U.S. patent application number 12/912254 was filed with the patent office on 2011-05-12 for exhaust gas purification catalyst.
This patent application is currently assigned to MAZDA MOTOR CORPORATION. Invention is credited to Masaaki AKAMINE, Masahiko SHIGETSU, Akihide TAKAMI, Hiroshi YAMADA.
Application Number | 20110107751 12/912254 |
Document ID | / |
Family ID | 43533347 |
Filed Date | 2011-05-12 |
United States Patent
Application |
20110107751 |
Kind Code |
A1 |
AKAMINE; Masaaki ; et
al. |
May 12, 2011 |
EXHAUST GAS PURIFICATION CATALYST
Abstract
In an exhaust gas purification catalyst in which Rh-doped
CeZr-based mixed oxide powder and precious-metal (at least one of
Pt and Pd)-supporting heat-resistant powder are included in a
catalyst layer 2 provided on a support 1, Rh-doped CeZr-based mixed
oxide particles either contain at least one of Pr, La, and Y, or
are complexed with Al.sub.2O.sub.3, and support none of Pt and Pd,
and heat-resistant particles supporting the precious metal are one
of at least one of activated Al.sub.2O.sub.3 particles containing
La, BaSO.sub.4 particles, and complex particles made of CeZr-based
mixed oxide and Al.sub.2O.sub.3.
Inventors: |
AKAMINE; Masaaki;
(Hiroshima-shi, JP) ; YAMADA; Hiroshi;
(Hiroshima-shi, JP) ; SHIGETSU; Masahiko;
(Higashi-Hiroshima-shi, JP) ; TAKAMI; Akihide;
(Hiroshima-shi, JP) |
Assignee: |
MAZDA MOTOR CORPORATION
Hiroshima
JP
|
Family ID: |
43533347 |
Appl. No.: |
12/912254 |
Filed: |
October 26, 2010 |
Current U.S.
Class: |
60/299 |
Current CPC
Class: |
B01J 21/066 20130101;
F01N 2510/06 20130101; B01J 23/63 20130101; Y02T 10/22 20130101;
B01J 37/0244 20130101; B01J 37/0248 20130101; B01J 23/464 20130101;
B01J 23/002 20130101; B01D 53/945 20130101; B01J 35/04 20130101;
B01J 23/10 20130101; Y02T 10/12 20130101; B01J 37/038 20130101 |
Class at
Publication: |
60/299 |
International
Class: |
F01N 3/10 20060101
F01N003/10 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 10, 2009 |
JP |
2009-257280 |
Claims
1. An exhaust gas purification catalyst, comprising a support and a
catalyst layer provided on the support, wherein the catalyst layer
includes Rh-doped CeZr-based mixed oxide powder in which Rh is
dissolved in CeZr-based mixed oxide particles containing Ce and Zr,
and also includes precious-metal-supporting heat-resistant powder
in which a precious metal of at least one of Pt and Pd is supported
on heat-resistant particles, the CeZr-based mixed oxide particles
in which Rh is dissolved either contain at least a material
selected from the group consisting of Pr, La, and Y, or are
complexed with Al.sub.2O.sub.3, and support none of Pt and Pd, and
the heat-resistant particles supporting the precious metal are at
least one type of particles selected from the group consisting of
activated Al.sub.2O.sub.3 particles containing La, BaSO.sub.4
particles, and complex particles made of CeZr-based mixed oxide and
Al.sub.2O.sub.3.
2. The exhaust gas purification catalyst of claim 1, wherein the
catalyst layer includes a layer containing the Rh-doped CeZr-based
mixed oxide powder and a layer containing the
precious-metal-supporting heat-resistant powder, and the layer
containing the Rh-doped CeZr-based mixed oxide powder is located
above the layer containing the precious-metal-supporting
heat-resistant powder.
3. The exhaust gas purification catalyst of claim 1, including, as
the precious-metal-supporting heat-resistant powder, Pt-supporting
heat-resistant powder in which Pt is supported on the
heat-resistant particles, and Pd-supporting heat-resistant powder
in which Pd is supported on the heat-resistant particles, the
catalyst layer includes a layer containing the Rh-doped CeZr-based
mixed oxide powder and a layer containing the Pd-supporting
heat-resistant powder, the layer containing the Rh-doped CeZr-based
mixed oxide powder is located above the layer containing the
Pd-supporting heat-resistant powder, and the Pt-supporting
heat-resistant powder is included in at least one of the layer
containing the Rh-doped CeZr-based mixed oxide powder and the layer
containing the Pd-supporting heat-resistant powder.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to Japanese Patent
Application No. 2009-257280 filed on Nov. 10, 2009, the disclosure
of which including the specification, the drawings, and the claims
is hereby incorporated by reference in its entirety.
BACKGROUND
[0002] The present disclosure relates to exhaust gas purification
catalysts.
[0003] Catalysts for purification of HC (hydrocarbon), CO, and NOx
(nitrogen oxides) in engine exhaust gas are required of having high
purification efficiencies in the wide temperature ranges from about
200.degree. C. to about 1100.degree. C. Thus, rare metals such as
Pt, Pd, and Rh are used as catalytic metals, and are contained in
catalyst layers on a support while being supported on
heat-resistant oxide particles such as activated alumina, zirconium
oxide, or Ce-based oxide having an oxygen storage/release capacity.
However, it is known that when a catalyst is exposed to
high-temperature exhaust gas, a catalytic metal gradually
agglomerates to have its surface area reduced, and as a result,
performance of the catalyst degrades. For this reason, a catalyst
layer contains a relatively large amount of a catalytic metal in
expectation of this agglomeration.
[0004] On the other hand, some attempts have been made to prevent
agglomeration of a catalytic metal. For example, Japanese Patent
Publications Nos. 2006-35043 and 2008-62156 propose that CeZr-based
mixed oxide (composite oxide) is doped with Rh and, in addition,
some Rh particles are partially exposed at the surface of this
mixed oxide. This Rh-doped CeZr-based mixed oxide reduces
agglomeration of Rh, and also increases the oxygen storage/release
amount and the oxygen storage/release speed of the CeZr-based mixed
oxide. These functions are advantageous in solving problems
inherent in automobiles, i.e., Rh-doped CeZr-based mixed oxide is
capable of quickly returning an atmosphere around the catalyst to a
near-stoichiometric atmosphere suitable for purification of exhaust
gas, even with a variation in the exhaust gas air-fuel ratio
(A/F).
[0005] In addition, in exhaust gas purification catalysts, Pt or Pd
principally utilizing an oxidation catalytic activity and Rh
principally utilizing a reduction catalytic activity are combined
together. For example, as such an exhaust gas purification
catalyst, a bimetal catalyst made of a combination of two catalytic
metals, i.e., a combination of Pt and Rh or a combination of Pd and
Rh, and a trimetal catalyst, i.e., a combination of Pt, Pd, and Rh,
are known. In Japanese Patent Publications Nos. 2006-35043 and
2008-62156 mentioned above, Pt and Pd are supported on activated
alumina.
SUMMARY
[0006] In Rh-doped CeZr mixed oxide powder as a catalytic
component, an increase in the Ce content increases the oxygen
storage/release amount but might reduce the thermal resistance,
whereas an increase in the Zr content increases the thermal
resistance but might reduce the oxygen storage/release amount.
Precious-metal-supporting heat-resistant powder supporting Pt or Pd
needs to have its purification performance enhanced in
consideration of a relationship with the Rh-doped CeZr mixed oxide
powder.
[0007] In view of such a requirement, the present disclosure
provides a bimetal catalyst or a trimetal catalyst showing high
purification performance in a long period even under situations of
being exposed to high-temperature exhaust gas.
[0008] An exhaust gas purification catalyst according to the
present disclosure includes a support and a catalyst layer provided
on the support. In this catalyst, the catalyst layer includes
Rh-doped CeZr-based mixed oxide powder in which Rh is dissolved in
CeZr-based mixed oxide particles containing Ce and Zr, and also
includes precious-metal-supporting heat-resistant powder in which a
precious metal of at least one of Pt and Pd is supported on
heat-resistant particles. The CeZr-based mixed oxide particles in
which Rh is dissolved either contain at least a material selected
from the group consisting of Pr, La, and Y, or are complexed with
Al.sub.2O.sub.3, and support none of Pt and Pd. The heat-resistant
particles supporting the precious metal are at least one type of
particles selected from the group consisting of activated
Al.sub.2O.sub.3 particles containing La, BaSO.sub.4 particles, and
complex particles made of CeZr-based mixed oxide and
Al.sub.2O.sub.3.
[0009] In this exhaust gas purification catalyst, CeZr-based mixed
oxide in the Rh-doped CeZr-based mixed oxide powder contains at
least one of Pr, La, and Y, or is complexed with Al.sub.2O.sub.3,
and thus, shows an enhanced oxygen storage/release capacity and a
high thermal resistance. Specifically, in the case of containing at
least one of Pr, La, and Y, this rare earth metal dissolved in CeZr
mixed oxide can increase the thermal resistance and cause
distortion of crystal of the mixed oxide, thereby enhancing the
oxygen storage/release capacity. As the rare earth metal, Y is the
most preferable, and is followed by La and Pr in this order. In a
complex of CeZr-based mixed oxide and Al.sub.2O.sub.3,
Al.sub.2O.sub.3 serves as steric hindrance, thereby reducing
sintering of CeZr-based mixed oxide primary particles (i.e.,
reducing a decrease in the oxygen storage/release capacity). In
addition, dissolving of Rh in Al.sub.2O.sub.3 (i.e., degradation of
the oxygen storage/release capacity or catalyst performance) is
also reduced.
[0010] Further, since the heat-resistant particles supporting a
precious metal of at least one of Pt and Pd are at least one of
La-containing activated Al.sub.2O.sub.3 (La-containing
Al.sub.2O.sub.3) particles, BaSO.sub.4 particles, and complex
particles of CeZr-based mixed oxide and Al.sub.2O.sub.3, high
catalyst performance and high thermal resistance can be obtained.
In this case, as the heat-resistant particles, La-containing
Al.sub.2O.sub.3 particles are the most preferable, and are followed
by complex particles of CeZr-based mixed oxide and Al.sub.2O.sub.3
and BaSO.sub.4 particles in this order. In the case of
La-containing Al.sub.2O.sub.3 particles, these particles have high
thermal resistance and a large number of pores, and thus have a
large surface area. Accordingly, La-containing Al.sub.2O.sub.3
particles can support Pt or Pd with high dispersivity, thereby
reducing sintering of Pt or Pd supported on these particles. The
complex particles of CeZr-based mixed oxide and Al.sub.2O.sub.3 are
formed by agglomeration of CeZr-based mixed oxide primary particles
and Al.sub.2O.sub.3 primary particles. Accordingly, the
Al.sub.2O.sub.3 primary particles can reduce sintering of
CeZr-based mixed oxide primary particles, and can maintain a large
specific surface area even after a long-term use. On the other
hand, in the case of the BaSO.sub.4 particles, although the
BaSO.sub.4 particles do not have a specific surface area as large
as activated Al.sub.2O.sub.3, but do not substantially show a
decrease in the specific surface area even after exposure to
high-temperature exhaust gas, and thus, are very stable as a
support for Pt and Pd. In addition, the poisoning with P, Zn, or S
mixed into exhaust gas from engine oil (i.e., degradation of the
catalyst) can be reduced.
[0011] Accordingly, the present disclosure can provide an exhaust
gas purification catalyst showing high purification performance for
a long period even after exposure to high-temperature exhaust
gas.
[0012] In a preferred embodiment, the catalyst layer includes a
layer containing the Rh-doped CeZr-based mixed oxide powder and a
layer containing the precious-metal-supporting heat-resistant
powder, and the layer containing the Rh-doped CeZr-based mixed
oxide powder is located above the layer containing the
precious-metal-supporting heat-resistant powder. Specifically,
although a precious metal (i.e., Pt or Pd) in the
precious-metal-supporting heat-resistant powder easily causes
sintering as compared to Rh, the precious-metal-supporting
heat-resistant powder is provided in the lower layer, and thus, is
advantageous in reducing sintering of Pt or Pd.
[0013] In another preferred embodiment, exhaust gas purification
catalyst includes, as the precious-metal-supporting heat-resistant
powder, Pt-supporting heat-resistant powder in which Pt is
supported on the heat-resistant particles, and Pd-supporting
heat-resistant powder in which Pd is supported on the
heat-resistant particles, the catalyst layer includes a layer
containing the Rh-doped CeZr-based mixed oxide powder and a layer
containing the Pd-supporting heat-resistant powder, the layer
containing the Rh-doped CeZr-based mixed oxide powder is located
above the layer containing the Pd-supporting heat-resistant powder,
and the Pt-supporting heat-resistant powder is included in at least
one of the layer containing the Rh-doped CeZr-based mixed oxide
powder and the layer containing the Pd-supporting heat-resistant
powder.
[0014] Accordingly, the three types of catalytic metals, i.e., Pt,
Pd, and Rh, efficiently contribute to exhaust gas purification,
thereby enhancing purification performance of the exhaust gas
purification catalyst. In this case, Pt-supporting heat-resistant
powder is preferably included in the layer containing the Rh-doped
CeZr-based mixed oxide powder.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a cross-sectional view illustrating a structure of
a catalyst layer of an exhaust gas purification catalyst according
to a first embodiment of the present disclosure.
[0016] FIG. 2 is a cross-sectional view illustrating a structure of
a catalyst layer of an exhaust gas purification catalyst according
to a second embodiment of the present disclosure.
DETAILED DESCRIPTION
[0017] Embodiments of the present disclosure will be described
hereinafter 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 present disclosure.
First Embodiment
[0018] In an engine exhaust gas purification catalyst illustrated
in FIG. 1, reference numeral 1 denotes a honeycomb support, and a
catalyst layer 2 is formed on a cell wall surface 1a of the
honeycomb support 1. This catalyst layer 2 contains a mixture of
Rh-doped CeZr-based mixed oxide powder having an oxygen
storage/release capacity and precious-metal-supporting
heat-resistant powder.
[0019] In the Rh-doped CeZr-based mixed oxide powder, Rh is
dissolved in CeZr-based mixed oxide particles containing Ce and Zr.
The CeZr-based mixed oxide particles contain at least one of Pr,
La, and Y, or are complexed with Al.sub.2O.sub.3. The CeZr-based
mixed oxide particles (i.e., secondary particles) complexed with
Al.sub.2O.sub.3 are formed by agglomeration of primary particles of
CeZr-based mixed oxide and primary particles of
Al.sub.2O.sub.3.
[0020] In the precious-metal-supporting heat-resistant powder, a
precious metal of at least one of Pt and Pd is supported on
heat-resistant oxide particles. Heat-resistant particles thereof
are at least one of activated Al.sub.2O.sub.3 particles containing
La (i.e., La-containing Al.sub.2O.sub.3), BaSO.sub.4 particles, and
complex particles of CeZr-based mixed oxide and Al.sub.2O.sub.3
(i.e., CeZrAl).
EXAMPLE AND COMPARATIVE EXAMPLES
Rh-Doped CeZr-Based Mixed Oxide Powder
[0021] As the Rh-doped CeZr-based mixed oxide powder, powders of
Rh--CeZrPr in which Rh was dissolved in CeZrPr mixed oxide
particles, Rh--CeZrLa in which Rh was dissolved in CeZrLa mixed
oxide particles, Rh--CeZrY in which Rh was dissolved in CeZrY mixed
oxide particles, and Rh--CeZrAl as a complex of Al.sub.2O.sub.3 and
CeZr mixed oxide in which Rh was dissolved, were prepared. None of
these powders contained Nd.
[0022] Each of the Rh--CeZrPr, Rh--CeZrLa, and Rh--CeZrY powders
was prepared by coprecipitation. Specifically, as an example, the
Rh--CeZrPr powder was prepared in the following manner. First,
aqueous ammonia was added to a solution containing nitrates of Ce,
Zr, Pr, and Rh with the solution being stirred, and the resultant
mixture was neutralized. Then, the obtained coprecipitate was
rinsed with water, was dried for one day and night at 150.degree.
C. in an atmospheric environment, was pulverized, and then was
calcined by being held at 500.degree. C. for two hours. In this
manner, the Rh--CeZrPr powder was obtained. At least part of Rh
used for doping was exposed at the surface of the mixed oxide
particles. In each Rh-doped CeZr-based mixed oxide, the composition
except Rh was CeO.sub.2:ZrO.sub.2:(Pr.sub.2O.sub.3 or
La.sub.2O.sub.3 or Y.sub.2O.sub.3)=45:45:10 (% by mass), and the
amount of Rh used for doping was 0.1% by mass.
[0023] The Rh--CeZrAl powder was prepared in the following manner.
First, aqueous ammonia was added to an aluminum nitrate solution
with the solution being stirred, thereby obtaining a precipitate of
aluminium hydroxide as a precursor of alumina particles. Then, an
aqueous ammonia solution was added to the solution from which the
above precipitate was obtained. Thereafter, solutions of nitrates
of Ce, Zr, and Rh were further added to, and mixed with, the
solution, thereby obtaining coprecipitates of hydroxides of Ce, Zr,
and Rh and the aluminium hydroxide. This mixture of precipitates
was rinsed with water, was dried for one day and night at
150.degree. C. in an atmospheric environment, was pulverized, and
then was calcined by being held at 500.degree. C. for two hours. In
this manner, the Rh--CeZrAl powder as an agglomeration of primary
particles of Rh-doped CeZr mixed oxide containing Ce and Zr, doped
with Rh, and having a particle surface at which part of Rh used for
doping was exposed, and primary particles of alumina, was obtained.
The composition except Rh was
CeO.sub.2:ZrO.sub.2:Al.sub.2O.sub.3=25:25:50 (% by mass), and the
amount of Rh used for doping was 0.1% by mass.
[0024] Rh-Supporting CeZr-Based Mixed Oxide Powder
[0025] Powders of Rh/CeZrPr in which Rh was supported on CeZrPr
mixed oxide particles by evaporation to dryness, Rh/CeZrLa in which
Rh was supported on CeZrLa mixed oxide particles by evaporation to
dryness, Rh/CeZrY in which Rh was supported on CeZrY mixed oxide
particles by evaporation to dryness, and Rh/CeZrAl in which Rh was
supported on CeZrAl mixed oxide as a complex of CeZr mixed oxide
and Al.sub.2O.sub.3 by evaporation to dryness, were prepared.
[0026] The powders of CeZrPr mixed oxide, CeZrLa mixed oxide, CeZrY
mixed oxide, and CeZrAl mixed oxide were prepared in the same
manner that for the powders of Rh--CeZrPr, Rh--CeZrLa, Rh--CeZrY,
and Rh--CeZrAl described above, except that Rh nitrate was not
added.
[0027] The composition of each of the CeZrPr mixed oxide powder,
the CeZrLa mixed oxide powder, the CeZrY mixed oxide powder, and
the CeZrAl mixed oxide powder was
CeO.sub.2:ZrO.sub.2:(Pr.sub.2O.sub.3, La.sub.2O.sub.3, or
Y.sub.2O.sub.3)=45:45:10 (% by mass), and the amount of Rh
supported on each powder was 0.1% by mass.
[0028] Precious-Metal-Supporting Heat-Resistant Powder
[0029] As the precious-metal-supporting heat-resistant powder,
La-containing Al.sub.2O.sub.3 supporting Pd, BaSO.sub.4 supporting
Pd, CeZrAl supporting Pd, La-containing Al.sub.2O.sub.3 supporting
Pt, BaSO.sub.4 supporting Pt, and CeZrAl supporting Pt, were
prepared. CeZrAl was mixed oxide particles formed by agglomeration
of primary particles of CeZr mixed oxide (not doped with Rh)
described above, and primary particles of alumina, and had a
composition of CeO.sub.2:ZrO.sub.2:Al.sub.2O.sub.3=25:25:50 (% by
mass). La-containing Al.sub.2O.sub.3 contained 4%, by mass, of
La.sub.2O.sub.3. The amount of supported Pt or Pd was adjusted such
that the amount of Pt or Pd supported on the honeycomb support was
1.4 g/L when the amount of the precious-metal-supporting
heat-resistant powder supported on the honeycomb support was 70
g/L.
[0030] No-Precious-Metal-Supporting Heat-Resistant Powder
[0031] Powders of La-containing Al.sub.2O.sub.3, BaSO.sub.4, and
CeZrAl mixed oxide each of which supported no precious metal were
prepared.
[0032] Preparation of Catalysts According to Example
[0033] The Rh-doped CeZr-based mixed oxide powder (which is one of
Rh--CeZrPr, Rh--CeZrLa, Rh--CeZrY, and Rh--CeZrAl) and the
precious-metal-supporting heat-resistant powder (which is one of
Pd-supporting La-containing Al.sub.2O.sub.3, Pd-supporting
BaSO.sub.4, Pd-supporting CeZrAl, Pt-supporting La-containing
Al.sub.2O.sub.3, Pt-supporting BaSO.sub.4, and Pt-supporting
CeZrAl) were mixed together as appropriate, and the honeycomb
support was coated with this mixture, thereby preparing various
types of catalysts according to Example having different
compositions of catalyst layers. With respect to the amount of a
material supported on 1 L of the honeycomb support, the Rh-doped
CeZr-based mixed oxide powder was 100 g/L, the
precious-metal-supporting heat-resistant powder was 70 g/L, and Pd
or Pt was 1.4 g/L. The coating with catalyst powder such as the
Rh-doped CeZr-based mixed oxide powder was performed by adding a
binder and water to the catalyst powder to change the catalyst
powder into slurry (the same hereinafter).
[0034] As the honeycomb support, a support (having a volume of 25
ml) having a cell wall thickness of 3.5 mil (i.e.,
8.89.times.10.sup.-2 mm), including 600 cells per square inch
(i.e., 645.16 mm.sup.2), made of cordierite, and having a
cylindrical shape with a diameter of 25.4 mm and a length of 50 mm,
was used. This holds true for other examples and comparative
examples.
Preparation of Catalysts According to Comparative Example 1
[0035] Various types of catalysts according to Comparative Example
1 having different compositions of catalyst layers were prepared in
the same manner as that for the catalysts of Example, except that
the Rh-doped CeZr-based mixed oxide powder was replaced by
Rh-supporting CeZr-based mixed oxide powder (which is one of
Rh/CeZrPr, Rh/CeZrLa, Rh/CeZrY, and Rh/CeZrAl). The amount of the
supported Rh-supporting CeZr-based mixed oxide powder was 100 g/L,
the amount of the supported precious-metal-supporting
heat-resistant powder was 70 g/L, and amount of supported Pd or Pt
was 1.4 g/L.
Preparation of Catalysts According to Comparative Example 2
[0036] In Comparative Example 2, Rh-supporting CeZr-based mixed
oxide powder (which is one of Rh/CeZrPr, Rh/CeZrLa, Rh/CeZrY, and
Rh/CeZrAl) and no-precious-metal-supporting heat-resistant powder
(which is one of La-containing Al.sub.2O.sub.3, BaSO.sub.4, and
CeZrAl mixed oxide) were mixed together as appropriate, and the
honeycomb support was coated with this mixture. Then, this coating
layer was impregnated with a Pd solution or a Pt solution, and was
dried and calcined, thereby preparing various types of catalysts
according to Comparative Example 2 having different compositions of
the catalyst layers. The amount of the supported Rh-supporting
CeZr-based mixed oxide powder was 100 g/L, and the amount of the
supported no-precious-metal-supporting heat-resistant powder was 70
g/L, and the amount of Pd or Pt supported by impregnation was 1.4
g/L.
[0037] The catalysts of Comparative Example 2 differ from those of
Example in that the Rh-doped CeZr-based mixed oxide powder was
replaced by the Rh-supporting CeZr-based mixed oxide powder, the
precious-metal-supporting heat-resistant powder was replaced by the
heat-resistant powder supporting no precious metal, and a precious
metal was supported by impregnation (i.e., Pd or Pt was supported
by impregnation on the Rh-supporting CeZr-based mixed oxide powder
and the heat-resistant powder).
[0038] Evaluation of Exhaust Gas Purification Performance
[0039] The catalysts of Example and Comparative Examples were aged
by keeping these catalysts at 1000.degree. C. for 24 hours in an
atmospheric environment. Then, these catalysts were placed in a
model gas flow reactor, and light-off temperatures T50 concerning
purification of HC, CO, and NOx were measured using model gas for
evaluation. The light-off temperature T50 is a gas temperature at a
catalyst entrance when purification efficiency reaches 50% by
gradually increasing the temperature of model gas flowing in the
catalyst from room temperature. The evaluation model gas had an A/F
ratio of 14.7.+-.0.9. Specifically, a mainstream gas with an A/F
ratio of 14.7 was allowed to constantly flow, 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. The space velocity SV was set at
60000/h.sup.-1, and the rate of temperature increase was set at
30.degree. C./min.
[0040] Table 1 shows results of Example, Table 2 shows results of
Comparative Example 1, and Table 3 shows results of Comparative
Example 2. In Tables 1-3, "Al.sub.2O.sub.3" means "Al.sub.2O.sub.3"
and "BaSO.sub.4" means "BaSO.sub.4," and the same holds for other
tables.
TABLE-US-00001 TABLE 1 First Embodiment T50 Single-layer Rh-doped
CeZr-based (.degree. C.) Structure Mixed Oxide Powder
Heat-resistant Powder HC CO NOx Precious Metal Mixture of Rh-doped
Rh--CeZrPr La-containing Al2O3 268 260 263 Pd-supporting CeZr-based
Mixed BaSO4 293 284 289 Oxide Powder and CeZrAl Mixed Oxide 281 272
274 Pd-supporting Rh--CeZrLa La-containing Al2O3 267 259 261
Heat-resistant BaSO4 289 278 281 Powder CeZrAl Mixed Oxide 276 269
272 Rh--CeZrY La-containing Al2O3 265 257 257 BaSO4 288 279 281
CeZrAl Mixed Oxide 275 267 266 Rh--CeZrAl La-containing Al2O3 264
257 258 BaSO4 285 277 279 CeZrAl Mixed Oxide 273 267 267 Mixture of
Rh--CeZrPr La-containing Al2O3 276 268 267 Pt-supporting
Rh-supporting BaSO4 297 288 288 CeZr-based CeZrAl Mixed Oxide 285
278 276 Mixed Oxide Rh--CeZrLa La-containing Al2O3 273 265 266
Powder and BaSO4 293 285 285 Pt-supporting CeZrAl Mixed Oxide 282
276 275 Heat-resistant Rh--CeZrY La-containing Al2O3 272 265 265
Particles BaSO4 293 285 286 CeZrAl Mixed Oxide 282 276 276
Rh--CeZrAl La-containing Al2O3 271 263 262 BaSO4 292 283 283 CeZrAl
Mixed Oxide 281 274 273
TABLE-US-00002 TABLE 2 Comparative Rh-supporting T50 Example 1
CeZr-based Heat-resistant (.degree. C.) Single-layer Structure
Mixed Oxide Powder Powder HC CO NOx Precious Metal Mixture of
Rh-supporting CeZrPr La-containing 284 277 277 Pd-supporting
Rh-supporting Al2O3 CeZr-based BaSO4 305 297 298 Mixed Oxide Powder
CeZrAl Mixed 293 287 286 and Pd-supporting Oxide Heat-resistant
Rh-supporting CeZrLa La-containing 281 274 276 Particles Al2O3
BaSO4 301 294 295 CeZrAl Mixed 290 285 285 Oxide Rh-supporting
CeZrY La-containing 280 274 275 Al2O3 BaSO4 301 294 296 CeZrAl
Mixed 290 285 286 Oxide Rh-supporting CeZrAl La-containing 280 272
271 Al2O3 BaSO4 305 296 297 CeZrAl Mixed 293 284 282 Oxide Mixture
of Rh-supporting CeZrPr La-containing 292 284 284 Pt-supporting
Rh-supporting Al2O3 CeZr-based BaSO4 312 304 303 Mixed Oxide Powder
CeZrAl Mixed 301 295 293 and Pt-supporting Oxide Heat-resistant
Rh-supporting CeZrLa La-containing 289 281 283 Particles Al2O3
BaSO4 314 305 309 CeZrAl Mixed 302 293 294 Oxide Rh-supporting
CeZrY La-containing 288 281 282 Al2O3 BaSO4 309 301 303 CeZrAl
Mixed 298 292 293 Oxide Rh-supporting CeZrAl La-containing 286 280
277 Al2O3 BaSO4 306 300 296 CeZrAl Mixed 295 291 286 Oxide
TABLE-US-00003 TABLE 3 Comparative Rh-supporting T50 Example 2
CeZr-based Heat-resistant (.degree. C.) Single-layer Structure
Mixed Oxide Powder Powder HC CO NOx Precious Metal Pd-impregnated
Rh-supporting CeZrPr La-containing 291 283 281 Pd-impregnated
Mixture Layer of Al2O3 Rh-supporting BaSO4 314 305 305 CeZr-based
CeZrAl Mixed 301 293 290 Mixed Oxide Powder Oxide and No-precious-
Rh-supporting CeZrLa La-containing 288 281 279 metal-supporting
Al2O3 Heat-resistant BaSO4 309 301 300 Powder CeZrAl Mixed 297 291
288 Oxide Rh-supporting CeZrY La-containing 286 277 278 Al2O3 BaSO4
308 296 298 CeZrAl Mixed 295 287 289 Oxide Rh-supporting CeZrAl
La-containing 286 277 278 Al2O3 BaSO4 307 297 299 CeZrAl Mixed 296
288 289 Oxide Pt-impregnated Rh-supporting CeZrPr La-containing 295
289 284 Pt-impregnated Mixture Layer of Al2O3 Rh-supporting BaSO4
317 308 304 CeZr-based CeZrAl Mixed 304 299 295 Mixed Oxide Powder
Oxide and No-precious- Rh-supporting CeZrLa La-containing 293 286
283 metal-supporting Al2O3 Heat-resistant BaSO4 314 306 304 Powder
CeZrAl Mixed 303 297 294 Oxide Rh-supporting CeZrY La-containing
292 286 284 Al2O3 BaSO4 312 306 303 CeZrAl Mixed 301 297 293 Oxide
Rh-supporting CeZrAl La-containing 291 284 283 Al2O3 BaSO4 312 304
304 CeZrAl Mixed 300 294 292 Oxide
[0041] Tables 1 and 2 show that in purification of each of HC, CO,
and NOx, if the types of CeZr-based mixed oxide powder and
precious-metal-supporting heat-resistant powder are the same, the
temperature T50 in the first embodiment using Rh-doped CeZr-based
mixed oxide is lower than that in Comparative Example 1 using
Rh-supporting CeZr-based mixed oxide. Tables 2 and 3 show that the
temperature T50 in Comparative Example 1 is lower than that in
Comparative Example 2 (i.e., catalysts in which a mixture layer of
Rh-supporting CeZr-based mixed oxide powder and heat-resistant
powder supporting no precious metal is impregnated with Pd or Pd).
Accordingly, it is preferable that Pd or Pt is supported on
heat-resistant powder beforehand and Pd or Pt is not supported on
oxide powder supporting Rh.
[0042] Regarding the influence of the type of CeZr-based mixed
oxide in the Rh-doped CeZr-based mixed oxide powder on the
temperature T50 in the first embodiment (see, Table 1), the
temperature T50 of Rh--CeZrAl is basically the lowest, and is
followed by the those of Rh--CeZrY, Rh--CeZrLa, and Rh--CeZrPr in
this order (i.e., the temperature T50 of Rh--CeZrY is the second
lowest). However, with respect to purification of NOx in the case
where Pd is supported on heat-resistant powder, the temperature T50
of Rh--CeZrY is exceptionally lower than that of Rh--CeZrAl.
[0043] Regarding the influence of the type of heat-resistant
particles in the precious-metal-supporting heat-resistant powder,
the temperature T50 in the case of using La-containing
Al.sub.2O.sub.3 is the lowest, and is followed by those of CeZrAl
and BaSO.sub.4 in this order (i.e., the temperature T50 of CeZrAl
is the second lowest). Comparison of precious metal supported on
heat-resistant particles shows that the temperature T50 in the case
of supporting Pd is lower than that in the case of supporting
Pt.
Second Embodiment
[0044] FIG. 2 illustrates a structure of a catalyst layer of an
engine exhaust gas purification catalyst according to this
embodiment. Unlike the catalyst layer 2 of the first embodiment, a
catalyst layer 2 formed on a cell wall surface 1a of a honeycomb
support 1 according to the second embodiment has a double-layer
structure including an upper layer 2a containing Rh-doped
CeZr-based mixed oxide powder and a lower layer 2b containing
precious-metal-supporting heat-resistant powder.
Example
Preparation of Catalysts According to Example
[0045] Various types of catalysts according to Example having
different compositions were prepared by combining various types of
Rh-doped CeZr-based mixed oxide powder and
precious-metal-supporting heat-resistant powder described above as
appropriate. These catalysts were prepared in the same manner as in
the first embodiment, except that precious-metal-supporting
heat-resistant powder was first supported on the honeycomb support
to form the lower layer 2b and then Rh-doped CeZr-based mixed oxide
powder was supported on the honeycomb support to form the upper
layer 2a. With respect to the amount of a material supported on 1 L
of the honeycomb support, the Rh-doped CeZr-based mixed oxide
powder was 100 g/L, the precious-metal-supporting heat-resistant
powder was 70 g/L, and the amount of Pd or Pt was 1.4 g/L.
[0046] Evaluation of Exhaust Gas Purification Performance
[0047] The above-described catalysts of Example were aged under the
same conditions as those in the first embodiment, and light-off
temperatures T50 concerning purification of HC, CO, and NOx were
measured. Table 4 shows results.
TABLE-US-00004 TABLE 4 Second Embodiment T50 Double-layer Rh-doped
CeZr-based (.degree. C.) Structure Mixed Oxide Powder
Heat-resistant Powder HC CO NOx Precious Metal Upper Layer: Rh
Rh--CeZrPr La-containing Al2O3 259 252 253 Pd-supporting Lower
Layer: Pd BaSO4 282 274 277 CeZrAl Mixed Oxide 269 262 262
Rh--CeZrLa La-containing Al2O3 256 250 251 BaSO4 277 270 272 CeZrAl
Mixed Oxide 265 260 260 Rh--CeZrY La-containing Al2O3 254 246 250
BaSO4 276 265 270 CeZrAl Mixed Oxide 263 256 261 Rh--CeZrAl
La-containing Al2O3 253 247 248 BaSO4 273 267 267 CeZrAl Mixed
Oxide 262 258 257 Upper Layer: Rh Rh--CeZrPr La-containing Al2O3
266 258 259 Pt-supporting Lower Layer: Pt BaSO4 286 278 278 CeZrAl
Mixed Oxide 275 269 268 Rh--CeZrLa La-containing Al2O3 263 255 258
BaSO4 288 279 284 CeZrAl Mixed Oxide 276 267 269 Rh--CeZrY
La-containing Al2O3 262 255 257 BaSO4 283 275 278 CeZrAl Mixed
Oxide 272 266 268 Rh--CeZrAl La-containing Al2O3 261 253 254 BaSO4
282 273 275 CeZrAl Mixed Oxide 270 263 263
[0048] Comparison with the catalysts of Example of the first
embodiment (see, Table 1) shows that in purification of each of HC,
CO, and NOx, if the types of Rh-doped CeZr-based mixed oxide powder
and precious-metal-supporting heat-resistant powder are the same,
the temperature T50 in the second embodiment is lower than that in
the first embodiment. This is considered to be because the
precious-metal-supporting heat-resistant powder was provided in the
lower layer 2b in the second embodiment, and thus, sintering of Pt
or Pd supported on this powder was reduced by the upper layer 2a.
The influence of the type of Rh-doped CeZr-based mixed oxide powder
on the temperature T50, the influence of the type of CeZr-based
mixed oxide powder in the Rh-doped CeZe-based mixed oxide powder on
the temperature T50, the influence of the type of heat-resistant
particles in the precious-metal-supporting heat-resistant powder on
the temperature T50, and the influence of the type of precious
metal supported on the heat-resistant particles show similar
tendencies as those in the first embodiment. However, purification
of CO in the case of supporting Pd on the heat-resistant powder,
the temperature T50 of Rh--CeZrY is exceptionally lower than that
of Rh--CeZrAl.
Third Embodiment
[0049] In a third embodiment of the present disclosure, in an
engine exhaust gas purification catalyst including a catalyst layer
2 with a double-layer structure as illustrated in FIG. 2, one of an
upper layer and a lower layer is a mixture layer of two types of
catalyst powder and the other of the upper layer and the lower
layer is a single layer of a single type of catalyst powder
(including a binder, however). This structure may be implemented in
two ways. In a first case, the upper layer 2a is a mixture layer of
Rh-doped CeZr-based mixed oxide powder and Pt-supporting
heat-resistant powder, and the lower layer 2b is a single layer of
Pd-supporting heat-resistant powder. In a second case, the upper
layer 2a is a single layer of Rh-doped CeZr-based mixed oxide
powder, and the lower layer 2b is a mixture layer of Pd-supporting
heat-resistant powder and Pt-supporting heat-resistant powder.
Example and Comparative Example
Preparation of Catalysts According to Example
[0050] Various types of catalysts according to Example having
different compositions of catalyst layers 2 were prepared by
combining various types of Rh-doped CeZr-based mixed oxide powder
and precious-metal-supporting heat-resistant powder described above
as appropriate. These catalysts were prepared in the same manner as
in the second embodiment, except that in the first case,
Pd-supporting heat-resistant powder was first supported on a
honeycomb support to form the lower layer 2b and then a mixture of
Rh-doped CeZr-based mixed oxide powder and Pt-supporting
heat-resistant powder was supported on the honeycomb support, and
in the second case, a mixture of Pd-supporting heat-resistant
powder and Pt-supporting powder was first supported on the
honeycomb support to form the lower layer 2b and then Rh-doped
CeZr-based mixed oxide powder was supported on the honeycomb
support to form the upper layer 2a.
[0051] In each of the first and second cases, with respect to the
amount of a material supported on 1 L of the honeycomb support, the
Rh-doped CeZr-based mixed oxide powder was 100 g/L, each of the
Pd-supporting heat-resistant powder and the Pt-supporting
heat-resistant powder was 35 g/L (i.e., 70 g/L in total), and each
of Pd and Pt was 0.7 g/L (i.e., 1.4 g/L in total).
Preparation of Catalysts According to Comparative Example 3
[0052] The Rh-supporting CeZr-based mixed oxide powder and the
Pd-supporting heat-resistant powder described above were combined
together as appropriate, and were mixed with heat-resistant powder
supporting no precious metal (i.e., the same heat-resistant powder
as Pd-supporting heat-resistant powder), and a honeycomb support
was coated with the resultant mixture. Then, this coating layer was
impregnated with a Pt solution, and was dried and calcined, thereby
preparing catalysts according to Comparative Example 3 having
different compositions of catalyst layers. With respect to the
amount of a material supported on 1 L of the honeycomb support, the
Rh-supporting CeZr-based mixed oxide powder was 100 g/L, the
Pd-supporting heat-resistant powder was 35 g/L, the
no-precious-metal-supporting heat-resistant powder was 35 g/L, and
each of Pd supported on heat-resistant powder and Pt supported by
impregnation was 0.7 g/L (i.e., 1.4 g/L in total).
[0053] Evaluation of Exhaust Gas Purification Performance
[0054] The above-described catalysts of Example and Comparative
Example were aged under the same conditions as those in the first
embodiment, and light-off temperatures T50 concerning purification
of HC, CO, and NOx were measured. Table 5 shows results of Example,
and Table 6 shows results of Comparative Example 3.
TABLE-US-00005 TABLE 5 Third Embodiment T50 Double-layer Rh-doped
CeZr-based (.degree. C.) Structure Mixed Oxide Powder
Heat-resistant Powder HC CO NOx Precious Metal Upper Layer: Rh + Pt
Rh--CeZrPr La-containing Al2O3 254 247 245 Pd-supporting, Lower
Layer: Pd BaSO4 276 266 265 Pt-supporting (First Case) CeZrAl Mixed
Oxide 263 257 256 Rh--CeZrLa La-containing Al2O3 252 244 244 BaSO4
273 264 265 CeZrAl Mixed Oxide 262 255 255 Rh--CeZrY La-containing
Al2O3 251 244 245 BaSO4 271 264 264 CeZrAl Mixed Oxide 260 255 254
Rh--CeZrAl La-containing Al2O3 251 242 243 BaSO4 276 266 269 CeZrAl
Mixed Oxide 264 254 254 Upper Layer: Rh Rh--CeZrPr La-containing
Al2O3 257 250 249 Pd-supporting, Lower Layer: Pd + Pt BaSO4 280 272
273 Pt-supporting (Second Case) CeZrAl Mixed Oxide 267 260 258
Rh--CeZrLa La-containing Al2O3 254 248 247 BaSO4 275 268 268 CeZrAl
Mixed Oxide 263 258 256 Rh--CeZrY La-containing Al2O3 252 244 246
BaSO4 274 263 266 CeZrAl Mixed Oxide 261 254 257 Rh--CeZrAl
La-containing Al2O3 252 245 246 BaSO4 273 265 267 CeZrAl Mixed
Oxide 261 255 255
TABLE-US-00006 TABLE 6 Comparative Rh-supporting T50 Example 3
CeZr-based Heat-resistant (.degree. C.) Single-layer Structure
Mixed Oxide Powder Powder HC CO NOx Precious Metal Pt-impregnated
Rh-supporting CeZrPr La-containing 294 288 287 Pd-supporting
Mixture Layer of Al2O3 Pt-impregnated Rh-supporting BaSO4 317 310
311 CeZr-based CeZrAl Mixed 304 298 296 Mixed Oxide Powder Oxide
and Pd-supporting Rh-supporting CeZrLa La-containing 291 286 285
Heat-resistant Al2O3 particles BaSO4 312 306 306 CeZrAl Mixed 300
296 294 Oxide Rh-supporting CeZrY La-containing 289 282 284 Al2O3
BaSO4 311 301 304 CeZrAl Mixed 298 292 295 Oxide Rh-supporting
CeZrAl La-containing 288 283 282 Al2O3 BaSO4 308 303 301 CeZrAl
Mixed 297 294 291 Oxide
[0055] Comparison with the catalysts of Example of the second
embodiment (see, Table 4) shows that in purification of each of HC,
CO, and NOx, if the types of the Rh-doped CeZr-based mixed oxide
powder and precious-metal-supporting heat-resistant powder are the
same in a first case and a second case, the temperature T50 is
lower than that in the second embodiment. This is because of the
use of three types of precious metals (i.e., Ru h, Pd, and Pt).
[0056] Comparison of the first case (where the upper layer is
Rh+Pt, and the lower layer is Pd) and the second case (where the
upper layer is Rh, and the lower layer is Pd+Pt) shows that the
temperature in the first case is generally lower than that in the
second case. The influence of the type of CeZr-based mixed oxide
powder in the Rh-doped CeZr-based mixed oxide powder on the
temperature T50 and the influence of the type of heat-resistant
particles in the precious-metal-supporting heat-resistant powder on
the temperature T50 show similar tendencies as those in the first
embodiment. However, the temperature T50 does not significantly
differ between Rh--CeZrAl and Rh--CeZrY, and thus, in some cases of
using some types of heat-resistant powder, the temperature T50 in
the second case is lower than the temperature T50 in the first
case.
[0057] In Comparative Example 3 (see, Table 6), three types of
precious metals (i.e., Rh, Pd, and Pt) were used as in the third
embodiment. However, if the types of the CeZr-based mixed oxide
powder and precious-metal-supporting heat-resistant powder are the
same, the temperature T50 in Comparative Example 3 is lower than
the temperature T50 not only in the third embodiment but also in
the first embodiment.
[0058] In the first through third embodiments,
precious-metal-supporting heat-resistant powder supports one of Pt
and Pd as a precious metal, but may support both Pt and Pd.
[0059] In addition, Rh--CeZrAl may be a complex of Al.sub.2O.sub.3
and CeZr-based mixed oxide in which Rh is dissolved and which
contains at least one of Pr, La, and Y.
* * * * *