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CN111774055B - Perovskite type monolithic catalyst and preparation method and application thereof - Google Patents

Perovskite type monolithic catalyst and preparation method and application thereof Download PDF

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CN111774055B
CN111774055B CN202010788891.7A CN202010788891A CN111774055B CN 111774055 B CN111774055 B CN 111774055B CN 202010788891 A CN202010788891 A CN 202010788891A CN 111774055 B CN111774055 B CN 111774055B
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perovskite
catalyst
sulfur
monolithic catalyst
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CN111774055A (en
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赵琳
胡芝娟
李帅帅
王永刚
程兆环
张明飞
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TIANJIN SINOMA ENGINEERING RESEARCH CENTER CO LTD
Tianjin Cement Industry Design and Research Institute Co Ltd
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    • 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
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    • 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
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/02—Impregnation, coating or precipitation
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Abstract

The invention relates to a perovskite type monolithic catalyst, a preparation method and application thereof3The composite metal oxide is an active component, the components also comprise a carrier subjected to sulfur-thinning treatment and a forming auxiliary agent, and the active component, the carrier subjected to sulfur-thinning treatment and the forming auxiliary material respectively account for 5-30%, 50-80% and 2-25% of the total mass of the catalyst; the catalyst can be applied to low-temperature SCR denitration of fixed source flue gas, does not contain highly toxic substances such as vanadium pentoxide and the like, and has NO higher than 80 percent within the range of 80-180 DEG CxThe conversion rate and the stability are good, the sulfur resistance and the water resistance are good, the preparation process is relatively simple, the repeatability is strong, and the large-scale mass production is easy.

Description

Perovskite type monolithic catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of industrial catalysis, and particularly relates to a perovskite type monolithic catalyst, and a preparation method and application thereof.
Background
In recent years, the emission standard of nitrogen oxides is becoming stricter, and enterprises are required to reach the emission concentration of 100mg/m by multiple standards3In some areas, some cement enterprises are required to reduce the emission concentration of nitrogen oxides to 80mg/m3The following. The denitration technology adopting the ammonia Selective Catalytic Reduction (SCR) technology is simple, the elimination rate of nitrogen oxides is high (can reach more than 85 percent), and the emission requirement can be met, wherein the catalyst is a core material of the technology.
At present, the activity temperature of the existing high-temperature denitration catalyst in industrial application is 300-450 ℃, the catalyst is generally titanium dioxide loaded vanadium-tungsten oxide and vanadium-molybdenum oxide, vanadium pentoxide has ecological toxicity and biological toxicity, is a highly toxic substance, has half lethal dose of 10mg/kg, has great influence on respiratory system due to acute poisoning, and can cause bronchitis, kidney damage, visual disturbance and the like due to chronic poisoning. In addition, medium-high temperature catalytic denitration is adopted, the dust content in the temperature interval is high, the catalyst is easy to scour or block, and the normal operation of the system is influenced; when the flue gas temperature is lower, the denitration requirement can not be met, and the emission is not up to the standard.
Therefore, non-vanadium-based low-temperature denitration catalysts are receiving more and more extensive attention from academia and industry. The low-temperature denitration catalyst can be used for denitration at the temperature lower than 200 ℃ or even lower than 150 ℃, but the stability of the catalyst is poor, and the catalyst reported in relevant documents and patents is especially used for removing SO2And H2O is easily deactivated in an atmosphere where it exists. Therefore, there is an urgent need to develop a low-temperature denitration catalyst having high sulfur-resistant and water-resistant properties.
Disclosure of Invention
Aiming at the problems that the prior high-temperature denitration catalyst contains highly toxic substances such as vanadium pentoxide and the like and the low-temperature denitration catalyst has poor sulfur-resistant and water-resistant performances, the invention aims to provide a perovskite type monolithic catalyst which is prepared from perovskite ABO3The composite metal oxide is an active component, and other components also comprise a carrier subjected to sulfur-thinning treatment and a forming auxiliary material, and the composite metal oxide does not contain highly toxic substances such as vanadium pentoxide and the like.
The invention also aims to provide a preparation method of the perovskite type monolithic catalyst, which has the advantages of simple process, strong repeatability and easy realization of large-scale mass production.
It is a further object of the present invention to provide the use of a perovskite-type monolithic catalyst as described above, which catalyst has NO at a temperature of 80 ℃ to 180 ℃xThe removal efficiency of the catalyst is more than 80 percent, and the catalyst has higher sulfur resistance and water resistance.
The invention is realized by that a perovskite type monolithic catalyst comprises an active component and sulfur-phobicTreated carriers and forming aids; wherein the active component is perovskite ABO3The active component of the composite metal oxide accounts for 5-30% of the total mass of the catalyst, the sulfur-thinning carrier accounts for 50-80% of the total mass of the catalyst, and the forming auxiliary material accounts for 2-25% of the total mass of the catalyst; the sum of the mass percentages of the active component, the sulfur-thinning treated carrier and the forming auxiliary material is 100 percent.
In the above technical solution, preferably, the element at the a site in the active component is Bi and one or a combination of more selected from La, Ce, Ba, Ca, Pr, Sr and Ce, and the molar percentage of the element at the a site is not less than 30%; the B site element in the active component is Zr and one or a combination of more of Cu, Fe, Ni, Mn, Cr and Co, and the mol percentage of the Zr element at the B site is not less than 5%.
In the above technical solution, preferably, the carrier for sulfur-phobic treatment is cerium oxysulfate and one or a combination of several selected from titanium dioxide, aluminum oxide, cerium oxide, zirconium oxide, magnesium oxide, calcium oxide, cerium-zirconium solid solution, silicon dioxide, cerium sulfate, MCM-41 molecular sieve and ZSM-5 molecular sieve.
In the above technical solution, preferably, the forming auxiliary material is a combination of two or more of deionized water, dilute nitric acid, alumina, methylcellulose, asphalt, cement, carnauba wax, paraffin, clay, kaolin, montmorillonite, guar gum, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, alumina sol, silica sol, carboxymethyl cellulose, hydroxypropyl cellulose, lubricating oil, glycerin, paraffin, starch, sesbania powder, talc powder, activated carbon, graphite, monoethanolamine, and glass fiber.
The preparation method of the perovskite type monolithic catalyst comprises the following steps:
(1) firstly, a sol-gel method is adopted to prepare perovskite ABO3A type composite metal oxide;
(2) prepared perovskite ABO3Mixing the type composite metal oxide, the sulfur-thinning treated carrier and the forming auxiliary material;
(3) ball-milling the mixture for 1-6h, and grinding to a particle size of 200-400 meshes;
(4) mixing the ball-milled mixture for 2-3h to prepare pug;
(5) the prepared pug is refined in a pug mill for 1 to 2 times and then aged for 12 to 24 hours;
(6) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(7) drying the blank at 80-150 ℃ for 24-48h, and calcining at 300-800 ℃ for 2-8h to form the perovskite type monolithic catalyst.
In the above technical solution, preferably, the perovskite ABO3The preparation method of the composite metal oxide comprises the following steps:
(1) adding soluble salt of A, B site element, complexing agent, dispersant and deionized water into a beaker, and mixing uniformly to form solution;
(2) putting the solution in the step (1) in a water bath at 70-90 ℃ under the condition of continuous stirring, and gradually evaporating to form gel;
(3) drying the gel obtained in the step (2) at 90-120 ℃ for 12-48h to form spongy loose porous solid;
(4) the solid obtained in the step (3) is calcined by sectional heating, the temperature rise rate of 2-10 ℃/min is increased to 300-350 ℃ and the temperature is kept for 2-4h, then the temperature rise rate of 2-10 ℃/min is increased to 600-700 ℃ and the temperature is kept for 5-8h, and the perovskite ABO is obtained3And (3) a type of composite metal oxide.
In the above technical solution, it is further preferable that the soluble salt of the A, B th element is one or a combination of several of nitrate, sulfate and acetate.
In the above technical solution, it is further preferable that the complexing agent is citric acid, and the mole number of the citric acid is 1.1 to 1.5 times of the total mole number of the a site and the B site elements; the dispersing agent is one or a combination of more of ethylenediamine tetraacetic acid, formaldehyde, ethylene glycol, polyethylene glycol 400, resorcinol, polyacrylic acid and hydroxypropyl cellulose, and the mole number of the dispersing agent is 0.2-0.3 times of the total mole number of the A-site element and the B-site element.
In the above technical solution, preferably, a part of sulfate, such as ceric sulfate, is introduced into the precursor of the sulfur-phobized carrier, and the adding proportion of the sulfate accounts for 5% -20% of the total mass of the sulfur-phobized carrier.
Application of perovskite type monolithic catalyst to nitrogen oxide NOxWhen the catalytic reduction treatment is carried out, the treatment temperature is 80-180 ℃.
The principle of the invention is as follows:
bi is used as a necessary element of the active component A site element, so that the acid site on the surface of the catalyst can be improved, the concentration of oxygen adsorbed on the surface of the catalyst can be improved, Zr is used as a doping element of the active component B site, the water resistance of the catalyst can be obviously improved, the performance of the catalyst can be improved to a certain extent, and sulfate and a certain proportion of mesopores in a carrier can effectively inhibit the adsorption of the catalyst on sulfur dioxide, so that the catalyst has better sulfur resistance and water resistance.
The invention has the advantages and positive effects that:
(1) compared with vanadium-titanium catalyst, the invention uses perovskite ABO3The monolithic catalyst with the active component of the composite metal oxide does not contain highly toxic substances such as vanadium pentoxide and the like.
(2) Compared with medium-high temperature denitration catalyst, the invention uses perovskite ABO3The monolithic catalyst with composite metal oxide as active component can reduce nitrogen oxide at 80-180 deg.c and has low conversion temperature.
(3) The perovskite type monolithic catalyst has better sulfur resistance and water resistance, and can be used for treating nitrogen oxides in industrial waste gases of power plants, cement plants, coking plants and the like.
(4) The preparation process of the perovskite type monolithic catalyst is relatively simple, easy to operate, strong in repeatability and easy to realize large-scale mass production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A perovskite type monolithic catalyst, said catalyst being formed of La0.3Bi0.7Mn0.8Zr0.2O3As active components, cerous oxysulfate, TiO2And CeO2The preparation method is as follows:
(1) firstly, preparing La by adopting a sol-gel method0.3Bi0.7Mn0.8Zr0.2O3Composite metal oxide: adding a certain amount of lanthanum nitrate, bismuth nitrate, manganese acetate, zirconyl nitrate, citric acid, polyethylene glycol 400 and deionized water into a beaker, and uniformly mixing to form a solution; placing the solution in water bath at 80 deg.C under continuously stirring, and gradually evaporating to gel state; drying the obtained gel at 120 ℃ for 24h to form spongy loose porous solid; the obtained solid is calcined by temperature programming and section by section, the temperature is raised to 350 ℃ at the temperature rise rate of 5 ℃/min and is kept for 2h, then the temperature is raised to 650 ℃ at the temperature rise rate of 5 ℃/min and is kept for 5h, and the perovskite type composite metal oxide La is obtained0.3Bi0.7Mn0.8Zr0.2O3；
(2) 100g of prepared perovskite type composite metal oxide La0.3Bi0.7Mn0.8Zr0.2O3120g of ceric sulfate, 200g of CeO2And 200g of TiO2Mixing to obtain a mixed dry material, and carrying out ball milling treatment for 1 h;
(3) adding 250g of deionized water, 25g of dilute nitric acid, 50g of alumina, 20g of carboxymethyl cellulose and 15g of glass fiber into the ball-milled mixture, and mixing for 2 hours to prepare pug;
(4) the prepared pug is refined in a pug mill for 1 time, and then is aged for 12 hours;
(5) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(6) and drying the blank at 120 ℃ for 24h, and calcining at 400 ℃ for 5h to form the perovskite type monolithic catalyst.
Example 2
Calcium titaniumA mineral-type monolithic catalyst comprising BiMn0.6Cu0.2Zr0.2O3As active components, cerous oxysulfate, ZSM-5 and cerium-zirconium solid solution Ce0.5Zr0.5O2The preparation method is as follows:
(1) firstly, preparing BiMn by adopting a sol-gel method0.6Cu0.2Zr0.2O3Composite metal oxide: adding a certain amount of bismuth nitrate, manganese acetate, copper nitrate, zirconium acetate solution, citric acid, ethylene glycol and deionized water into a beaker, and uniformly mixing to form a solution; placing the solution in a water bath at 85 ℃ under the condition of continuous stirring, and gradually evaporating to form gel; drying the obtained gel at 110 ℃ for 24h to form spongy loose porous solid; the obtained solid is calcined by temperature programming and section by section, the temperature is increased to 300 ℃ at the temperature increase rate of 2 ℃/min and is kept for 2h, then the temperature is increased to 600 ℃ at the temperature increase rate of 2 ℃/min and is kept for 5h, and the perovskite type composite metal oxide BiMn is obtained0.6Cu0.2Zr0.2O3。
(2) 150g of prepared perovskite type composite metal oxide BiMn0.6Cu0.2Zr0.2O3100g of ceric sulfate, 50g of ZSM-5 and 450g of Ce0.5Zr0.5O2Mixing to obtain dry materials, and carrying out ball milling treatment for 2 hours;
(3) adding 350g of deionized water, 30g of kaolin, 20g of guar gum and 10g of glass fiber into the ball-milled mixture, and mixing for 2.5 hours to prepare pug;
(4) the prepared pug is refined in a pug mill for 1 time, and then is aged for 12 hours;
(5) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(6) and drying the blank body at 120 ℃ for 24h, and calcining the blank body at 450 ℃ for 5h to form the perovskite type monolithic catalyst.
Example 3
A perovskite-type monolithic catalyst, said catalyst being formed from Bi0.6Sr0.4Cu0.6Co0.2Zr0.2O3As active components, cerous oxysulfate and TiO2To be loadedThe preparation method comprises the following steps:
(1) firstly, preparing Bi by adopting a sol-gel method0.6Sr0.4Cu0.6Co0.2Zr0.2O3Composite metal oxide: adding a certain amount of strontium nitrate, bismuth nitrate, copper nitrate, cobalt acetate, zirconyl nitrate, citric acid, ethylene diamine tetraacetic acid and deionized water into a beaker, and uniformly mixing to form a solution; placing the solution in water bath at 80 deg.C under continuously stirring, and gradually evaporating to gel state; drying the obtained gel at 120 ℃ for 24h to form spongy loose porous solid; the obtained solid is calcined by temperature programming and section by section, the temperature is raised to 300 ℃ at the temperature rise rate of 2 ℃/min and is kept for 2h, then the temperature is raised to 700 ℃ at the temperature rise rate of 5 ℃/min and is kept for 5h, and the perovskite type composite metal oxide Bi is obtained0.6Sr0.4Cu0.6Co0.2Zr0.2O3。
(2) 100g of prepared perovskite type composite metal oxide Bi0.6Sr0.4Cu0.6Co0.2Zr0.2O3110g of ceric sulfate and 600g of TiO2Mixing to obtain dry materials, and performing ball milling treatment for 1.5 h;
(3) adding 300g of deionized water, 20g of silica sol, 30g of montmorillonite, 10g of glycerol and 30g of glass fiber into the ball-milled mixture, and mixing for 1.5 hours to prepare pug;
(4) the prepared pug is refined in a pug mill for 1 time, and then is aged for 12 hours;
(5) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(6) and drying the blank at 120 ℃ for 24h, and calcining at 550 ℃ for 5h to form the perovskite type monolithic catalyst.
Comparative example 1:
firstly, preparing Cu by adopting a sol-gel method0.8Co0.2O3Composite metal oxide: adding a certain amount of copper nitrate, cobalt acetate, citric acid, polyethylene glycol and deionized water into a beaker, and uniformly mixing to form a solution; placing the solution in water bath at 80 deg.C under continuously stirring, and gradually evaporating to gel state; the obtained gel is added inDrying for 24h at 120 ℃ to form spongy loose porous solid; calcining the obtained solid by adopting programmed heating, heating to 300 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2h to obtain the composite metal oxide Cu0.8Co0.2O3。
(2) 100g of prepared perovskite type composite metal oxide Cu0.8Co0.2O3And 600g TiO2Mixing to obtain dry materials, and performing ball milling treatment for 1.5 h;
(3) adding 300g of deionized water, 20g of silica sol, 30g of montmorillonite, 10g of glycerol and 30g of glass fiber into the ball-milled mixture, and mixing for 1.5 hours to prepare pug;
(4) the prepared pug is refined in a pug mill for 1 time, and then is aged for 12 hours;
(5) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(6) and drying the blank body at 120 ℃ for 24h, and calcining the blank body at 450 ℃ for 5h to form the monolithic catalyst.
Performance testing
The monolithic catalysts prepared in examples 1 to 3 and having a perovskite-type composite metal oxide as an active component and the monolithic catalyst prepared in comparative example 1 and having a composite metal oxide as an active component were each subjected to a test for eliminating nitrogen oxides under the conditions of introduction of sulfur dioxide and water.
And (3) testing conditions are as follows: the test temperature is 120 ℃, and the NO inlet concentration is 500mg/Nm3，NH3The inlet concentration is 500mg/Nm3、O2Is 5% (v/v), N2The gas volume space velocity is 4000h for balancing gas-1. The concentration of NO at the inlet and outlet of the monolithic catalyst is detected by a nitrogen oxide detector, and the analysis result is shown in Table 1.
TABLE 1 test results
Figure BDA0002623048450000061
From the test results in table 1, it can be seen that the perovskite monolithic catalyst prepared by the method of the present invention has high denitration efficiency and effectively improved sulfur-resistant and water-resistant properties compared with the composite metal oxide catalyst prepared by the conventional method.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and the modifications or the replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. A perovskite-type monolithic catalyst characterized in that: comprises an active component, a carrier for sulfur-thinning treatment and a forming auxiliary material; wherein the active component is perovskite ABO3The active component accounts for 5-30% of the total mass of the catalyst, the sulfur-thinning carrier accounts for 50-80% of the total mass of the catalyst, and the forming auxiliary material accounts for 2-25% of the total mass of the catalyst; the sum of the mass percentages of the active component, the sulfur-thinning treated carrier and the forming auxiliary material is 100%;
the A site element in the active component is Bi and one or a combination of more of La, Ce, Ba, Ca, Pr, Sr and Ce, and the molar percentage of the Bi element at the A site is not less than 30%;
b site elements in the active components are Zr and one or a combination of more of Cu, Fe, Ni, Mn, Cr and Co, and the mol percentage of the Zr element at the B site is not less than 5%;
the carrier for sulfur-thinning treatment is ceric sulfate and one or a combination of more of titanium dioxide, aluminum oxide, cerium oxide, zirconium oxide, magnesium oxide, calcium oxide, cerium-zirconium solid solution, silicon dioxide, MCM-41 molecular sieve and ZSM-5 molecular sieve.
2. A process for the preparation of a perovskite-type monolithic catalyst according to claim 1, characterized by comprising the steps of:
(1) firstly, the sol-gel method is adopted for preparationPerovskite ABO3A type composite metal oxide;
(2) prepared perovskite ABO3Mixing the type composite metal oxide, the sulfur-thinning treated carrier and the forming auxiliary material;
(3) ball-milling the mixture for 1-6h, and grinding to a particle size of 200-400 meshes;
(4) mixing the ball-milled mixture for 2-3h to prepare pug;
(5) the prepared pug is refined in a pug mill for 1 to 2 times and then aged for 12 to 24 hours;
(6) extruding the aged pug by an extruder to form a honeycomb-shaped blank body;
(7) drying the blank at 80-150 ℃ for 24-48h, and calcining at 300-800 ℃ for 2-8h to form the perovskite type monolithic catalyst.
3. The process for preparing a perovskite-type monolithic catalyst as claimed in claim 2, wherein the perovskite ABO3The preparation method of the composite metal oxide comprises the following steps:
(1) adding soluble salt of A, B site element, complexing agent, dispersant and deionized water into a beaker, and mixing uniformly to form solution;
(2) putting the solution in the step (1) in a water bath at 70-90 ℃ under the condition of continuous stirring, and gradually evaporating to form gel;
(3) drying the gel obtained in the step (2) at 90-120 ℃ for 12-48h to form spongy loose porous solid;
(4) the solid obtained in the step (3) is calcined by sectional heating, the temperature rise rate of 2-10 ℃/min is increased to 300-350 ℃ and the temperature is kept for 2-4h, then the temperature rise rate of 2-10 ℃/min is increased to 600-700 ℃ and the temperature is kept for 5-8h, and the perovskite ABO is obtained3And (3) a type of composite metal oxide.
4. The preparation method of the perovskite monolithic catalyst as claimed in claim 3, wherein the soluble salt of the A, B th element is one or more of nitrate, sulfate and acetate.
5. The process for producing a perovskite monolithic catalyst as claimed in claim 3, wherein the complexing agent is citric acid, and the molar number of the citric acid is 1.1 to 1.5 times the total molar number of the A site and the B site elements; the dispersing agent is one or a combination of more of ethylenediamine tetraacetic acid, formaldehyde, ethylene glycol, polyethylene glycol 400, resorcinol, polyacrylic acid and hydroxypropyl cellulose, and the mole number of the dispersing agent is 0.2-0.3 times of the total mole number of the A-site element and the B-site element.
6. The process for preparing a perovskite type monolithic catalyst as claimed in claim 2, wherein a part of sulfate is introduced into the precursor of the sulfur-phobized carrier, and the addition proportion of the sulfate is 5-20% of the total mass of the sulfur-phobized carrier.
7. Use of a perovskite-type monolithic catalyst according to claim 1, characterized in that: the perovskite type monolithic catalyst is used for treating nitrogen oxide NOxWhen the catalytic reduction treatment is carried out, the treatment temperature is 80-180 ℃.
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