CN114797840A - Manganese-based denitration catalyst and preparation method and application thereof - Google Patents
Manganese-based denitration catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a manganese-based denitration catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a manganese source, a cerium source, a titanium source and a solvent to obtain a mixed solution; (2) grinding the mixed solution obtained in the step (1), and washing and drying to obtain a precursor; (3) roasting the precursor obtained in the step (2) to obtain the manganese-based denitration catalyst, wherein the catalyst is applied to NH 3 The SCR denitration reaction has good low-temperature activity and strong water-resistant and sulfur-resistant performance. The preparation method of the catalyst has the advantages of simple process, low cost, no pollution and easy implementation.
Description
Technical Field
The invention belongs to low-temperature NH 3 An SCR denitration catalyst material and the preparation technical field thereof, relating to a manganese-based denitration catalyst and the preparation method and the application thereof.
Background
Ammonia process selective catalytic reduction (NH) 3 -SCR) is the most mature technology applied in the field of fixed source flue gas denitration and mobile source tail gas denitration at present, and the denitration efficiency can reach more than 90%. V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The catalyst has been widely used in power plants, steel mills and as a typical commercial SCR catalystGlass kiln and the like. However, since the conventional SCR operating temperature is generally 300-400 ℃ or higher, SO can occur in the flue gas at the temperature 2 And NH 3 Oxidation and the like, and in addition, long term exposure to such high reaction temperatures, vanadium-based catalysts are readily deactivated. In addition, in China, many running industrial boiler (kiln) equipment (such as industrial boilers, glass ceramic kilns, cement kilns, ferrous metallurgy sintering furnaces and the like) smoke and technological processes related to nitric acid production and use exist, and due to the use of waste heat power generation and energy-saving equipment, the smoke emission temperature is low (120-300 ℃), and the direct use of the medium-high temperature SCR catalytic process for NO is difficult to realize x The discharge is controlled. The working temperature of the low-temperature SCR technology catalyst is below 250 ℃, and the reactor can be placed after desulfurization and dust removal, thereby avoiding SO 2 Smoke and high temperature. Compared with a high-temperature SCR technology, the low-temperature SCR technology has higher economic practicability. The development of the high-efficiency low-temperature SCR catalyst is the core of the low-temperature SCR denitration technology and is the key point of the current research in the field of domestic and foreign SCR denitration.
The transition metal oxides such as Mn, Fe and Ce based oxides reported in the current research have better NH 3 -SCR activity. Among them, the Mn-based denitration catalyst material has excellent denitration activity at low temperature due to its superior redox ability. However, the Mn-based denitration catalyst material has the disadvantage of being not resistant to sulfur and water in a low temperature range, and greatly hinders the application process of the SCR denitration catalyst.
Many researchers have introduced other elements into oxides of manganese to improve their water and sulfur resistance.
Jin et al (Applied Catalysis B: Environmental,2014,148-149:582-588) reported a sol-gel method for preparing Mn-Ce/TiO 2 Method of (1), Mn-Ce/TiO prepared by the method 2 The catalyst shows good water resistance and sulfur resistance in low-temperature denitration reaction, but the water vapor content of the catalyst is only 3%, the preparation period of the catalyst is long, and the industrial application significance is not great.
CN104289227A discloses a supported four-component metal catalyst for low-temperature denitration of flue gas and a preparation method thereof. The catalyst is prepared by loading nitrates of Mn, Co, Ce and the like on a nano-scale P25 and roasting by adopting an impregnation method, and the NO conversion rate is higher than 90% in a low-temperature range of 150-200 ℃.
CN104785246A discloses a supported low-temperature SCR catalyst and a preparation method thereof. The catalyst is prepared from gamma-Al 2 O 3 Is used as a carrier, manganese oxide is used as an active component, cerium oxide is used as a modifier, and the activity reaches 100 percent under the reaction condition of 120-240 ℃. However, the activity temperature windows of the two types of catalysts are narrow, and the water resistance and sulfur resistance of the catalysts are not researched.
CN111992203A discloses a Mn-Ce-O/TiO 2 The preparation method of the catalyst comprises the steps of dissolving manganese nitrate, cerium nitrate and fuel in deionized water, and adding TiO into the mixed solution 2 Stirring uniformly, placing the obtained product in a preheated combustion chamber for quick combustion, and continuously roasting for a certain time to obtain Mn-Ce-O/TiO 2 A denitration catalyst. The catalyst prepared by the method shows good water resistance and sulfur resistance in low-temperature denitration reaction, but the preparation method is complex and dangerous, and raw materials need to be combusted in the preparation process, so that the environmental pollution is large.
The manganese-based catalyst in the scheme has the defects of poor low-temperature performance, poor sulfur-resistant and water-resistant effects, long preparation process, difficulty in operation, environmental pollution, high production cost and the like, so that the development of the low-temperature NH catalyst with simple preparation method 3 The manganese-based catalyst with high SCR denitration efficiency, good sulfur resistance and water resistance and low cost is necessary.
Disclosure of Invention
The invention aims to provide a manganese-based denitration catalyst, and a preparation method and application thereof 3 The SCR denitration reaction has good low-temperature activity and strong water-resistant and sulfur-resistant performance. The preparation method of the catalyst has the advantages of simple process, low cost, no pollution and easy implementation.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a manganese-based denitration catalyst, comprising the steps of:
(1) mixing a manganese source, a cerium source, a titanium source and a solvent to obtain a mixed solution;
(2) grinding the mixed solution obtained in the step (1), and washing and drying to obtain a precursor;
(3) and (3) roasting the precursor obtained in the step (2) to obtain the manganese-based denitration catalyst.
In the preparation method of the manganese-based denitration catalyst, manganese oxide is taken as a main body, a cerium source and a titanium source are added, the double metal monoatomic Ce and Ti are limited in manganese oxide crystal lattices, and the Ce-Ti double metal monoatomic synergistic effect improves the NH content of the manganese-based catalyst at low temperature 3 Water and sulfur resistance in SCR denitration reactions.
Preferably, the manganese source of step (1) comprises potassium permanganate and a manganous salt.
Preferably, the divalent manganese salt comprises any one of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate or a combination of at least two of them.
Preferably, the manganese source comprises potassium permanganate and manganese nitrate.
Preferably, the cerium source comprises any one of cerium nitrate, cerium carbonate, cerium chloride or cerium acetate or a combination of at least two thereof.
Preferably, the titanium source comprises any one of titanium tetrachloride, tetrabutyl titanate or titanyl sulfate or a combination of at least two thereof.
Preferably, the solvent comprises deionized water.
Preferably, the molar ratio of the potassium permanganate to the divalent manganese salt is 1 (0.5-2), such as: 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:2, etc.
Preferably, the mass ratio of the manganese source, the cerium source and the titanium source in the step (1) is (0.5-2): (0.0007-0.05): (0.002-0.13), such as: 0.8:0.001:0.002, 1:0.005:0.01, 1.2:0.008:0.05, 1.5:0.009:0.008, 1:0.01:0.02 or 1:0.03:0.13, etc.
Preferably, the grinding treatment in step (2) comprises ball milling.
Preferably, the speed of the ball mill is 100 to 1000rpm, such as 200rpm, 400rpm, 600rpm, 800rpm or 1000rpm, etc., preferably 400 to 600 rpm.
Preferably, the ball milling time is 0.5-6 h, such as 0.5h, 1h, 2h, 4h, 5h or 6h, and preferably 0.5-3 h.
Preferably, in the grinding treatment process in the step (2), the mass ratio of the grinding beads to the solute in the mixed solution is (10-40): 1, for example: 10:1, 15:1, 20:1, 30:1 or 40:1, preferably (10-20): 1.
Preferably, the temperature of the roasting treatment in the step (3) is 300 to 600 ℃, for example 300 ℃, 400 ℃, 500 ℃ or 600 ℃, preferably 300 to 400 ℃.
Preferably, the time of the roasting treatment is 2-6 h, such as 2h, 3h, 4h, 5h or 6h, preferably 3-5 h.
As a preferable scheme of the invention, the preparation method comprises the following steps:
(1) mixing a manganese source, a cerium source and a titanium source with a solvent according to the mass ratio of 1 (0.001-3) to obtain a mixed solution;
(2) grinding the mixed solution obtained in the step (1) at 400-600 rpm for 0.5-3 h, and washing and drying to obtain a precursor;
(3) and (3) roasting the precursor obtained in the step (2) at the temperature of 300-400 ℃ for 3-5 h to obtain the manganese-based denitration catalyst.
In a second aspect, the present invention provides a manganese-based denitration catalyst prepared by the method according to the first aspect.
Preferably, the mass ratio of titanium in the manganese-based denitration catalyst is 0.1-3%, for example: 0.1%, 0.2%, 0.5%, 1%, 2%, or 3%, etc., preferably 0.1 to 1%;
preferably, the mass ratio of cerium in the manganese-based denitration catalyst is 0.1-3%, for example: 0.1%, 0.2%, 0.5%, 1%, 2%, or 3%, etc., preferably 0.1 to 1%.
In a third aspect, the present invention provides a use of the manganese-based denitration catalyst as described in the second aspect, the manganese-based denitration catalystCatalyst for low temperature NH 3 -SCR denitration reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst of the invention is used in NH 3 The SCR denitration reaction has good low-temperature activity and strong water-resistant and sulfur-resistant performance. The preparation method of the catalyst has the advantages of simple process, low cost, no pollution and easy implementation.
(2) The manganese-based denitration catalyst disclosed by the invention has the advantages that the conversion rate of catalytic denitration NO at 100 ℃ can reach more than 40.2%, the conversion rate of catalytic denitration NO at 150 ℃ can reach more than 93.3%, the conversion rate of catalytic denitration NO at 200 ℃ can reach more than 94.3%, the conversion rate of catalytic denitration NO at 250 ℃ can reach more than 92.3%, and the conversion rate of catalytic denitration NO at 300 ℃ can reach more than 92.8%.
Drawings
FIG. 1 is an electron micrograph of a manganese-based denitration catalyst prepared in example 1 of the present invention.
FIG. 2 is NH of example 1 of the present invention and comparative examples 1 to 4 3 -SCR water and sulfur resistance performance diagram.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 1.23g of manganese chloride, 0.02g of cerium acetate, 0.03g of titanyl sulfate and 3.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 125.6g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 580rpm, carrying out ball milling for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 6 hours in a tubular furnace at the temperature of 400 ℃ to obtain the manganese-based denitration catalyst, wherein the load of Ce is 1 percent, and the load of Ti is 1 percent.
The spherical aberration electron microscope image of the manganese-based denitration catalyst is shown in fig. 1.
Example 2
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 2.3g of manganese sulfate, 0.19g of cerium carbonate, 0.08g of titanium tetrachloride and 2ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 60.7g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 500rpm, carrying out ball milling for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 6 hours in a tubular furnace at 450 ℃ to obtain the manganese-based denitration catalyst, wherein the loading of Ce is 3%, and the loading of Ti is 1%.
Example 3
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 4.9g of manganese acetate, 0.18g of cerium nitrate, 0.014g of tetrabutyl titanate and 1.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 78.1g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 100rpm, carrying out ball milling for 0.5h to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 6 hours in a tubular furnace at the temperature of 300 ℃ to obtain the manganese-based denitration catalyst, wherein the loading of Ce is 3%, and the loading of Ti is 0.1%.
Example 4
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 2.9g of manganese chloride, 0.18g of cerium nitrate, 0.24g of titanium tetrachloride and 3ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 80.9g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 580rpm, carrying out ball milling for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 2 hours in a tubular furnace at 500 ℃ to obtain the manganese-based denitration catalyst, wherein the load of Ce is 3%, and the load of Ti is 3%.
Example 5
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 2.3g of manganese sulfate, 0.003g of cerium chloride, 0.21g of titanyl sulfate and 3ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 104.2g of ball milling beads, carrying out ball milling on the mixed raw materials at a set rotating speed of 600rpm for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 2 hours in a tubular furnace at 350 ℃ to obtain the manganese-based denitration catalyst, wherein the loading capacity of Ce is 0.1%, and the loading capacity of Ti is 3%.
Example 6
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 5.4g of manganese nitrate, 0.06g of cerium nitrate, 0.04g of titanium tetrachloride and 3.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 162.1g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 800rpm, carrying out ball milling for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 2 hours in a tubular furnace at the temperature of 600 ℃ to obtain the manganese-based denitration catalyst, wherein the loading of Ce is 1%, and the loading of Ti is 0.5%.
Example 7
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 2.3g of manganese sulfate, 0.04g of cerium chloride, 0.23g of titanium tetrachloride and 4ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 161.4g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 1000rpm, carrying out ball milling for 4 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 5 hours in a tubular furnace at 500 ℃ to obtain the manganese-based denitration catalyst, wherein the load of Ce is 1%, and the load of Ti is 3%.
Example 8
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 3.6g of manganese acetate, 0.12g of cerium nitrate, 0.14g of tetrabutyl titanate and 2.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 154.3g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 400rpm, carrying out ball milling for 1h to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 2 hours in a tubular furnace at the temperature of 400 ℃ to obtain the manganese-based denitration catalyst, wherein the loading capacity of Ce is 2%, and the loading capacity of Ti is 1%.
Example 9
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 3.1g of manganese oxalate, 0.06g of cerium chloride, 0.13g of titanyl sulfate and 2.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 165.1g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 600rpm, carrying out ball milling for 6 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) roasting the manganese-based denitration catalyst for 3 hours in a tubular furnace at 350 ℃, wherein the loading capacity of Ce is 2%, and the loading capacity of Ti is 2%.
Example 10
The embodiment provides a manganese-based denitration catalyst, and the preparation method of the manganese-based denitration catalyst comprises the following steps:
(1) weighing 1.5g of potassium permanganate, 2.9g of manganese chloride, 0.06g of cerium nitrate, 0.28g of tetrabutyl titanate and 2.5ml of deionized water, and mixing to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 180.2g of ball milling beads, carrying out ball milling on the mixed raw materials, setting the rotating speed to be 700rpm, carrying out ball milling for 2 hours to obtain solid powder, washing the solid powder with deionized water for several times, and drying;
(3) and roasting the mixture for 3 hours in a tubular furnace at the temperature of 600 ℃ to obtain the manganese-based denitration catalyst, wherein the loading capacity of Ce is 1 percent, and the loading capacity of Ti is 2 percent.
Comparative example 1
The comparative example is different from example 1 only in that only Ce is loaded, and other parameters and conditions are completely the same as those in example 1, so that the monatomic Ce-modified manganese oxide catalyst is obtained, wherein the loading amount of Ce is 1%, and the other conditions and parameters are the same as those in example 1.
Comparative example 2
This comparative example differs from example 1 only in that only Ti was supported, and other parameters and conditions were exactly the same as in example 1, to obtain a monatomic Ti-modified manganese oxide catalyst, in which the amount of Ti supported was 1%.
Comparative example 3
This comparative example differs from example 1 only in that Ce and Ti were not supported and other parameters and conditions were exactly the same as in example 1, to obtain a manganese oxide catalyst.
Comparative example 4
This comparative example is commercial MnO 2 A catalyst.
And (3) performance testing:
NH treatment of the catalysts obtained in examples 1 to 10 and comparative examples 1 to 4 3 -SCR catalytic activity test, said catalyst performance test being carried out in a miniature fixed bed unit, comprising in particular: respectively weighing a certain amountThe catalyst and the quartz sand are mixed evenly, and the mixture is placed in a fixed bed reactor self-made in a laboratory, and the filling volume of the catalyst is ensured to be 1.5 mL. Then 600ppm NO/600ppm NH was introduced 3 /6％O 2 SO 2 Per 50ppm and 10% H 2 O，N 2 As balance gas, the space velocity (GHSV) is 40000h -1 . The reactor temperature was increased from 100 ℃ to 300 ℃ at a rate of 5 ℃/min, and after 30min of stabilization at each test temperature point, the NO concentration was recorded by a testo 350 flue gas analyzer, the NO conversion was calculated in the following manner:
wherein [ NO ]] in Means the NO concentration at the inlet of the reactor, [ NO ]] out Refers to the reactor outlet NO concentration. Test results
The test results are shown in table 1:
TABLE 1
As can be seen from table 1, in examples 1 to 10, the conversion rate of catalytic denitration NO at 100 ℃ can reach 40.2% or more, the conversion rate of catalytic denitration NO at 150 ℃ can reach 93.3% or more, the conversion rate of catalytic denitration NO at 200 ℃ can reach 94.3% or more, the conversion rate of catalytic denitration NO at 250 ℃ can reach 92.3% or more, and the conversion rate of catalytic denitration NO at 300 ℃ can reach 92.8% or more.
Compared with the examples 2 to 10, the manganese-based denitration catalyst disclosed by the invention has the advantages that the mass ratio of cerium to titanium in the manganese-based denitration catalyst influences the performance of the manganese-based denitration catalyst, the mass ratio of cerium to titanium in the manganese-based denitration catalyst is controlled to be 0.1-1%, and the catalytic effect of the manganese-based denitration catalyst is good.
In the preparation method, the roasting temperature can influence the catalytic performance of the prepared manganese-based denitration catalyst, the roasting temperature is controlled to be 300-400 ℃, the catalytic performance of the prepared manganese-based denitration catalyst is good, if the roasting temperature is too low, the decomposition of precursor salt is incomplete, the grain size of manganese oxide is reduced, side reactions are increased in the reaction process, and the selectivity of a product N2 is reduced; if the roasting temperature is too high, the single atoms are easy to agglomerate and sinter, the grain size is increased, and the activity of the catalyst is reduced.
As can be seen from the comparison of example 1 with comparative examples 1-4, the adjacent bimetallic monoatomic atoms Ce and Ti in the catalyst of the invention are limited in the manganese oxide crystal lattice, and the synergistic effect of the bimetallic monoatomic atoms Ce-Ti improves the low-temperature NH 3 Water and sulfur resistance in SCR denitration reactions.
Water and sulfur resistance of the catalysts obtained in examples 1 to 10 and comparative examples 1 to 4 were measured in NH 3 -in an SCR reactor. Detailed operation of the experiment and NH 3 SCR experiments were essentially identical, but the reaction atmosphere was changed to 600ppm NO/600ppm NH 3 /6％O 2 /50ppm SO 2 /10％H 2 O/N 2 The experimental temperature was 150 ℃. FIG. 2 shows the catalyst in the presence of 10% H 2 O and 50ppm SO 2 The activity profile under atmosphere, as can be seen from fig. 2, the NO conversion of example 1 is clearly better than the four comparative examples within 10 h. Therefore, the Ce-Ti bimetallic monatomic modified manganese oxide catalyst prepared by the preparation method has excellent low-temperature denitration activity and water and sulfur resistance, and is mainly due to the synergistic effect of the Ce-Ti bimetallic monatomic in the catalyst.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the manganese-based denitration catalyst is characterized by comprising the following steps of:
(1) mixing a manganese source, a cerium source, a titanium source and a solvent to obtain a mixed solution;
(2) grinding the mixed solution obtained in the step (1), and washing and drying to obtain a precursor;
(3) and (3) roasting the precursor obtained in the step (2) to obtain the manganese-based denitration catalyst.
2. The method of claim 1, wherein the manganese source of step (1) comprises potassium permanganate and a manganous salt;
preferably, the divalent manganese salt comprises any one of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate or a combination of at least two of the same;
preferably, the manganese source comprises potassium permanganate and manganese nitrate;
preferably, the cerium source comprises any one or a combination of at least two of cerium nitrate, cerium carbonate, cerium chloride or cerium acetate;
preferably, the titanium source comprises any one of titanium tetrachloride, tetrabutyl titanate or titanyl sulfate or a combination of at least two thereof;
preferably, the solvent comprises deionized water.
3. The preparation method according to claim 2, wherein the molar ratio of the potassium permanganate to the divalent manganese salt is 1 (0.5-2).
4. The method according to any one of claims 1 to 3, wherein the manganese source, the cerium source and the titanium source in the step (1) are present in a molar ratio of (0.5 to 2): (0.0007 to 0.05): (0.002 to 0.13).
5. The production method according to any one of claims 1 to 4, wherein the grinding treatment in the step (2) comprises ball milling;
preferably, the speed of the ball milling is 100-1000 rpm, preferably 400-600 rpm;
preferably, the ball milling time is 0.5-6 h, preferably 0.5-3 h.
6. The production method according to any one of claims 1 to 5, wherein during the grinding treatment in the step (2), the mass ratio of the grinding beads to the solute in the mixed solution is (10-40): 1, preferably (10-20): 1.
7. The method according to any one of claims 1 to 6, wherein the temperature of the roasting treatment in the step (3) is 300 to 600 ℃, preferably 300 to 400 ℃;
preferably, the roasting treatment time is 2-6 hours, and preferably 3-5 hours.
8. A manganese-based denitration catalyst, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. The manganese-based denitration catalyst according to claim 8, wherein the mass ratio of titanium in the manganese-based denitration catalyst is 0.1 to 3%, preferably 0.1 to 1%;
preferably, the mass ratio of cerium in the manganese-based denitration catalyst is 0.1-3%, and preferably 0.1-1%.
10. Use of the manganese-based denitration catalyst according to claim 8 or 9, wherein the manganese-based denitration catalyst is used for low-temperature NH 3 -SCR denitration reaction.
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