# Patent

## Title
Exhaust purification system of internal combustion engine

## Abstract

An exhaust purification system of an internal combustion engine including an ammonia oxidation catalyst device and an ammonia holding device arranged immediately upstream of the ammonia oxidation catalyst device is provided. The ammonia holding device has a solid acid, holds ammonia to restrain the ammonia from flowing into the ammonia oxidation catalyst device when a temperature of the ammonia oxidation catalyst device is within a N2O producing temperature range, and releases the held ammonia to make the ammonia flow into the ammonia oxidation catalyst device when the temperature of the ammonia oxidation catalyst device is out of the N2O producing temperature range.

## Background
TECHNICAL FIELD
The present invention relates to an exhaust purification system of an internal combustion engine.
BACKGROUND ART
In an exhaust system of an internal combustion engine which performs lean combustion such as in a diesel engine, a NOx catalyst device is arranged to purify NOx in the exhaust gas. A known NOx catalyst device produces ammonia by hydrolysis of urea supplied with the exhaust gas and selectively reduces NOx in the exhaust gas by use of the produced ammonia NH3 as a reducing material.
To decrease ammonia which is not used to reduce NOx in such a selectively reduction type NOx catalyst device and which is released into the atmosphere, it has been suggested that an ammonia oxidation catalyst device be arranged downstream of the selectively reduction type NOx catalyst device.
However, in such an ammonia oxidation catalyst device, when ammonia is oxidized at a relatively low temperature, dinitrogen monoxide (or nitrous oxide) N2O is produced. It is undesirable to release N2O into the atmosphere. Accordingly, it has been suggested that the temperature of the ammonia oxidation catalyst device be elevated not so as to oxidize ammonia at a relatively low temperature (for example, refer to Japanese Unexamined Patent Publication No. 2008-255899).
DISCLOSURE OF THE INVENTION
If ammonia is oxidized when the temperature of the ammonia oxidation catalyst device is elevated, the amount of produced N2O can be decreased. However, to elevate the temperature of the ammonia oxidation catalyst, fuel, electrical energy, or the like is necessary, and therefore fuel consumption deteriorates as a result.
Accordingly, an object of the present invention is to provide an exhaust purification system of an internal combustion engine, comprising an ammonia oxidation catalyst device, which can sufficiently decrease an amount of produced N2O without the deterioration of fuel consumption.
An exhaust purification system of an internal combustion engine as set forth in claim 1 of the present invention is provided, characterized in that the system comprises an ammonia oxidation catalyst device and an ammonia holding device arranged immediately upstream of the ammonia oxidation catalyst device, the ammonia holding device has zeolite, holds ammonia to restrain the ammonia from flowing into the ammonia oxidation catalyst device when a temperature of the ammonia oxidation catalyst device is within a N2O producing temperature range, and releases the held ammonia to make the ammonia flow into the ammonia oxidation catalyst device when the temperature of the ammonia oxidation catalyst device is out of the N2O producing temperature range.
An exhaust purification system of an internal combustion engine as set forth in claim 2 of the present invention is provided as the exhaust purification system of an internal combustion engine as set forth in claim 1 characterized in that the ammonia oxidation catalyst device has a particulate trapping function.
According to the exhaust purification system of an internal combustion engine as set forth in claim 1 of the present invention, the system comprises an ammonia oxidation catalyst device and an ammonia holding device arranged immediately upstream of the ammonia oxidation catalyst device. The ammonia holding device has zeolite and holds ammonia to restrain the ammonia from flowing into the ammonia oxidation catalyst device when a temperature of the ammonia oxidation catalyst device is within a N2O producing temperature range. Therefore, when the temperature of the ammonia oxidation catalyst device is low and is within the N2O producing temperature range, and although the temperature of the ammonia oxidation catalyst device is not elevated without the fuel consumption, a large amount of ammonia is not oxidized and a large amount of N2O is not produced. On the other hand, when the temperature of the ammonia oxidation catalyst device is out of the N2O producing temperature range, the system releases the held ammonia to make the ammonia flow into the ammonia oxidation catalyst device. Therefore, when the temperature of the ammonia oxidation catalyst device becomes high and out of the N2O producing temperature range, an amount of ammonia released from the ammonia holding device can be easily oxidized without the production of a large amount of N2O. Thus, an amount of produced N2O can be sufficiently decreased without the deterioration of fuel consumption.
According to the exhaust purification system of the internal combustion engine as set forth in claim 2 of the present invention, in the exhaust purification system of an internal combustion engine as set forth in claim 1, the ammonia oxidation catalyst device has a particulate trapping function. Therefore, the particulates trapped on the ammonia oxidation catalyst device can be automatically burned by the reaction heat when the ammonia is oxidized, and thus it is not necessary that a particulate filter be separately arranged and the temperature thereof be elevated to burn the trapped particulates.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view showing an embodiment of the exhaust purification system of an internal combustion engine according to the present invention.
FIG. 2 is an enlarged partial vertical sectional view of an ammonia oxidation catalyst device with a particulate trapping function.
FIG. 3 is an A-A sectional view of FIG. 2.
FIG. 4 are graphs slowing changes in an amount of produced N2O and an amount of produced NO according to the temperature of the ammonia oxidation catalyst device.
FIG. 5 is a graph showing a change in an amount of released ammonia according the temperature of zeolite.



BEST MODE FOR CARRYING OUT THE INVENTION
FIG. 1 is a schematic view showing the exhaust purification system of an internal combustion engine according to the present invention. In FIG. 1, reference numeral 1 is an exhaust passage of a diesel engine or a direct fuel injection-type spark-ignition engine which performs lean combustion. The exhaust gas of such an engine includes a relatively large amount of NOx so that a NOx catalyst device 2 for purifying NOx is arranged in the exhaust passage 1.
The NOx catalyst device 2 is a selectively reducing-type NOx catalyst device which produces ammonia by hydrolysis of urea supplied with the exhaust gas and selectively reduces NOx in the exhaust gas by using of the produced ammonia NH3 as reducing material.
In the case that a selectively reducing type NOx catalyst device 2 is arranged in the exhaust passage 1, to decrease ammonia which is not used to reduce NOx and is released to the atmosphere, an ammonia oxidation catalyst device 3 for oxidizing the ammonia is arranged downstream of the selectively reduction type NOx catalyst device 2. The ammonia oxidation catalyst device 3 carries, for example, platinum Pt on a monolith carrier by alumina.
FIG. 4 are graphs slowing an amount of produced N2O (dinitrogen monoxide or nitrous oxide) and an amount of produced NO when ammonia is oxidized by such an ammonia oxidation catalyst device. As shown in FIG. 4, when the temperature of the ammonia oxidation catalyst device 3 is relatively low as equal to or lower than 350 degrees C. and the ammonia is oxidized by it, an amount of produced NO remarkably decreases and an amount of produced N2O remarkably increases. It is undesirable to release N2O into the atmosphere.
In the present embodiment, an ammonia holding device 4 is arranged immediately upstream of the ammonia oxidation catalyst device 3. As shown in FIG. 1, the ammonia holding device 4 is arranged in a case common to the ammonia oxidation catalyst device 3.
The ammonia holding device 4 provides solid acid for holding ammonia on a monolith carrier and, for example, forms a zeolite layer as a solid acid on the monolith carrier, or may be zeolite having a monolith shape.
FIG. 5 is a graph showing a change in an amount of released ammonia according to the temperature of zeolite. A solid acid, such as zeolite, sufficiently holds ammonia when the temperature thereof is equal to or lower than 350 degrees C. and releases the held ammonia when the temperature thereof is over 350 degrees C.
Accordingly, if the ammonia holding device 4 provided with the zeolite layer is arranged immediately upstream of the ammonia oxidation catalyst device 3, the temperature of the ammonia holding device 4 is equal to about the temperature of the ammonia oxidation catalyst device 3. Thus, when the temperature of the ammonia oxidation catalyst device 3 is within a N2O producing temperature range (for example, equal to or lower than 350 degrees C.), the ammonia holding device 4 sufficiently holds ammonia flowing out from the selectively reducing type NOx catalyst device 2 and can sufficiently restrain the ammonia from flowing into the ammonia oxidation catalyst device 3.
When the temperature of the ammonia oxidation catalyst device 3 is out of the N2O producing temperature range (for example, higher than 350 degrees C.), the ammonia holding device 4 releases the held ammonia and makes the ammonia flow into the ammonia oxidation catalyst device 3. In this case, when the ammonia is oxidized in the ammonia oxidation catalyst device 3, N2O is not easily produced, but NO or N2 is easily produced. Thus, an amount of N2O produced when ammonia is oxidized can be sufficiently decreased especially without the elevation of the temperature of the ammonia oxidation catalyst device 3.
If the ammonia holding device 4 has any solid acid, which is not limited to zeolite, it can hold ammonia within the N2O producing temperature range and can releases the ammonia out of the N2O producing temperature range. Solid acid such as for example, titania, zirconia, or silica may be carried on the monolith carrier by alumina.
Incidentally, particulates are included in the exhaust gas of a diesel engine and a particulate filter may be arranged in the exhaust passage 1 to restrain the particulates from being emitted into the atmosphere. Accordingly, the ammonia oxidation catalyst device 3 may function as the particulate filter. FIG. 2 is an enlarged partial vertical sectional view of the ammonia oxidation catalyst device 3 with a particulate trapping function. FIG. 3 is an A-A sectional view of FIG. 2.
As shown in FIGS. 2 and 3, the carrier of the ammonia oxidation catalyst device 3 is formed of a porous material, such as cordierite, and has many spaces in the axial direction divided by many partition walls 31 extending in the axial direction. One of any two neighboring spaces in the axial direction is closed by a plug 32 on the exhaust gas downstream side, and the other one is closed by a plug on the exhaust gas upstream side. Thus, one of the two neighboring spaces in the axial direction serves as an exhaust gas flow-in passage 33 and the other one serves as an exhaust gas flow-out passage 34, causing the exhaust gas to pass through the partition wall 31 as indicated by arrows in FIG. 2. The particulates in the exhaust gas are much smaller than the pores of the partition wall 31, but collide with and are trapped on the exhaust gas upstream side surface of the partition wall 31 and the pores surface in the partition wall 31. Thus, each partition wall 31 can work as a trapping wall for trapping the particulates. Platinum Pt as an oxidation catalyst is carried on both side surfaces of the partition wall 31 by use of alumina.
In this way, if the ammonia oxidation catalyst device 3 also functions as the particulate filter, the particulates trapped on the partition wall 31 can be automatically burned by the reaction heat when the ammonia is oxidized. Therefore, in comparison with arranging a particulate filter separately in the exhaust passage, the cost of the exhaust gas purification system can be reduced and it is not necessary that, for example, an oxidation catalyst be arranged on the particulate filter and fuel is supplied to the particulate filter in order to burn the trapped particulates.
LIST OF REFERENCE NUMERALS
1: exhaust passage
2: NOx catalyst device
3: ammonia oxidation catalyst device
4: ammonia holding device

## Claims

1. An exhaust purification system of an internal combustion engine, comprising:
an ammonia oxidation catalyst device;
an ammonia holding device arranged immediately upstream of and in a case with said ammonia oxidation catalyst device; and
a selectively reducing NOx catalyst device upstream of said ammonia holding device;
wherein:
said ammonia holding device has zeolite and is configured to:
hold ammonia to restrain the ammonia from flowing into said ammonia oxidation catalyst device when a temperature of said ammonia oxidation catalyst device is within a N2O producing temperature range, and
release the held ammonia to make the ammonia flow into said ammonia oxidation catalyst device when the temperature of said ammonia oxidation catalyst device is out of the N2O producing temperature range; and

said N2O producing temperature range is not more than 350° C.

2. The exhaust purification system of an internal combustion engine according to claim 1, wherein said ammonia oxidation catalyst device has a particulate trapping function.