U.S. patent application number 12/903721 was filed with the patent office on 2011-02-10 for exhaust gas purifying catalyst and production method thereof.
This patent application is currently assigned to NISSAN MOTOR CO., LTD.. Invention is credited to Hiroto KIKUCHI, Toshiharu Miyamura, Hideaki Morisaka, Masanori Nakamura, Kazuyuki Shiratori, Katsuo Suga, Kenji Uesugi, Hironori Wakamatsu, Hirofumi Yasuda.
Application Number | 20110034331 12/903721 |
Document ID | / |
Family ID | 38655290 |
Filed Date | 2011-02-10 |
United States Patent
Application |
20110034331 |
Kind Code |
A1 |
KIKUCHI; Hiroto ; et
al. |
February 10, 2011 |
EXHAUST GAS PURIFYING CATALYST AND PRODUCTION METHOD THEREOF
Abstract
An exhaust gas purifying catalyst including: a plurality of
first compounds 5 which have precious metal particles 3 supported
thereon and are formed into a particle shape; and second compounds
7 which are arranged among the plurality of first compounds 5 and
separate the first compounds 5 from one another, wherein pore
volumes of the precious metal particles 3, the first compounds 5
and the second compounds 7 are 0.24 to 0.8 cm.sup.3/g.
Inventors: |
KIKUCHI; Hiroto;
(Hiratsuka-shi, JP) ; Nakamura; Masanori;
(Yokosuka-shi, JP) ; Wakamatsu; Hironori;
(Yokohama-shi, JP) ; Morisaka; Hideaki;
(Yokohama-shi, JP) ; Yasuda; Hirofumi;
(Yokosuka-shi, JP) ; Suga; Katsuo; (Yokohama-shi,
JP) ; Shiratori; Kazuyuki; (Yokohama-shi, JP)
; Uesugi; Kenji; (Miura-shi, JP) ; Miyamura;
Toshiharu; (Yokohama-shi, JP) |
Correspondence
Address: |
FOLEY AND LARDNER LLP;SUITE 500
3000 K STREET NW
WASHINGTON
DC
20007
US
|
Assignee: |
NISSAN MOTOR CO., LTD.
RENAULT s.a.s.
|
Family ID: |
38655290 |
Appl. No.: |
12/903721 |
Filed: |
October 13, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12298461 |
Oct 24, 2008 |
7833930 |
|
|
PCT/JP2007/058076 |
Apr 12, 2007 |
|
|
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12903721 |
|
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Current U.S.
Class: |
502/303 ;
502/300; 502/304; 502/325; 502/339; 502/349; 502/355 |
Current CPC
Class: |
B01J 37/0248 20130101;
B01D 2255/10 20130101; B01J 35/1042 20130101; F01N 3/0224 20130101;
B01J 37/0201 20130101; B01J 23/63 20130101; B01J 23/6562 20130101;
Y02T 10/22 20130101; B01J 37/0244 20130101; F01N 3/10 20130101;
Y02T 10/12 20130101; B01J 35/0013 20130101; B01J 35/1038 20130101;
B01J 37/0221 20130101; B01J 35/10 20130101; B01D 53/945 20130101;
Y02T 10/20 20130101 |
Class at
Publication: |
502/303 ;
502/300; 502/304; 502/355; 502/349; 502/325; 502/339 |
International
Class: |
B01J 23/10 20060101
B01J023/10; B01J 23/00 20060101 B01J023/00; B01J 21/04 20060101
B01J021/04; B01J 21/06 20060101 B01J021/06; B01J 23/46 20060101
B01J023/46; B01J 23/42 20060101 B01J023/42; B01J 23/44 20060101
B01J023/44 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 28, 2006 |
JP |
2006-126557 |
Feb 13, 2007 |
JP |
2007-032269 |
Claims
1. An exhaust gas purifying catalyst, comprising: a honeycomb
carrier; and a catalyst layer provided on the honeycomb carrier,
the catalyst layer comprising: precious metal particles; a
plurality of first compounds on which the precious metal particles
are supported; and second compounds which cover the plurality of
first compounds on which the precious metal particles are supported
and separate the first compounds from one another, wherein a pore
volume of the catalyst layer is within a range of 0.24 to 0.8
cm.sup.3/g.
2. The exhaust gas purifying catalyst according to claim 1, wherein
the first compounds are an oxide containing Ce.
3. The exhaust gas purifying catalyst according to claim 1, wherein
the first compounds contain CeO.sub.2.
4. The exhaust gas purifying catalyst according to claim 1, wherein
the first compounds contain a composite oxide of Ce and Zr.
5. The exhaust gas purifying catalyst according to claim 1, wherein
the second compounds comprises Al.sub.2O.sub.3.
6. The exhaust gas purifying catalyst according to claim 1, wherein
the second compounds are an oxide containing at least either of Al
and Zr.
7. The exhaust gas purifying catalyst according to claim 1, wherein
both of the first compounds and the second compounds are formed
into a particle shape, and an average particle diameter of the
second compounds is 10 to 100 nm.
8. The exhaust gas purifying catalyst according to claim 1, wherein
the precious metal particles comprises at least one selected from
the group consisting of Pt, Pd and Rh.
9. The exhaust gas purifying catalyst according to claim 1, wherein
the pore volume of the first compounds is within a range of 0.18 to
0.38 cm.sup.3/g.
10. The exhaust gas purifying catalyst according to claim 1,
wherein the first compounds are composed of CeO.sub.2 that occupies
74 to 80% and ZrO.sub.2 that occupies 20 to 26%.
11. The exhaust gas purifying catalyst according to claim 1,
wherein the first compounds are composed of ZrO.sub.2 that occupies
95 to 99% and La.sub.2O.sub.3 that occupies 1 to 5%.
12. The exhaust gas purifying catalyst according to claim 1,
wherein a pore volume of a precursor of the second compounds after
being calcined is within a range of 0.8 to 1.0 cm.sup.3/g.
13. The exhaust gas purifying catalyst according to claim 5,
wherein the alumina comprises CeO.sub.2 that occupies 5 to 15% and
ZrO.sub.2 that occupies 3 to 7%.
14. The exhaust gas purifying catalyst according to claim 1,
wherein an aspect ratio of the precursor of the second compounds is
within a range of 0.5 to 10.
15. The exhaust gas purifying catalyst according to claim 1,
wherein the second compounds comprise Al.sub.2O.sub.3 derived from
boehmite of which an aspect ratio is within a range of 0.5 to
10.
16. The exhaust gas purifying catalyst according to claim 1,
wherein a degree of dispersion of the precious metal particles in
powder of the exhaust gas purifying catalyst is within a range of
35 to 80%.
17. The exhaust gas purifying catalyst according to claim 1,
wherein a degree of dispersion of the precious metal particles
supported on the first compounds is within a range of 50 to 100%.
Description
[0001] This application is a divisional application of U.S.
application Ser. No. 12/298,461, filed Oct. 24, 2008, which is the
National Stage application of International Application No.
PCT/JP2007/058076, filed Apr. 12, 2007, which claims priority to
Japanese Application No. 2006-126557, filed Apr. 28, 2006, and
Japanese Application No. 2007-032269, filed Feb. 13, 2007. All of
which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The present invention relates to an exhaust gas purifying
catalyst that purifies exhaust gas discharged from a vehicle such
as an automobile, and to a production method of the exhaust gas
purifying catalyst.
BACKGROUND ART
[0003] In recent years, an emission control for an automobile has
been tightened up more and more, and an exhaust gas purifying
catalyst has been required to purify harmful components contained
in exhaust gas, for example, unburned hydrocarbon (HC) and carbon
monoxide with high efficiency. The exhaust gas purifying catalyst
is one in which precious metal particles are supported on a surface
of a base material such as alumina. The exhaust gas purifying
catalyst oxidizes the harmful components contained in the exhaust
gas by the precious metal particles, and converts the harmful
components into water and gas, which are harmless components.
Moreover, in general, purification performance of the catalyst is
enhanced as a surface area of the precious metal particles is
larger, and accordingly, a particle diameter of the precious metal
particles is reduced, whereby the surface area of the precious
metal particles is increased, and surface energy thereof is
increased.
[0004] Here, at an initial stage, the precious metal particles of
the exhaust gas purifying catalyst are in a state of ultrafine
particles with a diameter of several nanometers or less. However,
there is a problem that, as the exhaust gas purifying catalyst is
being exposed to a high-temperature oxidizing atmosphere, the
surface of the precious metal particles is oxidized, the precious
metal particles located in mutual vicinities are coagulated with
each other and are coarsened to several ten nanometers, and the
surface area of the precious metal particles is decreased,
resulting in a decrease of a purification rate for such harmful
substances. In order to prevent the decrease of the surface area
owing to the coarsening of the precious metal particles,
development regarding a production method of precious metal
particles with a large surface area, such as a reversed micelle
method, has been advanced.
[0005] In this reversed micelle method, first, an aqueous solution
containing a surfactant and a catalyst active component (for
example, a precious metal element) is mixed into an organic
solvent. Thereafter, an emulsion solution, in which reversed
micelles containing the aqueous solution containing the precious
metal are formed, is prepared in the organic solvent, and the
precious metal is deposited therein. Thereafter, the precious metal
is reduced or insolubilized, and the precious metal atomized in the
reversed micelle is precipitated. The reversed micelle method is a
method as described above. Moreover, in Japanese Patent Laid-Open
Publication No. 2000-42411, a method is disclosed, which is for
producing a catalyst in such a manner that an element having an
oxygen occlusion function is contained in the reversed micelles in
an emulsion solution preparation step. In this reversed micelle
method, the catalyst active component is supported on the base
material in the reversed micelles contained in the emulsion
solution, and thereafter, the reversed micelles are collapsed, and
an obtained deposit is subjected to the respective steps of
filtration, drying, milling and calcining, whereby the catalyst is
produced. The catalyst produced by using this production method not
only can support the element having the oxygen occlusion function
on the base material but also supports the catalyst active
component also on an outermost surface of the base material and
pore surfaces formed in the base material, and accordingly, can
enhance activity thereof.
[0006] However, in the above-described reversed micelle method,
there has been a problem that, since the catalyst is produced by
spraying and calcining the emulsion solution in which the reversed
micelles are formed, a production process of the catalyst becomes
complicated, leading to an increase of production cost thereof.
[0007] In this connection, it is an object of the present invention
to provide an exhaust gas purifying catalyst in which a production
process is simple and a high purification rate can be maintained
for a long term, and to provide a production method of the exhaust
gas purifying catalyst. [0008] Patent Document 1: Japanese Patent
Laid-Open Publication No. 2000-42411
DISCLOSURE OF THE INVENTION
[0009] An exhaust gas purifying catalyst according to the present
invention includes: precious metal particles which contact exhaust
gas and purify harmful components; a plurality of first compounds
on which the precious metal particles are supported; and second
compounds which are arranged among these first compounds and
separate the first compounds from one another, wherein pore volumes
of these precious metal particles, first compounds and second
compounds are within a range of 0.24 to 0.8 cm.sup.3/g. Moreover, a
production method of an exhaust gas purifying catalyst according to
the present invention includes: a supporting step of supporting
precious metal particles on first compounds; a slurrying step of
slurrying second compounds or a precursor of the second compounds
by performing water dispersion therefor; a dispersion step of
dispersing the first compounds having the precious metal particles
supported thereon into the slurry of the second compounds; and a
drying/calcining step of drying the slurry of the second compounds,
into which the first compounds are dispersed, followed by
calcining, wherein, in the dispersion step, treatment is performed
under a condition where aggregates of the first compounds having
the precious metal particles supported thereon are decomposed.
[0010] In accordance with the exhaust gas purifying catalyst
according to the present invention and with the production method
thereof, the second compounds are arranged among the plurality of
first compounds having the precious metal particles supported
thereon, whereby the first compounds are separated from one another
by interposing the second compounds thereamong. Accordingly, even
after the catalyst is used for a long term, the precious metal
particles are not coagulated with each other, or the first
compounds are not coagulated with each other. In such a way, a
catalyst that maintains a large surface area can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic view enlargedly showing an exhaust gas
purifying catalyst according to an embodiment of the present
invention.
[0012] FIG. 2 is a schematic view enlargedly showing an exhaust gas
purifying catalyst according to a comparative example.
[0013] FIGS. 3A to 3C are schematic views showing a production
process of the exhaust gas purifying catalyst according to the
embodiment of the present invention: FIG. 3A shows a precious metal
particle; FIG. 3B shows a state where the precious metal particle
is supported on a first compound; and FIG. 3C shows a state where
the first compounds having the precious metal particles supported
thereon are covered with second compounds.
[0014] FIG. 4 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 1 to 10 and Comparative examples 1 and 2 become 50%.
[0015] FIG. 5 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 11 to 16 and Comparative examples 3 to 6 become 50%.
[0016] FIG. 6 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 17 to 19 and Comparative examples 7 and 8 become 50%.
[0017] FIG. 7 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 20 to 22 and Comparative examples 9 and 10 become 50%.
[0018] FIG. 8 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 23 to 25 and Comparative examples 11 and 12 become
50%.
[0019] FIG. 9 is a graph for comparing temperatures at which
HC(C.sub.3H.sub.6) purification rates of respective catalysts in
Examples 26 to 28 and Comparative example 13 become 50%.
BEST MODE FOR CARRYING OUT THE INVENTION
[0020] A description will be made below of an embodiment of the
present invention based on the drawings.
[Catalyst]
[0021] FIG. 1 is a schematic view enlargedly showing a state of a
cross section of an exhaust gas purifying catalyst according to the
present invention.
[0022] As shown in FIG. 1, the exhaust gas purifying catalyst 1
according to the present invention includes: precious metal
particles 3 as active metal that contacts exhaust gas and purifies
harmful components; a plurality of first compounds 5 on which the
precious metal particles 3 are supported; and second compounds 7
which are arranged among the plurality of first compounds 5 and
separate the first compounds 5 from one another, wherein pore
volumes of these precious metal particles 3, first compounds 5 and
second compounds 7 are set within a range of 0.24 to 0.8
cm.sup.3/g. In such a way, movement and coagulation of the precious
metal particles 3 can be suppressed, and in addition, mutual
coagulation of the first compounds 5 can also be suppressed. Hence,
a surface area of a precious metal layer composed of groups of the
precious metal particles 3 can be suitably suppressed from being
decreased after the catalyst 1 is exposed to the exhaust gas.
[0023] In the case of suppressing the movement of the precious
metal particles 3, there is considered: (1) a chemical restraint
method (anchoring method) of suppressing the movement of the
precious metal particles 3 by chemically boding to the precious
metal particles 3; or (2) a physical restraint method (inclusion
method) of suppressing the movement of the precious metal particles
3 by covering the precious metal particles 3 with compounds. In
addition to these (1) and (2), and in addition to suppression of
the first compounds 5 themselves supported on the precious metal
particles 3, the present invention further suppresses sintering of
the precious metal particles 3.
[0024] In the case of covering the first compounds 5 having the
precious metal particles 3 supported thereon with the second
compounds 7, it is necessary that the exhaust gas be diffused and
reach surfaces of the precious metal particles 3. For this purpose,
gaps with a size of a predetermined range are required for the
first compounds 5 and the second compounds 7, and these gaps just
need to be formed so that the pore volumes of the precious metal
particles 3, the first compounds 5 and the second compounds 7 can
be set within the predetermined range. It is sufficient if an
initial pore volume of the catalyst, that is, a pore volume of the
catalyst before the catalyst is exposed to the exhaust gas is
within a range of 0.3 to 0.8 cm.sup.3/g, and if a pore volume of
the catalyst after the catalyst is exposed to the exhaust gas is
within a range of 0.24 to 0.45 cm.sup.3/g. Hence, a condition to be
defined is to set the pore volumes of the precious metal particles
3, the first compounds 5 and the second compounds 7 within a range
of 0.24 to 0.8 cm.sup.3/g.
[Precious Metal Particle]
[0025] It is preferable that the precious metal particles 3 be
composed of at least any selected from platinum (Pt), palladium
(Pd) and rhodium (Rh). It is preferable that a particle diameter of
the precious metal particles 3 be 1 nm to 5 nm.
[First Compound]
[0026] It is preferable that the first compounds 5 on which the
precious metal particles 3 are supported be formed into a particle
shape. Moreover, it is preferable that the first compounds 5 be an
oxide containing Ce. Specifically, a compound containing CeO.sub.2
and a composite oxide of Ce and Zr can be used. In the case where
the first compounds 5 are the oxide containing Ce, the following
combinations are preferable for the precious metal particles 3, the
first compounds 5 and the second compounds 7. [0027] (a-1)
Preferable is a combination of Pt particles as the precious metal
particles 3, CeO.sub.2 particles as the first compounds 5, and
Al.sub.2O.sub.3 particles as the second compounds 7, that is, a
combination in which the Al.sub.2O.sub.3 particles are arranged
among the CeO.sub.2 particles on which the Pt particles are
supported. [0028] (a-2) Preferable is a combination of the Pt
particles as the precious metal particles 3, CeZrO.sub.x particles
as the first compounds 5, and Al.sub.2O.sub.3 particles as the
second compounds 7. Specifically, it is preferable to arrange the
Al.sub.2O.sub.3 particles among the CeZrO.sub.x particles on which
the Pt particles are supported. [0029] (a-3) Preferable is a
combination of the Pt particles as the precious metal particles 3,
the CeO.sub.2 particles as the first compounds 5, and ZrO.sub.2
particles as the second compounds 7. Specifically, it is preferable
to arrange the ZrO.sub.2 particles among the CeO.sub.2 particles on
which the Pt particles are supported. [0030] (a-4) Preferable is a
combination of the Pt particles as the precious metal particles 3,
the CeO.sub.2 particles as the first compounds 5, and a composite
oxide of Al.sub.2O.sub.3 and ZrO.sub.2 as the second compounds 7.
Specifically, it is preferable to arrange the composite oxide of
Al.sub.2O.sub.3 and ZrO.sub.2 among the CeO.sub.2 particles on
which the Pt particles are supported. [0031] (a-5) Preferable is a
combination of the Pt particles as the precious metal particles 3,
the CeZrO.sub.x particles as the first compounds 5, and the
composite oxide of Al.sub.2O.sub.3 and ZrO.sub.2 as the second
compounds 7. Specifically, it is preferable to arrange the
composite oxide of Al.sub.2O.sub.3 and ZrO.sub.2 among the
CeZrO.sub.x particles on which the Pt particles are supported.
[0032] In the case where the first compounds 5 are the oxide
containing CeO.sub.2, the following combinations are preferable for
the precious metal particles 3, the first compounds 5 and the
second compounds 7. [0033] (b-1) Preferable is a combination of the
Pt particles as the precious metal particles 3, the CeO.sub.2
particles as the first compounds 5, and the Al.sub.2O.sub.3
particles as the second compounds 7, that is, a combination in
which the Al.sub.2O.sub.3 particles are arranged among the
CeO.sub.2 particles on which the Pt particles are supported. [0034]
(b-2) Preferable is a combination of the Pt particles as the
precious metal particles 3, the CeO.sub.2 particles as the first
compounds 5, and the ZrO.sub.2 particles as the second compounds 7.
Specifically, it is preferable to arrange the ZrO.sub.2 particles
among the CeO.sub.2 particles on which the Pt particles are
supported. [0035] (b-3) Preferable is a combination of the Pt
particles as the precious metal particles 3, the CeO.sub.2
particles as the first compounds 5, and the composite oxide of
Al.sub.2O.sub.3 and ZrO.sub.2 as the second compounds 7.
Specifically, it is preferable to arrange the composite oxide of
Al.sub.2O.sub.3 and ZrO.sub.2 among the CeO.sub.2 particles on
which the Pt particles are supported.
[0036] In the case where the first compounds 5 are a composite
oxide containing Ce and Zr, the following combinations are
preferable for the precious metal particles 3, the first compounds
5 and the second compounds 7. [0037] (c-1) Preferable is a
combination of the Pt particles as the precious metal particles 3,
the CeZrO.sub.x particles as the first compounds 5, and the
Al.sub.2O.sub.3 particles as the second compounds 7. Specifically,
it is preferable to arrange the Al.sub.2O.sub.3 particles among the
CeZrO.sub.x particles on which the Pt particles are supported.
[0038] (c-2) Preferable is a combination of the Pt particles as the
precious metal particles 3, the CeZrO.sub.x particles as the first
compounds 5, and the composite oxide of Al.sub.2O.sub.3 and
ZrO.sub.2 as the second compounds 7. Specifically, it is preferable
to arrange the composite oxide of Al.sub.2O.sub.3 and ZrO.sub.2
among the CeZrO.sub.x particles on which the Pt particles are
supported.
[0039] In the case where the first compounds 5 are a composite
oxide of Mn and Al, the following combinations are preferable for
the precious metal particles 3, the first compounds 5 and the
second compounds 7. [0040] (c-1) Preferable is a combination of the
Pt particles as the precious metal particles 3, MnAl.sub.2O.sub.4
particles as the first compounds 5, and the Al.sub.2O.sub.3
particles as the second compounds 7. Specifically, it is preferable
to arrange the Al.sub.2O.sub.3 particles among the
MnAl.sub.2O.sub.4 particles on which the Pt particles are
supported.
[Second Compound]
[0041] It is preferable tat the above-described second compounds 7
be an oxide containing at least any of Al and Zr. In a combination
in the present invention, the best combination is a combination in
which Pt--CeO.sub.2 is covered with Al.sub.2O.sub.3, or in which
Pt--CeZrO.sub.x is covered with Al.sub.2O.sub.3. Moreover, a
combination in which Pt--CeO.sub.2 is covered with ZrO.sub.2 is
also good. Furthermore, a combination in which Pt--CeO.sub.2 or
Pt--CeZrO.sub.x is covered with the composite oxide of
Al.sub.2O.sub.3 and ZrO.sub.2 is also good. Moreover, it is
preferable that the above-described second compounds 7 be formed
into a particle shape, and that an average particle diameter of the
above-described second compounds 7 be 10 to 100 nm.
[0042] In the catalyst 1 according to the embodiment of the present
invention, as shown in FIG. 1, pores 7 are formed by gaps among the
particles of the second compounds 7, and by gaps among the
particles of the first compounds 5 and the second compounds 7.
Here, in the case where the particle diameter of the particles of
the second compounds 7 is smaller than 10 nm, then, like a catalyst
11 shown in FIG. 2, the pores 9 formed of the particles of the
second compounds 7 become small, and the pore volume becomes small.
Therefore, the exhaust gas becomes less likely to be diffused
through the pores 9, and catalyst activity of the catalyst 11 is
decreased. Meanwhile, in the case where the particle diameter of
the particles of the second compounds 7 becomes larger than 100 nm,
then the pores formed thereof become large, and the particles of
the first compounds 5 on which the precious metal particles are
supported come off from the gaps among the particles of the second
compounds 7, causing such an influence that the particles of the
first compounds 5 are coagulated with one another.
[Production Method of Catalyst]
[0043] A production method of the catalyst according to this
embodiment includes: a supporting step of supporting the precious
metal particles 3 on the first compounds 5; a slurrying step of
slurrying the second compounds 7 or a precursor of the second
compounds 7 by performing water dispersion therefor; a dispersion
step of dispersing the first compounds 5 having the precious metal
particles 3 supported thereon into the slurry of the second
compounds 7; and a drying/calcining step of drying the slurry of
the second compounds, into which the first compounds are dispersed,
followed by calcining, wherein, in the dispersion step, treatment
is performed under a condition where aggregates of the first
compounds 5 having the precious metal particles 3 supported thereon
are decomposed.
[0044] FIGS. 3A to 3C are schematic views showing a production
process of the catalyst 1 according to the embodiment of the
present invention: FIG. 3A shows the precious metal particle 3;
FIG. 3B shows a state where the precious metal particle 3 is
supported on the first compound 5; and FIG. 3C shows the catalyst 1
in which the first compounds 5 having the precious metal particles
3 supported thereon are covered with the second compounds 7. For
such treatment of decomposing the aggregates of the first compounds
5 on which the precious metal particles 3 are supported and
dispersing the first compounds 5 into the second compounds 7, a
method using a dispersant such as polyvinylpyrrolidone, a physical
method using shear force brought by high-speed stirring, and the
like can be used.
Examples
[0045] Subsequently, a description will be specifically made of the
present invention through examples.
Example 1
[0046] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85 wt % (these are
referred to as "ceria particles A") were formed. 118.42 g of
needle-like boehmite (o10 nm.times.100 nm) in which moisture was
contained by 24 wt % was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the ceria particles A prepared in advance was added, and was
dispersed thereinto by high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder a-1 in which the
ceria particles A were coated with alumina was prepared. 173.4 g of
this powder a-1 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were added to the ball mill, and the powder a-1 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry a-1") was formed.
[0047] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B of the second compounds 7, which had
rhodium supported thereon by 0.814%, were prepared. 118.42 g of
needle-like boehmite in which moisture was contained by 24 wt % was
put into a beaker, dispersed into water, and deflocculated by acid.
To a resultant thus obtained, 90 g of the particles B prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-1 in which the particles B were coated with
alumina was prepared. 172 g of this powder b-1 and 3 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10 wt % nitric acid solution were further added to the
ball mill, and the powder b-1 was milled, whereby slurry with an
average particle diameter of 3 .mu.m (this is referred to as
"slurry b-1") was formed. The slurry a-1 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of 036 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry b-1 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Example 1 was obtained. The
obtained sample of Example 1 is a catalyst that individually
carries thereon Pt by 0.593 g/L and Rh by 0.236 g/L.
Example 2
[0048] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85 wt % (these are
referred to as "ceria particles A") were formed. 113.92 g of
plate-like boehmite (20.times.20.times.10 nm) in which moisture was
contained by 21 wt % was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the ceria particles A prepared in advance was added, and was
dispersed thereinto by high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder a-2 in which the
ceria particles A were coated with alumina was prepared. 173.4 g of
this powder a-2 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were added to the ball mill, and the powder a-2 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry a-2") was formed.
[0049] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 113.92 g of needle-like boehmite (in which
moisture was contained by 21 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-2 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-2 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-2 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-2") was formed. The
slurry a-2 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of 036 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-2 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 2 was obtained. The obtained sample of Example 2 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 3
[0050] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85 wt % (these are
referred to as "ceria particles A") were formed. 105.88 g of
cube-like boehmite with a dimension of 20.times.20.times.20 nm (in
which moisture was contained by 15 wt %) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the ceria particles A prepared in advance
was added, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder a-3 in which the ceria particles A were coated with alumina
was prepared. 173.4 g of this powder a-3 and 1.6 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10 wt % nitric acid solution were added to the ball
mill, and the powder a-3 was milled, whereby slurry with an average
particle diameter of 3 .mu.m (this is referred to as "slurry a-3")
was formed.
[0051] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 105.88 g of cube-like boehmite in which
moisture was contained by 15 wt % was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-3 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-3 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-3 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-3") was formed. The
slurry a-3 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of 036 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-3 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 3 was obtained. The obtained sample of Example 3 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 4
[0052] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85 wt % (these are
referred to as "ceria particles A") were formed. 102.27 g of
prism-like boehmite (20.times.20.times.60 nm) in which moisture was
contained by 12 wt % was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the ceria particles A prepared in advance was added, and was
dispersed thereinto by high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder a-4 in which the
ceria particles A were coated with alumina was prepared. 173.4 g of
this powder a-4 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were added to the ball mill, and the powder a-4 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry a-4") was formed.
[0053] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 102.27 g of prism-like boehmite (in which
moisture was contained by 12 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-4 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-4 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-4 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-4") was formed. The
slurry a-4 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-4 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 4 was obtained. The obtained sample of Example 4 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 5
[0054] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85 wt % (these are
referred to as "ceria particles A") were formed. 90.9 g of alumina
nanoparticles with an average particle diameter of 40 nm (in which
moisture was contained by 1 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the ceria particles A prepared in advance was
added, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder a-5 in which the ceria particles A were coated with alumina
was prepared. 173.4 g of this powder a-5 and 1.6 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10 wt % nitric acid solution were added to the ball
mill, and the powder a-5 was milled, whereby slurry with an average
particle diameter of 3 .mu.m (this is referred to as "slurry a-5")
was formed.
[0055] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 90.9 g of alumina nanoparticles with an
average particle diameter of 40 nm (in which moisture was contained
by 1 wt %) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles B prepared in advance was added, and was dispersed
thereinto by the high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder b-5 in which the
particles B were coated with alumina was prepared. 172 g of this
powder b-5 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were further added to the ball mill, and the powder b-5
was milled, whereby slurry with an average particle diameter of 3
.mu.m (this is referred to as "slurry b-5") was formed. The slurry
a-5 was coated by 141 g/L on a honeycomb carrier (capacity: 0.04 L)
having a diameter of o36 mm and 400 cells with a wall thickness of
6 mils, followed by drying, and thereafter, the slurry b-5 was
coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 5 was obtained. The obtained sample of Example 5 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 6
[0056] Cerium-zirconium composite oxide particles with an average
particle diameter of 20 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85 wt % (these are referred to as "particles C") were
formed. 118.42 g of needle-like boehmite (in which moisture was
contained by 24 wt %) was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the particles C prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder ac-6 in which the particles
C were coated with alumina was prepared. 173.4 g of this powder
ac-6 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were added to the ball mill, and the powder ac-6 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry ac-6") was formed.
[0057] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 118.42 g of needle-like boehmite (in which
moisture was contained by 24 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-1 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-1 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-1 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-1") was formed. The
slurry ac-6 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-1 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 6 was obtained. The obtained sample of Example 6 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 7
[0058] Cerium-zirconium composite oxide particles with an average
particle diameter of 20 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85 wt % (these are referred to as "particles C") were
formed. 113.92 g of plate-like boehmite (in which moisture was
contained by 21 wt %) was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the particles C prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder ac-7 in which the particles
C were coated with alumina was prepared. 173.4 g of this powder
ac-7 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were added to the ball mill, and the powder ac-7 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry ac-7") was formed.
[0059] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 113.92 g of plate-like boehmite (in which
moisture was contained by 21 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-2 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-2 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-2 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-2") was formed. The
slurry ac-7 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-2 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 7 was obtained. The obtained sample of Example 7 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 7
[0060] Cerium-zirconium composite oxide particles with an average
particle diameter of 20 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85 wt % (these are referred to as "particles C") were
formed. 105.88 g of cube-like boehmite (in which moisture was
contained by 15 wt %) was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the particles C prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder ac-8 in which the particles
C were coated with alumina was prepared. 173.4 g of this powder
ac-8 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were added to the ball mill, and the powder ac-8 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry ac-8") was formed.
[0061] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 105.88 g of cube-like boehmite (in which
moisture was contained by 15 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-3 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-3 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-3 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-3") was formed. The
slurry ac-8 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-3 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 8 was obtained. The obtained sample of Example 8 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 9
[0062] Manganese aluminate particles with an average particle
diameter of 40 nm were used as the first compounds 5.
Dinitrodiamine Pd was impregnated into the particles, whereby
manganese aluminate particles having Pd supported thereon by 0.85
wt % (these are referred to as "particles D") were formed. 113.92 g
of plate-like boehmite (in which moisture was contained by 21 wt %)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles D
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder ad-9 in which the particles D were coated
with alumina was prepared. 173.4 g of this powder ad-9 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10 wt % nitric acid solution were added to
the ball mill, and the powder ad-9 was milled, whereby slurry with
an average particle diameter of 3 .mu.m (this is referred to as
"slurry ad-9") was formed.
[0063] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 113.92 g of plate-like boehmite (in which
moisture was contained by 21 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-2 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-2 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-2 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-2") was formed. The
slurry ad-9 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-2 was coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 9 was obtained. The obtained sample of Example 9 is a
catalyst that individually carries thereon Pd by 0.593 g/L and Rh
by 0.236 g/L.
Example 10
[0064] Manganese aluminate particles with an average particle
diameter of 40 nm were used as the first compounds 5.
Dinitrodiamine Pd was impregnated into the particles, whereby
manganese aluminate particles having Pd supported thereon by 0.85
wt % (these are referred to as "particles D") were formed. 105.88 g
of cube-like boehmite (in which moisture was contained by 15 wt %)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles D
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder ad-10 in which the particles D were coated
with alumina was prepared. 173.4 g of this powder ad-10 and 1.6 g
of boehmite alumina were added to a ball mill. Thereafter, 307.5 g
of water and 17.5 g of a 10 wt % nitric acid solution were added to
the ball mill, and the powder ad-10 was milled, whereby slurry with
an average particle diameter of 3 .mu.m (this is referred to as
"slurry ad-10") was formed.
[0065] Next, rhodium nitrate was impregnated into a
zirconium-cerium composite oxide with an average particle diameter
of 20 nm, whereby particles B having rhodium supported thereon by
0.814% were prepared. 105.88 g of cube-like boehmite (in which
moisture was contained by 15 wt %) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-3 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-3 and 3 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were further added to the ball mill, and the powder
b-3 was milled, whereby slurry with an average particle diameter of
3 .mu.m (this is referred to as "slurry b-3") was formed. The
slurry ad-10 was coated by 141 g/L on a honeycomb carrier
(capacity: 0.04 L) having a diameter of o36 mm and 400 cells with a
wall thickness of 6 mils, followed by drying, and thereafter, the
slurry b-3 was coated by 59 g/L thereon, followed by drying.
Thereafter, a resultant was calcined at 400.degree. C., whereby a
sample of Example 10 was obtained. The obtained sample of Example
10 is a catalyst that individually carries thereon Pt by 0.593 g/L
and Rh by 0.236 g/L.
Example 11
[0066] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. 118.42 g of needle-like boehmite (100 nm.times.010 nm;
aspect ratio: 10) (in which moisture was contained by 24%) was put
into a beaker, dispersed into water, and deflocculated by acid. To
a resultant thus obtained, 90 g of the particles A prepared in
advance was added, and was dispersed thereinto by high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder a-11 in which the particles A were coated with
alumina was prepared (only this needle-like boehmite was calcined,
and a pore volume thereof was investigated, then the pore volume
was 0.8 cm.sup.3/g). 173.4 g of this powder a-11 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder a-11 was milled, whereby slurry a-11 with
an average particle diameter of 3 .mu.m was formed.
[0067] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814 were prepared. 118.42 g of needle-like
boehmite (100 nm.times.o10 nm; aspect ratio: 10) (in which moisture
was contained by 24%) was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the particles B prepared in advance was added, and was dispersed
thereinto by the high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder b-11 in which the
particles B were coated with alumina was prepared. 172 g of this
powder b-11 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 of a 10% nitric acid solution
were further added to the ball mill, and the powder b-11 was
milled, whereby slurry b-11 with an average particle diameter of 3
.mu.m was formed. The slurry a-11 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry b-11 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Example 11 was obtained. The
obtained sample of Example 11 is a catalyst that individually
carries thereon Pt by 0.593 g/L and Rh by 0.236 g/L.
Example 12
[0068] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the ceria-zirconium
particles, whereby cerium-zirconium composite oxide particles
having Pt supported thereon by 0.85% (these are referred to as
"particles A") were formed. 113.92 g of plate-like boehmite
(10.times.20.times.20 nm; aspect ratio: 0.5) (in which moisture was
contained by 21%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-12 in which the particles
A were coated with alumina was prepared (only this plate-like
boehmite was calcined, and a pore volume thereof was investigated,
then the pore volume was 0.85 cm.sup.3/g). 173.4 g of this powder
a-12 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-12 was
milled, whereby slurry a-12 with an average particle diameter of 3
.mu.m was formed.
[0069] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 113.92 g of plate-like
boehmite (10.times.20.times.20 nm; aspect ratio: 0.5) (in which
moisture was contained by 21%) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-12 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-12 and 3 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were further added to the ball mill, and the powder
b-12 was milled, whereby slurry b-12 with an average particle
diameter of 3 .mu.m was formed. The slurry a-12 was coated by 141
g/L on a honeycomb carrier (capacity: 0.04 L) having a diameter of
o36 mm and 400 cells with a wall thickness of 6 mils, followed by
drying, and thereafter, the slurry b-12 was coated by 59 g/L
thereon, followed by drying. Thereafter, a resultant was calcined
at 400.degree. C., whereby a sample of Example 12 was obtained. The
obtained sample of Example 12 is a catalyst that individually
carries thereon Pt by 0.593 g/L and Rh by 0.236 g/L.
Example 13
[0070] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, whereby cerium-zirconium composite oxide
particles having Pt supported thereon by 0.85% (these are referred
to as "particles A") were formed. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm; aspect ratio: 1) (in which moisture was
contained by 15%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-13 in which the particles
A were coated with alumina was prepared (only this cube-like
boehmite was calcined, and a pore volume thereof was investigated,
then the pore volume was 0.9 cm.sup.3/g). 173.4 g of this powder
a-13 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-13 was
milled, whereby slurry a-13 with an average particle diameter of 3
.mu.m was formed.
[0071] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 105.88 g of cube-like
boehmite (20.times.20.times.20 nm; aspect ratio: 1) (in which
moisture was contained by 15%) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-13 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-13 and 3 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were further added to the ball mill, and the powder
b-13 was milled, whereby slurry b-13 with an average particle
diameter of 3 .mu.m was formed. The slurry a-13 was coated by 141
g/L on a honeycomb carrier (capacity: 0.04 L) having a diameter of
o36 mm and 400 cells with a wall thickness of 6 mils, followed by
drying, and thereafter, the slurry b-13 was coated by 59 g/L
thereon, followed by drying. Thereafter, a resultant was calcined
at 400.degree. C., whereby a sample of Example 13 was obtained. The
obtained sample of Example 13 is a catalyst that individually
carries thereon Pt by 0.593 g/L and Rh by 0.236 g/L.
Example 14
[0072] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, whereby cerium-zirconium composite oxide
particles having Pt supported thereon by 0.85% (these are referred
to as "particles A") were formed. 102.27 g of prism-like boehmite
(60.times.20.times.20 nm; aspect ratio: 3) (in which moisture was
contained by 12%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-14 in which the particles
A were coated with alumina was prepared (only this prism-like
boehmite was calcined, and a pore volume thereof was investigated,
then the pore volume was 1.0 cm.sup.3/g). 173.4 g of this powder
a-14 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-14 was
milled, whereby slurry a-14 with an average particle diameter of 3
.mu.m was formed.
[0073] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 102.27 g of prism-like
boehmite (60.times.20.times.20 nm; aspect ratio: 3) (in which
moisture was contained by 12%) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-14 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-14 and 3 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were further added to the ball mill, and the powder
b-14 was milled, whereby slurry b-14 with an average particle
diameter of 3 .mu.m was formed. The slurry a-14 was coated by 141
g/L on a honeycomb carrier (capacity: 0.04 L) having a diameter of
o36 mm and 400 cells with a wall thickness of 6 mils, followed by
drying, and thereafter, the slurry b-14 was coated by 59 g/L
thereon, followed by drying. Thereafter, a resultant was calcined
at 400.degree. C., whereby a sample of Example 14 was obtained. The
obtained sample of Example 14 is a catalyst that individually
carries thereon Pt by 0.593 g/L and Rh by 0.236 g/L.
Example 15
[0074] Cerium-zirconium composite oxide particles with an average
particle diameter of 20 nm were used as the first compounds 5.
Dinitrodiamine Pd was impregnated into the cerium-zirconium
composite oxide particles, whereby cerium-zirconium composite oxide
particles having Pd supported thereon by 0.85% (these are referred
to as "particles C") were formed. 113.92 g of plate-like boehmite
(10.times.20.times.20 nm; aspect ratio: 0.5) (in which moisture was
contained by 21%) was put into a beaker, dispersed into water, and
made acidic. To a resultant thus obtained, 90 g of the particles C
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder ad-15 in which the particles C were coated
with alumina was prepared. 173.4 g of this powder ad-15 and 1.6 g
of boehmite alumina were added to a ball mill. Thereafter, 307.5 g
of water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder ad-15 was milled, whereby slurry ad-15
with an average particle diameter of 3 .mu.m was formed.
[0075] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 113.92 g of plate-like
boehmite (10.times.20.times.20 nm; aspect ratio: 0.5) (in which
moisture was contained by 21%) was put into a beaker, dispersed
into water, and made acidic. To a resultant thus obtained, 90 g of
the particles B prepared in advance was added, and was dispersed
thereinto by the high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder b-12 in which the
particles B were coated with alumina was prepared. 172 g of this
powder b-12 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder b-12
was milled, whereby slurry b-12 with an average particle diameter
of 3 .mu.m was formed. The slurry ad-15 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry b-12 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Example 15 was obtained. The
obtained sample of Example 15 is a catalyst that individually
carries thereon Pd by 0.593 g/L and Rh by 0.236 g/L.
Example 16
[0076] Cerium-zirconium composite oxide particles with an average
particle diameter of 20 nm were used as the first compounds 5.
Dinitrodiamine Pd was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pd supported
thereon by 0.85% (these are referred to as "particles C") were
formed. 105.88 g of cube-like boehmite (20.times.20.times.20 nm;
aspect ratio: 1) (in which moisture was contained by 15%) was put
into a beaker, dispersed into water, and made acidic. To a
resultant thus obtained, 90 g of the particles C prepared in
advance was added, and was dispersed thereinto by high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder ad-16 in which the particles C were coated with
alumina was prepared. 173.4 g of this powder ad-16 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder ad-16 was milled, whereby slurry ad-16
with an average particle diameter of 3 .mu.m was formed.
[0077] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 105.88 g of cube-like
boehmite (20.times.20.times.20 nm; aspect ratio: 1) (in which
moisture was contained by 15%) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by the high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder b-13 in
which the particles B were coated with alumina was prepared. 172 g
of this powder b-13 and 3 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were further added to the ball mill, and the powder
b-13 was milled, whereby slurry b-13 with an average particle
diameter of 3 .mu.m was formed. The slurry ad-16 was coated by 141
g/L on a honeycomb carrier (capacity: 0.04 L) having a diameter of
o36 mm and 400 cells with a wall thickness of 6 mils, followed by
drying, and thereafter, the slurry b-13 was coated by 59 g/L
thereon, followed by drying. Thereafter, a resultant was calcined
at 400.degree. C., whereby a sample of Example 16 was obtained. The
obtained sample of Example 16 is a catalyst that individually
carries thereon Pd by 0.593 g/L and Rh by 0.236 g/L.
Example 17
[0078] Cerium-zirconium composite oxide particles with a pore
volume of 0.18 cm.sup.3/g were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles D1") were
formed. 105.88 g of cube-like boehmite (20.times.20.times.20 nm)
(in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles D1 prepared in advance was
added, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder a-17 in which the particles D1 were coated with alumina was
prepared. 173.4 g of this powder a-17 and 1.6 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were added to the ball mill, and the
powder a-17 was milled, whereby slurry a-17 with an average
particle diameter of 3 .mu.m was formed.
[0079] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with a pore volume of
0.28 cm.sup.3/g, whereby particles El having rhodium supported
thereon by 0.814% were prepared. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles E1
prepared in advance was added, and was dispersed thereinto by the
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder b-17 in which the particles E1 were coated
with alumina was prepared. 172 g of this powder b-17 and 3 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were further added
to the ball mill, and the powder b-17 was milled, whereby slurry
b-17 with an average particle diameter of 3 .mu.m was formed. The
slurry a-17 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-17 was coated by 59 g/L thereon, followed by drying. Thereafter,
a resultant was calcined at 400.degree. C., whereby a sample of
Example 17 was obtained. The obtained sample of Example 17 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 18
[0080] Cerium-zirconium composite oxide particles with a pore
volume of 0.28 cm.sup.3/g were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles D2") were
formed. 105.88 g of cube-like boehmite (20.times.20.times.20 nm)
(in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles D2 prepared in advance was
added, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder a-18 in which the particles D2 were coated with alumina was
prepared. 173.4 g of this powder a-18 and 1.6 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were added to the ball mill, and the
powder a-18 was milled, whereby slurry a-18 with an average
particle diameter of 3 .mu.m was formed.
[0081] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with a pore volume of
0.30 cm.sup.3/g, whereby particles E2 having rhodium supported
thereon by 0.814% were prepared. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles E2
prepared in advance was added, and was dispersed thereinto by the
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder b-18 in which the particles E2 were coated
with alumina was prepared. 172 g of this powder b-18 and 3 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were further added
to the ball mill, and the powder b-18 was milled, whereby slurry
b-18 with an average particle diameter of 3 .mu.m was formed. The
slurry a-18 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-18 was coated by 59 g/L thereon, followed by drying. Thereafter,
a resultant was calcined at 400.degree. C., whereby a sample of
Example 18 was obtained. The obtained sample of Example 18 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 19
[0082] Cerium-zirconium composite oxide particles with a pore
volume of 0.30 cm.sup.3/g were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles D3") were
formed. 105.88 g of cube-like boehmite (20.times.20.times.20 nm)
(in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles D3 prepared in advance was
added, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder a-19 in which the particles D3 were coated with alumina was
prepared. 173.4 g of this powder a-19 and 1.6 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were added to the ball mill, and the
powder a-19 was milled, whereby slurry a-19 with an average
particle diameter of 3 .mu.m was formed.
[0083] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with a pore volume of
0.32 cm.sup.3/g, whereby particles E3 having rhodium supported
thereon by 0.814% were prepared. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles E3
prepared in advance was added, and was dispersed thereinto by the
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder b-19 in which the particles E3 were coated
with alumina was prepared. 172 g of this powder b-19 and 3 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were further added
to the ball mill, and the powder b-19 was milled, whereby slurry
b-19 with an average particle diameter of 3 .mu.m was formed. The
slurry a-19 was coated by 141 g/L on a honeycomb carrier (capacity:
0.04 L) having a diameter of o36 mm and 400 cells with a wall
thickness of 6 mils, followed by drying, and thereafter, the slurry
b-19 was coated by 59 g/L thereon, followed by drying. Thereafter,
a resultant was calcined at 400.degree. C., whereby a sample of
Example 19 was obtained. The obtained sample of Example 19 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 20
[0084] Cerium-zirconium composite oxide particles in which cerium
occupied 74% and zirconium occupied 26% in terms of composition
were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the particles, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles F1") were formed. 105.88 g of cube-like
boehmite (20.times.20.times.20 nm) (in which moisture was contained
by 15%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles F1 prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-20 in which the particles
F1 were coated with alumina was prepared. 173.4 g of this powder
a-20 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-20 was
milled, whereby slurry a-20 with an average particle diameter of 3
.mu.m was formed.
[0085] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles in which zirconium
occupied 95% and lanthanum occupied 5% in terms of composition,
whereby particles G1 having rhodium supported thereon by 0.814%
were prepared. 105.88 g of cube-like boehmite (20.times.20.times.20
nm) (in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles G1 prepared in advance was
added, and was dispersed thereinto by the high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder b-20 in which the particles G1 were coated with alumina was
prepared. 172 g of this powder b-20 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were further added to the ball mill,
and the powder b-20 was milled, whereby slurry b-20 with an average
particle diameter of 3 .mu.m was formed. The slurry a-20 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-20 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 20 was
obtained. The obtained sample of Example 20 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Example 21
[0086] Cerium-zirconium composite oxide particles in which cerium
occupied 78% and zirconium occupied 22% in terms of composition
were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the particles, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles F2") were formed. 105.88 g of cube-like
boehmite (20.times.20.times.20 nm) (in which moisture was contained
by 15%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles F2 prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-21 in which the particles
F2 were coated with alumina was prepared. 173.4 g of this powder
a-21 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-21 was
milled, whereby slurry a-21 with an average particle diameter of 3
.mu.m was formed.
[0087] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles in which zirconium
occupied 97% and lanthanum occupied 3% in terms of composition,
whereby particles G2 having rhodium supported thereon by 0.814%
were prepared. 105.88 g of cube-like boehmite (20.times.20.times.20
nm) (in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles G2 prepared in advance was
added, and was dispersed thereinto by the high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder b-21 in which the particles G2 were coated with alumina was
prepared. 172 g of this powder b-21 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were further added to the ball mill,
and the powder b-21 was milled, whereby slurry b-21 with an average
particle diameter of 3 .mu.m was formed. The slurry a-21 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-21 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 21 was
obtained. The obtained sample of Example 21 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Example 22
[0088] Cerium-zirconium composite oxide particles in which cerium
occupied 80% and zirconium occupied 20% in terms of composition
were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the particles, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles F3") were formed. 105.88 g of cube-like
boehmite (20.times.20.times.20 nm) (in which moisture was contained
by 15%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles F3 prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-22 in which the particles
F3 were coated with alumina was prepared. 173.4 g of this powder
a-22 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-22 was
milled, whereby slurry a-22 with an average particle diameter of 3
.mu.m was formed.
[0089] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles in which zirconium
occupied 99% and lanthanum occupied 1% in terms of composition,
whereby particles G3 having rhodium supported thereon by 0.814%
were prepared. 105.88 g of cube-like boehmite (20.times.20.times.20
nm) (in which moisture was contained by 15%) was put into a beaker,
dispersed into water, and deflocculated by acid. To a resultant
thus obtained, 90 g of the particles G3 prepared in advance was
added, and was dispersed thereinto by the high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder b-22 in which the particles G3 were coated with alumina was
prepared. 172 g of this powder b-22 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were further added to the ball mill,
and the powder b-22 was milled, whereby slurry b-22 with an average
particle diameter of 3 .mu.m was formed. The slurry a-22 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-22 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 22 was
obtained. The obtained sample of Example 22 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Example 23
[0090] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. 105.04 g of needle-like boehmite (o10 nm.times.100 nm) (in
which moisture was contained by 24.6%) was put into a beaker into
which water was poured, cerium nitrate was added thereto so that an
amount thereof as cerium oxide could be 4.5 g, and zirconyl nitrate
was dispersed into the water so that an amount thereof as zirconium
oxide could be 6.3 g. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-23 in which the particles
A were coated with alumina was prepared. 173.4 g of this powder
a-23 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-23 was
milled, whereby slurry a-23 with an average particle diameter of 3
.mu.m was formed.
[0091] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 118.42 g of needle-like
boehmite (in which moisture was contained by 24%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles B prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-11 in which the particles B were coated with
alumina was prepared. 172 g of this powder b-11 and 3 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10% nitric acid solution were further added to the ball
mill, and the powder b-11 was milled, whereby slurry b-11 with an
average particle diameter of 3 .mu.m was formed. The slurry a-23
was coated by 141 g/L on a honeycomb carrier (capacity: 0.04 L)
having a diameter of o36 mm and 400 cells with a wall thickness of
6 mils, followed by drying, and thereafter, the slurry b-11 was
coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 23 was obtained. The obtained sample of Example 23 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 24
[0092] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. 101.46 g of needle-like boehmite (o10 nm.times.100 nm) (in
which moisture was contained by 24.6%) was put into a beaker into
which water was poured, cerium nitrate was added thereto so that an
amount thereof as cerium oxide could be 9 g, and zirconyl nitrate
was dispersed into the water so that an amount thereof as zirconium
oxide could be 4.5 g. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-24 in which the particles
A were coated with alumina was prepared. 173.4 g of this powder
a-24 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-24 was
milled, whereby slurry a-24 with an average particle diameter of 3
.mu.m was formed.
[0093] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 118.42 g of needle-like
boehmite (in which moisture was contained by 24%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles B prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-11 in which the particles B were coated with
alumina was prepared. 172 g of this powder b-11 and 3 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10% nitric acid solution were further added to the ball
mill, and the powder b-11 was milled, whereby slurry b-11 with an
average particle diameter of 3 .mu.m was formed. The slurry a-24
was coated by 141 g/L on a honeycomb carrier (capacity: 0.04 L)
having a diameter of o36 mm and 400 cells with a wall thickness of
6 mils, followed by drying, and thereafter, the slurry b-11 was
coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 24 was obtained. The obtained sample of Example 24 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 25
[0094] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. 97.88 g of needle-like boehmite (o10 nm.times.100 nm) (in
which moisture was contained by 24.6%) was put into a beaker into
which water was poured, cerium nitrate was added thereto so that an
amount thereof as cerium oxide could be 13.5 g, and zirconyl
nitrate was dispersed into the water so that an amount thereof as
zirconium oxide could be 2.7 g. To a resultant thus obtained, 90 g
of the particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder a-25 in which the particles
A were coated with alumina was prepared. 173.4 g of this powder
a-25 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder a-25 was
milled, whereby slurry a-25 with an average particle diameter of 3
.mu.m was formed.
[0095] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 118.42 g of needle-like
boehmite (in which moisture was contained by 24%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles B prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-11 in which the particles B were coated with
alumina was prepared. 172 g of this powder b-11 and 3 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10% nitric acid solution were further added to the ball
mill, and the powder b-11 was milled, whereby slurry b-11 with an
average particle diameter of 3 .mu.m was formed. The slurry a-25
was coated by 141 g/L on a honeycomb carrier (capacity: 0.04 L)
having a diameter of o36 mm and 400 cells with a wall thickness of
6 mils, followed by drying, and thereafter, the slurry b-11 was
coated by 59 g/L thereon, followed by drying. Thereafter, a
resultant was calcined at 400.degree. C., whereby a sample of
Example 25 was obtained. The obtained sample of Example 25 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Example 26
[0096] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, and a resultant was calcined at
700.degree. C. for two hours, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles I1") were formed. A degree of dispersion
of Pt in the particles I1 was 50%. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles I1
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder a-26 in which the particles I1 were coated
with alumina was prepared. A degree of dispersion of Pt in the
particles was 35%. 173.4 g of this powder a-26 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder a-26 was milled, whereby slurry a-26 with
an average particle diameter of 3 .mu.m was formed.
[0097] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, and a resultant was calcined at
400.degree. C. for one hour, whereby zirconium-lanthanum composite
oxide particles having rhodium supported thereon by 0.814% (these
are referred to as "particles J1") were prepared. A degree of
dispersion of Rh in the particles J1 was 56%. 105.88 g of cube-like
boehmite (in which moisture was contained by 15%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles J1 prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-26 in which the particles J1 were coated with
alumina was prepared. A degree of dispersion of Rh in the powder
was 38%. 172 g of this powder b-26 and 3 g of boehmite alumina were
added to a ball mill. Thereafter, 307.5 g of water and 17.5 g of a
10% nitric acid solution were further added to the ball mill, and
the powder b-26 was milled, whereby slurry b-26 with an average
particle diameter of 3 .mu.m was formed. The slurry a-26 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-26 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 26 was
obtained. The obtained sample of Example 26 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Example 27
[0098] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, and a resultant was calcined at
600.degree. C. for two hours, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles I2") were formed. A degree of dispersion
of Pt in the particles I2 was 50%. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles 12
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder a-27 in which the particles 12 were coated
with alumina was prepared. A degree of dispersion of Pt in the
particles a-27 was 50%. 173.4 g of this powder a-27 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder a-27 was milled, whereby slurry a-27 with
an average particle diameter of 3 .mu.m was formed.
[0099] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, and a resultant was calcined at
400.degree. C. for one hour, whereby the particles J1 having
rhodium supported thereon by 0.814% were prepared. A degree of
dispersion of Rh in the particles J1 was 56%. 105.88 g of cube-like
boehmite (in which moisture was contained by 15%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles J1 prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-27 in which the particles J1 were coated with
alumina was prepared. A degree of dispersion of Rh in the powder
b-27 was 38%. 172 g of this powder b-27 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were further added to the ball mill,
and the powder b-27 was milled, whereby slurry b-27 with an average
particle diameter of 3 .mu.m was formed. The slurry a-27 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-27 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 27 was
obtained. The obtained sample of Example 27 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Example 28
[0100] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, and a resultant was calcined at
400.degree. C. for one hour, whereby cerium-zirconium composite
oxide particles having Pt supported thereon by 0.85% (these are
referred to as "particles I3") were formed. A degree of dispersion
of Pt in the particles I3 was 100%. 105.88 g of cube-like boehmite
(20.times.20.times.20 nm) (in which moisture was contained by 15%)
was put into a beaker, dispersed into water, and deflocculated by
acid. To a resultant thus obtained, 90 g of the particles I3
prepared in advance was added, and was dispersed thereinto by
high-speed stirring. Thereafter, slurry thus obtained was dried and
calcined, whereby powder a-28 in which the particles I3 were coated
with alumina was prepared. A degree of dispersion of Pt in the
powder was 80%. 173.4 g of this powder a-28 and 1.6 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10% nitric acid solution were added to the ball mill,
and the powder a-28 was milled, whereby slurry a-28 with an average
particle diameter of 3 .mu.m was formed.
[0101] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, and a resultant was calcined at
400.degree. C. for one hour, whereby the particles J1 having
rhodium supported thereon by 0.814% were prepared. A degree of
dispersion of Rh in the particles J1 was 56%. 105.88 g of cube-like
boehmite (in which moisture was contained by 15%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles J1 prepared in
advance was added, and was dispersed thereinto by the high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder b-28 in which the particles J1 were coated with
alumina was prepared. A degree of dispersion of Rh in the powder
b-28 was 38%. 172 g of this powder b-28 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10% nitric acid solution were further added to the ball mill,
and the powder b-28 was milled, whereby slurry b-28 with an average
particle diameter of 3 .mu.m was formed. The slurry a-28 was coated
by 141 g/L on a honeycomb carrier (capacity: 0.04 L) having a
diameter of o36 mm and 400 cells with a wall thickness of 6 mils,
followed by drying, and thereafter, the slurry b-28 was coated by
59 g/L thereon, followed by drying. Thereafter, a resultant was
calcined at 400.degree. C., whereby a sample of Example 28 was
obtained. The obtained sample of Example 28 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 1
[0102] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85% (these are referred
to as "ceria particles A") were formed. Aluminum isopropoxide
equivalent to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
ceria particles A was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder c-1 in which the
particles A were coated with alumina was prepared. An average
particle diameter of the alumina was 7 to 8 nm. 173.4 g of this
powder c-1 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were added to the ball mill, and the powder c-1 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry c-1") was formed.
[0103] Next, rhodium nitrate was impregnated into zirconium-cerium
composite oxide particles with an average particle diameter of 20
nm, whereby particles B having rhodium supported thereon by 0.814%
were prepared. 562.5 g of zirconia sol with an average particle
diameter of 8 nm (in which moisture was contained by 84%) was put
into a beaker, and 90 g of the particles B prepared in advance was
added thereto, and was dispersed thereinto by high-speed stirring.
Thereafter, slurry thus obtained was dried and calcined, whereby
powder cb-1 in which the particles B were coated with alumina was
prepared. 172 g of this powder cb-1 and 3 g of boehmite alumina
were added to a ball mill. Thereafter, 307.5 g of water and 17.5 g
of a 10 wt % nitric acid solution were further added to the ball
mill, and the powder cb-1 was milled, whereby slurry with an
average particle diameter of 3 .mu.m (this is referred to as
"slurry cb-1") was formed. The slurry c-1 was coated by 141 g/L on
a honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-1 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 1 was
obtained. The obtained sample of Comparative example 1 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative example 2
[0104] CeO.sub.2 particles with an average particle diameter of 30
nm were used as the first compounds 5. Dinitrodiamine Pt was
impregnated into the CeO.sub.2 particles, whereby CeO.sub.2
particles having Pt supported thereon by 0.85% (these are referred
to as "ceria particles A") were formed. 90.9 g of alumina
nanoparticles with an average particle diameter of 110 nm (in which
moisture was contained by 1 wt %) was put into a beaker, dispersed
into water, and made acidic. To a resultant thus obtained, 90 g of
the ceria particles A prepared in advance was added, and was
dispersed thereinto by high-speed stirring. Thereafter, slurry thus
obtained was dried and calcined, whereby powder c-2 in which the
ceria particles A were coated with alumina was prepared. 173.4 g of
this powder c-2 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric
acid solution were added to the ball mill, and the powder c-2 was
milled, whereby slurry with an average particle diameter of 3 .mu.m
(this is referred to as "slurry c-2") was formed.
[0105] Next, rhodium nitrate was impregnated into zirconium-cerium
composite oxide particles with an average particle diameter of 20
nm, whereby particles B having rhodium supported thereon by 0.814%
were prepared. 90.9 g of alumina nanoparticles with an average
particle diameter of 110 nm (in which moisture was contained by 1%)
was put into a beaker, dispersed into water, and made acidic. To a
resultant thus obtained, 90 g of the particles B prepared in
advance was added, and was dispersed thereinto by high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder cb-2 in which the particles B were coated with
alumina was prepared. 172 g of this powder cb-2 and 3 g of boehmite
alumina were added to a ball mill. Thereafter, 307.5 g of water and
17.5 g of a 10 wt % nitric acid solution were further added to the
ball mill, and the powder cb-2 was milled, whereby slurry with an
average particle diameter of 3 .mu.m (this is referred to as
"slurry cb-2") was formed. The slurry c-2 was coated by 141 g/L on
a honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-2 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 2 was
obtained. The obtained sample of Comparative example 2 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 3
[0106] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, whereby cerium-zirconium composite oxide
particles having Pt supported thereon by 0.85% (these are referred
to as "particles A") were formed. Aluminum isopropoxide equivalent
to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles A was added, and water was further added thereto, whereby
hydrolysis was performed therefor. The water and organic matter
such as the 2-methyl-2,4-pentanediol were evaporated and dried,
followed by calcining, whereby powder c-3 in which the particles A
were coated with alumina was prepared. An average particle diameter
of the alumina was 7 to 8 nm. 173.4 g of this powder c-3 and 1.6 g
of boehmite alumina were added to a ball mill. Thereafter, 307.5 g
of water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder c-3 was milled, whereby slurry c-3 with
an average particle diameter of 3 .mu.m was formed.
[0107] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. Aluminum isopropoxide
equivalent to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles B was added, and water was further added thereto, whereby
hydrolysis was performed therefor. The water and organic matter
such as the 2-methyl-2,4-pentanediol were evaporated and dried,
followed by calcining, whereby powder cb-3 in which the particles B
were coated with alumina was prepared. 172 g of this powder cb-3
and 3 g of boehmite alumina were added to a ball mill. Thereafter,
307.5 g of water and 17.5 g of a 10% nitric acid solution were
further added to the ball mill, and the powder cb-3 was milled,
whereby slurry cb-3 with an average particle diameter of 3 .mu.m
was formed. The slurry c-3 was coated by 141 g/L on a honeycomb
carrier (capacity: 0.04 L) having a diameter of o36 mm and 400
cells with a wall thickness of 6 mils, followed by drying, and
thereafter, the slurry cb-3 was coated by 59 g/L thereon, followed
by drying. Thereafter, a resultant was calcined at 400.degree. C.,
whereby a sample of Comparative example 3 was obtained. The
obtained sample of Comparative example 3 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 4
[0108] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
composite oxide particles, whereby cerium-zirconium composite oxide
particles having Pt supported thereon by 0.85% (these are referred
to as "particles A") were formed. 90.9 g of alumina nanoparticles
with an average particle diameter of 130 nm (in which moisture was
contained by 1 wt %) was put into a beaker, dispersed into water,
and made acidic. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder c-4 in which the particles A
were coated with alumina was prepared. 173.4 g of this powder c-4
and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10 wt % nitric acid
solution were added to the ball mill, and the powder c-4 was
milled, whereby slurry c-4 with an average particle diameter of 3
.mu.m was formed.
[0109] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 90.9 g of alumina
nanoparticles with an average particle diameter of 130 nm (in which
moisture was contained by 1%) was put into a beaker, dispersed into
water, and made acidic. To a resultant thus obtained, 90 g of the
particles B prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder cb-4 in which the particles
B were coated with alumina was prepared. 172 g of this powder cb-4
and 3 g of boehmite alumina were added to a ball mill. Thereafter,
307.5 g of water and 17.5 g of a 10% nitric acid solution were
further added to the ball mill, and the powder cb-4 was milled,
whereby slurry cb-4 with an average particle diameter of 3 .mu.m
was formed. The slurry c-4 was coated by 141 g/L on a honeycomb
carrier (capacity: 0.04 L) having a diameter of o36 mm and 400
cells with a wall thickness of 6 mils, followed by drying, and
thereafter, the slurry cb-4 was coated by 59 g/L thereon, followed
by drying. Thereafter, a resultant was calcined at 400.degree. C.,
whereby a sample of Comparative example 4 was obtained. The
obtained sample of Comparative example 4 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 5
[0110] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. 120 g of needle-like boehmite (150 nm.times.010 nm; aspect
ratio: 15) (in which moisture was contained by 25%) was put into a
beaker, dispersed into water, and deflocculated by acid. To a
resultant thus obtained, 90 g of the particles A prepared in
advance was added, and was dispersed thereinto by high-speed
stirring. Thereafter, slurry thus obtained was dried and calcined,
whereby powder c-5 in which the particles A were coated with
alumina was prepared (only this needle-like boehmite was calcined,
and a pore volume thereof was investigated, then the pore volume
was 0.7 cm.sup.3/g). 173.4 g of this powder c-5 and 1.6 g of
boehmite alumina were added to a ball mill. Thereafter, 307.5 g of
water and 17.5 g of a 10% nitric acid solution were added to the
ball mill, and the powder c-5 was milled, whereby slurry c-5 with
an average particle diameter of 3 .mu.m was formed.
[0111] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 120 g of needle-like
boehmite (150 nm.times.o10 nm; aspect ratio: 15) (in which moisture
was contained by 25%) was put into a beaker, dispersed into water,
and deflocculated by acid. To a resultant thus obtained, 90 g of
the particles B prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder cb-5 in which the particles
B were coated with alumina was prepared. 172 g of this powder cb-5
and 3 g of boehmite alumina were added to a ball mill. Thereafter,
307.5 g of water and 17.5 g of a 10% nitric acid solution were
further added to the ball mill, and the powder cb-5 was milled,
whereby slurry cb-5 with an average particle diameter of 3 .mu.m
was formed. The slurry c-5 was coated by 141 g/L on a honeycomb
carrier (capacity: 0.04 L) having a diameter of o36 mm and 400
cells with a wall thickness of 6 mils, followed by drying, and
thereafter, the slurry cb-5 was coated by 59 g/L thereon, followed
by drying. Thereafter, a resultant was calcined at 400.degree. C.,
whereby a sample of Comparative example 5 was obtained. The
obtained sample of Comparative example 5 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 6
[0112] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the cerium-zirconium
particles, whereby cerium-zirconium composite oxide particles
having Pt supported thereon by 0.85% (these are referred to as
"particles A") were formed. 113.92 g of plate-like boehmite
(5.times.20.times.20 nm; aspect ratio: 0.25) (in which moisture was
contained by 21%) was put into a beaker, dispersed into water, and
deflocculated by acid. To a resultant thus obtained, 90 g of the
particles A prepared in advance was added, and was dispersed
thereinto by high-speed stirring. Thereafter, slurry thus obtained
was dried and calcined, whereby powder c-6 in which the particles A
were coated with alumina was prepared (only this plate-like
boehmite was calcined, and a pore volume thereof was investigated,
then the pore volume was 0.85 cm.sup.3/g). 173.4 g of this powder
c-6 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder c-6 was
milled, whereby slurry c-6 with an average particle diameter of 3
.mu.m was formed.
[0113] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. 113.92 g of plate-like
boehmite (5.times.20.times.20 nm; aspect ratio: 0.25) (in which
moisture was contained by 21%) was put into a beaker, dispersed
into water, and deflocculated by acid. To a resultant thus
obtained, 90 g of the particles B prepared in advance was added,
and was dispersed thereinto by high-speed stirring. Thereafter,
slurry thus obtained was dried and calcined, whereby powder cb-6 in
which the particles B were coated with alumina was prepared. 172 g
of this powder cb-6 and 3 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were further added to the ball mill, and the powder
cb-6 was milled, whereby slurry cb-6 with an average particle
diameter of 3 .mu.m was formed. The slurry c-6 was coated by 141
g/L on a honeycomb carrier (capacity: 0.04 L) having a diameter of
o36 mm and 400 cells with a wall thickness of 6 mils, followed by
drying, and thereafter, the slurry cb-6 was coated by 59 g/L
thereon, followed by drying. Thereafter, a resultant was calcined
at 400.degree. C., whereby a sample of Comparative example 6 was
obtained. The obtained sample of Comparative example 6 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 7
[0114] Cerium-zirconium composite oxide particles with a pore
volume of 0.15 cm.sup.3/g were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles D4") were
formed. Aluminum isopropoxide equivalent to 90 g of Al.sub.2O.sub.3
was dissolved into 2-methyl-2,4-pentanediol. To a solution thus
obtained, 90 g of the particles D4 was added, and water was further
added thereto, whereby hydrolysis was performed therefor. The water
and organic matter such as the 2-methyl-2,4-pentanediol were
evaporated and dried, followed by calcining, whereby powder c-7 in
which the particles D4 were coated with alumina was prepared. 173.4
g of this powder c-7 and 1.6 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10 wt %
nitric acid solution were added to the ball mill, and the powder
c-7 was milled, whereby slurry c-7 with an average particle
diameter of 3 .mu.m was formed.
[0115] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with a pore volume of
0.16 cm.sup.3/g, whereby particles E4 having rhodium supported
thereon by 0.814% were prepared. Aluminum isopropoxide equivalent
to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles E4 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder cb-7 in which the
particles E4 were coated with alumina was prepared. 172 g of this
powder cb-7 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder cb-7
was milled, whereby slurry cb-7 with an average particle diameter
of 3 .mu.m was formed. The slurry c-7 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-7 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 7 was
obtained. The obtained sample of Comparative example 7 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 8
[0116] Cerium-zirconium composite oxide particles with a pore
volume of 0.4 cm.sup.3/g were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles D5") were
formed. Aluminum isopropoxide equivalent to 90 g of Al.sub.2O.sub.3
was dissolved into 2-methyl-2,4-pentanediol. To a solution thus
obtained, 90 g of the particles D5 was added, and water was further
added thereto, whereby hydrolysis was performed therefor. The water
and organic matter such as the 2-methyl-2,4-pentanediol were
evaporated and dried, followed by calcining, whereby powder c-8 in
which the particles D5 were coated with alumina was prepared. 173.4
g of this powder c-8 and 1.6 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were added to the ball mill, and the powder c-8 was
milled, whereby slurry c-8 with an average particle diameter of 3
.mu.m was formed.
[0117] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with a pore volume of
0.41 cm.sup.3/g, whereby particles E5 having rhodium supported
thereon by 0.814% were prepared. Aluminum isopropoxide equivalent
to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles E5 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder cb-8 in which the
particles E5 were coated with alumina was prepared. 172 g of this
powder cb-8 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder cb-8
was milled, whereby slurry cb-8 with an average particle diameter
of 3 .mu.m was formed. The slurry c-8 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-8 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 8 was
obtained. The obtained sample of Comparative example 8 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 9
[0118] Cerium-zirconium composite oxide particles in which cerium
oxide occupied 70% and zirconium oxide occupied 30% in terms of
composition were used as the first compounds 5. Dinitrodiamine Pt
was impregnated into the particles, whereby cerium-zirconium
composite oxide particles having Pt supported thereon by 0.85%
(these are referred to as "particles F4") were formed. Aluminum
isopropoxide equivalent to 90 g of Al.sub.2O.sub.3 was dissolved
into 2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of
the particles F4 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder c-9 in which the
particles F4 were coated with alumina was prepared. 173.4 g of this
powder c-9 and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder c-9 was
milled, whereby slurry c-9 with an average particle diameter of 3
.mu.m was formed.
[0119] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles in which zirconium
occupied 90% and lanthanum occupied 10%, whereby particles G4
having rhodium supported thereon by 0.814% were prepared. Aluminum
isopropoxide equivalent to 90 g of Al.sub.2O.sub.3 was dissolved
into 2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of
the particles G4 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder cb-9 in which the
particles G4 were coated with alumina was prepared. 172 g of this
powder cb-9 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder cb-9
was milled, whereby slurry cb-9 with an average particle diameter
of 3 .mu.m was formed. The slurry c-9 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-9 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 9 was
obtained. The obtained sample of Comparative example 9 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 10
[0120] Cerium-zirconium composite oxide particles in which cerium
oxide occupied 90% and zirconium oxide occupied 10% in terms of
composition were used as the first compounds 5. Dinitrodiamine Pt
was impregnated into the particles, whereby cerium-zirconium
composite oxide particles having Pt supported thereon by 0.85%
(these are referred to as "particles F5") were formed. Aluminum
isopropoxide equivalent to 90 g of Al.sub.2O.sub.3 was dissolved
into 2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of
the particles F5 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder c-10 in which the
particles F5 were coated with alumina was prepared. 173.4 g of this
powder c-10 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder c-10 was
milled, whereby slurry c-10 with an average particle diameter of 3
.mu.m was formed.
[0121] Next, rhodium nitrate was impregnated into zirconia
particles in which zirconia occupied 100%, whereby particles G5
having rhodium supported thereon by 0.814% were prepared. Aluminum
isopropoxide equivalent to 90 g of Al.sub.2O.sub.3 was dissolved
into 2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of
the particles G5 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder cb-10 in which the
particles G5 were coated with alumina was prepared. 172 g of this
powder cb-10 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder cb-10
was milled, whereby slurry cb-10 with an average particle diameter
of 3 .mu.m was formed. The slurry c-10 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-10 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 10 was
obtained. The obtained sample of Comparative example 10 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
Comparative Example 11
[0122] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. Aluminum isopropoxide equivalent to 87.3 g of
Al.sub.2O.sub.3 was dissolved into 2-methyl-2,4-pentanediol. To a
solution thus obtained, cerium acetylacetonate was added so that an
amount thereof as cerium oxide could be 1.8 g, and moreover,
zirconium acetylacetonate was added so that an amount thereof as
zirconium oxide could be 0.9 g. To a resultant thus obtained, 90 g
of the particles A was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder c-11 in which the
particles A were coated with alumina was prepared. 173.4 g of this
powder c-11 and 1.6 g of boehmite alumina were added to a ball
mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder c-11 was
milled, whereby slurry c-11 with an average particle diameter of 3
.mu.m was formed.
[0123] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. Aluminum isopropoxide
equivalent to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles B was added, and water was further added thereto, whereby
hydrolysis was performed therefor. The water and organic matter
such as the 2-methyl-2,4-pentanediol were evaporated and dried,
followed by calcining, whereby powder cb-3 in which the particles B
were coated with alumina was prepared. 172 g of this powder cb-3
and 3 g of boehmite alumina were added to a ball mill. Thereafter,
307.5 g of water and 17.5 g of a 10% nitric acid solution were
further added to the ball mill, and the powder cb-3 was milled,
whereby slurry cb-3 with an average particle diameter of 3 .mu.m
was formed. The slurry c-11 was coated by 141 g/L on a honeycomb
carrier (capacity: 0.04 L) having a diameter of o36 mm and 400
cells with a wall thickness of 6 mils, followed by drying, and
thereafter, the slurry cb-3 was coated by 59 g/L thereon, followed
by drying. Thereafter, a resultant was calcined at 400.degree. C.,
whereby a sample of Comparative example 11 was obtained. The
obtained sample of Comparative example 11 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 12
[0124] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles A") were
formed. Aluminum isopropoxide equivalent to 63 g of Al.sub.2O.sub.3
was dissolved into 2-methyl-2,4-pentanediol. To a solution thus
obtained, cerium acetylacetonate was added so that an amount
thereof as cerium oxide could be 18.0 g, and moreover, zirconium
acetylacetonate was added so that an amount thereof as zirconium
oxide could be 9.0 g. To a resultant thus obtained, 90 g of the
particles A was added, and water was further added thereto, whereby
hydrolysis was performed therefor. The water and organic matter
such as the 2-methyl-2,4-pentanediol were evaporated and dried,
followed by calcining, whereby powder c-12 in which the particles A
were coated with alumina was prepared. 173.4 g of this powder c-12
and 1.6 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were added to the ball mill, and the powder c-12 was
milled, whereby slurry c-12 with an average particle diameter of 3
.mu.m was formed.
[0125] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, whereby particles B having rhodium
supported thereon by 0.814% were prepared. Aluminum isopropoxide
equivalent to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles B was added, and water was further added thereto, whereby
hydrolysis was performed therefor. The water and organic matter
such as the 2-methyl-2,4-pentanediol were evaporated and dried,
followed by calcining, whereby powder cb-3 in which the particles B
were coated with alumina was prepared. 172 g of this powder cb-3
and 3 g of boehmite alumina were added to a ball mill. Thereafter,
307.5 g of water and 17.5 g of a 10% nitric acid solution were
further added to the ball mill, and the powder cb-3 was milled,
whereby slurry cb-3 with an average particle diameter of 3 .mu.m
was formed. The slurry c-12 was coated by 141 g/L on a honeycomb
carrier (capacity: 0.04 L) having a diameter of o36 mm and 400
cells with a wall thickness of 6 mils, followed by drying, and
thereafter, the slurry cb-3 was coated by 59 g/L thereon, followed
by drying. Thereafter, a resultant was calcined at 400.degree. C.,
whereby a sample of Comparative example 12 was obtained. The
obtained sample of Comparative example 12 is a catalyst that
individually carries thereon Pt by 0.593 g/L and Rh by 0.236
g/L.
Comparative Example 13
[0126] Cerium-zirconium composite oxide particles with an average
particle diameter of 30 nm were used as the first compounds 5.
Dinitrodiamine Pt was impregnated into the particles, and a
resultant was calcined at 800.degree. C. for two hours, whereby
cerium-zirconium composite oxide particles having Pt supported
thereon by 0.85% (these are referred to as "particles I4") were
formed. A degree of dispersion of Pt in the particles I4 was 40%.
Aluminum isopropoxide equivalent to 90 g of Al.sub.2O.sub.3 was
dissolved into 2-methyl-2,4-pentanediol. To a solution thus
obtained, 90 g of the particles I4 was added, and water was further
added thereto, whereby hydrolysis was performed therefor. The water
and organic matter such as the 2-methyl-2,4-pentanediol were
evaporated and dried, followed by calcining, whereby powder c-13 in
which the particles I4 were coated with alumina was prepared. 173.4
g of this powder c-13 and 1.6 g of boehmite alumina were added to a
ball mill. Thereafter, 307.5 g of water and 17.5 g of a 10% nitric
acid solution were added to the ball mill, and the powder c-13 was
milled, whereby slurry c-13 with an average particle diameter of 3
.mu.m was formed.
[0127] Next, rhodium nitrate was impregnated into
zirconium-lanthanum composite oxide particles with an average
particle diameter of 20 nm, and a resultant was calcined at
700.degree. C. for two hours, whereby particles J4 having rhodium
supported thereon by 0.814% were prepared. A degree of dispersion
of Rh in the particles J4 was 45%. Aluminum isopropoxide equivalent
to 90 g of Al.sub.2O.sub.3 was dissolved into
2-methyl-2,4-pentanediol. To a solution thus obtained, 90 g of the
particles J4 was added, and water was further added thereto,
whereby hydrolysis was performed therefor. The water and organic
matter such as the 2-methyl-2,4-pentanediol were evaporated and
dried, followed by calcining, whereby powder cb-13 in which the
particles J4 were coated with alumina was prepared. A degree of
dispersion of Rh in the powder cb-13 was 30%. 172 g of this powder
cb-13 and 3 g of boehmite alumina were added to a ball mill.
Thereafter, 307.5 g of water and 17.5 g of a 10% nitric acid
solution were further added to the ball mill, and the powder cb-13
was milled, whereby slurry cb-13 with an average particle diameter
of 3 .mu.m was formed. The slurry c-13 was coated by 141 g/L on a
honeycomb carrier (capacity: 0.04 L) having a diameter of o36 mm
and 400 cells with a wall thickness of 6 mils, followed by drying,
and thereafter, the slurry cb-13 was coated by 59 g/L thereon,
followed by drying. Thereafter, a resultant was calcined at
400.degree. C., whereby a sample of Comparative example 13 was
obtained. The obtained sample of Comparative example 13 is a
catalyst that individually carries thereon Pt by 0.593 g/L and Rh
by 0.236 g/L.
[Evaluation]
[0128] The catalysts prepared according to Examples 1 to 28 and
Comparative examples 1, 2 and 3 to 13 were used, and five pieces of
each were mounted per bank in exhaust portions of a V-engine with a
displacement of 3500 cc. A durability test was performed in such a
manner that Japanese-domestic regular gasoline was used, a catalyst
inlet temperature was set at 650.degree. C., and the engine was
operated for 30 hours. Then, a thermal history was inspected.
Moreover, each of the catalysts after the durability test was built
in a simulation exhaust gas flowing device, simulation exhaust gas
with a composition shown in Table 1 was flown through the
simulation exhaust gas flowing device, and temperatures at which
purification rates for NOx, CO and HC(C.sub.3H.sub.6) became 50%
(T50 temperature) were investigated while raising a catalyst
temperature at a rate of 30.degree. C./min. Furthermore, a first
layer and second layer of each of the catalysts after the
durability test were scraped off, and pore volumes of such catalyst
layers, which were measured by a gas adsorption method, were
inspected.
TABLE-US-00001 TABLE 1 REACTION GAS COMPOSITION NO 1000 ppm O.sub.2
0.60% H.sub.2 0.20% HC(C.sub.3H.sub.6) .sup. 1665 ppmC CO 0.60%
CO.sub.2 15.50% H.sub.2O .sup. 10% N.sub.2 RESIDUE SPACE VELOCITY:
SV = 60000/h
[0129] Table 2 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 1 to Example
10 and Comparative example 1 and Comparative example 2. Moreover,
FIG. 4 shows HC T50 temperatures, at which HC(C.sub.3H.sub.6)
purification rates became 50%, for Example 1 to Example 10 and
Comparative example 1 and Comparative example 2.
TABLE-US-00002 TABLE 2 FIRST LAYER SECOND LAYER PRE- PORE PRE-
CIOUS FIRST SECOND VOLUME CIOUS FIRST METAL COMPOUND COMPOUND
(cm.sup.3/g) METAL COMPOUND EXAMPLE 1 Pt CeO.sub.2 Al.sub.2O.sub.3
0.25 Rh ZrCe COMPOSITE OXIDE EXAMPLE 2 Pt CeO.sub.2 Al.sub.2O.sub.3
0.31 Rh ZrCe COMPOSITE OXIDE EXAMPLE 3 Pt CeO.sub.2 Al.sub.2O.sub.3
0.33 Rh ZrCe COMPOSITE OXIDE EXAMPLE 4 Pt CeO.sub.2 Al.sub.2O.sub.3
0.35 Rh ZrCe COMPOSITE OXIDE EXAMPLE 5 Pt CeO.sub.2 Al.sub.2O.sub.3
0.60 Rh ZrCe COMPOSITE OXIDE EXAMPLE 6 Pt CeZr Al.sub.2O.sub.3 0.24
Rh ZrCe COMPOSITE COMPOSITE OXIDE OXIDE EXAMPLE 7 Pt CeZr
Al.sub.2O.sub.3 0.30 Rh ZrCe COMPOSITE COMPOSITE OXIDE OXIDE
EXAMPLE 8 Pt CeZr Al.sub.2O.sub.3 0.32 Rh ZrCe COMPOSITE COMPOSITE
OXIDE OXIDE EXAMPLE 9 Pd MANGANESE Al.sub.2O.sub.3 0.32 Rh ZrCe
ALUMINATE COMPOSITE OXIDE EXAMPLE 10 Pd MANGANESE Al.sub.2O.sub.3
0.35 Rh ZrCe ALUMINATE COMPOSITE OXIDE COMPARATIVE Pt CeO.sub.2
Al.sub.2O.sub.3 0.22 Rh ZrCe EXAMPLE 1 COMPOSITE OXIDE COMPARATIVE
Pt CeO.sub.2 Al.sub.2O.sub.3 0.65 Rh ZrCe EXAMPLE 2 COMPOSITE OXIDE
SECOND LAYER NOx50% HC 50% CO 50% PORE PURIFICATION PURIFICATION
PURIFICATION SECOND VOLUME TEMPERATURE TEMPERATURE TEMPERATURE
COMPOUND (cm.sup.3/g) (.degree. C.) (.degree. C.) (.degree. C.)
EXAMPLE 1 Al.sub.2O.sub.3 0.24 286 284 268 EXAMPLE 2
Al.sub.2O.sub.3 0.30 284 282 266 EXAMPLE 3 Al.sub.2O.sub.3 0.32 282
280 264 EXAMPLE 4 Al.sub.2O.sub.3 0.34 280 278 262 EXAMPLE 5
Al.sub.2O.sub.3 0.57 278 276 260 EXAMPLE 6 Al.sub.2O.sub.3 0.24 285
283 266 EXAMPLE 7 Al.sub.2O.sub.3 0.30 283 281 264 EXAMPLE 8
Al.sub.2O.sub.3 0.32 281 279 262 EXAMPLE 9 Al.sub.2O.sub.3 0.30 277
275 260 EXAMPLE 10 Al.sub.2O.sub.3 0.32 275 273 258 COMPARATIVE
ZrO.sub.2 0.19 299 297 293 EXAMPLE 1 COMPARATIVE Al.sub.2O.sub.3
0.63 305 303 300 EXAMPLE 2
[0130] Comparative example 1 is the catalyst, in which alumina from
aluminum isopropoxide is used for the first layer, and zirconia was
used for the second layer. In both of the layers, the pore volumes
were the smallest among the examples. When the Pt particles after
the durability test were observed by a TEM, a particle diameter of
the Pt particles was approximately 10 nm, coagulation of the Pt
particles was small, and coagulation of the Rh particles was also
small. However, catalyst activity was low. This is considered to be
because, though the particle diameter of the Pt particles is small,
the pore volumes are small, the exhaust gas is difficult to pass
through the pores, and the exhaust gas is less likely to reach the
Pt particles.
[0131] In Comparative example 2, alumina particles with a particle
diameter as large as 110 nm are used for the first layer.
Therefore, the pore volume also becomes large. When the Pt
particles were observed by the TEM for the catalyst after the
durability test, a particle diameter of the Pt particles became as
large as approximately 20 nm or more, the coagulation of the Pt
particles was confirmed, and the coagulation of the CeO2 particles
was also observed. This is considered to be because, since the
alumina particles are large, gaps among the alumina particles are
large, the Pt-attached ceria particles moved from the gaps during
the durability test, and the coagulation among the ceria particles
occurred. It is also considered that the Pt particles were
coagulated following the coagulation of the ceria particles,
leading to an increase of the diameter of the Pt particles
concerned. In a similar way, an increase of the particle diameter
of the. Rh particles in the second layer was observed to 15 nm. It
is considered that the catalyst activity therefore became low
though the pore volumes were large.
[0132] As opposed to this, in each of the catalysts in Example 1 to
Example 8, the particle diameter of the Pt particles after the
durability test was approximately 10 nm, and the coagulation of the
Pt particles was small. Moreover, the particle diameter of the Rh
particles was approximately 6 nm, and the coagulation thereof was
small. Furthermore, in each of Example 9 and Example 10, the
diameter of the Pd particles was as small as 7 nm to 8 nm, and the
coagulation of the Pd particles was small. Also with regard to the
Rh particles, the diameter thereof was approximately 6 nm, and the
coagulation thereof was small. The catalyst activity of each of
these Examples 1 to 10 was extremely good in comparison with those
of Comparative examples 1 and 2, and high activity was able to be
obtained.
[0133] Table 3 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 11 to
Example 16 and Comparative example 3 to Comparative example 6.
Moreover, FIG. 5 shows HC T50 temperatures, at which the
HC(C.sub.3H.sub.6) purification rates became 50%, for Example 11 to
Example 16 and Comparative example 3 to Comparative example 6.
TABLE-US-00003 TABLE 3 FIRST LAYER SECOND LAYER PRE- PORE PRE-
CIOUS FIRST SECOND VOLUME CIOUS FIRST METAL COMPOUND COMPOUND
(cm.sup.3/g) METAL COMPOUND EXAMPLE 11 Pt CeZr Al.sub.2O.sub.3 0.24
Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE EXAMPLE 12 Pt CeZr
Al.sub.2O.sub.3 0.34 Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE
EXAMPLE 13 Pt CeZr Al.sub.2O.sub.3 0.49 Rh ZrLa COMPOSITE COMPOSITE
OXIDE OXIDE EXAMPLE 14 Pt CeZr Al.sub.2O.sub.3 0.80 Rh ZrLa
COMPOSITE COMPOSITE OXIDE OXIDE EXAMPLE 15 Pd CeZr Al.sub.2O.sub.3
0.33 Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE EXAMPLE 16 Pd CeZr
Al.sub.2O.sub.3 0.47 Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE
COMPARATIVE Pt CeZr Al.sub.2O.sub.3 0.21 Rh ZrLa EXAMPLE 3
COMPOSITE COMPOSITE OXIDE OXIDE COMPARATIVE Pt CeZr Al.sub.2O.sub.3
0.83 Rh ZrLa EXAMPLE 4 COMPOSITE COMPOSITE OXIDE OXIDE COMPARATIVE
Pt CeZr Al.sub.2O.sub.3 0.82 Rh ZrLa EXAMPLE 5 COMPOSITE COMPOSITE
OXIDE OXIDE COMPARATIVE Pt CeZr Al.sub.2O.sub.3 0.22 Rh ZrLa
EXAMPLE 6 COMPOSITE COMPOSITE OXIDE OXIDE SECOND LAYER NOx50% HC
50% CO 50% PORE PURIFICATION PURIFICATION PURIFICATION SECOND
VOLUME TEMPERATURE TEMPERATURE TEMPERATURE COMPOUND (cm.sup.3/g)
(.degree. C.) (.degree. C.) (.degree. C.) EXAMPLE 11
Al.sub.2O.sub.3 0.25 323 317 315 EXAMPLE 12 Al.sub.2O.sub.3 0.33
321 316 314 EXAMPLE 13 Al.sub.2O.sub.3 0.51 320 314 312 EXAMPLE 14
Al.sub.2O.sub.3 0.78 317 310 308 EXAMPLE 15 Al.sub.2O.sub.3 0.32
319 313 310 EXAMPLE 16 Al.sub.2O.sub.3 0.49 318 314 311 COMPARATIVE
Al.sub.2O.sub.3 0.22 329 325 321 EXAMPLE 3 COMPARATIVE
Al.sub.2O.sub.3 0.82 328 326 322 EXAMPLE 4 COMPARATIVE
Al.sub.2O.sub.3 0.81 328 325 321 EXAMPLE 5 COMPARATIVE
Al.sub.2O.sub.3 0.22 329 326 322 EXAMPLE 6
[0134] Comparative example 3 is the catalyst, in which alumina from
aluminum isopropoxide is used for the first layer, and zirconia was
used for the second layer. In both of the layers, the pore volumes
were the smallest among the examples. When the Pt particles after
the durability were observed by the TEM, a particle diameter of the
Pt particles was approximately 10 nm, and the coagulation of the Pt
particles was small. Moreover, the coagulation of Rh was also
small. However, catalyst activity was low. This is considered to be
because, though the diameter of the Pt particles is small, the pore
volumes are small, the exhaust gas is difficult to pass through the
pores, and the exhaust gas is less likely to reach the Pt
particles.
[0135] In Comparative example 4, alumina particles with a particle
diameter as large as 130 nm are used for the first layer.
Therefore, the pore volume also takes a large value. When the Pt
particles were observed by the TEM for the catalyst after the
durability, a diameter of the Pt particles became as large as
approximately 20 nm or more, the coagulation of the Pt particles
was confirmed, and the coagulation of the cerium-zirconium
composite oxide particles was also observed. This is considered to
be because, since the alumina particles are large, gaps among the
alumina particles are large, the Pt-attached cerium-zirconium
composite oxide particles moved from the gaps during the
durability, and the coagulation among the cerium-zirconium
composite oxide particles occurred. It is also considered that Pt
was coagulated following the coagulation of the cerium-zirconium
composite oxide particles, leading to an increase of the diameter
of the Pt particles concerned. In a similar way, an increase of the
particle diameter of the Rh particles in the second layer was
observed to 15 nm. It is considered that the catalyst activity
therefore became low though the pore volumes were large.
[0136] Comparative example 5 is one using, for the source of the
alumina, the boehmite in which the aspect ratio is as large as 15,
in which the pore volumes are large. When the Pt particles after
the durability were observed by the TEM, a diameter of the Pt
particles became as large as 20 nm or more, the coagulation of the
Pt particles was confirmed, and the coagulation of the
cerium-zirconium composite oxide particles was also observed. This
is considered to be because, since the alumina particles are long,
gaps among the alumina particles become large, the Pt-attached
cerium-zirconium composite oxide particles moved from the gaps
during the durability, and the coagulation among the
cerium-zirconium composite oxide particles occurred. It is also
considered that Pt was coagulated following the coagulation of the
cerium-zirconium composite oxide particles, leading to an increase
of the diameter of the Pt particles concerned. In a similar way, an
increase of the particle diameter of the Rh particles in the second
layer was observed to 15 nm. It is considered that the catalyst
activity therefore became low though the pore volumes were
large.
[0137] Comparative example 6 is one using, for the source of the
alumina, the boehmite in which the aspect ratio is as small as
0.25, in which the pore volumes are small in both of the first
layer and the second layer. When the Pt particles after the
durability were observed by the TEM, a diameter of the Pt particles
was approximately 10 nm, and the coagulation of the Pt particles
was small. Moreover, the coagulation of Rh was also small. However,
catalyst activity was low. This is considered to be because, though
the diameter of the Pt particles is small, the pore volumes are
small, the exhaust gas is difficult to pass through the pores, and
the exhaust gas is less likely to reach Pt.
[0138] As opposed to this, in each of the catalysts in Example 11
to Example 14, the diameter of the Pt particles after the
durability was approximately 10 nm, and the coagulation of the Pt
particles was small. Moreover, the particle diameter of the Rh
particles was approximately 6 nm, and the coagulation thereof was
small. Furthermore, in each of Example 15 and Example 16, the
diameter of the Pd particles was approximately 6 nm, and the
coagulation of the Pd particles was small. Also with regard to the
Rh particles, the diameter thereof was approximately 6 nm, and the
coagulation thereof was also small. From the above, the catalyst
activity of each of these Examples 11 to 16 was extremely good in
comparison with those of Comparative examples 3 to 6, and high
activity was able to be obtained.
[0139] Table 4 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 17 to
Example 19 and Comparative examples 7 and 8. Moreover, FIG. 6 shows
HC T50 temperatures, at which the HC(C.sub.3H.sub.6) purification
rates became 50%, for Example 17 to Example 19 and Comparative
examples 7 and 8.
TABLE-US-00004 TABLE 4 FIRST LAYER SECOND LAYER FIRST FIRST PRE-
COMPOUND/ PORE PRE- COMPOUND/ CIOUS PORE VOLUME SECOND VOLUME CIOUS
PORE VOLUME METAL (cm.sup.3/g) COMPOUND (cm.sup.3/g) METAL
(cm.sup.3/g) EXAMPLE 17 Pt CeZr Al.sub.2O.sub.3 0.43 Rh ZrLa
COMPOSITE COMPOSITE OXIDE 0.18 OXIDE 0.28 EXAMPLE 18 Pt CeZr
Al.sub.2O.sub.3 0.47 Rh ZrLa COMPOSITE COMPOSITE OXIDE 0.28 OXIDE
0.30 EXAMPLE 19 Pt CeZr Al.sub.2O.sub.3 0.49 Rh ZrLa COMPOSITE
COMPOSITE OXIDE 0.30 OXIDE 0.32 COMPARATIVE Pt CeZr Al.sub.2O.sub.3
0.20 Rh ZrLa EXAMPLE 7 COMPOSITE COMPOSITE OXIDE 0.15 OXIDE 0.16
COMPARATIVE Pt CeZr Al.sub.2O.sub.3 0.23 Rh ZrLa EXAMPLE 8
COMPOSITE COMPOSITE OXIDE 0.40 OXIDE 0.41 SECOND LAYER NOx50% HC
50% CO 50% PORE PURIFICATION PURIFICATION PURIFICATION SECOND
VOLUME TEMPERATURE TEMPERATURE TEMPERATURE COMPOUND (cm.sup.3/g)
(.degree. C.) (.degree. C.) (.degree. C.) EXAMPLE 17
Al.sub.2O.sub.3 0.45 321 316 314 EXAMPLE 18 Al.sub.2O.sub.3 0.47
320 314 311 EXAMPLE 19 Al.sub.2O.sub.3 0.51 318 312 309 COMPARATIVE
Al.sub.2O.sub.3 0.21 328 326 323 EXAMPLE 7 COMPARATIVE
Al.sub.2O.sub.3 0.22 327 323 321 EXAMPLE 8
[0140] Comparative example 7 is one using one, in which the pore
volume of the cerium-zirconium composite oxide is 0.15 cm.sup.3/g,
and the volume of the zirconium-lanthanum composite oxide is 0.16
cm.sup.3/g, and catalyst activity thereof was low. Catalyst
activity was similarly low also in Comparative example 8. This is
considered to be because, since the pore volumes of the
cerium-zirconium composite oxide and the zirconium-lanthanum
composite oxide are small, the pore volumes of the catalyst layers
also became small. As opposed to this, in each of the catalysts in
Example 17 to Example 19, the diameter of the Pt particles after
the durability was approximately 10 nm, and the coagulation of the
Pt particles was small. Moreover, the particle diameter of the Rh
particles was approximately 6 nm, and the coagulation thereof was
also small. From the above, the catalyst activity of each of these
Examples 17 to 19 was extremely good in comparison with those of
Comparative examples 7 and 8, and high activity is able to be
obtained.
[0141] Table 5 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 20 to
Example 22 and Comparative examples 9 and 10. Moreover, FIG. 7
shows HC T50 temperatures, at which the HC(C.sub.3H.sub.6)
purification rates became 50%, for Example 20 to Example 22 and
Comparative examples 9 and 10.
TABLE-US-00005 TABLE 5 FIRST LAYER SECOND LAYER FIRST FIRST PRE-
COMPOUND/ PORE PRE- COMPOUND/ CIOUS CeO.sub.2:ZrO.sub.2 SECOND
VOLUME CIOUS ZrO.sub.2:La.sub.2O.sub.2 METAL (%) COMPOUND
(cm.sup.3/g) METAL (%) EXAMPLE 20 Pt CeZr Al.sub.2O.sub.3 0.49 Rh
ZrLa COMPOSITE COMPOSITE OXIDE 74:26 OXIDE 95:5 EXAMPLE 21 Pt CeZr
Al.sub.2O.sub.3 0.50 Rh ZrLa COMPOSITE COMPOSITE OXIDE 78:22 OXIDE
97:3 EXAMPLE 22 Pt CeZr Al.sub.2O.sub.3 0.49 Rh ZrLa COMPOSITE
COMPOSITE OXIDE 80:10 OXIDE 99:1 COMPARATIVE Pt CeZr
Al.sub.2O.sub.3 0.23 Rh ZrLa EXAMPLE 9 COMPOSITE COMPOSITE OXIDE
70:30 OXIDE 90:10 COMPARATIVE Pt CeZr Al.sub.2O.sub.3 0.22 Rh ZrLa
EXAMPLE 10 COMPOSITE COMPOSITE OXIDE 90:10 OXIDE 100:0 SECOND LAYER
NOx50% HC 50% CO 50% PORE PURIFICATION PURIFICATION PURIFICATION
SECOND VOLUME TEMPERATURE TEMPERATURE TEMPERATURE COMPOUND
(cm.sup.3/g) (.degree. C.) (.degree. C.) (.degree. C.) EXAMPLE 20
Al.sub.2O.sub.3 0.51 321 314 309 EXAMPLE 21 Al.sub.2O.sub.3 0.52
319 313 307 EXAMPLE 22 Al.sub.2O.sub.3 0.51 321 315 309 COMPARATIVE
Al.sub.2O.sub.3 0.22 329 326 322 EXAMPLE 9 COMPARATIVE
Al.sub.2O.sub.3 0.22 329 327 323 EXAMPLE 10
[0142] In Comparative example 9 and Comparative example 10, as the
first compounds 5, those were used, in which composite ratios of
the cerium oxide, the zirconium oxide and the like were changed. In
Comparative example 9, the composite ratios of the cerium oxide and
the zirconium oxide in the first layer are 70% and 30%, the
composite ratios of the zirconium oxide and the lanthanum oxide in
the second layer are 90% and 10%, and catalyst activity thereof is
low in comparison with those of Examples 20 to 22. In accordance
with the observation using the TEM, the diameter of the Pt
particles in the first layer was approximately 10 nm. The diameter
of the Rh particles in the second layer was as small as
approximately 6 nm; however, a state was observed, in which the Rh
particles were buried in aggregates of the zirconium-lanthanum
composite oxide particles. Moreover, in Comparative example 10, the
composite ratios of the cerium oxide and the zirconium oxide in the
first layer are 90% and 10%, the zirconium oxide occupied 100% in
the second layer, and catalyst activity thereof is low in
comparison with those of Examples 20 to 22.
[0143] In accordance with the observation using the TEM, the
diameter of the Pt particles in the first layer was approximately
10 nm. Although the diameter of the Rh particles in the second
layer was as small as approximately 6 nm, the state was observed,
in which the Rh particles were buried in the aggregates of the
zirconium oxide particles. It is considered that this is caused by
the fact that the composite oxide of the cerium oxide and the
zirconium oxide is inferior in oxygen evolution capability, as well
as that the pore volumes of the catalysts of Comparative examples 9
and 10 are small. Moreover, it is considered that this is caused by
the fact that, owing to the composite ratios of the zirconium oxide
and the lanthanum oxide, the zirconium-lanthanum composite oxide
particles become likely to be coagulated, and the Rh particles are
buried in the zirconium-lanthanum composite oxide particles and the
zirconium oxide particles, and become difficult to contact the
exhaust gas.
[0144] Table 6 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 23 to
Example 25 and Comparative examples 11 and 12. Moreover, FIG. 8
shows HC T50 temperatures, at which the HC(C.sub.3H.sub.6)
purification rates became 50%, for Example 23 to Example 25 and
Comparative examples 11 and 12.
TABLE-US-00006 TABLE 6 FIRST LAYER SECOND LAYER PRE- SECOND PORE
PRE- CIOUS FIRST COMPOUND/ VOLUME CIOUS FIRST METAL COMPOUND
CeO.sub.2:ZrO.sub.2 (cm.sup.3/g) METAL COMPOUND EXAMPLE 23 Pt CeZr
Al.sub.2O.sub.3 5:7 0.27 Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE
EXAMPLE 24 Pt CeZr Al.sub.2O.sub.3 10:5 0.31 Rh ZrLa COMPOSITE
COMPOSITE OXIDE OXIDE EXAMPLE 25 Pt CeZr Al.sub.2O.sub.3 15:3 0.28
Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE COMPARATIVE Pt CeZr
Al.sub.2O.sub.3 2:1 0.22 Rh ZrLa EXAMPLE 11 COMPOSITE COMPOSITE
OXIDE OXIDE COMPARATIVE Pt CeZr Al.sub.2O.sub.3 20:10 0.23 Rh ZrLa
EXAMPLE 12 COMPOSITE COMPOSITE OXIDE OXIDE SECOND LAYER NOx50% HC
50% CO 50% PORE PURIFICATION PURIFICATION PURIFICATION SECOND
VOLUME TEMPERATURE TEMPERATURE TEMPERATURE COMPOUND (cm.sup.3/g)
(.degree. C.) (.degree. C.) (.degree. C.) EXAMPLE 23
Al.sub.2O.sub.3 0.26 322 316 316 EXAMPLE 24 Al.sub.2O.sub.3 0.26
320 315 313 EXAMPLE 25 Al.sub.2O.sub.3 0.26 321 316 315 COMPARATIVE
Al.sub.2O.sub.3 0.22 328 326 322 EXAMPLE 11 COMPARATIVE
Al.sub.2O.sub.3 0.22 328 326 322 EXAMPLE 12
[0145] In Comparative examples 11 and 12, catalyst activities
thereof are low in comparison with those of Examples 23 to 25. In
Examples 23 to 25, the cerium compound and the zirconium compound
are added to such an alumina precursor, whereby heat resistance of
the alumina after being calcined is enhanced, and the pore volumes
after the durability are maintained largely. However, in
Comparative examples 11 and 12, there is no effect of adding the
cerium compound and the zirconium compound, the pore volumes after
the durability cannot be ensured, and the pore volumes become
small, and therefore, it is considered that the exhaust gas becomes
less likely to reach the precious metals, leading to such a
decrease of the catalyst activity.
[0146] Table 7 shows evaluation results and the pore volumes of the
catalyst layers in the respective catalysts of Example 26 to
Example 28 and Comparative example 13. Moreover, FIG. 9 shows HC
T50 temperatures, at which the HC(C.sub.3H.sub.6) purification
rates became 50%, for Example 26 to Example 28 and Comparative
examples 13.
TABLE-US-00007 TABLE 7 FIRST LAYER SECOND LAYER PRE- PORE PRE-
CIOUS FIRST SECOND VOLUME CIOUS FIRST METAL COMPOUND COMPOUND
(cm.sup.3/g) METAL COMPOUND EXAMPLE 26 Pt CeZr Al.sub.2O.sub.3 0.49
Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE EXAMPLE 27 Pt CeZr
Al.sub.2O.sub.3 0.49 Rh ZrLa COMPOSITE COMPOSITE OXIDE OXIDE
EXAMPLE 28 Pt CeZr Al.sub.2O.sub.3 0.49 Rh ZrLa COMPOSITE COMPOSITE
OXIDE OXIDE COMPARATIVE Pt CeZr Al.sub.2O.sub.3 0.22 Rh ZrLa
EXAMPLE 13 COMPOSITE COMPOSITE OXIDE OXIDE SECOND LAYER NOx50% HC
50% CO 50% PORE PURIFICATION PURIFICATION PURIFICATION SECOND
VOLUME TEMPERATURE TEMPERATURE TEMPERATURE COMPOUND (cm.sup.3/g)
(.degree. C.) (.degree. C.) (.degree. C.) EXAMPLE 26
Al.sub.2O.sub.3 0.50 324 318 315 EXAMPLE 27 Al.sub.2O.sub.3 0.50
322 315 312 EXAMPLE 28 Al.sub.2O.sub.3 0.50 320 311 309 COMPARATIVE
Al.sub.2O.sub.3 0.22 330 328 325 EXAMPLE 13
[0147] In Comparative example 13, catalyst activity thereof is low
in comparison with those of Examples 26 to 28. In Examples 26 to
28, the diameter of the Pt particles in the first layer was
approximately 10 nm or less in accordance with the observation
using the TEM. The diameter of the Rh particles in the second layer
was as small as approximately 6 nm or less. This is considered to
be because the initial degrees of dispersion of the precious metal
particles were high and effects of the precious metals lasted even
after the durability. As opposed to this, in Comparative example
13, the diameter of the Pt particles in the first layer was
approximately 15 nm in accordance with the observation using the
TEM. The diameter of the Rh particles in the second layer was
approximately 10 nm, and the particle diameters became somewhat
larger in comparison with those of Examples 26 to 28. This is
considered to be because the initial degrees of dispersion of the
precious metals were low and the coagulation of the precious metal
particles owing to the durability became likely to progress.
INDUSTRIAL APPLICABILITY
[0148] The present invention can be applied to the exhaust gas
purifying catalyst that purifies the exhaust gas discharged from a
vehicle such as an automobile.
* * * * *