Patent Application
20100099554
This application claims priority to Japanese Patent Applications Nos. 2008-269016 and 2008-269018 both filed on Oct. 17, 2008, the disclosure of each of which including the specification, the drawings, and the claims is hereby incorporated by reference in its entirety.
Exhaust gas from diesel engines and lean-burn gasoline engines contains a relatively large amount of nitrogen oxide (NOx). To purify this NOx, so-called lean NOx trap catalysts are used. Such a lean NOx trap catalyst stores NOx in an oxygen-rich atmosphere (i.e., when the air-fuel ratio of exhaust gas is lean), and releases the stored NOx when the oxygen concentration in an atmosphere becomes low (i.e., when the air-fuel ratio of the exhaust gas comes close to the stoichiometric air-fuel ratio or becomes richer than the stoichiometric air-fuel ratio), thereby performing reduction purification with a reducing agent such as hydrocarbon (HC) in the exhaust gas.
The lean NOx trap catalyst is generally made of a mixture of a catalytic metal such as Pt or Rh, a NOx storage material of an alkali metal, an alkali earth metal, or a rare earth metal, and an oxygen storage material of a Ce-based oxide. In this catalyst, the oxygen storage material functions to promote NOx storage by the NOx storage material.
Specifically, the oxygen storage material stores oxygen in an oxygen-rich atmosphere, and releases the oxygen as active oxygen when the oxygen concentration in the atmosphere decreases. This active oxygen promotes oxidation of HC and CO by the catalytic metal. Heat of this catalytic reaction causes the temperature of the NOx storage material to increase, thereby increasing the NOx storage capacity of the NOx storage material. In an oxygen-rich atmosphere, the oxygen storage material also performs oxygen exchange, i.e., takes oxygen in exhaust gas and exchanges the oxygen with oxygen in the oxygen storage material by the valence change of Ce ions. Active oxygen released by this oxygen exchange contributes to conversion from NO in the exhaust gas to NO2 which is easily stored in the NOx storage material.
Known oxygen storage materials are, for example, a CeZr-based mixed oxide and a CePr-based mixed oxide. Specifically, Japanese Laid-Open Patent Publication No. 2004-267843 discloses a lean NOx catalyst intended for an ignition-type engine and containing a CeZrSr mixed oxide. Japanese Laid-Open Patent Publication No. 2003-245552 discloses a lean NOx trap catalyst containing a CePr mixed oxide.
Mixed oxide particles formed by dissolving a catalytic metal in a Ce-based oxide are also currently used as an oxygen storage material. A catalytic metal dissolved in a Ce-based oxide is less likely to be agglomerated and sintered, and has a higher oxygen storage/release capacity, than a catalytic metal supported on the surfaces of Ce-based oxide particles. For example, Japanese Laid-Open Patent Publication No. 2004-174490 discloses a CeZrNd mixed oxide in which a catalytic metal Rh is dissolved. Japanese Laid-Open Patent Publication No. 10-182155 discloses a CeZrAl mixed oxide in which a catalytic metal Pd or Pt is dissolved. Such CeZr-based mixed oxides have higher thermal resistances than CeO2 that is also known as an oxygen storage material. However, these high thermal resistances are considered to be obtained owing to the function of Zr. It is also considered that Zr increases oxygen deficiency which contributes to oxygen storage/release.
Japanese Laid-Open Patent Publication No. 50-73893 discloses a CePr mixed oxide containing, as a component for separating oxygen from air, a small amount of at least one surface dopant selected from the group consisting of V, Mn, Cu, Mo, W, Pt, Tl, Pb, and Bi. It should be noted that the surface dopant proposed in an embodiment in this publication is Ag, and there are no embodiments suggesting the use of other metals such as Pt as dopants. Moreover, the publication discloses neither the oxygen storage/release capacity of the CePr mixed oxide, nor the use of the CePr mixed oxide for exhaust gas purification.
Exhaust gas from a diesel engine or a lean-burn gasoline engine is at a low temperature from about 250° C. to about 400° C. during steady state operation, and is required of having a high NOx purification efficiency even in such a low-temperature range. It is also required to enhance the NOx purification efficiency at lower exhaust-gas temperatures in a period of time from startup of the engine to the steady state operation. In addition, in a case where a hybrid vehicle including an engine and a motor as power sources employs a diesel engine, this engine is expected to be frequently switched between operation and stopping, resulting in that the exhaust-gas temperature decreases to 250° C. or less. If this hybrid vehicle uses a mixed fuel in which alcohol is added to light oil, the exhaust-gas temperature is expected to become lower.
It is therefore an object of the present invention to enhance the NOx purification performance of a catalyst at low exhaust-gas temperatures.
To achieve the object, according to the present invention, an exhaust gas purification catalyst is produced by using a CePr-based mixed oxide (composite oxide) in which a catalytic metal is dissolved.
In an aspect of the present invention, an exhaust gas purification catalyst includes a support and a catalytic layer provided on the support. This catalytic layer contains: a NOx storage material which stores NOx in exhaust gas when an air-fuel ratio of the exhaust gas is leaner than a stoichiometric air-fuel ratio, and releases the NOx when the air-fuel ratio is close to the stoichiometric air-fuel ratio or richer than the stoichiometric air-fuel ratio; and CePr-based mixed oxide particles doped with a catalytic metal and formed by complexing at least Ce and Pr. In this catalyst, the CePr-based mixed oxide particles contain a Ce oxide and a Pr oxide which are at least partially dissolved in each other, and the catalytic metal is dissolved in the CePr-based mixed oxide particles.
In these CePr-based mixed oxide particles, the combination of Ce and Pr as metal components allows a high oxygen storage/release capacity to be obtained. In addition, the catalytic metal dissolved in the CePr-based mixed oxide promotes storage and release of oxygen in/from these particles, thereby also allowing a high oxygen storage/release capacity to be obtained at low temperatures. The CePr-based mixed oxide particles adsorb NOx contained in the exhaust gas.
Accordingly, even at low exhaust-gas temperatures, in an oxygen-rich atmosphere having a high oxygen concentration (i.e., when the air-fuel ratio of the exhaust gas is leaner than the stoichiometric air-fuel ratio), the CePr-based mixed oxide particles release active oxygen through the aforementioned oxygen exchange to convert NO contained in the exhaust gas to NO2, thereby increasing the NOx storage capacity of the NOx storage material. On the other hand, when the oxygen concentration in the exhaust gas becomes low (i.e., when the oxygen concentration comes close to the stoichiometric air-fuel ratio or becomes richer than the stoichiometric air-fuel ratio), active oxygen released from the CePr-based mixed oxide particles promotes oxidation of HC and CO in the exhaust gas. Accordingly, the catalyst temperature, i.e., the temperature of the NOx storage material, increases, thereby increasing the NOx storage/release capacity. In addition, since the CePr-based mixed oxide particles adsorb NOx in the exhaust gas, it is possible to suppress a discharge of unpurified NOx in the exhaust gas at low exhaust-gas temperatures.
The NOx storage material may be made of at least one material selected from the group consisting of an alkali metal, an alkali earth metal, and a rare earth metal.
Part of the catalytic metal dissolved in the CePr-based mixed oxide particles is preferably dispersed and exposed at surfaces of the mixed oxide particles. In this case, the oxygen storage/release capacity of the mixed oxide particles can be increased. In addition, oxidation of HC and CO in the exhaust gas caused by the mixed oxide particles and oxidation of NO into NO2 are promoted.
In a preferred embodiment, the part of the catalytic metal dispersed and exposed at the surfaces of the CePr-based mixed oxide particles has a grain diameter of 3 nm or less when observed with an electron microscope after heating at 1000° C. for 24 hours in an atmospheric environment. This means that even if the catalytic metal is sintered at the surfaces of the particles, the degree of this sintering is small, and therefore, oxygen storage/release or purification of the exhaust gas does not deteriorate significantly.
In a surface region of the CePr-based mixed oxide particles extending from the surfaces thereof to a depth of 2 nm, the catalytic metal preferably has a concentration equal to or less than 2.5 times as high as an average concentration of the catalytic metal in the entire mixed oxide particles. This surface catalytic metal concentration ratio is more preferably less than 2.0 times, much more preferably equal to or less than 1.8 times, and still more preferably equal to or less than 1.5 times, as high as an average concentration.
Specifically, in conventional mixed oxide particles, a large part of a catalytic metal is in the form of an oxide, and is carried on the surfaces of the particles. Thus, the catalytic metal concentration in the particle surface is high. Such a catalytic metal carried as an oxide is coupled to, for example, Ce through oxygen in an oxygen-rich atmosphere. However, when the oxygen concentration in the atmosphere becomes low, the bonding is considered to be broken so that the catalytic metal is easily agglomerated or sintered. Accordingly, when such a mixed oxide is exposed to high-temperature exhaust gas, the catalytic metal on the particle surfaces is sintered, thereby causing the oxygen storage/release capacity or exhaust gas purification performance of the mixed oxide to significantly deteriorate.
On the other hand, according to the present invention, part of the catalytic metal concentration in the particle surfaces is reduced to a value equal to or less than 2.5 times as high as the average concentration of the entire particles, as described above. This means that a small amount of a catalytic metal is carried, in the form of an oxide, on the particle surfaces, i.e., a large part of the catalytic metal is dissolved in the mixed oxide particles. Accordingly, even when the mixed oxide particles are exposed to high-temperature exhaust gas, the catalytic metal is not likely to be agglomerated and sintered, or even if the catalytic metal is agglomerated and sintered, the degree of this sintering is small. In other words, even when part of the catalytic metal at the particle surface is sintered, active sites effective for the oxygen storage/release capacity or exhaust gas purification do not greatly decrease. Moreover, dissolving of the catalytic metal suppresses sintering of the mixed oxide particles themselves. Accordingly, even when the mixed oxide particles are exposed to high-temperature exhaust gas, the pore volume can be kept large, thus maintaining a high gas diffusivity.
Preferably, the catalytic metal dissolved in the CePr-based mixed oxide particles is Pt, and the catalytic layer further carries Pt as a result of impregnation with a Pt solution, in addition to Pt dissolved in the CePr-based mixed oxide particles.
In this manner, Pt carried on the CePr-based mixed oxide particles as a result of impregnation contributes to conversion of NO in the exhaust gas to NO2 which is easily stored in the NOx storage material, and also contributes to an increases in the catalyst temperature, i.e., the temperature of the NOx storage material, through oxidation purification of HC and CO contained in the exhaust gas, and thereby to an increase in the NOx storage capacity of the NOx storage material. These functions of Pt are advantageous in increasing the NOx purification performance.
A proportion of the amount of Pt dissolved in the CePr-based mixed oxide particles with respect to a sum of the amount of Pt dissolved in the CePr-based mixed oxide particles and the amount of Pt carried on the catalytic layer as a result of impregnation is preferably in the range from 20% by mass to 60% by mass, both inclusive. This proportion is hereinafter referred to as a “doping proportion.”
That is, an experiment shows that the NOx purification efficiency varies with the doping proportion. The NOx purification efficiency is high when the doping proportion is in the range from 20% by mass to 60% by mass, both inclusive. More preferably, the doping proportion is in the range from 20% by mass to 45% by mass, both inclusive.
A catalytic layer containing oxide particles carrying Rh is preferably provided on or above the catalytic layer containing the NOx storage material and the CePr-based mixed oxide particles.
In this manner, in an oxygen-rich atmosphere having a high oxygen concentration in the exhaust gas, the lower catalytic layer containing the NOx storage material and the CePr-based mixed oxide particles mainly stores NOx, and suppresses release of NOx. When the oxygen concentration in the exhaust gas becomes low, Rh carried on oxide particles in the upper catalytic layer effectively contributes to reduction purification of NOx released from the NOx storage material by using HC and CO in the exhaust gas as reducing agents.
Preferably, in the lower catalytic layer, at least part of the NOx storage material is supported on the CePr-based mixed oxide particles. This causes the CePr-based mixed oxide to contribute to an increase in the NOx storage capacity of the NOx storage material. In a preferred embodiment, the NOx storage material and Rh are carried on the CePr-based mixed oxide particles.
In the lower catalytic layer, the Pr/(Ce+Pr) mole percentage of the CePr-based mixed oxide particles is preferably 50% or less. Then, the NOx purification performance is enhanced.
The CePr mixed oxide (i.e., a mixed oxide in which Ce, Pr, and the catalytic metal are complexed with each other to form oxide particles, a Ce oxide and a Pr oxide are at least partially dissolved in each other, the catalytic metal is dissolved in the oxide particles, and the dissolved catalytic metal is partially dispersed and exposed at the surfaces of the oxide particles) can be obtained by the following manner. First, an acid source solution containing Ce ions, Pr ions, and a hydroxo complex of the catalytic metal is mixed with a basic solution, thereby precipitating a hydroxide containing the Ce and Pr ions and the catalytic metal. Then, the obtained precipitate is calcined.
More specifically, a dinitrodiammine platinum (II) nitric acid solution, which is conventionally widely used as a catalytic metal source such as a Pt source material, contains an amino group and a nitro group. The amino group has a high affinity for an ammonia solvent, and is likely to form hydrogen bonds of N—H . . . N. Accordingly, when aqueous ammonia is used as a basic solution for obtaining a hydroxide precipitate, the Pt source material is bonded to the ammonia solvent, and thus a hydroxide precipitate of Pt is not likely to be formed. That is, a large amount of the Pt source material does not become a hydroxide, and is attached to a hydroxide of Ce and Pr, or otherwise, when the hydroxide precipitate is washed, a large amount of the Pt source material is washed out with the ammonia solvent.
On the other hand, in the hydroxo complex used as a catalytic metal source in the aforementioned method, OH groups coordinate to the catalytic metal. Thus, the hydroxo complex is easily bonded to hydroxides of Ce and Pr produced by mixing the source solution and the basic solution. Accordingly, a small amount of the catalytic metal remains in the solvent, thereby obtaining a CePr-based mixed oxide in which the catalytic metal is dissolved at a concentration substantially corresponding to the charge amount. The fact that the hydroxo complex of the catalytic metal is easily bonded to the hydroxides of Ce and Pr means that the catalytic metal is not carried in the form of an oxide on the particle surfaces but is easily dissolved in the CePr-based mixed oxide particles. As a result, the concentration of the catalytic metal in the surface region of the particles can be reduced to a small value equal to or less than 2.5 times as large as, and more preferably less than twice, the average concentration of the catalytic metal in the entire particles.
Hereinafter, preferred embodiments of the invention will be described with reference to the drawings. Note that the following description of the preferred embodiments is merely illustrative in nature, and is not intended to limit the scope, applications, and use of the invention.
Preferably, CePr-based mixed oxide particles doped with Pt as a catalytic metal and activated alumina particles are provided in the lower catalyst layer 2, activated alumina particles carrying Rh as a catalytic metal are provided in the upper catalyst layer 3, and the upper and lower catalyst layers 2 and 3 are impregnated with Pt, Rh, and NOx storage materials to carry these materials. This carrying as a result of impregnation is performed by impregnating the catalyst layers 2 and 3 with a Pt solution, a Rh solution, and a NOx storage material solution and then drying and calcining these layers. Accordingly, each of the Pt, Rh, and NOx storage materials after the impregnation is at least partially supported on at least part of the CePr-based mixed oxide particles in the lower catalyst layer 2. As the NOx storage material, an alkali metal, an alkali earth metal, or a rare earth metal may be used, and in particular, an alkali earth metal such as Ba or Sr is preferably used.
In this case, in an oxygen-rich atmosphere, Pt supported on activated alumina in the lower catalyst layer 2 converts NO in the exhaust gas to NO2 which is easily stored in the NOx storage material. The Pt-doped CePr-based mixed oxide powder stores oxygen in an oxygen-rich atmosphere, and releases the stored oxygen as active oxygen when the oxygen concentration in an atmosphere becomes low. In an oxygen-rich atmosphere, this Pt-doped CePr-based mixed oxide powder also performs oxygen exchange of taking oxygen in the exhaust gas and exchanging the oxygen with oxygen in the mixed oxide particles by the valence change of Ce ions. Active oxygen released by this oxygen exchange contributes to conversion of NO in the exhaust gas to NO2. When the oxygen concentration in the exhaust gas becomes low, Pt supported on activated alumina causes oxidation of HC and CO in the exhaust gas with the active oxygen released from the mixed oxide powder to increase the catalyst temperature with heat of the reaction, while performing reduction purification of NOx released from the NOx storage material with HC and CO used a reducing agents. Rh supported on activated alumina in the upper catalyst layer 3 effectively acts on the reduction purification of NOx using HC and CO as reducing agents in a state in which the oxygen concentration in an atmosphere is low.
An important feature of the present invention is using CePr-based mixed oxide particles doped with a catalytic metal as a component of an exhaust gas purification catalyst. Hereinafter, features of this exhaust gas purification catalyst, particularly the aforementioned feature, will be described.
An acid solution containing Ce ions, Pr ions, and a hydroxo complex of Pt is prepared. Cerium nitrate (III) hexahydrate may be used as a Ce source material, praseodymium nitrate (III) hexahydrate may be used as a Pr source material, and a hexahydroxo platinate (IV) ethanolamine solution or a hexahydroxo platinate (IV) nitric acid solution may be used as a Pt source material (i.e., a hydroxo complex). Given amounts of the Ce source material, the Pr source material, and the Pt source material are mixed with water, thereby obtaining a source solution (having acidity).
A basic solution is added to, and mixed with, the source solution, thereby producing precipitated particles of a mixed hydroxide of Ce, Pr, and Pt which is a precursor of the mixed oxide particles. In this case, the source solution is stirred at room temperature for about one hour, and then aqueous ammonia at a concentration of about 7% is added as a basic solution to this source solution. Another basic solution, e.g., an aqueous solution of caustic soda, may be used.
The solution containing the precursor precipitated particles is subjected to centrifugation, thereby removing the supernatant liquid. Ion-exchanged water is further added to the dehydrated precipitate obtained by the removal of the supernatant liquid. Then, the resultant precipitate is stirred, and is subjected to centrifugation (i.e., dehydrated) again. This cycle of rinsing and dehydration is repeated the necessary number of times. By repeating the cycle of rinsing and dehydration, the redundant basic solution is removed.
The dehydrated precipitate is dried, then calcined and ground. The drying can be performed by, for example, keeping the dehydrated precipitate in an atmospheric environment at a temperature of about 100° C. to about 250° C. for a given period of time. The calcining can be performed by, for example, keeping the dehydrated precipitate in the atmospheric environment at a temperature of about 400° C. to about 600° C. for several hours.
In this manner, mixed oxide particles doped with Pt and formed by complexing at least Ce and Pr. These mixed particles contain a Ce oxide and a Pr oxide which are at least partially dissolved in each other. In the mixed particles, Pt is dissolved in the mixed oxide particles, and part of the Pt is dispersed and exposed at the surfaces of the oxide particles.
Mixed oxide powder of each of EXAMPLES 1 to 4 and COMPARATIVE EXAMPLE 1 was prepared to obtain the ratio of Pt concentration in the surface region with respect to the average concentration of Pt in the entire particles for each example.
Mixed oxide powder of EXAMPLE 1 was prepared by using a hexahydroxo platinate (IV) ethanolamine solution as a Pt source material with the aforementioned method for forming Pt-doped CePr-based mixed oxide powder. The Ce/Pr mole ratio was 9/1. The amount of the charged Pt source material was adjusted such that the Pt concentration in the entire particles was 0.5% by mass. The obtained mixed oxide powder is referred to as “Ethanol Pt-doped Ce/Pr=9/1” or “Ethanol Pt-doped Ce0.9Pr0.1O2” in the drawings and tables.
Mixed oxide powder of EXAMPLE 2 was prepared under the same conditions in the same manner as those in EXAMPLE 1 except that the Ce/Pr mole ratio was 1/9. The obtained mixed oxide powder is referred to as “Ethanol Pt-doped Ce/Pr=1/9” or “Ethanol Pt-doped Ce0.1Pr0.9O2” in the drawings and tables.
Mixed oxide powder of EXAMPLE 3 was prepared by using a dinitrodiammine platinum (II) nitric acid solution (which is so-called platinum P salt) shown in
Mixed oxide powder of EXAMPLE 4 was prepared under the same condition in the same manner as those for EXAMPLE 3 except that the Ce/Pr mole ratio was 1/9. The obtained mixed oxide powder is referred to as “Pt—P-doped Ce/Pr=1/9” or “Pt—P-doped Ce0.1Pr0.9O2” in the drawings and tables.
CePr mixed oxide powder having a Ce/Pr mole ratio of 9/1 and a dinitrodiammine platinum (II) nitric acid solution were mixed, and evaporated to dryness, thereby preparing mixed oxide powder of COMPARATIVE EXAMPLE 1. The amount of carried Pt was set to be 0.5% by mass of the mixed oxide powder. The obtained mixed oxide powder is referred to as “Pt—P dried Ce/Pr=9/1” or “Pt—P dried Ce0.9Pr0.1O2” in the drawings and tables.
The Pt concentration in the surface region (i.e., a region from the surface to a depth of 2 nm) of the mixed oxide particles of each of EXAMPLES 1 to 4 and COMPARATIVE EXAMPLE 1 was measured with X-ray photoelectron spectroscopy (XPS), thereby obtaining the surface Pt concentration ratio (i.e., the Pt concentration in the surface region/the Pt concentration in the entire particles). Here, the depth of “2 nm” was selected in this case because it is known that the depth of characteristic X-rays entering from the surface depends on the intensity of the characteristic X-rays, and because X rays having an intensity of 1000 eV were used in this case. The results are shown in
The surface Pt concentration ratio of the mixed oxide particles is 2.5 or less for EXAMPLES 1 to 4, but is higher than 2.5 for COMPARATIVE EXAMPLE 1. Specifically, the amount of Pt supported, in an oxide form, on the surface of the mixed oxide particles is smaller in EXAMPLES 1 to 4 than that in COMPARATIVE EXAMPLE 1, and thus a large part of Pt is dissolved in the mixed oxide particles. The surface Pt concentration ratio is preferably less than 2.0, more preferably 1.8 or less, and much more preferably 1.5 or less. The surface Pt concentration ratio is preferably higher than one. These values are selected for the purpose of causing a catalytic metal exposed at the surfaces of the mixed oxide particles to be present as a medium for storing and releasing oxygen, and for the purpose of causing the catalytic metal to contribute to purification of the exhaust gas.
In addition to the mixed oxide powder of EXAMPLES 1 to 4 and COMPARATIVE EXAMPLE 1, mixed oxide powder of EXAMPLES 5 to 7 and COMPARATIVE EXAMPLES 2 and 3 were prepared, and the pore volumes and other factors thereof were obtained.
Mixed oxide powder of EXAMPLE 5 was prepared under the same conditions in the same manner as those in EXAMPLE 1 except that the Ce/Pr mole ratio was 7/3. The obtained mixed oxide powder is referred to as “Ethanol Pt-doped Ce/Pr=7/3” or “Ethanol Pt-doped Ce0.7Pr0.3O2” in the drawings and tables.
Mixed oxide powder of EXAMPLE 6 was prepared under the same conditions in the same manner as those in EXAMPLE 1 except that the Ce/Pr mole ratio was 5/5. The obtained mixed oxide powder is referred to as “Ethanol Pt-doped Ce/Pr=5/5” or “Ethanol Pt-doped Ce0.5Pr0.5O2” in the drawings and tables.
Mixed oxide powder of EXAMPLE 7 was prepared under the same conditions in the same manner as those in EXAMPLE 3 (i.e., Pt—P doping) except that the Ce/Pr mole ratio was 5/5. The obtained mixed oxide powder is referred to as “Pt—P-doped Ce/Pr=5/5” or “Pt—P-doped Ce0.5Pr0.5O2” in the drawings and tables.
Mixed oxide powder of COMPARATIVE EXAMPLE 2 was prepared under the same conditions in the same manner as those in COMPARATIVE EXAMPLE 1 (i.e., Pt—P dried) except that the Ce/Pr mole ratio was 5/5. The obtained mixed oxide powder is referred to as “Pt—P dried Ce/Pr=5/5” or “Pt—P dried Ce0.5Pr0.5O2” in the drawings and tables.
Mixed oxide powder of COMPARATIVE EXAMPLE 3 was prepared under the same conditions in the same manner as those in COMPARATIVE EXAMPLE 1 (i.e., Pt—P dried) except that the Ce/Pr mole ratio was 1/9. The obtained mixed oxide powder is referred to as “Pt—P dried Ce/Pr=1/9” or “Pt—P dried Ce0.1Pr0.9O2” in the drawings and tables.
Table 1 shows measurement results on the pore volume, the pore diameter, the crystallite diameter, and the BET specific surface area of the mixed oxide of each of EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3 described above after aging performed in an atmospheric environment at a temperature of 750° C. or 1000° C. for 24 hours. In Table 1, the “pore diameter” is the average pore diameter, and the “crystallite diameter” is obtained, with an X-ray diffractometer, by Scherrer equation (i.e., crystallite diameter (hkl)=0.9 λ/(β1/2·cos θ) where hkl are Miller indices, λ is a wavelength (angstrom) of characteristic X-rays, β1/2 is a half-power bandwidth (radian) of the (hkl) plane, and θ is the reflection angle of X rays. Since a split phase of Pr6O11 is produced from the “Ethanol Pt-doped Ce/Pr=1/9” and “Pt—P dried Ce/Pr=1/9” after aging performed at 1000° C. for 24 hours, the crystallite diameter after the aging is the average value of a parent-phase oxide and the split-phase oxide.
Except for the case of Ce/Pr=1/9, the “Ethanol Pt-doped” products basically have large pore volumes relative to the average pore diameter, and also have large BET specific surface areas, unlike the “Pt—P-doped” products and the “Pt—P dried” products. This means that the “Ethanol Pt-doped” products have a large number of pores and a high gas diffusivity, and thus exhibits a large oxygen storage/release capacity. A comparison between the “Pt—P-doped” products and the “Pt—P dried” products shows that the “Pt—P-doped” products have smaller pore volumes and smaller pore diameters than the “Pt—P dried” products, and that the BET specific surface area of the former is larger than that of the latter. Accordingly, the “Pt—P-doped” products are considered to have a larger number of pores, and thus have a higher gas diffusivity and a larger oxygen storage/release capacity, than the “Pt—P dried” products.
The average crystallite diameters obtained by Scherrer equation of the “Ethanol Pt-doped” products are smaller than those of the “Pt—P dried” products. This fact shows that grain growth due to aging is not considerable, i.e., the thermal resistance is high.
Preferably, in a “Ethanol Pt-doped” mixed oxide having a Ce/Pr mole ratio of 1/9 to 9/1, both inclusive, the crystallite diameter obtained by Scherrer equation after 1000° C.-24 hour aging is less than 60 nm, the pore volume after 750° C.-24 hour aging is 0.12 cm3/g or more, or the average pore diameter after 750° C.-24 hour aging is less than 35 nm.
The amounts of stored/released oxygen after aging performed at 750° C. for 24 hours in an atmospheric environment was measured for the mixed oxide powder of the EXAMPLES 1 to 3 and 5 to 7 and COMPARATIVE EXAMPLE 1 and “Ethanol Pt-doped CeO2” powder. The “Ethanol Pt-doped CeO2” powder was obtained by setting the amount of the Pr source material at zero in the method of EXAMPLE 1. The Pt concentration therein was 0.5% by mass. In measuring the amount of stored/released oxygen, a pretreatment (i.e., an oxygen storage treatment) was performed in the following manner. First, while a 5% O2 gas (where the balance was H) was supplied to a 0.10 g of a sample at a flow rate of 100 mL/min, the gas temperature was increased at a rate of 20° C./min. Subsequently, the temperature was kept at 600° C. for 20 minutes, and then cooled to room temperature. Thereafter, while a 2% CO gas (where the balance was He) was supplied at a flow rate of 100 mL/min, the gas temperature was increased at a rate of 10° C./min. In this state, it was measured how the amount of CO2 released from the sample varies with the temperature. This amount of released CO2 corresponds to the amount of oxygen released from the sample.
The results are shown in
NOx adsorption/desorption properties of mixed oxide powder of each of EXAMPLES 1, 2, 5, and 6, “Ethanol Pt-doped CeO2,” and “Ethanol Pt-doped Pr6O11” were evaluated with a NO-TPD (temperature programmed desorption) test. The “Ethanol Pt-doped Pr6O11” powder was prepared with the amount of a Ce source material set at zero in the method of EXAMPLE 1. The Pt concentration was 0.5% by mass.
First, while a reducing gas (where the proportion of H2 was 0.45%, the balance was H, and the flow rate was 100 mL/min) was supplied to sample powder, the gas temperature was increased from room temperature (i.e., 25° C.) at a rate of 30° C./min. Thereafter, the temperature was kept at 600° C. for 10 minutes, and then cooled to room temperature. Next, a NO-containing gas (where the amount of NO was 4000 ppm, the proportion of O2 was 3.0%, the balance was He, and the flow rate was 100 mL/min) was supplied at room temperature for 15 minutes. Subsequently, while a He gas (at a flow rate of 100 mL/min) was supplied, the gas temperature was increased to 600° C. at a rate of 20° C./min, thereby causing desorption of NOx from the sample powder and measuring the amount of this desorption.
The results are shown in
Based on the structure of the exhaust gas purification catalyst shown in
Regarding the amounts of the carried components per liter of the support, the CePr mixed oxide powder and the activated alumina powder in the lower catalyst layer 2 were each set at 135 g/L, the activated alumina powder in the upper catalyst layer 3 was set at 50 g/L. The amount of carried Pt was adjusted such that the sum of the amount of Pt contained in the CePr mixed oxide and the amount of Pt carried on the catalyst layers 2 and 3 as a result of impregnation was 2.0 g/L. The amount of Rh carried as a result of impregnation was 0.1 g/L, the amount of Ba carried as a result of impregnation was 30 g/L, and the amount of Sr carried as a result of impregnation was 10 g/L. The amount of Rh carried on the upper catalyst layer 3 as Rh-carrying activated alumina powder was 0.4 g/L.
The four types of sample catalysts have different amounts of Pt added to the CePr mixed oxide particles by doping, i.e., 0% by mass, 0.1% by mass, 0.5% by mass, and 1.0% by mass, respectively. Accordingly, the Pt doping proportions (i.e., the Pt-doping amount/(the Pt doping amount+the Pt impregnation carrying amount)) of the four types of sample catalysts are calculated to be 0%, 6.75%, 33.75%, and 67.5%, respectively. The Pt-doped CePr mixed oxide powder was prepared by using a hexahydroxo platinate (IV) ethanolamine solution as a Pt source material, as in EXAMPLE 1.
These sample catalysts were subjected to aging in which these catalysts were held in an atmospheric environment at 750° C. for 24 hours. Then, the NOx purification performance was evaluated with a model gas flow reactor and an exhaust gas analyzer. First, a pretreatment gas shown in Table 2 was allowed to flow at 600° C. for 10 minutes. Then, a lean model exhaust gas (whose A/F was 22) was allowed to flow for 60 seconds, and the gas composition was switched to a rich model exhaust gas (whose A/F was 14.5), this rich model exhaust gas was allowed to flow for 60 seconds. This cycle of gas flow was repeated several times. Thereafter, the lean NOx purification efficiency for 60 seconds starting from the gas composition switch from rich to lean, and the rich NOx purification efficiency for 60 seconds starting from the gas composition switch from lean to rich, were measured, and the average value thereof was obtained. The compositions of the lean model exhaust gas and the rich model exhaust gas are shown in Table 2 where the space velocity is 35000/h. The three temperatures, i.e., 150° C., 175° C., and 200° C., of the model exhaust gas were selected.
The results are shown in
The results of measurement of the NOx purification efficiency at 150° C. show that the Pt doping proportion is preferably in the range from 20% to 60%, both inclusive. The results of measurement of the NOx purification efficiency at 200° C. show that the Pt doping proportion is preferably in the range from 20% to 45%, both inclusive.
Multiple samples of Pt-doped CePr mixed oxide powder having different Pr/(Ce+Pr) mole percentages were prepared with the Pt-doping amount set at 0.5% by mass, and multiple samples of Pt-carrying CePr mixed oxide powder having different Pr/(Ce+Pr) mole percentages were prepared with the Pt-doping amount set at 0.5% by mass. Each sample of the Pt-doped CePr mixed oxide powder was prepared by coprecipitation with a hexahydroxo platinate (IV) ethanolamine solution used as a Pt source material, as in EXAMPLE 1. Each sample of the Pt-carrying CePr mixed oxide powder was prepared by evaporation to dryness with a dinitrodiammine platinum (II) nitric acid solution used as a Pt source material, as in COMPARATIVE EXAMPLE 1.
In this manner, as in the evaluation of the NOx purification performance described above, sample catalysts were prepared by using the Pt-doped CePr mixed oxide powder and the Pt-carrying CePr mixed oxide powder. These sample catalysts were obtained by providing 50 g/L (where Rh was 0.4 g/L) of the Rh-carrying activated alumina powder in the upper catalyst layer 3, by providing 135 g/L of the Pt-doped CePr mixed oxide powder and 135 g/L of activated alumina powder in the lower catalyst layer 2, and by impregnating these catalyst layers 2 and 3 with 1.325 g/L of Pt, 0.1 g/L of Rh, 30 g/L of Ba, and 10 g/L of Sr.
The lean NOx purification efficiency and the rich NOx purification efficiency of each of the sample catalysts were measured at model-exhaust-gas temperatures of 200° C., 250° C., and 300° C., under the same conditions in the same manner as those for the aforementioned evaluation of the NOx purification performance. The results are shown in
The metal components of the mixed oxide of the aforementioned examples are Ce, Pr, and Pt. Other metal components such as Zr may also be mixed in the metal oxide.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-269016 | Oct 2008 | JP | national |
| 2008-269018 | Oct 2008 | JP | national |
