Exhaust gas purification device for an internal combustion...

Power plants – Internal combustion engine with treatment or handling of... – By means producing a chemical reaction of a component of the...

Reexamination Certificate

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C502S304000

Reexamination Certificate

active

06499294

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an exhaust gas purification device for an internal combustion engine. More specifically, the invention relates to an exhaust gas purification device equipped with a NOx absorbing and reducing catalyst which absorbs NOx in the exhaust gas when the air-fuel ratio of the exhaust gas flowing in is lean, and releases and purifies by reduction the absorbed NOx when the air-fuel ratio of the exhaust gas flowing in is rich.
2. Description of the Related Art
There has been known a NOx absorbing and reducing catalyst which absorbs NOx (nitrogen oxides) in the exhaust gas when the air-fuel ratio of the exhaust gas flowing in is lean, and releases and purifies, by reduction, the absorbed NOx when the air-fuel ratio of the exhaust gas flowing in becomes rich.
An exhaust gas purification device using the NOx absorbing and reducing catalyst of this type has been disclosed in, for example, Japanese Patent No. 2600492. In the exhaust gas purification device of the above patent, the NOx absorbing and reducing catalyst is disposed in the exhaust passage of an engine that operates at a lean air-fuel ratio. During a lean air-fuel ratio operation of the engine, NOx in the exhaust gas is absorbed by the NOx absorbing and reducing catalyst. When NOx is absorbed in an increased amount by the NOx absorbing and reducing catalyst, the rich spike operation is executed to operate the engine at an air-fuel ratio (or rich air-fuel ratio) smaller than the stoichiometric air-fuel ratio for a short period of time. Thus, the NOx that is absorbed is released from the NOx absorbing and reducing catalyst, and the released NOx is purified by reduction. That is, when the engine operating air-fuel ratio becomes rich, the oxygen concentration in the exhaust gas sharply drops compared with when the engine is operated at a lean air-fuel ratio, and the amounts of unburned HC and CO components sharply increase in the exhaust gas. Therefore, when the operating air-fuel ratio is changed over to a rich air-fuel ratio by the rich spike operation, NOx is released from the NOx absorbing and reducing catalyst and is reduced by being reacted with the unburned HC and CO components in the exhaust gas on the NOx absorbing and reducing catalyst.
The above-mentioned Japanese Patent No. 2600492 further discloses a constitution for purifying the HC and CO components emitted from the engine at the start of the engine by disposing a three-way catalyst in the exhaust passage on the upstream side of the NOx absorbing and reducing catalyst. The three-way catalyst of the above patent is disposed near the engine exhaust manifold through which the exhaust gas of a high temperature from the engine passes, and is heated to the activated temperature within a short period of time after the start of the engine. Therefore, HC and CO emitted in relatively large amounts from the engine are oxidized by the three-way catalyst after the engine started, and the quality of the exhaust gas, before the engine is warmed-up, is improved.
With the three-way catalyst being disposed in the exhaust passage on the upstream side of the NOx absorbing and reducing catalyst as taught in the above-mentioned Japanese Patent No. 2600492, it was considered that the ability of the NOx absorbing and reducing catalyst for purifying the exhaust gas often drops when the three-way catalyst possesses an O
2
storage capability due to a delay in the change of the air-fuel ratio of the exhaust gas flowing into the NOx absorbing and reducing catalyst.
As is widely known, the three-way catalyst carries, as an additive, a metal component such as cerium Ce in addition to noble metal catalyst components such as platinum Pt, palladium Pd and rhodium Rh, so as to exhibit the O
2
storage capability. That is, cerium carried as an additive by the catalyst bonds to oxygen in the exhaust gas when the air-fuel ratio of the exhaust gas flowing into the catalyst is higher than the stoichiometric air-fuel ratio (when the air-fuel ratio of the exhaust gas is lean) to form ceria (cerium oxide IV: CeO
2
) which stores oxygen. Further, when the air-fuel ratio of the exhaust gas flowing in is smaller than the stoichiometric air-fuel ratio (when the air-fuel ratio of the exhaust gas is rich), ceria releases oxygen and is transformed into cerium oxide III (Ce
2
O
3
); i.e., oxygen is released. Thus, the three-way catalyst having an O
2
storage capability releases oxygen when the air-fuel ratio of the exhaust gas changes from the lean side to the rich side, and the air-fuel ratio of the exhaust gas that has passed through the three-way catalyst is maintained to be close to the stoichiometric air-fuel ratio, as long as oxygen is released from the three-way catalyst, even when the air-fuel ratio of the exhaust gas flowing into the three-way catalyst has changed to the rich side.
However, when the three-way catalyst disposed in the exhaust passage on the upstream side of the NOx absorbing and reducing catalyst possesses an O
2
storage capability, the exhaust gas flowing into the NOx absorbing and reducing catalyst does not readily acquire a rich air-fuel ratio but is temporarily maintained near the stoichiometric air-fuel ratio even when the air-fuel ratio of the exhaust gas from the engine has changed from the lean side to the rich side due to the rich spike operation of the engine. When the air-fuel ratio of the exhaust gas is changed from a lean air-fuel ratio to an air-fuel ratio close to the stoichiometric air-fuel ratio, NOx is released from the NOx absorbing and reducing catalyst. However, in this case, the air-fuel ratio of the exhaust gas is not rich enough, i.e., the exhaust gas is not containing HC and CO components in amounts sufficient for reducing all of NOx released and, hence, NOx that has not been reduced flows out to the downstream side of the NOx absorbing and reducing catalyst.
When the NOx absorbing and reducing catalyst was used, therefore, it was not considered desirable to dispose the three-way catalyst having an O
2
storage capability in the exhaust passage on the upstream side of the NOx absorbing and reducing catalyst. When the three-way catalyst was disposed in the exhaust passage on the upstream side, therefore, it was considered that some countermeasure is required, for example, to remove cerium from the three-way catalyst, in order to lower the O
2
storage capability.
According to the study conducted by the present inventors, however, it was found that when NOx is to be released from the NOx absorbing and reducing catalyst, the NOx absorbing and reducing catalyst exhibits enhanced performance for purifying NOx when the three-way catalyst or the like catalyst having O
2
storage components is disposed at a position close to the NOx absorbing and reducing catalyst on the upstream side thereof. That is, when NOx is to be released from the NOx absorbing and reducing catalyst, the exhaust gas flowing into the catalyst must have a rich air-fuel ratio. In this case, when oxygen is released from the O
2
storage components disposed at a position close to the NOx absorbing and reducing catalyst on the upstream side thereof, it has been found that NOx is released and reduced at a greatly increased rate.
It has not been clarified yet why the catalyst having O
2
storage components disposed near the NOx absorbing and reducing catalyst on the upstream side thereof helps improve the performance of the NOx absorbing and reducing catalyst for purifying the exhaust gas. However, one of the causes is considered to be that, if the O
2
storage components exist at a position close to the upstream side of the NOx absorbing and reducing catalyst when the exhaust gas of a rich air-fuel ratio is supplied, the HC and CO components in the exhaust gas are oxidized by the oxygen released from the O
2
storage components and the temperature of the catalyst components on the NOx absorbing and reducing catalyst rises due to the heat of reaction. That is, one of the reasons is attributed to the release of NOx from the N

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