CN110508274B - Modified biochar low-temperature denitration catalyst and application thereof - Google Patents
Modified biochar low-temperature denitration catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a modified biochar low-temperature denitration catalyst and application thereof, and belongs to the field of air pollution treatment and environmental functional carbon materials. The invention provides a modified biochar low-temperature denitration catalyst, which aims to solve the technical problems of low-temperature denitration rate, complex preparation method and high cost of the existing denitration catalyst and is prepared by the following method: carrying out pre-oxidation treatment on the biochar to obtain a carbon carrier; and ultrasonically dipping the carbon carrier in a metal salt solution, drying, and calcining at a low temperature in an oxidizing atmosphere to obtain the carbon carrier. According to the invention, through the steps of oxidizing atmosphere pre-oxidation, metal salt solution ultrasonic impregnation and low-temperature oxidizing atmosphere calcination, the denitration performance of the modified charcoal denitration catalyst is obviously improved, so that the modified charcoal denitration catalyst has better activity under the low-temperature condition (100-200 ℃), and the denitration rate reaches up to 99%.
Description
Technical Field
The invention belongs to the technical field of air pollution treatment and environmental functional carbon materials, and particularly relates to a modified biochar low-temperature denitration catalyst and application thereof.
Background
Industrial flue gas is an important source of flue gas emission in China, and boilers or thermal power plants taking coal as fuel, iron and steel plants taking iron ore as raw materials and the like emit a large amount of polluted flue gas every year. Nitrogen Oxides (NO) in flue gasesX) Can cause a plurality of environmental problems such as dust haze, ozone pollution and the like, and is a main source of air pollution. Effective control of NOx emissions is an important issue in the management of atmospheric pollution. Selective Catalytic Reduction (SCR) is one of the most effective flue gas denitration technologies at present, in particular NH3Etc. as a reducing agent under certain temperature and catalyst action to selectively reduce NOx to N2And H2O, due to the characteristics of simple operation process, high denitration efficiency and the like, has become a research hotspot in the field of domestic and foreign flue gas denitration. In recent years, vanadium-titanium oxide-based denitration catalysts are widely used industrially for reducing NOx in flue gas to N at a temperature of 300 to 450 ℃2. However, in order to effectively avoid the abrasion, blockage and poisoning effects of the fly ash and other components on the catalyst, the denitration catalyst is generally placed behind the dust removal and desulfurization device, and the temperature of the flue gas is generally 100-150 ℃ at this time, so that the flue gas needs to be heated to more than 300 ℃ for denitration, and the energy consumption is increased. In order to avoid the increase of treatment cost caused by flue gas reheating, the development of efficient low-temperature denitration catalytic materials is urgent to solve the technical problem of low-temperature denitration.
At present, the research on low-temperature denitration catalysts at home and abroad mainly focuses on metal oxides (such as Mn, Ce, V, Fe, Cu and the like), wherein manganese oxides such as MnO and MnO2、Mn2O3、Mn3O4、Mn5O8And the like, because of the multi-valence oxidation-reduction cyclic reaction, rich acid sites and surface active oxygen, excellent low-temperature catalytic activity and low price, the catalyst is widely concerned. In addition, the Mn is loaded on the carrier, so that the dispersion degree of the active components can be improved, the specific surface area can be increased, and the catalyst activity can be further improved. In contrast to TiO2、Al2O3、SiO2And the porous carbon such as biological carbon, activated carbon fiber and the like has the advantages of wide sources, ecological sustainability, low cost and the like, meanwhile, the porous structure can provide places for the loading of active components and the diffusion, adsorption and reaction of reaction gas molecules, and rich surface functional groups of the porous carbon can be used as active sites for catalytic conversion, so that the porous carbon can show good catalytic activity at a lower temperature (80-150 ℃), and is very suitable for being used as a carrier of a low-temperature SCR catalyst. Therefore, the manganese-loaded porous carbon catalyst is a low-temperature denitration catalyst with great application prospect.
CN107115868A discloses a low-temperature SCR denitration catalyst based on activated carbon and a preparation method thereof: pulverizing Taixi anthracite, Taiyuan valley coal and Guilin brown coal, mixing uniformly according to a certain proportion, adding a binder, and forming to obtain a cylindrical honeycomb-shaped blank; placing the dried honeycomb-shaped blank in a calcining furnace, and heating to 240-250 ℃ under the nitrogen atmosphere; then introducing air for oxidation for 6 h; then introducing nitrogen, heating to 650-700 ℃, carrying out carbonization reaction for 1h, and continuously heating to 900-950 ℃; thereby improving CO communication2Carrying out activation reaction for 2h, and cooling to room temperature under the protection of nitrogen to obtain a carbon-based honeycomb structure carrier; then ultrasonically dipping the carrier in concentrated nitric acid for 1h at room temperature, washing to be neutral, and then placing the carrier in an oven for drying; soaking the dried carrier in Ce (NO)3)3、Fe(NO3)3、Cu(NO3)2With Mn (NO)3)2And (3) heating the mixed solution of the solution to 600-700 ℃ under the protection of nitrogen, and calcining for 3 hours to obtain the low-temperature denitration catalyst. The preparation process of the catalyst is complex, and the denitration rate at 150 ℃ is only 84%.
CN106000415A discloses a denitration catalyst, a preparation method and a preparation system thereof, which are characterized in that a carbon material is soaked in a zinc chloride solution, then is subjected to radiation activation by microwaves in an inert gas atmosphere, is dried to obtain a modified carbon material, is soaked in a manganese salt and cobalt salt mixed solution, is dried, and finally is calcined in the inert gas atmosphere. The catalyst in the invention has complex preparation process, and the zinc chloride can be hydrolyzed to generate volatile HCl in the heating process, thereby seriously polluting the environment.
Therefore, the low-temperature denitration catalyst which is simple and safe in preparation method, strong in catalytic capability and low in price is significant to find.
Disclosure of Invention
The invention aims to solve the technical problems of low-temperature denitration rate, complex preparation method and high cost of the existing denitration catalyst.
The technical scheme adopted by the invention for solving the technical problems is to provide a modified biochar low-temperature denitration catalyst, which is prepared by the following method:
A. carrying out pre-oxidation treatment on the biochar in an oxidation atmosphere to obtain a carbon carrier;
B. ultrasonically dipping a carbon carrier in a metal salt solution, and then drying;
C. and calcining the dried material at low temperature in an oxidizing atmosphere to obtain the modified biochar denitration catalyst.
In the step A, the oxidation atmosphere is air or oxygen; when the air is used, controlling the air flow to be 100-300 mL/min; when the oxygen is used, the flow rate of the oxygen is controlled to be 20-60 mL/min.
In the step A, the temperature is controlled to be 300-400 ℃ and the time is 0.5-4 h during pre-oxidation treatment.
In the step A, the modified biochar denitration catalyst is at least one of coconut shell carbon, charcoal, peanut shell carbon, walnut shell carbon, straw carbon or bamboo charcoal.
In the step A, the modified biochar denitration catalyst is particles with the particle size range of 5-20 meshes.
In the step B, the metal salt solution is a manganese nitrate solution, a manganese acetate solution, a manganese carbonate solution or a manganese chloride solution, and the mass concentration of the metal salt solution is 1-20%.
Preferably, in the step B, the metal salt solution is a manganese nitrate solution.
In the step B, the mass-volume ratio of the carbon carrier to the metal salt solution is 1-20 g: 1-60 mL.
In the step B, the ultrasonic time is 0.5-3 h.
In the step B, the drying temperature is 100-140 ℃ and the drying time is 6-24 h.
In the step C, the oxidation atmosphere is air or oxygen; when the air is used, controlling the air flow to be 100-300 mL/min; when the oxygen is used, the flow rate of the oxygen is controlled to be 20-60 mL/min.
In the step C, the low-temperature calcination is carried out at 200-300 ℃ for 0.5-3 h.
The modified biochar denitration catalyst provided by the invention has excellent low-temperature denitration activity, and the denitration rate can reach 99% at the working temperature of 100-200 ℃.
Has the advantages that:
according to the invention, the biological carbon is subjected to pre-oxidation treatment, so that lignin carbon in the biological carbon can be selectively oxidized and removed, the pore structure of the carbon material is improved, the entering and the dispersion of active components in the impregnation treatment process are facilitated, the exposure of more active sites is promoted, the adsorption and the activation of reactant molecules are facilitated, and the denitration reaction is promoted. In addition, oxygen-containing functional groups and acid point positions can be modified and grafted on the surface of the catalyst, so that the denitration performance of the catalyst can be obviously improved.
The invention adopts a method of directly calcining at low temperature in oxidizing atmosphere after soaking in biochar metal salt solution. The low-temperature treatment can effectively save energy; meanwhile, the high-valence manganese oxide is more favorably formed by calcining in an oxidizing atmosphere, and the denitration performance of the high-valence manganese oxide can be remarkably improved.
According to the invention, through pre-oxidation, ultrasonic impregnation of a metal salt solution and calcination in a low-temperature oxidation atmosphere, the obtained modified biochar denitration catalyst has better activity under the low-temperature (100-200 ℃) condition in denitration application, the energy consumption in the application process can be obviously reduced, and the denitration rate is as high as 99%.
The modified biochar denitration catalyst carrier takes biochar as a raw material, belongs to waste resource recycling, and has high economic feasibility; the preparation method is mild in condition, simple to operate and free of polluting byproducts, and is an environment-friendly preparation method.
Drawings
FIG. 1 is a diagram showing the SCR denitration effect of the modified biochar denitration catalyst obtained in example 1.
FIG. 2 is a diagram showing the SCR denitration effect of the modified biochar denitration catalyst obtained in example 2.
FIG. 3 is a diagram showing the SCR denitration effects of the modified biochar denitration catalyst obtained in example 3 and the denitration catalysts in comparative examples 1 to 6.
FIG. 4 is a diagram showing the SCR denitration effects of the modified biochar denitration catalyst obtained in example 3 and the denitration catalyst obtained in comparative example 7.
Detailed Description
Specifically, the modified biochar low-temperature denitration catalyst is prepared by the following method:
A. carrying out pre-oxidation treatment on the biochar in an oxidation atmosphere to obtain a carbon carrier;
B. ultrasonically dipping a carbon carrier in a metal salt solution, and then drying;
C. and calcining the dried material at low temperature in an oxidizing atmosphere to obtain the modified biochar denitration catalyst.
In order to realize the resource recycling of wastes, coconut shell carbon, charcoal, peanut shell carbon, walnut shell carbon, straw carbon, bamboo charcoal and the like can be used as biochar raw materials; the particle size of the biochar is controlled to be 5-20 meshes. It is preferable to use biochar particles having a particle size in the range of 6 to 10 mesh.
According to the invention, the biological carbon is subjected to pre-oxidation treatment, and lignin carbon in the biological carbon is selectively oxidized and removed, so that the pore structure of the carbon material is improved. Analyzing the decomposition and weight loss conditions of the biochar in an oxidizing atmosphere, and controlling the air flow to be 100-300 mL/min when the biochar is air; when the catalyst is oxygen, the flow of the oxygen is controlled to be 20-60 mL/min, the temperature is controlled to be 300-400 ℃, and the time is 0.5-4 h, pre-oxidation is carried out, so that the dispersion of active components in the dipping treatment process is facilitated, the exposure of more active sites is promoted, the adsorption and activation of reactant molecules are facilitated, and the denitration reaction is promoted. In addition, the surface of the denitration catalyst is modified and grafted with oxygen-containing functional groups, so that the denitration performance of the denitration catalyst can be obviously improved. The temperature is low or high, which is not beneficial to the improvement of the pore structure.
In the step B of the invention, the metal salt solution is a manganese nitrate solution, a manganese acetate solution, a manganese carbonate solution or a manganese chloride solution, the mass concentration of the metal salt solution is 1-20%, and the mass volume ratio of the carbon carrier to the metal salt solution is controlled to be 1-20 g: 1-60 mL, wherein the loading amount of the metal manganese salt in the modified charcoal denitration catalyst can be controlled to be 1-10%, so that high-valence manganese oxide can be formed in the subsequent low-temperature calcination, and the low-temperature denitration capability can be improved; preferably, a manganese nitrate solution is used.
In order to load manganese on the carbon carrier, in the step B, ultrasonic treatment is adopted, and ultrasonic treatment is generally required for 0.5-3 hours; and after the ultrasonic treatment is finished, drying the materials at 100-140 ℃ for 6-24 h.
The method comprises the step of calcining the manganese-loaded carbon carrier at low temperature in an oxidizing atmosphere. When air is adopted, controlling the air flow to be 100-300 mL/min; when oxygen is adopted, the flow rate of the oxygen is controlled to be 20-60 mL/min. The calcination temperature is controlled to be 200-300 ℃, the calcination time is 0.5-3 h, the high-valence manganese oxide can be more favorably formed by calcination in an oxidizing atmosphere, and the combination between the catalyst and the carrier is firmer, so that the denitration performance of the catalyst is obviously improved, and the energy consumption is effectively reduced in the low-temperature treatment process.
The modified biochar denitration catalyst provided by the invention has excellent low-temperature denitration activity, and the denitration rate can reach 99% at the working temperature of 100-200 ℃.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Mixing coconutGrinding shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 300 ℃ under the condition that the air flow is 150mL/min to obtain a carbon carrier; 10g of the carbon support was immersed in 20mL of Mn (NO) having a mass concentration of 6.5% at room temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 1h, wherein the drying time is 12 h; and finally calcining for 4 hours at 250 ℃ in an air atmosphere, wherein the air flow is 150mL/min, so as to obtain the modified biochar denitration catalyst.
The modified charcoal denitration catalyst is adopted to evaluate the denitration performance of flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、400ppm NO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 2000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 1.
Example 2
Grinding coconut shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 400 ℃ under the condition that the air flow is 150mL/min to obtain a carbon carrier; 10g of the carbon support was immersed in 20mL of Mn (NO) having a mass concentration of 9.8% at room temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2 hours at 300 ℃ in an air atmosphere, wherein the air flow is 150mL/min, so as to obtain the modified biochar denitration catalyst.
The modified charcoal denitration catalyst is adopted to evaluate the denitration performance of flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、400ppm NO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 4000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 2.
Example 3
Grinding coconut shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 380 ℃ under the condition that the air flow is 150mL/min to obtain a carbon carrier; 10g of the carbon support was immersed in 20mL of Mn (NO) having a mass concentration of 13% at room temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2 hours at 250 ℃ in an air atmosphere, wherein the air flow is 150mL/min, so as to obtain the modified biochar denitration catalyst.
Modified organisms obtained by the above methodThe carbon denitration catalyst is used for evaluating the denitration performance of flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、400ppm NO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 1
Grinding coconut shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 380 ℃ under the nitrogen flow of 150mL/min to obtain a carbon carrier; 10g of the carbon support was immersed in 20mL of Mn (NO) having a mass concentration of 13% at room temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2 hours at 250 ℃ in an air atmosphere, wherein the air flow is 150mL/min, so as to obtain the biochar denitration catalyst.
The denitration catalyst obtained by the method is used for evaluating the denitration performance of the flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、 400ppm NO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 2
Grinding coconut shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 380 ℃ under the nitrogen flow of 150mL/min to obtain a carbon carrier; 10g of the carbon support was immersed in 20mL of Mn (NO) having a mass concentration of 13% at room temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2h at 250 ℃ in a nitrogen atmosphere at the nitrogen flow of 150mL/min to obtain the biochar denitration catalyst.
The denitration catalyst obtained by the method is used for evaluating the denitration performance of the flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、400ppmNO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 3
Grinding coconut shell biochar into particles with the particle size range of 6-10 meshes, and calcining for 2h at 380 ℃ under the condition that the air flow is 150mL/min to obtain a carbon carrier; 10g of the carbon support were impregnated at ambient temperatureMn (NO) at a concentration of 13% by mass in 20mL3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2h at 250 ℃ in a nitrogen atmosphere at the nitrogen flow of 150mL/min to obtain the biochar denitration catalyst.
The denitration catalyst obtained by the method is used for evaluating the denitration performance of the flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、 400ppmNO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 4
Grinding coconut shell biochar into particles with particle size range of 6-10 meshes, and soaking 10g of biochar in 20mL of Mn (NO) with mass concentration of 13% at normal temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2 hours at 250 ℃ in an air atmosphere, wherein the air flow is 150mL/min, so as to obtain the biochar denitration catalyst.
The denitration catalyst obtained by the method is used for evaluating the denitration performance of the flue gas, and the flue gas atmosphere conditions simulated in a laboratory are as follows: 5% O2、 400ppmNO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 5
Grinding coconut shell biochar into particles with particle size range of 6-10 meshes, and soaking 10g of biochar in 20mL of Mn (NO) with mass concentration of 13% at normal temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2h at 250 ℃ in a nitrogen atmosphere at the nitrogen flow of 150mL/min to obtain the biochar denitration catalyst.
And (3) evaluating the denitration performance of the flue gas by using the obtained denitration catalyst. Laboratory simulated flue gas atmosphere conditions: 5% O2、 400ppmNO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 6
Grinding the coconut shell biochar into particles with the particle size range of 6-10 meshes, and evaluating the flue gas denitration performance. Laboratory simulated flue gas atmosphere conditions: 5% O2、400ppm NO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 3.
Comparative example 7
Grinding coconut shell biochar into particles with particle size range of 6-10 meshes, and soaking 10g of biochar in 20mL of Mn (NO) with mass concentration of 13% at normal temperature3)2In the solution, drying at 105 ℃ after ultrasonic treatment for 0.5h, wherein the drying time is 12 h; and finally calcining for 2h at 450 ℃ in a nitrogen atmosphere at the nitrogen flow of 150mL/min to obtain the biochar denitration catalyst. And (3) evaluating the denitration performance of the flue gas by using the prepared denitration catalyst.
Laboratory simulated flue gas atmosphere conditions: 5% O2、400ppmNO、NH3：NO＝1.1：1、N2As carrier gas, its space velocity is 6000h-1The reaction temperature was 150 ℃ and the NO conversion was shown in FIG. 4.
As can be seen from fig. 3 and 4, the catalyst prepared by air pre-oxidation treatment and then impregnation with a metal salt solution and final air calcination has the best denitration performance, the denitration rate can reach 97%, and compared with comparative examples 1 to 7, the catalytic activity of the modified biochar denitration catalyst is significantly improved.
Claims (8)
1. Modified biological charcoal low temperature denitration catalyst which is characterized in that: the preparation method comprises the following steps:
A. carrying out pre-oxidation treatment on the biochar in an oxidation atmosphere to obtain a carbon carrier;
B. ultrasonically dipping a carbon carrier in a metal salt solution, and then drying;
C. calcining the dried material at low temperature in an oxidizing atmosphere to obtain a modified biochar denitration catalyst;
in the step A, the oxidizing atmosphere is air or oxygen; when the air is used, controlling the air flow to be 100-300 mL/min; when the oxygen is used, controlling the flow of the oxygen to be 20-60 mL/min;
in the step A, during pre-oxidation treatment, the temperature is controlled to be 300-400 ℃, and the time is 0.5-4 hours;
in the step B, the metal salt solution is a manganese nitrate solution, a manganese acetate solution, a manganese carbonate solution or a manganese chloride solution, and the mass concentration of the metal salt solution is 1-20%;
in the step C, the low-temperature calcination is carried out at the temperature of 200-300 ℃ for 0.5-3 h.
2. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step A, the biochar is at least one of coconut shell carbon, charcoal, peanut shell carbon, walnut shell carbon, straw carbon or bamboo charcoal; the biochar is particles with the particle size range of 5-20 meshes.
3. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step B, the metal salt solution is a manganese nitrate solution.
4. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step B, the mass volume ratio of the carbon carrier to the metal salt solution is 1-20 g: 1-60 mL.
5. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step B, the ultrasonic time is 0.5-3 h.
6. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step B, the drying temperature is 100-140 ℃, and the drying time is 6-24 h.
7. The modified biochar low-temperature denitration catalyst according to claim 1, characterized in that: in the step C, the oxidizing atmosphere is air or oxygen; when the air is used, controlling the air flow to be 100-300 mL/min; when the oxygen is used, the flow rate of the oxygen is controlled to be 20-60 mL/min.
8. The application of the modified biochar low-temperature denitration catalyst in low-temperature flue gas denitration of any one of claims 1 to 7 is characterized in that: the denitration temperature is 100-200 ℃.
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| CN111099591B (en) * | 2019-12-30 | 2022-04-01 | 四川大学 | Surface-modified high-activity low-temperature denitration active coke and preparation method thereof |
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| CN113083320A (en) * | 2021-04-14 | 2021-07-09 | 安徽工业大学 | Low-temperature SCR denitration catalyst and preparation method thereof |
| CN114471458A (en) * | 2021-10-21 | 2022-05-13 | 北京清新环境技术股份有限公司 | Modified activated carbon and preparation method thereof |
| CN114588891A (en) * | 2022-02-18 | 2022-06-07 | 国电电力发展股份有限公司 | Denitration catalyst and preparation method and application thereof |
| CN114849699A (en) * | 2022-06-09 | 2022-08-05 | 中国科学院过程工程研究所 | Biochar-based supported catalyst and preparation method and application thereof |
| CN116571234B (en) * | 2023-07-12 | 2023-09-08 | 江苏宁天环境科技有限公司 | High-performance flue gas denitration catalyst and preparation method thereof |
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