Honeycomb catalyst suitable for denitration and oxidation and quantitative brushing method thereof

Abstract

The invention discloses a denitration and oxidation type honeycomb catalyst and a quantitative brush coating method thereof, and belongs to the field of industrial waste gas purification catalysts.The quantitative brush coating method suitable for the denitration and oxidation type honeycomb catalysts.The quantitative brush coating method comprises the following steps that S110, resin emulsion and a first part of auxiliary materials are mixed and stirred, and a mixture is obtained; a resin mixed material B is obtained; s120, mixing and stirring the active component salt, the carrier material and the second part of auxiliary material to obtain an effective component D; s130, mixing and stirring the resin mixed material B, the effective component D and the remaining auxiliary materials to obtain a catalyst brush coating paint body G; and S200, quantitatively brushing the catalyst brushing paint body G into pores of the honeycomb ceramic material, and calcining to obtain the honeycomb catalyst. Compared with traditional slurry coating, dependence on organic solvents is reduced, meanwhile, the coating amount is accurately controlled, and resources are saved.

Description

Technical Field

[0001] The invention belongs to the field of industrial waste gas purification catalysts, and in particular relates to a novel quantitative brushing method and application suitable for denitration and oxidation type honeycomb catalysts. Background Art

[0002] The root cause of the smog phenomenon is deeply rooted in the coal-burning process, especially in industrial boilers, coal-fired power generation and chemical production. These activities release a large amount of pollutants such as sulfur dioxide (SO2), volatile organic compounds (VOCs), carbon monoxide (CO) and dust. Among these pollutants, VOCs and CO are particularly noteworthy because of their far-reaching impact on the environment and health.

[0003] VOCs, as a class of compounds with significant toxicity and carcinogenicity, not only directly threaten human health, but also trigger complex photochemical reactions under light conditions, generating harmful byproducts such as ozone and peroxynitroacyl, exacerbating the photochemical smog problem. CO, a colorless and odorless invisible killer, quietly destroys the atmospheric ozone layer and enhances ultraviolet radiation, thereby threatening human health and damaging crop growth. More importantly, some VOCs are converted into secondary organic aerosols through photochemical reactions, which seriously deteriorate air quality and destroy the ecological balance.

[0004] The emission sources of VOCs are extensive and complex, including natural volcanic activities, forest fires, etc., and mainly industrial production, transportation and daily life. The printing, coating, chemical and other industries use a large amount of raw materials containing VOCs in the production process, which has become one of the main emission sources. At the same time, the fuel combustion of vehicles such as cars and ships, as well as household detergents, paints, perfumes and other items used in daily life, all inadvertently release VOCs into the atmosphere, exacerbating environmental pollution.

[0005] Similarly, CO emissions also come from both natural and human sources. Although natural phenomena such as volcanoes and forest fires contribute a certain amount of CO, human activities, especially the burning of fossil fuels (such as automobile exhaust, industrial production, etc.), have become the dominant factor in CO emissions. In cities, automobile exhaust is the largest anthropogenic source of CO emissions, and its contribution far exceeds that of natural sources, exacerbating the problem of urban air pollution. Summary of the invention

[0006] In view of the defects of the honeycomb catalyst in the prior art in denitrification and CO oxidation, the technical problem to be solved by the present invention is to provide a honeycomb catalyst suitable for denitrification and oxidation and a quantitative brushing method thereof, so as to reduce the dependence on organic solvents, curb air pollution, and accurately control the coating amount, save resources and improve production efficiency.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0008] On the one hand, a quantitative brushing method for denitration and oxidation honeycomb catalysts is provided, comprising the following steps:

[0009] S110, mixing and stirring the resin emulsion and the first part of the auxiliary material to obtain a resin mixed material B; S120, mixing and stirring the active component salt, the carrier material and the second part of the auxiliary material to obtain an effective component D, wherein the active component salt includes an active component salt for denitration and an active component salt for VOCs oxidation, and the carrier material includes a carrier material for denitration and a carrier material for VOCs oxidation; S130, mixing and stirring the resin mixed material B, the effective component D and the remaining auxiliary materials to obtain a catalyst brush coating body G;

[0010] S200, quantitatively brushing the catalyst coating body G into the pores of the honeycomb ceramic material, and calcining to obtain a honeycomb catalyst.

[0011] Preferably, the resin emulsion is selected from any two of water-based acrylic resin, water-based alkyd resin, and water-based amino resin, and the ratio of the two resin emulsions is 1:(0.8-1.2);

[0012] And / or, the active component salt for denitration is selected from one of vanadium salts, tungsten salts, iron salts, manganese salts and cobalt salts;

[0013] And / or, the active component salt for VOCs oxidation is selected from one of copper salt, iron salt, manganese salt and cobalt salt; and / or, the carrier material for denitrification is selected from one of TiO2 and Al2O3;

[0014] And / or, the carrier material for VOCs oxidation is selected from one of SiO2 and Al2O3;

[0015] And / or, the auxiliary materials include defoamers, leveling agents, neutralizers, thickeners and dispersants;

[0016] And / or, the honeycomb ceramic material is a cordierite block.

[0017] Preferably, the quantitative brush coating is calculated according to the following formula: W = (m1-m0) / V, where W is the catalyst coating amount in g / dm 3 , m0 is the mass of the blank carrier, m1 is the total mass of the sample coated with the catalyst after calcination, and V is the volume of the honeycomb ceramic material; and / or, the calcination conditions include: temperature 500-600°C, time 3-6h; heating rate of 2-10°C / min in an oxygen atmosphere.

[0018] Preferably, the resin mixed material B is prepared by the following method:

[0019] S111, mixing and stirring the two resin emulsions at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a resin mixture A;

[0020] S112, mixing the defoamer into the resin mixture A during stirring, stirring at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a resin mixed material B.

[0021] Preferably, the effective component D is prepared by the following method:

[0022] S121, mixing the active component salt and the carrier material powder into deionized water, stirring at a temperature of 20-40° C. and a speed of 400-600 r / min for 0.5-2 h, and ball milling to obtain an effective component C;

[0023] S122. Mix the leveling agent and the dispersant into the effective component C during stirring, and stir at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain the effective component D.

[0024] Preferably, the catalyst brush-coated paint body G is prepared by the following method:

[0025] S131, mixing the effective component D into the resin mixed material B during stirring, stirring at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a paint body material E;

[0026] S132, mixing the neutralizer into the paint material E during stirring, adjusting the pH to 7.0-7.5, stirring at a temperature of 20-40° C. and a speed of 400-600 r / min for 0.5-2 h to obtain a paint material F;

[0027] S133, mixing the thickener into the paint material F during stirring, adjusting the consistency to 2000-4000 mPa.s, stirring at a temperature of 20-40°C and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a catalyst brush-coated paint body G.

[0028] Preferably, the catalyst brush paint body G includes 20-30wt% of resin emulsion, 26-28wt% of carrier component material component, 2-4wt% of active component, 0.1-0.5wt% of defoamer, 0.5-1wt% of leveling agent, 0.5-1wt% of neutralizer, 0.5-1wt% of thickener and 0.5-1wt% of dispersant, and the balance is deionized water.

[0029] Preferably, the ball milling conditions in step S121 include: the ball milling speed is 4000-6000 r / min, and the ball milling time is 1-4 cycles of forward rotation for 5-20 min, stop for 20-60 s, reverse rotation for 5-20 min, stop for 20-60 s.

[0030] Preferably, the catalyst paint body G is quantitatively brushed into the pores of the honeycomb ceramic material using a brushing tool, wherein the brushing tool comprises a constant pressure tank, a liquid guide tube connected to the constant pressure tank, and a brush connected to the liquid guide tube.

[0031] On the other hand, the present invention also provides a honeycomb catalyst suitable for denitration and oxidation, which is prepared by the above method.

[0032] The technical solution adopted by the present invention has the following beneficial effects:

[0033] The present invention mixes and stirs the resin mixed material, the effective component and the remaining auxiliary material to obtain a catalyst brush-coated paint body, and then quantitatively brushes the catalyst brush-coated paint body G into the pores of the honeycomb ceramic material, and calcines to obtain a honeycomb catalyst.

[0034] Due to the use of a paint material brushing method, compared with traditional slurry coating, this technology reduces dependence on organic solvents, curbs air pollution, and accurately controls the coating amount, saves resources, and improves production efficiency, which is in line with the concept of green production and sustainable development. The preparation method of the present invention is simple to operate and has simple equipment requirements. The present invention provides an efficient and environmentally friendly solution for denitration and oxidation honeycomb catalysts, and has broad application prospects.

[0035] Furthermore, the catalyst of the present invention has lower denitration and oxidation treatment temperatures and higher reaction catalytic activity by rationally adding active component salts for denitration and active component salts for VOCs oxidation.

[0036] The specific technical solutions of the present invention and the beneficial effects thereof will be disclosed in detail in the following specific implementation methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 A schematic diagram of a novel painting tool proposed by the present invention;

[0038] Figure 2 This is an enlarged view of a part A of a novel painting tool proposed by the present invention;

[0039] In the figure: 1- scale paint bucket, 11- liquid outlet, B- brush assembly, 2- constant pressure tank, 3- liquid guide tube, 4- brush, 5- cordierite block, 6- slide rail;

[0040] Figure 3This is a graph showing the results of the denitrification experiment of Application Example 1;

[0041] Figure 4 This is a graph showing the results of the VOCs oxidation experiment in Application Example 2;

[0042] Figure 5 The SEM images corresponding to the dispersion of Application Example 3, wherein (a) is Example 1 and (b) is Comparative Example 3. DETAILED DESCRIPTION

[0043] The technical solution of the present invention is explained and described below in conjunction with the embodiments of the present invention, but the following embodiments are only preferred embodiments of the present invention, not all. Based on the embodiments in the implementation mode, other embodiments obtained by those skilled in the art without creative work are all within the protection scope of the present invention.

[0044] Those skilled in the art will appreciate that, in the absence of conflict, the features in the following embodiments and implementations may be combined with each other.

[0045] The embodiment of the present invention provides a quantitative brushing method suitable for denitration and oxidation honeycomb catalysts, using Figure 1 and Figure 2 The new type of painting tool shown in the figure comprises a graduated paint bucket 1 storing a catalyst paint body G and a painting assembly B for painting, the painting assembly B comprises a constant pressure tank 2, a liquid guide tube 3 connected to the constant pressure tank, and a brush 4 connected to the liquid guide tube, and the painting assembly B can slide along the slide rail 6. The constant pressure tank 2 is connected to the graduated paint bucket 1, specifically, it can be connected by a telescopic tube, which does not affect the painting assembly B, and slides along the slide rail, and the liquid guide tube 3 is provided with a liquid outlet 11 to transport the paint body material to the brush 4.

[0046] The quantitative brushing process includes the following steps:

[0047] S110, mixing and stirring the resin emulsion and part of the auxiliary material to obtain a resin mixed material B;

[0048] S120, mixing and stirring an active component salt, a carrier material and a part of an auxiliary material to obtain an effective component D, wherein the active component salt includes an active component salt for denitration and an active component salt for VOCs oxidation, and the carrier material includes a carrier material for denitration and a carrier material for VOCs oxidation;

[0049] S130, mixing and stirring the resin mixed material B, the effective component D and the remaining auxiliary materials to obtain a catalyst brush-coated paint body G;

[0050] S200, using a brushing tool to quantitatively brush the catalyst paint body G into the pores of the honeycomb ceramic material, and calcining to obtain a honeycomb catalyst.

[0051] By adopting the above technical solution, the method of brushing the paint material reduces the dependence on organic solvents and curbs air pollution compared to traditional slurry coating. At the same time, it accurately controls the coating amount, saves resources, improves production efficiency, and complies with the concept of green production and sustainable development. The preparation method of the present invention is simple to operate and has simple equipment requirements. The present invention provides an efficient and environmentally friendly solution for denitration and oxidation honeycomb catalysts, which has broad application prospects.

[0052] Furthermore, the honeycomb catalyst prepared by the novel quantitative brushing method of the denitration and oxidation type honeycomb catalyst has a lower exhaust gas treatment temperature and a higher reaction catalytic activity.

[0053] The honeycomb ceramic material has square channels of different specifications, and brushes 4 of different specifications can be replaced for brushing. Generally, the channels are square, and the coating is applied inside the entire channel. The outside does not need to be brushed, so the outside is usually wrapped with iron sheets for easy use. The honeycomb ceramic material is preferably cordierite block 5, and can also be other similar materials, such as honeycomb ceramic matrix materials made of aluminum oxide and titanium oxide.

[0054] The resin emulsion is added to shape the paint and facilitate brushing. The resin emulsion is selected from two of water-based acrylic resin, water-based alkyd resin, water-based amino resin, etc. More preferably, the ratio of the two resin emulsions is 1: (0.8-1.2), for example, 1:1.

[0055] The active component salt for denitration is selected from vanadium salt, tungsten salt, iron salt, manganese salt and cobalt salt, and the active component salt for VOCs oxidation is selected from copper salt, iron salt, manganese salt and cobalt salt. The carrier material for denitration is selected from TiO2 and Al2O3, and the carrier material for VOCs oxidation is selected from SiO2 and Al2O3. The auxiliary material includes a defoamer, a leveling agent, a neutralizer, a thickener and a dispersant.

[0056] Preferably, the quantitative coating rate in S200 is calculated according to the following formula: W = (m1-m0) / V, where W is the catalyst coating amount in g / dm 3 , m0 is the mass of the blank carrier, m1 is the total mass of the sample coated with the catalyst after calcination, and V is the volume of the cordierite bulk material.

[0057] Preferably, the resin mixed material B in S110 is prepared by the following method:

[0058] S111, mixing the two resin emulsions and stirring, preferably, stirring at a temperature of 20-40° C. and a rotation speed of 500 r / min for 0.5-2 h to obtain a resin mixture A;

[0059] S112, mixing the defoamer into the resin mixture A during stirring, and stirring, preferably, stirring at a temperature of 20-40° C. and a rotation speed of 500 r / min for 0.5-2 h to obtain a resin mixed material B.

[0060] Preferably, the effective component D in S120 is prepared by the following method:

[0061] S121, mixing the active component salt and the carrier material powder into deionized water, stirring, preferably, stirring at a temperature of 20-40° C. and a speed of 500 r / min for 0.5-2 h, and ball milling to obtain an effective component C;

[0062] S122, mixing the leveling agent and the dispersant into the effective component C during stirring, and stirring, preferably, stirring at a temperature of 20-40° C. and a rotation speed of 500 r / min for 0.5-2 h to obtain the effective component D.

[0063] Preferably, the catalyst brush-coated paint body G in S130 is prepared by the following method:

[0064] S131, mixing the effective component D into the resin mixed material B during stirring, and stirring, preferably, stirring at a temperature of 20-40° C. and a rotation speed of 500 r / min for 0.5-2 h to obtain a paint material E;

[0065] S132, mixing the neutralizing agent into the paint material E during stirring, adjusting the pH to 7.0-7.5, and stirring.

[0066] Preferably, the mixture is stirred at a temperature of 20-40° C. and a rotation speed of 500 r / min for 0.5-2 h to obtain a paint material F;

[0067] S133, mixing the thickener into the paint material F during the stirring process, adjusting the consistency to 2000-4000 mPa.s, and stirring.

[0068] Preferably, the catalyst-coated paint body G is obtained by stirring at a temperature of 20-40° C. and a speed of 500 r / min for 0.5-2 h;

[0069] Preferably, the vanadium salt is selected from NH4VO3, VOC2O4, VOCl3 or hydrates of the above components;

[0070] The tungsten salt is selected from (NH4)6W7O 24 、(NH4) 10 W 12 O 41 or hydrates of the above components;

[0071] The iron salt is selected from Fe(NO3)3, FeCl3 or hydrates of the above components;

[0072] The manganese salt is selected from MnCl2, Mn(NO3)2 or hydrates of the above components;

[0073] The cobalt salt is selected from Co(NO3)2, CoCl2 or hydrates of the above components;

[0074] The copper salt is selected from Cu(OH)2, Cu(NO3)2, CuCl2 or hydrates of the above components;

[0075] The defoamer is selected from commercially available A-2502, A-2508, BYK-208, and LD-3028;

[0076] The leveling agent is selected from commercially available LGH-7499 and BYK-333;

[0077] The neutralizing agent is selected from TEA, DMEA, and AMP-95;

[0078] The thickener is selected from HEC and HPMC;

[0079] The dispersant is selected from HY-235, HY-238, and HY-268.

[0080] Preferably, the ball milling conditions in step S121 include: the ball milling speed is 4000-6000 r / min, and the ball milling time is 1-4 cycles of forward rotation for 5-20 min, stop for 20-60 s, reverse rotation for 5-20 min, stop for 20-60 s.

[0081] Preferably, the calcination conditions in step S200 include: temperature 500-600°C, more preferably 530-560°C, and time 3-6 hours. Preferably, the calcination conditions in step S200 also include: under oxygen atmosphere, and heating rate 2-10°C / min, preferably 4-6°C / min.

[0082] Example 1

[0083] This embodiment is used to illustrate a novel quantitative brush coating method applicable to a denitration honeycomb catalyst and the honeycomb catalyst prepared therefrom.

[0084] 1) 150 g of waterborne acrylic resin and 150 g of waterborne alkyd resin were added into a container, and stirred at room temperature at a speed of 500 r / min for 1 h to obtain a resin mixture A.

[0085] 2) 3 g of BYK-208 defoamer was added to the resin mixture A, and the mixture was stirred at 500 r / min for 1 h at room temperature to obtain a resin mixture B.

[0086] 3) Combine 25.73g NH4VO3 and 23.26g(NH4)6W7O 24 and 280 g of TiO2 were dissolved in 345 g of deionized water and stirred at a speed of 500 r / min for 1 h to obtain effective component C.

[0087] 4) 8g LGH-7499 and 8g HY-235 were mixed into the effective component C, and stirred at 500r / min for 1h at room temperature, then added into the ball mill, and the mill was rotated at 5400r / min, and the mixture was rotated forward for 10min, stopped for 30s, reversed for 10min, and stopped for 30s for 2 cycles to obtain a uniformly dispersed effective component D.

[0088] 5) The resin mixed material B and the effective component D are mixed, and stirred at a rotation speed of 500 r / min for 1 hour at room temperature to obtain a paint body material E.

[0089] 6) 8 g of TEA was added to the paint material E, the pH was adjusted to 7.0-7.5, and the mixture was stirred at 500 r / min for 1 h at room temperature to obtain a paint material F.

[0090] 7) 8 g of HEC was added to the paint material F, the consistency was adjusted to 2000-4000 mPa.s, and the mixture was stirred at 500 r / min for 1 h at room temperature to obtain a catalyst brush-coated paint body G.

[0091] 8) The catalyst is brushed with paint body G, a new type of brushing tool is selected according to the pore size of the cordierite block, and the coating amount is set according to 150g / L according to the size, and the paint is placed in a container tank, and flows to the brush head through the liquid guide tube for repeated brushing, and timely heating is performed. Calcination is carried out at 550℃ for 4h in an air atmosphere, and the heating rate is 5℃ / min. The obtained material is the denitrification sample 1.

[0092] Example 2

[0093] This embodiment is used to illustrate a novel quantitative brush coating method applicable to toluene oxidation honeycomb catalyst and the honeycomb catalyst prepared therefrom.

[0094] The difference between this embodiment and embodiment 1 is that 25.73 g NH4VO3 and 23.26 g (NH4)6W7O in step 3) are used. 24 and 280 g TiO2 are converted into 121.50 g Cu(NO3)2·3H2O and 280 g Al2O3. The obtained material is oxidation sample 1.

[0095] Comparative Example 1

[0096] The difference between this comparative example and Example 1 is that step 4) is changed to mixing 8g of LGH-7499 and 8g of HY-235 into effective component C, and stirring at room temperature at a speed of 500 r / min for 1 hour to obtain effective component D. The obtained material is denitration sample 2.

[0097] Comparative Example 2

[0098] The difference between this comparative example and Example 1 is that 8g of LGH-7499 and 8g of HY-235 in step 4) are replaced with 16g of deionized water. The obtained material is denitrification sample 3.

[0099] Comparative Example 3

[0100] 1) 280 g of TiO2 was added to 320 g of deionized water during stirring, and the mixture was stirred at room temperature at a speed of 500 r / min for 1 h to obtain carrier material A.

[0101] 2) Combine 25.73g NH4VO3 and 23.26g(NH4)6W7O 24 The active material B was obtained by adding the active material to the support material A during stirring and stirring at a speed of 500 r / min for 1 h at room temperature.

[0102] 3) 50 g of titanium colloid was added to the active material B during the stirring process, and stirred at a speed of 500 r / min at room temperature for 1 h to obtain a coating slurry C.

[0103] 4) Coat the coating slurry C on the cordierite block. Calcine at 550°C for 4 hours in an air atmosphere with a heating rate of 5°C / min. The obtained material is the denitrification sample 4.

[0104] Comparative Example 4

[0105] The difference between this comparative example and Example 1 is that step 4) is changed to mixing 8g of LGH-7499 and 8g of HY-235 into effective component C, and stirring at room temperature at a speed of 500 r / min for 1 hour to obtain effective component D. The obtained material is oxidized sample 2.

[0106] Comparative Example 5

[0107] The difference between this comparative example and Example 1 is that 8g of LGH-7499 and 8g of HY-235 in step 4) are replaced with 16g of deionized water. The obtained material is oxidation sample 3.

[0108] Comparative Example 6

[0109] The difference between this comparative example and comparative example 3 is that 280g TiO2 in step 1) is replaced with 280g Al2O3; 25.73g NH4VO3 and 23.26g (NH4)6W7O in step 2) are replaced with 24 The 50g titanium colloid in step 3) is changed to 50g aluminum colloid. The obtained material is the oxidized sample 4.

[0110] In the second aspect, the present application also proposes a honeycomb catalyst suitable for denitration and oxidation, and the denitration and oxidation honeycomb catalyst is made by the method described in the first aspect.

[0111] Preferably, the catalyst brush-coated paint body comprises 20-30wt% of resin emulsion, 26-28wt% of carrier component material components, 2-4wt% of active components, 0.1-0.5wt% of defoamer, 0.5-1wt% of leveling agent, 0.5-1wt% of neutralizer, 0.5-1wt% of thickener and 0.5-1wt% of dispersant, and the balance is deionized water; more preferably, the catalyst brush-coated paint body comprises 25-30wt% of resin emulsion, 27-28wt% of carrier component material components, 3-4wt% of active components, 0.2-0.4wt% of defoamer, 0.7-0.9wt% of leveling agent, 0.7-0.9wt% of neutralizer, 0.7-0.9wt% of thickener and 0.7-0.9wt% of dispersant, and the balance is deionized water.

[0112] In a third aspect, the present application also proposes the application of a honeycomb catalyst prepared by a novel quantitative brushing method suitable for denitration and oxidation honeycomb catalysts in denitration and oxidation.

[0113] Application Example 1

[0114] The materials obtained in the above-mentioned Example 1 and Comparative Examples 1, 2, and 3 were used as catalysts to carry out a denitration experiment. The experimental conditions were as follows: the concentration of each gas (vol%) was controlled by a mass flow meter: NO: 500ppm, NH3: 500ppm, O2: 5%, N2 was the balance gas, and the volumetric space velocity of the honeycomb catalyst was 10000h -1 The calculation formula of denitrification efficiency is η = (C1-C2) / C1×100%, where C1 is the concentration of NOx at the inlet and C2 is the concentration of NOx at the outlet, which is obtained by flue gas analysis test.

[0115] Application Example 2

[0116] The materials obtained in the above-mentioned Example 2 and Comparative Examples 4, 5, and 6 were used as catalysts to carry out VOC oxidation experiments. The selected VOC was benzene. The experimental conditions were as follows: the concentration of each gas (vol%) was controlled by a mass flow meter, benzene: 500 ppm, O2: 5%, N2 as the balance gas, and the volumetric space velocity of the honeycomb catalyst was 10000 h -1 The calculation formula for toluene removal efficiency is η = (C1-C2) / C1×100%, where C1 is the concentration of toluene at the inlet and C2 is the concentration of toluene at the outlet, which is obtained by testing with a flue gas analyzer.

[0117] Application Example 3

[0118] The materials obtained in Example 1 and Comparative Examples 1, 2, and 3 were characterized by SEM and their dispersion was compared.

[0119] Application Example 4

[0120] The materials obtained in Example 1 and Comparative Example 3 were subjected to an adhesion test. The adhesion test conditions were as follows: an ultrasonic oscillation test was performed using a numerically controlled ultrasonic cleaning machine, and the coated catalyst was placed in an ultrasonic machine for ultrasonic oscillation for 10 minutes. The coating adhesion rates of multiple groups of tested catalysts were calculated according to the following formula: η = (m2-m0) / (m1-m0) × 100%, where m0 is the mass of the cordierite carrier, m1 is the mass of the catalyst before the oscillation test, and m2 is the mass of the catalyst after the oscillation test.

[0121] The results of the denitrification experiment in Application Example 1 are as follows: Figure 3 As shown. Figure 3 The data show that the honeycomb catalyst prepared by the novel quantitative brushing method suitable for denitrification honeycomb catalyst of the present invention can achieve the best low-temperature SCR activity, and the NOx removal rate reaches 100% in the temperature range of 225-450°C, and the temperature window is widened; and the preparation process is simple, and the raw materials are cheap and easily available.

[0122] The results of the detoluene experiment in Application Example 2 are as follows: Figure 4 As shown. Figure 4 The data show that the honeycomb catalyst prepared by the novel quantitative brushing method suitable for denitration honeycomb catalyst of the present invention can achieve the best low-temperature catalytic oxidation activity, reaching 80% conversion rate at 240°C and 100% conversion rate at 280°C; and the preparation process is simple, and the raw materials are cheap and easily available.

[0123] The dispersion SEM characterization of Application Example 3 is as follows Figure 5As shown, it can be found that the dispersion of Example 1 is the best, which is better than that of Comparative Example 3. It can be shown that the honeycomb catalyst prepared by the novel quantitative brush coating method suitable for denitration honeycomb catalyst of the present invention also has better dispersibility than the conventional coating method.

[0124] The results of the adhesion rate experiment of Application Example 4 are shown in Table 1. It can be found from Table 1 that the honeycomb catalyst prepared by the novel quantitative brush coating method suitable for denitration honeycomb catalyst of the present invention can obtain a higher adhesion rate.

[0125] Table 1: Adhesion rate of three groups

[0126]

[0127] When we deeply explore the significant advantages of the new quantitative brush coating method compared to traditional slurry coating, it is not difficult to find that this innovative technology not only sets a new benchmark in the field of environmental protection, but also demonstrates unprecedented advantages in efficient resource utilization and improved production efficiency.

[0128] From the perspective of green environmental protection, the core competitiveness of the new quantitative brush coating method lies in its complete abandonment of dependence on organic solvents. This revolutionary measure directly reduces the emission of organic waste gas, fundamentally curbs the air pollution problem caused by solvent volatilization, and contributes to the protection of blue sky and white clouds. In contrast, the traditional slurry coating method uses a large amount of organic solvents, which inevitably produces volatile organic compounds (VOCs) during the coating process, posing a potential threat to the atmospheric environment, and requires additional resources for tail gas treatment.

[0129] In terms of resource conservation and efficient utilization, the new quantitative brush coating method also demonstrates excellent performance. This method not only significantly reduces water consumption by precisely controlling the coating amount, but also ensures that the paint is used without waste, thus maximizing resource utilization, which coincides with the current global concept of circular economy and sustainable development. In contrast, the traditional slurry coating process is often accompanied by the consumption of a large amount of water resources and the difficulty in recycling the remaining paint, resulting in low resource utilization efficiency, which does not meet the requirements of the era of green production.

[0130] In addition, the new quantitative brush coating method also shows great potential in improving production efficiency. Its process design is concise and clear, easy to operate, and the highly automated production line configuration greatly shortens the production cycle and improves the overall operating efficiency of the production line. In contrast, the traditional slurry coating method often requires multiple coating and drying, which is a cumbersome process and has high requirements on the operator's skill level, thus limiting the further improvement of production efficiency.

[0131] In the face of the urgent requirements of the "dual carbon" goals, we need to take active and effective measures to deal with the tail gas problems generated in industrial production. Specifically, we should focus on strengthening the denitrification and removal of VOCs (volatile organic compound removal) of tail gas, and contribute to the realization of carbon peak and carbon neutrality goals through advanced purification technology.

[0132] In summary, compared with the prior art, the present invention has the following beneficial technical effects:

[0133] (1) The catalyst of the present invention has a lower denitration and oxidation treatment temperature and a higher reaction catalytic activity, and the preparation method of the present invention is simple to operate and has simple equipment requirements. A catalyst brush-coated paint body is prepared with active components, resin emulsion, carrier material and a variety of auxiliary ingredients, and is brushed onto a cordierite block using a new type of brushing tool proposed in the present application to prepare a coated honeycomb catalyst. Such a catalyst has a higher denitration and VOCs oxidation catalytic activity, and has a better dispersion and a lower shedding rate.

[0134] (2) The preparation method of the present invention is simple to operate and requires simple equipment, which is conducive to industrial promotion and application.

[0135] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that the present invention includes but is not limited to the contents described in the above specific embodiments. Any modification that does not deviate from the functional and structural principles of the present invention will be included in the scope of the claims.

Claims

1. A quantitative brushing method suitable for denitration and oxidation honeycomb catalysts, characterized in that: The steps include: S110, mixing and stirring the resin emulsion and the first part of the auxiliary material to obtain a resin mixed material B; S120, mixing and stirring the active component salt, the carrier material and the second part of the auxiliary material to obtain an effective component D, wherein the active component salt includes an active component salt for denitration and an active component salt for VOCs oxidation, and the carrier material includes a carrier material for denitration and a carrier material for VOCs oxidation; S130, mixing and stirring the resin mixed material B, the effective component D and the remaining auxiliary materials to obtain a catalyst brush coating body G; S200, quantitatively brushing the catalyst coating body G into the pores of the honeycomb ceramic material, and calcining to obtain a honeycomb catalyst.

2. A quantitative brushing method for denitration and oxidation honeycomb catalysts according to claim 1, characterized in that: The resin emulsion is selected from any two of water-based acrylic resin, water-based alkyd resin, and water-based amino resin, and the ratio of the two resin emulsions is 1:(0.8-1.2); And / or, the active component salt for denitration is selected from one of vanadium salts, tungsten salts, iron salts, manganese salts and cobalt salts; And / or, the active component salt for VOCs oxidation is selected from one of copper salt, iron salt, manganese salt and cobalt salt; and / or, the carrier material for denitrification is selected from one of TiO2 and Al2O3; And / or, the carrier material for VOCs oxidation is selected from one of SiO2 and Al2O3; And / or, the auxiliary materials include defoamers, leveling agents, neutralizers, thickeners and dispersants; And / or, the honeycomb ceramic material is a cordierite block.

3. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 1, characterized in that: The quantitative brush coating is calculated according to the following formula: W = (m1-m0) / V, where W is the catalyst coating amount, in g / dm 3 , m0 is the mass of the blank carrier, m1 is the total mass of the sample coated with the catalyst after calcination, and V is the volume of the honeycomb ceramic material; and / or, the calcination conditions include: temperature 500-600°C, time 3-6h; heating rate of 2-10°C / min in an oxygen atmosphere.

4. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 1, characterized in that: The resin mixed material B is prepared by the following method: S111, mixing and stirring the two resin emulsions at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a resin mixture A; S112, mixing the defoamer into the resin mixture A during stirring, stirring at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a resin mixed material B.

5. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 4, characterized in that: The effective component D is prepared by the following method: S121, mixing the active component salt and the carrier material powder into deionized water, stirring at a temperature of 20-40° C. and a speed of 400-600 r / min for 0.5-2 h, and ball milling to obtain an effective component C; S122. Mix the leveling agent and the dispersant into the effective component C during stirring, and stir at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain the effective component D.

6. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 5, characterized in that: The catalyst brush paint body G is prepared by the following method: S131, mixing the effective component D into the resin mixed material B during stirring, stirring at a temperature of 20-40° C. and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a paint body material E; S132, mixing the neutralizer into the paint material E during stirring, adjusting the pH to 7.0-7.5, stirring at a temperature of 20-40° C. and a speed of 400-600 r / min for 0.5-2 h to obtain a paint material F; S133, mixing the thickener into the paint material F during stirring, adjusting the consistency to 2000-4000 mPa.s, stirring at a temperature of 20-40°C and a rotation speed of 400-600 r / min for 0.5-2 h to obtain a catalyst brush-coated paint body G.

7. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 6, characterized in that: The catalyst brush paint body G includes 20-30wt% of resin emulsion, 26-28wt% of carrier component material component, 2-4wt% of active component, 0.1-0.5wt% of defoamer, 0.5-1wt% of leveling agent, 0.5-1wt% of neutralizer, 0.5-1wt% of thickener and 0.5-1wt% of dispersant, and the balance is deionized water.

8. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 6, characterized in that: The ball milling conditions in step S121 include: the ball milling speed is 4000-6000 r / min, and the ball milling time is 1-4 cycles of forward rotation of 5-20 min, stop of 20-60 s, reverse rotation of 5-20 min, stop of 20-60 s.

9. A quantitative brush coating method for denitration and oxidation honeycomb catalysts according to claim 1, characterized in that: The catalyst paint body G is quantitatively brushed into the pores of the honeycomb ceramic material using a brushing tool, wherein the brushing tool comprises a constant pressure tank, a liquid guide tube connected to the constant pressure tank, and a brush connected to the liquid guide tube.

10. A honeycomb catalyst suitable for denitration and oxidation, characterized in that: The method is prepared by any one of claims 1 to 9.

Images