CN112844374A - Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof - Google Patents

Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof Download PDF

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CN112844374A
CN112844374A CN202110086449.4A CN202110086449A CN112844374A CN 112844374 A CN112844374 A CN 112844374A CN 202110086449 A CN202110086449 A CN 202110086449A CN 112844374 A CN112844374 A CN 112844374A
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denitration catalyst
salt
oxide aerogel
cerium
catalyst
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张睿
王严
金双玲
霍婉颖
郑添
汪奇尧
王晓瑞
秦嘉威
金鸣林
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Shanghai Institute of Technology
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    • 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
    • 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
    • B01J23/16—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
    • B01J35/23—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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

Abstract

The invention discloses a Mn-Ce-Ti oxide aerogel denitration catalyst and a preparation method and application thereof, wherein the catalyst takes manganese salt, cerium salt and titanium salt as precursors, takes a condensation polymer of resorcinol and furfural as a sacrificial template agent, takes epoxypropane as a network gel initiator and ethyl acetoacetate as a complexing agent, and adopts a sol-gel method and a supercritical drying technology to prepare the Mn-Ce-Ti oxide aerogel denitration catalyst with larger specific surface area, pore diameter and pore volume. The catalyst has fine crystal grains, and effectively promotes the electron transfer between manganese, cerium and titanium metal oxides, thereby improving the catalytic reduction capability and surface acidity of the catalyst, and enabling the catalyst to have good low-temperature activity, sulfur resistance and water resistance.

Description

Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof
Technical Field
The invention relates to a Mn-Ce-Ti oxide aerogel denitration catalyst and a preparation method and application thereof, belonging to the technical field of chemical catalysis.
Background
Nitrogen Oxides (NO)x) Is one of the main pollutants of the atmosphere and is O3The generated important precursors can cause environmental problems such as acid rain, photochemical smog, haze and the like. In recent years, most coal-fired power plants have been equipped with denitration apparatuses, however, in the industrial kiln field such as industries of steel, cement, glass, ceramics and the like, NOxThe contamination was still severe. By NH3Selective catalytic reduction technology (NH) as a reducing agent3-SCR) denitration efficiency is high, application is wide, NOxAnd NH3Can be converted into nontoxic N under the action of catalyst2And H2O, currently most commercially available NH3The SCR type catalyst is V2O5-WO3(MoO3)/TiO2Because of the high temperature activity of vanadium-based catalysts, the existing SCR denitration devices are generally arranged in front of the electrostatic dust collector and the desulfurization device, which easily causes the catalysts to be dusted, alkali metals and SO2And the like, which leads to the reduction of the service life of the catalyst and the increase of the operation cost of denitration.
MnOx-CeO2-TiO2The three-way composite catalyst is currently NH3Research hotspots in the direction of SCR can be generally prepared by hydrothermal, sol-gel, wet impregnation, co-precipitation and the like. However, the catalyst has a narrow working temperature range, and N is generated at high temperature2Poor selectivity to SO2Are poor in tolerance, limiting their practical application. Thus, for MnOx-CeO2-TiO2The ternary composite catalyst needs to further improve the low-temperature (T is less than or equal to 200 ℃) activity and the sulfur resistance.
Disclosure of Invention
Technical problem solved by the inventionThe title is: existing MnOx-CeO2-TiO2The active temperature range of the ternary composite catalyst is narrow, and N is generated at high temperature2Poor selectivity and poor sulfur resistance.
In order to solve the technical problems, the invention provides a Mn-Ce-Ti oxide aerogel denitration catalyst which is prepared by taking manganese salt, cerium salt and titanium salt as precursors, taking a condensation polymer of resorcinol and furfural as a sacrificial template agent, taking propylene oxide as a network gel initiator and taking ethyl acetoacetate as a complexing agent through one-pot sol-gel, aging, solvent replacement, drying and roasting.
Preferably, the manganese salt is at least one of manganese nitrate, manganese chloride, manganese sulfate and manganese acetate or a crystalline hydrate thereof; the cerium salt is at least one of cerium nitrate, cerium chloride, cerium sulfate and cerium acetate or a crystalline hydrate thereof; the titanium salt is titanium tetrachloride or titanium sulfate.
The invention also provides a preparation method of the Mn-Ce-Ti oxide aerogel denitration catalyst, which comprises the following steps:
step 1: adding ethyl acetoacetate into a solvent, then adding titanium salt, manganese salt, cerium salt and propylene oxide for reaction, finally adding an alcoholic solution of resorcinol and furfural, and continuing the reaction to prepare sol;
step 2: aging the sol obtained in the step 1, and then placing the sol in a solvent for solvent replacement to obtain wet gel;
and step 3: drying the wet gel obtained in the step 2 to obtain dry gel;
and 4, step 4: and (4) calcining the xerogel obtained in the step (3) to obtain the Mn-Ce-Ti oxide aerogel denitration catalyst.
Preferably, the molar ratio of resorcinol, furfural, propylene oxide and ethyl acetoacetate in the step 1 is 1:1:3: 0.3-1: 3:6: 0.6; the molar concentration of the ethyl acetoacetate in the solvent is 0.03-0.1 mol/L; the molar ratio of the titanium salt to the manganese salt to the cerium salt is 1:0.1: 0.02-1: 0.6: 0.09; the molar ratio of the titanium salt to the resorcinol is 5: 1-15: 1.
preferably, the solvent in the step 1 is methanol and/or ethanol, the reaction time is 20-40 min, the continuous reaction time is 15-30 min, and the reaction temperature and the continuous reaction temperature are both 0-5 ℃.
Preferably, the aging in step 2 is specifically: the method comprises the steps of firstly aging in a water bath at 20-40 ℃ for 1-3 days, and then aging in a water bath at 60-80 ℃ for 4-6 days.
Preferably, the solvent in the step 2 is at least one of n-hexane, cyclohexane and n-heptane; the solvent replacement time is 8-16 h.
Preferably, the drying method in step 3 is supercritical drying, the medium of the supercritical drying is n-hexane, and the process conditions of the supercritical drying are as follows: the heating rate is 1-2 ℃/min, the temperature is 235-260 ℃, the pressure is 5-7 MPa, and the holding time is 1-2 h.
Preferably, the calcination process conditions in step 4 are as follows: the temperature is 400-700 ℃, and the time is 2-4 h.
The invention also provides application of the Mn-Ce-Ti oxide aerogel denitration catalyst in SCR flue gas denitration treatment.
Compared with the prior art, the invention has the following beneficial effects:
1. the Mn-Ce-Ti oxide aerogel denitration catalyst provided by the invention adopts a carbon source as a sacrificial template, and can effectively promote the dispersion of Mn, Ce and Ti components in a sol-gel process and inhibit the sintering of a manganese-cerium-titanium metal oxide component in a later calcining process, so that the grain size is effectively reduced, the interaction and electron transfer among manganese-cerium-titanium metal oxides are promoted, the specific surface area, the aperture, the surface acidity and the reducible species number of the aerogel are improved, and the catalytic reduction performance, the low-temperature activity and the sulfur-resistant and water-resistant performance of the catalyst are improved;
2. the preparation method has simple process, is easy for industrial production, and has potential practical application value in the field of environmental protection;
3. the catalyst disclosed by the invention has the advantages that the conversion rate of nitrogen oxides can reach nearly 100% in SCR denitration application for treating flue gas, and the economic value is high.
Drawings
Fig. 1 is a graph showing SCR activity evaluation of catalysts prepared in examples and comparative examples.
FIG. 2 is a graph showing the evaluation of sulfur resistance and water resistance of the catalysts prepared in example 1, example 2 and example 3;
FIG. 3 is a graph showing the life evaluation of the catalyst prepared in example 2.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Each of the raw materials used in the following examples is a commercially available product.
Example 1
A preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst comprises the following steps:
(1) 95mL of absolute ethanol was placed in a conical flask, 0.6929g of ethyl acetoacetate was added dropwise to the absolute ethanol under magnetic stirring, and the mixture was placed in an ice bath. Then, 0.1mol of TiCl is added dropwise to the solution via a syringe4Subsequently, 0.04mol of Mn (NO) was added to the solution3)2·4H2O and 0.007mol of Ce (NO)3)3·6H2O, and stirring thoroughly until dissolved. Finally, 2.47g of propylene oxide was added dropwise to the mixed solution and stirred for 30min to obtain a solution a, and resorcinol (F, 1.146g) and furfural (R, 2g) in a molar ratio of 1:2 were added to anhydrous ethanol, respectively, and stirred uniformly until resorcinol was sufficiently dissolved, to obtain a solution B. Finally, the solution B is added into the solution A drop by drop and stirred for 20min to obtain sol.
(2) And (3) putting the mixed sol into a 30mL ampoule, carrying out constant-temperature water bath at 30 ℃ for 2 days, and then carrying out constant-temperature water bath at 70 ℃ for 5 days to obtain a mixed wet gel.
(3) And (3) putting the wet gel into n-hexane for solvent replacement for 12h, then putting the wet gel into a high-pressure reaction kettle, and performing supercritical drying by taking the n-hexane as a medium. The operation steps are as follows: and (3) heating the temperature of the high-pressure kettle to 240 ℃ at the speed of 2 ℃/min, adjusting a regulating valve of the high-pressure kettle to release pressure, maintaining the pressure in the high-pressure kettle to be 6MPa, keeping the sample in the high-pressure kettle in a supercritical state for 1h, slowly releasing the pressure, and naturally cooling to room temperature to obtain the precursor of the Mn-Ce-Ti oxide aerogel denitration catalyst.
(4) Putting the Mn-Ce-Ti oxide aerogel precursor into a muffle furnace, heating the temperature in the furnace to 400 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3 hours to obtain the RF-MCTO-400 composite aerogel, namely the catalyst I.
Example 2
A preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst comprises the following steps:
(1) 95m of absolute ethanol was placed in an Erlenmeyer flask, 0.6929g of ethyl acetoacetate was added dropwise to the absolute ethanol under magnetic stirring, and the mixture was placed in an ice bath. Then, 0.1mol of TiCl is added dropwise to the solution via a syringe4Subsequently, 0.04mol of Mn (NO) was added to the solution3)2·4H2O and 0.007mol of Ce (NO)3)3·6H2O, and stirring thoroughly until dissolved. Finally, 2.47g of propylene oxide was added dropwise to the mixed solution and stirred for 30min to obtain a solution a, and resorcinol (F, 1.146g) and furfural (R, 2g) in a molar ratio of 1:2 were added to anhydrous ethanol, respectively, and stirred uniformly until resorcinol was sufficiently dissolved, to obtain a solution B. Finally, the solution B is added into the solution A drop by drop and stirred for 20min to obtain sol.
(2) And (3) putting the mixed sol into a 30mL ampoule, carrying out constant-temperature water bath at 30 ℃ for 2 days, and then carrying out constant-temperature water bath at 70 ℃ for 5 days to obtain a mixed wet gel.
(3) And (3) putting the wet gel into n-hexane for solvent replacement for 12h, then putting the wet gel into a high-pressure reaction kettle, and performing supercritical drying by taking the n-hexane as a medium. The operation steps are as follows: and (3) heating the temperature of the high-pressure kettle to 240 ℃ at the speed of 2 ℃/min, adjusting a regulating valve of the high-pressure kettle to release pressure, maintaining the pressure in the high-pressure kettle to be 6MPa, keeping the sample in the high-pressure kettle in a supercritical state for 1h, slowly releasing the pressure, and naturally cooling to room temperature to obtain the precursor of the Mn-Ce-Ti oxide aerogel denitration catalyst.
(4) And (3) putting the Mn-Ce-Ti oxide aerogel precursor into a muffle furnace, heating the temperature in the furnace to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3 hours to obtain the RF-MCTO-500 composite aerogel, namely the catalyst II.
Example 3
A preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst comprises the following steps:
(1) 95mL of absolute ethanol was placed in a conical flask, 0.6929g of ethyl acetoacetate was added dropwise to the absolute ethanol under magnetic stirring, and the mixture was placed in an ice bath. Then, 0.1mol of TiCl is added dropwise to the solution via a syringe4Subsequently, 0.04mol of Mn (NO) was added to the solution3)2·4H2O and 0.007mol of Ce (NO)3)3·6H2O, and stirring thoroughly until dissolved. Finally, 2.47g of propylene oxide was added dropwise to the mixed solution and stirred for 30min to obtain a solution a, and resorcinol (F, 1.146g) and furfural (R, 2g) in a molar ratio of 1:2 were added to anhydrous ethanol, respectively, and stirred uniformly until resorcinol was sufficiently dissolved, to obtain a solution B. Finally, the solution B is added into the solution A drop by drop and stirred for 20min to obtain sol.
(2) And (3) putting the mixed sol into a 30mL ampoule, carrying out constant-temperature water bath at 30 ℃ for 2 days, and then carrying out constant-temperature water bath at 70 ℃ for 5 days to obtain a mixed wet gel.
(3) And (3) putting the wet gel into n-hexane for solvent replacement for 12h, then putting the wet gel into a high-pressure reaction kettle, and performing supercritical drying by taking the n-hexane as a medium. The operation steps are as follows: and (3) heating the temperature of the high-pressure kettle to 240 ℃ at the speed of 2 ℃/min, adjusting a regulating valve of the high-pressure kettle to release pressure, maintaining the pressure in the high-pressure kettle to be 6MPa, keeping the sample in the high-pressure kettle in a supercritical state for 1h, slowly releasing the pressure, and naturally cooling to room temperature to obtain the precursor of the Mn-Ce-Ti oxide aerogel denitration catalyst.
(4) And (3) putting the Mn-Ce-Ti oxide aerogel precursor into a muffle furnace, heating the temperature in the furnace to 600 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3 hours to obtain the RF-MCTO-600 composite aerogel, namely the catalyst III.
Example 4
A preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst comprises the following steps:
(1) in a conical flaskTo the solution was added 95mL of anhydrous ethanol, 0.6929g of ethyl acetoacetate was added dropwise to the anhydrous ethanol under magnetic stirring, and the mixture was placed in an ice bath. Then, 0.1mol of TiCl is added dropwise to the solution via a syringe4Subsequently, 0.04mol of Mn (NO) was added to the solution3)2·4H2O and 0.007mol of Ce (NO)3)3·6H2O, and stirring thoroughly until dissolved. Finally, 2.47g of propylene oxide was added dropwise to the mixed solution and stirred for 30min to obtain a solution a, and resorcinol (F, 1.146g) and furfural (R, 2g) in a molar ratio of 1:2 were added to anhydrous ethanol, respectively, and stirred uniformly until resorcinol was sufficiently dissolved, to obtain a solution B. Finally, the solution B is added into the solution A drop by drop and stirred for 20min to obtain sol.
(2) And (3) putting the mixed sol into a 30mL ampoule, carrying out constant-temperature water bath at 30 ℃ for 2 days, and then carrying out constant-temperature water bath at 70 ℃ for 5 days to obtain a mixed wet gel.
(3) And (3) putting the wet gel into n-hexane for solvent replacement for 12h, then putting the wet gel into a high-pressure reaction kettle, and performing supercritical drying by taking the n-hexane as a medium. The operation steps are as follows: and (3) heating the temperature of the high-pressure kettle to 240 ℃ at the speed of 2 ℃/min, adjusting a regulating valve of the high-pressure kettle to release pressure, maintaining the pressure in the high-pressure kettle to be 6MPa, keeping the sample in the high-pressure kettle in a supercritical state for 1h, slowly releasing the pressure, and naturally cooling to room temperature to obtain the precursor of the Mn-Ce-Ti oxide aerogel denitration catalyst.
(4) And (3) putting the Mn-Ce-Ti oxide aerogel precursor into a muffle furnace, heating the temperature in the furnace to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3 hours to obtain the RF-MCTO-700 composite aerogel, namely the catalyst IV.
Comparative example 1
A preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst comprises the following specific steps:
(1) 95mL of absolute ethanol was placed in a conical flask, 0.6929g of ethyl acetoacetate was added dropwise to the absolute ethanol under magnetic stirring, and the mixture was placed in an ice bath. Then, 0.1mol of TiCl is added dropwise to the solution via a syringe4Subsequently, 0.04mol of Mn (NO) was added to the solution3)2·4H2O and 0.007mol of Ce (NO)3)3·6H2O, and stirring thoroughly until dissolved. Finally, 2.47g of propylene oxide was added dropwise to the mixed solution, and stirred for 30min to obtain a yellow transparent sol.
(2) And (3) putting the mixed sol into a 30mL ampoule, carrying out constant-temperature water bath at 30 ℃ for 2 days, and then carrying out constant-temperature water bath at 70 ℃ for 5 days to obtain a mixed wet gel.
(3) And putting the wet gel into n-hexane for solvent standing for 12h, then putting the wet gel into a high-pressure reaction kettle, and performing supercritical drying by taking the n-hexane as a medium. The operation steps are as follows: and (3) heating the temperature of the high-pressure kettle to 240 ℃ at the speed of 2 ℃/min, adjusting a regulating valve of the high-pressure kettle to release pressure, maintaining the pressure in the high-pressure kettle to be 6MPa, keeping the sample in the high-pressure kettle in a supercritical state for 1h, slowly releasing the pressure, and naturally cooling to room temperature to obtain the precursor of the Mn-Ce-Ti oxide aerogel denitration catalyst.
(4) And (3) putting the Mn-Ce-Ti oxide aerogel precursor into a muffle furnace, heating the temperature in the furnace to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3 hours to obtain the MCTO-500 composite aerogel, namely the catalyst V.
The Mn-Ce-Ti oxide aerogel denitration catalyst prepared in the embodiment and the comparative example is placed in a fixed bed quartz tube reactor for denitration performance test, and the simulation of flue gas consisting of NO and NH3、O2And N2Composition of, wherein NO is 500ppm, NH3Is 500ppm, SO2100ppm (introduced when testing the sulfur resistance), O25.0 vol%, N2As the balance gas, the total flow is 120mL/min, and the reaction space velocity is 14400h-1. The concentration of NO in the reaction tail gas is detected on line by adopting an ECO PHYSICS nCLD62s type nitrogen-oxygen analyzer at the same time, and the detection precision is 0.25 ppm. Collecting data 30min after the SCR reaction reaches a stable state, wherein the temperature range of activity evaluation is 120-320 ℃, and the NO conversion rate is calculated according to the following formula:
ηNO＝([NO]in-[NO]out)/[NO]in
in the formula etaNOFor NO conversion, [ NO ]]inAnd [ NO]outRespectively the inlet and the outlet of the reactor under the steady stateConcentration of NO at the mouth. The activity evaluation (denitration rate) of the catalysts prepared in examples 1 to 4 and comparative example 1 is shown in table 1, and the SCR activity evaluation chart of the catalysts prepared in examples 1 to 4 and comparative example 1 is shown in fig. 1.
Table 1 denitration activity of catalysts prepared in examples and comparative examples
Figure BDA0002910942220000071
As shown in Table 1, the catalysts I to IV prepared in examples 1 to 4 all have better low-temperature activity, wherein the removal rate of NO of the catalyst prepared in example 2 is more than 90% at 140 to 320 ℃, and the conversion rate of NO reaches 100% at 160 to 300 ℃. The comparative example 1 is a Mn-Ce-Ti oxide aerogel denitration catalyst without adding a sacrificial template, the low-temperature activity and the activity temperature interval of the Mn-Ce-Ti oxide aerogel denitration catalyst are far lower than those of the catalyst prepared in the example, and the NO conversion rate is more than 90% at 200-300 ℃.
The mesoporous Mn-Ce-Ti oxide aerogel denitration catalysts prepared in the embodiments 1, 2 and 3 are screened to 40-80 meshes, placed in a fixed bed quartz tube reactor for a sulfur-resistant and water-resistant performance test, and simulated smoke is made of NO and NH3、O2、SO2、N2And H2O, wherein NO is 500ppm, NH3500ppm, O25.0 vol%, SO2Is 100ppm, H2O is 5 vol%, N2As the balance gas, the reaction space velocity is 14400h-1. The NO in the gas before and after the reaction was detected by a model ECOPHYSICS Ncld62s nitrogen-oxygen analyzer. The temperature for activity evaluation is 220 ℃, the reaction time is 10 hours, firstly NO and NH are introduced3、O2And N2The mixed gas is introduced with SO after 2 hours2Stopping the introduction of SO after 8 hours2And the mixed gas was continuously introduced for 2 hours, and the evaluation of the sulfur resistance activity was as shown in FIG. 2. Wherein the conversion of NO can be maintained above 80% after the sulfur dioxide and water are introduced into the catalyst prepared in example 2, while the catalysts prepared in examples 1 and 3 are shown in the table after the sulfur dioxide and water are introduced into the catalystThe activity is now lower than in example 2, but the NO conversion remains above 50%.
The Mn-Ce-Ti oxide aerogel denitration catalyst prepared in the example 2 is placed in a fixed bed quartz tube reactor to test the service life of the catalyst, the activity evaluation temperature is 220 ℃, and the simulation of the flue gas consisting of NO and NH3、O2And N2Composition of, wherein NO is 500ppm, NH3500ppm, O25.0 vol%, N2As the balance gas, the reaction space velocity is 14400h-1. The NO in the gas before and after the reaction was detected by an ecophysis Ncld62s model nitrogen oxygen analyzer, sampling was performed every two hours until the reaction was carried out for 24 hours, and a life evaluation graph of the catalyst prepared in example 2 was obtained, as shown in fig. 3, it can be seen from fig. 3 that the removal efficiency of the catalyst prepared in example 2 to NO was stable at 100% within 24 hours, which indicates that the catalytic performance of the catalyst prepared in the present invention remained stable for a long period of time.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. The Mn-Ce-Ti oxide aerogel denitration catalyst is characterized by being prepared by taking manganese salt, cerium salt and titanium salt as precursors, taking a condensation polymer of resorcinol and furfural as a sacrificial template agent, taking propylene oxide as a network gel initiator and taking ethyl acetoacetate as a complexing agent through one-pot sol-gel, aging, solvent replacement, drying and roasting.
2. A Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 1, wherein the manganese salt is at least one of manganese nitrate, manganese chloride, manganese sulfate and manganese acetate or a crystalline hydrate thereof; the cerium salt is at least one of cerium nitrate, cerium chloride, cerium sulfate and cerium acetate or a crystalline hydrate thereof; the titanium salt is titanium tetrachloride or titanium sulfate.
3. The preparation method of an Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 1 or 2, characterized by comprising the steps of:
step 1: adding ethyl acetoacetate into a solvent, then adding titanium salt, manganese salt, cerium salt and propylene oxide for reaction, finally adding an alcoholic solution of resorcinol and furfural, and continuing the reaction to prepare sol;
step 2: aging the sol obtained in the step 1, and then placing the sol in a solvent for solvent replacement to obtain wet gel;
and step 3: drying the wet gel obtained in the step 2 to obtain dry gel;
and 4, step 4: and (4) calcining the xerogel obtained in the step (3) to obtain the Mn-Ce-Ti oxide aerogel denitration catalyst.
4. The preparation method of a Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the molar ratio of resorcinol, furfural, propylene oxide and acetoacetyl acetate in the step 1 is 1:1:3: 0.3-1: 3:6: 0.6; the molar concentration of the ethyl acetoacetate in the solvent is 0.03-0.1 mol/L; the molar ratio of the titanium salt to the manganese salt to the cerium salt is 1:0.1: 0.02-1: 0.6: 0.09; the molar ratio of the titanium salt to the resorcinol is 5: 1-15: 1.
5. the preparation method of the Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the solvent in the step 1 is methanol and/or ethanol, the reaction time is 20-40 min, and the continuous reaction time is 15-30 min; the temperature of the reaction and the temperature of the continuous reaction are both 0-5 ℃.
6. The preparation method of the Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the aging in the step 2 is specifically: the method comprises the steps of firstly aging in a water bath at 20-40 ℃ for 1-3 days, and then aging in a water bath at 60-80 ℃ for 4-6 days.
7. A method for preparing a Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the solvent in the step 2 is at least one of n-hexane, cyclohexane and n-heptane; the solvent replacement time is 8-16 h.
8. The preparation method of the Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the drying method in the step 3 is supercritical drying, the supercritical drying medium is n-hexane, and the supercritical drying process conditions are as follows: the heating rate is 1-2 ℃/min, the temperature is 235-260 ℃, the pressure is 5-7 MPa, and the holding time is 1-2 h.
9. The preparation method of the Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 3, wherein the calcination in the step 4 is carried out under the following process conditions: the temperature is 400-700 ℃, and the time is 2-4 h.
10. The use of a Mn-Ce-Ti oxide aerogel denitration catalyst according to claim 1 or 2 in an SCR flue gas denitration treatment.
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