Metal-ceramic composite dedusting integrated filter material loaded with catalyst

Abstract

The invention discloses a catalyst-loaded metal-ceramic composite dedusting integrated filter material, and belongs to the technical field of filter material preparation. The invention discloses a metal-ceramic composite dedusting integrated filter material loaded with a catalyst. The ceramic material is prepared from the following components in parts by weight: 12-17 parts of nickel-based alloy, 14-23 parts of cobalt-based alloy, 5-10 parts of titanium alloy, 30-55 parts of oxide ceramic, 20-26 parts of carbide ceramic, 5-8 parts of corn starch, 6-10 parts of polyvinyl alcohol, 0.8-1.5 parts of a noble metal catalyst, 1-5 parts of a rare earth composite catalyst and 18-22 parts of a composite reinforcing agent. The filter material prepared from the substances has excellent filtering efficiency and corrosion resistance.

Description

Technical Field

[0001] This invention belongs to the field of filter material preparation technology, specifically relating to a metal-ceramic composite dust removal integrated filter material supported on a catalyst. Background Technology

[0002] Traditional flue gas purification processes typically employ a series connection of dust removal, desulfurization, and denitrification units. This step-by-step approach not only results in large equipment footprints and high system redundancy, but also necessitates coordinating the operation of multiple units during maintenance, leading to high labor and material costs. Furthermore, the poor compatibility of individual components during fluctuations in operating conditions can easily cause a decline in purification efficiency. With increasingly stringent environmental emission restrictions, the pressure on flue gas treatment in industrial furnaces such as glass melting furnaces, coking furnaces, and biomass boilers in non-power sectors has increased dramatically—their emissions generally exhibit characteristics such as low temperatures, complex pollutant compositions, and dynamically changing concentrations, making it difficult for traditional processes to achieve efficient and stable compliance. Against this backdrop, catalyst-loaded metal-ceramic composite integrated dust removal filter media has emerged.

[0003] Patent CN118698235A discloses a regenerable purification filter bag for denitrification and its preparation method. Compared with traditional filter bags, this filter bag mainly uses a filter catalyst membrane layer formed by setting a filter substrate membrane layer and a catalyst membrane layer as the filter element. The filter substrate membrane layer includes a flexible metal support layer and a porous metal powder layer attached to the flexible metal support layer. The catalyst membrane layer is attached to the inner side of the filter substrate membrane layer. This filter element has good plasticity, toughness, and strength, and can simultaneously perform filtration and denitrification functions. It solves the technical problems of ceramic filter materials being brittle, thick, and having limited application range, as well as the technical problems of catalyst clogging and deactivation easily caused by dust removal and denitrification separation. Furthermore, it further controls the membrane pore size, making the inner catalyst membrane layer have a larger pore size and the surface filter substrate membrane layer have a smaller pore size, solving the problems of difficulty in backflushing and cleaning / regeneration. Although the aforementioned patents achieve integrated dust removal and denitrification through filtration and catalytic membrane layers and improve the problems of high brittleness and difficulty in regeneration of ceramic filter materials, their flexible metal support layer is prone to creep under long-term high-temperature flue gas scouring, leading to the risk of membrane peeling; and the pore structure of the metal powder porous layer is difficult to be further refined due to process limitations, resulting in limited efficiency in capturing ultrafine particles. Summary of the Invention

[0004] The purpose of this invention is to provide a metal-ceramic composite dust removal filter material with a catalyst loading, which solves the technical problems of poor filtration effect and corrosion resistance of existing filter materials.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a catalyst-supported metal-ceramic composite dust removal integrated filter material, which is composed of the following parts by weight: 12-17 parts nickel-based alloy, 14-23 parts cobalt-based alloy, 5-10 parts titanium alloy, 30-55 parts oxide ceramic, 20-26 parts carbide ceramic, 5-8 parts corn starch, 6-10 parts polyvinyl alcohol, 0.8-1.5 parts precious metal catalyst, 1-5 parts rare earth composite catalyst, and 18-22 parts composite reinforcing agent.

[0006] Preferably, the oxide ceramic is composed of one or more of alumina, zirconium oxide, magnesium oxide, beryllium oxide and titanium dioxide; the carbide ceramic is composed of one or more of silicon carbide, boron carbide, titanium carbide, tungsten carbide, zirconium carbide and tantalum carbide; the noble metal catalyst is composed of one or more of platinum, palladium, rhodium, silver, ruthenium and gold; and the rare earth composite catalyst is composed of one or more of cerium oxide, lanthanum oxide, samarium oxide and neodymium oxide.

[0007] Preferably, the preparation method of the composite reinforcing agent includes the following steps: Q1: Methyl 3,5-dihydroxybenzoate, 8-bromo-1-octene, anhydrous potassium carbonate, and tetrabutylammonium bromide were added to a container containing acetone, stirred evenly at room temperature, and then refluxed. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated again to obtain organic compound 1. Organic compound 1 was added to a container containing tetrahydrofuran, and lithium aluminum hydride was slowly added under an ice bath atmosphere. The mixture was then reacted at room temperature under a nitrogen atmosphere. After the reaction was completed, hydrochloric acid aqueous solution was added under an ice bath atmosphere, filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated again to obtain organic compound 2. Q2: Organic compound 2 was added to a container containing dichloromethane. Phosphorus tribromide was added under nitrogen atmosphere and an ice bath. After stirring in the ice bath, the reaction was carried out at room temperature. After the reaction was completed, methanol was added, stirred, extracted, washed, dried, and rotary evaporated to obtain organic compound 3. Organic compound 3 was added to a container containing N,N-dimethylformamide, followed by sodium azide. After stirring at room temperature, the reaction was carried out at elevated temperature. After the reaction was completed, saturated sodium bicarbonate aqueous solution was added, stirred, followed by sodium hypochlorite. After stirring, extracted, washed, dried, and rotary evaporated to obtain organic compound 4. Q3: Add organic compound 4 to a container containing tetrahydrofuran. Under ice bath conditions, add lithium aluminum hydride and react at room temperature under nitrogen atmosphere. After the reaction is complete, under ice bath conditions, add distilled water and sodium hydroxide aqueous solution, filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and organic compound 5 to a container containing toluene. After reflux reaction, cool, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add organic compound 6 to a container containing toluene, add bis(trimethylsiloxymethylsilane) and Karstedt catalyst under nitrogen atmosphere, stir at room temperature, heat to react, cool, rotary evaporate, dissolve, purify, and obtain composite reinforcing agent.

[0008] The synthesis reaction formula for the composite reinforcing agent in the above process is as follows:

[0009] The mass spectrometry analysis results for organic compound 1 were: m / z: 388.26 (100.0%), 389.26 (26.0%), 390.27 (4.2%); for organic compound 2: m / z: 360.27 (100.0%), 361.27 (25.4%), 362.27 (3.6%); for organic compound 3: m / z: 422.18 (100.0%), 424.18 (97.3%), 423.19 (25.4%), 425.18 (24.3%), 424.19 (3.5%), 426.19 (3.0%); and for organic compound 4: m / z: 385.27 (100.0%), 386.28. (25.4%), 387.28 (3.5%), 386.27 (1.1%); Mass spectrometry analysis results of organic compound 5: m / z: 359.28 (100.0%), 360.29 (25.4%), 361.29 (3.5%); Mass spectrometry analysis results of organic compound 6: m / z: 1126.55 (100.0%), 1127.55 (71.3%), 1128.56 (25.2%), 1129.56 (7.0%), 1128.55 (2.2%), 1130.56 (1.4%); Mass spectrometry analysis results of composite reinforcing agent: m / z: 2015.92 (100.0%), 2016.92 (73.8%), 2014.92 (61.6%), 2017.92 (52.3%), 2016.93 (35.4%), 2017.93 (34.4%), 2018.93 (28.0%), 2018.92 (25.7%), 2019.92 (16.8%), 2019.93 (11.0%), 2020.92 (7.5%), 2020.93 (5.7%), 2021.92 (2.9%), 2018.94 (2.8%), 2021.93 (2.7%), 2019.91 (2.4%), 2015.93 (1.5%), 2022.92 (1.4%), 2019.94 (1.1%), 2020.91 (1.1%).

[0010] Preferably, in Q1, the ratio of methyl 3,5-dihydroxybenzoate, 8-bromo-1-octene, anhydrous potassium carbonate, tetrabutylammonium bromide, and acetone is (2.25-3.72) g : (6.02-6.84) g : (5.88-6.26) g : (0.42-0.56) g : (220-280) mL. The mixture is heated to 70-80℃ and refluxed for 20-24 h. It is then dissolved in dichloromethane, washed with distilled water and saturated sodium chloride solution, and dried with anhydrous magnesium sulfate. The ratio of organic compound 1, tetrahydrofuran, and lithium aluminum hydride is (4.52-5.46) g : (70-75) mL : (0.81-0.92) g. The reaction time is 10-12 h at room temperature, and hydrochloric acid solution is added to adjust the pH to 5-5.5.

[0011] Preferably, in Q2, the ratio of organic compound 2, dichloromethane, phosphorus tribromide, and methanol is (2.88-3.12) g : (46-54) mL : (7.82-8.22) g : (1.58-2.36) mL, the stirring time in an ice bath is 10-15 min, the reaction is carried out at room temperature for 2-4 h, the stirring time is 1-2 h, and the mixture is washed with distilled water, 5 wt% sodium bicarbonate solution, and saturated sodium chloride aqueous solution, and dried with anhydrous magnesium sulfate; the ratio of organic compound 3, N,N-dimethylformamide, sodium azide, and sodium hypochlorite is (2.2-3.1) g : (10-12) mL : (0.72-0.78) g : (1.8-2.3) mL, the mixture is stirred at room temperature for 10-14 h, the temperature is raised to 40-45℃ and the reaction is carried out for 3-5 h, and the mixture is extracted with dichloromethane.

[0012] Preferably, in Q3, the ratio of organic compound 4, tetrahydrofuran, and lithium aluminum hydride is (1.68-2.33) g : (60-75) mL : (0.41-0.52) g, the reaction is carried out at room temperature for 10-12 h, and the concentration of sodium hydroxide aqueous solution is 1 g / mL; the ratio of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, organic compound 5, and toluene is (0.42-0.57) g : (0.55-0.72) g : (75-85) mL, the reaction is carried out at 100-120℃ under reflux for 10-12 h.

[0013] Preferably, in Q4, the ratio of organic compound 6, toluene, bis(trimethylsiloxymethylsilane) and Karstedt catalyst is (0.32-0.48) g : (80-90) mL : (0.21-0.33) g : (4-6) μL, and the mixture is stirred at room temperature for 10-14 min, and then heated to 110-120℃ for 3-5 h.

[0014] Preferably, the preparation method of the catalyst-supported metal-ceramic composite dust removal integrated filter material includes the following steps: Step 1: Ball mill the nickel-based alloy, cobalt-based alloy, titanium alloy, oxide ceramic and carbide ceramic together. Polyvinyl alcohol and corn starch are added during the ball milling process to obtain a mixed powder. Step 2: Add the precious metal catalyst and rare earth composite catalyst to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry-press the mixed powder, sinter it, cool it, then immerse it in a catalyst solution and calcine it to obtain the filter material; Step 4: Spray the composite reinforcing agent onto the surface of the filter material to obtain a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

[0015] Preferably, in step three, the sintering process is as follows: first, the temperature is increased from room temperature to 350-500℃ at a heating rate of 0.5-1℃ / min, and held at 350℃, 400℃, 450℃ and 500℃ for 1-2 hours each; then, the temperature is increased to 800-1000℃ at a heating rate of 3-5℃ / min and held for 1-2 hours; then, the temperature is increased to 1300-1500℃ and held for 1-3 hours in an argon atmosphere.

[0016] Preferably, in step four, the composite reinforcing agent is loaded into an air compressor and then sprayed onto the filter material at an air pressure of 0.3-0.5 MPa. The nozzle moves at a speed of 10-20 cm / s and the vertical distance between the nozzle and the filter material is 30-35 cm.

[0017] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. The filter material of this invention integrates high-efficiency filtration and catalysis functions through an integrated design. The metal-ceramic composite matrix combines toughness and hardness, ensuring excellent mechanical strength, thermal stability, and corrosion resistance, providing support for long-term operation. By loading a catalyst on the surface, it deeply filters dust while catalyzing gaseous pollutants, achieving synergistic purification of multiple pollutants. The added composite reinforcing agent forms a hydrophobic / oleophobic protective layer on the surface of the filter material, significantly reducing dust adhesion, making dust removal easier, and effectively resisting catalyst poisoning and pore blockage caused by moisture, acid mist, and sticky particles. Thus, while maintaining high collection efficiency, it maintains stable low filtration resistance for a long time, significantly extending its service life.

[0018] 2. The present invention sprays the prepared composite reinforcing agent onto the surface of the filter material, which can effectively enhance the hydrophobicity of the filter material surface and prevent water vapor blockage. The fluorinated groups and siloxane segments contained in the composite reinforcing agent have low surface energy. After spraying, the contact angle of the filter material surface increases, forming a "lotus effect", which avoids water vapor condensation and blockage of pores, maintains high air permeability, and facilitates dust removal. It can also protect the catalyst and extend its service life. The composite reinforcing agent has acid and alkali resistance, which prevents the catalyst from being corroded by substances such as SO2 and HCl. At the same time, the rigid polyimide segments and flexible siloxane segments contained in the composite reinforcing agent form an interpenetrating network, forming chemical bonds with the filter material, resulting in strong adhesion and resistance to airflow scouring during filter material cleaning. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1: This example discloses a method for preparing a composite reinforcing agent, including the following steps: Q1: 3.02 g of methyl 3,5-dihydroxybenzoate, 6.43 g of 8-bromo-1-octene, 6.03 g of anhydrous potassium carbonate, and 0.48 g of tetrabutylammonium bromide were added to a container containing 250 mL of acetone. The mixture was stirred evenly at room temperature and then refluxed at 80 °C for 24 h. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved in dichloromethane, washed with distilled water and saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 1. 5.03 g of organic compound 1 was added to a container containing 72.5 mL of tetrahydrofuran. Under an ice bath, 0.86 g of lithium aluminum hydride was slowly added. The mixture was reacted at room temperature under nitrogen for 12 h. After the reaction was completed, hydrochloric acid solution was added to pH=5 under an ice bath. The mixture was filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated to obtain organic compound 2. Q2: Add 3.05g of organic compound 2 to a container containing 50mL of dichloromethane. Under nitrogen atmosphere and ice bath conditions, add 8.02g of phosphorus tribromide. After stirring in the ice bath for 15min, react at room temperature for 2h. After the reaction is complete, add 1.97mL of methanol, stir for 1h, extract, wash with distilled water, 5wt% sodium bicarbonate solution and saturated sodium chloride aqueous solution, dry with anhydrous magnesium sulfate, and rotary evaporate to obtain organic compound 3. Add 2.65g of organic compound 3 to a container containing 11mL of N,N-dimethylformamide, then add 0.75g of sodium azide. After stirring at room temperature for 12h, heat to 40℃ and react for 4h. After the reaction is complete, add saturated sodium bicarbonate aqueous solution, stir, add 2.1mL of sodium hypochlorite, stir, extract with dichloromethane, wash, dry, and rotary evaporate to obtain organic compound 4. Q3: Add 1.95g of organic compound 4 to a container containing 67.5mL of tetrahydrofuran. Under ice bath conditions, add 0.48g of lithium aluminum hydride. Under nitrogen atmosphere, react at room temperature for 12h. After the reaction is complete, under ice bath conditions, add 1mL of distilled water and 2mL of sodium hydroxide aqueous solution with a concentration of 1g / mL. Filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 0.51g of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 0.63g of organic compound 5 to a container containing 80mL of toluene. Heat to 100℃ and reflux for 12h. After cooling, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add 0.4g of organic compound 6 to a container containing 85mL of toluene. Under nitrogen atmosphere, add 0.27g of bis(trimethylsiloxymethylsilane) and 5μL of Karstedt catalyst. Stir at room temperature for 14min, then heat to 110℃ and react for 5h. Cool, rotary evaporate, dissolve, and purify to obtain the composite reinforcing agent.

[0021] This embodiment discloses a catalyst-supported metal-ceramic composite dust removal integrated filter material, which is composed of the following parts by weight: 14.5 parts nickel-based alloy, 18 parts cobalt-based alloy, 7.5 parts titanium alloy, 42 parts alumina, 23 parts silicon carbide, 6.5 parts corn starch, 8 parts polyvinyl alcohol, 1.1 parts platinum, 3 parts cerium oxide and 20 parts composite reinforcing agent.

[0022] This embodiment discloses a method for preparing a catalyst-supported metal-ceramic composite dust removal integrated filter material, including the following steps: Step 1: Ball mill the nickel-based alloy, cobalt-based alloy, titanium alloy, alumina and silicon carbide together, adding polyvinyl alcohol and corn starch during the ball milling process to obtain a mixed powder; Step 2: Add platinum and cerium oxide to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry-press the mixed powder and sinter it. The sintering process is as follows: First, heat the powder from room temperature to 350-500℃ at a heating rate of 0.6℃ / min, and hold it at 350℃, 400℃, 450℃ and 500℃ for 2 hours each. Then, heat the powder to 1000℃ at a heating rate of 3℃ / min and hold it for 2 hours. Then, continue to heat the powder to 1400℃ and hold it for 2 hours in an argon atmosphere. After cooling, immerse the powder in a catalyst solution and calcine it to obtain the filter material. Step 4: Spray the composite reinforcing agent onto the surface of the filter material. The process is as follows: Load the composite reinforcing agent into the air compressor and then spray it onto the filter material with an air pressure of 0.5MPa. The nozzle moves at a speed of 15cm / s and the vertical distance between the nozzle and the filter material is 30cm, thus obtaining a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

[0023] Example 2: This example discloses a method for preparing a composite reinforcing agent, including the following steps: Q1: 2.25 g of methyl 3,5-dihydroxybenzoate, 6.02 g of 8-bromo-1-octene, 5.88 g of anhydrous potassium carbonate, and 0.42 g of tetrabutylammonium bromide were added to a container containing 220 mL of acetone. The mixture was stirred evenly at room temperature, heated to 80 °C, and refluxed for 24 h. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved in dichloromethane, washed with distilled water and saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 1. 4.52 g of organic compound 1 was added to a container containing 75 mL of tetrahydrofuran. Under ice bath conditions, 0.81 g of lithium aluminum hydride was slowly added. The mixture was reacted at room temperature under nitrogen atmosphere for 12 h. After the reaction was completed, hydrochloric acid solution was added to pH=5 under ice bath conditions. The mixture was filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated to obtain organic compound 2. Q2: Add 2.88g of organic compound 2 to a container containing 46mL of dichloromethane. Under nitrogen atmosphere and ice bath conditions, add 7.82g of phosphorus tribromide. After stirring in the ice bath for 15min, react at room temperature for 2h. After the reaction is complete, add 1.58mL of methanol, stir for 1h, extract, wash with distilled water, 5wt% sodium bicarbonate solution and saturated sodium chloride aqueous solution, dry with anhydrous magnesium sulfate, and rotary evaporate to obtain organic compound 3. Add 2.2g of organic compound 3 to a container containing 12mL of N,N-dimethylformamide, then add 0.72g of sodium azide. After stirring at room temperature for 12h, heat to 40℃ and react for 4h. After the reaction is complete, add saturated sodium bicarbonate aqueous solution, stir, add 1.8mL of sodium hypochlorite, stir, extract with dichloromethane, wash, dry, and rotary evaporate to obtain organic compound 4. Q3: Add 1.68g of organic compound 4 to a container containing 60mL of tetrahydrofuran. Under ice bath conditions, add 0.41g of lithium aluminum hydride. Under nitrogen atmosphere, react at room temperature for 12h. After the reaction is complete, under ice bath conditions, add 1mL of distilled water and 2mL of sodium hydroxide aqueous solution with a concentration of 1g / mL. Filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 0.42g of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 0.55g of organic compound 5 to a container containing 85mL of toluene. Heat to 100℃ and reflux for 12h. After cooling, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add 0.32g of organic compound 6 to a container containing 80mL of toluene. Under nitrogen atmosphere, add 0.21g of bis(trimethylsiloxymethylsilane) and 4μL of Karstedt catalyst. Stir at room temperature for 14min, then heat to 110℃ and react for 5h. Cool, rotary evaporate, dissolve, and purify to obtain the composite reinforcing agent.

[0024] This embodiment discloses a catalyst-supported metal-ceramic composite dust removal integrated filter material, which is composed of the following parts by weight: 12 parts nickel-based alloy, 23 parts cobalt-based alloy, 10 parts titanium alloy, 30 parts zirconium oxide, 26 parts titanium carbide, 5 parts corn starch, 10 parts polyvinyl alcohol, 0.8 parts palladium, 1 part samarium oxide and 18 parts composite reinforcing agent.

[0025] This embodiment discloses a method for preparing a catalyst-supported metal-ceramic composite dust removal integrated filter material, including the following steps: Step 1: Ball mill the nickel-based alloy, cobalt-based alloy, titanium alloy, zirconium oxide and titanium carbide together, adding polyvinyl alcohol and corn starch during the ball milling process to obtain a mixed powder; Step 2: Add palladium and samarium oxide to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry-press the mixed powder and sinter it. The sintering process is as follows: First, heat the powder from room temperature to 350-500℃ at a heating rate of 0.5℃ / min, and hold it at 350℃, 400℃, 450℃ and 500℃ for 2 hours each. Then, heat the powder to 900℃ at a heating rate of 4℃ / min and hold it for 2 hours. Then, continue to heat the powder to 1300℃ and hold it for 2 hours in an argon atmosphere. After cooling, immerse the powder in a catalyst solution and calcine it to obtain the filter material. Step 4: Spray the composite reinforcing agent onto the surface of the filter material. The process is as follows: Load the composite reinforcing agent into the air compressor and then spray it onto the filter material with an air pressure of 0.3MPa. The nozzle moves at a speed of 10cm / s and the vertical distance between the nozzle and the filter material is 32cm, thus obtaining a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

[0026] Example 3: This example discloses a method for preparing a composite reinforcing agent, including the following steps: Q1: 3.72 g of methyl 3,5-dihydroxybenzoate, 6.84 g of 8-bromo-1-octene, 6.26 g of anhydrous potassium carbonate, and 0.56 g of tetrabutylammonium bromide were added to a container containing 280 mL of acetone. The mixture was stirred evenly at room temperature and then refluxed at 80 °C for 24 h. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved in dichloromethane, washed with distilled water and saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 1. 5.46 g of organic compound 1 was added to a container containing 70 mL of tetrahydrofuran. Under ice bath conditions, 0.92 g of lithium aluminum hydride was slowly added. The mixture was reacted at room temperature under nitrogen atmosphere for 12 h. After the reaction was completed, hydrochloric acid solution was added to pH=5 under ice bath conditions. The mixture was filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated to obtain organic compound 2. Q2: 3.12g of organic compound 2 was added to a container containing 54mL of dichloromethane. Under nitrogen atmosphere and an ice bath, 8.22g of phosphorus tribromide was added. After stirring in the ice bath for 15min, the mixture was reacted at room temperature for 2h. After the reaction was completed, 2.36mL of methanol was added, and the mixture was stirred for 1h. The mixture was extracted, washed with distilled water, 5wt% sodium bicarbonate solution, and saturated sodium chloride aqueous solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 3. 3.1g of organic compound 3 was added to a container containing 10mL of N,N-dimethylformamide, followed by 0.78g of sodium azide. After stirring at room temperature for 12h, the temperature was raised to 40℃ and the mixture was reacted for 4h. After the reaction was completed, saturated sodium bicarbonate aqueous solution was added, and after stirring, 2.3mL of sodium hypochlorite was added. After stirring, the mixture was extracted with dichloromethane, washed, dried, and rotary evaporated to obtain organic compound 4. Q3: Add 2.33g of organic compound 4 to a container containing 75mL of tetrahydrofuran. Under ice bath conditions, add 0.52g of lithium aluminum hydride. Under nitrogen atmosphere, react at room temperature for 12h. After the reaction is complete, under ice bath conditions, add 1mL of distilled water and 2mL of sodium hydroxide aqueous solution with a concentration of 1g / mL. Filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 0.57g of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 0.72g of organic compound 5 to a container containing 75mL of toluene. Heat to 100℃ and reflux for 12h. After cooling, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add 0.48g of organic compound 6 to a container containing 90mL of toluene. Under nitrogen atmosphere, add 0.33g of bis(trimethylsiloxymethylsilane) and 6μL of Karstedt catalyst. Stir at room temperature for 14min, then heat to 110℃ and react for 5h. Cool, rotary evaporate, dissolve, and purify to obtain the composite reinforcing agent.

[0027] This embodiment discloses a catalyst-supported metal-ceramic composite dust removal integrated filter material, which is composed of the following parts by weight: 17 parts nickel-based alloy, 14 parts cobalt-based alloy, 5 parts titanium alloy, 55 parts magnesium oxide, 20 parts tungsten carbide, 8 parts corn starch, 6 parts polyvinyl alcohol, 1.5 parts silver, 5 parts neodymium oxide and 22 parts composite reinforcing agent.

[0028] This embodiment discloses a method for preparing a catalyst-supported metal-ceramic composite dust removal integrated filter material, including the following steps: Step 1: Mix nickel-based alloy, cobalt-based alloy, titanium alloy, magnesium oxide and tungsten carbide by ball milling. Add polyvinyl alcohol and corn starch during the ball milling process to obtain a mixed powder. Step 2: Add silver and neodymium oxide to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry press and sinter the mixed powder. The sintering process is as follows: First, heat the powder from room temperature to 350-500℃ at a heating rate of 0.8℃ / min, and hold it at 350℃, 400℃, 450℃ and 500℃ for 2 hours each. Then, heat the powder to 1000℃ at a heating rate of 5℃ / min and hold it for 2 hours. Then, continue to heat the powder to 1500℃ and hold it for 2 hours in an argon atmosphere. After cooling, immerse the powder in a catalyst solution and calcine to obtain the filter material. Step 4: Spray the composite reinforcing agent onto the surface of the filter material. The process is as follows: Load the composite reinforcing agent into the air compressor and then spray it onto the filter material with an air pressure of 0.4 MPa. The nozzle moves at a speed of 17 cm / s and the vertical distance between the nozzle and the filter material is 33 cm, thus obtaining a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

[0029] Example 4: This example discloses a method for preparing a composite reinforcing agent, including the following steps: Q1: 3.34 g of methyl 3,5-dihydroxybenzoate, 6.25 g of 8-bromo-1-octene, 5.92 g of anhydrous potassium carbonate and 0.52 g of tetrabutylammonium bromide were added to a container containing 240 mL of acetone. The mixture was stirred evenly at room temperature and then refluxed at 80 °C for 24 h. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved in dichloromethane, washed with distilled water and saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 1. 4.68 g of organic compound 1 was added to a container containing 71 mL of tetrahydrofuran. Under ice bath conditions, 0.83 g of lithium aluminum hydride was slowly added. The mixture was reacted at room temperature under nitrogen atmosphere for 12 h. After the reaction was completed, hydrochloric acid solution was added to pH=5 under ice bath conditions. The mixture was filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated to obtain organic compound 2. Q2: 2.96g of organic compound 2 was added to a container containing 48mL of dichloromethane. Under nitrogen atmosphere and an ice bath, 8.11g of phosphorus tribromide was added. After stirring in the ice bath for 15min, the mixture was reacted at room temperature for 2h. After the reaction was completed, 1.69mL of methanol was added, and the mixture was stirred for 1h. The mixture was extracted, washed with distilled water, 5wt% sodium bicarbonate solution, and saturated sodium chloride aqueous solution, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain organic compound 3. 2.4g of organic compound 3 was added to a container containing 10.5mL of N,N-dimethylformamide, followed by 0.73g of sodium azide. After stirring at room temperature for 12h, the temperature was raised to 40℃ and the mixture was reacted for 4h. After the reaction was completed, saturated sodium bicarbonate aqueous solution was added, and after stirring, 1.9mL of sodium hypochlorite was added. After stirring, the mixture was extracted with dichloromethane, washed, dried, and rotary evaporated to obtain organic compound 4. Q3: Add 1.81g of organic compound 4 to a container containing 62mL of tetrahydrofuran. Under ice bath conditions, add 0.46g of lithium aluminum hydride. Under nitrogen atmosphere, react at room temperature for 12h. After the reaction is complete, under ice bath conditions, add 1mL of distilled water and 2mL of sodium hydroxide aqueous solution with a concentration of 1g / mL. Filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 0.46g of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and 0.58g of organic compound 5 to a container containing 78mL of toluene. Heat to 100℃ and reflux for 12h. After cooling, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add 0.35g of organic compound 6 to a container containing 82mL of toluene. Under nitrogen atmosphere, add 0.24g of bis(trimethylsiloxymethylsilane) and 4.5μL of Karstedt catalyst. Stir at room temperature for 14min, then heat to 110℃ and react for 5h. Cool, rotary evaporate, dissolve, and purify to obtain the composite reinforcing agent.

[0030] This embodiment discloses a catalyst-supported metal-ceramic composite dust removal integrated filter material, which is composed of the following parts by weight: 13 parts nickel-based alloy, 16 parts cobalt-based alloy, 8 parts titanium alloy, 32 parts beryllium oxide, 21 parts tantalum carbide, 7 parts corn starch, 7 parts polyvinyl alcohol, 1.3 parts ruthenium, 2 parts lanthanum oxide and 19 parts composite reinforcing agent.

[0031] This embodiment discloses a method for preparing a catalyst-supported metal-ceramic composite dust removal integrated filter material, including the following steps: Step 1: Ball mill the nickel-based alloy, cobalt-based alloy, titanium alloy, beryllium oxide and tantalum carbide together, adding polyvinyl alcohol and corn starch during the ball milling process to obtain a mixed powder; Step 2: Add ruthenium and lanthanum oxide to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry press and sinter the mixed powder. The sintering process is as follows: First, heat the powder from room temperature to 350-500℃ at a heating rate of 1℃ / min, and hold it at 350℃, 400℃, 450℃ and 500℃ for 1 hour each. Then, heat the powder to 950℃ at a heating rate of 4℃ / min and hold it for 2 hours. Then, continue to heat the powder to 1450℃ and hold it for 3 hours in an argon atmosphere. After cooling, immerse the powder in a catalyst solution and calcine to obtain the filter material. Step 4: Spray the composite reinforcing agent onto the surface of the filter material. The process is as follows: Load the composite reinforcing agent into the air compressor and then spray it onto the filter material with an air pressure of 0.5MPa. The nozzle moves at a speed of 15cm / s and the vertical distance between the nozzle and the filter material is 30cm, thus obtaining a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

[0032] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not spray composite reinforcing agent during the preparation of metal-ceramic composite dust removal integrated filter material, and all other conditions remained unchanged.

[0033] I. Basic Performance Testing: The metal-ceramic composite dust collector filter materials prepared in Examples 1-4 and Comparative Example 1 were subjected to performance tests. The fracture toughness of the samples was tested according to GB / T 4161-2007, the contact angle according to GB / T 30447-2013, the filtration efficiency according to ISO 16890, the acid and alkali resistance according to ISO-175, and the salt spray corrosion test according to ASTM B117. The test results are shown in Table 1. Table 1

[0034] As shown in Table 1, the fracture toughness of Examples 1-4 was slightly improved, indicating that a good bond was formed between the composite reinforcing agent and the metal-ceramic matrix. The interpenetrating network structure of its own polyimide rigid segments and siloxane flexible segments played a role in bridging microcracks and consuming fracture energy, thereby slightly improving the material's resistance to crack propagation and enhancing the overall mechanical reliability. The ultra-high contact angle of Examples 1-4 indicates that its surface has extremely strong hydrophobicity, proving that the low surface energy characteristics of the fluorinated groups and siloxane segments in the composite reinforcing agent successfully constructed a hydrophobic protective layer on the filter material surface, forming a "lotus effect," which can make the filter material... In practical applications, it prevents water vapor condensation from clogging pores, resists the adhesion of wet dust, and facilitates dust removal. The filtration efficiency of Examples 1-4 is higher than that of Comparative Example 1, indicating that the hydrophobic layer formed by the composite reinforcing agent avoids the wetting and clogging of the internal pores of the filter material by water or oily substances, ensuring unobstructed airflow and making it easier for dust to be captured at a deeper level, thereby achieving ultra-low emissions. In corrosive media, the weight loss rate of Examples 1-4 is reduced by more than half compared to Comparative Example 1, indicating that the presence of the composite reinforcing agent can effectively isolate the direct erosion of the matrix material and the supported catalyst by corrosive media, greatly extending the service life and stability of the filter material in complex and harsh flue gas environments.

[0035] II. Dust removal frequency performance test: At a gas velocity of 0.05 m / s, a concentration of 30 g / m³ was introduced into the filter media. 3 For test dust with a particle size range of 20-80μm, the pressure difference across the filter media was monitored in real time until it reached 2-3 times the initial resistance. At 0.5MPa, pulse-jet cleaning (pulse width 50-150ms) was performed on the filter media, and the residual pressure difference after cleaning stabilization was recorded. This process was repeated 1-5 times, and the residual pressure difference and dust stripping rate were recorded. The test results are shown in Table 2. Table 2

[0036] As shown in Table 2, under the same test conditions, the time required for Examples 1-4 to reach the dust removal trigger pressure differential in each cycle was significantly longer than that of Comparative Example 1, and the decrease over time was slower. This indicates that the dust adhesion speed of the filter media in Examples 1-4 was slow, allowing for a longer dust removal cycle and a significantly reduced dust removal frequency. The residual pressure differential after dust removal in Examples 1-4 remained at a low level and increased slowly, while the residual pressure differential in Comparative Example 1 rose rapidly. Simultaneously, the dust stripping rate in Examples 1-4 remained consistently above 96%, far exceeding that of Comparative Example 1. This indicates that the hydrophobic / oleophobic protective layer of the composite reinforcing agent effectively reduced dust adhesion, resulting in more thorough dust removal. With increasing cycle count, the performance indicators of Examples 1-4 decreased only slightly, demonstrating excellent stability, while the performance of Comparative Example 1 deteriorated significantly. This indicates that the composite reinforcing agent effectively resists pore blockage and maintains low filtration resistance during long-term operation, thereby significantly extending the service life of the filter media.

[0037] III. Test of filter media activity retention rate: The samples prepared according to Examples 1-4 and Comparative Example 1 were tested to determine their initial conversion rate. Then, SO2, HCl, and alkali metals were introduced into the gas stream and treated for 24 hours. The conversion rate of the samples was then measured again. The activity retention rate was calculated as (conversion rate after treatment / initial conversion rate) × 100%. The test results are shown in Table 3. Table 3

[0038] As shown in Table 3, the samples prepared according to Examples 1-4 have excellent activity retention rates, and the addition of composite reinforcing agents can effectively improve the activity retention rates of the samples.

[0039] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0040] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A catalyst-supported metal-ceramic composite dust removal integrated filter material, characterized in that, It is composed of the following components by weight: 12-17 parts nickel-based alloy, 14-23 parts cobalt-based alloy, 5-10 parts titanium alloy, 30-55 parts oxide ceramic, 20-26 parts carbide ceramic, 5-8 parts corn starch, 6-10 parts polyvinyl alcohol, 0.8-1.5 parts precious metal catalyst, 1-5 parts rare earth composite catalyst and 18-22 parts composite reinforcing agent.

2. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 1, characterized in that, The oxide ceramic is composed of one or more of alumina, zirconium oxide, magnesium oxide, beryllium oxide and titanium dioxide; the carbide ceramic is composed of one or more of silicon carbide, boron carbide, titanium carbide, tungsten carbide, zirconium carbide and tantalum carbide; the noble metal catalyst is composed of one or more of platinum, palladium, rhodium, silver, ruthenium and gold; the rare earth composite catalyst is composed of one or more of cerium oxide, lanthanum oxide, samarium oxide and neodymium oxide.

3. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 1, characterized in that, The preparation method of the composite reinforcing agent includes the following steps: Q1: Methyl 3,5-dihydroxybenzoate, 8-bromo-1-octene, anhydrous potassium carbonate, and tetrabutylammonium bromide were added to a container containing acetone, stirred evenly at room temperature, and then refluxed. After the reaction was completed, the mixture was rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated again to obtain organic compound 1. Organic compound 1 was added to a container containing tetrahydrofuran, and lithium aluminum hydride was slowly added under an ice bath atmosphere. The mixture was then reacted at room temperature under a nitrogen atmosphere. After the reaction was completed, hydrochloric acid aqueous solution was added under an ice bath atmosphere, filtered, rotary evaporated, extracted, dissolved, washed, dried, and rotary evaporated again to obtain organic compound 2. Q2: Organic compound 2 was added to a container containing dichloromethane. Phosphorus tribromide was added under nitrogen atmosphere and an ice bath. After stirring in the ice bath, the reaction was carried out at room temperature. After the reaction was completed, methanol was added, stirred, extracted, washed, dried, and rotary evaporated to obtain organic compound 3. Organic compound 3 was added to a container containing N,N-dimethylformamide, followed by sodium azide. After stirring at room temperature, the reaction was carried out at elevated temperature. After the reaction was completed, saturated sodium bicarbonate aqueous solution was added, stirred, followed by sodium hypochlorite. After stirring, extracted, washed, dried, and rotary evaporated to obtain organic compound 4. Q3: Add organic compound 4 to a container containing tetrahydrofuran. Under ice bath conditions, add lithium aluminum hydride and react at room temperature under nitrogen atmosphere. After the reaction is complete, under ice bath conditions, add distilled water and sodium hydroxide aqueous solution, filter, rotary evaporate, extract, dissolve, wash, dry, and rotary evaporate again to obtain organic compound 5. Add 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride and organic compound 5 to a container containing toluene. After reflux reaction, cool, rotary evaporate, dissolve, and purify to obtain organic compound 6. Q4: Add organic compound 6 to a container containing toluene, add bis(trimethylsiloxymethylsilane) and Karstedt catalyst under nitrogen atmosphere, stir at room temperature, heat to react, cool, rotary evaporate, dissolve, purify, and obtain composite reinforcing agent.

4. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 3, characterized in that, In Q1, the ratio of methyl 3,5-dihydroxybenzoate, 8-bromo-1-octene, anhydrous potassium carbonate, tetrabutylammonium bromide, and acetone is (2.25-3.72) g : (6.02-6.84) g : (5.88-6.26) g : (0.42-0.56) g : (220-280) mL; the ratio of organic compound 1, tetrahydrofuran, and lithium aluminum hydride is (4.52-5.46) g : (70-75) mL : (0.81-0.92) g.

5. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 3, characterized in that, In Q2, the ratio of organic compound 2, dichloromethane, phosphorus tribromide and methanol is (2.88-3.12) g : (46-54) mL : (7.82-8.22) g : (1.58-2.36) mL; the ratio of organic compound 3, N,N-dimethylformamide, sodium azide and sodium hypochlorite is (2.2-3.1) g : (10-12) mL : (0.72-0.78) g : (1.8-2.3) mL.

6. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 3, characterized in that, In Q3, the ratio of organic compound 4, tetrahydrofuran, and lithium aluminum hydride is (1.68-2.33) g : (60-75) mL : (0.41-0.52) g; the ratio of 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, organic compound 5, and toluene is (0.42-0.57) g : (0.55-0.72) g : (75-85) mL.

7. The catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 3, characterized in that, In Q4, the ratio of organic compound 6, toluene, bis(trimethylsiloxymethylsilane) and Karstedt catalyst is (0.32-0.48) g : (80-90) mL : (0.21-0.33) g : (4-6) μL.

8. The method for preparing the catalyst-supported metal-ceramic composite dust removal integrated filter material according to any one of claims 1-7, characterized in that, Includes the following steps: Step 1: Ball mill the nickel-based alloy, cobalt-based alloy, titanium alloy, oxide ceramic and carbide ceramic together. Polyvinyl alcohol and corn starch are added during the ball milling process to obtain a mixed powder. Step 2: Add the precious metal catalyst and rare earth composite catalyst to distilled water and stir ultrasonically to obtain a catalyst solution; Step 3: Dry-press the mixed powder, sinter it, cool it, then immerse it in a catalyst solution and calcine it to obtain the filter material; Step 4: Spray the composite reinforcing agent onto the surface of the filter material to obtain a catalyst-loaded metal-ceramic composite dust removal integrated filter material.

9. The method for preparing the catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 8, characterized in that, In step three, the sintering process is as follows: First, the temperature is increased from room temperature to 350-500℃ at a heating rate of 0.5-1℃ / min, and held at 350℃, 400℃, 450℃ and 500℃ for 1-2 hours each. Then, the temperature is increased to 800-1000℃ at a heating rate of 3-5℃ / min and held for 1-2 hours. Then, the temperature is increased to 1300-1500℃ and held for 1-3 hours in an argon atmosphere.

10. The method for preparing the catalyst-supported metal-ceramic composite dust removal integrated filter material according to claim 8, characterized in that, In step four, the composite reinforcing agent is loaded into the air compressor and then sprayed onto the filter material with an air pressure of 0.3-0.5 MPa. The nozzle moves at a speed of 10-20 cm / s and the vertical distance between the nozzle and the filter material is 30-35 cm.

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