CN112717927A - Preparation method and application of automobile exhaust treatment catalyst - Google Patents
Preparation method and application of automobile exhaust treatment catalyst Download PDFInfo
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- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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Abstract
The invention provides an automobile exhaust treatment catalyst, and belongs to the field of catalysts. The catalyst sequentially comprises a substrate layer, a coating layer and a loading layer, wherein the substrate layer is honeycomb ceramic; the coating layer comprises La2O3/Al2O3And a cerium-zirconium composite metal oxide; the load layer is a noble metal, and the noble metal is one or more of Pt, Rh and Pd; the dynamic oxygen storage capacity of the cerium-zirconium composite metal oxide at 300 ℃ is 30-40 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205-; the porosity of the honeycomb ceramic is 38-45%, and the water absorption is 23-32%. The catalyst has the characteristics of good catalytic effect, low cost and easy industrial application.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a preparation method and application of an automobile exhaust treatment catalyst.
Background
In 2019, the total emission amount of four pollutants of motor vehicles in China is 1603.8 ten thousand tons. Wherein carbon monoxide (C)CO), Hydrocarbons (HC), Nitrogen Oxides (NO)x) And the emission amount of the Particulate Matter (PM) is 771.6 ten thousand tons, 189.2 ten thousand tons, 635.6 ten thousand tons and 7.4 ten thousand tons respectively. Among them, carbon monoxide (CO) and Hydrocarbon (HC) account for nearly 60% of the total amount of emissions. Automobiles are the main contributors to the total amount of pollutants emitted by carbon monoxide (CO), Hydrocarbons (HC), and Nitrogen Oxides (NO)x) And Particulate Matter (PM) exceeding 90%.
In 1978, effective purification of CO, HC and NO at the same time was first introducedxThe catalytic conversion efficiency of the Pt-Pd-Rh noble metal three-way catalyst reaches over 90 percent. Noble metal catalysts have significant drawbacks. (1) The influence of the air-fuel ratio is large, and the catalyst can be used for CO, HC and NO only when the air-fuel ratio is stable in an ideal control range (14.5-14.7)xThe purification ability of (a) is simultaneously at an optimum value, and outside this range, the catalytic purification effect is poor. (2) High cost and large dosage.
CeO2Has good oxygen storage and release capacity, can be used as a promoter added into a three-way catalyst for automobile exhaust to serve as an oxygen buffer, and passes through Ce when oxygen is rich3+Conversion to Ce4+Absorbing oxygen to ensure NOxReduced by CO and HC, CeO when oxygen is insufficient2Releasing oxygen to oxidize CO and HC, thereby achieving effective purification of CO, HC and NOxThe purpose of (1). But due to the high temperature of the exhaust gas discharged by automobiles (>1000 c), the ceria catalyst is easily aged and sintered to cause a decrease in oxygen storage capacity. The temperature resistance can be improved by introducing zirconium ions into cerium crystals to form cerium-zirconium solid solution, and the cerium-zirconium solid solution is commonly added into the catalyst as a cocatalyst.
CO is an important pollutant of automobile exhaust, and the oxidation performance of the catalyst can be indirectly reflected by the test result of Dynamic Oxygen Storage (DOSC) taking CO as a reducing agent. Therefore, the dynamic oxygen storage and release performance of the cerium-zirconium solid solution can ensure that the catalyst can keep working near the theoretical air-fuel ratio (A/F =14.6) and efficiently remove CO and NO in the tail gas of the gasoline vehiclexAnd one of the key factors of HC.
The physical and chemical properties of the honeycomb ceramic used as a carrier of the TWC catalyst have a key influence on the catalytic activity. The porosity, water absorption, geometric internal surface area, open porosity, etc. of the honeycomb ceramic all affect catalytic activity.
Based on the above circumstances, a three-way catalyst excellent in catalytic oxidation effect is still a hot spot of current research.
Disclosure of Invention
The invention provides a preparation method and application of a low-cost automobile exhaust treatment catalyst based on the defects of the existing three-way catalytic system. Specifically, the inventor of the present invention provides a benefit of improving catalytic performance by improving the pore structure distribution of the honeycomb ceramic, adjusting porosity and absorption rate, and combining with the dynamic oxygen storage amount of the cerium-zirconium composite oxide, through long-term theoretical derivation and experimental research, and breaks through the conventional benefit of improving catalytic active components such as noble metals to improve catalytic performance, thereby obtaining a certain technical breakthrough.
The cerium-zirconium composite oxide is prepared by a hydrothermal method, and preferably, the cerium and the zirconium are subjected to oxidation pretreatment. More preferably, the cerium-zirconium composite oxide includes cerium, zirconium and a rare earth metal, and the method for producing the cerium-zirconium composite oxide is the method described in CN 110327909A.
The automobile exhaust treatment catalyst sequentially comprises a substrate layer, a coating layer and a load layer, wherein the substrate layer is honeycomb ceramic; the coating layer comprises La2O3/Al2O3And a cerium-zirconium composite metal oxide; the load layer is a noble metal, and the noble metal is one or more of Pt, Rh and Pd; the dynamic oxygen storage capacity of the cerium-zirconium composite metal oxide at 300 ℃ is 30-40 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205-; the porosity of the honeycomb ceramic is 38-45%, and the water absorption is 23-32%.
Preferably, the noble metal is Pt and Rh, and the mass ratio of the Pt to the Rh is (3-6): 1. Specifically, the mass ratio of Pt and Rh may be 3:1, 4:1, 5:1, or 6: 1.
Preferably, the coating layer further comprises an oxide of a rare earth element including La, Y,Pr and Nd. Specifically, the rare earth oxide may be selected from La2O3、Y2O3、Pr6O11、Nd2O3At least one of (1).
Preferably, in the coating layer, La2O3/Al2O3The mass ratio of the cerium-zirconium composite metal oxide to the cerium-zirconium composite metal oxide is (0.5-2) 1;
in the coating layer, the mass percent of the rare earth element oxide is 5-15%, and CeO in the cerium-zirconium composite oxide220-45% by mass of ZrO2The mass percentage of the components is 50-70%;
the honeycomb ceramic is cordierite honeycomb ceramic, and the cordierite honeycomb ceramic comprises the following components in percentage by mass: al (Al)2O3:30-35%，SiO2:45-50%，MgO:10-15%。
Preferably, the La is2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3Is added in an amount of 4.2 to 5.2wt%, and the Al is2O3Is amorphous Al2O3、γAl2O3One kind of (1).
Preferably, the powder particle size of the coating layer is 50 to 100 μm.
The conversion rate of the catalyst in CO oxidation reaction, hydrocarbon oxidation reaction and nitrogen oxide reduction is as follows, and the percentage is mole percentage:
the conversion rate under each temperature condition of CO oxidation reaction is as follows: 300 ℃ C: 18-25%, 400 ℃: 78-90%, 500 ℃: 100 percent;
C3H6the conversion rate under each temperature condition of the oxidation reaction is as follows: 300 ℃ C: 5-15%, 400 ℃: 75-85%, 500 ℃: 100 percent;
NOXthe conversion rate under each temperature condition of the reduction reaction is as follows: 300 ℃ C: 15-22%, 400 ℃: 65-75%, 500 ℃: 100 percent.
The invention also provides a preparation method of the automobile exhaust treatment catalyst, which comprises the following steps:
1) firing and molding the honeycomb ceramic to obtain a carrier;
2) la2O3/Al2O3The cerium-zirconium composite metal oxide and the rare earth element oxide are dispersed in deionized water to obtain a coating liquid, the coating liquid is coated on the surface of the carrier, and the load capacity of the coating layer on the honeycomb carrier is 200-230 g/L; calcining at the temperature of 300-500 ℃ for 1-12h to obtain a coated carrier;
3) dipping the coated carrier obtained in the step 2) in a noble metal solution, and calcining at the temperature of 300-800 ℃ for 1-24h to obtain the tail gas treatment catalyst.
Step 3) adopting an isometric impregnation method, wherein the impregnation times are 1-3; the loading amount of the noble metal on the honeycomb carrier is 0.5-1 g/L.
Preferably, the noble metal is Rh and Pt, the Rh is impregnated firstly, and then the Pt is impregnated after drying, wherein the mass ratio of the Pt to the Rh is (3-6): 1.
In another aspect of the invention, the application of the catalyst in tail gas purification is provided.
Compared with the prior art, the invention has the advantages and positive effects that:
the catalyst has good tail gas catalytic conversion effect, remarkably improves the conversion of nitrogen oxides, hydrocarbons and CO at low temperature and high temperature, and has the characteristics of low cost and easy industrial application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 20g of La2O3/Al2O3And 40g of cerium zirconium composite metal oxideSubstance (wherein, CeO)220% by mass of ZrO2Is 68% by mass, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder was 50 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 200g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 300 ℃ for 12 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.5g/L, and impregnation was performed 3 times, wherein Pt: rh = 3:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 24 hours at 300 ℃ to obtain the monolithic catalyst.
Wherein the honeycomb ceramic carrier has the water absorption rate of 32 percent and the porosity of 45 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 30 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 621 mu mol/g.
Example 2
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively take 30gLa2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 36% by mass, ZrO2Is 58% by mass, La2O3、Y2O3And Pr6O116 percent of the total weight of the components) is added into 200ml of purified water and stirred evenly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass ofQuasi, La2O3The amount of (B) was 5.2 wt%. The particle size of the powder is 60 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 205g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 350 ℃ for 8 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.6g/L, and impregnation was performed 2 times, wherein Pt: rh = 4:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 20 hours at 400 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic carrier is 32 percent, the porosity is 45 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 39 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 246 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 671 mu mol/g.
Example 3
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 40g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 45% by mass, ZrO2Is 50% by mass and Y2O3And Nd2O35%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.5 wt%. The particle size of the powder was 70 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50% of MgO, 10-15% of carrier (phi 10mm and 15mm high) is dipped in the coating liquid prepared in the step (1) until the loading amount reachesAnd (3) calcining the mixture in a muffle furnace under the conditions of: calcining at 400 ℃ for 5 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method with a noble metal supporting amount of 0.7g/L, and impregnated 2 times, wherein Pt: rh = 5:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 16h at 500 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic carrier is 32 percent, the porosity is 45 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 34 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 278 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 723 mu mol/g.
Example 4
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively take 50gLa2O3/Al2O3And 40g of CeO, a cerium zirconium composite metal oxide220% by mass of ZrO2Is 68% by mass, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.7 wt%. The particle size of the powder is 100 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 215g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 450 ℃ for 4 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount being 0.8g/L, wherein Pt: rh = 6:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 12h at 600 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic carrier is 28 percent, the porosity is 41 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 30 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 621 mu mol/g.
Example 5
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: 60g of La were taken out separately2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 36% by mass, ZrO2Is 58% by mass, La2O3、Y2O3And Pr6O116 percent of the total weight of the components) is added into 200ml of purified water and stirred evenly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder was 90 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 220g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 500 ℃ for 1 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.9g/L, and impregnation was performed 1 time, wherein Pt: rh = 3.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 8 hours at 700 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic is 28 percent, the porosity is 41 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 39 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 246 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 671 mu mol/g.
Example 6
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 70g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 45% by mass, ZrO2Is 50% by mass and Y2O3And Nd2O35%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder is 80 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 225g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 320 ℃ for 10 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 1.0g/L, and impregnation was performed 1 time, wherein Pt: rh = 4.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 1h at 800 ℃ to obtain the monolithic catalyst.
The honeycomb ceramic (water absorption rate of 28 percent and porosity of 41 percent), the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 34 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 278 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 723 mu mol/g.
Example 7
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 80g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO220% by mass of ZrO2Is 68% by mass, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 5.2 wt%. The particle size of the powder was 65 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the loading amount reaches 230g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 360 ℃ for 7 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method with a noble metal supporting amount of 0.65g/L, and impregnated 2 times, wherein Pt: rh = 4.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 16h at 450 ℃ to obtain the monolithic catalyst.
Wherein the water absorption of the honeycomb ceramic carrier is 23 percent, the porosity is 38 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 30 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 621 mu mol/g.
Example 8
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 40g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 36% by mass, ZrO2Is 58% by mass, La2O3、Y2O3And Pr6O116 percent of the total weight of the components) is added into 200ml of purified water and stirred evenly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 5.2 wt%. The particle size of the powder was 75 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 225g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 430 ℃ for 3.5 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.85g/L, and impregnation was performed 2 times, wherein Pt: rh = 6:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And after drying, putting the mixture into a muffle furnace for calcination, and calcining the mixture for 7 hours at 650 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic is 23 percent, the porosity is 38 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 39 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 246 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 671 mu mol/g.
Example 9
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 40g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 45% by mass, ZrO2Is 50% by mass and Y2O3And Nd2O35%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) is 5 wt%. The particle size of the powder was 85 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 218g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 480 ℃ for 2 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.8g/L, and impregnation was performed 1 time, wherein Pt: rh = 5.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 3h at 750 ℃ to obtain the monolithic catalyst.
Wherein the water absorption of the honeycomb ceramic is 23 percent, the porosity is 38 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 34 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 278 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 723 mu mol/g.
COMPARATIVE EXAMPLE 1 (COMPARATIVE EXAMPLE 1)
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 20g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 15% by mass, ZrO2Is 73% by mass, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder was 50 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 200g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 300 ℃ for 12 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.5g/L, and impregnation was performed 3 times, wherein Pt: rh = 3:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 24 hours at 300 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic is 20 percent, the porosity is 32 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 20 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 185 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 596 mu mol/g.
COMPARATIVE EXAMPLE 2 (COMPARATIVE EXAMPLE 6)
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 70g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO2Is 50% by mass, ZrO2Is 45% by mass, La2O3And Y2O35%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder is 80 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 225g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 320 ℃ for 10 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 1.0g/L, and impregnation was performed 1 time, wherein Pt: rh = 4.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 1h at 800 ℃ to obtain the monolithic catalyst.
Wherein the water absorption rate of the honeycomb ceramic is 35 percent, the porosity is 50 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 42 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 298 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 741 mu mol/g.
Comparative example 3 (comparative example 1)
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 15g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO220% by mass of ZrO2Quality of (1)The amount percentage is 68 percent, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 4.2 wt%. The particle size of the powder was 50 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the load reaches 200g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 300 ℃ for 12 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method, the noble metal supporting amount was 0.5g/L, and impregnation was performed 3 times, wherein Pt: rh = 3:1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 24 hours at 300 ℃ to obtain the monolithic catalyst.
The honeycomb ceramic has the water absorption rate of 20 percent and the porosity of 32 percent, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 42 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 298 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 741 mu mol/g.
COMPARATIVE EXAMPLE 4 (COMPARATIVE EXAMPLE 7)
The preparation method of the automobile exhaust treatment catalyst comprises the following steps:
(1) preparing a coating solution: respectively taking 85g of La2O3/Al2O3And 40g of a cerium-zirconium composite metal oxide (wherein, CeO220% by mass of ZrO2Is 68% by mass, La2O3And Y2O312%) into 200ml of purified water, and stirring uniformly to prepare slurry. The La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3The amount of (B) was 5.2 wt%. The particle size of the powder was 65 μm.
(2) The treated honeycomb ceramic (cordierite honeycomb ceramic, wherein the mass percent of each component is Al)2O3:30-35%，SiO245-50 percent of MgO, 10-15 percent of carrier (phi 10mm and 15mm in height) is dipped in the coating liquid prepared in the step (1) until the loading amount reaches 230g/L, and the coating liquid is put into a muffle furnace for calcination under the conditions that: calcining at 360 ℃ for 7 h.
(3) Noble metal was supported on the above-obtained substrate by an equivalent impregnation method with a noble metal supporting amount of 0.65g/L, and impregnated 2 times, wherein Pt: rh = 4.5: 1 (mass ratio), Rh was impregnated first, and Pt was impregnated after drying. And (3) after drying, putting the mixture into a muffle furnace for calcining, and calcining for 16h at 450 ℃ to obtain the monolithic catalyst.
The honeycomb ceramic has 35 percent of water absorption and 50 percent of porosity, the dynamic oxygen storage capacity of the cerium-zirconium composite oxide at 300 ℃ is 20 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 185 mu mol/g, and the dynamic oxygen storage capacity at 500 ℃ is 596 mu mol/g.
Performance testing
The performance tests of examples 1 to 9 and comparative examples 1 to 4 obtained by the present invention were conducted, and the main test items included a dynamic oxygen storage amount test, a catalytic effect evaluation, a water absorption test, and a porosity test; wherein the water absorption test is carried out according to a test method in the No. 3 part of the test method of the ceramic tile GB/T3810.3-2006 for measuring water absorption, apparent porosity, apparent relative density and volume weight; porosity test the pore size distribution and porosity of solid materials were determined according to "GB/T21650.1-2008 mercury intrusion method and gas adsorption method part 1: mercury intrusion method ".
Dynamic oxygen storage amount test:
the test is carried out by adopting an Omnisar gas analysis mass spectrometer and a self-made seven-path automatic reaction evaluation platform, and the specific steps are as follows
1. Preparing sample, tabletting and sieving cerium-zirconium powder, and taking 50mg of particles with 40-60 meshes for later use.
2. Pretreatment with 5% O2and/Ar is pretreated for 30min at the flow rate of 50ml/min, the temperature of the pretreatment process is increased to 500 ℃ at the speed of 20 ℃/min and is kept for 30min, and then the temperature is reduced to 200 ℃ and is kept.
3. Purging with high purity He for 30 min.
4. Pulsed, with 4% CO2Introducing Ar/He 1% at 300ml/min for 10s, and switching to 2% O2the/Ar/He was passed through the system at a flow rate of 300ml/min for a period of 10s, thus cycling the pulse 30 set. The He purge was switched and the temperature was raised to 250 ℃ at a rate of 10 ℃/min, the same was done for 30 groups of pulses. One spot was taken every 50 degrees to 500 ℃.
5. And (5) cooling, and ending the experiment.
Evaluation of catalytic Effect:
specification of monolithic catalyst: diameter of 10mm and height of 15mm
Space velocity: 30000h-1
Total flow rate: 585ml/min
Simulated gas composition:
O2 6942.1ppm，NO 1000ppm，C3H6 1000ppm，CO 5000ppm，H21667ppm, Ar is balance gas
The reaction temperature was measured as a temperature (T) -conversion (%) activity curve in the interval of 100 to 550 ℃ at an air-fuel ratio, i.e., λ =0.95, with a temperature interval of 50 ℃. The specific process is as follows: under a simulated atmosphere, the temperature is programmed from room temperature to 100 ℃ at a speed of 10 ℃/min, the steady-state pollutant conversion result is recorded, the temperature is continuously increased to 150, 200, 250, 300, 350, 400, 450, 500 and 550 ℃ in sequence, and the gas conversion results of the temperature points are recorded respectively as shown in tables 1 to 3.
TABLE 1
TABLE 2
TABLE 3
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. The automobile exhaust treatment catalyst sequentially comprises a substrate layer, a coating layer and a load layer, and is characterized in that the substrate layer is honeycomb ceramic; the coating layer comprises La2O3/Al2O3And a cerium-zirconium composite metal oxide; the load layer is a noble metal, and the noble metal is one or more of Pt, Rh and Pd;
the dynamic oxygen storage capacity of the cerium-zirconium composite metal oxide at 300 ℃ is 30-40 mu mol/g, the dynamic oxygen storage capacity at 400 ℃ is 205-; the porosity of the honeycomb ceramic is 38-45%, and the water absorption is 23-32%.
2. The catalyst of claim 1, wherein the noble metal is Pt and Rh, and the mass ratio of Pt to Rh is (3-6): 1.
3. The catalyst of claim 1 or 2, wherein the coating layer further comprises an oxide of a rare earth element comprising one or more of La, Y, Pr, Nd.
4. The catalyst of claim 3, wherein in the coating layer, La2O3/Al2O3The mass ratio of the cerium-zirconium composite metal oxide to the cerium-zirconium composite metal oxide is (0.5-2) 1;
in the coating layer, the mass percent of the rare earth element oxide is 5-15%, and CeO in the cerium-zirconium composite oxide220-45% by mass of ZrO2The mass percentage of the components is 50-70%;
the honeycomb ceramic is cordierite honeycomb ceramic, and the mass percent of each component in the cordierite honeycomb ceramicThe ratio of the components is as follows: al (Al)2O3:30-35%，SiO2:45-50%，MgO:10-15%。
5. The catalyst of claim 3, wherein the La2O3/Al2O3With Al as the middle2O3Based on the mass of La2O3Is added in an amount of 4.2 to 5.2wt%, and the Al is2O3Is amorphous Al2O3、γAl2O3One kind of (1).
6. The catalyst of claim 3, wherein the powder particle size of the coating layer is 50-100 μm.
7. A method of preparing the catalyst of claim 3, comprising the steps of:
1) firing and molding the honeycomb ceramic to obtain a carrier;
2) la2O3/Al2O3The cerium-zirconium composite metal oxide and the rare earth element oxide are dispersed in deionized water to obtain a coating liquid, the coating liquid is coated on the surface of the carrier, and the load capacity of the coating layer on the honeycomb carrier is 200-230 g/L; calcining at the temperature of 300-500 ℃ for 1-12h to obtain a coated carrier;
3) dipping the coated carrier obtained in the step 2) in a noble metal solution, and calcining at the temperature of 300-800 ℃ for 1-24h to obtain the tail gas treatment catalyst.
8. The method of claim 7, wherein step 3) employs an isovolumetric impregnation method, the number of impregnations being from 1 to 3; the loading amount of the noble metal on the honeycomb carrier is 0.5-1 g/L.
9. The method according to claim 8, wherein the noble metal in step 3) is Rh and Pt, Rh is impregnated first, and Pt is impregnated after drying, wherein the mass ratio of Pt to Rh is (3-6): 1.
10. Use of a catalyst according to any one of claims 1 to 9 in the treatment of automobile exhaust gases.
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