U.S. patent application number 12/243063 was filed with the patent office on 2009-04-02 for exhaust gas purifying catalyst system.
This patent application is currently assigned to MAZDA MOTOR CORPORATION. Invention is credited to Hideharu IWAKUNI, Koji MINOSHIMA, Seiji MIYOSHI, Masahiko SHIGETSU, Akihide TAKAMI.
Application Number | 20090084092 12/243063 |
Document ID | / |
Family ID | 40506644 |
Filed Date | 2009-04-02 |
United States Patent
Application |
20090084092 |
Kind Code |
A1 |
MIYOSHI; Seiji ; et
al. |
April 2, 2009 |
EXHAUST GAS PURIFYING CATALYST SYSTEM
Abstract
Disclosed is an exhaust gas purifying catalyst system, which
comprises an upstream catalyst disposed in an exhaust gas passage
of an engine at a position on an upstream side with respect to a
direction of an exhaust gas stream, and a downstream catalyst
disposed in the exhaust gas passage at a position on a downstream
side with respect to the direction of the exhaust gas stream. In
the exhaust gas purifying catalyst system, the downstream catalyst
includes a cerium (Ce)-containing rhodium-doped composite oxide and
an Ni component, and the upstream catalyst includes a cerium
(Ce)-containing composite oxide other than the rhodium-doped
composite oxide, and a Ni component. A ratio of Ni to CeO.sub.2 in
the upstream catalyst is in the range of 15 to 20 mass %, and a
ratio of Ni to CeO.sub.2 in the downstream catalyst is in the range
of 10 to 60 mass %. The exhaust gas purifying catalyst system of
the present invention can reduce an amount of H.sub.2S emission
while achieving high purification performance.
Inventors: |
MIYOSHI; Seiji; (Hiroshima,
JP) ; IWAKUNI; Hideharu; (Hiroshima, JP) ;
MINOSHIMA; Koji; (Hiroshima, JP) ; TAKAMI;
Akihide; (Hiroshima, JP) ; SHIGETSU; Masahiko;
(Hiroshima, JP) |
Correspondence
Address: |
Studebaker & Brackett PC
1890 Preston White Drive, Suite 105
Reston
VA
20191
US
|
Assignee: |
MAZDA MOTOR CORPORATION
Hiroshima
JP
|
Family ID: |
40506644 |
Appl. No.: |
12/243063 |
Filed: |
October 1, 2008 |
Current U.S.
Class: |
60/299 |
Current CPC
Class: |
F01N 3/10 20130101; F01N
13/009 20140601; F01N 2510/067 20130101; F01N 2570/16 20130101 |
Class at
Publication: |
60/299 |
International
Class: |
F01N 3/10 20060101
F01N003/10 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 2, 2007 |
JP |
2007-259109 |
Claims
1. An exhaust gas purifying catalyst system comprising an upstream
catalyst disposed in an exhaust gas passage of an engine at a
position on an upstream side with respect to a direction of an
exhaust gas stream, and a downstream catalyst disposed in said
exhaust gas passage at a position on a downstream side with respect
to the direction of said exhaust gas stream, wherein: said
downstream catalyst includes a cerium (Ce)-containing oxygen
storage material consisting of a rhodium-doped composite oxide
having rhodium arranged at a lattice position or interlattice
position of a crystal structure thereof, and at least either one of
nickel (Ni) and nickel oxide (NiO); and said upstream catalyst
includes a cerium (Ce)-containing oxygen storage material
consisting of a composite oxide other than said rhodium-doped
composite oxide, and at least either one of nickel (Ni) and nickel
oxide (NiO), wherein a ratio of Ni to CeO.sub.2 in said upstream
catalyst is in the range of 15 to 20 mass %, and a ratio of Ni to
CeO.sub.2 in said downstream catalyst is in the range of 10 to 60
mass %.
2. The exhaust gas purifying catalyst system as defined in claim 1,
wherein each of said respective composite oxides included in said
upstream catalyst and said downstream catalyst includes zirconium
and neodymium.
3. The exhaust gas purifying catalyst system as defined in claim 1,
wherein the ratio of Ni to CeO.sub.2 in said upstream catalyst is
greater than the ratio of Ni to CeO.sub.2 in said downstream
catalyst.
4. The exhaust gas purifying catalyst system as defined in claim 1,
wherein each of said respective composite oxides included in said
upstream catalyst and said downstream catalyst supports a catalytic
noble metal thereon.
5. The exhaust gas purifying catalyst system as defined in claim 4,
wherein: said catalytic noble metal supported on said composite
oxide included in said upstream catalyst and said downstream
catalyst is rhodium; said upstream catalyst includes palladium; and
said downstream catalyst includes platinum.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an exhaust gas purifying
catalyst system useful in purifying exhaust gas discharged from an
internal combustion engine, such as a vehicle engine.
[0003] 2. Background Art
[0004] As an exhaust gas purifying catalyst system for purifying
exhaust gas discharged from an engine, there has been known one
type comprising a manifold catalyst (close-coupled catalyst)
disposed in such a manner as to be directly coupled to an
exhaust-gas merging portion of an exhaust manifold of an engine,
and an underfloor catalyst (underbody catalyst) disposed downstream
of the manifold catalyst. In this type of exhaust gas purifying
catalyst system, the manifold catalyst disposed adjacent to the
engine is designed to reach its catalytic activation temperature as
quickly as possible so as to purify unburned exhaust gas
components, such as hydrocarbon (HC) and carbon monoxide (CO),
particularly when an exhaust gas temperature is relatively low, for
example, in a certain period after engine start-up. The underfloor
catalyst is designed to purify exhaust gas components which have
not been able to be purified by the manifold catalyst, particularly
during a normal operation and a high-speed operation of the
engine.
[0005] In many cases, an oxygen storage material is contained in
each of the manifold and underfloor catalysts. Such a catalyst
containing the oxygen storage material is capable of absorbing and
storing oxygen in exhaust gas by the oxygen storage material when
the exhaust gas is in an oxygen-excess state (an exhaust air-fuel
ratio (exhaust A/F) is in a lean region), and then releasing the
stored oxygen into exhaust gas when the exhaust gas is in an
oxygen-deficient state (the exhaust A/F is in a rich region), so as
to adjust the exhaust A/F approximately at a stoichiometric value
to provide enhanced catalytic activity and enhanced exhaust gas
purification performance.
[0006] Generally, gasoline as a fuel for an engine, and engine oil
as a lubricant for an engine, contains sulfur (S), and therefore
exhaust gas discharged from an engine contains an S component, such
as sulfur oxides (SOx). In this connection, it is known that the S
component causes sulfur (S) poisoning of an exhaust gas purifying
catalyst used in an exhaust gas purifying catalyst system, which
leads to a deterioration in catalytic activity.
[0007] The S component is likely to be absorbed and stored in an
oxygen storage material contained in an exhaust gas purifying
catalyst, in the form of SOx. Then, when exhaust gas is placed in
the oxygen-deficient state, the S component stored in the form of
SOx is released while being converted to hydrogen sulfide
(H.sub.2S). H.sub.2S is known as an off-flavor component, and
therefore it is required to reduce an amount of H.sub.2S emission.
Moreover, H.sub.2S also causes the S poisoning of the exhaust gas
purifying catalyst to accelerate the deterioration in catalytic
activity.
[0008] With a view to suppressing generation of H.sub.2S to reduce
an amount of H.sub.2S emission and S poisoning of an exhaust gas
purifying catalyst, there has been known a technique of
incorporating a Ni component, such as nickel (Ni) which is a
transition metal, or nickel oxide (NiO), into an exhaust gas
purifying catalyst, wherein the Ni component is capable of tapping
the S component to form nickel sulfide so as to suppress the
generation of H.sub.2S.
[0009] As one example of the exhaust gas purifying catalyst
containing Ni or NiO, JP 01-242149A discloses an exhaust gas
purifying catalyst comprising a support substrate, a nickel
oxide-containing activated alumina covering layer formed on the
support substrate, a composite oxide made of cerium oxide and
zirconium oxide and supported by the activated alumina covering
layer, and a catalytic noble metal supported on the activated
alumina covering layer.
[0010] Further, JP 08-290063A discloses an exhaust gas purifying
catalyst comprising a support, and a plurality of catalyst layers
formed on the support in a multi-layered manner, wherein a given
catalyst layer located on a lower side of an uppermost catalyst
layer contains nickel oxide and palladium.
[0011] As mentioned above, the Ni or NiO-containing exhaust gas
purifying catalyst as disclosed in the JP 01-242149A and the JP
08-290063A has a capability to suppress the generation of H.sub.2S.
Thus, it would also be advantageous for the above exhaust gas
purifying catalyst system comprising the manifold catalyst and the
underfloor catalyst, that the Ni component capable of trapping the
S component is added to each of the manifold and underfloor
catalysts. In this case, it is contemplated to add the Ni component
in a larger amount in order to more effectively suppress the
generation of H.sub.2S. However, the Ni component added in a larger
amount causes a problem about deterioration in purification
performance, such as HC, CO and NOx purification performance,
although it definitely has the advantageous effect of reducing an
amount of H.sub.2S emission.
SUMMARY OF THE INVENTION
[0012] In view of the above circumstances, it is an object of the
present invention to provide an exhaust gas purifying catalyst
system capable of reducing an amount of H.sub.2S emission while
achieving high purification performance.
[0013] In order to achieve the above object, according to one
aspect of the present invention, there is provided an exhaust gas
purifying catalyst system which comprises an upstream catalyst
disposed in an exhaust gas passage of an engine at a position on an
upstream side with respect to a direction of an exhaust gas stream,
and a downstream catalyst disposed in the exhaust gas passage at a
position on a downstream side with respect to the direction of the
exhaust gas stream. In the exhaust gas purifying catalyst system,
the downstream catalyst includes a cerium (Ce)-containing oxygen
storage material consisting of a rhodium-doped composite oxide
having rhodium arranged at a lattice position or interlattice
position of a crystal structure thereof, and at least either one of
nickel (Ni) and nickel oxide (NiO), and the upstream catalyst
includes a cerium (Ce)-containing oxygen storage material
consisting of a composite oxide other than the rhodium-doped
composite oxide, and at least either one of nickel (Ni) and nickel
oxide (NiO). A ratio of Ni to CeO.sub.2 in the upstream catalyst is
in the range of 15 to 20 mass %, and a ratio of Ni to CeO.sub.2 in
the downstream catalyst is in the range of 10 to 60 mass %.
[0014] In the exhaust gas purifying catalyst system of the present
invention, when exhaust gas passes through the upstream catalyst
and the downstream catalyst, exhaust gas components, such as HC, CO
and NOx, are purified by both the upstream and downstream
catalysts. Thus, even if each of the upstream and downstream
catalysts has a slightly lower purification performance as compared
with a catalyst without an addition of nickel, the exhaust gas
purifying catalyst system can adequately reduce an amount of
emission of CO, HC, NOx, etc., to maintain high purification
performance as a whole. In addition, the generation of H.sub.2S is
suppressed in both the upstream and downstream catalysts. Thus,
even if each of the upstream and downstream catalysts is set to
have a slightly lower capability of suppressing the generation of
H.sub.2S as compared with a catalyst added with a large amount of
Ni, the exhaust gas purifying catalyst system can adequately reduce
an amount of H.sub.2S emission as a whole.
[0015] The oxygen storage material included in the downstream
catalyst is a rhodium-doped composite oxide having rhodium arranged
at a lattice position or interlattice position of a crystal
structure thereof. Such a composite oxide has a capability to
absorb/release oxygen at a relatively high speed, and store oxygen
in a relatively large amount. Thus, even if an oxygen concentration
in exhaust gas varies, the oxygen concentration can be readily
adjusted at a desired value to allow the downstream catalyst to
effectively perform a catalytic action thereof. That is, exhaust
gas components which have not been able to be purified by the
upstream catalyst, can be efficiently purified by the downstream
catalyst. This also contributes to achievement of high purification
performance.
[0016] As above, the exhaust gas purifying catalyst system of the
present invention can reduce an amount of H.sub.2S emission while
achieving high purification performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a schematic diagram showing an exhaust gas
purifying catalyst system according to one embodiment of the
present invention.
[0018] FIG. 2A is a schematic diagram simplistically showing a
structure of an Rh-doped Zr--Ce--Nd composite oxide.
[0019] FIG. 2B is a schematic diagram simplistically showing a
structure of an Rh-post-supporting Zr--Ce--Nd composite oxide.
[0020] FIG. 3A is a schematic diagram simplistically showing a
presumed oxygen storage mechanism in the Rh-doped Zr--Ce--Nd
composite oxide.
[0021] FIG. 3B is a schematic diagram simplistically showing a
presumed oxygen storage mechanism in the Rh-post-supporting
Zr--Ce--Nd composite oxide.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] An exhaust gas purifying catalyst system according to one
embodiment of the present invention will now be described.
[0023] FIG. 1 is a schematic diagram showing the exhaust gas
purifying catalyst system according to this embodiment. The exhaust
gas purifying catalyst system comprises an upstream catalyst 3 and
a downstream catalyst 4 each interposed in an exhaust gas passage 2
connected to a vehicle engine 1. The upstream catalyst 3 is
disposed on an upstream side with respect to a direction of an
exhaust gas stream, and the downstream catalyst 4 is disposed on a
downstream side with respect to the direction of the exhaust gas
stream. The upstream catalyst 3 and the downstream catalyst 4 are
provided in spaced-apart relation to each other to purify air
pollutants, such as HC, CO and NOx, in exhaust gas
individually.
[0024] Firstly, the upstream catalyst 3 will be specifically
described. The upstream catalyst 3 comprises a Ce-containing
composite oxide having an oxygen storage capacity, and a Ni
component which is at least either one of Ni and NiO. In the
upstream catalyst 3, a ratio of Ni to CeO.sub.2 is set in the range
of 15 to 20 mass %. If the Ni/CeO.sub.2 ratio becomes less than 15
mass %, an effect of suppressing generation of H.sub.2S is reduced,
and resulting sulfur (S) poisoning of a catalytic noble metal
supported on the upstream catalyst 3 and the downstream catalyst 4
is liable to cause deterioration in catalytic activity of the
upstream and downstream catalysts 3, 4 and an increase in amount of
H.sub.2S emission. If the Ni/CeO.sub.2 ratio becomes greater than
20 mass %, the catalytic activity of the upstream catalyst 3 is
liable to deteriorate.
[0025] The composite oxide in the upstream catalyst 3 is a
composite oxide other than an after-mentioned Rh-doped composite
oxide. Preferably, the composite oxide further includes zirconium
(Zr) and neodymium (Nd). Preferably, the composite oxide
fundamentally supports a catalytic noble metal thereon. The
catalytic noble metal to be supported on the upstream catalyst 3
may be at least one selected, for example, from the group
consisting of platinum (Pt), palladium (Pd) and rhodium (Rh). Among
them, it is particularly preferable that Pd and Rh are supported on
the upstream catalyst 3.
[0026] The upstream catalyst 3 may be constructed as above. In this
embodiment, the following catalyst is shown as a specific example.
The upstream catalyst 3 in this embodiment comprises: a catalyst
support consisting of a honeycomb support made of cordierite or
heat-resistant ceramics such as SiC or Si.sub.3N.sub.4; a lower
catalyst layer (lower layer) formed on the honeycomb support, and
an upper catalyst layer (upper layer) formed on the lower catalyst
layer. Although the honeycomb support is used in this embodiment as
the catalyst support, the catalyst support is not limited to the
honeycomb support, but may be any other suitable type of catalyst
support.
[0027] The lower layer of the upstream catalyst 3 includes a
catalyst substrate supporting thereon Pd as a catalytic noble
metal. The catalyst substrate is made, for example, of
lanthanum-containing alumina, and a composite oxide containing Ce,
Zr, La, yttrium (Y) and aluminum (Al) (Ce--Zr--La--Y--Al composite
oxide). As one example, the lanthanum-containing alumina may be
alumina containing La.sub.2O.sub.3 in an amount of 4 mass %, and
the Ce--Zr--La--Y--Al composite oxide may be a composite oxide
containing CeO.sub.2 in an amount of 10 mass %, and alumina in an
amount of about 80 mass %.
[0028] In this embodiment, the lower layer of the upstream catalyst
3 also includes CeO.sub.2, and a composite oxide containing Zr, Ce
and Nd (Zr--Ce--Nd composite oxide), as a promoter (OSC) for
enhancing exhaust gas purification performance and heat resistance
of palladium. The lower layer further includes zirconia as a binder
for enhancing binding between the respective components. The lower
layer further includes NiO as the Ni component for suppressing the
generation of H.sub.2S and the S poisoning of Pd. ZrO.sub.2, i.e.,
an oxide of Zr, has an additional function of enhancing heat
resistance of CeO.sub.2. As one example, the Zr--Ce--Nd composite
oxide may be a composite oxide containing CeO.sub.2 in an amount of
35 mass %. The NiO may be a NiO powder. Although NiO is shown as an
example of the Ni component, the Ni component may be Ni, such as a
Ni powder.
[0029] With regard to the above components of the lower layer, the
La-containing alumina, the Ce--Zr--La--Y--Al composite oxide, the
CeO.sub.2, and the Zr--Ce--Nd composite oxide, may be contained in
the lower layer, for example, in amounts of 45 g/L, 20 g/L, 6 g/L,
and 6 g/L, respectively, wherein the NiO may be contained in the
lower layer in a given ratio, and the zirconia as a binder may be
contained as the remnant.
[0030] In this embodiment, the upper layer comprises a catalyst
substrate supporting thereon Rh as a catalytic noble metal. The
catalyst substrate is made of alumina containing a Zr--La composite
oxide (Zr--La composite oxide-containing alumina), and a Zr--Ce--Nd
composite oxide. As one example, the Zr--Ce--Nd composite oxide may
be a composite oxide containing CeO.sub.2 in an amount of 10 mass
%.
[0031] In this embodiment, the upper layer also includes
La-containing alumina. The upper layer further includes zirconia as
a binder for enhancing binding between the respective components.
The upper layer further includes NiO as the Ni component for
suppressing the generation of H.sub.2S and the S poisoning of Pd.
As one example, the La-containing alumina may be alumina containing
La.sub.2O.sub.3 in an amount of 4 mass %. The NiO may be a NiO
powder. Although NiO is shown as an example of the Ni component,
the Ni component may be Ni, such as a Ni powder.
[0032] With regard to the above components of the upper layer, the
Zr--La composite oxide-containing alumina, the Zr--Ce--Nd composite
oxide, and the La-containing alumina, may be contained in the upper
layer, for example, in amounts of 30 g/L, 75 g/L and 15 g/L,
respectively, wherein the NiO may be contained in the upper layer
in a given ratio, and the zirconia as a binder may be contained as
the remnant.
[0033] A production method for the above upstream catalyst 3 in
this embodiment will be described below.
[0034] Firstly, Pd is supported (post-supported) on each of a
La-containing alumina and a Ce--Zr--La--Y--Al composite oxide.
Then, the Pd-supporting La-containing alumina, the Pd-supporting
Ce--Zr--La--Y--Al composite oxide, CeO.sub.2, a Zr--Ce--Nd
composite oxide, NiO and zirconyl nitrate each prepared in a given
amount, are mixed together, and an appropriate amount of water is
added to the mixture to form a slurry. Then, a honeycomb support is
wash-coated with the slurry. The wash-coated honeycomb support is
dried at 150.degree. C., and sintered at 500.degree. C., so that a
lower layer is formed on the honeycomb support.
[0035] Then, Rh is supported (post-supported) on each of a Zr--La
composite oxide-containing alumina and a Zr--Ce--Nd composite
oxide. Then, the Rh-supporting Zr--La composite oxide-containing
alumina, the Rh-supporting Zr--Ce--Nd composite oxide,
La-containing alumina, NiO and zirconyl nitrate each prepared in a
given amount, are mixed together, and an appropriate amount of
water is added to the mixture to form a slurry. Then, the honeycomb
support formed with the lower layer is wash-coated with the slurry.
The wash-coated honeycomb support is dried at 150.degree. C., and
sintered at 500.degree. C., so that an upper layer is formed on the
lower layer.
[0036] In the above manner, the upstream catalyst 3 is
produced.
[0037] The downstream catalyst 4 will be specifically described
below. The downstream catalyst 4 comprises a Ce-containing
composite oxide having an oxygen storage capacity, and a Ni
component which is at least either one of Ni and NiO. In the
downstream catalyst 4, a ratio of Ni to CeO.sub.2 is set in the
range of 10 to 60 mass %. If the Ni/CeO.sub.2 ratio becomes less
than 10 mass %, an effect of suppressing generation of H.sub.2S is
reduced, and resulting S poisoning of a catalytic noble metal
supported on the downstream catalyst 4 is liable to cause
deterioration in catalytic activity of the downstream catalyst 4
and an increase in amount of H.sub.2S emission. If the Ni/CeO.sub.2
ratio becomes greater than 60 mass %, the catalytic activity of the
downstream catalyst 4 is liable to deteriorate. Preferably, the
Ni/CeO.sub.2 ratio in the upstream catalyst 3 is greater than the
Ni/CeO.sub.2 ratio in the downstream catalyst 4.
[0038] Preferably, the Ce-containing composite oxide in the
downstream catalyst 4 consists of an Rh-doped composite oxide
having Rh arranged at a lattice position or interlattice position
of a crystal structure thereof, and further includes Zr and Nd.
Preferably, the Ce-containing composite oxide fundamentally
supports a catalytic noble metal thereon. The catalytic noble metal
to be supported on the downstream catalyst 4 may be at least one
selected, for example, from the group consisting of Pt, Pd and Rh.
Among them, it is particularly preferable that Pd and Rh are
supported on the downstream catalyst 4. The Rh-doped composite
oxide is prepared by doping (incorporating as a solid solution) Rh
into a Ce-containing composite oxide (oxygen storage material) so
as to fix the Rh to the Ce-containing composite oxide.
[0039] The downstream catalyst 4 may be constructed as above. In
this embodiment, the following catalyst is shown as a specific
example. The downstream catalyst 4 in this embodiment comprises: a
catalyst support consisting of a honeycomb support made of
cordierite or heat-resistant ceramics such as SiC or
Si.sub.3N.sub.4; and a catalyst layer formed on the honeycomb
support, in a similar manner to the upstream catalyst 3. Although
the honeycomb support is used in this embodiment as the catalyst
support, the catalyst support is not limited to the honeycomb
support, but may be any other suitable type of catalyst
support.
[0040] The catalyst layer of the downstream catalyst 4 includes a
La-containing alumina supporting thereon Pt as a catalytic noble
metal, and an Rh-doped Zr--Ce--Nd composite oxide supporting
thereon Rh as a catalytic noble metal. The Rh-supporting Rh-doped
Zr--Ce--Nd composite oxide means a composite oxide prepared by
additionally supporting (post-supporting) Rh on an after-mentioned
Rh-doped Zr--Ce--Nd composite oxide. As one example, the
La-containing alumina may be alumina containing La in an amount of
4 mass %, and the Rh-doped Zr--Ce--Nd composite oxide may be a
composite oxide containing CeO2 in an amount of 22 mass %.
[0041] In this embodiment, the catalyst layer further includes
zirconia as a binder for enhancing binding between the respective
components. The catalyst layer further includes NiO as the Ni
component for suppressing the generation of H.sub.2S. As one
example, the NiO may be a NiO powder. Although NiO is shown as an
example of the Ni component, the Ni component may be Ni, such as a
Ni powder.
[0042] With regard to the above components of the catalyst layer,
and the La-containing alumina, the Rh-doped Zr--Ce--Nd composite
oxide, may be contained in the catalyst layer, for example, in
amounts of 50 g/L and 110 g/L, respectively, wherein the NiO may be
contained in the lower layer in a given ratio, and the zirconia as
a binder may be contained as the remnant.
[0043] FIG. 2A is a schematic diagram simplistically showing a
structure of the Rh-doped Zr--Ce--Nd composite oxide. FIG. 2B is a
schematic diagram simplistically showing a structure of an
Rh-post-supporting Zr--Ce--Nd composite oxide.
[0044] The Rh-doped Zr--Ce--Nd composite oxide has the structure as
shown in FIG. 2A. In the Rh-doped Zr--Ce--Nd composite oxide, Rh is
arranged at a lattice position (i.e., at a position of a lattice
point) of a crystal structure of the composite oxide, in the same
manner as that for Zr, Ce and Nd. In other words, Rh is strongly
bound to the composite oxide in the form of RhMOx (wherein M is
another metal atom, and x is the number of oxygen atoms).
Alternatively, Rh is arranged at an interlattice position (i.e., at
a position between lattice points) of the crystal structure of the
composite oxide. In either case, a composite oxide is obtained in
such a manner that Rh atoms are evenly dispersed over a surface and
an inside of the composite oxide.
[0045] Differently, the Rh-post-supporting Zr--Ce--Nd composite
oxide has the structure as shown in FIG. 2B. For example, the
Rh-post-supporting Zr--Ce--Nd composite oxide is obtained by
forming a composite oxide containing Zr, Ce and Nd, through a
coprecipitation process using ammonia, and then post-supporting Rh
on the composite oxide through an evaporative drying process. In
this case, Rh is unevenly distributed on a surface of the
composite.
[0046] Thus, as compared with the Rh-post-supporting Zr--Ce--Nd
composite oxide, the Rh-doped Zr--Ce--Nd composite oxide has the
following two advantages.
[0047] In the Rh-post-supporting Zr--Ce--Nd composite oxide,
binding between Rh and the composite oxide is weak, and thereby Rh
is sintered by heating while moving on the surface of the composite
oxide. Differently, in the Rh-doped Zr--Ce--Nd composite oxide, as
shown in FIG. 2A, a movement of Rh arranged at a lattice position
or interlattice position of the crystal structure of the composite
oxide is constrained by a strong interaction with the composite
oxide. In addition, it is considered that Rh in the inside of the
composite oxide serves as a steric barrier to suppress sintering of
the composite oxide.
[0048] Further, in the Rh-doped Zr--Ce--Nd composite oxide, an
oxygen-absorbing speed is quickly increased while increasing a
minimum value thereof, and an oxygen storage amount is increased,
as compared with the Rh-post-supporting Zr--Ce--Nd composite oxide.
The difference in oxygen storage characteristics would arise for
the following reason.
[0049] FIG. 3A is a schematic diagram simplistically showing a
presumed oxygen storage mechanism in the Rh-doped Zr--Ce--Nd
composite oxide. FIG. 3B is a schematic diagram simplistically
showing a presumed oxygen storage mechanism in the
Rh-post-supporting Zr--Ce--Nd composite oxide. In FIGS. 3A and 3B,
Zr atoms and Nd atoms are omitted.
[0050] As shown in FIG. 3B, in the Rh-post-supporting Zr--Ce--Nd
composite oxide, it is assumed that, although oxygen (O.sub.2) is
stored in an oxygen vacancy (O vacancy) existing in a vicinity of a
surface of the composite oxide, in the form of an oxygen ion, it
cannot reach an oxygen vacancy existing in a relatively deep region
of an inside of the composite oxide, and the oxygen vacancy in the
relatively deep region is not effectively used for oxygen
storage.
[0051] Differently, as shown in FIG. 3A, in the Rh-doped Zr--Ce--Nd
composite oxide, it is assumed that Rh atoms residing in the inside
of the composite oxide draw oxygen (O.sub.2) in the form of an
oxygen ion to allow the oxygen ion to momentarily move to the
oxygen vacancy in the inside of the composite oxide. In addition,
the Rh atoms dispersedly exist in the inside of the composite
oxide. Thus, it is assumed that the oxygen ion moves from the
surface of the composite oxide via two or more of the Rh atoms in a
hopping manner, and reaches an oxygen vacancy in the relatively
deep region of the inside of the composite oxide. In view of the
above assumptions, in the Rh-doped Zr--Ce--Nd composite oxide, when
exhaust gas has an oxygen-excess atmosphere, the oxygen-absorbing
speed is quickly increased while increasing the maximum value
thereof. In addition, an oxygen vacancy in the relatively deep
region of the inside of the oxygen storage material is effectively
used for oxygen storage to increase the oxygen storage amount.
[0052] A production method for the Rh-doped composite oxide will be
described below.
[0053] Firstly, a row material preparation step is performed to
prepare an acid solution containing Rh, Ce and Zr. For example, in
the row material preparation step, the acid solution may be
prepared by mixing respective solution of Rh, Ce and Zr nitrates
together. As needed, another metal, such as Nd, may be additionally
contained in the acid solution.
[0054] Then, a step of preparing a composite oxide precursor
through a coprecipitation process using ammonia is performed. In
this step, an excess amount of aqueous ammonia is quickly added and
mixed to/with the acid solution as a starting material while
stirring the acid solution, or the acid solution and aqueous
ammonia are simultaneously supplied to a rotating cup-shaped mixer
and quickly mixed together, so that Rh, Ce and Zr in the starting
material are coprecipitated as a metal hydroxide to obtain a
composite oxide precursor.
[0055] Then, the following steps are performed in turn. A
precipitation/separation step is performed which comprises leaving
the solution with the coprecipitate for one day, removing a
supernatant solution to obtain a cake, placing the cake in a
centrifugal machine, and rinsing the cake with water. Then, the
rinsed cake is subjected to a drying step of drying it by heating
at a temperature of about 150.degree. C. Then, the dried cake is
subjected to a firing step of firing it by heating. The firing step
is performed by placing the dried cake in an ambient atmosphere,
for example, which is held at a temperature of 400.degree. C. for 5
hours, and then held at a temperature of 500.degree. C. for 2
hours. Then, the fired product is subjected to a reducing step of
placing it in a reduction atmosphere held at a temperature of about
500.degree. C.
[0056] Through the above steps, the Rh-doped composite oxide is
prepared.
[0057] The downstream catalyst 4 is produced as follows, using the
Rh-doped composite oxide prepared by the above preparation
process.
[0058] Firstly, Pt is supported (post-supported) on a La-containing
alumina, and Rh is supported (post-supported) on the Rh-doped
composite oxide. Then, the Pt-supporting La-containing alumina, the
Rh-supporting Rh-doped composite oxide, NiO, and zirconyl nitrate
as a binder material, each prepared in a given amount, are mixed
together, and an appropriate amount of water is added to the
mixture to form a slurry. Then, a honeycomb support is wash-coated
with the slurry. The wash-coated honeycomb support is dried at
150.degree. C., and sintered at 500.degree. C., so that a catalyst
layer is formed on the honeycomb support. In this manner, the
downstream catalyst 4 is produced.
EXAMPLES
[0059] Although the exhaust gas purifying catalyst system according
to the embodiment of the present invention will be described based
on specific examples, the present invention is not limited to the
specific examples.
Inventive Examples 1 to 7 and Comparative Examples 1 to 6
[0060] Each of the components, except the Ni component and the
binder material, was supported on the support in an amount per
liter of the support (g/L), as shown in Table 1, and each of the Ni
component (NiO) was supported on the support in a mass ratio (mass
%), as shown in Table 2. In this manner, an upstream catalyst and a
downstream catalyst in each of Inventive Examples 1 to 7 and
Comparative Examples 1 to 6 were produced.
[0061] Then, the obtained upstream catalyst and downstream catalyst
were disposed at given positions as shown in FIG. 1 to produce an
exhaust gas purifying catalyst system in each of Inventive Examples
1 to 7 and Comparative Examples 1 to 6.
[0062] A light-off performance and an amount of H.sub.2S emission
of the exhaust gas purifying catalyst system in each of Inventive
Examples 1 to 7 and Comparative Examples 1 to 6 were measured as
follows. A result of the measurement is shown in Table 2.
[0063] [Light-Off Performance]
[0064] The exhaust gas purifying catalyst system was connected to a
2 L gasoline engine. The engine was adjusted to allow an exhaust
gas temperature at an inlet of the upstream catalyst to be
900.degree. C. and allow an exhaust A/F to be maintained in a
stoichiometric region for 60 sec. in a lean region for 10 sec and
in a rich region for 30 sec, in one cycle. Then, the upstream and
the downstream catalysts were subjected to an aging treatment by
repeating the cycle for 50 hours. In this exhaust gas purifying
catalyst system, a volume of each of the upstream and the
downstream catalysts was set at 1 L.
[0065] A columnar-shaped evaluation catalyst sample having a
diameter of 25 mm and a height of 50 mm was cut from each of the
upstream and the downstream catalysts after being subjected to the
aging treatment, and set in a model-gas flow-type catalyst
evaluation apparatus. Simulated exhaust gas (model gas) was
circulated through the catalyst evaluation apparatus at a space
velocity of 60000/h while raising its temperature at a rate of
30.degree. C./min. Under this condition, a simulated exhaust gas
temperature at the inlet of each of the catalysts at a time when
each of HC, CO and NOx concentrations at a position just after an
outlet of the catalyst is increased up to 50% (i.e., light-off
temperature T50), was measured. The columnar-shaped core sample cut
from each of the aged upstream and the downstream catalysts to have
a diameter of 25 mm and a height of 50 mm was used as the catalyst
for this measurement. The simulated exhaust gas was adjusted to
have an A/F of 14.7.+-.0.9. Specifically, mainstream gas having an
A/F of 14.7 was constantly supplied, and a given amount of
variation gas was added at a frequency of 1 Hz in a pulsed manner
to forcedly fluctuate the A/F up and down at a fluctuation range of
.+-.0.9. The light-off temperature T50 is an index for evaluating
the catalyst activity and the exhaust gas purification performance,
wherein a lower light-off temperature T50 indicates higher catalyst
activity and exhaust gas purification performance at a low
temperature.
[0066] [Amount of H.sub.2S Emission]
[0067] The same exhaust gas purifying catalyst system having the
aged upstream and downstream catalysts as that in the light-off
performance evaluation was mounted to a vehicle equipped with a 2 L
gasoline engine, and the vehicle was run in the following running
pattern. This running pattern consists of a vehicle running at 30
km/h for 4 min, a subsequent vehicle running at 50 km/h for 1 min,
and a subsequent vehicle deceleration from 50 km/h to zero km/h.
During the vehicle deceleration from 50 km/h to zero km/h in the
above running pattern, a maximum concentration of H.sub.2S was
measured. The reason why the maximum concentration of H.sub.2S is
measured during the vehicle deceleration from 50 km/h to zero km/h
is that sulfur (S) is attached on the catalyst during a steady
operation, such as the vehicle running at 30 km/h and the vehicle
running at 50 km/h, and H.sub.2S is generated and emitted when an
exhaust A/F is placed in a rich region, in response to restart of
fuel supply after fuel is cut during deceleration subsequent to the
steady operation.
TABLE-US-00001 TABLE 1 SUPPORTED COMPONENT AMOUNT(g/L) UPSTREAM
CATALYST UPPER LAYER Rh-SUPPORTING Zr--Ce--Nd COMPOSITE OXIDE 75
CATALYST (CeO.sub.2 CONTENT %: 10 MASS %) Zr--La COMPOSITE 30
OXIDE-CONTAINING ALUMIN ALUMINA La-CONTAINING ALUMINA 15
(La-CONTENT %: 4 MASS %) LOWER LAYER OSC CeO.sub.2 6 Zr--Ce--Nd
COMPOSITE OXIDE 6 (CeO.sub.2 CONTENT %: 10 MASS %) Pd-SUPPORTING
La-CONTAINING ALUMINA 45 CATALYST (La-CONTENT %: 4 MASS %)
Ce--Zr--LA--Y--Al COMPOSITE 20 OXIDE (CeO.sub.2 CONTENT %: 10 MASS
%) DOWNSTREAM Pt-SUPPORTING La-CONTAINING ALUMINA 50 CATALYST
CATALYST (La-CONTENT %: 4 MASS %) Rh-SUPPORTING Rh-DOPED Zr-CE-Nd
110 CATALYST COMPOSITE OXIDE (CeO.sub.2 CONTENT %: 22 MASS %)
TABLE-US-00002 TABLE 2 H.sub.2S EMISSION UPSTREAM AFTER H.sub.2S
EMISSION CATALYST LIGHT-OFF PASSING LIGHT-OFF OF AFTER PASSING
Ni/CeO.sub.2 OF UPSTREAM THROUGH DOWNSTREAM DOWNSTREAM THROUGH MASS
CATALYST UPSTREAM CATALYST CATALYST UPSTREAM AND RATIO (.degree.
C.) CATALYST Ni/CeO.sub.2 MASS (.degree. C.) DOWNSTREAM (MASS %) HC
CO NOx (ppm) RATIO (MASS %) HC CO NOx CATALYSTS (ppm) INVENTIVE
EXAMPLE 1 20 249 244 240 24 60 258 250 246 5 INVENTIVE EXAMPLE 2 20
249 244 240 24 40 257 249 245 9 INVENTIVE EXAMPLE 3 20 249 244 240
24 10 255 247 242 10 INVENTIVE EXAMPLE 4 18 247 243 239 28 12 256
248 245 10 INVENTIVE EXAMPLE 5 15 247 243 237 35 40 257 249 245 13
INVENTIVE EXAMPLE 6 15 247 243 237 35 12 256 248 245 10 INVENTIVE
EXAMPLE 7 15 247 243 237 35 10 255 247 242 11 COMPARATIVE EXAMPLE 1
30 258 255 250 17 65 265 255 250 7 COMPARATIVE EXAMPLE 2 30 258 255
250 17 40 257 249 245 9 COMPARATIVE EXAMPLE 3 20 249 244 240 24 65
265 255 250 9 COMPARATIVE EXAMPLE 4 20 249 244 240 24 5 250 241 237
20 COMPARATIVE EXAMPLE 5 15 247 243 237 35 65 265 255 250 11
COMPARATIVE EXAMPLE 6 10 247 243 234 50 70 279 265 262 7
[0068] As seen in Table 2, in each of Inventive Examples 1 to 7
where a ratio of Ni to CeO2 in the upstream catalyst is in the
range of 15 to 20 mass %, and a ratio of Ni to CeO.sub.2 in the
downstream catalyst is in the range of 10 to 60 mass %, an amount
of H2S emission after passing through both the upstream and
downstream catalysts is low, and a light-off temperature in each of
the upstream and downstream catalysts is low, as compared with each
of Comparative Examples 1 to 6 where at least one of the
Ni/CeO.sub.2 ratio in the upstream catalyst and the Ni/CeO.sub.2
ratio in the downstream catalyst is out of the above range.
[0069] As mentioned above in detail, an exhaust gas purifying
catalyst system according to one aspect of the present invention
comprises an upstream catalyst disposed in an exhaust gas passage
of an engine at a position on an upstream side with respect to a
direction of an exhaust gas stream, and a downstream catalyst
disposed in the exhaust gas passage at a position on a downstream
side with respect to the direction of the exhaust gas stream. In
the exhaust gas purifying catalyst system, the downstream catalyst
includes a cerium (Ce)-containing oxygen storage material
consisting of a rhodium-doped composite oxide having rhodium
arranged at a lattice position or interlattice position of a
crystal structure thereof, and at least either one of nickel (Ni)
and nickel oxide (NiO), and the upstream catalyst includes a cerium
(Ce)-containing oxygen storage material consisting of a composite
oxide other than the rhodium-doped composite oxide, and at least
either one of nickel (Ni) and nickel oxide (NiO). A ratio of Ni to
CeO.sub.2 in the upstream catalyst is in the range of 15 to 20 mass
%, and a ratio of Ni to CeO.sub.2 in the downstream catalyst is in
the range of 10 to 60 mass %.
[0070] In the exhaust gas purifying catalyst system according to
the aspect of the present invention, when exhaust gas passes
through the upstream catalyst and the downstream catalyst, exhaust
gas components, such as HC, CO and NOx, are purified by both the
upstream and downstream catalysts. Thus, even if each of the
upstream and downstream catalysts has a slightly lower purification
performance as compared with a catalyst without an addition of
nickel, the exhaust gas purifying catalyst system can adequately
reduce an amount of emission of CO, HC, NOx, etc., to maintain high
purification performance as a whole. In addition, the generation of
H.sub.2S is suppressed in both the upstream and downstream
catalysts. Thus, even if each of the upstream and downstream
catalysts is set to have a slightly lower capability of suppressing
the generation of H.sub.2S as compared with a catalyst added with a
large amount of Ni, the exhaust gas purifying catalyst system can
adequately reduce an amount of H.sub.2S emission as a whole.
[0071] The oxygen storage material included in the downstream
catalyst is a rhodium-doped composite oxide having rhodium arranged
at a lattice position or interlattice position of a crystal
structure thereof. Such a composite oxide has a capability to
absorb/release oxygen at a relatively high speed, and store oxygen
in a relatively large amount. Thus, even if an oxygen concentration
in exhaust gas varies, the oxygen concentration can be readily
adjusted at a desired value to allow the downstream catalyst to
effectively perform a catalytic action thereof. That is, exhaust
gas components which have not been able to be purified by the
upstream catalyst, can be efficiently purified by the downstream
catalyst. This also contributes to achievement of high purification
performance.
[0072] Thus, the exhaust gas purifying catalyst system according to
the aspect of the present invention can reduce an amount of
H.sub.2S emission while achieving high purification
performance.
[0073] Preferably, in the exhaust gas purifying catalyst system
according to the aspect of the present invention, each of the
respective composite oxides included in the upstream catalyst and
the downstream catalyst includes zirconium and neodymium.
[0074] The above composite oxide can store oxygen in a relatively
large amount. This makes it possible to effectively operate the
catalysts even if an oxygen concentration in exhaust gas relatively
largely varies, so as to more enhance the purification
performance.
[0075] Preferably, in the exhaust gas purifying catalyst system
according to the aspect of the present invention, the ratio of Ni
to CeO.sub.2 in the upstream catalyst is greater than the ratio of
Ni to CeO.sub.2 in the downstream catalyst.
[0076] According to this feature, the generation of H.sub.2S can be
more effectively suppressed in the upstream catalyst, so that
sulfur (S) poisoning of the downstream catalyst can be more
suppressed. In addition, exhaust gas components, such as HC, CO and
NOx, which have not been able to be purified by the upstream
catalyst, can be more efficiently purified by the downstream
catalyst.
[0077] Preferably, in the exhaust gas purifying catalyst system
according to the aspect of the present invention, each of the
respective composite oxides included in the upstream catalyst and
the downstream catalyst supports a catalytic noble metal
thereon.
[0078] According to this feature, exhaust gas components, such as
HC, CO and NOx, can be more efficiently purified to achieve higher
purification performance.
[0079] Preferably, in the above exhaust gas purifying catalyst
system, the catalytic noble metal supported on the composite oxide
included in the upstream catalyst and the downstream catalyst is
rhodium, the upstream catalyst includes palladium, and the
downstream catalyst includes platinum.
[0080] This application is based on Japanese Patent Application
Serial No. 2007-259109 filed in Japan Patent Office on Oct. 2,
2007, the contents of which are hereby incorporated by
reference.
[0081] 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.
* * * * *