CN117414821B - High-temperature-resistant sintering Pt-based three-way catalyst and preparation method thereof - Google Patents

High-temperature-resistant sintering Pt-based three-way catalyst and preparation method thereof Download PDF

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CN117414821B
CN117414821B CN202311679744.6A CN202311679744A CN117414821B CN 117414821 B CN117414821 B CN 117414821B CN 202311679744 A CN202311679744 A CN 202311679744A CN 117414821 B CN117414821 B CN 117414821B
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catalyst
way catalyst
powder
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dispersed
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CN117414821A (en
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赖荣辉
杨怡
李大成
彭婷婷
谢兴宇
刘志敏
王云
李云
陈启章
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Sinocat Environmental Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9413Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
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    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652Chromium, molybdenum or tungsten
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/502Carbon monoxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702Hydrocarbons

Abstract

The invention discloses a high-temperature-resistant sintering Pt-based three-way catalyst and a preparation method thereof, belonging to the technical field of gasoline car catalysts, wherein the catalyst comprises metal Pt and a carrier material, the total loading amount of the metal Pt is 0.2-3.0 wt%, and the carrier material comprises a mixture of an oxygen storage material and alumina or a cerium-aluminum solid solution material. According to the invention, in the pre-dispersion process, the material with weak acting force provides a larger specific surface area, so that noble metal Pt can be in a highly dispersed state on the surface of the catalytic material, when the noble metal Pt is in a high Wen Zaifen dispersion process, pt migrates due to high temperature, part of Pt migrates from the surface of the material with weak acting force and is then trapped and fixed by the material with strong acting force, so that Pt can be redispersed on the surface of the material in an atomic state, and the purposes of no agglomeration sintering of Pt at high temperature and excellent catalytic activity are achieved.

Description

High-temperature-resistant sintering Pt-based three-way catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of gasoline car catalysts, in particular to a high-temperature-resistant sintering Pt-based three-way catalyst and a preparation method thereof.
Background
With the year by year increase of the quantity of automobile maintenance, automobile exhaust emission has become a main source of air pollution. The main pollutants of automobile exhaust are carbon monoxide (CO), hydrocarbons (HC) and Nitrogen Oxides (NO) x ) The method for treating the pollutants in the tail gas of the gasoline vehicle adopts an automobile tail gas purifier, wherein the most core part is a three-way catalyst which can simultaneously perform the catalytic purification function on the main pollutants in the tail gas, and the three-way catalyst can effectively treat CO, HC and NO in the tail gas of the automobile x Respectively into carbon dioxide (CO) 2 ) Water (H) 2 O) and nitrogen (N) 2 )。
The three-way catalyst comprises a catalyst carrier and a catalyst coating coated on the catalyst carrier, wherein the catalyst coating is an oxide coating for supporting a noble metal active component, and the noble metal active component is Pt, pd, rh, ir, ru. With the deep understanding of the national environment, pollutant emission is more strict, and the six-B emission standard is currently implemented, so that the requirements on high-temperature sintering resistance or durability of the catalyst are higher than those of the five-state emission standard. The aging sintering of the noble metal Pt catalyst mainly comprises the step of migration agglomeration of noble metal particles immersed on the surface of an oxide at high temperature, so that the catalytic activity is reduced, and the performance of the catalyst is obviously reduced.
In order to make up the defect of poor performance of the catalyst after high-temperature sintering, the most direct method is to increase the consumption of noble metal, but noble metal resources are rare, the price is high, the catalyst is not renewable, and in order to reduce the cost and increase the efficiency, so that the improvement of the high-temperature sintering resistance of the noble metal Pt catalyst is particularly important.
In the prior art, pt is loaded on a single material CeO by an isovolumetric impregnation method 2 The surface is subjected to high temperature heat treatment to obtain the single-atom dispersed Pt/CeO 2 The catalyst has good CO catalytic conversion activity and single CeO 2 Although the material has strong bonding force with Pt, the strong bonding force can lead Pt to form a monoatomic dispersion state after high-temperature treatment, but stable Pt-O-Ce bond also leads to lower activity of Pt catalyst, especially poor catalytic activity on hydrocarbon, and single CeO 2 The material has unstable structure, is easy to collapse at high temperature, and is not suitable for being independently applied to the three-way catalyst.
The invention of China patent publication No. CN112808270A discloses a high-durability Pt-based integral gasoline car three-way catalyst, a preparation method and application thereof, wherein Pt is loaded on CeZrO by a strong and weak double-reducing agent liquid phase reduction impregnation method 2 The catalyst powder material is obtained on a carrier, and then the catalyst powder material is coated on a cordierite matrix to prepare the high-temperature-resistant sintering Pt catalyst.
The invention of China patent publication No. CN115770570A discloses a cerium oxide loaded atomic level dispersed Pt catalyst and a redispersion preparation method thereof, which comprises the steps of preparing cubic nano CeO 2 Dispersing in proper solvent, ultrasonic stirring to disperse Pt nanometer particle homogeneously, and adding CeO to the mixture 2 (100) Redispersion occurs on the crystal face, the dispersity of Pt is regulated and controlled by regulating the load of Pt,to disperse it in atomic level to obtain the CeO 2 Supported atomically dispersed Pt catalysts. The obtained supported Pt/CeO 2 The catalyst is subjected to high-temperature roasting treatment in an oxidizing atmosphere to obtain redispersed supported Pt/CeO 2 Catalyst, directly by having CeO 2 (100) Cubic nano CeO with crystal face 2 As a carrier material, although the dispersion degree of Pt particles can be greatly improved and the utilization rate of Pt can be improved, the catalytic activity and the durability are still questionable, and the cubic nano CeO 2 The control difficulty is high, the production cost is high, and the industrial large-scale production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and aims to provide a high-temperature-resistant sintering Pt-based three-effect catalyst, which adopts two conventional materials with different Pt acting force as carrier materials, and improves the dispersity of Pt through a two-step dispersion method, so that the Pt catalyst has excellent fresh low-temperature performance and excellent high-temperature aging resistance.
The invention is realized by the following technical scheme:
the high temperature resistant sintering Pt-based three-way catalyst comprises metal Pt and a carrier material, wherein the total loading amount of the metal Pt is 0.2-3.0 wt%, and the carrier material comprises a mixture of an oxygen storage material and alumina or a cerium-aluminum solid solution material; the metal Pt is pre-dispersed and re-dispersed to obtain catalyst powder, and the catalyst powder is fixed on the surface of a carrier material containing Ce and Al which are different from Pt in acting force; also comprises a structure auxiliary agent, wherein the structure auxiliary agent comprises MoO 3 ,WO 3 ,SnO 2 The content of the structural aid is preferably 3 to 10wt%.
Further, the oxygen storage material and the alumina mixture have the oxygen storage material content of 30 to 90 weight percent and the alumina content of 10 to 70 weight percent;
CeO in the oxygen storage material 2 The content is 10 to 60 weight percent, zrO 2 The content is preferably 90 to 40wt%.
Further, the cerium-aluminum solid solution materialIn the material, ceO 2 The content is 10-50wt%, al 2 O 3 The content is 30-90wt%, zrO 2 The content is 0-30wt%.
The preparation method of the high-temperature-resistant sintering Pt-based three-way catalyst comprises the following steps:
1) Pre-dispersing: dispersing a Pt precursor and soluble salts of a structure auxiliary agent on the surfaces of two carrier materials by adopting an impregnation method, wherein the material with weak acting force provides a larger specific surface area, so that noble metal Pt can be in a highly dispersed state on the surface of a catalytic material, and pre-dispersed powder is obtained through standing and Pt fixing;
2) Redispersing: placing the pre-dispersed powder in the step 1) in a muffle furnace at 700-900 ℃, roasting for 5-10h in an oxidizing atmosphere, when the powder is in a high Wen Zaifen dispersion process, transferring Pt due to high temperature, transferring part of Pt from the surface of a material with weaker acting force, and then capturing and fixing the Pt by the material with stronger acting force, so that the Pt can be redispersed on the surface of the material in an atomic state, and further dispersing the Pt to obtain the catalyst powder without agglomerating and sintering the Pt at high temperature;
3) Pulping: mixing the catalyst powder in the step 2) according to 90-99 parts by weight of adhesive, 1-10 parts by weight of adhesive and 100-300 parts by weight of water, and ball milling to obtain coating slurry;
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Further, the Pt precursor in the step 1) is any one of platinum nitrate and platinum chlorate.
Further, the adhesive in the step 3) is any one of silica sol, alumina sol and zirconium sol.
Further, the impregnation method in the step 1) is any one of an isovolumetric impregnation method, an excessive impregnation method, a precipitation method and a reductive impregnation method.
Further, the soluble salts of the Pt precursor and the structure aid in the step 1) are dispersed on the surfaces of the two carrier materials, including the surfaces of the two independent carrier materials or the surfaces of the two carrier materials after being mixed.
Further, the fixing of Pt in step 1) further includes drying or roasting at 500 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, two conventional materials with different acting force from Pt are adopted as carrier materials, and the dispersity of Pt is improved through a two-step dispersion method, so that the Pt catalyst has excellent fresh low-temperature performance and excellent high-temperature aging resistance, and the principle is that the material with weaker acting force provides larger specific surface area in the pre-dispersion process, so that noble metal Pt can be in a highly dispersed state on the surface of the catalytic material, when the material is in a high Wen Zaifen dispersion process, pt migrates due to high temperature, part of Pt migrates from the surface of the material with weaker acting force, and then is trapped and fixed by the material with stronger acting force, so that Pt can be redispersed on the surface of the material in an atomic state, and the purposes of no agglomeration sintering of Pt at high temperature and excellent catalytic activity are achieved;
2. the invention has simple operation, no harmful substances, low cost and easy realization of industrial mass production.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a graph showing the conversion of CO with respect to temperature for the fresh catalyst of example 4 and comparative example 4 of the present invention;
FIG. 2 is a graph showing the conversion of NO with respect to temperature for the fresh catalyst of example 4 and comparative example 4 of the present invention;
FIG. 3 is a graph showing the conversion of fresh catalyst to Total Hydrocarbons (THC) as a function of temperature for example 4 and comparative example 4 of the present invention;
FIG. 4 is a graph showing the conversion of CO with temperature for the aged catalyst of example 4 and comparative example 4 of the present invention;
FIG. 5 is a graph showing the conversion of NO with respect to temperature for the aged catalyst of example 4 and comparative example 4 of the present invention;
fig. 6 is a graph of the conversion of Total Hydrocarbons (THC) with temperature for the aged catalyst of example 4 and comparative example 4 of the present invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
Example 1
This example provides a Pt content of 0.2wt%, moO 3 Pt-Mo/Al-Ce with 3wt percent 0.1 Zr 0.9 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 10wt%, ce 0.1 Zr 0.9 O 2 The oxygen storage material was 90wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate and ammonium molybdate in water to form an active component solution, and dispersing the active component solution in aluminum oxide and Ce by an isovolumetric impregnation method 0.1 Zr 0.9 O 2 The surface of the oxygen storage material mixed material is subjected to standing, drying and roasting at 500 ℃ to obtain pre-dispersed powder.
2) Redispersing: and (3) placing the pre-dispersed powder in the step (1) in a muffle furnace at 700 ℃, and roasting for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of silica sol and 100 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Note that: ce (Ce) 0.1 Zr 0.9 O 2 Representing CeO 2 The content is 10%, zrO 2 The content was 90%, as follows.
Example 2
This example provides a Pt content of 0.5wt%, WO 3 Pt-W/Al-Ce with 5wt% 0.2 Zr 0.8 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 20wt%, ce 0.2 Zr 0.8 O 2 The oxygen storage material was 80wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum chlorate and ammonium tungstate in water to form an active component solution, and dispersing the active component solution in alumina and Ce by an excessive impregnation method 0.2 Zr 0.8 O 2 The surface of the oxygen storage material is mixed with the material, and the pre-dispersed powder is obtained through filtration, drying and roasting at 500 ℃.
2) Redispersing: and (3) placing the pre-dispersed powder in the step (1) in a muffle furnace at 800 ℃ and roasting for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 90 parts by weight, 10 parts by weight of silica sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 3
This example provides a composition of 3wt% Pt and SnO 2 Pt-Sn/Al-Ce with a content of 3wt% 0.4 Zr 0.6 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 20wt%, ce 0.4 Zr 0.6 O 2 The oxygen storage material was 80wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate and tin chloride in water to form an active component solution, and dispersing the active component solution in aluminum oxide and Ce by an isovolumetric impregnation method 0.4 Zr 0.6 O 2 The surface of the oxygen storage material mixed material is subjected to standing, drying and roasting at 500 ℃ to obtain pre-dispersed powder.
2) Redispersing: and (3) placing the pre-dispersed powder in the step (1) in a muffle furnace at 800 ℃ and roasting for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 99 parts by weight, 1 part by weight of zirconium sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 4
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al-Ce with a content of 10wt% 0.6 Zr 0.4 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 50wt%, ce 0.6 Zr 0.4 O 2 The oxygen storage material was 50wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate and ammonium tungstate in water to form an active component solution, and dispersing the active component solution in aluminum oxide and Ce by an isovolumetric impregnation method 0.6 Zr 0.4 O 2 And (3) standing and drying the surface of the oxygen storage material mixed material to obtain pre-dispersed powder.
2) Redispersing: and (3) placing the pre-dispersed powder in the step (1) in a muffle furnace at 800 ℃ and roasting for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry;
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 5
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al-Ce with a content of 10wt% 0.6 Zr 0.4 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 50wt%, ce 0.6 Zr 0.4 O 2 The oxygen storage material was 50wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum chlorate and ammonium tungstate in water to form an active component solution, dividing the active component solution into two parts, and dispersing the active component solution in aluminum oxide and Ce respectively by an isovolumetric impregnation method 0.6 Zr 0.4 O 2 And (3) standing, drying and roasting at 500 ℃ the surface of the oxygen storage material to obtain pre-dispersed powder.
2) Redispersing: mixing the two pre-dispersed powder materials in the step 1), placing the mixture in a muffle furnace at 800 ℃, and roasting the mixture for 10 hours in an oxidizing atmosphere to obtain the catalyst powder material with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 6
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al content of 10wt% 0.9 -Ce 0.1 O 2 The honeycomb monolithic catalyst has carrier material of Ce-Al solid solution material and Al composition 2 O 3 90wt% of CeO 2 10wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate and ammonium tungstate in water to form an active component solution, dispersing the active component solution on the surface of the cerium-aluminum solid solution material by an isovolumetric impregnation method, standing, drying and roasting at 500 ℃ to obtain pre-dispersed powder.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of zirconium sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 7
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al content of 10wt% 0.85 Ce 0.1 Zr 0.05 O 2 The honeycomb monolithic catalyst has carrier material of Ce-Al solid solution material and Al composition 2 O 3 85wt% of CeO 2 10wt%, zrO 2 5%. The preparation method comprises the following steps:
1) Pre-dispersing: platinum chlorate and ammonium tungstate are dissolved in water to form an active component solution, then the active component solution is dispersed on the surface of the cerium-aluminum solid solution material by an isovolumetric impregnation method, and pre-dispersed powder is obtained by standing, drying and roasting at 500 ℃.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 8
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al content of 10wt% 0.4 Ce 0.3 Zr 0.3 O 2 The honeycomb monolithic catalyst has carrier material of Ce-Al solid solution material and Al composition 2 O 3 40wt% of CeO 2 30wt%, zrO 2 30%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate and ammonium tungstate in water to form an active component solution, dispersing the active component solution on the surface of the cerium-aluminum solid solution material by an isovolumetric impregnation method, standing, drying and roasting at 500 ℃ to obtain pre-dispersed powder.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Example 9
This example provides a Pt content of 1wt%, WO 3 Pt-W/Al content of 10wt% 0.3 Ce 0.5 Zr 0.2 O 2 The honeycomb monolithic catalyst has carrier material of Ce-Al solid solution material and Al composition 2 O 3 30wt% of CeO 2 50wt%, zrO 2 20%. The preparation method comprises the following steps:
1) Pre-dispersing: platinum chlorate and ammonium tungstate are dissolved in water to form an active component solution, then the active component solution is dispersed on the surface of the cerium-aluminum solid solution material by an isovolumetric impregnation method, and pre-dispersed powder is obtained by standing, drying and roasting at 500 ℃.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Comparative example 1
This comparative example provides a Pt/Al-Ce with a Pt content of 1wt% 0.6 Z r0.4 O 2 Honeycomb monolithCatalyst, its carrier material composition includes Al 2 O 3 50wt%, ce 0.6 Zr 0.4 O 2 The oxygen storage material was 50wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate in water to form an active component solution, and dispersing the active component solution in alumina and Ce by an isovolumetric impregnation method 0.6 Zr 0.4 O 2 The surface of the oxygen storage material mixed material is subjected to standing, drying and roasting at 500 ℃ to obtain pre-dispersed powder.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Comparative example 2
This comparative example provides a Pt/Al having a Pt content of 1wt% 2 O 3 Honeycomb monolithic catalyst, its carrier material composition is Al 2 O 3 100wt%. The preparation method comprises the following steps:
1) Pre-dispersing: platinum chlorate is dissolved in water to form an active component solution, then the active component solution is dispersed on the surface of an alumina material by an equal volume impregnation method, and pre-dispersed powder is obtained by standing, drying and roasting at 500 ℃.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry;
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Comparative example 3
This comparative example provides a Pt/Ce with a Pt content of 1wt% 0.6 Zr 0.4 O 2 Honeycomb monolithic catalyst, the carrier material composition of which comprises Ce 0.6 Zr 0.4 O 2 The oxygen storage material was 100wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum nitrate in water to form an active component solution, and dispersing the active component solution in Ce by an isovolumetric impregnation method 0.6 Zr 0.4 O 2 And (3) standing, drying and roasting at 500 ℃ the surface of the oxygen storage material to obtain pre-dispersed powder.
2) Redispersing: and (2) mixing the pre-dispersed powder in the step (1), and then placing the mixture in a muffle furnace at 800 ℃ to bake for 10 hours in an oxidizing atmosphere to obtain the catalyst powder with further dispersed Pt.
3) Pulping: mixing the catalyst powder in the step 2) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
4) Coating: and (3) coating the coating slurry in the step (3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
Comparative example 4
This comparative example provides a Pt content of 1wt%, WO 3 Pt-W/Al-Ce with a content of 10wt% 0.6 Zr 0.4 O 2 Honeycomb monolithic catalyst having a support material composition comprising Al 2 O 3 50wt%, ce 0.6 Zr 0.4 O 2 The oxygen storage material was 50wt%. The preparation method comprises the following steps:
1) Pre-dispersing: dissolving platinum chlorate and ammonium tungstate in water to form an active component solution, and dispersing the active component solution in aluminum oxide and Ce by an isovolumetric impregnation method 0.6 Zr 0.4 O 2 The surface of the oxygen storage material is mixed with the material, and the pre-dispersed powder is obtained through filtration, drying and roasting at 500 ℃.
2) Pulping: mixing the pre-dispersed powder in the step 1) according to 95 parts by weight, 5 parts by weight of aluminum sol and 200 parts by weight of water, and ball milling to obtain coating slurry.
3) Coating: and (3) coating the coating slurry in the step (2) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain the Pt-based three-way catalyst.
The composition and treatment of the components of each example and comparative example are shown in Table 1.
The catalysts obtained in examples 1 to 9 and comparative examples 1 to 4 above were subjected to an aging treatment, and the fresh and aged samples were subjected to an activity test, specifically, the aging conditions were: the aging atmosphere is as follows: air and catalyst are continuously aged for 10 hours at 900 ℃. The conditions for the test were: the activity evaluation of the catalyst is carried out in a multi-path fixed continuous flow micro-reactor, and the simulated gasoline car tail gas comprises the following components: NO1250ppm, CO4600ppm, THC (C) 3 H 6 220ppm、C 3 H 8 110ppm)、H 2 1530ppm、O 2 10%、CO 2 11%、N 2 As carrier gas, space velocity was 40000h -1 . All catalyst samples were pretreated in a reaction atmosphere (simulated gasoline car exhaust) at 550 ℃ for 2 hours prior to reaction. The activity test was then carried out at a rate of 5℃per minute. CO, NO, C 3 H 6 、C 3 H 8 The concentration of (2) is tested by a Fourier infrared gas analyzer (MKS multigGas 6030 in U.S.), and the test temperature is 160-400 ℃; temperature points were obtained for 50% and 90% conversion of contaminants before and after aging of the catalysts as shown in table 2, and catalyst fresh and aged sample to contaminant conversion curves shown in fig. 1 to 6 were obtained.
As can be seen from Table 2, the Pt was dispersed and fixed to the base material by a two-step dispersion methodThe catalyst (examples 1-9) prepared by adding the structural auxiliary agents and the common carrier material surfaces of the two different elements Ce and Al has good catalytic activity on the purification of pollutants CO, NO and THC, and after continuous aging for 10 hours at 900 ℃, the temperature point of the catalyst with the pollutant conversion rate of 50% and 90% still has NO obvious rising phenomenon, so that the catalyst prepared by dispersing and fixing Pt on the common carrier material surfaces containing the two elements Ce and Al with different Pt acting forces by adopting a two-step dispersion method and adding the structural auxiliary agents has good high-temperature sintering resistance. For comparative examples 1-4, no structural aid was added (comparative example 1), or common carrier materials of two elements Ce and Al with different Pt acting forces (comparative example 2 and comparative example 3) or catalysts prepared by a Pt two-step dispersion method (comparative example 4) were not adopted, and comparative examples 1, 3 and 4 have good fresh performance, but after continuous aging for 10 hours at 900 ℃, the temperature points of the catalyst with 50% and 90% pollutant conversion rate are obviously increased, which indicates that the catalyst performance of the three samples is reduced after aging. For comparative example 2, the fresh sample showed poor catalytic activity towards contaminants due to Al 2 O 3 Weak acting force on Pt, single Al 2 O 3 In the two-step dispersion method, pt cannot be stabilized, and Pt is sintered at a high temperature, so that the fresh performance activity is low.
As shown in fig. 1 to 3, the conversion rate of the fresh catalyst of example 4 and comparative example 4 to CO, NO, total Hydrocarbons (THC) varies with temperature; wherein the ordinate indicates the conversion rate in units; the abscissa indicates temperature in degrees celsius; curves a and B are fresh-like changes for example 4 and comparative example 4, respectively. Referring to FIGS. 4 to 6, the conversion rate of CO, NO, HC with respect to the aged catalyst of example 4 and comparative example 4 varies with temperature; wherein the ordinate indicates the conversion rate in units; the abscissa indicates temperature in degrees celsius; curves a-a and B-a are the aging-like changes for example 4 and comparative example 4, respectively.
With respect to the fresh properties, it can be seen from FIGS. 1-3 that the conversion of the three pollutants CO, NO, THC in example 4 is slightly better than that in comparative example 4, because the Pt dispersion on the surface of the catalytic material after two steps of redispersion is better, thus leading to a higher catalytic activity towards pollution. After continuous aging at 900 ℃ for 10 hours, as can be seen from fig. 4-6, the conversion curve of the pollutant in example 4 did not change significantly, while the conversion curve of the aged sample against the pollutant in comparative example 4 all showed a backward shift phenomenon, i.e. the conversion temperature was increased, indicating that the activity of comparative example 4 was severely reduced after continuous aging at 900 ℃ for 10 hours. This is because the comparative example 4 does not fix Pt through the two-step dispersion method, so that Pt is sintered at a high temperature upon aging of the catalyst, and thus the catalyst activity is lowered.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (8)

1. The preparation method of the high-temperature-resistant sintering Pt-based three-way catalyst is characterized by comprising the following steps of:
1) Pre-dispersing: dispersing a Pt precursor and soluble salts of a structure auxiliary agent on the surfaces of two carrier materials by adopting an impregnation method, wherein the material with weak acting force provides a larger specific surface area, so that noble metal Pt can be in a highly dispersed state on the surface of a catalytic material, and pre-dispersed powder is obtained through standing and Pt fixing;
2) Redispersing: placing the pre-dispersed powder in the step 1) in a muffle furnace at 700-900 ℃, roasting for 5-10h in an oxidizing atmosphere, when the powder is in a high Wen Zaifen dispersion process, transferring Pt due to high temperature, transferring part of Pt from the surface of a material with weaker acting force, and then capturing and fixing the Pt by the material with stronger acting force, so that the Pt can be redispersed on the surface of the material in an atomic state, and further dispersing the Pt to obtain the catalyst powder without agglomerating and sintering the Pt at high temperature;
3) Pulping: mixing the catalyst powder in the step 2) according to 90-99 parts by weight of adhesive, 1-10 parts by weight of adhesive and 100-300 parts by weight of water, and ball milling to obtain coating slurry;
4) Coating: coating the coating slurry in the step 3) on the surface of a honeycomb ceramic carrier, and drying and calcining to obtain a Pt-based three-way catalyst;
the Pt-based three-way catalyst comprises metal Pt and a carrier material, wherein the total loading amount of the metal Pt is 0.2-3.0 wt%, and the carrier material comprises a mixture of an oxygen storage material and alumina or a cerium-aluminum solid solution material;
the metal Pt is subjected to pre-dispersion and re-dispersion in a muffle furnace at 700-900 ℃ to obtain catalyst powder, and the catalyst powder is fixed on the surface of a carrier material containing two elements Ce and Al with different acting forces from Pt;
also comprises a structure auxiliary agent, wherein the structure auxiliary agent comprises MoO 3 ,WO 3 ,SnO 2 At least one of the structural auxiliary agents is 3-10wt%.
2. The method for preparing the high temperature resistant sintering Pt-based three-way catalyst according to claim 1, wherein the oxygen storage material and alumina mixture contains 30-90wt% of oxygen storage material and 10-70 wt% of alumina;
CeO in the oxygen storage material 2 The content is 10 to 60 weight percent, zrO 2 The content is 90-40 wt%.
3. The method for preparing the high temperature resistant sintering Pt-based three-way catalyst according to claim 1, wherein CeO in the cerium-aluminum solid solution material 2 The content is 10-50wt%, al 2 O 3 The content is 30-90wt%, zrO 2 The content is 0-30wt%.
4. The method for preparing the high temperature resistant sintering Pt-based three-way catalyst according to claim 1, wherein the Pt precursor in the step 1) is any one of platinum nitrate and platinum chlorate.
5. The method for preparing the high temperature resistant sintering Pt-based three-way catalyst according to claim 1, wherein the binder in the step 3) is any one of silica sol, alumina sol and zirconium sol.
6. The method for preparing the high temperature resistant sintered Pt-based three-way catalyst according to claim 1, wherein the impregnation method in step 1) is any one of an isovolumetric impregnation method, an excessive impregnation method, a precipitation method and a reductive impregnation method.
7. The method for preparing the high temperature resistant sintering Pt-based three-way catalyst according to claim 1, wherein the soluble salts of the Pt precursor and the structure aid in step 1) are dispersed on the surfaces of two carrier materials, including on the surfaces of two independent carrier materials or on the surfaces of the two carrier materials after mixing.
8. The method for preparing a high temperature resistant sintered Pt-based three-way catalyst as claimed in claim 1, wherein the fixing of Pt in step 1) further comprises drying or baking at 500 ℃.
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