CN111530454B - Low-temperature denitration catalyst and preparation method and application thereof - Google Patents
Low-temperature denitration catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111530454B CN111530454B CN202010386555.XA CN202010386555A CN111530454B CN 111530454 B CN111530454 B CN 111530454B CN 202010386555 A CN202010386555 A CN 202010386555A CN 111530454 B CN111530454 B CN 111530454B
- Authority
- CN
- China
- Prior art keywords
- gamma
- low
- temperature
- catalyst
- denitration catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
The invention discloses a low-temperature denitration catalyst, and a preparation method and application thereof. The catalytic active components of the denitration catalyst comprise manganese oxide, cerium oxide and mercury, and the carrier is gamma-Al2O3The preparation method is that manganese salt and cerium salt are loaded on gamma-Al by impregnation method2O3After being carried on the carrier, carrying out high-temperature activation and mercury adsorption doping to obtain the carrier; the denitration catalyst can be used for selective catalytic denitration of SCR, has good low-temperature denitration activity and high mercury resistance, can realize high-efficiency removal of NO within the range of 100-400 ℃, has removal rate of 90%, is simple in preparation process and low in cost, and is beneficial to industrial production.
Description
Technical Field
The invention relates to a denitration catalyst, a preparation method and application thereof, in particular to a denitration catalyst with high catalytic denitration activity in a low-temperature and high-mercury environment, and also relates to a preparation method of the denitration catalyst and application of the denitration catalyst in selective catalytic denitration, belonging to the field of air pollution emission control.
Background
China is a large resource country, and the metal smelting industry plays a key role in the economic development process. But the atmospheric pollutants discharged in the smelting process, such as NOx, heavy metal mercury and the like. The threat to the environment is very great. NOx is an important precursor for greenhouse effect, photochemical smog, acid rain, and ozone layer depletion; therefore, the issue of emission control and management of NOx in countries around the world is becoming more and more important.
The concentration of nitrogen oxides in the smoke discharged by metallurgy is low, and the attention has not been paid enough, but the forty-third item of the atmospheric pollution prevention and treatment law of the people's republic of China in 2018 indicates that' dust, sulfide and nitrogen oxides are discharged in the production process of enterprises such as steel, building materials, nonferrous metals, petroleum, chemical engineering and the like, a clean production process is adopted, and a dust removal device, a desulfurization device and a denitration device are constructed in a matched manner, or other measures for controlling the emission of atmospheric pollutants such as technical transformation and the like are adopted. The nitrogen oxide aiming at the colored smoke is treated. Therefore, the development of the denitration catalyst applied to the colored flue gas with low nitrogen oxide concentration and high mercury concentration is significant.
Chinese patent (CN110368950A) discloses a method for loading Cu, Fe and Sn on TiO2The preparation method of the catalyst and the application of the catalyst in low-temperature denitration. In this patent, different metal ratios are different, and thus different catalytic effects are obtained. Wherein Cu3-Fe1/Sn0.33Ti0.67O2The denitration performance of the catalyst is optimal, and the reaction temperature is 300 DEG CThe conversion rate of NOx is as high as 91%. However, the catalytic material has low catalytic reaction activity in a low-temperature reaction range of 150-250 ℃, and is not suitable for a low-temperature denitration process after a dedusting process. Chinese patent (CN110639507A) discloses a Li-Mn bimetal oxide composite denitration catalyst. The catalyst has good catalytic activity at about 150 ℃, but the window of the activity temperature is narrow, the preparation process is complex, and the catalyst cannot be applied to the industries with large actual flue gas temperature fluctuation and large demand. And few researches are made on low-temperature denitration agents for flue gas with high mercury concentration. Therefore, the development of SCR catalysts with low and wide active temperature and mercury resistance still faces great challenges.
Disclosure of Invention
Aiming at the problem that the denitration catalyst in the prior art is difficult to be applied to low-temperature flue gas denitration after dust removal due to poor low-temperature removal performance, the invention aims to provide the composite denitration catalyst which has better denitration performance at a lower temperature, has wide active temperature, is resistant to a high-mercury environment and has no secondary pollution.
The second purpose of the invention is to provide a method for preparing the denitration catalyst, which is simple to operate and low in cost and meets the requirements of industrial production and application.
The third purpose of the invention is to provide an application of the denitration catalyst, which is applied to catalytic reduction of nitrogen oxides, can realize catalytic reduction of nitrogen oxides at a lower temperature and in a wider temperature range compared with the denitration catalyst in the prior art, and is particularly suitable for the denitration process of low-temperature and high-mercury metal smelting flue gas.
In order to achieve the technical purpose, the invention provides a low-temperature denitration catalyst, and the catalytic active components of the low-temperature denitration catalyst comprise manganese oxide, cerium oxide and mercury.
According to the technical scheme, the manganese oxide and the cerium oxide are used as main active ingredients of the composite denitration catalyst, the two components have an obvious synergistic interaction effect in the denitration process, and the denitration efficiency is higher compared with that of a single metal oxide catalyst. The catalytic performance of the metal oxide is obviously affected by temperature, the catalytic activity is improved correspondingly when the temperature is increased generally, the denitration performance at lower temperature is generally poor, for example, the single manganese oxide is taken as a catalyst, the denitration efficiency is about 14 percent when the flue gas temperature is 150 ℃, the denitration efficiency at 350 ℃ is only about 39 percent, the manganese oxide and the cerium oxide are taken as catalysts, the denitration efficiency is about 21 percent when the flue gas temperature is 150 ℃, the denitration efficiency at 350 ℃ is about 65 percent, and the denitration efficiency is obviously improved relative to the single oxide. On the basis, by introducing the elemental mercury as the cocatalyst, the low-temperature denitration performance of the catalyst can be obviously improved, and the denitration temperature window is widened, for example, the denitration efficiency is about 97% at the flue gas temperature of 150 ℃, and about 89% at the high temperature of 350 ℃.
The technical scheme of the invention simulates a large amount of flue gas (NH)3、O2NO) atmosphere, and summarizing the main possible denitration mechanisms as follows:
2NO+2NH3+2CeO2→2N2+Ce2O3+3H2O (1)
2NO+2NH3+3MnO2→2N2+Mn3O4+4H2O (2)
O2+2Ce2O3→4CeO2 (3)
O2+Mn3O4→3MnO2 (4)
O2+2Hg0 (g)→2HgO(s) (5)
HgO+Ce2O3→2CeO2+Hg0 (a) (6)
HgO+Mn3O4→3MnO2+Hg0 (a) (7)
2NO+2NH3+HgO→2N2+Hg0 (a)+3H2O (8)
it can be seen from the above reaction mechanism that the elemental mercury mainly promotes the oxidation-reduction process of the manganese oxide and the cerium oxide, thereby improving the catalytic activity of the manganese oxide and the cerium oxide.
As a preferable scheme, the catalytic active component is loaded on gamma-Al2O3On a carrier. The carrier mainly plays a role in dispersing catalytically active components to expose more catalytically active sites and show better catalytic activity, and can be selected from common materials in the prior art, such as solid materials with better stability and larger specific surface, for example, gamma-Al2O3。
As a preferable scheme, manganese oxide and cerium oxide are dispersedly loaded on gamma-Al2O3On the carrier, mercury is adsorbed and doped on manganese oxide, cerium oxide and gamma-Al2O3A carrier surface.
As a preferable mode, the total mass of the manganese oxide and the cerium oxide is gamma-Al2O32-20% of the mass of the carrier. The catalyst has poor catalytic effect because the catalyst is easy to sinter and block molecular channels when the content of the catalytic active component is too high.
Preferably, the molar ratio of the manganese oxide to the cerium oxide is (2-5): 1; manganese oxide is used as a main catalytic component, cerium oxide is used as a cocatalyst component, and the catalytic effect is poor due to insufficient oxygen vacancies when the proportion is too low.
As a preferred embodiment, the mercury is in gamma-Al2O3The loading amount on the carrier is 0.01 wt% -0.2 wt%.
The invention also provides a preparation method of the low-temperature denitration catalyst, which loads manganese salt and cerium salt on gamma-Al through an impregnation method2O3After being loaded on the carrier, the manganese oxide-cerium oxide/gamma-Al is obtained by high-temperature activation2O3Catalyst, said manganese oxide-cerium oxide/gamma-Al2O3The catalyst is obtained by adsorbing doped mercury.
As a preferred scheme, the high-temperature activation condition is as follows: and under the protective atmosphere, heating to 400-600 ℃ at the heating rate of 5-20 ℃/min, and preserving the heat for 5-10 h. A protective atmosphere such as nitrogen. The most preferable scheme is that the temperature rising speed is 10 ℃/min, and the temperature is kept at 550 ℃ for 2 h. The optimal activation condition can ensure that the manganese-cerium catalyst is completely decomposed and provides more oxygen vacancies, thereby achieving good catalytic effect.
As a preferred scheme, the process for adsorbing the doped mercury is as follows: manganese oxide-cerium oxide/gamma-Al2O3The catalyst is placed in Hg0The concentration is 100-300 mg/m3Adsorbing for 2-10 h in the atmosphere. The invention can adopt the smelting flue gas with higher mercury content to treat manganese oxide-cerium oxide/gamma-Al2O3The catalyst is subjected to adsorption and doping treatment, so that waste utilization can be realized.
The invention also provides an application of the low-temperature denitration catalyst, which is applied to catalyzing the reduction of nitrogen oxides.
As a preferable scheme, the method is applied to denitration of smelting flue gas.
As a preferable scheme, the temperature range of the smelting flue gas is 100-200 ℃, and the concentration of elemental mercury is more than or equal to 100mg/m3. The denitration catalyst provided by the invention is suitable for a wider range of flue gas temperature, can keep higher denitration activity at 100-400 ℃, and has outstanding denitration efficiency at 100-200 ℃. And the denitration catalyst has better tolerance to elemental mercury in the smelting flue gas, and can be used for reducing and removing nitrogen oxides in the smelting flue gas with higher mercury content.
The denitration catalyst provided by the invention can be used for removing NOx in coal-fired flue gas, and can also be used for removing mercury-containing and even high-mercury-containing conditions (containing Hg)0≥100mg/m3) And NOx in the smelting flue gas. The denitration process mainly utilizes ammonia gas to reduce nitrogen oxides into nitrogen gas.
The preparation method of the denitration catalyst comprises the following specific steps: (1) firstly, manganese nitrate and cerous nitrate solution are dipped into gamma-Al2O3Carrying out ultrasonic treatment, and drying to obtain a sample; (2) sample is placed in N2Under the atmosphere, at 5-20 ℃The temperature rise speed is increased to 400-600 ℃ in min, and the temperature is kept for 2-5 h at the temperature; n is a radical of2Blowing and cooling to obtain MnOx-CeOx/gamma-Al2O3. (3) The obtained MnOx-CeOx/gamma-Al2O3The denitration catalyst is arranged in Hg0The concentration is 100-300 mg/m3Adsorbing the flue gas for 2-10 h to obtain the product.
Compared with the prior art, the technical scheme provided by the invention has the beneficial technical effects that:
1. the denitration catalyst disclosed by the invention is simple in preparation process and low in cost, and meets the requirements of industrial production;
2. the denitration catalyst has high NO catalytic efficiency (the removal rate is more than 90 percent), and can keep high-efficiency removal performance at low temperature (within the range of 100-200 ℃);
3. the denitration catalyst has excellent high-mercury resistance, and has high elemental mercury (Hg) concentration0≥100mg/m3) In the smelting flue gas, NO can be efficiently catalytically reduced.
Drawings
FIG. 1 is a graph of MnOx-CeOx/γ -Al of comparative examples 1 to 7 with different ratios of manganese oxide to cerium oxide without supporting Hg2O3XRD pattern of catalyst, on XRD characterization of catalyst loaded with MnOx and CeOx, only Mn is detected2O3The crystal form shows that other metal oxides are uniformly dispersed and in an amorphous state.
FIG. 2 shows Hg-unloaded and Hg-loaded 5% MnOx-3% CeOx/γ -Al for comparative example 6 and example 12O3XPS plot of catalyst. In the Mn 2p diagram, the peak value of 644.5eV represents incomplete decomposition of manganese nitrate, and the peak value of 642.6eV represents MnO2The peak value of 641.2eV is Mn2O3(ii) a In the Ce 3d diagram, at v0(917.2eV),v’(907.9eV),v”(904.6eV),v’”(901.1eV),u0(897.7eV), u '(886.8 eV), u "(884.2 eV), u'" (881.7eV) have eight characteristic peaks, wherein v is0,v”,v’”,u0U 'and u' represent Ce4+I.e. CeO2V 'and u' represent Ce2O3。
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the claims of the present invention.
Comparative example 1
0.302g of manganese nitrate Mn (NO) was taken3)2·4H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Blowing and cooling to obtain the catalyst MnOx (2%)/gamma-Al2O3。
Comparative example 2
0.753g of manganese nitrate Mn (NO) was taken3)2·4H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Blowing and cooling to obtain the catalyst MnOx (5%)/gamma-Al2O3。
Comparative example 3
1.506g of manganese nitrate Mn (NO)3)2·4H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a rate of 5 deg.C/min under atmosphereRoasting for 3 hours at the temperature. N is a radical of2Blowing cold to obtain the catalyst MnOx (10%)/gamma-Al2O3。
Comparative example 4
0.753g of manganese nitrate Mn (NO) was taken3)2·4H2O and 0.09g of cerium nitrate Ce (NO)3)2·6H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Cooling by blowing to obtain a catalyst MnOx (5%) -CeOx (1%)/gamma-Al2O3。
Comparative example 5
0.753g of manganese nitrate Mn (NO) was taken3)2·4H2O and 0.18g of cerium nitrate Ce (NO)3)2·6H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Cooling by blowing to obtain a catalyst MnOx (5%) -CeOx (2%)/gamma-Al2O3。
Comparative example 6
0.753g of manganese nitrate Mn (NO) was taken3)2·4H2O and 0.27g of cerium nitrate Ce (NO)3)2·6H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; impregnating superfinesSounding for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 ℃ for 2h, and adding the catalyst into N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Cooling by blowing to obtain a catalyst MnOx (5%) -CeOx (3%)/gamma-Al2O3。
Comparative example 7
1.506g of manganese nitrate Mn (NO)3)2·4H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Blowing cold to obtain the catalyst MnOx (10%)/gamma-Al2O3. Placing the obtained catalyst in Hg0The concentration is 230-260 mg/m3Adsorbing the smoke for 5 hours to obtain Hg-MnOx (10%)/gamma-Al2O3。
Example 1
0.753g of manganese nitrate Mn (NO) was taken3)2·4H2O and 0.27g of cerium nitrate Ce (NO)3)2·6H2Dissolving the obtained product in 30mL of deionized water to prepare a dipping solution; gamma-Al with the diameter of 1.5-2 mm is used2O3As a catalyst carrier, 3g of gamma-Al is weighed by adopting a wet impregnation method2O3Immersing in the solution; soaking and ultrasonic treating for 4h, vacuum distilling to remove excessive deionized water, air drying the obtained catalyst for 12h, drying at 105 deg.C for 2h, and adding N2Heating to 600 deg.C at a speed of 5 deg.C/min under atmosphere, and calcining at the temperature for 3 hr. N is a radical of2Cooling by blowing to obtain a catalyst MnOx (5%) -CeOx (3%)/gamma-Al2O3. Placing the obtained catalyst in Hg0The concentration is 230-260 mg/m3The flue gas is absorbed for 5 hours to obtain Hg-MnOx (5%) -CeOx (3%)/gamma-Al2O3。
Application example 1
The prepared catalyst is applied to the denitration and demercuration of flue gas and mainly comprises the following steps: weighing 100mg of the catalyst, placing the catalyst in a tubular fixed reactor, and introducing NO 400ppm and NH3400ppm, oxygen O2Simulated flue gas with concentration of 4% (mixed gas and carrier gas of elemental mercury are both N)2). Under the condition that the temperature is 150-350 ℃, when the catalyst reaches a stable catalysis stage, the removal rate of the catalyst on nitrogen oxides and elemental mercury in the flue gas is considered. The results are shown in the table:
TABLE 1 denitration Performance comparison of catalysts
Reaction conditions are as follows: GHSV 24,0000h-1、NO 400ppm、NH3 400ppm、O2 4％。
Application example 2
The prepared catalyst is applied to the denitration and demercuration of flue gas and mainly comprises the following steps: weighing 100mg of the catalyst, placing the catalyst in a tubular fixed reactor, and introducing NO 400ppm and NH3400ppm, 230-260 mu g/m of simple substance mercury3Meta, oxygen O2Simulated flue gas with concentration of 4% (mixed gas and carrier gas of elemental mercury are both N)2). Under the condition that the temperature is 150 ℃, when the catalyst reaches a stable catalysis stage, the removal rate of the catalyst to nitrogen oxides and elemental mercury in the flue gas is considered. The results are shown in the table:
TABLE 2 denitration performance of catalyst under high mercury concentration flue gas condition
Reaction conditions are as follows: GHSV 24,0000h-1、NO 400ppm、NH3 400ppm、Hg0 230～260μg/m3、O2 4％。
Claims (8)
1. A preparation method of a low-temperature denitration catalyst is characterized by comprising the following steps: manganese salt and cerium salt are loaded on gamma-Al by an impregnation method2O3After being loaded on the carrier, the manganese oxide-cerium oxide/gamma-Al is obtained by high-temperature activation2O3Catalyst, said manganese oxide-cerium oxide/gamma-Al2O3The catalyst is doped with mercury through adsorption, and the low-temperature denitration catalyst is obtained; the catalytic active ingredients of the low-temperature denitration catalyst comprise manganese oxide, cerium oxide and mercury; the process of adsorbing the doped mercury comprises the following steps: manganese oxide-cerium oxide/gamma-Al2O3The catalyst is placed in Hg0The concentration is 100-300 mg/m3Adsorbing for 2-10 h in the atmosphere.
2. The method for preparing a low-temperature denitration catalyst according to claim 1, characterized in that: the catalytic active component is loaded on gamma-Al2O3On a carrier.
3. The method for preparing a low-temperature denitration catalyst according to claim 1 or 2, characterized in that: manganese oxide and cerium oxide are dispersedly loaded on gamma-Al2O3On the carrier, mercury is adsorbed and doped on manganese oxide, cerium oxide and gamma-Al2O3A carrier surface.
4. The method for preparing a low-temperature denitration catalyst according to claim 3, characterized in that:
the total mass of the manganese oxide and the cerium oxide is gamma-Al2O32-20% of the mass of the carrier;
the molar ratio of the manganese oxide to the cerium oxide is (2-5) to 1;
mercury in gamma-Al2O3The loading amount on the carrier is 0.01 wt% -0.2 wt%.
5. The method for preparing a low-temperature denitration catalyst according to claim 1, characterized in that: the high-temperature activation conditions are as follows: and under the protective atmosphere, heating to 400-600 ℃ at the heating rate of 5-20 ℃/min, and preserving the heat for 5-10 h.
6. The application of the low-temperature denitration catalyst obtained by the preparation method of any one of claims 1 to 5 is characterized in that: the method is applied to catalyzing the reduction of nitrogen oxides.
7. The use of the low-temperature denitration catalyst according to claim 6, wherein: the method is applied to denitration of smelting flue gas.
8. The use of the low-temperature denitration catalyst according to claim 7, wherein: the temperature range of the smelting flue gas is 100-200 ℃, and the concentration of elemental mercury is more than or equal to 100mg/m3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010386555.XA CN111530454B (en) | 2020-05-09 | 2020-05-09 | Low-temperature denitration catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010386555.XA CN111530454B (en) | 2020-05-09 | 2020-05-09 | Low-temperature denitration catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111530454A CN111530454A (en) | 2020-08-14 |
| CN111530454B true CN111530454B (en) | 2021-08-24 |
Family
ID=71977601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010386555.XA Active CN111530454B (en) | 2020-05-09 | 2020-05-09 | Low-temperature denitration catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111530454B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126825A (en) * | 2015-08-21 | 2015-12-09 | 盐城工学院 | Low temperature flue gas denitration catalyst and preparation method thereof |
| CN109569587A (en) * | 2019-01-10 | 2019-04-05 | 西南化工研究设计院有限公司 | A kind of manganese-based low-temperature catalyst for denitrating flue gas and preparation method thereof |
-
2020
- 2020-05-09 CN CN202010386555.XA patent/CN111530454B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126825A (en) * | 2015-08-21 | 2015-12-09 | 盐城工学院 | Low temperature flue gas denitration catalyst and preparation method thereof |
| CN109569587A (en) * | 2019-01-10 | 2019-04-05 | 西南化工研究设计院有限公司 | A kind of manganese-based low-temperature catalyst for denitrating flue gas and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "汞在MnOx-CeO2/γ-Al2O3催化剂表面的赋存形态分析";罗小雨等;《化工学报》;20150630;第66卷(第6期);第2083页右栏第1.1节、第2084页右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111530454A (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101352681B (en) | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof | |
| Li et al. | Hierarchical three-dimensionally ordered macroporous Fe-V binary metal oxide catalyst for low temperature selective catalytic reduction of NOx from marine diesel engine exhaust | |
| CN101602018B (en) | Method for preparing rare-earth element doped composite metal oxide mercury removal catalyst | |
| CN106582606B (en) | Non-vanadium low-temperature denitration catalyst and preparation method thereof | |
| CN111097442B (en) | Flue gas synergistic denitration and demercuration catalyst and preparation method thereof | |
| WO2015161627A1 (en) | Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method therefor | |
| CN111569953B (en) | Preparation method of denitration catalyst | |
| CN110052264B (en) | Preparation method of SCR denitration catalyst used under low temperature condition | |
| Liu et al. | Transition metals modified commercial SCR catalysts as efficient catalysts in NH3-SCO and NH3-SCR reactions | |
| CN110605114A (en) | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration | |
| CN112316946A (en) | Low-temperature CO-SCR denitration Cu-Ni/AC catalyst and preparation method thereof | |
| CN101972652A (en) | Preparation method of compound SCR catalyst with zero-valent mercury conversion function | |
| CN107413350A (en) | Mischmetal denitrating catalyst and preparation method thereof | |
| Li et al. | Characterization and performance of V 2 O 5/CeO 2 for NH 3-SCR of NO at low temperatures | |
| CN114870833A (en) | Low-temperature low-vanadium SCR denitration catalyst and preparation method thereof | |
| CN112718018B (en) | Lanthanum cobaltite perovskite catalyst treated by acetic acid and preparation method thereof | |
| CN112264033A (en) | Preparation method and application of ternary-loaded mesoporous silicon sphere low-temperature denitration catalyst | |
| CN111530454B (en) | Low-temperature denitration catalyst and preparation method and application thereof | |
| CN103480371A (en) | Denitration and demercuration catalyst as well as preparing method and application thereof | |
| CN107486206B (en) | Manganese-based material and preparation method and application thereof | |
| EP1360006B1 (en) | Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides | |
| CN108067247B (en) | Preparation method of iron oxide pillared layered manganese oxide low-temperature denitration catalyst | |
| KR100275301B1 (en) | Method for removing nox using the natural manganese ores | |
| KR100473080B1 (en) | Method for Improving NOx Removal Efficiency from Flue Gas and Reducing Consumption of Ammonia and Emission of Nitrogen Dioxide Using Modified Natural Manganese Ores | |
| CN103480271A (en) | Smoke treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |