Honeycomb-shaped denitration catalyst prepared based on modified supported manganese oxide of industrial waste catalyst, preparation method and application

Abstract

The invention provides a honeycomb denitration catalyst prepared on the basis of an industrial waste catalyst modified loaded manganese oxide, a preparation method and application, and belongs to the field of industrial waste catalyst resource utilization and catalyst preparation. The preparation method comprises the following steps: preparing manganese-based catalyst powder, mixing the manganese-based catalyst powder with a forming aid, kneading, refining mud, aging, extruding, drying, calcining and other forming processes to prepare the honeycomb-shaped manganese-based low-temperature SCR denitration catalyst, and the honeycomb-shaped catalyst has reliable low-temperature SCR denitration performance and good mechanical strength at the same time. The active powder prepared by the method has the advantages of more uniform dispersion of active components, higher denitration efficiency at low temperature, larger specific surface area and higher blank strength after molding. And the whole preparation process is green and environment-friendly, secondary pollutant emission pollution is avoided, and the catalyst preparation time is short.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of industrial waste catalyst resource utilization and catalyst preparation, and particularly relates to a honeycomb-shaped denitration catalyst prepared based on modification of industrial waste catalyst and loading of manganese oxides, a preparation method and application. BACKGROUND

[0002] Nitrogen oxides are one of the main atmospheric pollutants, and are an important reason for the formation of acid rain, the generation of photochemical smog, the destruction of the ozone layer and the intensification of the greenhouse effect. In addition, it can also cause respiratory, cardiovascular, nervous and other system diseases in humans, and has a bad impact on the environment and human health. In the current environmental protection technology field, the NH3-SCR denitration technology has become a mainstay in the treatment of nitrogen oxides, and with its excellent performance and wide application prospect, it contributes indispensable power to the air pollution control.

[0003] In addition, in the fluid catalytic cracking process, the catalyst is gradually deactivated due to mechanical wear, coke deposition and heavy metal ion poisoning after long-term use, and eventually becomes an industrial waste catalyst. How to realize the reuse of waste catalysts is a problem to be solved.

[0004] A patent with publication number CN 116943636 A was published on October 27, 2023, which discloses a molding preparation method of waste FCC supported manganese oxide columnar low-temperature SCR denitration catalyst. It discloses a disposal problem for hazardous waste waste FCC catalyst (SFCCC) generated in the petroleum chemical process. By adding harmful metal immobilization additives and loading manganese oxide active components, a catalyst powder with low-temperature SCR denitration activity is prepared. Then, by optimizing the bonding formula system, the columnar particle of the catalyst is formed, and the columnar low-temperature SCR denitration catalyst is prepared. However, the catalyst prepared by in-situ growth method has the disadvantages of poor dispersion of active components, small specific surface area, small temperature window and low mechanical strength. SUMMARY

[0005] The purpose of the present application is to provide a honeycomb-shaped denitration catalyst prepared based on modification of industrial waste catalyst and loading of manganese oxides and a preparation method thereof. The solid-phase ball milling method is used to prepare a manganese-based low-temperature SCR denitration catalyst powder. The active components are highly dispersed, the catalyst has excellent denitration performance, and the technical problem of difficulty in extruding the honeycomb body of the supported manganese-based catalyst powder is solved.

[0006] Another purpose of the present application is to provide an application of a honeycomb-shaped denitration catalyst prepared based on modification of industrial waste catalyst and loading of manganese oxides, which is used for industrial denitration.

[0007] The specific technical solutions of the present application are as follows:

[0008] A preparation method of a honeycomb denitration catalyst based on an industrial waste catalyst modified to load manganese oxide, comprising the following steps:

[0009] 1) uniformly mixing the modified industrial waste catalyst and inorganic clay, then mixing with a manganese source, ball milling to obtain powder 1;

[0010] 2) mixing powder 1 and potassium permanganate, ball milling to obtain powder 2;

[0011] 3) washing, filtering and drying powder 2 to obtain manganese-based catalyst powder;

[0012] 4) mixing the manganese-based catalyst powder with a molding aid, honeycomb molding, and the method is completed.

[0013] The mass ratio of the modified industrial waste catalyst to the inorganic clay in step 1) is 10-100:10-100; the inorganic clay is one or a combination of halloysite, attapulgite and bentonite;

[0014] The mass ratio of the modified industrial waste catalyst to the manganese source in step 1) is 10-100:10-50;

[0015] The manganese source is manganese acetate tetrahydrate;

[0016] The ball milling in step 1) is at a speed of 400-600 r / min for 5-7 h;

[0017] The preparation method of the modified industrial waste catalyst in step 1) is: calcining magnesium-aluminum hydrotalcite at 450-550°C in an air atmosphere for 2-4 h, cooling, mixing with industrial waste catalyst, adding water, stirring, standing, and vacuum drying to obtain the modified industrial waste catalyst; wherein the industrial waste catalyst is more than 200 mesh; the industrial waste catalyst is derived from catalytic cracking, catalytic cracking, catalytic hydrogenation and the like; the amount of water added is controlled to have a liquid-solid ratio of 0.6±0.05. That is, the modified industrial waste catalyst is prepared according to the method described in the patent "Method for harmless fixation of harmful metal elements in waste petroleum catalytic cracking catalyst" with application number 202211642117.0. The calcination of magnesium-aluminum hydrotalcite in an air atmosphere achieves partial removal of structural water and partial decomposition of carbonate, causing a large number of structural defect positions, which provides functional positions for structural reconstruction in the subsequent rehydration reaction process of heavy metal element immobilization, i.e. the so-called structural memory effect.

[0018] The modification of industrial waste catalyst in the application: the industrial waste catalyst is modified by using a solidifying agent (calcined magnesium-aluminum hydrotalcite), the purpose is to fix the heavy metal ions therein, inhibit the risk of leaching and migration of harmful heavy metal ions in the environment, and make it out of the attribute of hazardous waste. At high temperature, the free water and bound water in the magnesium-aluminum hydrotalcite can be completely removed, and the anions such as carbonate in it can also be decomposed, at this time, the specific surface area of the magnesium-aluminum hydrotalcite reaches the maximum, which can capture the heavy metal ions in the industrial waste catalyst and form structural reconstruction to be solidified, thereby playing a role in fixing the heavy metal ions.

[0019] In step 1), the manganese oxide is loaded on the modified industrial waste catalyst by using a solid phase ball milling method (SO method for short); the solid phase reaction is carried out by using ball milling, so that the particle carrier and manganese acetate tetrahydrate are refined to the nanometer level, thereby forming a highly dispersed powder.

[0020] In step 2), the ball milling is carried out at a speed of 400-600 r / min for 5-7 h.

[0021] In step 2), the ratio of the modified industrial waste catalyst to potassium permanganate is 10-100:1-20.

[0022] In step 2), after the introduction of potassium permanganate particles, the solid phase powder changes as follows: the potassium permanganate particles are first uniformly mixed with the highly dispersed powder 1 in step 1), and with the continuous ball milling, the particle size in the tank is refined, and the super-high heat is generated due to the collision and friction between the mill ball and the tank body and between the mill balls, which can promote the reaction between the potassium permanganate particles and the manganese acetate particles to form manganese oxide particles, and these manganese oxide particles are again refined and can be more fully mixed with the carrier, so that the manganese oxide is more dispersed, which is called mechanical activation effect. With the continuous ball milling, the manganese oxide particles formed by activation are further refined to the nanometer level and can be uniformly dispersed on the surface of the carrier.

[0023] In step 4), the forming aid includes chopped glass fiber, pseudo-boehmite, lubricant, pore-forming agent and water.

[0024] The lubricant is one or more of talc powder, zinc stearate, stearic acid, liquid paraffin and graphite powder.

[0025] The pore-forming agent is one or more of polyethylene glycol or activated carbon.

[0026] The chopped glass fiber is 3 mm chopped glass fiber.

[0027] The water is desalted water.

[0028] The step 4) is specifically: taking manganese-based catalyst powder, chopped glass fiber, pseudoboehmite, lubricant, pore-forming agent and water, mixing and then kneading for the first time; then adding manganese-based catalyst powder again and kneading for the second time; then vacuum refining, sealing and aging, and finally extruding, cutting, drying and calcining in air, to obtain the manganese-based honeycomb denitration catalyst.

[0029] The mass ratio of the manganese-based catalyst powder, the chopped glass fiber, the pseudoboehmite, the lubricant, the pore-forming agent, the water and the manganese-based catalyst powder added for the second time is 60-75:2-5:5-10:1-3:1-2:40-50:25-40.

[0030] The kneading time for the first time in the step 4) is 8-16h; and the kneading time for the second time is 2-4h.

[0031] The sealing and aging time in the step 4) is 24-48h.

[0032] The mud after the aging in the step 4) is honeycomb extruded, and the honeycomb catalyst blank is cut by molybdenum wire, to obtain the honeycomb denitration catalyst wet blank prepared based on the modified manganese oxide supported on the industrial waste catalyst.

[0033] The drying in the step 4) is: first sealed and dried for 3-6 days, and then moved to a constant temperature and humidity oven for drying for 1-3 days, with the oven temperature being 30-80℃ and the humidity being 30-80%.

[0034] The calcining in the step 4) is performed in air, with the temperature being raised to 450-550℃ at a temperature raising rate of 1-2℃ / min and calcined for 10-30h, and then naturally cooled to room temperature in the furnace.

[0035] Finally, the honeycomb catalyst is cut at both ends, to obtain the honeycomb manganese-based low-temperature SCR denitration catalyst.

[0036] In the step 4), the manganese-based catalyst powder, the inorganic structure aid (chopped glass fiber and pseudoboehmite), the lubricant, the pore-forming agent and the like are uniformly dry mixed, and then introduced into the desalted water for wet mixing, and mixed under the condition that the mud has a high water content (40%). If the aging, extrusion, cutting, drying and calcining processes are performed at this time, the extruded honeycomb blank collapses seriously. Therefore, the water content of the mud as a whole needs to be reduced, and when the water content is less than 34% (after the second kneading), the vacuum refining, aging, extrusion, cutting, drying and calcining processes are performed, to obtain the honeycomb manganese-based catalyst.

[0037] The inventors find that the catalyst can be modified to realize resource utilization. The modified industrial waste catalyst has a larger specific surface area, good pore volume and pore size characteristics, and is an excellent carrier for preparing supported catalysts. In addition, in order to solve the problems of uneven distribution of active components and difficulty in forming of manganese oxide supported powder during the forming process, the solid phase ball milling method is proposed. The manganese-based low-temperature SCR denitration catalyst powder prepared by the solid phase ball milling method has high dispersion of active components, excellent denitration performance, and solves the technical problem of difficulty in extruding the manganese oxide-based supported catalyst powder into a honeycomb body, realizing the industrial application value of the industrial waste catalyst.

[0038] The application provides a honeycomb denitration catalyst prepared based on an industrial waste catalyst modified to load manganese oxide.

[0039] The application provides application of a honeycomb denitration catalyst prepared based on an industrial waste catalyst modified to load manganese oxide, and the honeycomb denitration catalyst is used for industrial denitration.

[0040] The application uses calcined and activated magnesium-aluminum hydrotalcite as a heavy metal solidifying agent to harmlessly dispose and modify the industrial waste catalyst, loads manganese oxide on the catalyst by a solid phase ball milling method, prepares manganese-based catalyst powder, mixes the catalyst powder with a forming aid, and then performs kneading, knead-molding, aging, extrusion, drying, calcination and other forming processes to prepare a honeycomb manganese-based low-temperature SCR denitration catalyst. The honeycomb catalyst has reliable low-temperature SCR denitration performance and good mechanical strength. The application loads active components on the carrier by the solid phase ball milling method, and the catalyst powder prepared by the method has reliable denitration efficiency in a low-temperature zone, higher dispersion of active components, higher denitration efficiency at low temperature, larger specific surface area and higher strength of the blank after forming, compared with the in-situ growth method. In addition, the application optimizes the bonding formula and the forming process, realizes the industrial application value of the industrial waste catalyst, and the whole preparation process is green and environmentally friendly, does not cause secondary pollutant emission pollution, and has a short catalyst preparation time.

[0041] Compared with the prior art, the active component of the active powder prepared by the solid phase ball milling method has better dispersion, higher denitration efficiency and a wider temperature window. Moreover, the solid phase ball milling method has simple preparation process, short catalyst preparation period, nano-level powder particle size, easy forming and high strength after forming. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 A denitration efficiency diagram of catalyst powder prepared by a solid phase ball milling method and an in-situ growth method;

[0043] Figure 2 A denitration efficiency diagram of a manganese-based honeycomb denitration catalyst;

[0044] Figure 3 EDS images of Mn and O elements for catalyst powder prepared by in-situ growth method and solid phase ball milling method. DETAILED DESCRIPTION

[0045] To make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0046] The test materials and reagents used in the following examples, and the like, can be obtained from commercial channels unless otherwise specified.

[0047] The specific techniques or conditions not specified in the examples can be carried out according to the techniques or conditions described in the literature in the art or according to the product instructions.

[0048] The modified industrial waste catalyst powder used in the examples refers to the modified industrial waste catalyst powder prepared according to the method described in Example 1 of the patent “Method for harmless fixation of harmful metal elements in waste petroleum catalytic cracking catalyst” with application number 202211642117.0;

[0049] The modified industrial waste catalyst used in the preparation is a modified industrial waste catalyst with a mesh size of 200 or more; the nanotubular halloysite has a mesh size of 325.

[0050] Example 1

[0051] A preparation method (SO method) of a honeycomb-shaped denitration catalyst based on a modified manganese oxide loaded on an industrial waste catalyst, comprising the following steps:

[0052] S1, 60 parts by mass of modified industrial waste catalyst powder with a mesh size of 200 or more and 40 parts by mass of nanotubular halloysite with a mesh size of 325 are mixed to obtain 100 parts by mass of mixed powder, then 21 parts by mass of manganese acetate tetrahydrate is added, and the mixture is mixed again to obtain a uniform powder I, which is placed in a ball mill tank, and the ball mill is operated at a speed of 400 r / min for 6 h to obtain a homogeneous powder II;

[0053] S2, 9 parts by mass of potassium permanganate particles are mixed with the homogeneous powder II, and then the mixture is placed in a ball mill again for ball milling, and the ball mill is still operated at a speed of 400 r / min for 6 h, and then the mechanically activated powder III is taken out;

[0054] S3, the powder III obtained in step S2 is washed with water, filtered, dried, and crushed to a mesh size of 200 or more to obtain a manganese-based catalyst powder;

[0055] S4, batch feeding: first feeding: 65 parts by mass of manganese-based catalyst powder, 2 parts by mass of 3 mm chopped glass fiber, 5 parts by mass of pseudo-boehmite, 2 parts by mass of zinc stearate, 1 part by mass of polyethylene glycol, and 45 parts by mass of water in step S3, kneading for 10 h, second feeding: adding 35 parts by mass of manganese-based catalyst powder, and secondary kneading for 2 h.

[0056] S5, after the above kneading, vacuum kneading and sealing for 48 h.

[0057] S6, the green body completed in step S5 is vacuum extruded, and the honeycomb-shaped catalyst body is cut off with a molybdenum wire to obtain a honeycomb-shaped denitration catalyst prepared based on an industrial waste catalyst modified and loaded with manganese oxide, then sealed and dried for 4 days, then moved to a constant temperature and humidity drying oven for drying for 2 days, the oven temperature is 50°C and the humidity is 50%, and the temperature is raised to 500°C at a rate of 1°C / min and calcined for 12 h, after completion, the furnace is naturally cooled to room temperature, and the honeycomb-shaped denitration catalyst prepared based on the industrial waste catalyst modified and loaded with manganese oxide is obtained.

[0058] Example 2 (in-situ growth method as a comparison, in-situ growth method is referred to as SP method)

[0059] The manganese-based catalyst powder is prepared according to the in-situ growth method disclosed in Example 1 of CN116943636A, except that the mass ratio of the modified industrial waste catalyst powder to clay halloysite is controlled to be 6:4 when preparing the manganese-based catalyst powder, and then the manganese-based catalyst powder is prepared according to the raw materials and amounts in steps S4-S6 of Example 1 of the present application to obtain a honeycomb-shaped denitration catalyst.

[0060] Example 3 (as a comparison)

[0061] A method for preparing a honeycomb-shaped denitration catalyst based on an industrial waste catalyst modified and loaded with manganese oxide, comprising the following steps:

[0062] According to steps S1-S6 in Example 1, except that 1 part by mass of carboxymethyl cellulose and 1 part by mass of polyacrylamide are additionally added.

[0063] Example 4

[0064] A method for preparing a honeycomb-shaped denitration catalyst based on an industrial waste catalyst modified and loaded with manganese oxide, comprising the following steps:

[0065] According to steps S1-S6 in Example 1, except that the addition amount of the modified industrial waste catalyst and halloysite is 50 parts by mass.

[0066] The test method for the denitration efficiency of the honeycomb-shaped catalyst of each example is as follows:

[0067] The honeycomb catalyst (100x100x100mm) was cut into small pieces (10x10x20mm) for testing the denitration efficiency in a fixed bed reactor. The simulated flue gas was composed of NH3, NO, O2, and N2, with a total gas volume of 360ml / min and a reaction space velocity of 10500h-1. The reaction temperature was 100-300℃. The denitration efficiency test calculation method was as follows: -1

[0068] The denitration efficiency calculation formula = [(C0-C) / C0]x100%. In the formula, C0 is the initial concentration of NO, and C is the NO concentration tested at different temperatures.

[0069] The mechanical strength test method of the honeycomb catalyst was as follows:

[0070] The honeycomb catalyst (100x100x100mm) was polished flat at both ends, and the mechanical strength test of the catalyst was carried out by means of a universal pressure testing machine. The pressure disc of the press machine was set to drop at a speed of 10mm / min. The axial and radial compressive strengths of the honeycomb catalyst were tested respectively. Each direction was tested for 3 times, and the compressive strength deviation was less than 5%. After three times of compression test, the average value was taken as the final data of the axial and radial compressive strengths of the honeycomb catalyst.

[0071] Figure 1 The denitration efficiency diagram of the catalyst powder prepared by the solid phase ball milling method in Example 1 and the in-situ growth method in Example 2 is shown in FIG. 1, Figure 2 The denitration efficiency diagram of the manganese-based honeycomb denitration catalyst of each example is shown in FIG. 2.

[0072] The denitration efficiency of the catalyst powder prepared by the solid phase ball milling method in Example 1 is better than that of the manganese-based catalyst powder prepared by the in-situ growth method in Example 2. This is because the ball milling can refine the powder particles to the nanometer level, and the super high energy generated by the impact and friction between the grinding balls promotes the redox reaction of manganese acetate and potassium permanganate particles to generate manganese oxide uniformly distributed on the surface of the carrier. Therefore, the solid phase ball milling method can obtain a catalyst powder with highly dispersed active components. From the macroscopic point of view, the powder will be refined due to ball milling, which is more conducive to molding. The honeycomb body after molding has higher compressive strength. As can be seen from the EDS diagram of the catalyst powder prepared by the two methods, Figure 3 the manganese element of the catalyst prepared by the solid phase ball milling method is more uniformly dispersed. This is because the redox reaction occurs in the liquid phase, the liquid cannot flow through every pore of the carrier, and the particle size of the generated potassium permanganate particles is different. The larger manganese dioxide particles are blocked at the pore mouth of the carrier, and subsequent other ions cannot enter. The catalyst powder prepared by the in-situ growth method and the solid phase ball milling method and the honeycomb body were detected by the present application, and the results are shown in Table 1.

[0073] ​Table 1 is the BET analysis of catalyst powder prepared by in-situ growth method and solid phase ball milling method and honeycomb

[0074]

[0075] The mechanical strength of the honeycomb catalyst prepared in each embodiment is tested, and the results are shown in Table 2.

[0076] Table 2 Comparison of mechanical strength of honeycomb catalysts of each embodiment

[0077] Example Axial compressive strength (MPa) Radial compressive strength (MPa) Example 1 3.61 1.26 Example 2 3.24 1.05 Example 3 1.46 0.38 Example 4 4.24 1.41

[0078] In Example 3, the introduction of the organic binder has an adverse effect on the adhesion and molding of the powder. The plasticity of the clay is poor, the molding effect is poor, and the green body shrinks and deforms severely during drying, and the surface cracks. The introduction of the organic binder causes poor molding effect, and the extruded green body is not dense enough. Moreover, during calcination, these organic binders will produce gas and escape from the inside of the catalyst, leaving many micropores and affecting the mechanical strength of the green body. According to the Figure 2 It can be seen that, in Example 3, the organic binder decomposes at high temperature, which can increase the specific surface area of the catalyst, and the catalytic performance is slightly higher than that of Example 1, but the mechanical performance is poor, and it cannot be used for industrial production.

[0079] According to the active powder preparation process in Example 1 and Example 4, the manganese-based honeycomb catalyst prepared by molding and drying process is compared. The honeycomb green body in Example 4 exhibits higher mechanical strength performance, which is because the nanotubular halloysite can guarantee the mechanical strength of the catalyst after calcination. Increasing the proportion of clay has little effect on the specific surface area of the catalyst and the denitration effect of the catalyst. However, the amount of clay added in Example 4 is large, and the cost of clay is high. Therefore, the embodiment 1 of the present application is the best, not only has good catalytic performance and good mechanical performance of honeycomb molding, but also has low clay usage and low cost.

[0080] In summary, the application discloses a honeycomb forming preparation method of a low-temperature SCR denitration catalyst based on modified industrial waste catalyst loaded with manganese oxide and application thereof. The application continues the previous invention of the inventor team, i.e. using calcined and activated magnesium-aluminum hydrotalcite as a heavy metal solidifying agent to harmlessly dispose and modify the industrial waste catalyst, using the modified catalyst as a carrier for preparing a denitration catalyst, using a solid-phase ball milling method to load active component manganese dioxide, and preparing a low-temperature SCR denitration catalyst powder. In a temperature window of 100-300 DEG C, the denitration efficiency of the powder catalyst is kept above 90%; in a temperature window of 150-250 DEG C, the denitration efficiency of the honeycomb-shaped low-temperature SCR denitration catalyst is kept above 85%. In addition, the honeycomb-shaped denitration catalyst has reliable mechanical strength, and the axial and radial mechanical strengths are 3.61 MPa and 1.26 MPa respectively. Therefore, according to the method disclosed in the application, the prepared honeycomb-shaped low-temperature SCR denitration catalyst has reliable low-temperature SCR denitration performance and good mechanical strength, and has high industrial application value.

[0081] The above description of the embodiments is to enable those skilled in the art to understand and use the application. Those skilled in the art can easily make various modifications to the embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the application is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art based on the disclosure of the application without departing from the scope of the application should be within the protection scope of the application.

Claims

1. A method for preparing a honeycomb denitration catalyst based on a modification of a supported manganese oxide prepared using an industrial waste catalyst, characterized by, The preparation method comprises the following steps: 1) mixing the modified industrial waste catalyst and inorganic clay uniformly, then mixing with a manganese source, and ball milling to obtain powder 1; 2) mixing the powder 1 and potassium permanganate, and ball milling to obtain powder 2; 3) washing the powder 2 with water, filtering and drying to obtain a manganese-based catalyst powder; 4) mixing the manganese-based catalyst powder with a forming aid, and honeycomb forming to obtain the product.

2. The production method according to claim 1, characterized by, In step 1), the mass ratio of the modified industrial waste catalyst and inorganic clay is 10-100:10-100; the mass ratio of the modified industrial waste catalyst and the manganese source is 10-100:10-50; and the manganese source is manganese acetate tetrahydrate.

3. The preparation method according to claim 1, characterized in that, In step 1), the ball milling is performed at a speed of 400-600 r / min for 5-7 h.

4. The method of claim 1, wherein, In step 2), the ball milling is performed at a speed of 400-600 r / min for 5-7 h.

5. The production method according to claim 1 or 5, characterized by, In step 2), the amount ratio of the modified industrial waste catalyst and potassium permanganate is 10-100:1-20.

6. The method of claim 1, wherein, In step 4), the manganese-based catalyst powder, chopped glass fiber, pseudoboehmite, lubricant, pore-forming agent and water are mixed and then kneaded for the first time; then the manganese-based catalyst powder is added and kneaded for the second time; vacuum kneading, sealing and aging are performed, and finally extrusion, cutting, drying and calcination are performed in an air atmosphere to obtain the manganese-based honeycomb denitration catalyst; the mass ratio of the first-time-added manganese-based catalyst powder, chopped glass fiber, pseudoboehmite, lubricant, pore-forming agent, water and second-time-added manganese-based catalyst powder is 60-75:2-5:5-10:1-3:1-2:40-50:25-40.

7. The production method according to claim 6, wherein In step 4), the drying is performed by sealing and drying for 3-6 days, and then drying in a constant-temperature and constant-humidity oven for 1-3 days; the oven temperature is 30-80 ℃, and the humidity is 30-80%.

8. The production method according to claim 6 or 7, characterized by, In step 4), the calcination is performed by increasing the temperature to 450-550 ℃ at a temperature increasing rate of 1-2 ℃ / min and calcining for 10-30 h; after completion, the temperature is naturally decreased to room temperature in the furnace.

9. A honeycomb denitration catalyst based on an industrial waste catalyst modified and loaded with manganese oxide, which is prepared by the preparation method of any one of claims 1-8.

10. The use of the honeycomb denitration catalyst prepared based on the modified supported manganese oxides of industrial waste catalysts according to claim 9, characterized in that, The catalyst is used for denitration.

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