary low-temperature denitrification filter material with a simple preparation process and high catalytic activity, thereby solving problems such as insufficient low-temperature activity below 200℃ and poor bonding strength between the active component and the filter material during low-temperature denitrification.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A method for preparing a COF-enhanced PPS-supported ternary Mn-based catalyst includes the following steps: (1) PPS filter media are placed in different solvents and heated under reflux, then rinsed and dried to obtain pretreated PPS filter media; the solvent is any one or more of ethanol, cyclohexane, distilled water and acetone; (2) Chloromethylation of PPS filter media: Pretreated PPS filter media, paraformaldehyde, tin tetrachloride, trimethylchlorosilane and 1,2-dichloroethane are added to a hydrothermal reactor and then placed in an oven for reaction. After the reaction is completed, the filter media is taken out and cleaned with ethanol. After drying, chloromethylated PPS filter media PPS-Cl is obtained. (3) Amination of PPS filter media: After mixing and reacting PPS-Cl with ammonia water, the filter media is taken out and washed with water. After drying, the amination of PPS filter media PPS-NH2 is obtained. (4) In-situ supported ternary Mn-based catalyst: PPS-NH2, FeCl3, CeCl3•7H2O• and water were mixed evenly and stirred at room temperature. Then potassium permanganate was added and stirred evenly and heated and stirred to react. After the reaction was completed, the PPS filter material was taken out and washed with water. After drying, the PPS supported ternary Mn-based catalyst PPS-Cat was obtained. (5) COF-enhanced PPS-supported ternary Mn-based catalyst: PPS-Cat was added to a dialdehyde acetonitrile solution and stirred at room temperature. 1,3,5-tris(4-aminophenyl)benzene (TPB) and Sc(OTf)3 were added to the reaction solution and mixed evenly. The mixture was allowed to stand at room temperature for a certain period of time. The filter material was removed and cleaned with methanol. After drying, the COF-enhanced PPS-supported ternary Mn-based catalyst PPS-Cat-COF was obtained.

[0007] Furthermore, in step (1), the solvent is any one or more of ethanol, cyclohexane, distilled water, and acetone; the mass-volume ratio of PPS filter media to solvent is 1:15-1:30 g / mL, and the reflux time is 4-10 h.

[0008] Furthermore, in step (2), the reaction solution is composed of paraformaldehyde, tin tetrachloride, trimethylchlorosilane and 1,2-dichloroethane. The mass-to-volume ratio of PPS filter media to the reaction solution is 1:20-1:80 g / mL. The molar concentrations of paraformaldehyde, tin tetrachloride and trimethylchlorosilane in the reaction solution are 0.5-1.5 mol / L, 0.25-0.75 mol / L and 0.5-1.5 mol / L, respectively. The molar ratio of paraformaldehyde, tin tetrachloride and trimethylchlorosilane is 2:1:2.

[0009] Furthermore, the reaction temperature in step (2) is 50-100℃, and the reaction time is 24-72 h.

[0010] Furthermore, in step (3), the mass concentration of ammonia is 10-30%, the mass-volume ratio of PPS-Cl to ammonia is 1:30-1:60 g / mL, the reaction temperature is 60-100℃, and the reaction time is 2-12 h.

[0011] Furthermore, in step (4), the molar ratio of FeCl3 to CeCl3•7H2O is 1:5-1:30, the molar concentration of FeCl3 is 20 mmol / L; the mass-volume ratio of PPS-NH2 to FeCl3 and CeCl3•7H2O solution is 1:30-1:80 g / mL; and the reaction time in the mixed solution of PPS-NH2 with FeCl3 and CeCl3•7H2O is 18-36 h.

[0012] Furthermore, in step (4), after adding potassium permanganate, the molar ratio of iron to manganese in the solution is 1:3-1:22; after adding potassium permanganate, the reaction temperature is 25-100℃; and the reaction time is 20-30 h.

[0013] Further, in step (5), the dialdehyde is one of 1,4-dialdehyde-2,5-divinylbenzene (DVA), 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP), and 1,3,5-tris(p-formylphenyl)benzene (TFPB), and the concentration of the dialdehyde acetonitrile solution is 30-100 mmol / L.

[0014] Furthermore, in step (5), the mass-to-volume ratio of PPS-Cat to dialdehyde solution is 1:50-1:100 g / mL, the stirring reaction time is 2-8 h, the amount of TPB added is the same as the amount of dialdehyde in the solution, the amount of Sc(OTf)3 added is 2-6% of the amount of dialdehyde, and the static reaction time is 0.5-4 h.

[0015] Furthermore, the preparation method according to any one of claims 1-9 provides the application of COF-enhanced PPS-supported ternary Mn-based catalysts in catalytic denitrification.

[0016] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows: This invention prepares a COF-enhanced PPS-supported ternary Mn-based catalyst. This catalyst has advantages such as simple preparation process and excellent catalytic effect. It effectively solves the problems of insufficient activity below 200℃ and poor bonding strength between the active component and the filter media in existing low-temperature denitrification processes. Attached Figure Description

[0017] Figure 1 Preparation route of COF-enhanced PPS-supported ternary Mn-based catalyst. Detailed Implementation

[0018] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and not for limiting the scope of the invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above-described invention. Where specific experimental steps or conditions are not specified in the embodiments, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Where the manufacturers of reagents or instruments are not specified, they are all commercially available conventional reagent products.

[0019] The following examples illustrate the preparation route of the COF-enhanced PPS-supported ternary Mn-based catalyst. Figure 1 As shown. Example 1

[0020] This embodiment provides a method for preparing a COF-enhanced PPS-supported ternary Mn-based catalyst, comprising the following steps: (1) After refluxing and stirring 5 g of PPS filter material and 75 mL of water in a round-bottom flask for 4 h, the filter material was removed and placed in a round-bottom flask containing 75 mL of acetone and refluxed and stirred for 4 h. After rinsing and drying, the pretreated PPS filter material was obtained.

[0021] (2) Chloromethylation of PPS filter media: 1 g of PPS filter media was added to 20 mL of a 1,2-dichloroethane solution containing paraformaldehyde, tin tetrachloride, and trimethylchlorosilane, wherein the molar concentrations of paraformaldehyde, tin tetrachloride, and trimethylchlorosilane were 0.5 mol / L, 0.25 mol / L, and 0.5 mol / L, respectively. The above filter media and solution mixture was added to a hydrothermal reactor and heated to 50 °C. o After reacting in an oven at C for 24 h, the filter material was removed, cleaned with ethanol, and dried to obtain chloromethylated PPS filter material PPS-Cl.

[0022] (3) Amination of PPS filter media: 1 g of PPS-Cl filter media was added to 30 mL of a 10% ammonia solution. The mixture of the above filter media and solution was added to a hydrothermal reactor and reacted at 60°C for 2 h. Finally, the filter media was removed and washed with distilled water until neutral. After drying, amination of PPS-NH2 was obtained.

[0023] (4) In-situ supported ternary Mn-based catalyst: 1 g of PPS-NH2 was added to 30 mL of a solution composed of FeCl3, CeCl3•7H2O and water and mixed evenly. The concentration of FeCl3 was 20 mmol / L and the concentration of CeCl3•7H2O was 100 mmol / L. After stirring at room temperature for 18 h, 1.8 mmol of potassium permanganate was added and stirred evenly. After stirring and reacting at room temperature for 20 h, the PPS filter material was removed, cleaned with water, and dried to obtain the PPS-supported ternary Mn-based catalyst PPS-Cat.

[0024] (5) COF-enhanced PPS-supported ternary Mn-based catalyst: 1 g PPS-Cat was added to 50 mL of 30 mmol / L DVA acetonitrile solution and stirred at room temperature for 2 h. 1.5 mmol TPB and 30 mmol / L DVA acetonitrile solution were then added to the reaction solution. μ mol Sc(OTf)3 was mixed evenly and allowed to stand at room temperature for 0.5 h. The filter material was then removed, washed with methanol, and dried to obtain COF-enhanced PPS-supported ternary Mn-based catalyst PPS-Cat-COF. Example 2

[0025] This embodiment provides a method for preparing a COF-enhanced PPS-supported ternary Mn-based catalyst, comprising the following steps: (1) After refluxing and stirring 5 g of PPS filter material and 100 mL of cyclohexane in a round-bottom flask for 6 h, the filter material was removed and placed in a round-bottom flask containing 100 mL of ethanol and refluxed and stirred for 6 h. After rinsing and drying, the pretreated PPS filter material was obtained.

[0026] (2) Chloromethylation of PPS filter media: 1 g of PPS filter media was added to 50 mL of a 1,2-dichloroethane solution containing paraformaldehyde, tin tetrachloride, and trimethylchlorosilane, wherein the molar concentrations of paraformaldehyde, tin tetrachloride, and trimethylchlorosilane were 1 mol / L, 0.5 mol / L, and 1 mol / L, respectively. The above mixture of filter media and solution was added to a hydrothermal reactor and heated to 80 °C. o After reacting in an oven at C for 48 h, the filter material was removed, cleaned with ethanol, and dried to obtain chloromethylated PPS filter material PPS-Cl.

[0027] (3) Amination of PPS filter media: 1 g of PPS-Cl filter media was added to 50 mL of ammonia solution with a mass concentration of 15%. The above filter media and solution mixture was added to a hydrothermal reactor and reacted at 80℃ for 8 h. Finally, the filter media was taken out and washed with distilled water until neutral. After drying, amination of PPS-NH2 was obtained.

[0028] (4) In-situ supported ternary Mn-based catalyst: 1 g of PPS-NH2 was added to 50 mL of a solution composed of FeCl3, CeCl3•7H2O and water and mixed evenly. The concentration of FeCl3 was 20 mmol / L and the concentration of CeCl3•7H2O was 150 mmol / L. After stirring at room temperature for 28 h, 12 mmol of potassium permanganate was added and stirred evenly. After stirring and reacting at 50 °C for 24 h, the PPS filter material was removed, cleaned with water, and dried to obtain the PPS-supported ternary Mn-based catalyst PPS-Cat.

[0029] (5) COF-enhanced PPS-supported ternary Mn-based catalyst: 1 g of PPS-Cat was added to 80 mL of 80 mmol / L DVA acetonitrile solution and stirred at room temperature for 6 h. 6.4 mmol TPB and 0.256 mmol Sc(OTf)3 were added to the reaction solution and mixed thoroughly. After standing at room temperature for 2.5 h, the filter material was removed, washed with methanol, and dried to obtain the COF-enhanced PPS-supported ternary Mn-based catalyst PPS-Cat-COF. Example 3

[0030] This embodiment provides a method for preparing a COF-enhanced PPS-supported ternary Mn-based catalyst, comprising the following steps: (1) After refluxing and stirring 5 g of PPS filter material and 150 mL of cyclohexane in a round-bottom flask for 10 h, the filter material was removed and placed in a round-bottom flask containing 150 mL of ethanol and refluxed and stirred for 10 h. After rinsing and drying, the pretreated PPS filter material was obtained.

[0031] (2) Chloromethylation of PPS filter media: 1 g of PPS filter media was added to 80 mL of a 1,2-dichloroethane solution containing paraformaldehyde, tin tetrachloride, and trimethylchlorosilane, wherein the molar concentrations of paraformaldehyde, tin tetrachloride, and trimethylchlorosilane were 1.5 mol / L, 0.75 mol / L, and 1.5 mol / L, respectively. The above filter media and solution mixture was added to a hydrothermal reactor and heated to 100 °C. o After reacting in an oven at C for 72 h, the filter material was removed, cleaned with ethanol, and dried to obtain chloromethylated PPS filter material PPS-Cl.

[0032] (3) Amination of PPS filter media: 1 g of PPS-Cl filter media was added to 60 mL of ammonia solution with a mass concentration of 30%. The above filter media and solution mixture was added to a hydrothermal reactor and reacted at 100℃ for 12 h. Finally, the filter media was taken out and washed with distilled water until neutral. After drying, amination of PPS-NH2 was obtained.

[0033] (4) In-situ supported ternary Mn-based catalyst: 1 g of PPS-NH2 was added to 80 mL of a solution composed of FeCl3, CeCl3•7H2O and water and mixed evenly. The concentration of FeCl3 was 20 mmol / L and the concentration of CeCl3•7H2O was 0.6 mol / L. After stirring at room temperature for 36 h, 35.2 mmol of potassium permanganate was added and stirred evenly. After stirring and reacting at 100℃ for 30 h, the PPS filter material was removed, cleaned with water, and dried to obtain the PPS-supported ternary Mn-based catalyst PPS-Cat.

[0034] (5) COF-enhanced PPS-supported ternary Mn-based catalyst: 1 g PPS-Cat was added to 100 mL of 100 mmol / L DVA acetonitrile solution and stirred at room temperature for 8 h. 10 mmol TPB and 0.6 mmol Sc(OTf)3 were added to the reaction solution and mixed evenly. After standing at room temperature for 4 h, the filter material was removed, washed with methanol, and dried to obtain the COF-enhanced PPS-supported ternary Mn-based catalyst PPS-Cat-COF.

[0035] Comparative Example 1 The preparation method of the PPS-supported ternary Mn-based catalyst without COF enhancement in this comparative example is as follows: (1) After refluxing and stirring 5 g of PPS filter material and 100 mL of cyclohexane in a round-bottom flask for 6 h, the filter material was removed and placed in a round-bottom flask containing 100 mL of ethanol and refluxed and stirred for 6 h. After rinsing and drying, the pretreated PPS filter material was obtained.

[0036] (2) Chloromethylation of PPS filter media: 1 g of PPS filter media was added to 50 mL of a 1,2-dichloroethane solution containing paraformaldehyde, tin tetrachloride, and trimethylchlorosilane, wherein the molar concentrations of paraformaldehyde, tin tetrachloride, and trimethylchlorosilane were 1 mol / L, 0.5 mol / L, and 1 mol / L, respectively. The above mixture of filter media and solution was added to a hydrothermal reactor and heated to 80 °C. o After reacting in an oven at C for 48 h, the filter material was removed, cleaned with ethanol, and dried to obtain chloromethylated PPS filter material PPS-Cl.

[0037] (3) Amination of PPS filter media: 1 g of PPS-Cl filter media was added to 50 mL of ammonia solution with a mass concentration of 15%. The above filter media and solution mixture was added to a hydrothermal reactor and reacted at 80℃ for 8 h. Finally, the filter media was taken out and washed with distilled water until neutral. After drying, amination of PPS-NH2 was obtained.

[0038] (4) In-situ supported ternary Mn-based catalyst: 1 g of PPS-NH2 was added to 50 mL of a solution composed of FeCl3, CeCl3•7H2O and water and mixed evenly. The concentration of FeCl3 was 20 mmol / L and the concentration of CeCl3•7H2O was 150 mmol / L. After stirring at room temperature for 28 h, 12 mmol of potassium permanganate was added and stirred evenly. After stirring and reacting at 50 °C for 24 h, the PPS filter material was removed, cleaned with water, and dried to obtain the PPS-supported ternary Mn-based catalyst PPS-Cat.

[0039] Comparative Example 2 The preparation method of the PPS-supported ternary Mn-based catalyst without COF enhancement in this comparative example is as follows: (1) After refluxing and stirring 5 g of PPS filter material and 150 mL of cyclohexane in a round-bottom flask for 10 h, the filter material was removed and placed in a round-bottom flask containing 150 mL of ethanol and refluxed and stirred for 10 h. After rinsing and drying, the pretreated PPS filter material was obtained.

[0040] (2) Chloromethylation of PPS filter media: 1 g of PPS filter media was added to 80 mL of a 1,2-dichloroethane solution containing paraformaldehyde, tin tetrachloride, and trimethylchlorosilane, wherein the molar concentrations of paraformaldehyde, tin tetrachloride, and trimethylchlorosilane were 1.5 mol / L, 0.75 mol / L, and 1.5 mol / L, respectively. The above filter media and solution mixture was added to a hydrothermal reactor and heated to 100 °C. o After reacting in an oven at C for 72 h, the filter material was removed, cleaned with ethanol, and dried to obtain chloromethylated PPS filter material PPS-Cl.

[0041] (3) Amination of PPS filter media: 1 g of PPS-Cl filter media was added to 60 mL of ammonia solution with a mass concentration of 30%. The above filter media and solution mixture was added to a hydrothermal reactor and reacted at 100℃ for 12 h. Finally, the filter media was taken out and washed with distilled water until neutral. After drying, amination of PPS-NH2 was obtained.

[0042] (4) In-situ supported ternary Mn-based catalyst: 1 g of PPS-NH2 was added to 80 mL of a solution composed of FeCl3, CeCl3•7H2O and water and mixed evenly. The concentration of FeCl3 was 20 mmol / L and the concentration of CeCl3•7H2O was 0.6 mol / L. After stirring at room temperature for 36 h, 35.2 mmol of potassium permanganate was added and stirred evenly. After stirring and reacting at 100℃ for 30 h, the PPS filter material was removed, cleaned with water, and dried to obtain the PPS-supported ternary Mn-based catalyst PPS-Cat.

[0043] Performance testing The PPS filter media catalysts prepared in the above examples and comparative examples were applied to the denitrification reaction according to the following scheme: The catalyst was evaluated in a self-made tubular SCR reactor. The reactor was externally electrically heated, and thermocouples were placed next to the catalyst bed in the reaction tube to measure the temperature. A steel gas cylinder was used to simulate the flue gas composition, which included NO, O2, N2, and NH3 as the reducing gas. The volume fractions of NO and NH3 were both 0.04-0.06%, the volume fraction of O2 was 5%, and the remainder was N2. The gas flow rate was 700 mL·min. -1 The temperature was controlled between 120-200℃, and gas analysis was performed using a British KM940 flue gas analyzer. The experimental results are shown in Table 1.

[0044]

[0045] As shown in Table 1 above, the catalysts of Examples 1-3 of this invention exhibit higher catalytic activity compared to Comparative Examples 1-2. This may be due to the activation function of the COF microenvironment on the catalytic sites. Among them, Example 3 can achieve a denitrification rate of 91% at a lower temperature, and even after introducing SO2, the denitrification rate can still reach 82%, demonstrating excellent sulfur resistance performance.

[0046] The foregoing has shown and described the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a COF-enhanced PPS-supported ternary Mn-based catalyst, characterized in that, Includes the following steps: (1) PPS filter media are placed in different solvents and heated under reflux, then rinsed and dried to obtain pretreated PPS filter media; the solvent is any one or more of ethanol, cyclohexane, distilled water and acetone; (2) Chloromethylation of PPS filter media: Pretreated PPS filter media, paraformaldehyde, tin tetrachloride, trimethylchlorosilane and 1,2-dichloroethane are added to a hydrothermal reactor and then placed in an oven for reaction. After the reaction is completed, the filter media is taken out and cleaned with ethanol. After drying, chloromethylated PPS filter media PPS-Cl is obtained. (3) Amination of PPS filter media: After mixing and reacting PPS-Cl with ammonia water, the filter media is taken out and washed with water. After drying, the amination of PPS filter media PPS-NH2 is obtained. (4) In-situ supported ternary Mn-based catalyst: PPS-NH2, FeCl3, CeCl3•7H2O• and water were mixed evenly and stirred at room temperature. Then potassium permanganate was added and stirred evenly and heated and stirred to react. After the reaction was completed, the PPS filter material was taken out and washed with water. After drying, the PPS supported ternary Mn-based catalyst PPS-Cat was obtained. (5) COF-enhanced PPS-supported ternary Mn-based catalyst: PPS-Cat was added to a dialdehyde acetonitrile solution and stirred at room temperature. 1,3,5-tris(4-aminophenyl)benzene (TPB) and Sc(OTf)3 were added to the reaction solution and mixed evenly. The mixture was allowed to stand at room temperature for a certain period of time. The filter material was removed and cleaned with methanol. After drying, the COF-enhanced PPS-supported ternary Mn-based catalyst PPS-Cat-COF was obtained.

2. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (1), the mass-to-volume ratio of PPS filter media to solvent is 1:15-1:30 g / mL, and the reflux time is 4-10 h.

3. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (2), the reaction solution is composed of paraformaldehyde, tin tetrachloride, trimethylchlorosilane and 1,2-dichloroethane. The mass-to-volume ratio of PPS filter media to the reaction solution is 1:20-1:80 g / mL. The molar concentrations of paraformaldehyde, tin tetrachloride and trimethylchlorosilane in the reaction solution are 0.5-1.5 mol / L, 0.25-0.75 mol / L and 0.5-1.5 mol / L, respectively. The molar ratio of paraformaldehyde, tin tetrachloride and trimethylchlorosilane is 2:1:

2.

4. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: The reaction temperature in step (2) is 50-100℃ and the reaction time is 24-72 h.

5. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (3), the mass concentration of ammonia is 10-30%, the mass-volume ratio of PPS-Cl to ammonia is 1:30-1:60 g / mL, the reaction temperature is 60-100℃, and the reaction time is 2-12 h.

6. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (4), the molar ratio of FeCl3 to CeCl3•7H2O is 1:5-1:30, and the molar concentration of FeCl3 is 20 mmol / L; the mass-volume ratio of PPS-NH2 to FeCl3 and CeCl3•7H2O solution is 1:30-1:80 g / mL; and the reaction time in the mixed solution of PPS-NH2, FeCl3, and CeCl3•7H2O is 18-36 h.

7. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (4), after adding potassium permanganate, the molar ratio of iron to manganese in the solution is 1:3-1:22; after adding potassium permanganate, the reaction temperature is 25-100℃; and the reaction time is 20-30 h.

8. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (5), the dialdehyde is one of 1,4-dialdehyde-2,5-divinylbenzene and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, and the concentration of the dialdehyde acetonitrile solution is 30-100 mmol / L.

9. The method for preparing the COF-enhanced PPS-supported ternary Mn-based catalyst according to claim 1, characterized in that: In step (5), the mass-to-volume ratio of PPS-Cat to dialdehyde solution is 1:50-1:100 g / mL, the stirring reaction time is 2-8 h, the amount of TPB added is the same as the amount of dialdehyde in the solution, the amount of Sc(OTf)3 added is 2-6% of the amount of dialdehyde, and the static reaction time is 0.5-4 h.

10. The application of the COF-enhanced PPS-supported ternary Mn-based catalyst obtained by the preparation method according to any one of claims 1-9 in catalytic denitrification.

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