U.S. patent application number 12/155382 was filed with the patent office on 2008-12-11 for exhaust purification device of internal combustion engine.
This patent application is currently assigned to TOYOTA JIDOSHA KABUSHIKI KAISHA. Invention is credited to Takamitsu Asanuma, Shinya Hirota, Hiromasa Nishioka, Hiroshi Otsuki, Kohei Yoshida.
Application Number | 20080302090 12/155382 |
Document ID | / |
Family ID | 40030981 |
Filed Date | 2008-12-11 |
United States Patent
Application |
20080302090 |
Kind Code |
A1 |
Yoshida; Kohei ; et
al. |
December 11, 2008 |
Exhaust purification device of internal combustion engine
Abstract
An SO.sub.X trap catalyst 12 and NO.sub.X purification catalyst
13 are arranged in an engine exhaust passage. A substrate 50 of the
NO.sub.X purification catalyst 13 is formed with a coat layer
comprised of at least the two layers of an upper coat layer 51 and
a lower coat layer 52. The lower coat layer 52 is formed from an
NO.sub.X storage catalyst storing the NO.sub.X contained in the
exhaust gas when the air-fuel ratio of the exhaust gas is lean and
releasing the stored NO.sub.X when the air-fuel ratio of the
exhaust gas is a stoichiometric air-fuel ratio or rich. The upper
coat layer 51 is formed from a material of a weaker basicity than
this NO.sub.X storage catalyst.
Inventors: |
Yoshida; Kohei;
(Gotenba-shi, JP) ; Asanuma; Takamitsu;
(Mishima-shi, JP) ; Nishioka; Hiromasa;
(Susono-shi, JP) ; Hirota; Shinya; (Susono-shi,
JP) ; Otsuki; Hiroshi; (Susono-shi, JP) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 320850
ALEXANDRIA
VA
22320-4850
US
|
Assignee: |
TOYOTA JIDOSHA KABUSHIKI
KAISHA
Toyota-Shi
JP
|
Family ID: |
40030981 |
Appl. No.: |
12/155382 |
Filed: |
June 3, 2008 |
Current U.S.
Class: |
60/286 ; 423/235;
60/281; 60/299; 60/300 |
Current CPC
Class: |
F01N 3/0842 20130101;
F01N 3/085 20130101; F01N 2570/04 20130101; F01N 13/009 20140601;
F01N 2510/0684 20130101; F01N 13/0097 20140603; F01N 3/0814
20130101; F01N 2510/06 20130101; F01N 13/0093 20140601; F01N
2610/03 20130101 |
Class at
Publication: |
60/286 ; 60/281;
60/299; 60/300; 423/235 |
International
Class: |
F01N 3/20 20060101
F01N003/20; F01N 3/28 20060101 F01N003/28 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 7, 2007 |
JP |
2007-151876 |
Claims
1. An exhaust purification device of an internal combustion engine
arranging an SO.sub.X trap catalyst able to trap SO.sub.X contained
in exhaust gas in an engine exhaust passage and arranging NO.sub.X
purification catalyst having a function of storing and releasing
NO.sub.X contained in exhaust gas in the exhaust passage downstream
of the SO.sub.X trap catalyst, wherein a coat layer comprised of at
least two layers of an upper coat layer and a lower coat layer is
formed on a substrate of said NO.sub.X purification catalyst, the
lower coat layer is formed from an NO.sub.X storage catalyst
storing the NO.sub.X contained in exhaust gas when an air-fuel
ratio of the exhaust gas is lean and releasing the stored NO.sub.X
when the air-fuel ratio of the exhaust gas is a stoichiometric
air-fuel ratio or rich, and the upper coat layer is formed from a
material weaker in basicity than said NO.sub.X storage
catalyst.
2. An exhaust purification device of an internal combustion engine
as set forth in claim 1, wherein said upper coat layer is formed
from a material able to hold SO.sub.2.
3. An exhaust purification device of an internal combustion engine
as set forth in claim 1, wherein said upper coat layer is formed
from an acid material.
4. An exhaust purification system of an internal combustion engine
as set forth in claim 1, wherein said upper coat layer is formed
from a material not having an oxidizing function.
5. An exhaust purification device of an internal combustion engine
as set forth in claim 1, wherein said upper coat layer is formed
from an NO.sub.X selective reducing catalyst able to selectively
reduce NO.sub.X.
6. An exhaust purification device of an internal combustion engine
as set forth in claim 1, wherein when SO.sub.X should be released
from the SO.sub.X trap catalyst, the air-fuel ratio of the exhaust
gas flowing into the SO.sub.X trap catalyst is made rich.
7. An exhaust purification device of an internal combustion engine
as set forth in claim 6, wherein when SO.sub.X should be released
from the SO.sub.X trap catalyst, the air-fuel ratio of the exhaust
gas flowing into the SO.sub.X trap catalyst is made rich when the
exhaust gas flowing into the SO.sub.X trap catalyst has more than a
predetermined spatial velocity.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an exhaust purification
device of an internal combustion engine.
[0003] 2. Description of the Related Art
[0004] Known in the art is an internal combustion engine arranging
in an engine exhaust passage an NO.sub.X storage catalyst storing
NO.sub.X contained in exhaust gas when the air-fuel ratio of the
inflowing exhaust gas is lean and releasing the stored NO.sub.X
when the air-fuel ratio of the inflowing exhaust gas becomes a
stoichiometric air-fuel ratio or rich. In this internal combustion
engine, NO.sub.X formed when burning fuel under a lean air-fuel
ratio is stored in the NO.sub.X storage catalyst. On the other
hand, as the NO.sub.X storage catalyst approaches saturation of the
NO.sub.X storage ability, the air-fuel ratio of the exhaust gas is
temporarily made rich, whereby NO.sub.X is released from the
NO.sub.X storage catalyst and reduced.
[0005] However, fuel and lubrication oil contain sulfur. Therefore,
the exhaust gas also contains SO.sub.X. This SO.sub.X is stored
together with the NO.sub.X in the NO.sub.X storage catalyst. This
SO.sub.X is not released from the NO.sub.X storage catalyst by just
making the air-fuel ratio of the exhaust gas rich. Therefore, the
amount of SO.sub.X stored in the NO.sub.X storage catalyst
gradually increases. As a result, the storable NO.sub.X amount ends
up gradually decreasing.
[0006] Therefore, to inhibit SO.sub.X from being sent into the
NO.sub.X storage catalyst, there is known an internal combustion
engine arranging an SO.sub.X trap catalyst in the engine exhaust
passage upstream of the NO.sub.X storage catalyst (see Japanese
Patent Publication (A) No. 2005-133610). In this internal
combustion engine, the SO.sub.X contained in the exhaust gas is
trapped by the SO.sub.X trap catalyst, therefore the flow of
SO.sub.X into the NO.sub.X storage catalyst is inhibited. As a
result, it is possible to prevent the storage of SO.sub.X from
causing the storage ability of the NO.sub.X to drop.
[0007] Note that when using this SO.sub.X trap catalyst, if the
SO.sub.X trap catalyst falls in SO.sub.X trap ability, SO.sub.X
ends up flowing into the NO.sub.X storage catalyst. In this
SO.sub.X trap catalyst, however, if raising the SO.sub.X trap
catalyst in temperature and making the exhaust gas flowing into the
SO.sub.X trap catalyst a rich air-fuel ratio, it is possible to
make the SO.sub.X trap catalyst release the absorbed SO.sub.X,
therefore it is possible to regenerate the SO.sub.X trap catalyst.
However, if making the SO.sub.X trap catalyst release SO.sub.X in
this way, since the NO.sub.X storage catalyst has a strong
basicity, even if the air-fuel ratio of the exhaust gas is rich,
the problem arises that the released SO.sub.X ends up being stored
in the NO.sub.X storage catalyst.
SUMMARY OF THE INVENTION
[0008] An object of the present invention is to provide an exhaust
purification device of an internal combustion engine capable of
suppressing the SOx released from an SOx trap catalyst to be stored
in an NOx storage catalyst.
[0009] According to the present invention, there is provided an
exhaust purification device of an internal combustion engine
arranging an SO.sub.X trap catalyst able to trap SO.sub.X contained
in exhaust gas in an engine exhaust passage and arranging NO.sub.X
purification catalyst having a function of storing and releasing
NO.sub.X contained in exhaust gas in the exhaust passage downstream
of the SO.sub.X trap catalyst, wherein a coat layer comprised of at
least two layers of an upper coat layer and a lower coat layer is
formed on a substrate of the NO.sub.X purification catalyst, the
lower coat layer is formed from an NO.sub.X storage catalyst
storing the NO.sub.X contained in exhaust gas when the air-fuel
ratio of the exhaust gas is lean and releasing the stored NO.sub.X
when the air-fuel ratio of the exhaust gas is a stoichiometric
air-fuel ratio or rich, and the upper coat layer is formed from a
material weaker in basicity than said NO.sub.X storage
catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] These and other objects and features of the present
invention will become more apparent from the following description
of the preferred embodiments given with reference to the attached
drawings, in which:
[0011] FIG. 1 is an overview of a compression ignition type
internal combustion engine;
[0012] FIG. 2 is a cross-sectional view of the surface part of a
substrate of an NO.sub.X purification catalyst;
[0013] FIG. 3 is a cross-sectional view of the surface part of a
substrate of an SO.sub.X trap catalyst;
[0014] FIG. 4 is a flow chart for an exhaust purification
processing; and
[0015] FIGS. 5A and 5B are views showing maps of a stored NO.sub.X
amount NOXA etc.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] FIG. 1 is an overview of a compression ignition type
internal combustion engine.
[0017] Referring to FIG. 1, 1 indicates an engine body, 2 a
combustion chamber of each cylinder, 3 an electronically controlled
fuel injector injecting fuel into each combustion chamber 2, 4 an
intake manifold, and 5 an exhaust manifold. The intake manifold 4
is connected through an intake duct 6 to a compressor 7a of an
exhaust turbocharger 7, while an inlet of the compressor 7a is
connected through an intake air detector 8 to an air cleaner 9.
Inside the intake duct 6, a throttle valve 10 driven by the step
motor is arranged. Further, around the intake duct 6, a cooling
device 11 for cooling the intake air flowing through the intake
duct 6 is arranged. In the embodiment shown in FIG. 1, the engine
cooling water is led into the cooling device 11 where the engine
cooling water is used to cool the intake air.
[0018] On the other hand, the exhaust manifold 5 is connected to an
inlet of an exhaust turbine 7b of the exhaust turbocharger 7. The
outlet of the exhaust turbine 7b is connected to an inlet of an
SO.sub.X trap catalyst 12 able to trap SO.sub.X contained in the
exhaust gas. Further, the outlet of the SO.sub.X trap catalyst 12
is connected to an NO.sub.X purification catalyst 13 having a
function of storing and releasing NO.sub.X contained in the exhaust
gas. On the other hand, inside the exhaust manifold 5, a reducing
agent feed valve 14 for feeding reducing agent comprised of for
example a hydrocarbon into the exhaust gas flowing through the
exhaust manifold 5 is attached.
[0019] The exhaust manifold 5 and intake manifold 4 are connected
to each other through an exhaust gas recirculation (hereinafter
referred to as "EGR") passage 15. Inside the EGR passage 15, an
electronic control type EGR control valve 16 is arranged. Further,
around the EGR passage 15, a cooling device 17 for cooling the EGR
gas flowing through the EGR passage 15 is arranged. In the
embodiment shown in FIG. 1, engine cooling water is led to the
cooling device 17 where the engine cooling water cools the EGR gas.
On the other hand, each fuel injector 3 is connected through a fuel
tube 18 to a common rail 19. This common rail 19 is fed with fuel
from an electronically controlled variable discharge fuel pump 20.
The fuel fed into the common rail 19 is fed through each fuel tube
18 into the fuel injector 3.
[0020] The electronic control unit 30 is comprised of a digital
computer and is provided with a ROM (read only memory) 32, RAM
(random access memory) 33, CPU (microprocessor) 34, input port 35,
and output port 36 which are interconnected to each other by a
bi-directional bus 31. As shown in FIG. 1, the output signal of the
intake air detector 8 is input through a corresponding AD converter
37 to the input port 35. Further, the accelerator pedal 40 is
connected to a load sensor 41 generating an output voltage
proportional to the amount of depression L of an accelerator pedal
40. The output voltage of the load sensor 41 is input through the
corresponding AD converter 37 to the input port 35. Further, the
input port 35 is connected to a crank angle sensor 42 generating an
output pulse each time the crankshaft rotates by for example
15.degree.. On the other hand, the output port 36 is connected
through corresponding drive circuits 38 to the fuel injector 3, the
step motor for driving the throttle valve 10, the reducing agent
feed valve 14, the EGR control valve 16, and the fuel pump 20.
[0021] First, the NO.sub.X purification catalyst 13 shown in FIG. 1
will be explained. The substrate of this NO.sub.X purification
catalyst 13 is for example formed from cordierite. FIG. 2
illustrates the cross-section of the surface part of this substrate
50. As shown in FIG. 2, the substrate 50 is formed with a coat
layer comprised of at least the two layers of an upper coat layer
51 and lower coat layer 52.
[0022] The lower coat layer 52 is comprised of a layer of an
NO.sub.X absorbent 53 formed on the surface of the substrate 50 and
a precious metal catalyst 54 carried and diffused on the layer of
this NO.sub.X absorbent 53. In this embodiment of the present
invention, platinum Pt is used as this precious metal catalyst 54.
As the ingredient forming the NO.sub.X absorbent 53, for example,
at least one element selected from potassium K, sodium Na, cesium
Cs, and other such alkali metals, barium Ba, calcium Ca, and other
such alkali earths, lanthanum La, yttrium Y, and other rare earths
is used. Note that in FIG. 2, platinum Pt 54 is drawn greatly
exaggerated. The actual dimensions are considerably small.
[0023] Now, if the ratio of the air and fuel (hydrocarbons) fed
into the engine intake passage, combustion chamber 2, and exhaust
passage upstream of the NO.sub.X purification catalyst 13 is called
the "air-fuel ratio of the exhaust gas", an NO.sub.X absorption and
release action such that the NO.sub.X absorbent 53 absorbs the
NO.sub.X when the air-fuel ratio of the exhaust gas is lean and
releases the absorbed NO.sub.X when the oxygen concentration in the
exhaust gas falls is performed.
[0024] That is, explaining this taking as an example the case of
using barium Ba as the ingredient forming the NO.sub.X absorbent
53, when the air-fuel ratio of the exhaust gas is lean, that is,
the oxygen concentration in the exhaust gas is high, the NO
contained in the exhaust gas diffuses in the upper coat layer 51 as
shown in FIG. 2, reaches the deep part of the upper coat layer 51,
then is oxidized on the platinum Pt 54 to become NO.sub.2, next is
absorbed in the NO.sub.X absorbent 53 and bonds with the barium
carbonate BaCO.sub.3 to diffuse in the form of nitrate ions
NO.sub.3.sup.- into the NO.sub.X absorbent 53. In this way,
NO.sub.X is absorbed in the NO.sub.X absorbent 53. So long as the
oxygen concentration in the exhaust gas is high, NO.sub.2 is formed
on the platinum Pt 54. So long as the NO.sub.X absorbent 53 is not
saturated in NO.sub.X absorption ability, NO.sub.2 is absorbed in
the NO.sub.X absorbent 53 and nitrate ions NO.sub.3.sup.- are
formed.
[0025] As opposed to this, for example if the reducing agent feed
valve 14 feeds the reducing agent to make the exhaust gas a rich
air-fuel ratio or stoichiometric air-fuel ratio, the oxygen
concentration in the exhaust gas falls, so the reaction proceeds in
the reverse direction (NO.sub.3.sup.-.fwdarw.NO.sub.2), therefore
the nitrate ions NO.sub.3.sup.- in the NO.sub.X absorbent 53 are
released in the form of NO.sub.2 from the NO.sub.X absorbent 53.
Next, the released NO.sub.X diffuses in the upper coat layer 51,
then is reduced by the unburned HC and CO contained in the exhaust
gas. In this way, the lower coat layer 52 is formed from an
NO.sub.X storage catalyst storing the NO.sub.X contained in the
exhaust gas when the air-fuel ratio of the exhaust gas is lean and
releases the stored NO.sub.X when the exhaust gas is a
stoichiometric air-fuel ratio or rich.
[0026] However, as explained above, when the air-fuel ratio of the
exhaust gas is lean, that is, when burning the fuel under a lean
air-fuel ratio, the NO.sub.X in the exhaust gas is absorbed in the
NO.sub.X absorbent 53. However, when the fuel continues to be
burned under a lean air-fuel ratio, the NO.sub.X absorbent 53
eventually ends up becoming saturated in NO.sub.X absorption
ability, therefore the NO.sub.X absorbent 53 ends up becoming
unable to absorb the NO.sub.X. Therefore, in this embodiment of the
present invention, before the NO.sub.X absorbent 53 becomes
saturated in absorption ability, the reducing agent feed valve 14
feeds the reducing agent to make the exhaust gas temporarily rich
in air-fuel ratio and thereby make the NO.sub.X absorbent 53
release the NO.sub.X.
[0027] On the other hand, the exhaust gas contains SO.sub.X, that
is, SO.sub.2. If this SO.sub.2 flows into the lower coat layer 52,
this SO.sub.2 is oxidized on the platinum Pt 54 and becomes
SO.sub.3. Next, this SO.sub.3 is absorbed in the NO.sub.X absorbent
53, bonds with the barium carbonate BaCO.sub.3, is diffused in the
form of sulfate ions SO.sub.4.sup.2- in the NO.sub.X absorbent 53,
and forms stable sulfate BaSO.sub.4. However, the NO.sub.X
absorbent 53 has a strong basicity, so this sulfate BaSO.sub.4 is
stable and hard to break down. If just making the air-fuel ratio of
the exhaust gas rich, the sulfate BaSO.sub.4 remains as it is
without breaking down. Therefore, in the NO.sub.X absorbent 53, the
sulfate BaSO.sub.4 increases along with the elapse of time,
therefore the NO.sub.X amount which the NO.sub.X absorbent 53 can
absorb falls along with the elapse of time.
[0028] Therefore, in an embodiment of the present invention, an
SO.sub.X trap catalyst 12 is arranged upstream of the NO.sub.X
purification catalyst 13 to trap the SO.sub.X contained in the
exhaust gas by this SO.sub.X trap catalyst 12 and thereby prevent
SO.sub.X from flowing into the NO.sub.X absorbent 53. Next this
SO.sub.X trap catalyst 12 will be explained.
[0029] This SO.sub.X trap catalyst 12 is for example comprised of a
honeycomb structure monolithic catalyst. FIG. 3 illustrates the
cross-section of the surface part of the substrate 55 of the
SO.sub.X trap catalyst 12. As shown in FIG. 3, a coat layer 56 is
formed on the surface of the substrate 55. A precious metal
catalyst 57 is carried and diffused on the surface of this coat
layer 56.
[0030] In this embodiment of the present invention, platinum is
used as the precious metal catalyst 57. As the part forming the
coat layer 56, for example, at least one element selected from
potassium K, sodium Na, cesium Cs, or another alkali metal, barium
Ba, calcium Cs, or other alkali earth, lanthanum La, yttrium Y, or
other rare earth may be used. That is, the coat layer 56 of the
SO.sub.X trap catalyst 12 exhibits a strong basicity.
[0031] Now, SO.sub.X contained in the exhaust gas, that is,
SO.sub.2, is, as shown in FIG. 3, oxidized on the platinum Pt 57,
then is trapped by the coat layer 56. That is, SO.sub.2 diffuses in
the form of sulfate ions SO.sub.4.sup.2- into the coat layer 56 and
forms a sulfate. Note that as explained above, the coat layer 56
exhibits a strong basicity. Therefore, as shown in FIG. 3, part of
the SO.sub.2 contained in the exhaust gas is directly trapped in
the coat layer 56.
[0032] In FIG. 3, the shading in the coat layer 56 shows the
concentration of the trapped SO.sub.X. As will be understood from
FIG. 3, the SO.sub.X concentration in the coat layer 56 is highest
near the surface of the coat layer 56. The further in, the lower it
becomes. If the SO.sub.X concentration near the surface of the coat
layer 56 increases, the surface of the coat layer 56 weakens in
basicity and the SO.sub.X trap ability weakens. That is, the
SO.sub.X trap rate drops. In this case, at this SO.sub.X trap
catalyst 12, if raising the SO.sub.X trap catalyst 12 in
temperature under a lean air-fuel ratio of the exhaust gas, the
SO.sub.X trap rate can be restored.
[0033] That is, if making the SO.sub.X trap catalyst 12 rise in
temperature under a lean air-fuel ratio of the exhaust gas, the
SO.sub.X present concentrated near the surface of the coat layer 56
diffuses toward the deep part of the coat layer 56 so that the
SO.sub.X concentration in the coat layer 56 becomes uniform. That
is, the sulfate produced in the coat layer 56 changes from an
unstable state where it concentrates near the surface of the coat
layer 56 to the stable state where it diffuses uniformly in the
coat layer 56 as a whole. If the SO.sub.X present near the surface
of the coat layer 56 diffuses toward the deep part of the coat
layer 56, the SO.sub.X concentration near the surface of the coat
layer 56 falls, therefore if the SO.sub.X trap catalyst 12 is
raised in temperature, the SO.sub.X trap rate is restored.
[0034] On the other hand, if the SO.sub.X trap catalyst 12 is
further increased in SO.sub.X trap amount, even if the SO.sub.X
trap catalyst 12 is raised in temperature, the SO.sub.X trap rate
will no longer be restored. However, this SO.sub.X trap catalyst 12
has the property of releasing the trapped SO.sub.X in the form of
SO.sub.2 if making the exhaust gas flowing into the SO.sub.X trap
catalyst 12 rich in the state of raising the SO.sub.X trap catalyst
12 in temperature to about 600.degree. C. or more.
[0035] Therefore, in an embodiment in the present invention, when
SO.sub.X should be released from the SO.sub.X trap catalyst 12, the
reducing agent is fed from the reducing agent feed valve 14 to make
the SO.sub.X trap catalyst 12 rise in temperature to about
600.degree. C. or more and make the exhaust gas flowing into the
SO.sub.X trap catalyst 12 a rich air-fuel ratio to thereby restore
the SO.sub.X trap rate of the SO.sub.X trap catalyst 12.
[0036] Note that by making the exhaust gas a rich air-fuel ratio in
this way, if the SO.sub.X trap catalyst 12 releases SO.sub.X in the
form of SO.sub.2, this SO.sub.2 flows into the NO.sub.X
purification catalyst 13. On the other hand, if the exhaust gas is
made a rich air-fuel ratio in this way, the exhaust gas flowing
into the NO.sub.X purification catalyst 13 will not contain almost
any oxygen O.sub.2. In this case, in the same way as the case of
the SO.sub.X trap catalyst 12 shown in FIG. 3, SO.sub.2 is oxidized
in the NO.sub.X purification catalyst 13 as well, so is trapped in
the NO.sub.X purification catalyst 13. Therefore, as explained
above, when the exhaust gas has almost no oxygen O.sub.2, SO.sub.2
would appear not to be trapped in the NO.sub.X purification
catalyst 13.
[0037] However, even if the exhaust gas contains almost no oxygen
O.sub.2, when the surface of the NO.sub.X purification catalyst 13
or the vicinity of the surface is strong in basicity, the SO.sub.2
in the exhaust gas ends up being trapped in the NO.sub.X
purification catalyst 13. That is, as explained above, the NO.sub.X
storage catalyst forming the lower coat layer 52 is strong in
basicity, so when forming only a layer of this NO.sub.X storage
catalyst on the substrate 50, even when the exhaust gas contains
almost no oxygen O.sub.2, the NO.sub.X storage catalyst traps
SO.sub.X. As a result, the NO.sub.X storage catalyst falls in
NO.sub.X storage ability.
[0038] Therefore, in the present invention, as shown in FIG. 2, the
upper coat layer 51 comprised of a material with a weaker basicity
than the NO.sub.X storage catalyst is formed on the lower coat
layer 52 comprised of the NO.sub.X storage catalyst. In this way,
if forming the upper coat layer 51 from a material weaker in
basicity from the NO.sub.X storage catalyst, when the exhaust gas
is made a rich air-fuel ratio to make the SO.sub.X trap catalyst 12
release SO.sub.X, the SO.sub.2 becomes hard to trap in the upper
coat layer 51. As a result, it is possible to keep SO.sub.X from
being stored in the NO.sub.X storage catalyst forming the lower
coat layer 52.
[0039] Note that when the SO.sub.2 rides the exhaust gas and
diffuses inside the upper coat layer 51 toward the lower coat layer
52, if holding this SO.sub.2 in the upper coat layer 51, it is
possible to inhibit SO.sub.2 being trapped by the NO.sub.X storage
catalyst. Therefore, the upper coat layer 51 is preferably formed
from a material able to hold SO.sub.2. In this case, as the
material of the upper coat layer 51, it is possible to use various
types of zeolite or alumina able to adsorb SO.sub.2.
[0040] Further, if forming the upper coat layer 51 from an acid
material with less ability to attract SO.sub.2 compared with a
material weak in basicity, the trapping action of SO.sub.2 on the
upper coat layer 51 is further weakened. Therefore, the upper coat
layer 51 is preferably formed from an acid material. As this acid
material, various types of zeolite, alumina, titanium composite
oxides, and tungsten composite oxides may be used.
[0041] Further, if the upper coat layer 51 has a function of
oxidizing the SO.sub.2, the SO.sub.2 in the exhaust gas ends up
being trapped in the upper coat layer 51. Therefore, as the upper
coat layer 51, it is preferable to use a material not having an
oxidizing function, that is, a material not carrying a precious
metal catalyst. Note that if considering the above various
conditions, it is possible to form the upper coat layer 51 from
Fe-zeolite, titania-vanadium, or another NO.sub.X selective
reducing catalyst able to selectively reduce NO.sub.X in the
presence of for example ammonia.
[0042] Further, the faster the exhaust gas flowing through the
SO.sub.X trap catalyst 12 in spatial velocity, the harder it is for
the SO.sub.2 to diffuse in the upper coat layer 51. Therefore, in
this embodiment of the present invention, when SO.sub.X should be
released from the SO.sub.X trap catalyst 12, the exhaust gas
flowing into the SO.sub.X trap catalyst 12 is made a rich air-fuel
ratio when the exhaust gas flowing through the SO.sub.X trap
catalyst 12 has more than a predetermined spatial velocity.
[0043] Next, referring to FIG. 4, an example of the exhaust
purification processing method will be explained. Note that the
routine shown in FIG. 4 is executed by interruption every
predetermined time.
[0044] Referring to FIG. 4, first, at step 60, the NO.sub.X amount
NOXA stored in the lower coat layer 52, that is, in the NO.sub.X
storage catalyst, per unit time is calculated. This NO.sub.X amount
NOXA is stored as a function of the required torque TQ and engine
speed N in the form of the map shown in FIG. 5A in advance in the
ROM 32.
[0045] Next, at step 61, this NOXA is added to the NO.sub.X amount
.SIGMA.NOX stored in the NO.sub.X storage catalyst. Next, at step
62, it is judged if the stored NO.sub.X amount .SIGMA.NOX exceeds
the allowable value NX. When .SIGMA.NOX>NX, the routine proceeds
to step 63 where a rich processing of changing the air-fuel ratio
of the exhaust gas from lean to rich by feeding the reducing agent
from the reducing agent feed value 14 is performed and .SIGMA.NOX
is cleared. At this time, NO.sub.X is released from the NO.sub.X
storage catalyst.
[0046] Next, at step 64, the SO.sub.X amount exhausted from the
engine per unit time, that is, the SO.sub.X amount SOXA trapped in
the SO.sub.X trap catalyst 12 per unit time, is calculated. This
SO.sub.X amount SOXA is stored as a function of the required torque
TQ and engine speed N in the form of a map as shown in FIG. 5B in
advance in the ROM 32. Next, at step 65, this SOXA is added to the
SO.sub.X amount .SIGMA.SOX trapped in the SO.sub.X trap catalyst
12. Next, at step 66, it is judged if the trapped SO.sub.X amount
.SIGMA.SOX exceeds an allowable value SX.
[0047] When .SIGMA.SOX>SX, the routine proceeds to step 67 where
it is judged if the conditions for release of SO.sub.X stand or
not, for example, if the exhaust gas flowing through the SO.sub.X
trap catalyst 12 has more than a predetermined spatial velocity,
that is, if the amount of intake air is a set value or more. When
the amount of intake air is a set value or more, the routine
proceeds to step 68 where a temperature raising control is
performed. Namely, the exhaust gas is maintained at a lean air-fuel
ratio and, reducing agent is fed from the reducing agent feed valve
14 so as to make the SO.sub.X trap catalyst 12 rise in temperature
to the SO.sub.X release temperature. Next, at step 69, a rich
processing of maintaining the exhaust gas flowing into the SO.sub.X
trap catalyst 12 at a rich air-fuel ratio by the reducing agent fed
from the reducing agent feed valve 14 is performed and .SIGMA.SOX
is cleared. At this time, SO.sub.X is released from the SO.sub.X
trap catalyst 12.
[0048] While the invention has been described with reference to
specific embodiments chosen for purpose of illustration, it should
be apparent that numerous modifications could be made thereto by
those skilled in the art without departing from the basic concept
and scope of the invention.
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