U.S. patent number RE45,083 [Application Number 12/651,206] was granted by the patent office on 2014-08-19 for method for preparing metal oxide particles and an exhaust gas purifying catalyst.
This patent grant is currently assigned to Toyota Jidosha Kabushiki Kaisha. The grantee listed for this patent is Oji Kuno. Invention is credited to Oji Kuno.
United States Patent |
RE45,083 |
Kuno |
August 19, 2014 |
Method for preparing metal oxide particles and an exhaust gas
purifying catalyst
Abstract
The present invention relates to metal oxide particles having
cores comprising larger molar amounts of zirconia than of ceria,
and surface layers comprising larger molar amounts of ceria than of
zirconia. Further, the present invention relates to a method for
preparing the particles. The method comprises preparing a solution
comprising zirconia sol and ceria sol, adjusting the pH of the
solution within .+-.0.5 on the basis of the isoelectric point of
zirconia, and aggregating zirconia and then aggregating ceria
around the aggregated zirconia from the solution to make
aggregates. Furthermore, the present invention relates to an
exhaust gas purifying catalyst comprising the metal oxide
particles, and a noble metal carried by the metal oxide
particles.
Inventors: |
Kuno; Oji (Toyota,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Kuno; Oji |
Toyota |
N/A |
JP |
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Assignee: |
Toyota Jidosha Kabushiki Kaisha
(Toyota, JP)
|
Family
ID: |
32089468 |
Appl.
No.: |
12/651,206 |
Filed: |
December 31, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
10690240 |
Oct 22, 2003 |
7314846 |
Jan 1, 2008 |
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Foreign Application Priority Data
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Oct 28, 2002 [JP] |
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2002-312744 |
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Current U.S.
Class: |
423/213.2;
502/439; 502/326; 502/349; 423/239.1; 502/339; 502/304 |
Current CPC
Class: |
C01G
25/00 (20130101); B01J 23/63 (20130101); B82Y
30/00 (20130101); B01J 35/0006 (20130101); B01J
37/036 (20130101); B01J 23/10 (20130101); C01P
2006/12 (20130101); B01J 21/066 (20130101); C01P
2004/64 (20130101) |
Current International
Class: |
B01D
53/56 (20060101); B01D 53/94 (20060101); B01J
21/04 (20060101); B01J 23/40 (20060101); B01J
23/10 (20060101); B01J 23/02 (20060101); B01J
23/00 (20060101); B01J 8/00 (20060101); B01D
53/86 (20060101); C01G 30/00 (20060101); C01B
35/00 (20060101); C01B 33/00 (20060101); C01B
31/00 (20060101); C01B 25/00 (20060101); C01B
23/00 (20060101); C01B 21/00 (20060101); B01J
8/02 (20060101) |
Field of
Search: |
;423/213.2,239.1
;502/304,326,339,349,439 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1 315 316 |
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Oct 2001 |
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CN |
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1 035 074 |
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Sep 2000 |
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EP |
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1 516 855 |
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Mar 2005 |
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EP |
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06-279027 |
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Oct 1994 |
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JP |
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A 8-103650 |
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Apr 1996 |
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JP |
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A 8-109020 |
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Apr 1996 |
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JP |
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A 8-109021 |
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Apr 1996 |
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JP |
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A 2000-319019 |
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Nov 2000 |
|
JP |
|
A 2001-89143 |
|
Apr 2001 |
|
JP |
|
Other References
Decision in Opposition Proceeding in European Patent Office, dated
Dec. 30, 2009. cited by applicant .
Letter of Opponent, Rhodia Operations (with English translation),
dated Nov. 13, 2009. cited by applicant .
Reply to Letter of Opponent by Toyota Jidosha Kabushiki Kaisha,
dated Nov. 13, 2009. cited by applicant .
Summons to Attend Oral Proceeding in European Patent Office, dated
Apr. 24, 2009. cited by applicant .
Reply to Notice of Opposition by Toyota Jidosha Kabushiki Kaisha,
dated Dec. 30, 2008. cited by applicant .
Opposition Statement by Rhodia Operations (with English
translation), dated May 15, 2008. cited by applicant .
Li Wei-Bin et al., "Study on NO.sub.x Adsorption on
CeO.sub.2-supporting Nanometer ZrO.sub.2", Chemical Journal of
Chinese University, vol. 23, pp. 1-7, Jun. 2002. cited by applicant
.
Non-Final Rejection mailed May 16, 2006 in U.S. Appl. No.
10/690,240. cited by applicant .
Non-Final Rejection mailed Nov. 14, 2005 in U.S. Appl. No.
10/690,240. cited by applicant .
Final Rejection mailed Oct. 31, 2006 in U.S. Appl. No. 10/690,240.
cited by applicant .
A. F. Holleman et al., "Lehrbuch der Anorganischen Chemie", 1995,
p. 929. cited by applicant.
|
Primary Examiner: Nguyen; Cam N.
Attorney, Agent or Firm: Oliff PLC
Claims
What is claimed is:
1. An exhaust gas purifying catalyst comprising: metal oxide
particles comprising ceria and zirconia; and a noble metal carried
by said metal oxide particles, wherein said metal oxide particles
have cores comprising larger molar amounts of zirconia than of
ceria, and surface layers comprising larger molar amounts of ceria
than of zirconia.
2. The catalyst according to claim 1 wherein the metal oxide
particles have a mean particle diameter of 500 nm or less.
3. The catalyst according to claim 1 for purifying exhaust gas from
an internal combustion engine.
4. The catalyst according to claim 1 wherein the exhaust gas
purifying catalyst is exposed to an environment having a
temperature of 1,000.degree. C. or more.
5. The catalyst according to claim 1 wherein the molar ratio of
Zr:Ce in the metal oxide particles is 1:0.5 to 0.5:1.
6. The catalyst according to claim 1 further comprising one or more
metal oxides other than ceria and zirconia.
7. The catalyst according to claim 6 wherein the molar ratio of (Zr
and Ce):(the metal(s) of the one or more metal oxides other than
ceria and zirconia) is 5:1 to 20:1.
8. The catalyst according to claim 1 wherein the ceria covers more
than 80 mol % of the surface of the metal oxide particles, as
measured by the transmission electron microscope and energy
dispersive X-ray analyzer.
9. The catalyst according to claim 1 wherein the zirconia composes
more than 80 mol % of the cores of metal oxide particles, as
measured by the transmission electron microscope and energy
dispersive X-ray analyzer.
10. The catalyst according to claim 1 wherein the metal oxide
particles have a mean particle diameter of 50 nm or less.
11. Metal oxide particles having cores comprising larger molar
amounts of zirconia than of ceria, and surface layers comprising
larger molar amounts of ceria than of zirconia, wherein the metal
oxide particles carry a noble metal.
12. A method for preparing metal oxide particles, with said metal
oxide particles having cores comprising larger molar amounts of
zirconia than of ceria, and surface layers comprising larger molar
amounts of ceria than of zirconia, wherein the method comprises:
preparing a solution comprising zirconia sol and ceria sol;
adjusting the pH of the solution within .+-.0.5 on the basis of the
isoelectric point of zirconia; and aggregating zirconia and then
aggregating ceria around the aggregated zirconia from said solution
to make aggregates.
13. The method according to claim 12 further comprising drying and
firing the aggregates.
14. The method according to claim 12 wherein the metal oxide
particles have a mean particle diameter of 500 nm or less.
15. The method according to claim 12 wherein the molar ratio of
Zr:Ce in the metal oxide particles is 1:0.5 to 0.5:1.
16. The method according to claim 12 wherein the metal oxide
particles have a mean particle diameter of 50 nm or less.
17. The method according to claim 12 wherein the aggregation is
achieved by concentrating the solution.
18. The method according to claim 17 wherein the concentrating of
the solution is conducted by removing and drying out the
solvent.
.Iadd.19. Metal oxide particles having cores comprising larger
molar amounts of zirconia than of ceria, and surface layers
comprising larger molar amounts of ceria than of zirconia, wherein
the metal oxide particles have a BET specific surface area of 66.8
m.sup.2/g or more. .Iaddend.
.Iadd.20. A method of treating an exhaust gas, the method
comprising: exposing the exhaust gas to a catalyst comprised of the
metal oxide particles of claim 19. .Iaddend.
.Iadd.21. Metal oxide particles having cores comprising larger
molar amounts of zirconia than of ceria, and surface layers
comprising larger molar amounts of ceria than of zirconia, wherein
the metal oxide particles have a BET specific surface area of 52
m.sup.2/g or more, after endurance in which the catalyst is
contacted with a model gas at 800.degree. C. for five hours, the
model gas consisting of the following rich gas and lean gas which
are switched every minute: TABLE-US-00003 .Iadd.N.sub.2 CO.sub.2 NO
CO C.sub.3H.sub.6 H.sub.2 O.sub.2 H.sub.2O (%) (%) (ppm) (%) (ppmC)
*2 (%) (%) (%) rich balance 10 2200 2.80 2500 0.27 0.77 10 gas *1
lean balance 10 2200 0.81 2500 0 1.7 10 gas *1 *1 N2is the rest of
the contents. *2 The unit is based on an amount of carbon
atoms..Iaddend.
.Iaddend.
.Iadd.22. A method of treating an exhaust gas, the method
comprising: exposing the exhaust gas to a catalyst comprised of the
metal oxide particles of claim 21. .Iaddend.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a catalyst for purifying the
contents of exhaust gas from an internal combustion engine, and
metal oxide particles suitable as a carrier for an exhaust gas
purifying catalyst and a method for preparing this.
2. Description of the Related Art
Exhaust gas from an internal combusting engine such as an
automobile engine comprises nitrogen oxide (NO.sub.x), carbon
monoxide (CO), hydrocarbon (HC) and etc. These contents of the
exhaust gas can be purified by the use of an exhaust gas purifying
catalyst which oxidizes CO and HC while reduce NO.sub.x. A
representative exhaust gas purifying catalyst includes a three way
catalyst which comprises porous metal oxide carrier such as
.gamma.-alumina and a noble metal such as platinum (Pt), Rhodium
(Rh) and/or Palladium (Pd) carried thereon.
It is necessary that an internal combustion engine is driven at
stoichiometric air/fuel ratio (stoichiometry) in order for the
three way catalyst to achieve effective oxidation of CO and HC as
well as reduction of NO.sub.x. In the case that the internal
combustion engine is driven at excess oxygen atmosphere (lean) or
at excess fuel atmosphere (rich), the three-way catalyst cannot
demonstrate its purification ability as the oxygen concentration in
the exhaust gas becomes outside the range of the optimum oxygen
concentration for the three-way catalyst.
It is well known that a material having an oxygen storage capacity
(OSC) is used with an exhaust gas purifying catalyst. OSC means a
capacity enabling storing oxygen at the high oxygen concentration
and releasing oxygen at the low oxygen concentration. OSC is useful
to buffer the change of oxygen concentration in exhaust gas and
thereby enhances the exhaust gas purifying ability of the three way
catalyst. A representative material having OSC is ceria
(CeO.sub.2). Ceria has not only OSC but also large affinity with
noble metal carried thereon. Therefore, the ceria is also useful to
prevent particle growth (sintering) of the noble metal carried
thereon. Methods for preparing mixed metal oxide of ceria and
zirconia have been developed to provide materials having high heat
resistivity as ceria has small specific surface area and low heat
resistivity. Regarding the prior arts, refer to Japanese Unexamined
Patent Publication No. 8-103650, 8-109020, 8-109021, 2000-319019,
2001-89143 and etc.
According to the prior arts, as both ceria and zirconia exist on
the surface of the mixed metal oxide comprising uniformly mixed
ceria and zirconia, a noble metal carried by the mixed metal oxide
randomly deposits on both ceria and zirconia surface. Therefore, in
the prior arts, there is a problem that an affinity between the
mixed metal oxide and noble metal is lowered, the noble metal is
sintered and, then, the catalyst loses its ability to purify
exhaust gas.
That is, the previous catalysts comprising a cerium-zirconium mixed
metal oxide lose OSC, and an ability to purify exhaust gas, by the
sintering of noble metal on their surface, particularly when they
are exposed to a high temperature of 1000.degree. C. or more for a
long time.
Therefore, there remains a need for an exhaust gas purifying
catalyst which maintains a heat resistivity of mixed metal oxide,
has high affinity to a noble metal to maintain OSC, and only
slightly lose its ability to purify exhaust gas after being exposed
to a high temperature. Further, there remains a need for a method
for preparing a metal oxide suitable for the exhaust gas purifying
catalyst.
BRIEF SUMMARY OF INVENTION
In one aspect, the present invention is an exhaust gas purifying
catalyst. The exhaust gas purifying catalyst comprises metal oxide
particles comprising ceria and zirconia; and noble metal carried by
the metal oxide particles, wherein the metal oxide particles have
cores comprising larger molar amounts of zirconia than of ceria,
and surface layers comprising larger molar amounts of ceria than of
zirconia. The exhaust gas purifying catalyst may then have a
superior heat resistivity and a superior ability to purify exhaust
gas after enduring test at high temperature.
The metal oxide particles may have a mean particle diameter of 500
nm or less, 200 nm or less, 100 nm or less, or 50 nm or less, with
50 nm or less being preferred.
The catalyst may be used for purifying exhaust gas from an internal
combustion engine such as an automobile engine.
The catalyst may be used at the temperature of 1,000.degree. C. or
more.
The molar ratio of Zr:Ce in the metal oxide particles may be 1:0.5
to 0.5:1, 1:0.8 to 0.8:1, or about 1:1, with about 1:1 being
preferred.
The metal oxide particles may further comprise one or more metal
oxides other than ceria and zirconia.
The molar ratio of (Zr and Ce):(the other metals) may be 5:1 to
20:1, 8:1 to 10:1, or about 9:1.
The ceria may cover more than 80 mol %, 90 mol %, 95 mol % or 98
mol % of the surfaces of the metal oxide particles, and preferably
substantially all of the metal oxide surface, as measured by the
transmission electron microscope (TEM) and energy dispersive X-ray
analyzer (EDX).
The zirconia may form more than 80 mol %, 90 mol %, 95 mol % or 98
mol % of the cores of metal oxide particles, and preferably
substantially all of the cores, as measured by the transmission
electron microscope (TEM) and energy dispersive X-ray analyzer
(EDX).
In another aspect, the present invention is metal oxide particles
having cores comprising larger molar amounts of zirconia than of
ceria, and surface layers comprising larger molar amounts of ceria
than of zirconia.
The metal oxide particles may carry a noble metal.
In another aspect, the present invention is a method for preparing
metal oxide particles in which the metal oxide particles have cores
comprising larger molar amounts of zirconia than of ceria, and
surface layers comprising larger molar amounts of ceria than of
zirconia. The method comprises preparing a solution comprising
zirconia sol and ceria sol, adjusting the pH of the solution within
.+-.0.5 on the basis of the isoelectric point of zirconia, and
aggregating a zirconia and then aggregating ceria around the
aggregated zirconia from the solution to make aggregates. According
the method, the metal oxide particles of the present invention are
easily prepared, and the prepared metal oxide particles may have a
very small mean particle diameter and large specific surface
area.
The metal oxide particles may have a mean particle diameter of 500
nm or less, 200 nm or less, 100 nm or less, or 50 nm or less, with
50 nm or less being preferred.
The molar ratio of Zr:Ce in the metal oxide particles may be 1:0.5
to 0.5:1, 1:0.8 to 0.8:1, or about 1:1, with about 1:1 being
preferred.
These and other objects, feature and advantages of the present
invention will become apparent upon reading of the following
detailed description along with the accompanied drawings.
BRIEF DESCRIPTION OF DRAWING
FIG. 1 is a schematic sectional view of the metal oxide particle of
the present invention that can be used for a catalyst of the
present invention. However, it is not necessary for the core 2 and
surface layer 3 to be adjacent.
DETAILED DESCRIPTION OF INVENTION
The inventor of the present invention found that an exhaust gas
purifying catalyst comprising metal oxide particles 1 having
zirconia-rich core 2 and ceria-rich surface layer 3, and a noble
metal carried by the metal oxide particles, shows an improved
ability to purify exhaust gas even after an endurance test, and
conceived the catalyst of the present invention.
The inventor of the present invention found that the metal oxide
particles can be prepared by preparing a solution comprising
zirconia sol and ceria sol, adjusting the pH of the solution around
the isoelectric point of zirconia, aggregating and precipitating a
metal oxide from the solution, and firing the aggregate. Thus
prepared metal oxide particles have zirconia-rich core and
ceria-rich surface layers, and very small particle sizes.
The exhaust gas purifying catalyst according to the present
invention comprises metal oxide particles as a substrate and a
noble metal carried thereby, and is characterized in that the metal
oxide particles have cores comprising larger molar amounts of
zirconia than of ceria and surface layers comprising larger molar
amounts of ceria of zirconia.
It is also possible to prepare metal oxide particles having cores
comprising larger molar amounts of zirconia than of ceria and
surface layers comprising larger molar amounts of ceria than of
zirconia by a method comprising mixing zirconia particle and ceria
sol, aggregating ceria around the zirconia particle and firing it.
However, zirconia particles used in this method generally have a
mean diameter of a few micrometers or more and, then, the metal
oxide particles obtained by aggregating ceria around the zirconia
particles and firing it also have a mean particle diameter of a few
micrometer or more. The large particles comprising ceria and
zirconia such as particles having a mean particle diameter of a few
micrometer or more hardly improves the heat resistivity of ceria
for OSC (effect of improving heat resistivity) provided by a
cerium-zirconium mixed metal oxide, even if the metal oxide
particles comprise ceria and zirconia.
The method for preparing metal oxide particle of the present
invention comprises adjusting a pH of the solution comprising
zirconia sol and ceria sol to around the isoelectric point of
zirconia sol, and aggregating the sols into metal oxide particles.
The metal oxide particles prepared by this method are very small,
have large specific surface areas, and provide an effect of
improving the heat resistively of ceria by the use of zirconia.
The method for preparing metal oxide particles of the present
invention is further described at the following. The term "sol " in
the zirconia sol or ceria sol means a colloid of metal oxide or
metal hydride dispersed in liquid, especially water. Zirconia or
ceria may be provided by removing liquid from sol and being fired.
For example, the zirconia sol or ceria sol may be obtained by
hydrating or condensing alkoxide, acetylacetonate, acetate, nitrate
and etc. of zirconium or cerium in a solution. A zirconia sol and
ceria sol are well known and commercially available.
Although the method of the present invention uses a solution
comprising zirconia sol and ceria sol as raw material, the solution
may further comprise salt and/or sol of metals other than Ce and
Zr, and any the other material. The metals other than Ce and Zr may
be selected from the group consisting of s-block metals, d-block
metals, p-block metals, and f-block metals. More specially, the
metals other than Ce and Zr include Na, K, Mg, Ca, Ba, Sr, La, Y,
Pr, Nd, Sm, Eu, Gd, Ti, Sn, Mn, Fe, Co, Ni, Cr, Nb, Cu, V, Mo, W,
Zn, Al, Si and Ta. Preferably, the metals other than Ce and Zr
include rare earth metals such as one or more metals selected from
the group consisting of La, Y, Pr, Nd, Sm, Eu and Gd, especially
one or more metals selected from the group consisting of La, Y and
Pr.
Specially, a metal salt such as lanthanum nitrate and praseodymium
nitrate, and/or sol compound such as yttria sol may be add to
zirconia sol and ceria sol. A metal oxide formed from raw material
comprising salt and/or sol of rare earth metal has high heat
resistivity and shows a small reduction of OSC after being exposed
to a high temperature.
The mixing ratio of zirconia sol, ceria sol, and salt and/or sol of
the other metals may be optionally determined. It is, however,
preferable to use about the same amounts of Zr and Ce (e.g. molar
ratio of Zr:Ce:the other metals is 45:45:10) in order to maintain
heat resistivity.
According to the method for preparing metal oxide of the present
invention, the pH of the solution comprising zirconia sol and ceria
sol ("raw sol solution") is adjusted to about the isoelectric point
of zirconia, and aggregates sols into particles.
The isoelectric point of zirconia can be determined by a stopwatch
method which belongs to an electrophoresis-microscope method (c.f.
JIS (Japanese Industrial Standard) R1638). The isoelectric point of
the zirconia may be determined for zirconia obtained by drying and
firing the raw zirconia sol of same lot as the zirconia sol to be
used in examples.
The pH of the raw material may be adjusted by addition of any kind
of acid or base, with mineral acid such as nitric acid and/or
hydrogen chloride being preferred as an acid, and aqueous ammonia
and/or sodium hydroxide being preferred as a base. A commercially
available metal oxide sol solution has a pH that rather differs
from the isoelectric point of zirconia sol in order to prevent
aggregation, precipitation and solution of metal oxide sol.
Therefore, an acid is generally added to a basic zirconia sol
solution for the method of the present invention.
It is most preferable to precisely adjust the pH of a raw sol
solution to the isoelectric point of zirconia, but it is
practically very difficult. Therefore, it is preferable to adjust
the pH of the raw sol solution within .+-.0.5, more preferably
within .+-.0.2 on the basis of the isoelectric point of the
zirconia sol. The pH of the raw sol solution may be adjusted by
adding an acid or a base to the raw sol solution while measuring pH
of the raw sol solution by a pH meter. Alternatively, the pH of the
raw sol solution may be adjusted by sampling the raw sol solution
to predetermine an amount of acid or base required for adjusting pH
of the raw sol solution, and then adding the predetermined amount
of acid or base to the bulk raw sol solution.
A solvent for a raw sol solution is generally water, and may
comprise an organic solvent such as alcohol and acetlyacetone, if
required. The solvent may be removed and dried out from a raw sol
solution by any method and at any temperature, e.g. the solvent may
be removed and dried out by introducing the raw sol solution into
an oven at the temperature of 120.degree. C.
Metal oxide particles may be prepared by removing solvent from a
raw sol solution and firing the dried raw material. The firing step
may be performed at a temperature generally used for metal oxide
synthesis, e.g. 500.degree. C. or more such as 500 to 1,000.degree.
C.
The metal oxide particles prepared by the method of the present
invention have rather smaller diameters and larger specific surface
areas than those prepared by the well method wherein sintered metal
oxide is milled. Therefore, the metal oxide particles prepared by
the method of the present invention can carry a noble metal in a
highly dispersed manner. The metal oxide particles prepared by the
present invention has a diameter of 50 nm or less when a sol having
a mean diameter of about 5 nm is used as a raw material, while
metal oxide particles prepared by milling a bulk metal oxide have
mean particle diameters of 1 .mu.m or more.
The metal oxide particles prepared by the method of the present
invention have cores comprising a larger molar amounts of zirconia
than of ceria, and surface layers comprising larger molar amounts
of ceria than of zirconia. In fact, the metal oxide particle
prepared by the following examples has about same isoelectric point
about as that of ceria. Therefore, it is deemed that the ceria
covers substantially all the surface of the metal oxide particle.
The Ce and Zr distribution within the metal oxide particle obtained
by the transmission electron microscope (TEM) and energy dispersive
X-ray analyzer (EDX) shows that almost all metal elements at the
surfaces of the particles are Ce and that almost all metal elements
at the cores of the particles are Zr.
It is deemed that the method of the present invention provides a
metal oxide particles having zirconia-rich cores and ceria-rich
surface layers for the following reasons:
At the isoelectric point of the zirconia, zirconia particles tend
to aggregate since a zeta potential at the surface of the zirconia
particles become zero, and the surfaces of the zirconia particles
are electrically neutral and do not have electrical charge. At the
isoelectric point of the zirconia, ceria has a positive zeta
potential and positive electrical charge since ceria has higher
isoelectric point than zirconia. Therefore, when the pH of a
solution comprising ceria sol and zirconia sol is adjusted to the
isoelectric point of zirconia, zirconia having neutral electrical
potential tends to aggregate and ceria having positive potential
does not tend to aggregate. At this situation, firstly zirconia is
aggregated and then ceria is aggregated around the aggregated
zirconia cores when the metal oxide particles are aggregated, e.g.
by concentrating the solution. Therefore, the metal oxide particles
prepared by the method of the present invention have zirconia-rich
cores and ceria-rich surface layers.
An exhaust gas purifying catalyst may be prepared by carrying a
noble metal on the above metal oxide particles. The noble metal may
be carried on metal oxide particles by the any method, e.g. by
soaking an aqueous solution of salt and/or complex of noble metal
into the metal oxide particles, and then drying and firing the
metal oxide particles. It is preferable that the metal oxide
particles carry one or more noble metals selected from the group
consisting of Pt, Pd, Rh, Ir and Au, more preferably one or more
noble metals having high exhaust gas purification ability selected
from the group consisting of Pt, Pd and Rh, even more preferably
Pt. It is preferable that the metal oxide particles carry a noble
metal at an amount of 0.01 to 5 wt %, more preferably 0.1 to 2 wt %
on the basis of the amount of the metal oxide particles. The
exhaust gas purification ability is not sufficient when the noble
metal carried by the metal oxide particles is less than 0.01 wt %,
while cost is increased though the exhaust gas purification ability
is saturated when the noble metal carried by metal oxide particles
is more than 5 wt %.
Because the metal oxide particles prepared by the method of the
present invention have very small particle diameters and large
specific surface areas, the noble metal carried thereon can be
well-dispersed and has a small particle diameter.
The exhaust gas purifying catalyst of the present invention has a
superior ability for exhaust gas purification after a high
temperature endurance test and a superior heat resistivity relative
to the exhaust gas purifying catalyst comprising the noble metal
carried on the metal oxide particles composed of equally dispersed
ceria and zirconia.
The exhaust gas purifying catalyst of the present invention is very
useful for purifying an exhaust gas from an internal combustion
engine such as automobile engine. The method for preparing a metal
oxide particles of the present invention is very useful for
preparing metal oxide particles used for an exhaust gas purifying
catalyst.
The exhaust gas purifying catalyst of the present invention can be
used in coatings on a monolithic substrate such as a ceramic
honeycomb. The present invention is described, on the basis of
examples, as follows.
EXAMPLES
The same zirconia sol as that used for following examples was
dehydrated and dried to obtain ZrO.sub.2. The isoelectric point of
the obtained ZrO.sub.2 was determined by the stopwatch method that
is one of electrophoretic microscopy methods (JIS (Japanese
Industrial Standard) R1638). It was shown that the ZrO.sub.2 has an
isoelectric point of pH 4.0. Therefore, in the following examples,
the value of pH 4.0 was used as isoelectric point of ZrO.sub.2.
In the following examples, the pH of the metal oxide sol solution
is determined by a pH meter wherein the electrode of the pH meter
is directly dipped into the metal oxide sol solution.
Example 1
Preparation of Catalyst 1
A zirconia sol comprising 10.2 wt % of ZrO.sub.2 (TAKI CHEMICAL
CO., LTD., ECOLIGHT) (111.76 g) and yttria sol comprising 15 wt %
of Y.sub.2O.sub.3 (TAKI CHEMICAL CO., LTD., Y.sub.2O.sub.3 sol) (6
g) were added to a ceria sol comprising 15 wt % of CeO.sub.2 (TAKI
CHEMICAL CO., LTD., NEEDRAL U-15) (116 g), and mixed. The resulting
sol mixture had a pH of 5.8.
An aqueous nitric acid was added to the sol mixture to adjust pH of
the sol mixture to pH 4.0 that is the isoelectric point of the
ZrO.sub.2. The adjusted solution was dehydrated, and an resulting
solid material was dried at 120.degree. C. for 24 hours and then
fired at 700.degree. C. for 5 hours to obtain mixed metal oxide
particles. The obtained mixed metal oxide particles had a specific
surface area of 66.8 m.sup.2/g. To the solution consisting of water
particles (300 g) and the mixed metal oxide particles (30 g)
dispersed therein, a platinum dinitrodiammine solution (6.82 g)
comprising 4.4 wt % of Pt was added and stirred for two hours, and
then the resulting mixture was dehydrated to obtain solid material.
The obtained solid material was dried at 120.degree. C. and then
fired at 500.degree. C. for two hours to obtain Catalyst 1. The
Catalyst 1 had a weight ratio of
CeO.sub.2:ZrO.sub.2:Y.sub.2O.sub.3=58:38:4. The Catalyst 1 consists
of mixed metal oxide particles having a surface layer of CeO.sub.2
and core of ZrYO.sub.x, and Pt carried thereby. The amount of Pt
carried by mixed metal oxide particles was 1 wt % on the basis of
the weight of the mixed metal oxide particles.
Example 2
Preparation of Catalyst 2
Catalyst 2 was prepared according to the Example 1 except that
ceria sol (193.33 g), zirconia sol (156.85 g), and aqueous solution
(30 cc) comprising nitric lanthanum (3.99 g) and nitric
praseodymium (8.94 g) in solution were used as the substitute for
ceria sol (116 g), zirconia sol (111.76 g) and yttria sol (6 g).
The obtained Catalyst 2 had a weight ratio of
CeO.sub.2:ZrO.sub.2:La.sub.2O.sub.3:Pr.sub.6O.sub.11=58:32:3:7. The
Catalyst 2 consists of mixed metal oxide particles having a surface
layer of CeO.sub.2 and Pt carried thereby. The amount of Pt carried
by mixed metal oxide particles was 1 wt % on the basis of the
weight of the mixed metal oxide particles. The mixed metal oxide
had a specific surface area of 69.6 m.sup.2/g before carrying
Pt.
Comparative Example 1
Preparation of Catalyst 3
A same ceria sol (200 g) as that used in example 1 was dried at
120.degree. C. The resulting solid material was fired at
700.degree. C. for five hours to obtain CeO.sub.2. The obtained
CeO.sub.2 had a specific surface area of 23.4 m.sup.2/g. To the
CeO.sub.2 (30 g), water (300 g) and platinum dinitrodiammine
solution (6.82 g) comprising 4.4 wt % of Pt were added, and stirred
for two hours to obtain a mixture. The solid material obtained
after drying this mixture at 120.degree. C. was fired at
500.degree. C. for two hours to obtain Catalyst 3.
Comparative Example 2
Preparation of Catalyst 4
Cerium nitrate (73.165 g), zirconium oxynitrate (41.16 g) and
yttrium nitrate (6.48 g) was added to water (500 g), and mixed to
obtain uniform solution. While the pH of the solution was measured
by a pH meter, an aqueous ammonia was added to the solution to
adjust pH of the solution to 9 and provide a precipitate. A solid
material obtained after drying this solution at 120.degree. C. was
fired at 500.degree. C. for two hours to obtain mixed metal oxide
particles. To a solution comprising the mixed metal oxide particles
(50 g) dispersed in water (300 g), platinum dinitrodiammine
solution (11.36 g) comprising 4.4 wt % of Pt was added and stirred
for two hours to obtain a mixture. This mixture was dried at
120.degree. C., and fired at 500.degree. C. for two hours to obtain
Catalyst 4. The obtained Catalyst 4 had a weight ratio of
CeO.sub.2:ZrO.sub.2:Y.sub.2O.sub.3=58:38:4. An amount of Pt carried
by mixed metal oxide was 1 wt % on the basis of the weight of the
mixed metal oxide particles.
Comparative Example 3
Preparation of Catalyst 5
A cerium nitrate (73.17 g), zirconium oxynitrate (34.66 g),
lanthanum nitrate (3.99 g) and praseodymium nitrate (8.94 g) were
added to water (500 g), and mixed to obtain uniform solution. While
the pH of the solution was measured by a pH meter, aqueous ammonia
was added to the solution to adjust pH of the solution to 9 and
provide precipitate. A solid material obtained after drying this
solution at 120.degree. C. was fired at 700.degree. C. for five
hours to obtain mixed metal oxide particles. To this mixed metal
oxide (30 g), water (300 g) and platinum dinitrodiammine solution
(6.82 g) comprising 4.4 wt % of Pt were added and stirred for two
hours to obtain a mixture. The solid material obtained after drying
this mixture at 120.degree. C. was fired at 500.degree. C. for two
hours to obtain Catalyst 5. The obtained Catalyst 5 had a weight
ratio of
CeO.sub.2:ZrO.sub.2:La.sub.2O.sub.3:Pr.sub.6O.sub.11=58:32:3:7. An
amount of Pt carried on the mixed metal oxide particles was 1 wt %
on the basis of the weight of the mixed metal oxide particles.
Evaluation of the Catalysts
The mean particle diameters of the mixed metal oxide particles
prepared in above examples and comparative examples were determined
by measuring particle diameters of the randomly sampled 100
particles by TEM and calculating mean values of the particle
diameter for each examples and comparative examples.
1 mm square pellets made of Catalysts 1 to 5 in above examples and
comparative examples were evaluated for exhaust gas purifying
ability. Catalysts 1 to 5 were evaluated for specific surface area
and particle size of Pt carried thereby. The specific surface area
was evaluated by BET one point method. The diameter of the carried
Pt was evaluated by CO pulse method. In the CO pulse method for
determining Pt particle diameter, an amount of CO absorbed by
CeO.sub.2 family oxide before carrying Pt was deduced from an
amount of CO absorbed by Catalysts 1 to 5 for CO pulse method as
CeO.sub.2 also has a CO absorbing ability.
A rich gas and a lean gas were used as a model exhaust gas for
evaluating an exhaust gas purifying ability of catalyst. The
compositions of the rich and lean gases are shown in table 1.
TABLE-US-00001 TABLE 1 N.sub.2 CO.sub.2 NO CO C.sub.3H.sub.6
H.sub.2 O.sub.2 H.sub.2O (%) (%) (ppm) (%) (ppmC) *2 (%) (%) (%)
rich balance 10 2200 2.80 2500 0.27 0.77 10 gas *1 lean balance 10
2200 0.81 2500 0 1.7 10 gas *1 *1 N.sub.2 is the rest of the
contents. *2 The unit is based on an amount of carbon atoms.
Evaluation Procedure
Firstly, an enduring test was conducted wherein the catalysts were
contacted with a model gas at 800.degree. C. for five hours. The
model gas consisted of the rich gas and lean gas which were
switched every minute.
After enduring test, while rich and lean gases were switched at 1
Hz, the model gas was heated, and the temperature at which the
C.sub.3H.sub.6 content in model gas after passing the catalyst was
reduced to less than 50% was determined and considered as
HC-T50(.degree. C.). The lower the value of HC-T50(.degree. C.),
the higher the exhaust gas purification ability of the catalyst.
The results obtained for Catalysts 1 to 5 are listed in table
2.
TABLE-US-00002 TABLE 2 Mean Metals particle Par- whose Weight size
of ticle oxides ratio of Specific mixed size Catalyst to constitute
the oxide surface metal of HC- be evaluated catalysts of above area
oxide Pt T50 (Ex. No.) *1 metal (m.sup.2/g) (nm) (nm) (.degree. C.)
Catalyst 1 Ce/Zr/Y 58/38/4 52 32 3.8 224 (Example 1) Catalyst 2
Ce/Zr/la/ 58/32/3/7 59 26 3.2 222 (Example 2) Pr Catalyst 3 Ce 100
8 1260 6.2 325 (Comparative Example 1) Catalyst 4 Ce/Zr/Y 58/38/4
36 325 9.3 298 (Comparative Example 2) Catalyst 5 Ce/Zr/la/
58/32/3/7 28 490 9.9 293 (Comparative Pr Example 3)
From the results listed in table 2, it is apparent that Catalyst 1
prepared in example 1 has a smaller Pt particle size, lower HC-50
value and superior ability as an exhaust gas purifying catalyst
than Catalyst 4 prepared in comparative example 2 though Catalyst 1
has same composition as Catalyst 4. Further, it is apparent that
Catalyst 2 prepared in example 2 has a smaller Pt particle size,
lower HC-50 value and superior ability as an exhaust gas purifying
catalyst than Catalyst 5 prepared in comparative example 3 though
Catalyst 2 has same composition as Catalyst 5. Catalyst 3 prepared
in comparative example 1 has a moderate Pt particle size among
Catalysts 1 to 5, and large affinity between Pt and CeO.sub.2.
However, Catalyst 3 is not preferred, as an exhaust gas purifying
catalyst, as Catalyst 3 has smaller specific surface area and lower
heat resistivity of CeO.sub.2, and also has largest HC-T50
value.
Although the present invention has been fully described by way of
example with reference to the accompanying drawings, it is to be
understood that various changes and modifications will be apparent
to those skilled in the art. Therefore, unless otherwise such
changes and modifications depart from the scope of the present
invention hereinafter defined, they should be construed as being
included therein.
* * * * *