Catalytic filter bag for incineration flue gas fine particle removal and vocs catalytic oxidation and preparation method and application thereof

Abstract

The application discloses a kind of catalytic filter bag for incineration flue gas fine particle removal and VOCs catalytic oxidation and its preparation method and application, belong to waste incineration flue gas purification technical field.The method is uniformly ground CoO-MnO-In2O3@TiO2 and adjuvant, then water and nitric acid are sequentially added and uniformly mixed, to obtain matrix supported catalyst sol slurry;Catalytic filter material can be obtained by spraying matrix supported catalyst sol slurry on pretreated filter bag carrier and sequentially drying and calcining.The catalyst sol slurry formed by the application has stronger adhesion to the filter bag matrix and higher loading rate;The production efficiency of catalytic filter bag is improved by using automatic spraying technology.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of waste incineration flue gas purification, and particularly relates to a catalytic filter bag for removing fine particles and catalytically oxidizing VOCs in incineration flue gas, and a preparation method and application thereof. BACKGROUND

[0002] Volatile organic compounds (VOCs) are one of the main atmospheric pollutants, which have serious harm to human health and ecological environment. Industrial sources are the largest VOCs pollution sources, which have the characteristics of large emission intensity, high emission concentration, complex emission components, and long duration. Catalytic oxidation is a process of using catalysts to decompose toxic and harmful VOCs into non-toxic CO2 and H2O under certain reaction conditions, which has the advantages of mild reaction conditions, good safety, high conversion efficiency, etc., and is one of the most efficient technologies for VOCs treatment at present, and the high-efficiency oxidation catalyst is the core of VOCs catalytic oxidation technology. At present, the operating temperature of commercial VOCs catalysts is usually above 350℃, which is difficult to adapt to low-temperature flue gas. The low-temperature oxidation catalyst needs to be improved in terms of low-temperature activity, sulfur poisoning resistance, and thermal stability. On the other hand, a large amount of dust is also emitted in industrial flue gas, and multiple pollutants coexist, which requires multi-step removal and treatment technology, resulting in large equipment area, high treatment cost, and complex operation. The filter bag technology of fine particle filtration and VOCs catalytic oxidation can effectively solve this problem.

[0003] Patent CN 109954403 A discloses a plasma-catalyst oxidation degradation VOCs dust removal filter cloth, which is woven by warp yarns and weft yarns in the form of conventional plain weave, twill or satin. The dust removal filter cloth is powered on during dust removal, and plasma is generated by electrolyzing air through the conductive yarns on the filter bag, which cooperates with one of the catalysts in the blended CuO-ZnO-MgO-Al2O3 mixture, copper-manganese-cerium composite metal oxide, Cu-Al2O3, CuO-Mn2O4 composite metal oxide, AgO-Mn2O4 composite metal oxide, and Co3O4-Ce O2 composite metal oxide loaded on the filter bag to efficiently degrade gaseous volatile organic compounds in the tail gas. CN 107321348B discloses a catalytic fiber capable of catalytically removing organic gaseous pollutants, a preparation method thereof, a catalytic filter bag, and a bag filter, wherein the catalytic fiber comprises a PTFE fiber substrate and a catalyst filled in the PTFE fiber substrate by swelling and melting, and the catalyst comprises one or more active agents of vanadium pentoxide, platinum, and palladium, and one or two antioxidants of tungsten trioxide and molybdenum trioxide, which are supported on a catalyst carrier of titanium dioxide.

[0004] The prior art mainly has the following problems: 1. The conventional oxidation catalyst has a high operating temperature; 2. The low-temperature oxidation catalyst has defects such as low-temperature activity, sulfur resistance and thermal stability; 3. The catalyst has a low combination strength with the filter material, and the removal of fine particles and the oxidation efficiency of VOCs are relatively low. SUMMARY

[0005] In order to overcome the deficiencies of the prior art, the application provides a catalytic filter bag for incineration flue gas fine particle removal and VOCs catalytic oxidation, and a preparation method and application thereof.

[0006] In order to achieve the above-mentioned purpose, the application adopts the following technical solutions:

[0007] A preparation method of a catalytic filter bag, the preparation method comprising the following steps:

[0008] (1) adding dodecylamine and alcohol into deionized water to form a microemulsion liquid, adding cobalt salt, manganese salt and indium salt into the microemulsion liquid and mixing uniformly; after mixing uniformly, slowly adding into a precipitator, then stirring for 12-20h, and then sequentially performing standing, centrifugation, washing, drying, calcination and grinding on the obtained crystal, so as to obtain a CoO-MnO-In2O3 ternary metal oxide composition with a particle size of 5-15μm;

[0009] (2) adding the CoO-MnO-In2O3 ternary metal oxide composition into an alcohol aqueous solution and dispersing uniformly, then adding TiCl4 and reacting for 1.5-2h at a temperature of 75-85℃, and then drying the gel and performing calcination, so as to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure;

[0010] (3) grinding and mixing CoO-MnO-In2O3@TiO2 and an additive uniformly, then sequentially adding water and nitric acid and mixing uniformly, so as to obtain a matrix-supported catalyst sol slurry;

[0011] (4) spraying the matrix-supported catalyst sol slurry on a pretreated filter bag carrier and sequentially performing drying and calcination, so as to obtain a catalytic filter material.

[0012] In the above preparation method, the alcohol in step (1) is n-butanol, and the mass ratio of dodecylamine, n-butanol and deionized water in the microemulsion is 1-5:8-12:10-20;

[0013] The mass ratio of the microemulsion and the metal salt is 20-30:1-5, and the metal salt is cobalt salt, manganese salt and indium salt.

[0014] In the preparation method, the temperature for drying in step (1) is 120-150 DEG C, the drying time is 4-8 hours, the calcination temperature is 550-650 DEG C, and the calcination time is 4-10 hours.

[0015] The precipitating agent is a mixture of sodium hydroxide and sodium carbonate, and the molar ratio of sodium hydroxide to sodium carbonate is 1-3:1-3.

[0016] In the preparation method, the alcohol solution in step (2) is 40-60% ethanol solution; the drying temperature is 100-130 DEG C, and the drying time is 12-20 hours; the calcination temperature is first 400-450 DEG C for 2-4 hours, and then 630-680 DEG C for 4-8 hours.

[0017] In the preparation method, the mass concentration of the matrix-supported catalyst sol slurry in step (3) is 1-10%.

[0018] In the preparation method, the additive in step (3) is a combination of SB powder and carboxymethyl cellulose or a combination of SB powder and Tianjing powder with a mass ratio of 3-15:0.1-1, and the mass ratio of the additive to CoO-MnO-In2O3@TiO2 catalyst composition is 1-3:1-3.

[0019] In the preparation method, the filter bag pretreatment method in step (4) is soaking in 10-30% nitric acid at a temperature of 40-50 DEG C for 1-3 hours, then washing and drying at 100-110 DEG C for 1-3 hours; the filter bag material is tetrafluoroethylene PTFE, polyphenylene sulfide PPS or polyacyl P84.

[0020] In step (4), the drying temperature is 105-120 DEG C for 3-6 hours, and the calcination temperature is 180-220 DEG C for 1-8 hours.

[0021] A catalytic filter bag is prepared by the above method.

[0022] Further, in the catalytic filter bag, the weight ratio of CoO, MnO, In2O3 and TiO2 in the CoO-MnO-In2O3@TiO2 catalyst is 0.1-5:0.1-5:0.1-5:5-15, and the loading amount of the catalytic filter bag is 300-600 g / m 2 ;

[0023] Further, the mass ratio of CoO, MnO, In2O3 and TiO2 in the CoO-MnO-In2O3@TiO2 catalyst is 0.5-3.5:1.0-2.5:0.5-2.0:8-12.

[0024] The application discloses a method for preparing a catalyst for removing fine particles in incineration flue gas and catalytic oxidation of VOCs.

[0025] The application provides a catalytic filter bag for removing fine particles in incineration flue gas and catalytic oxidation of VOCs, a preparation method and application thereof, and a CoO-MnO-In2O3@TiO2 core-shell structure VOCs catalytic oxidation catalyst composition has high VOCs catalytic oxidation removal efficiency at a lower temperature; the TiO2 shell layer prevents SO2 and water vapor and the like from being toxic to the active component CoO-MnO-In2O3 of the catalyst, improves the sulfur resistance of the oxidation catalyst, improves the thermal stability of the active component of the catalyst, prolongs the service life of the catalyst, adopts a ball milling technology, makes the catalyst and the binder more uniformly mixed and the particle size smaller, and makes the catalyst sol slurry formed and the filter bag substrate have higher adhesion and higher loading rate, and adopts an automatic spraying technology, and the production efficiency of the catalytic filter bag is improved. DETAILED DESCRIPTION

[0026] The application will be further described through specific examples below, and all the examples are completely operated according to the steps described in the application.

[0027] Example 1

[0028] Treatment of the filter bag substrate

[0029] Polytetrafluoroethylene (PTFE) filter bag material is placed in a beaker, a 20% (mass concentration) nitric acid solution is added, and the filter bag material is immersed and treated at 45 DEG C for 2 hours, then washed with deionized water, and placed in a blast drying oven at 105 DEG C for 2 hours to obtain a pretreated filter bag substrate.

[0030] (1) Preparation of the CoO-MnO-In2O3@TiO2 core-shell structure catalyst

[0031] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5) and 1500 mL of deionized water into a three-necked flask and start stirring; make the dodecylamine completely dissolved in the n-butanol to obtain a microemulsion liquid; weigh 49.0 g of Co(NO3)2.6H2O (98.0%), 125.0 g of Mn(NO3)2.4H2O (97.5%) and 14.4 g of In(NO3)3.H2O (99.5%) respectively into the three-necked flask; after the solid is completely dissolved, drop the above mixed solution into a mixed solution of 5% sodium hydroxide and sodium carbonate (molar ratio of sodium hydroxide to ammonium carbonate is 1:1) at 60°C, adjust the pH value to 8.5, continue stirring for 20 hours after the dropping is completed, then stand, filter, wash to neutral, dry at 120°C for 5 hours, calcine at 550°C for 8 hours, naturally cool to room temperature, grind into 10 μm powder, and obtain a CoO-MnO-In2O3 ternary metal oxide composition;

[0032] (2) Measure 500 mL of an ethanol solution with a volume concentration of 60% into a beaker, add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, ultrasonic disperse for 30 minutes, after complete dispersion, slowly drop 170 g of TiCl4 under stirring, then increase the temperature to 80°C and stir for 2 hours to form a gel; dry the obtained gel at 120°C for 20 hours, then place it in a muffle furnace, calcine at 420°C for 3 hours, and then calcine at 650°C for 6 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure and a weight ratio of CoO:MnO:In2O3:TiO2 of 1.0:2.0:1.0:9.5.

[0033] (3) Preparation of a matrix-loaded catalyst slurry

[0034] Weigh 10.5 g of the CoO-MnO-In2O3@TiO2 catalyst composition, 8.5 g of SB powder and 0.2 g of carboxymethyl cellulose, grind and mix in a ball mill for 4 hours, fully mix and grind to a particle size of 10 μm; add 300 g of deionized water into a 1000 mL beaker, add the above ground mixed powder under stirring, then slowly drop 6.5 g of nitric acid with a concentration of 10%, and ultrasonic homogenize for 8 hours to obtain a matrix-loaded catalyst sol slurry with a mass concentration of 5.99%.

[0035] (4) Preparation of a catalytic filter material

[0036] The catalyst slurry is coated on the polytetrafluoroethylene (PTFE) filter bag substrate treated in step (1) by using an automatic spraying machine, dried at 110°C for 4 hours, and the spraying is repeated twice, and then baked at 220°C for 4 hours to obtain the catalyst-loaded filter material 1 of the present application with a catalyst loading of 438 g / m 2 .

[0037] Example 2

[0038] Treatment of filter bag substrate

[0039] The polyphenylene sulfide (PPS) filter bag material is placed in a beaker, a 20% (mass concentration) nitric acid solution is added, and the material is immersed at 45°C for 2 hours, then washed with deionized water, and placed in a forced air drying oven at 105°C for 2 hours to obtain the pretreated filter bag substrate.

[0040] (1) Preparation of CoO-MnO-In2O3@TiO2 core-shell structure catalyst

[0041] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5), and 1500 mL of deionized water into a three-necked flask and start stirring; dissolve the dodecylamine in the n-butanol to obtain a microemulsion; weigh 73.5 g of Co(NO3)2.6H2O (98.0%), 62.5 g of Mn(NO3)2.4H2O (97.5%), and 21.6 g of In(NO3)3.H2O (99.5%) into the three-necked flask; when the solids are completely dissolved, add the above mixture solution dropwise into a mixed solution of 5% sodium hydroxide and sodium carbonate (molar ratio of sodium hydroxide to ammonium carbonate is 1:1) at 60°C, adjust the pH value to 9.0, continue stirring for 18 hours after the dropwise addition is completed to form a nucleated crystal, then stand, suction filter, wash to neutral, dry at 140°C for 6 hours, bake at 580°C for 8 hours, naturally cool to room temperature, and grind into a 10 μm powder to obtain a CoO-MnO-In2O3 ternary metal oxide composition;

[0042] (2) Measure 500 mL of 60% volume concentration ethanol solution into a beaker, add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, ultrasonic disperse for 30 minutes, and then slowly drop 170 g of TiCl4 under stirring after the complete dispersion; then increase the temperature to 80°C and stir for 2 hours to form a gel; dry the obtained gel at 130°C for 20 hours, then place it in a muffle furnace, bake at 420°C for 3 hours, and then bake at 650°C for 8 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure having a weight ratio of CoO, MnO, In2O3, and TiO2 of 1.5:1.0:1.5:9.5.

[0043] (3) Preparation of matrix supported catalyst slurry

[0044] Weigh 6.5 g of CoO-MnO-In2O3@TiO2catalyst composition, 7.5 g of SB powder, and 0.2 g of carboxymethyl cellulose, and grind and mix them in a ball mill for 4 hours. Grind and mix them thoroughly, and the particle size reaches 10 μm. Add 300 g of deionized water into a 1000 mL beaker, and add the ground and mixed powder under stirring. Then, slowly drop 6.5 g of 10% nitric acid, and ultrasonically homogenize for 8 hours to obtain a matrix supported catalyst sol slurry with a mass concentration of 4.52%.

[0045] (4) Preparation of catalytic filter material

[0046] Use an automatic spraying machine to coat the catalyst slurry on the polyphenylene sulfide (PPS) filter bag substrate treated in step (1), dry at 110°C for 6 hours, repeat the spraying for 3 times, and calcine at 200°C for 4 hours to obtain the catalytic filter material 2 of the present application with a catalyst loading of 375 g / m 2 .

[0047] Example 3

[0048] Treatment of filter bag substrate

[0049] Place the polyacyl (P84) filter bag material in a beaker, add a 20% (mass concentration) nitric acid solution, and immerse and treat at 45°C for 2 hours. Then, wash with deionized water, and dry in a blast drying oven at 105°C for 2 hours to obtain the pretreated filter bag substrate.

[0050] (1) Preparation of CoO-MnO-In2O3@TiO2core-shell structure catalyst

[0051] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5) and 1500 mL of deionized water into a three-necked flask and start stirring; make the dodecylamine completely dissolved in the n-butanol to obtain a microemulsion liquid; weigh 89.1 g of Co(NO3)2.6H2O (98.0%), 90.9 g of Mn(NO3)2.4H2O (97.5%) and 10.4 g of In(NO3)3.H2O (99.5%) respectively into the three-necked flask; when the solids are completely dissolved, drop the above mixed solution into a mixed solution of 5% sodium hydroxide and sodium carbonate (molar ratio of sodium hydroxide to sodium carbonate is 1:1) at 60°C, adjust the pH value to 9.0, continue stirring for 18 hours after dropping, then stand, filter, wash to neutral, dry at 130°C for 4 hours, calcine at 650°C for 5 hours, naturally cool to room temperature, grind into 10 μm powder, and obtain a CoO-MnO-In2O3 ternary metal oxide composition;

[0052] (2) Measure 500 mL of an ethanol solution with a volume concentration of 60% into a beaker, add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, ultrasonic disperse for 30 minutes, slowly drop 170 g of TiCl4 into the mixture under stirring after complete dispersion, then increase the temperature to 80°C and stir for 2 hours to form a gel; dry the obtained gel at 130°C for 20 hours, then place it in a muffle furnace, calcine at 420°C for 3 hours, and then calcine at 650°C for 8 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure and a weight ratio of CoO:MnO:In2O3:TiO2 of 2.5:2.0:1.0:9.5.

[0053] (3) Preparation of a matrix-loaded catalyst slurry

[0054] Weigh 12.5 g of the CoO-MnO-In2O3@TiO2 catalyst composition, 10.5 g of SB powder and 0.3 g of tianq powder, mix and grind in a ball mill for 4 hours, and fully mix and grind to a particle size of 10 μm; add 300 g of deionized water into a 1000 mL beaker, add the above mixed and ground powder under stirring, then slowly drop 10.5 g of nitric acid with a concentration of 10%, and ultrasonic homogenize for 8 hours to obtain a matrix-loaded catalyst sol slurry with a mass concentration of 6.95%.

[0055] (4) Preparation of a catalytic filter material

[0056] The catalyst slurry is coated on the polyacyl (P84) filter bag substrate treated in step (1) by using an automatic spraying machine, dried at 110°C for 5 hours, repeated spraying 5 times, and baked at 180°C for 8 hours to obtain the catalyst-loaded filter material 3 of the present application with a catalyst loading of 516 g / m 2 .

[0057] Example 4

[0058] Treatment of filter bag substrate

[0059] The polytetrafluoroethylene (PTFE) filter bag material is placed in a beaker, a 20% (mass concentration) nitric acid solution is added, and the material is immersed at 45°C for 2 hours, then washed with deionized water, and placed in a forced air drying oven at 105°C for 2 hours to obtain the pretreated filter bag substrate.

[0060] (1) Preparation of CoO-MnO-In2O3@TiO2 core-shell structure catalyst

[0061] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5), and 1500 mL of deionized water into a three-necked flask and start stirring; dissolve the dodecylamine in the n-butanol to obtain a microemulsion; weigh 98.0 g of Co(NO3)2.6H2O (98.0%), 41.7 g of Mn(NO3)2.4H2O (97.5%), and 19.2 g of In(NO3)3.H2O (99.5%) into the three-necked flask; when the solids are completely dissolved, add the above mixture solution to a 5% sodium hydroxide and sodium carbonate mixed solution at 60°C, adjust the pH to 9.5, continue stirring for 20 hours after the addition is complete, then cool, filter, wash to neutral, dry at 150°C for 4 hours, calcine at 620°C for 8 hours, naturally cool to room temperature, and grind into a 10 μm powder to obtain a CoO-MnO-In2O3 ternary metal oxide composition;

[0062] (2) Measure 500 mL of 60% volume concentration ethanol solution into a beaker, add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, ultrasonic dispersion for 30 minutes, slowly add 170 g of TiCl4 dropwise under stirring after complete dispersion, then increase the temperature to 80°C and stir for 2 hours to form a gel; dry the obtained gel at 120°C for 20 hours, then place it in a muffle furnace, calcine at 420°C for 3 hours, and then calcine at 650°C for 5 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure and a weight ratio of CoO, MnO, In2O3, and TiO2 of 3.0:1.0:2.0:9.5.

[0063] (3) Preparation of matrix-supported catalyst slurry

[0064] Weigh 4.5 g of CoO-MnO-In2O3@TiO2catalyst composition, 4.5 g of SB powder, and 0.3 g of carboxymethyl cellulose, and grind and mix in a ball mill for 4 hours. After grinding and mixing thoroughly, the particle size reaches 10 μm. Add 300 g of deionized water into a 1000 mL beaker, and then add the above ground and mixed powder under stirring. Then slowly drop 5.5 g of 10% nitric acid, and ultrasonically homogenize for 8 hours to obtain a matrix-supported catalyst sol slurry with a mass concentration of 2.95%.

[0065] (4) Preparation of catalytic filter material

[0066] Use an automatic spraying machine to coat the catalyst slurry on the polytetrafluoroethylene (PTFE) filter bag matrix treated in step (1), dry at 120°C for 3 hours, repeat the spraying for 3 times, and then bake at 220°C for 5 hours to obtain the catalytic filter material 4 of the present application with a catalyst loading of 531 g / m 2 .

[0067] Example 5

[0068] Treatment of filter bag matrix

[0069] Place the polyphenylene sulfide (PPS) filter bag material in a beaker, and then add a 20% (mass concentration) nitric acid solution. After immersing and treating at 45°C for 2 hours, wash with deionized water, and then place in a blast drying oven at 105°C for 2 hours to obtain the pretreated filter bag matrix.

[0070] (1) Preparation of CoO-MnO-In2O3@TiO2core-shell structure catalyst

[0071] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5), and 1500 mL of deionized water into a three-necked flask, and start stirring. After the dodecylamine is completely dissolved in the n-butanol, a microemulsion liquid is obtained. Weigh 98.0 g of Co(NO3)2.6H2O (98.0%), 89.3 g of Mn(NO3)2.4H2O (97.5%), and 12.3 g of In(NO3)3.H2O (99.5%) into the three-necked flask, respectively. After the solids are completely dissolved, slowly drop the above mixed solution into a mixed solution of 5% sodium hydroxide and sodium carbonate at 60°C, adjust the pH value to 9.0, continue stirring for 18 hours after the dropping is completed, and then cool, filter, wash to neutral, dry at 135°C for 8 hours, bake at 650°C for 8 hours, naturally cool to room temperature, and grind into a 10 μm powder to obtain a CoO-MnO-In2O3ternary metal oxide composition.

[0072] (2) Measure 500 mL of 60% ethanol solution in a beaker, add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, ultrasonic dispersion for 30 minutes, after complete dispersion, slowly drop 170 g of TiCl4 under stirring, then increase the temperature to 80°C and stir for 2 hours to form a gel; dry the obtained gel at 120°C for 18 hours, then place it in a muffle furnace, calcine at 420°C for 4 hours, and then calcine at 650°C for 6 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure of CoO, MnO, In2O3 and TiO2 in a weight ratio of 3.5:2.0:1.5:9.5.

[0073] (3) Preparation of a catalyst slurry loaded on a substrate

[0074] Weigh 13.5 g of CoO-MnO-In2O3@TiO2 catalyst composition, 13.5 g of SB powder, and 0.3 g of carboxymethyl cellulose, grind and mix in a ball mill for 4 hours, and grind until the particle size reaches 20 μm; add 300 g of deionized water to a 1000 mL beaker, add the above ground mixture powder under stirring, then slowly drop 20.5 g of 10% nitric acid, and ultrasonic homogenization for 8 hours to obtain a catalyst sol slurry with a mass concentration of 7.85% loaded on a substrate.

[0075] (4) Preparation of a catalytic filter material

[0076] Use an automatic spraying machine to coat the catalyst slurry on the polyphenylene sulfide (PPS) filter bag substrate treated in step (1), dry at 120°C for 5 hours, repeat the spraying 4 times, and calcine at 190°C for 5 hours to obtain a catalytic filter material 5 with a catalyst loading of 506 g / m 2 of the present application.

[0077] Example 6

[0078] Treatment of filter bag substrate

[0079] Place the polyacyl (P84) filter bag material in a beaker, add a 20% (mass concentration) nitric acid solution, immerse and treat at 45°C for 2 hours, then wash with deionized water, and dry in a forced air drying oven at 105°C for 2 hours to obtain a pretreated filter bag substrate.

[0080] (1) Preparation of CoO-MnO-In2O3@TiO2 core-shell structure catalyst

[0081] Weigh 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5) and 1500 mL of deionized water into a three-necked flask, and start stirring; make the dodecylamine completely dissolved in the n-butanol to obtain a microemulsion liquid; weigh 65.4 g of Co(NO3)2.6H2O (98.0%), 83.3 g of Mn(NO3)2.4H2O (97.5%) and 19.2 g of In(NO3)3.H2O (99.5%) respectively into the three-necked flask; after the solid is completely dissolved, the above mixed solution is added dropwise into a mixed solution of 5% sodium hydroxide and sodium carbonate at 60°C, the pH value is adjusted to 9.5, and after the dropwise addition is completed, stirring is continued for 20 hours for nucleation and crystallization, and then cooling, suction filtration, washing to neutral, drying at 125°C for 8 hours, calcination at 580°C for 10 hours, natural cooling to room temperature, and grinding into a 10 μm powder to obtain a CoO-MnO-In2O3 ternary metal oxide composition;

[0082] (2) Measure 500 mL of an ethanol solution with a volume concentration of 60% into a beaker, and add 30 g of the CoO-MnO-In2O3 ternary metal oxide composition prepared in the above step under stirring at 50°C, and ultrasonic dispersion for 30 minutes; after complete dispersion, 170 g of TiCl4 is slowly added dropwise under stirring, and then the temperature is increased to 80°C for stirring for 2 hours to form a gel; the obtained gel is dried at 105°C for 20 hours, and then placed in a muffle furnace for calcination at 420°C for 3 hours and then at 650°C for 7 hours to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure and a weight ratio of CoO:MnO:In2O3:TiO2 of 1.0:1.0:1.0:9.5.

[0083] (3) Preparation of a matrix-supported catalyst slurry

[0084] Weigh 8.5 g of the CoO-MnO-In2O3@TiO2 catalyst composition, 9.5 g of SB powder and 0.3 g of tianq powder, and grind and mix in a ball mill for 4 hours; after sufficient mixing and grinding, the particle size reaches 15 μm; add 300 g of deionized water into a 1000 mL beaker, and then add the above ground and mixed powder under stirring, and then slowly add 15.5 g of nitric acid with a concentration of 10%, and ultrasonic homogenization for 8 hours to obtain a matrix-supported catalyst sol slurry with a mass concentration of 5.48%.

[0085] (4) Preparation of a catalytic filter material

[0086] The catalyst slurry is coated on the polyacyl (P84) filter bag matrix treated in step (1) by using an automatic spraying machine, dried at 120°C for 4 hours, and repeated spraying for 3 times, and then calcined at 185°C for 6 hours to obtain a catalyst loading of 378 g / m2.2 catalytic filter material 6.

[0087] Comparative Example 1

[0088] (1) The treatment of the filter bag substrate was the same as in Example 1.

[0089] (2) Preparation of the CoO-MnO-In2O3-TiO2 quaternary metal oxide catalyst

[0090] 1) 140 g of dodecylamine, 1000 mL of n-butanol (mass percentage concentration ≥ 99.5), and 1500 mL of deionized water were weighed into a three-necked flask and stirring was started; the dodecylamine was completely dissolved in the n-butanol to obtain a microemulsion liquid;

[0091] 2) 49.0 g of Co(NO3)2.6H2O (98.0%), 125.0 g of Mn(NO3)2.4H2O (97.5%), 14.4 g of In(NO3)3.H2O (99.5%), and 170.0 g of TiCl4 (99.5%) were weighed into the three-necked flask; after the solids were completely dissolved, the above-mentioned mixed solution was added dropwise into a mixed solution of 5% sodium hydroxide and sodium carbonate at 60°C, the pH value was adjusted to 9.5, stirring was continued for 20 hours after the dropwise addition was completed to form nuclei and crystallize, then cooling, suction filtration, washing to neutral, drying at 125°C for 6 hours, calcination at 580°C for 10 hours, natural cooling to room temperature, and grinding into a 10 μm powder were performed to obtain a CoO-MnO-In2O3-TiO2 quaternary metal oxide composition with a weight ratio of CoO:MnO:In2O3:TiO2 = 1.0:2.0:1.0:9.5.

[0092] (3) Preparation of the catalyst slurry loaded on the substrate

[0093] 10.5 g of the CoO-MnO-In2O3-TiO2 quaternary metal oxide composition, 8.5 g of SB powder, and 0.2 g of carboxymethyl cellulose were weighed into a ball mill and ground and mixed for 4 hours, the grinding and mixing were performed until the particle size reached 10 μm; 300 g of deionized water was added into a 1000 mL beaker, the above-mentioned ground and mixed powder was added into the beaker under stirring, then 6.5 g of 10% nitric acid was slowly added dropwise, and ultrasonic homogenization was performed for 8 hours to obtain a catalyst sol slurry loaded on the substrate with a mass concentration of 5.99%.

[0094] (4) The preparation of the catalytic filter material was the same as in step (4) of Example 1, and a comparative catalytic filter material 1 with a catalyst loading of 487 g / m 2 was obtained.

[0095] Comparative Example 2

[0096] (1) The treatment of filter bag substrate and (2) the preparation of CoO-MnO-In2O3@TiO2 core-shell structure catalyst are the same as steps (1) and (2) of Example 4, respectively.

[0097] (3) Preparation of catalyst slurry loaded on substrate

[0098] Take 4.5 g of CoO-MnO-In2O3@TiO2 catalyst composition and 4.8 g of carboxymethyl cellulose, mix and grind in a ball mill for 4 hours, and grind thoroughly to a particle size of 10 μm; add 300 g of deionized water into a 1000 mL beaker, and then add the above mixed and ground powder under stirring, followed by slowly adding 5.5 g of 10% nitric acid dropwise, and then ultrasonic homogenization for 8 hours to obtain a catalyst slurry loaded on substrate with a mass concentration of 2.95%.

[0099] (4) Preparation of catalytic filter material The preparation of catalytic filter material is the same as step (4) of Example 4, and a comparative catalytic filter material 2 with a catalyst loading of 241 g / m 2 is obtained.

[0100] Comparative Example 3

[0101] (1) The treatment of filter bag substrate and (2) the preparation of CoO-MnO-In2O3@TiO2 core-shell structure catalyst are the same as steps (1) and (2) of Example 6, respectively.

[0102] (3) Preparation of catalyst slurry loaded on substrate

[0103] Take 8.5 g of CoO-MnO-In2O3@TiO2 catalyst composition and 9.8 g of tianq powder, mix and grind in a ball mill for 4 hours, and grind thoroughly to a particle size of 15 μm; add 300 g of deionized water into a 1000 mL beaker, and then add the above mixed and ground powder under stirring, followed by slowly adding 15.5 g of 10% nitric acid dropwise, and then ultrasonic homogenization for 8 hours to obtain a catalyst slurry loaded on substrate with a mass concentration of 5.48%.

[0104] (4) Preparation of catalytic filter material The preparation of catalytic filter material is the same as step (4) of Example 6, and a comparative catalytic filter material 3 with a catalyst loading of 226 g / m 2 is obtained.

[0105] Performance test

[0106] The performance evaluation of the catalytic filter bag prepared in the above examples and comparative examples for incineration flue gas fine particle removal and VOCs catalytic oxidation is carried out by sleeving the catalytic filter bag on a sleeve. The evaluation conditions are as follows: the concentration of styrene in flue gas is 800 mg / m 3 , the volume fraction of O2 is 8%, the water vapor content is 15% (volume ratio), and the concentration of SO2 is 450 mg / m3 , dust concentration 1500 mg / m 3 , filtration air velocity 0.75 m / min (filter bag size). The performance of the catalytic filter bag was evaluated in terms of the change in inlet and outlet styrene and dust concentration. The results are shown in Table 1.

[0107] Table 1 Evaluation of the denitration, dioxin removal and dust removal performance of the catalytic filter bag

[0108] Group VOC removal efficiency, % Dust removal efficiency, % Example 1 93.1 99.1 Example 2 92.7 98.8 Example 3 92.6 98.6 Example 4 94.2 98.4 Example 5 93.2 98.5 Example 6 94.7 99.2 Comparative Example 1 82.2 97.4 Comparative Example 2 78.5 93.1 Comparative Example 3 72.8 92.6

[0109] The above-described examples are only used to illustrate the technical ideas and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and the patent scope of the present application cannot be limited only by the above examples, that is, any equivalent changes or modifications made in the spirit disclosed by the present application still fall within the patent scope of the present application.

Claims

1. A method for producing a catalytic filter bag, characterized by, The preparation method comprises the following steps: (1) adding dodecylamine and alcohol into deionized water to form a microemulsion, adding a cobalt salt, a manganese salt and an indium salt into the microemulsion and mixing uniformly, slowly adding into a precipitator after mixing uniformly, stirring for 12-20 hours, and obtaining a crystal, which is sequentially subjected to standing, centrifugation, washing, drying, calcination and grinding to obtain a CoO-MnO-In2O3 ternary metal oxide composition with a particle size of 5-15 µm; the alcohol in step (1) is n-butanol, and the mass ratio of dodecylamine, n-butanol and deionized water in the microemulsion is 1-5:8-12:10-20; the mass ratio of the microemulsion and the metal salt is 20-30:1-5, and the metal salt is a cobalt salt, a manganese salt and an indium salt; the precipitator is a mixed solution of sodium hydroxide and sodium carbonate, and the molar ratio of sodium hydroxide to sodium carbonate is 1-3:1-3; (2) adding the CoO-MnO-In2O3 ternary metal oxide composition into an alcohol aqueous solution and dispersing uniformly, then adding TiCl4 and reacting at a temperature of 75-85°C for 1.5-2 hours, and then drying the gel and calcining to obtain a CoO-MnO-In2O3@TiO2 catalyst composition with a core-shell structure; (3) grinding and mixing CoO-MnO-In2O3@TiO2 and an additive, then adding water and nitric acid in sequence and mixing uniformly to obtain a matrix-supported catalyst sol slurry; (4) spraying the matrix-supported catalyst sol slurry on a pretreated filter bag carrier and sequentially drying and calcining to obtain a catalytic filter bag.

2. The production method according to claim 1, characterized by, In step (1), the drying temperature is 120-150°C, the drying time is 4-8 hours, the calcination temperature is 550-650°C, and the calcination time is 4-10 hours.

3. The preparation method according to claim 1, characterized in that, In step (2), the alcohol aqueous solution is an ethanol solution with a concentration of 40-60%, the drying temperature is 100-130°C, the drying time is 12-20 hours, and the calcination temperature is first calcined at 400-450°C for 2-4 hours, and then calcined at 630-680°C for 4-8 hours.

4. The method of claim 1, wherein, In step (3), the mass concentration of the matrix-supported catalyst sol slurry is 1-10%.

5. The preparation method according to claim 1, characterized in that, In step (3), the additive is a combination of SB powder and carboxymethyl cellulose or a combination of SB powder and tianjing powder with a mass ratio of 3-15:0.1-1, and the mass ratio of the additive to the CoO-MnO-In2O3@TiO2 catalyst composition is 1-3:1-3.

6. The method of claim 1, wherein, In step (4), the filter bag carrier pretreatment method is soaking in 10-30% nitric acid at a temperature of 40-50°C for 1-3 hours, then washing and drying at 100-110°C for 1-3 hours; the filter bag carrier is made of tetrafluoroethylene PTFE, polyphenylene sulfide PPS or polyacyl P84; In step (4), the drying temperature is 105-120°C, the drying time is 3-6 hours, and the calcination temperature is 180-220°C for 1-8 hours.

7. A catalytic filter bag characterized in that, The catalytic filter bag is prepared by the preparation method of any one of claims 1-6.

8. The filter bag of claim 7, wherein, The weight ratio of CoO, MnO, In2O3 and TiO2 in the CoO-MnO-In2O3@TiO2 catalyst is 0.1-5:0.1-5:0.1-5:5-15; the loading of the catalytic filter bag is 300-600 g / m 2 .

9. The filter bag of claim 8, wherein, The mass ratio of CoO, MnO, In2O3 and TiO2 in the CoO-MnO-In2O3@TiO2 catalyst is 0.5-3.5:1.0-2.5:0.5-2.0:8-12.

10. The use of the catalytic filter bag prepared by the preparation method of claim 1 in the removal of fine particles in incineration flue gas and the catalytic oxidation of VOCs.