Patent Application
20060217263
This application claims priority under 35 USC 119 to Japanese Patent Applications Nos. 2005-85515, 2005-85516, 2005-85517, 2005-85518 and 2006-5263, the entire contents of all of which are incorporated herein by reference.
(a) Field of the Invention
This invention relates to exhaust gas purification catalysts and pertains to the technical field of exhaust gas purification for automobiles.
(b) Description of the Related Art
Three-way catalysts are conventionally known which can concurrently convert hydrocarbon (HC), carbon monoxide (CO) and nitrogen oxides (NOx) contained in exhaust gas from automobiles into carbon dioxide (CO2), water (H2O) and nitrogen (N2). There has recently been a demand for a three-way catalyst of such kind to attain high conversion efficiencies of all three pollutants from just after engine start. To satisfy this demand, a technique is employed which increases the catalyst temperature up to more than the catalytic reaction temperature in a short time after engine start, as by directly connecting the catalyst to the convergence of an exhaust manifold for the engine (close-coupled catalyst) or placing an underfloor catalyst at an upstream part of an exhaust passage as close to the engine as possible. If, however, the catalyst is placed close to or comparatively close to the engine, it will be exposed to extremely high-temperature exhaust gas during acceleration operation and other operations of the engine. This results in a problem that particles of catalytic precious metals, such as platinum (Pt), rhodium (Rh) and palladium (Pd), carried on alumina or an oxygen storage component in a catalytic coating move on the surface of the alumina or the oxygen storage component to coagulate and cause sintering, resulting in deteriorated conversion performance. In particular, if different kinds of catalytic precious metals sinter and alloy together, they will loose catalytic activity and thereby significantly deteriorate their catalytic conversion performance, which is a big problem.
To prevent different kinds of catalytic precious metals from sintering and alloying, a technique disclosed in Japanese Unexamined Patent Publication No. 2003-170047 can be applied. Specifically, as shown in
Generally, in carrying catalytic precious metal on alumina, the larger specific surface area of alumina provides higher dispersity of catalytic precious metal. As a result, it is believed that precious metal particles are less likely to be coagulated and thereby less likely to sinter, which prevents deterioration in conversion performance. If support materials bond together, i.e., different kinds of aluminas or alumina and oxygen storage component bond to each other to sinter, a problem arises that catalytic precious metal particles are buried inward of the surface of the sintered support material to further deteriorate the catalyst. However, when the specific surface area of alumina is large, it can be considered that even if support materials sinter, the loss of catalytic precious metal due to burial in the sintered support material is small and, therefore, deterioration in conversion performance is small.
It is being perceived that for lean NOx trap catalysts, for example, higher degree of basicity of alumina surface provides a larger number of sites to adsorb and hold negatively charged derivative molecules in exhaust gas, e.g., NO3− ions, which improves NOx conversion performance. If this perception is applied to three-way catalysts, it is inferred that when adsorbed NO3− ions are decomposed, active oxygen is released from them and released active oxygen exhibits the action to convert HC by oxidation. If this is true, it is probably preferable to employ high basicity alumina as all kinds of aluminas which are contained in a catalyst to carry various kinds of catalytic precious metals. However, as results of inventors' research and development of catalysts excellent in thermal resistance, they have found that when different kinds of catalytic precious metals including platinum, rhodium and palladium are individually carried on alumina particles of the same kind having the same specific surface area and the same basicity, a deterioration in conversion performance has been observed even if the alumina particles have a large specific surface area and a high basicity.
In addition, in the technique disclosed in the above patent document, platinum and palladium are each carried on alumina but not on the oxygen storage component. Further, rhodium is carried on the oxygen storage component but not on alumina. Therefore, interaction is not sufficiently established between each catalytic precious metal and its support material such as alumina or oxygen storage component and it cannot necessarily be said that the surface state of each catalytic precious metal is optimized for exhaust gas purification. Furthermore, it cannot be said that the dispersity of each catalytic precious metal over the support material is high. Therefore, there is a problem that when the catalyst is exposed to high-temperature exhaust gas, each catalytic precious metal may sinter and not sufficiently exhibit its catalytic property, resulting in deteriorated exhaust gas purification performance of the catalyst. Furthermore, if sintering occurs between different kinds of aluminas or between different kinds of oxygen storage components, catalytic precious metals are buried inward of the surfaces of the support materials to further deteriorate the catalyst.
To solve the above problems, it can be considered to carry the same kind of catalytic precious metal on both alumina and the oxygen storage component. Oxygen storage and release of the oxygen storage component is involved in the catalytic reaction of catalytic precious metal. Any proposal of in which distribution ratio the same kind of catalytic precious metal should been carried on alumina and the oxygen storage component, however, has not up to now been made.
It is also known that if zirconium dioxide (ZrO2) is compounded with cerium dioxide having oxygen storage capacity, the resultant mixed oxide has high thermal resistance and in turn improves the thermal resistance of the catalyst. If, however, the amount of ZrO2 added is increased, the content of cerium dioxide in the mixed oxide is correspondingly decreased so that the mixed oxide deteriorates its oxygen storage capacity, resulting in deteriorated conversion performance of the catalyst.
The present invention intends to solve the foregoing problems in catalysts susceptible to high heat load from engine exhaust gas, for example, catalysts placed close to engines or underfloor catalysts placed relatively close to engines.
Therefore, an object of the present invention is to provide a catalyst having improved catalytic conversion performance and excellent thermal resistance in consideration of the specific surface area and surface condition of alumina carrying catalytic precious metal.
Another object of the present invention is to prevent different kinds of catalytic precious metals from sintering and alloying together.
Still another object of the present invention is to enhance the dispersity of each catalytic precious metal, thereby preventing catalytic precious metal particles of the same kind from sintering together.
Still another object of the present invention is to provide an optimal combination of each catalytic precious metal and suitable support materials among different kinds of aluminas and different kinds of oxygen storage components.
Still another object of the present invention is to propose, when catalytic precious metal is carried on both alumina and an oxygen storage component, the ratio between the amount of catalytic precious metal carried on alumina and that on the oxygen storage component which can exhibit high conversion performance by optimizing the catalytic reaction of the catalytic precious metal and the action of the oxygen storage component.
Still another object of the present invention is to improve the conversion performance by improving both the thermal resistance and the oxygen storage capacity of the catalyst.
Solutions for attaining the above objects will be described below.
A first solution to the problem is directed to an exhaust gas purification catalyst in which a catalytic coating containing plural kinds of catalytic precious metals and plural kinds of particulate aluminas carrying the catalytic precious metals is coated on a honeycomb support, wherein
the plural kinds of particulate aluminas have different specific surface areas and carry the different kinds of catalytic precious metals,
one of the plural kinds of particulate aluminas is compounded with at least cerium to have oxygen storage capacity, and
palladium is carried as one said catalytic precious metal on the one kind of particulate alumina having oxygen storage capacity.
According to this solution, as compared with the case where all kinds of catalytic precious metals are individually carried on alumina particles of the same kind having the same specific surface area, the catalytic conversion performance is improved, thereby providing a catalyst having an excellent thermal resistance. According to the inventors' founding, palladium is preferably carried on particles of a particulate alumina having a large specific surface area and a high surface basicity, platinum is preferably carried on particles of a particulate alumina having a slightly smaller specific surface area and a lower surface basicity than the particulate alumina carrying palladium, and rhodium is preferably carried on particles of a particulate alumina which have a smaller specific surface area and an intermediate surface basicity as compared with the particulate alumina carrying palladium and the particulate alumina carrying platinum and whose surfaces are coated to prevent solid solution of rhodium in the alumina particles.
In particular, when palladium is carried on particles of the particulate alumina having a high surface basicity, it can be easily controlled into a good oxidation condition. Specifically, the oxidation condition of palladium reversibly changes so that Pd ←→PdO ←→PdO2←→ . . . and the ratio of coexistence of these oxidation conditions is a factor having a significant effect on oxidation reactions of hydrocarbon and carbon monoxide. When palladium is carried on particles of the particulate alumina having a high surface basicity, the ratio of coexistence of the oxidation conditions is made proper so that the efficiencies of palladium converting hydrocarbon and carbon monoxide by oxidation can be enhanced over a long period of time.
Further, as the surface basicity of particles of the particulate alumina carrying platinum is lower, platinum can be better prevented from being oxidized and can maintain its catalytic activity for a longer period of time. Furthermore, when the surfaces of the alumina particles carrying rhodium are coated with, for example, zirconium dioxide to prevent rhodium from solid solution in the alumina particles, rhodium can be stabilized over a long period of time, which is particularly advantageous in NOx conversion performance.
The particulate alumina compounded with at east cerium to have oxygen storage capacity has a more excellent thermal resistance than cerium dioxide and Ce—Zr—Nd mixed oxide. Therefore, palladium can be controlled to an excellent oxidation condition over a longer period of time by active oxygen supplied from the particulate alumina having oxygen storage capacity. Further, since the particulate alumina having oxygen storage capacity contains alumina, a large specific surface area can be maintained over a long period of time, which ensures an excellent catalytic activity.
A second solution of the invention is characterized in that in the first solution, the catalytic coating is formed of an upper layer and a lower layer and the lower layer contains the palladium-carried particulate alumina having oxygen storage capacity.
In the second solution, if a particulate oxygen storage component having a high oxygen storage capacity is disposed in the upper layer, the A/F ratio of exhaust gas flowing from upstream to downstream side and from upper to lower layer of the catalyst is controlled to be suitable for concurrent catalytic conversion of HC, CO and NOx. As a result, the Pd support material (i.e., the particulate alumina) in the lower layer effectively acts on purification of the exhaust gas, thereby improving catalytic performance. Further, palladium in the lower layer is prevented from being sintered and alloyed with catalytic precious metal in the upper layer, such as platinum or rhodium. Since palladium is protected by the upper layer, it can be prevented from being poisoned by S (sulfur) and P (phosphorus).
A third solution of the invention is characterized in that in the second solution, the plural kinds of particulate aluminas carrying the catalytic precious metals include the palladium-carried particulate alumina having oxygen storage capacity and two kinds of particulate aluminas having different specific surface areas, and
out of the two kinds of particulate aluminas having different specific surface areas, a particulate alumina having a smaller specific surface area is contained in the upper layer while a particulate alumina having a larger specific surface area is contained in the lower layer.
In the third solution, palladium in the lower layer is better dispersed than catalytic precious metal in the upper layer, such as platinum or rhodium. As a result, palladium particles are less likely to coagulate and therefore less likely to sinter, which restrains deterioration in conversion performance of palladium. Further, even if alumina particles carrying palladium or alumina particles having oxygen storage capacity in the lower layer sinter, the loss of palladium particles is reduced. This restrains deterioration in catalytic conversion performance.
A fourth solution of the invention is directed to an exhaust gas purification catalyst in which a catalytic coating containing plural kinds of catalytic precious metals and plural kinds of particulate aluminas is coated on a honeycomb support, wherein
the plural kinds of particulate aluminas include at least one kind of particulate alumina with relatively large specific surface area, at least one kind of particulate alumina with relatively small specific surface area and at least one kind of particulate alumina compounded with at least cerium to have oxygen storage capacity,
the catalytic coating is formed of an upper layer and a lower layer, the lower layer containing the at least one kind of particulate alumina with relatively large specific surface area and the at least one kind of particulate alumina having oxygen storage capacity, the upper layer containing the at least one kind of particulate alumina with relatively small specific surface area, and
out of the plural kinds of catalytic precious metals, palladium is carried on the at least one kind of particulate alumina with relatively large specific surface area and the at least one kind of particulate alumina having oxygen storage capacity and platinum and rhodium are carried on separate particles of the at least one kind of particulate alumina with relatively small specific surface area.
According to the fourth solution, the catalyst can be enhanced in thermal resistance and conversion performance.
A fifth solution of the invention is directed to an exhaust gas purification catalyst in which a catalytic coating containing plural kinds of catalytic precious metals, at least one kind of particulate alumina and at least one kind of particulate oxygen storage component is coated on a honeycomb support, wherein
each of particles of the at least one kind of particulate alumina and the at least one kind of particulate oxygen storage component carries only one of the plural kinds of catalytic precious metals, and
at least one of the plural kinds of catalytic precious metals is carried on both particles of the at least one kind of particulate alumina and particles of the at least one kind of particulate oxygen storage component.
In the fifth solution, each of particles of the at least one kind of particulate alumina and the at least one kind of particulate oxygen storage component carries only one of the plural kinds of catalytic precious metals, that is, only one kind of catalytic precious metal is carried on each particle of the particulate support materials. In other words, different kinds of catalytic precious metals are separately carried on different particles of particulate alumina or different particles of particulate oxygen storage component. Therefore, the different kinds of catalytic precious metals can be prevented from sintering and alloying together, thereby restraining deterioration of the catalyst.
In addition, since at least one of the plural kinds of catalytic precious metals is carried on both particles of the at least one kind of particulate alumina and particles of the at least one kind of particulate oxygen storage component, the catalytic precious metal is distributively carried on a larger number of alumina particles and a larger number of oxygen storage component particles. In other words, the catalytic precious metal is increased in dispersity (becomes more dispersive). As a result, precious metal particles are less likely to sinter, which prevents a significant reduction in the total surface area of the catalytic precious metal. Further, even if alumina particles or oxygen storage component particles sinter, the loss of catalytic precious metal particles due to burial in the sintered support material is reduced. This also reduces reduction in the total surface area of catalytic precious metal. Note that “one of the plural kinds of catalytic precious metals” is not particularly limited and, for three-way catalysts for exhaust gas purification, may be Pt, Pd or Rh which are known catalytic precious metals or may be any other catalytic precious metal. This is valid for the other solutions of the invention unless otherwise specified.
In the above manners, the above solution prevents different kinds of catalytic precious metals from sintering and alloying together and makes it difficult for particles of each catalytic precious metal to sinter by increasing the dispersity of each catalytic precious metal. Thus, the catalyst can be further enhanced in thermal resistance and can maintain its excellent catalytic conversion performance over a longer period of time.
A sixth solution of the invention is characterized in that in the fifth solution, the catalytic coating is formed of an upper layer and a lower layer, one of the plural kinds of catalytic precious metals is palladium, and said palladium is carried on particles of the particulate alumina and particles of the particulate oxygen storage component both of which are contained in the lower layer.
In the sixth solution, the catalytic coating is formed of an upper layer and a lower layer and palladium, which is relatively likely to thermally deteriorate and likely to be poisoned with S and P, is carried on particles of the particulate alumina and particulate oxygen storage component in the lower layer. Therefore, palladium is protected by the upper layer and thereby relieved from thermal deterioration and poisoning. In addition, palladium in the lower layer can be further restrained from being sintered and alloyed with catalytic precious metals in the upper layer, such as platinum and rhodium.
Further, since particulate aluminas generally have large specific surface area, palladium carried on the particulate alumina is highly dispersed. Therefore, even if the catalyst is exposed to high-temperature exhaust gas, palladium particles are less likely to coagulate and less likely to sinter, thereby lowering the reduction in the total surface area of the palladium particles. In addition, even if particles of the palladium-carried alumina or particles of palladium-carried oxygen storage component in the lower layer sinter each other, the loss of palladium particles due to burial in the sintered support material can be reduced, thereby restraining deterioration in catalytic conversion performance.
Furthermore, since palladium is carried on particles of the particulate oxygen storage component for releasing oxygen under rich exhaust gas conditions, palladium is controlled into an excellent oxidation condition by active oxygen supplied from particles of the particulate oxygen storage component. Specifically, the oxidation condition of palladium reversibly changes so that Pd←→PdO←→PdO2←→ . . . and the ratio of coexistence of these oxidation conditions is a factor having a significant effect on oxidation reactions of hydrocarbon and carbon monoxide. Since the ratio of coexistence of the oxidation conditions is made proper, the efficiencies of palladium converting hydrocarbon and carbon monoxide by oxidation can be enhanced over a long period of time.
A seventh solution of the invention is characterized in that in the fifth solution, the catalytic coating is formed of an upper layer and a lower layer, one of the plural kinds of catalytic precious metals is rhodium, and said rhodium is carried on particles of the particulate alumina and particles of the particulate oxygen storage component both of which are contained in the upper layer.
In the seventh solution, since the catalytic coating is formed of an upper layer and a lower layer and rhodium, which mainly contributes to NOx reduction conversion, is carried on particles of the particulate alumina and particulate oxygen storage component in the upper layer, rhodium in the upper layer can be restrained from being sintered and alloyed with the catalytic precious metal in the lower layer, such as palladium.
Further, since particulate aluminas generally have large specific surface area, rhodium carried on the particulate alumina is highly dispersed. Therefore, rhodium particles are less likely to coagulate and less likely to sinter, thereby lowering the reduction in the total surface area of the rhodium particles. In addition, even if particles of the rhodium-carried alumina or particles of rhodium-carried oxygen storage component in the upper layer sinter each other, the loss of rhodium particles due to burial in the sintered support material can be reduced, thereby restraining deterioration in catalytic conversion performance.
Furthermore, according to the above solution, the steam reforming reaction of hydrocarbon is promoted so that a large amount of active hydrogen is produced, thereby enhancing the efficiency of NOx reduction conversion of hydrogen. That is, rhodium carried on the oxygen storage component acts to promote the reduction reaction of NO+H2→N2+H2O using active hydrogen produced by the reactions of HC+H2O→CO+H2 (steam reforming reaction) and CO+H2O→CO2+H2 (water gas shift reaction). Note that in each reaction formula, description of factors are not given.
An eighth solution of the invention is characterized in that in the sixth solution, the particles of the particulate oxygen storage component carrying palladium are particles of alumina compounded with at least cerium.
In the eight solution, since the particulate oxygen storage component carrying palladium is made of alumina compounded with at least cerium, it has a more excellent thermal resistance than cerium dioxide and conventional Ce—Zr—Nd mixed oxides. Therefore, palladium can be controlled into an excellent oxidation condition over a longer period of time by active oxygen supplied from the particulate oxygen storage component. Further, since the particulate oxygen storage component contains alumina, it can maintain a large specific surface area over a long period of time, which ensures an excellent catalytic activity.
A ninth solution of the invention is characterized in that in the eighth solution, the alumina compounded with at least cerium is further compounded with one or more kinds of rare earth elements other than cerium and zirconium.
In the ninth solution, since the alumina compounded with cerium is further compounded with zirconium and one or more kinds of rare earth metals other than cerium, this particulate oxygen storage component is further improved in thermal resistance, thereby maintaining a large specific surface area over a longer period of time.
A tenth solution of the invention is directed to an exhaust gas purification catalyst in which a catalytic coating containing plural kinds of catalytic precious metals other than platinum, at least one kind of particulate alumina and at least one kind of particulate oxygen storage component is coated on a honeycomb support, wherein
the catalytic coating is formed of an upper layer and a lower layer,
each of particles of the at least one kind of particulate alumina and the at least one kind of particulate oxygen storage component carries only one of the plural kinds of catalytic precious metals,
the plural kinds of catalytic precious metals include palladium and rhodium,
said palladium is carried on particles of the particulate alumina and particles of the particulate oxygen storage component both of which are disposed in the lower layer,
said rhodium is carried on particles of the particulate alumina and particles of the particulate oxygen storage component both of which are disposed in the upper layer, and
the mass ratio Pd/Rh between said palladium and said rhodium is in the range from 4/1 to 7/1 both inclusive.
In the tenth solution, since each of particles of the at least one kind of particulate alumina and the at least one kind of particulate oxygen storage component carries only one of the plural kinds of catalytic precious metals, the different kinds of catalytic precious metals can be prevented from sintering and alloying together, like the fifth solution, thereby restraining deterioration in the catalytic conversion performance of the catalyst.
Further, although each of the upper and lower catalytic layers contains alumina particles and oxygen storage component particles, platinum is not carried on any alumina particles. Therefore, the oxygen storage/release capacity of the oxygen storage component particles is not restricted by platinum-carried alumina particles, so that the catalytic coating increases the amount of oxygen storage/release as compared with the conventional catalytic coating containing platinum-carried alumina particles (in this respect, further details will be given later with reference to evaluation tests).
In addition, in the upper layer, the alumina particles carrying rhodium promote oxygen storage/release of the oxygen storage component particles, thereby enhancing the activity of the catalyst. Also in this respect, further details will be given later with reference to the evaluation tests. This is believed to be as follows.
When the A/F ratio of automobile exhaust gas is lean, rhodium carried on alumina particles is oxidized. That is, active oxygen atoms exist on the surfaces of rhodium particles. When the A/F ratio of the exhaust gas becomes rich, the CO concentration in the exhaust gas becomes high.
In this connection, rhodium carried on alumina particles exhibits high CO oxidation capacity at relatively high exhaust gas temperatures from 300° C., at which oxygen release from oxygen storage component particles becomes active, to 500° C. Therefore, when the CO concentration in the exhaust gas becomes high, CO in the exhaust gas is oxidized by the action of active oxygen binding to rhodium. In other words, the reaction of CO+O→CO2 occurs on each rhodium particle so that the oxygen atom on the rhodium particle is removed.
Since rhodium, however, is by nature likely to bind to oxygen, it can be supposed that when oxygen is removed from a rhodium particle by the reaction with CO, the rhodium particle takes another oxygen atom from its ambient atmosphere. That is, when oxygen atoms are removed from rhodium particles, oxygen atoms are actively released from oxygen storage component particles in order to compensate for the loss of oxygen atoms on the rhodium particles. As a result, the catalyst exhibits high activity, i.e., enhances the performance of converting HC and CO in exhaust gas by oxidation.
Further, rhodium carried on oxygen storage component particles reaches near to metal form (a simple substance) by the action of the oxygen storage component particles. Therefore, the existence of rhodium in metal form smoothes oxygen storage/release of the oxygen storage component particles, thereby enhancing the activity of the catalyst. In addition, rhodium in metal form acts effectively on reduction of NOx in exhaust gas. This holds true for both the upper layer and the lower layer.
On the other hand, for platinum-carried alumina particles, almost all of the platinum particles are in metal form. Therefore, even under rich exhaust gas conditions, CO in exhaust gas is simply adsorbed to platinum. Specifically, since no oxygen atom binds to these platinum particles, the reaction of CO+O→CO2 is less likely to occur. By contrast, platinum adsorbs CO in exhaust gas to restrict oxygen release of the oxygen storage component particles. Thus, even if the oxygen storage component particles release oxygen, the released oxygen is not used for oxidation of CO so much. Therefore, the oxygen concentration around the oxygen storage component particles becomes high so that oxygen becomes less likely to be released from the oxygen storage component particles.
Further, in this solution, since rhodium and palladium are separately disposed in the upper layer and the lower layer, rhodium and palladium are surely prevented from being sintered or alloyed with each other.
Furthermore, since the mass ratio Pd/Rh between rhodium and palladium is in the range from 4/1 to 7/1 both inclusive, this is advantageous in improvement of low-temperature activity of the catalyst while providing an excellent high-temperature activity thereof.
An eleventh solution of the invention is directed to an exhaust gas purification catalyst in which a catalytic coating containing at least one kind of catalytic precious metal, at least one kind of particulate alumina and at least one kind of particulate oxygen storage component is coated on a honeycomb support, wherein
the catalytic coating contains rhodium as the at least one kind of catalytic precious metal,
said rhodium is carried on one said kind of particulate alumina and one said kind of particulate oxygen storage component,
the rhodium-carried particulate alumina has a larger specific surface area than the rhodium-carried particulate oxygen storage component, and
the one kind of particulate oxygen storage component carries a larger amount of rhodium per unit specific surface area than the one kind of particulate alumina.
In the eleventh solution, since a larger amount of rhodium per unit specific surface area is carried on the particulate oxygen storage component than on the particulate alumina, the steam reforming reaction of hydrocarbon is promoted even under rich exhaust gas conditions under which oxygen is released from the particulate oxygen storage component. As a result, a large amount of active hydrogen is produced and the produced hydrogen enhances the efficiency of NOx reduction conversion.
Further, when the A/F ratio is stoichiometric, Rh carried on the oxygen storage component particles works well on NOx conversion. At engine acceleration at which the A/F ratio becomes richer, Rh carried on the alumina particles works well on NOx conversion. Specifically, in the stoichiometric A/F ratio, variations in A/F are absorbed by the oxygen storage/release capacity of the oxygen storage component particles so that Rh effectively converts NOx. On the other hand, at engine acceleration at which the A/F ratio becomes richer, although Rh carried on the oxygen storage component particles promotes the steam reforming reaction, the surfaces of Rh particles carried on the oxygen storage component particles fall into excess oxygen condition by oxygen released from the oxygen storage component particles so that the catalytic conversion performance is deteriorated. Since, however, the alumina particles have no oxygen storage/release capacity, the surfaces of Rh particles carried on the alumina particles never fall into excess oxygen condition, which provides effective NOx conversion. Since Rh is thus carried on both the oxygen storage component particles and the alumina particles, NOx conversion performance can be enhanced.
A twelfth solution of the invention is characterized in that in the eleventh solution, the catalytic coating contains palladium and rhodium as said catalytic precious metals, the catalytic coating is formed of an upper layer and a lower layer, said palladium is disposed in the lower layer, and said rhodium is disposed in the upper layer.
In the twelfth solution, palladium is carried in the lower layer. Therefore, when a particulate oxygen storage component having a high oxygen storage capacity is disposed in the upper layer, the A/F ratio of exhaust gas flowing from upstream to downstream side and from upper to lower layer of the catalyst is controlled to be suitable for concurrent catalytic conversion of HC, CO and NOx. As a result, exhaust gas purification performance due to palladium in the lower layer is improved. Further, palladium in the lower layer is prevented from being sintered and alloyed with rhodium in the upper layer. Since palladium is protected by the upper layer, it can be prevented from being poisoned by S (sulfur) and P (phosphorus). Furthermore, since rhodium is carried on particles of the particulate oxygen storage component and particulate alumina in the upper layer, this enhances the reactivity of the oxygen storage component particles and the steam reforming reactivity, which can promote NOx reduction reaction.
A thirteenth solution of the invention is characterized in that in the eleventh or twelfth solution, the catalytic coating further contains platinum as said catalytic precious metal, and said platinum is carried on at least one of another kind of particulate alumina carrying neither palladium nor rhodium and another kind of particulate oxygen storage component carrying neither palladium nor rhodium.
In the thirteenth solution, since platinum is carried, away from palladium and rhodium, on support material or materials, each of the catalytic precious metals is highly dispersed so that sintering and alloying can be less likely to occur between these different kinds of catalytic precious metals.
A fourteenth solution of the invention is directed to an exhaust gas purification catalyst in which a catalytic coating containing a particulate oxygen storage component is coated on a honeycomb support, said particulate oxygen storage component containing cerium, zirconium and one or more rare earth elements other than cerium, wherein
the particulate oxygen storage component comprise different kinds of particulate oxygen storage components having different mass ratios, each of the mass ratios being expressed by ZrO2/(CeO2+ZrO2+one or more rare earth element oxides),
the catalytic coating is formed of an upper layer and a lower layer,
the lower layer contains said particulate oxygen storage component of the kind having a mass ratio of 70 mass % or less, and
the upper layer contains said particulate oxygen storage component of the kind having a mass ratio of more than 70 mass %.
In the fourteenth solution, the particulate oxygen storage component having a mass ratio of 70 mass % or less is contained not in the upper layer but in the lower layer which does not face the exhaust gas channel and is not so much thermally severe as the upper layer, and the particulate oxygen storage component having a larger mass ratio than the particulate oxygen storage component in the lower layer is contained in the upper layer exposed to high-temperature exhaust gas. Therefore, the catalytic conversion performance of the catalyst is improved while the thermal resistance of the upper layer and the oxygen storage capacity of the lower layer are both improved, which enables the catalyst to maintain high catalytic conversion performance over a long period of time.
A fifteenth solution of the invention is characterized in that in the fourteenth solution, the lower layer contains cerium dioxide and at least two said kinds of particulate oxygen storage components having different mass ratios.
In the fifteenth solution, oxygen can be stored and released over a wide temperature range. This provides extended A/F window to supply active oxygen to the upper layer as well as the lower layer and cause the active oxygen to involve in the catalytic reaction of catalytic precious metal, thereby improving the catalytic conversion activity.
A sixteenth solution of the invention is characterized in that in the fourteenth or fifteenth solution, one kind of catalytic precious metal is carried on the particulate oxygen storage component contained in the upper layer, and another kind of catalytic precious metal is carried on the particulate oxygen storage component contained in the lower layer.
In the sixteenth solution, two different kinds of catalytic precious metals are carried on the particulate oxygen storage components contained in the upper and lower catalytic layers, respectively. Therefore, the catalytic precious metals are highly dispersed so that sintering and alloying can be less likely to occur between these different kinds of catalytic precious metals. This improves the thermal resistance of the catalyst and enables the catalyst to maintain high catalytic conversion performance.
A seventeenth solution of the invention is characterized in that in any one of the fourteenth to sixteenth solutions, at least one of the different kinds of particulate oxygen storage components is compounded with alumina.
In the seventeenth solution, the specific surface area of the at least one particulate oxygen storage component can be increased to enhance the dispersity of catalytic precious metal carried thereon, thereby providing a particulate oxygen storage component having excellent thermal resistance.
An eighteenth solution of the invention is characterized in that in the seventeenth solution, said particulate oxygen storage component compounded with alumina is contained in the lower layer together with particulate alumina having a different specific surface area from said particulate oxygen storage component, and palladium is carried on said particulate oxygen storage component and said particulate alumina which have different specific surface areas.
In the eighteenth solution, since palladium is distributively carried on the particulate alumina and the particulate oxygen storage component, this increases the number of active sites for palladium and provides high activity particularly for conversion of hydrocarbon and carbon monoxide. Further, palladium can be controlled into an excellent oxidation condition by active oxygen supplied from the particulate oxygen storage component, thereby enhancing the efficiencies of palladium converting hydrocarbon and carbon monoxide by oxidation over a long period of time.
Hereinafter, further details of the present invention will be described with reference to its preferred embodiments.
[Structure of Three-Way Catalyst]
As shown in
As shown in
The catalytic coating 11b is composed of two layers; a lower layer containing the first alumina carrying Pd, the Ce—Zr—Nd mixed oxide and cerium dioxide; and an upper layer containing the second alumina carrying Pt, the third alumina carrying Rh and the Ce—Zr—Nd mixed oxide carrying Rh.
In another example of the catalytic coating 11b shown in
The first alumina, second alumina, third alumina, two kinds of Ce—Zr—Nd mixed oxides, Ce—Zr—La—Y-alumina compound and cerium dioxide are formed in particles.
The use of zirconium dioxide as a binder is for the purpose of improving the thermal resistance of the catalytic coating 11b.
[Preparation of Three-Way Catalyst]
The preparation of the three-way catalyst 11 is generally carried out in the following manner. The description thereof will be given taking as an example the case where the catalytic coating 11b is composed of an upper layer and a lower layer and the lower layer contains a Pd-carried Ce—Zr—La—Y-alumina compound as shown in
<Formation of Lower Catalytic Layer>
A Pd-carried first alumina is obtained by dropping a water solution of palladium nitrate on powder of active alumina to which 4 mass % of lanthanum (La) is added (first alumina) and drying and calcining the active alumina powder at 500° C. The Pd-carried first alumina, cerium dioxide, a Ce—Zr—Nd mixed oxide, a Pd-carried Ce—Zr—La—Y-alumina compound (whose preparation method will be described later) and a binder are mixed and water is also added and mixed by stirring with a disperser to obtain a slurry. A honeycomb support 11a made of cordierite is immersed in the slurry and then picked up and surplus slurry is removed by air blow. This process is repeated until the support 11a is coated with a predetermined amount of slurry. Thereafter, the honeycomb support 11a is heated from normal temperature up to 500° C. at a constant rate of temperature increase in 1.5 hours. The honeycomb support 11a is then dried and calcined by keeping it at 500° C. for two hours, resulting in the formation of a lower catalytic layer.
<Formation of Upper Catalytic Layer>
A Pt-carried second alumina is obtained by dropping a water solution of diamminedinitro platinum nitrate on powder of active alumina to which 4 mass % of La is added (second alumina) and drying and calcining the active alumina powder at 500° C. Further, a Rh-carried third alumina is obtained by dropping a water solution of rhodium nitrate on powder of active alumina to which 4 mass % of La is added (third alumina), each active alumina particle coated with 10 mass % of zirconium dioxide, and drying and calcining the active alumina powder at 500° C. Furthermore, a Rh-carried Ce—Zr—Nd mixed oxide is obtained by dropping a water solution of rhodium nitrate on a Ce—Zr—Nd mixed oxide and drying and calcining the Ce—Zr—Nd mixed oxide at 500° C. The Pt-carried second alumina, the Rh-carried third alumina, the Rh-carried Ce—Zr—Nd mixed oxide and a binder are mixed and water is also added and mixed by stirring with a disperser to obtain a slurry. The cordierite honeycomb support 11a having the lower catalytic layer formed as above is immersed in the slurry and then picked up and surplus slurry is removed by air blow. This process is repeated until the support 11a is coated with a predetermined amount of slurry. Thereafter, the honeycomb support 11a is heated from normal temperature up to 500° C. at a constant rate of temperature increase in 1.5 hours. The honeycomb support 11a is then dried and calcined by keeping it at 500° C. for two hours, resulting in the formation of an upper catalytic layer.
<Preparation of Pd-Carried Compound>
A Pd-carried Ce—Zr—La—Y-alumina compound, which will be contained in the lower catalytic layer, can be prepared by either hydrothermal synthesis using an autoclave or coprecipitation using acid-alkali neutralization. The preparation will be explained here with reference to the coprecipitation method. First, nitrate salts of Ce, Zr, La, Y (yttrium) and Al (aluminum) are mixed and water is further added and stirred at room temperature for about an hour. Next, the nitrate salt mixed solution and an alkaline solution (preferably, 28% ammonia water) are neutralized by mixing them at any temperature between room temperature and 80° C. When neutralization is carried out using a disperser, its number of revolutions is set at between about 4000 rpm and about 6000 rpm. Further, the rate of addition of the nitrate salt mixed solution is preferably about 53 mL/min and the rate of addition of the alkaline solution is preferably about 3 mL/min.
The white-turbid solution obtained by the above neutralization is left stand for one day and night to produce a precipitated cake. The precipitated cake is centrifuged by a centrifugal separator and then rinsed with water. The water-rinsed cake is dried at about 150° C., dried and calcined by keeping it at about 600° C. for about five hours and then keeping it at about 500° C. for two hours, then pulverized. Thereafter, the obtained powder is loaded with a solution of palladium nitrate and then evaporated to dryness. The resultant dried product is pulverized and then calcined by superheating to obtain a Pd-carried Ce—Zr—La—Y-alumina compound.
The preferable composition in mass ratio is, when components are accounted for in the form of their oxides, CeO2:ZrO2:La2O3:Y2O3:Al2O3=11.7:7.7:1.0:0.4:79.2, for example. In this case, the mass ratio expressed by ZrO2/(CeO2+ZrO2+La2O3+Y2O3) is 37 mass %.
<Oxygen Storage Component Structure and Alumina Solid State Properties>
Each of cerium oxide, the two types of Ce—Zr—Nd mixed oxides and the Ce—Zr—La—Y-alumina compound functions as an oxygen storage component that stores oxygen under lean exhaust gas conditions and releases oxygen under rich exhaust gas conditions. The Ce—Zr—Nd mixed oxides have a fluorite crystal structure as shown in
4 mass % of La is added to each of the first to third aluminas in order to thermally stabilize them. The third alumina is obtained by coating the surface of the second alumina with 10 mass % of zirconium dioxide, which prevents solid solution of Rh in alumina in a high-temperature atmosphere. The first to third aluminas and the Ce—Zr—La—Y-alumina compound have different micropore shapes owing to different preparation conditions and therefore have different specific surface areas and different surface basicities.
Specifically,
On the other hand, the surface condition of each alumina is indicated by a basicity when it has not yet been aged, i.e., when it is fresh. The Pd-carried first alumina has the highest surface basicity (i.e., has the greatest number of sites for adsorbing negatively charged molecules) and the Pd-carried Ce—Zr—La—Y-alumina compound, the Rh-carried third alumina and the Pt-carried second alumina have decreasing surface basicities in this order.
The surface basicity was measured by Fourier Transform Infrared Spectroscopy (FTIR). Specifically, the above kinds of aluminas when fresh were in-situ compared in the peak area of 1245 cm−1 to 1289 cm−1 with each other in a gaseous atmosphere of 500 ppm NO and 10% O2. The measurement results are shown in
Three-way catalysts having the following compositions were produced according to the above-mentioned preparation method. The carried amount of each catalytic precious metal and the carried amount of each support material are indicated by amount per 1 L of honeycomb support.
A three-way catalyst has two catalytic layers, upper and lower, as shown in
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.7 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Pt/second alumina: carried amount of 25.5 g/L (Pt: carried amount of 0.08 g/L)
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.1 g/L)
Rh/third alumina: carried amount of 17.0 g/L (Rh: carried amount of 0.04 g/L)
zirconia binder: carried amount of 11.0 g/L
The mass ratio expressed by ZrO2/(CeO2+ZrO2+Nd2O3) in the Ce—Zr—Nd mixed oxide is 80 mass % for the upper layer and 67 mass % for the lower layer.
In the three-way catalyst as in Example 1, the lower catalytic layer further contains a Pd-carried Ce—Zr—La—Y-alumina compound at a carried amount of 25.0 g/L (of which the carried amount of Pd is 0.35 g/L) and the other components are the same as those in Example 1 (see
As shown in
Further, the amounts of Rh carried per unit specific surface area (SSA) on the third alumina and the Ce—Zr—Nd mixed oxide in the upper layer are C=0.04/78 and D=0.10/17, respectively, and therefore the relation C<D holds.
As shown in
A three-way catalyst of this example is the same as that of Example 2 except that the mass ratio of Ce—Zr—Nd mixed oxide in the upper layer is 72 mass % (see
In the same three-way catalyst as in Example 1, each of the Pd-carried first alumina in the lower layer and the Rh-carried third alumina in the upper layer is changed to the same alumina as the second alumina and the other components are the same as those of Example 1 (see
This Comparative Example 1 is an example for the purpose of evaluating how the specific surface area or the surface basicity of alumina has an influence on the activity and thermal resistance of the catalyst in comparison with Example 1 but is also an example included in the scope of this invention and according to claims 5 and 14, for example.
In the three-way catalyst as in Example 1, each of the Pt-carried second alumina in the upper layer and the Rh-carried third alumina in the upper layer is changed to the same alumina as the first alumina and the other components are the same as those of Example 1 (see
This Comparative Example 2 is an example for the purpose of evaluating how the specific surface area or the surface basicity of alumina has an influence on the activity and thermal resistance of the catalyst in comparison with Example 1 but is also an example included in the scope of this invention and according to claims 5 and 14, for example.
As shown in
This Comparative Example 3 is an example for the purpose of evaluating how different the activity and thermal resistance of the catalyst is between the case of carrying a single kind of catalytic precious metal on a single kind of support material and the case of carrying plural kinds of catalytic precious metals on a single kind of support material in comparison with Example 2 but is also an example included in the scope of this invention and according to claim 14, for example.
In the three-way catalyst as in Example 2, the ratio of the amount of Pd carried per unit mass in the first alumina in the lower layer to that in the Ce—Zr—La—Y-alumina compound in the lower layer is changed to 1 to 2 and the other components are the same as those of Example 2 (see
This Comparative Example 4 is an example for the purpose of evaluating how the amount of Pd carried per unit mass on each support material has an influence on the activity and thermal resistance of the catalyst in comparison with Example 2 but is also an example included in the scope of this invention and according to claims 1 and 5, for example.
In the three-way catalyst as in Example 2, the amount of Rh carried per unit specific surface area on the third alumina in the upper layer is equal to that on the Ce—Zr—Nd mixed oxide in the upper layer and the other components are the same as those of Example 2 (see
This Comparative Example 5 is an example for the purpose of evaluating how the amount of Rh carried per unit specific surface area on each support material has an influence on the activity and thermal resistance of the catalyst in comparison with Example 2 but is also an example included in the scope of this invention and according to claims 1 and 5, for example.
In the three-way catalyst as in Example 2, the mass ratio expressed by ZrO2/(CeO2+ZrO2+Nd2O3) in the Ce—Zr—Nd mixed oxide is 70 mass % for both the upper and lower layers and the other components are the same as those of Example 2 (see
This Comparative Example 6 is an example for the purpose of evaluating how the above mass ratio in each of the Ce—Zr—Nd mixed oxides has an influence on the activity and thermal resistance of the catalyst in comparison with Example 2 but is also an example included in the scope of this invention and according to claims 1 and 5, for example.
In the three-way catalyst as in Example 2, the mass ratio expressed by ZrO2/(CeO2+ZrO2+Nd2O3) in the Ce—Zr—Nd mixed oxide is 67 mass % for the upper layer and 80 mass % for the lower layer and the other components are the same as those of Example 2 (see
This Comparative Example 7 is, like Comparative Example 6, an example included in the scope of this invention and according to claims 1 and 5, for example.
In the three-way catalyst as in Example 2, the mass ratio expressed by ZrO2/(CeO2+ZrO2+Nd2O3) in the Ce—Zr—Nd mixed oxide in the lower layer is 72 mass % and the other components are the same as those of Example 2 (see
This Comparative Example 8 is, like Comparative Example 6, an example included in the scope of this invention and according to claims 1 and 5, for example.
In the three-way catalyst as in Example 2, Pd in the lower layer is carried only on the first alumina and the other components are the same as those of Example 2 (see
This Comparative Example 9 is an example for the purpose of evaluating how different the activity and thermal resistance of the catalyst is between the case of carrying Pd on a single kind of support material and the case of distributively carrying Pd on plural kinds of support materials in comparison with Example 2 but is also an example included in the scope of this invention and according to claim 1, for example.
<Evaluation Tests>
The catalyst of each of Examples 1 to 4 and Comparative examples 1 to 9 was aged by keeping it at 1100° C. in an atmosphere of 2% of O2 and 10% of H2O for 24 hours and then measured in terms of T50 (° C.) and C500 (%), which are indices for conversion performance of HC, CO and NOx, by a rig test.
The rig test was implemented by cutting out each aged catalyst in a cylindrical shape of 2.54 cm diameter and 5 cm length and attaching the cylindrical cut piece to a fixed-bed flow reactor. The simulated exhaust gas (mainstream gas+gas for changing the A/F ratio) used had an A/F ratio of 14.7±0.9 and the flow rate of the simulated exhaust gas into the catalyst was set at 25 L/min. Specifically, a mainstream gas was allowed to flow constantly at an A/F ratio of 14.7 and a predetermined amount of gas for changing the A/F ratio was added in pulses at a rate of 1 Hz, so that the A/F ratio was forcedly oscillated within the range of ±0.9. O2 was used as the gas for changing the A/F ratio when the A/F ratio was oscillated to a leaner value (15.6), while a mixture of H2 and CO was used as the gas for changing the A/F ratio when the A/F ratio was oscillated to a richer value (13.8). The composition of the mainstream gas having an A/F ratio of 14.7 is as follows.
-Mainstream Gas-
CO2:13.9%, O2:0.6%, CO:0.6%, H2:0.2%, C3H6:0.056%, NO:0.1%, H2O:10% and N2: the rest
T50 (° C.) is the gas temperature at the entrance of each catalyst when the concentration of each exhaust gas component (HC, CO and NOx) detected downstream of the catalyst reaches half of that of the corresponding exhaust gas component flowing into the catalyst (when the conversion efficiency reaches 50%) after the temperature of the simulated exhaust gas is gradually increased (i.e., the light-off temperature), and indicates the low-temperature catalytic conversion performance of the catalyst. C500 (%) is the catalytic conversion efficiency of each exhaust gas component (HC, CO and NOx) when the simulated exhaust gas temperature at the catalyst entrance is 500° C. and indicates the high-temperature catalytic conversion performance of the catalyst. The results from tests for T50 (° C.) and the results from tests for C500 (%) are shown in
<Influences of the Specific Surface Area and the Surface Basicity of Alumina and Effects of Ce—Zr—La—Y-Alumina Compound>
The specific surface areas and surface basicities of various kinds of support materials in Examples 1 and 2 and Comparative Examples 1 and 2 are described in
For Comparative Example 1, all kinds of catalytic precious metals are individually carried on particles of the second alumina which has the second largest specific surface area and the lowest basicity. For Comparative Example 2, all kinds of catalytic precious metals are individually carried on particles of the first alumina which has the largest specific surface area and the highest basicity.
The evaluation results in
In the above case, since the evaluation results indicates that Comparative Example 2>Comparative Example 1, it can be considered that as the surface basicity of Pd-carried alumina is higher, Pd can be more easily controlled into a better oxidation condition and therefore the efficiency of Pd converting HC and CO by oxidation can be enhanced over a longer period of time.
In addition, it can be considered that as the surface basicity of Pt-carried alumina is lower, Pt can be better prevented from being oxidized and therefore can maintain its catalytic activity for a longer period of time.
For Examples 1 and 2, since the specific surface area of the Pd-carried first alumina in the lower layer is larger than those of the Pt-carried second alumina and the Rh-carried third alumina in the upper layer (see
In Comparative Examples 1 and 2, the NOx conversion efficiency is particularly reduced to a great degree as compared with Examples 1 and 2 though HC and CO conversion efficiencies are also reduced. One of the reasons is probably that since, in Comparative Examples 1 and 2, the surfaces of the Rh-carried alumina particles (first and second aluminas) were not coated with zirconium dioxide unlike the third alumina, Rh was exposed to high temperature to come into solid solution in alumina and become deactivated.
Next, a description will be made of the effects of employment of a Ce—Zr—La—Y-alumina compound as an oxygen storage component in comparison between Examples 1 and 2. The comparison shows that Example 2 provided a better result than Example 1. The reason is believed to be as follows.
In Example 2, Pd is carried on the oxygen storage component in which at least cerium and alumina are compounded to release oxygen under rich exhaust gas conditions (Ce—Zr—La—Y-alumina compound). Therefore, Pd is controlled into an excellent oxidation condition by active oxygen supplied from the oxygen storage component. Specifically, the oxidation condition of Pd reversibly changes so that Pd←→PdO←→PdO2←→ . . . and the ratio of coexistence of such different oxidation conditions is made proper. This enhances the efficiencies of Pd converting HC and CO by oxidation over a long period of time.
Since the Pd-carried Ce—Zr—La—Y-alumina compound (oxygen storage component) is more excellent in thermal resistance than cerium dioxide and Ce—Zr—Nd mixed oxide, Pd can be controlled into an excellent oxidation condition over a longer period of time by active oxygen supplied from the oxygen storage component. Further, since the oxygen storage component contains alumina, it can maintain a high specific surface area over a long period of time, thereby ensuring excellent catalytic activity of Pd.
Further, since the Ce—Zr—La—Y-alumina compound (oxygen storage component) is produced by compounding Ce, Zr, La (rare earth element excluding Ce) and Y, the oxygen storage component can further improve its thermal resistance and can maintain its large specific surface area over a longer period of time.
<Influences of Different Kinds of Catalytic Precious Metals Carried on Different Support Materials and Differences Between Monolayer Catalytic Coating and Double-Layer Catalytic Coating Structure>
The influences of different kinds of catalytic precious metals carried on different support materials will be examined with reference to the relation between Examples 2 and 3 and Comparative Example 3. In terms of all of HC, CO and NOx, Examples 2 and 3 were more excellent in T50 (° C.) and C500 (%) than Comparative Example 3. The reason can be considered as follows. In Examples 2 and 3, since only one of the plural kinds of catalytic precious metals, Pt, Rh and Pd, is carried on each of aluminas and oxygen storage components, this prevents various kinds of catalytic precious metals from sintering and alloying together, thereby significantly restraining deterioration in catalytic conversion performance. On the other hand, in Comparative Example 3, since Rh and Pd of the plural kinds of catalytic precious metals, Pt, Rh and Pd, are carried together on each of the third alumina and the oxygen storage component in the upper layer and on each of the first alumina and the oxygen storage component in the lower layer, it can be considered that different kinds of catalytic precious metals, i.e., Rh and Pd, sinter and alloy together by aging, which significantly deteriorates the catalytic conversion performance. Particularly, Comparative example 3 exhibited a remarkable deterioration in NOx conversion efficiency. This is probably because the catalytic activity of Rh mainly contributing to NOx reduction conversion has itself been lost owing to alloying of Rh and Pd.
In addition, in Examples 2 and 3, Rh and Pd of the plural kinds of catalytic precious metals, Pt, Rh and Pd, are each carried on both one alumina and one oxygen storage component. Therefore, the catalytic precious metals Rh and Pd are distributively carried on more kinds of aluminas and more kinds of oxygen storage components than Comparative Example 3. In other words, the catalytic precious metals Rh and Pd are increased in dispersity (become more dispersive). As a result, particles of catalytic precious metals Rh and Pd are less likely to coagulate and therefore less likely to sinter, which reduces the degree of reduction of the total surface areas of catalytic precious metals Rh and Pd. Further, even if alumina particles or oxygen storage component particles sinter, the loss of particles of precious metals Rh and Pd is reduced. This also reduces the degree of reduction of the total surface areas of catalytic precious metals Rh and Pd.
In the above manners, Examples 2 and 3 prevent different kinds of catalytic precious metals Pt, Rh and Pd from sintering and alloying together and restrain particles of each of catalytic precious metals Pt, Rh and Pd from sintering by increasing the dispersity of each precious metal. Thus, the catalyst can be further enhanced in thermal resistance and can maintain its catalytic conversion performance over a longer period of time.
Further, in Examples 2 and 3, since alumina has a larger specific surface area than, for example, oxygen storage components, catalytic precious metals Pd, Pt and Rh individually carried on the first to third aluminas are put into higher dispersion than in Comparative Example 3. Therefore, particles of catalytic precious metal Pd, Pt and Rh are less likely to coagulate and therefore less likely to sinter, which reduces the degree of reduction of the total surface area of each of catalytic precious metals Pd, Pt and Rh. In addition, even if sintering occurs between particles of each alumina or particles of each oxygen storage component on which one of catalytic precious metals Pd, Pt and Rh is carried, the degree of loss of particles of precious metals Pd, Pt and Rh is reduced. This reduces deterioration in the catalytic conversion performance of each of catalytic precious metals Pd, Pt and Rh.
Next, differences between monolayer catalytic coating and double-layer catalytic coating structure will be examined. Example 2 having a catalytic coating of double-layer structure was more excellent in T50 and C500 than Example 3 having a monolayer catalytic coating. The reason is believed to be as follows. In Example 2, since the catalytic coating has a double-layer structure of upper and lower layers and a Rh-carried oxygen storage component of high oxygen storage capacity is disposed in the upper layer, variations in A/F ratio are absorbed during flow of exhaust gas from upstream to downstream side and from upper to lower layer of the catalyst. As a result, the Pd support materials (i.e., alumina and oxygen storage component) in the lower layer increase their catalytic conversion performance, thereby improving the catalyst performance. In addition, the following reason is also conceivable. In Example 2, the catalytic coating has a double-layer structure of upper and lower layers, Pd is carried in the lower layer and Pt and Rh are carried in the upper layer separately from Pd. This further prevents Pd in the lower layer from being sintered and alloyed with catalytic precious metals in the upper layer, particularly Rh. Further, since Pd is protected by the upper layer, it can be prevented from being poisoned by S and P.
<Effects of the Ratio of Amount of Pd Carried and Effects of the Ratio of Amount of Rh Carried>
Effects of the ratio of amount of Pd carried in the lower layer will be described in comparison between Example 2 and Comparative Example 4. The amount A of Pd carried per unit mass on the first alumina is substantially equal to the amount B of Pd carried per unit mass on the Ce—Zr—La—Y-alumina compound in Example 2 as shown in
From the above results, it can be said that since the amounts A and B of Pd carried are substantially equal in Example 2, that is, Pd is evenly carried on the first alumina and the Ce—Zr—La—Y-alumina compound, both having relatively high specific surface area and thermal resistance, the number of active sites for Pd is increased to provide high conversion activities of HC and CO.
Next, in terms of NOx, Example 2 in which a larger amount of Rh is carried per unit specific surface area on the Ce—Zr—Nd mixed oxide for releasing oxygen under rich conditions than on the third alumina is better in T50 and C500 than Comparative Example 5. The reason is believed to be as follows.
First, under rich conditions, since active oxygen is supplied from the Ce—Zr—Nd mixed oxide, Rh carried on the Ce—Zr—Nd mixed oxide is less likely to be directly involved in reduction reaction of NOx. Therefore, it can be considered that in this case, Rh acts more intensively to promote the steam reforming reaction of HC so that the degree of production of active hydrogen is increased, thereby enhancing the efficiency of NOx reduction conversion of hydrogen. That is, Rh carried on the Ce—Zr—Nd mixed oxide acts to promote the reduction reaction of NO+H2→N2+H2O using active hydrogen produced by the reactions of HC+H2O CO→H2 and CO+H2O→CO2+H2.
Further, in the stoichiometric A/F ratio, Rh carried on the oxygen storage component (the Ce—Zr—Nd mixed oxide) works well on NOx conversion. At engine acceleration at which the A/F ratio becomes richer, Rh carried on alumina (the third alumina) works well on NOx conversion. Specifically, in the stoichiometric A/F ratio, variations in A/F are absorbed by the oxygen storage/release capacity of the oxygen storage component (the Ce—Zr—Nd mixed oxide) so that Rh effectively converts NOx. On the other hand, at engine acceleration at which the A/F ratio becomes richer, the surfaces of Rh particles carried on the oxygen storage component (the Ce—Zr—Nd mixed oxide) fall into excess oxygen condition by released oxygen so that the catalytic conversion performance is deteriorated. Since, however, alumina (the third alumina) has no oxygen storage/release capacity, the surfaces of Rh particles carried on alumina (the third alumina) never fall into excess oxygen condition, which provides effective NOx conversion. Since Rh is thus carried on both the oxygen storage component (the Ce—Zr—Nd mixed oxide) and alumina (the third alumina), NOx conversion performance can be enhanced.
Next, NOx conversion in rich and stoichiometric A/F ratios will be considered with reference to experimental examples.
(Catalyst Under Test)
(Test Evaluation Method)
Each of the catalysts in Experimental Examples 1 to 3 was aged at 1100° C. in the normal atmosphere for 24 hours and then measured in terms of NOx conversion efficiency under conditions that simulated gas was allowed to flow through each catalyst using a test device shown in
(Test Evaluation Results)
The results are shown in
The reason of the results in the stoichiometric A/F ratio is believed to be as follows. In Experimental Example 2, variations in air-fuel ratio (A/F) are absorbed by a high oxygen storage/release capacity of the Ce—Zr—Nd mixed oxide, so that Rh effectively exhibits its NOx conversion performance. On the other hand, in Experimental Examples 1 and 3, since ZrO2-coated third alumina or the third alumina has no oxygen storage/release capacity, NOx conversion performance is reduced as compared with Experimental Example 2.
The reason of the results in the rich A/F ratio is believed to be as follows. In Experimental Example 2, oxygen is released through the surfaces of Rh particles by the oxygen release capacity of the Ce—Zr—Nd mixed oxide, so that the surfaces of Rh particles fall into excess oxygen condition to make the adsorption and conversion of NOx difficult. On the other hand, in Experimental Examples 1 and 3, since ZrO2-coated third alumina or the third alumina has no oxygen storage/release capacity, this avoids production of oxygen as in Experimental Example 2 and in turn ill effects of such oxygen on the NOx conversion performance.
Therefore, in the catalyst of Example 2 including elements of both the Experimental Examples 1 and 2, a high NOx conversion performance is provided by the Rh/Ce—Zr—Nd mixed oxide in the stoichiometric A/F ratio and the deterioration in NOx conversion performance due to Rh/Ce—Zr—Nd mixed oxide is avoided by Rh/ZrO2-coated third alumina. As a result of combination of these effects, a high NOx conversion performance can be provided under a wide range of operating conditions.
A comparison between Experimental Examples 1 and 3 shows that Experimental Example 1 has a higher NOx conversion efficiency in both the stoichiometric and rich A/F ratios. Therefore, it is preferable that Rh-carried third alumina is coated with ZrO2.
Next, the amount of Rh carried will be examined. The third alumina has an extremely large specific surface area after aged as compared with the Ce—Zr—Nd mixed oxide. Therefore, in order that the third alumina and the Ce—Zr—Nd mixed oxide have the same amount of Rh carried per unit specific surface area, the amount of Rh carried on the third alumina will be increased or the amount of Rh carried on the Ce—Zr—Nd mixed oxide will be decreased.
In the former case, that is, if the amount of Rh carried on the third alumina is increased, the required amount of Rh is increased, thereby providing cost up. In addition, even if the third alumina is coated with ZrO2, some of Rh particles are brought into solid solution in the third alumina, thereby deteriorating catalytic conversion activity. On the other hand, in the latter case, that is, if the amount of Rh carried on the Ce—Zr—Nd mixed oxide is decreased, this makes it difficult to extend the A/F window under rich conditions, thereby not providing an expected improvement in catalytic conversion performance.
Therefore, if the amount D of Rh carried per unit specific surface area on the Ce—Zr—Nd mixed oxide is larger than the amount C of Rh carried per unit specific surface area on the third alumina, for example, as shown in
In particular, since Rh is carried on the Ce—Zr—Nd mixed oxide and the third alumina in the upper layer, this enhances the reactivity of the oxygen storage component (Ce—Zr—Nd mixed oxide) and the steam reforming reactivity, which can promote the reduction reaction of nitrogen oxides (NOx).
Further, since Pt is carried on the second alumina on which neither Pd nor Rh are carried, Pt is carried on the support material in a manner separated from Pd and Rh. This provides high dispersion of each catalytic precious metal and makes it difficult to cause sintering and alloying between these different kinds of catalytic precious metals.
<Influences of ZrO2 Mass Ratio in Ce—Zr—Nd Mixed Oxide>
Next, influences of the mass ratio in the Ce—Zr—Nd mixed oxide expressed by ZrO2/(CeO2+ZrO2+Nd2O3) will be examined in comparison of Examples 2 and 4 with Comparative Examples 6 to 8.
First, in Comparative Example 6, both the mass ratios in the upper and lower layers in the composition of Example 2 are changed to 70 mass %. Since Example 2 has better T50 and C500 values than Comparative Example 6, this shows that it is preferable that the mass ratio in the lower layer is 70 mass % or less and that the mass ratio in the upper layer is larger than the mass ratio in the lower layer.
Second, in Comparative Example 7, contrary to Example 2, the mass ratio in the upper layer is 67 mass % and the mass ratio in the lower layer is 80 mass %. As a result, Comparative Example 7 is further deteriorated in T50 and C500 as compared with Comparative Example 6. The reason is believed to be that the upper layer was deteriorated in thermal resistance because of reduction in ZrO2 amount in the mixed oxide while the lower layer was deteriorated in oxygen storage capacity because of reduction in CeO2 amount in the mixed oxide and that both the deteriorations deteriorated the catalytic conversion performance of Pd carried on the support materials in the lower layer.
Third, in Comparative Example 8, the mass ratio in the lower layer in the composition of Example 2 is changed from 67 mass % to 72 mass %. As a result, Comparative Example 8 became better in T50 and C500 than Comparative Example 6 but worse in those than Example 2. The reason is believed to be that out of oxygen storage components in the lower layer, the Ce—Zr—Nd mixed oxide starting to act at relatively low temperature contained a small amount of CeO2 to deteriorate the oxygen storage capacity of the mixed oxide, thereby deteriorating the catalytic conversion performance of Pd carried on the support materials.
In Example 4, the mass ratio in the upper layer in the composition of Example 2 is changed from 80 mass % to 72 mass %. As a result, in Example 4, the values of T50 and C500 became better than those of Comparative Example 6 and close to those of Example 2. The reason is believed to be that out of oxygen storage components in the lower layer, the Ce—Zr—Nd mixed oxide starting to act at relatively low temperature contained adequate amounts of ZrO2 and CeO2 to balance the thermal resistance with the oxygen storage capacity of the mixed oxide, thereby improving the catalytic conversion performance of Pd carried on the support materials as compared with Comparative Example 6. Likewise in the upper layer, it is believed that the Ce—Zr—Nd mixed oxide contained adequate amounts of ZrO2 and CeO2 to balance the thermal resistance with the oxygen storage capacity of the mixed oxide, thereby improving the catalytic conversion performance of Rh carried on the support materials as compared with Comparative Examples 6 to 8.
The above results can be summarized as follows. In Examples 2 and 4, the lower layer, which does not face the exhaust gas channel and is not so much thermally severe as the upper layer, contains the Ce—Zr—Nd mixed oxide having a mass ratio of 70 mass % or less, while the upper layer exposed to high-temperature exhaust gas contains the Ce—Zr—Nd mixed oxide having a larger mass ratio than the Ce—Zr—Nd mixed oxide in the lower layer. Therefore, the catalytic conversion performances of catalytic precious metals Pd and Rh are improved while the thermal resistance of the upper layer and the oxygen storage capacity of the lower layer are both improved, which enables the catalyst to maintain high catalytic conversion performance over a long period of time.
In view of balance between thermal resistance and oxygen storage capacity, it is believed that the mass ratio in the lower layer should be at least about 50 mass %.
<Effects of Pd in the Lower Layer Being Carried Distributively on Plural Support Materials>
Effects of Pd in the lower layer being carried distributively on the first alumina and the Ce—Zr—La—Y-alumina compound in Example 2 will be described in comparison with Comparative Example 9 in which Pd in the lower layer is carried only on the first alumina.
<Three-Way Catalyst Containing no Pt>
The lower catalytic layer contains a Pd-carried alumina, a Pd-carried Ce—Zr—La—Y-alumina compound, a Ce—Zr—Nd mixed oxide, cerium dioxide (CeO2) and a binder (zirconium dioxide (ZrO2)). The upper catalytic layer contains a Rh-carried Ce—Zr—Nd mixed oxide, a Rh-carried and ZrO2-coated alumina (called a third alumina in Embodiment 1) and a binder (zirconium dioxide (ZrO2)). The alumina, ZrO2-coated alumina, Ce—Zr—Nd mixed oxide, Ce—Zr—La—Y-alumina compound and cerium dioxide are formed in particles like the preceding embodiment.
[Preparation of Three-Way Catalyst]
The preparation of the three-way catalyst is generally carried out in the following manner.
<Formation of Lower Catalytic Layer>
4-mass % La containing, Pd-carried active alumina is prepared according to the method as described in the preceding embodiment. Powder of the Pd-carried active alumina, powder of Pd-carried Ce—Zr—La—Y-alumina compound, powder of Ce—Zr—Nd mixed oxide, powder of CeO2 and a binder are mixed, water is also added and the resultant mixture is further mixed by stirring with a disperser to obtain a slurry. A honeycomb support made of cordierite is immersed in the slurry and then picked up and surplus slurry is removed by air blow. This process is repeated until the support is coated with a predetermined amount of slurry. Thereafter, the honeycomb support is heated from normal temperature up to 500° C. at a constant rate of temperature increase in 1.5 hours. The honeycomb support is dried and calcined by keeping it at 500° C. for two hours, resulting in the formation of a lower catalytic layer.
<Formation of Upper Catalytic Layer>
Rh-carried Ce—Zr—Nd mixed oxide is prepared according to the method as described in the preceding embodiment. Powder of the Rh-carried Ce—Zr—Nd mixed oxide, powder of Rh-carried and ZrO2-coated alumina and a binder are mixed, water is also added and the resultant mixture is further mixed by stirring with a disperser to obtain a slurry. The cordierite honeycomb support having the lower catalytic layer formed as above is immersed in the slurry and then picked up and surplus slurry is removed by air blow. This process is repeated until the support is coated with a predetermined amount of slurry. Thereafter, the honeycomb support is heated from normal temperature up to 500° C. at a constant rate of temperature increase in 1.5 hours. The honeycomb support is dried and calcined by keeping it at 500° C. for two hours, resulting in the formation of an upper catalytic layer.
A three-way catalyst having the following composition was produced according to the above-mentioned preparation method. The mass ratio of the total amount of Pd carried in the lower catalytic layer to the total amount of Rh carried in the upper catalytic layer is Pd/Rh=4/1.
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.75 g/L)
Pd/Ce—Zr—La—Y-alumina compound: carried amount of 25.0 g/L (Pd: carried amount of 0.37 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.20 g/L)
Rh/ZrO2-coated alumina: carried amount of 42.5 g/L (Rh: carried amount of 0.08 g/L)
zirconia binder: carried amount of 11.0 g/L
A three-way catalyst having the following composition was produced according to the above-mentioned preparation method. The mass ratio of the total amount of Pd carried in the lower catalytic layer to the total amount of Rh carried in the upper catalytic layer is Pd/Rh=5/1.
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.78 g/L)
Pd/Ce—Zr—La—Y-alumina compound: carried amount of 25.0 g/L (Pd: carried amount of 0.39 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.17 g/L)
Rh/ZrO2-coated alumina: carried amount of 42.5 g/L (Rh: carried amount of 0.07 g/L)
zirconia binder: carried amount of 11.0 g/L
A three-way catalyst having the following composition was produced according to the above-mentioned preparation method. The mass ratio of the total amount of Pd carried in the lower catalytic layer to the total amount of Rh carried in the upper catalytic layer is Pd/Rh=7/1.
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.82 g/L)
Pd/Ce—Zr—La—Y-alumina compound: carried amount of 25.0 g/L (Pd: carried amount of 0.40 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.13 g/L)
Rh/ZrO2-coated alumina: carried amount of 42.5 g/L (Rh: carried amount of 0.05 g/L)
zirconia binder: carried amount of 11.0 g/L
A three-way catalyst having the following composition was produced according to the above-mentioned preparation method. The mass ratio of the total amount of Pd carried in the lower catalytic layer to the total amount of Rh carried in the upper catalytic layer is Pd/Rh=3/1.
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.70 g/L)
Pd/Ce—Zr—La—Y-alumina compound: carried amount of 25.0 g/L (Pd: carried amount of 0.35 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.25 g/L)
Rh/ZrO2-coated alumina: carried amount of 42.5 g/L (Rh: carried amount of 0.10 g/L)
zirconia binder: carried amount of 11.0 g/L
A three-way catalyst having the following composition was produced according to the above-mentioned preparation method. The mass ratio of the total amount of Pd carried in the lower catalytic layer to the total amount of Rh carried in the upper catalytic layer is Pd/Rh=10/1.
-Lower Catalytic Layer-
Ce—Zr—Nd mixed oxide: carried amount of 5.7 g/L
Pd/first alumina: carried amount of 50.0 g/L (Pd: carried amount of 0.85 g/L)
Pd/Ce—Zr—La—Y-alumina compound: carried amount of 25.0 g/L (Pd: carried amount of 0.42 g/L)
cerium dioxide: carried amount of 5.7 g/L
zirconia binder: carried amount of 8.5 g/L
-Upper Catalytic Layer-
Rh/Ce—Zr—Nd mixed oxide: carried amount of 56.0 g/L (Rh: carried amount of 0.09 g/L)
Rh/ZrO2-coated alumina: carried amount of 42.5 g/L (Rh: carried amount of 0.04 g/L)
zirconia binder: carried amount of 11.0 g/L
<Evaluation Tests>
The catalyst in each of Examples 5 to 9 was aged by keeping it at 1000° C. in an atmosphere of 2% of O2 and 10% of H2O for 24 hours and then measured in terms of T50 (° C.) and C500 (%), which are indices for conversion performance of HC, CO and NOx, by a rig test. The evaluation tests were implemented under the same conditions and by the same method as in the preceding embodiment. The test results are shown in
Example 6 has a mass ratio of Pd/Rh=5/1 which corresponds to Example 2 in which Pt-carried alumina is contained in the upper catalytic layer (i.e., Pd/(Rh+Pt)=approximately 5/1). Comparison of both examples shows that Example 6 containing no Pt-carried alumina in the upper catalytic layer is lower in T50 for all of HC, CO and NOx and higher in C500 for all of HC, CO and NOx than Example 2.
Consideration is made of influences of a difference in Pd/Rh mass ratio on T50 and C500.
It can be said from the above results that a preferable range of the Pd/Rh mass ratio is from 4/1 to 7/1 both inclusive.
<Influences of the Existence/Absence of Pt-Carried Alumina on Catalytic Activity>
As described above, Example 6 containing no Pt-carried alumina in the upper catalytic layer has a higher catalytic activity than Example 2 containing Pt-carried alumina. Further consideration will be given to this aspect below.
The measurement of oxygen release amount was implemented using the test device shown in
As seen from
In this connection, influences of each of Rh/Zr/Al2O3 and Pt/Al2O3 on the oxygen storage/release capacity of Rh/CZN10 will be considered.
The above fact is supported by data in
When Rh/Zr/Al2O3 and Pt/Al2O3 are examined for CO oxidation capacity, Rh/Zr/Al2O3 has a higher CO oxidation capacity than Pt/Al2O3 in the range from slightly over 300° C., at which oxygen release from Rh/CZN10 becomes active, to 500° C. as shown in
Therefore, behaviors of catalytic components when the exhaust gas conditions are changed from lean to rich in each of the catalyst in which Rh/CZN10 coexists with Rh/Zr/Al2O3 and the catalyst in which Rh/CZN10 coexists with Pt/Al2O3 are believed to be as follows.
In the case where Rh/CZN10 coexists with Rh/Zr/Al2O3, under rich conditions, CO ions are attracted to active oxygen atoms on the surfaces of Rh particles as shown in
On the other hand, in the case where Rh/CZN10 coexists with Pt/Al2O3, almost all of Pt particles exist in metal form. Therefore, even under rich conditions, CO in the ambient atmosphere is merely adsorbed to Pt as shown in
From the above, it can be believed that Example 6, in which the oxygen storage component Rh/CZN10 coexists with not Pt/Al2O3 but Rh/Zr/Al2O3, is enhanced in activity because of promoted oxygen release from Rh/CZN10 as compared with Example 2 in which Rh/CZN10 coexists with Pt/Al2O3.
The present invention is not limited to the above-described embodiments but includes various forms modified or changed without departing from its spirit and scope defined by the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-085515 | Mar 2005 | JP | national |
| 2005-085516 | Mar 2005 | JP | national |
| 2005-085517 | Mar 2005 | JP | national |
| 2005-085518 | Mar 2005 | JP | national |
| 2006-005263 | Jan 2006 | JP | national |
