# Patent

## Title
Exhaust purification system of internal combustion engine

## Abstract

In an internal combustion engine, inside of an engine exhaust passage, a hydrocarbon feed valve (15) and an exhaust purification catalyst (13) are arranged. The concentration of hydrocarbons which flow into the exhaust purification catalyst (13) is made to vibrate within 200 ppm or more predetermined amplitude and within a 5 second or more predetermined period. At this time, when a predetermined amount or more of NOx is stored in the exhaust purification catalyst (13) or can be stored, the concentration of hydrocarbons flowing into the exhaust purification catalyst (13) is temporarily increased to desorb NOx which is stored at the exhaust purification catalyst (13).

## Background
TECHNICAL FIELD
The present invention relates to an exhaust purification system of an internal combustion engine.
BACKGROUND ART
Known in the art is an internal combustion engine which arranges, in an engine exhaust passage, an NOx storage catalyst which stores NOx which is contained in exhaust gas when the air-fuel ratio of the inflowing exhaust gas is lean and which releases the stored NOx when the air-fuel ratio of the inflowing exhaust gas becomes rich, which arranges, in the engine exhaust passage upstream of the NOx storage catalyst, an oxidation catalyst which has an adsorption function, and which feeds hydrocarbons into the engine exhaust passage upstream of the oxidation catalyst to make the air-fuel ratio of the exhaust gas flowing into the NOx storage catalyst rich when releasing NOx from the NOx storage catalyst (for example, see Patent Literature 1).
In this internal combustion engine, the hydrocarbons which are fed when releasing NOx from the NOx storage catalyst are made gaseous hydrocarbons at the oxidation catalyst, and the gaseous hydrocarbons are fed to the NOx storage catalyst. As a result, the NOx which is released from the NOx storage catalyst is reduced well.
CITATION LIST
Patent Literature
Patent Literature 1: Japanese Patent No. 3969450
SUMMARY OF INVENTION
Technical Problem
However, there is the problem that when the NOx storage catalyst reaches a high temperature, the NOx purification rate falls.
An object of the present invention is to provide an exhaust purification system of an internal combustion engine which can obtain a high NOx purification rate even if the temperature of the exhaust purification catalyst becomes a high temperature.
Solution to Problem
According to the present invention, there is provided an exhaust purification system of an internal combustion engine in which an exhaust purification catalyst for reacting NOx contained in exhaust gas and reformed hydrocarbons is arranged inside of an engine exhaust passage, a precious metal catalyst is carried on an exhaust gas flow surface of the exhaust purification catalyst and a basic exhaust gas flow surface part is formed around the precious metal catalyst, the exhaust purification catalyst has a property of reducing the NOx which is contained in exhaust gas if a concentration of hydrocarbons flowing into the exhaust purification catalyst is made to vibrate within a predetermined range of amplitude and within a predetermined range of period and has a property of being increased in storage amount of NOx which is contained in exhaust gas if the vibration period of the hydrocarbon concentration is made longer than the predetermined range, at the time of engine operation, if the concentration of hydrocarbons flowing into the exhaust purification catalyst is made to vibrate within the predetermined range of amplitude and within the predetermined range of period, and, at this time, when a predetermined amount or more of NOx is stored at or can be stored at the exhaust purification catalyst, the concentration of hydrocarbons flowing into the exhaust purification catalyst is temporarily increased to desorb NOx which is stored at the exhaust purification catalyst.
Advantageous Effects of Invention
Even if the temperature of the exhaust purification catalyst becomes a high temperature, a high NOx purification rate can be obtained.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an overall view of a compression ignition type internal combustion engine.
FIG. 2 is a view schematically showing a surface part of a catalyst carrier.
FIG. 3 is a view for explaining an oxidation reaction in an exhaust purification catalyst.
FIG. 4 is a view showing a change of an air-fuel ratio of exhaust gas flowing into an exhaust purification catalyst.
FIG. 5 is a view showing an NOx purification rate.
FIGS. 6A and 6B are views for explaining an oxidation reduction reaction in an exhaust purification catalyst.
FIGS. 7A and 7B are views for explaining an oxidation reduction reaction in an exhaust purification catalyst.
FIG. 8 is a view showing a change of an air-fuel ratio of exhaust gas flowing into an exhaust purification catalyst.
FIG. 9 is a view of an NOx purification rate.
FIG. 10 is a time chart showing a change of an air-fuel ratio of exhaust gas flowing into an exhaust purification catalyst.
FIG. 11 is a time chart showing a change of an air-fuel ratio of exhaust gas flowing into an exhaust purification catalyst.
FIG. 12 is a view showing a relationship between an oxidizing strength of an exhaust purification catalyst and a demanded minimum air-fuel ratio X.
FIG. 13 is a view showing a relationship between an oxygen concentration in exhaust gas and an amplitude ΔH of a hydrocarbon concentration giving the same NOx purification rate.
FIG. 14 is a view showing a relationship between an amplitude ΔH of a hydrocarbon concentration and an NOx purification rate.
FIG. 15 is a view showing a relationship of a vibration period ΔT of a hydrocarbon concentration and an
NOx purification rate.
FIG. 16 is a view showing a map of the hydrocarbon feed amount W.
FIG. 17 is a view showing a change in the air-fuel ratio of the exhaust gas flowing to the exhaust purification catalyst etc.
FIG. 18 is a view showing a map of an exhausted NOx amount NOXA.
FIG. 19 is a view showing a fuel injection timing.
FIG. 20 is a view showing a map of a hydrocarbon feed amount WR.
FIG. 21 is a time chart showing changes in an amount active NOx*, a stored NOx amount SNOX, etc.
FIG. 22 is a view showing a storage rate SR and desorption rate DR.
FIG. 23 is a time chart showing NOx purification treatment as a whole.
FIG. 24 is a flow chart for NOx purification control.
FIG. 25 is a flow chart for NOx purification control of another embodiment.



DESCRIPTION OF EMBODIMENTS
FIG. 1 is an overall view of a compression ignition type internal combustion engine.
Referring to FIG. 1, 1 indicates an engine body, 2 a combustion chamber of each cylinder, 3 an electronically controlled fuel injector for 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 an outlet of a compressor 7a of an exhaust turbocharger 7, while an inlet of the compressor 7a is connected through an intake air amount detector 8 to an air cleaner 9. Inside the intake duct 6, a throttle valve 10 driven by a step motor is arranged. Furthermore, around the intake duct 6, a cooling device 11 is arranged for cooling the intake air which flows through the inside of the intake duct 6. In the embodiment shown in FIG. 1, the engine cooling water is guided to the inside of the cooling device 11 where the engine cooling water is used to cool the intake air.
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 through an exhaust pipe 12 to an inlet of the exhaust purification catalyst 13, an outlet of the exhaust purification catalyst 13 is connected to a particulate filter 14 for trapping particulate which is contained in exhaust gas. Inside the exhaust pipe 12 upstream of the exhaust purification catalyst 13, a hydrocarbon feed valve 15 is arranged for feeding hydrocarbons comprised of diesel oil or other fuel used as fuel for a compression ignition type internal combustion engine. In the embodiment shown in FIG. 1, diesel oil is used as the hydrocarbons which are fed from the hydrocarbon feed valve 15. Note that, the present invention can also be applied to a spark ignition type internal combustion engine in which fuel is burned under a lean air-fuel ratio. In this case, from the hydrocarbon feed valve 15, hydrocarbons comprised of gasoline or other fuel used as fuel of a spark ignition type internal combustion engine are fed.
On the other hand, the exhaust manifold 5 and the intake manifold 4 are connected with each other through an exhaust gas recirculation (hereinafter referred to as an “EGR”) passage 16. Inside the EGR passage 16, an electronically controlled EGR control valve 17 is arranged. Further, around the EGR passage 16, a cooling device 18 is arranged for cooling EGR gas flowing through the inside of the EGR passage 16. In the embodiment shown in FIG. 1, the engine cooling water is guided to the inside of the cooling device 18 where the engine cooling water is used to cool the EGR gas. On the other hand, each fuel injector 3 is connected through a fuel feed tube 19 to a common rail 20. This common rail 20 is connected through an electronically controlled variable discharge fuel pump 21 to a fuel tank 22. The fuel which is stored inside of the fuel tank 22 is fed by the fuel pump 21 to the inside of the common rail 20. The fuel which is fed to the inside of the common rail 20 is fed through each fuel feed tube 19 to the fuel injector 3.
An electronic control unit 30 is comprised of a digital computer provided with a ROM (read only memory) 32, a RAM (random access memory) 33, a CPU (microprocessor) 34, an input port 35, and an output port 36, which are connected with each other by a bidirectional bus 31. Downstream of the exhaust purification catalyst 13, a temperature sensor 23 for detecting the temperature of the exhaust purification catalyst 13 is attached. The output signals of this temperature sensor 23 and intake air amount detector 8 are input through respectively corresponding AD converters 37 to the input port 35. Further, an accelerator pedal 40 has a load sensor 41 connected to it which generates an output voltage proportional to the amount of depression L of the accelerator pedal 40. The output voltage of the load sensor 41 is input through a corresponding AD converter 37 to the input port 35. Furthermore, at the input port 35, a crank angle sensor 42 is connected which generates an output pulse every time a crankshaft rotates by, for example, 15°. On the other hand, the output port 36 is connected through corresponding drive circuits 38 to each fuel injector 3, step motor for driving the throttle valve 10, hydrocarbon feed valve 15, EGR control valve 17, and fuel pump 21.
FIG. 2 schematically shows a surface part of a catalyst carrier which is carried on a substrate of the exhaust purification catalyst 13. At this exhaust purification catalyst 13, as shown in FIG. 2, for example, there is provided a catalyst carrier 50 made of alumina on which precious metal catalysts 51 and 52 are carried. Furthermore, on this catalyst carrier 50, a basic layer 53 is formed which includes at least one element selected from potassium K, sodium Na, cesium Cs, or another such alkali metal, barium Ba, calcium Ca, or another such alkaline earth metal, a lanthanoid or another such rare earth metal and silver Ag, copper Cu, iron Fe, iridium Ir, or another metal able to donate electrons to NOx. The exhaust gas flows along the top of the catalyst carrier 50, so the precious metal catalysts 51 and 52 can be said to be carried on the exhaust gas flow surface of the exhaust purification catalyst 13. Further, the surface of the basic layer 53 exhibits basicity, so the surface of the basic layer 53 is called the basic exhaust gas flow surface part 54.
On the other hand, in FIG. 2, the precious metal catalyst 51 is comprised of platinum Pt, while the precious metal catalyst 52 is comprised of rhodium Rh. That is, the precious metal catalysts 51 and 52 which are carried on the catalyst carrier 50 are comprised of platinum Pt and rhodium Rh. Note that, on the catalyst carrier 50 of the exhaust purification catalyst 13, in addition to platinum Pt and rhodium Rh, palladium Pd may be further carried or, instead of rhodium Rh, palladium Pd may be carried. That is, the precious metal catalysts 51 and 52 which are carried on the catalyst carrier 50 are comprised of platinum Pt and at least one of rhodium Rh and palladium Pd.
If hydrocarbons are injected from the hydrocarbon feed valve 15 into the exhaust gas, the hydrocarbons are reformed by the exhaust purification catalyst 13. In the present invention, at this time, the reformed hydrocarbons are used to remove the NOx at the exhaust purification catalyst 13. FIG. 3 schematically shows the reforming action performed at the exhaust purification catalyst 13 at this time. As shown in FIG. 3, the hydrocarbons HC which are injected from the hydrocarbon feed valve 15 become radical hydrocarbons HC with a small carbon number by the catalyst 51.
Note that, even if the fuel injector 3 injects fuel, that is, hydrocarbons, into the combustion chamber 2 in the second half of the expansion stroke or exhaust stroke, the hydrocarbons are reformed in the combustion chamber 2 or exhaust purification catalyst 13, and the NOx which is contained in exhaust gas is removed by the reformed hydrocarbons in the exhaust purification catalyst 13. Therefore, in the present invention, instead of feeding hydrocarbons from the hydrocarbon feed valve 15 to the inside of an engine exhaust passage, it is also possible to feed hydrocarbons into the combustion chamber 2 in the second half of the expansion stroke or exhaust stroke. In this way, in the present invention, it is possible to feed hydrocarbons into the combustion chamber 2, but below, the present invention will be explained with reference to the case of trying to inject hydrocarbons from a hydrocarbon feed valve 15 to the inside of an engine exhaust passage.
FIG. 4 shows the feed timing of hydrocarbons from the hydrocarbon feed valve 15 and the change in the air-fuel ratio (A/F) in of the exhaust gas which flows into the exhaust purification catalyst 13. Note that, the changes in the air-fuel ratio (A/F) in depend on the change in concentration of the hydrocarbons in the exhaust gas which flows into the exhaust purification catalyst 13, so it can be said that the change in the air-fuel ratio (A/F) in shown in FIG. 4 expresses the change in concentration of the hydrocarbons. However, if the hydrocarbon concentration becomes higher, the air-fuel ratio (A/F) in becomes smaller, so, in FIG. 4, the more to the rich side the air-fuel ratio (A/F) in becomes, the higher the hydrocarbon concentration.
FIG. 5 shows the NOx purification rate by the exhaust purification catalyst 13 with respect to the catalyst temperatures of the exhaust purification catalyst 13 when periodically making the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 change so as to, as shown in FIG. 4, make the air-fuel ratio (A/F) in of the exhaust gas flowing to the exhaust purification catalyst 13 change. The inventors engaged in research relating to NOx purification for a long time. In the process of research, they learned that if making the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 vibrate within a predetermined range of amplitude and within a predetermined range of period, as shown in FIG. 5, an extremely high NOx purification rate is obtained even in a 400° C. or higher high temperature region.
Furthermore, at this time, a large amount of reducing intermediate containing nitrogen and hydrocarbons continues to be held or adsorbed on the surface of the basic layer 53, that is, on the basic exhaust gas flow surface part 54 of the exhaust purification catalyst 13. It is learned that this reducing intermediate plays a central role in obtaining a high NOx purification rate. Next, this will be explained with reference to FIGS. 6A and 6B. Note that, these FIGS. 6A and 6B schematically show the surface part of the catalyst carrier 50 of the exhaust purification catalyst 13. These FIGS. 6A and 6B show the reaction which is presumed to occur when the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is made to vibrate within a predetermined range of amplitude and within a predetermined range of period.
FIG. 6A shows when the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is low, while FIG. 6B shows when hydrocarbons are fed from the hydrocarbon feed valve 15 and the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 becomes higher.
Now, as will be understood from FIG. 4, the air-fuel ratio of the exhaust gas which flows into the exhaust purification catalyst 13 is maintained lean except for an instant, so the exhaust gas which flows into the exhaust purification catalyst 13 normally becomes a state of oxygen excess. Therefore, the NO which is contained in the exhaust gas, as shown in FIG. 6A, is oxidized on the platinum 51 and becomes NO2. Next, this NO2 is further oxidized and becomes NO3. Further, part of the NO2 becomes NO2−. In this case, the amount of production of NO3 is far greater than the amount of production of NO2−. Therefore, a large amount of NO3 and a small amount of NO2− are produced on the platinum Pt 51. These NO3 and NO2− are strong in activity. Below, these NO3 and NO2− are called NOx*.
Note that, at this time, depending on the engine operating state, as shown in FIG. 6A, part of the produced active NOx* is stored in the form of nitrate ions NO3− inside the basic layer 53. The storage action of the active NOx* will be explained in detail later. The explanation will be omitted here.
On the other hand, if hydrocarbons are fed from the hydrocarbon feed valve 15, as shown in FIG. 3, the hydrocarbons are reformed and become radicalized inside of the exhaust purification catalyst 13. As a result, as shown in FIG. 6B, the hydrocarbon concentration around the active NOx* becomes higher. In this regard, after the active NOx* is produced, if the state of a high oxygen concentration around the active NOx* continues for a predetermined time or more, the active NOx* is oxidized and the majority of the active NOx* is absorbed in the basic layer 53 in the form of nitrate ions NO3−. However, if the hydrocarbon concentration around the active NOx* is made higher before this predetermined time passes, as shown in FIG. 6B, the active NOx* reacts on the platinum 51 with the radical hydrocarbons HC whereby a reducing intermediate is produced. This reducing intermediate is adhered or adsorbed on the surface of the basic layer 53.
Note that, at this time, the first produced reducing intermediate is considered to be a nitro compound R—NO2. If this nitro compound R—NO2 is produced, the result becomes a nitrile compound R—CN, but this nitrile compound R—CN can only survive for an instant in this state, so immediately becomes an isocyanate compound R—NCO. This isocyanate compound R—NCO, when hydrolyzed, becomes an amine compound R—NH2. However, in this case, what is hydrolyzed is considered to be part of the isocyanate compound R—NCO. Therefore, as shown in FIG. 6B, the majority of the reducing intermediate which is held or adsorbed on the surface of the basic layer 53 is believed to be the isocyanate compound R—NCO and amine compound R—NH2.
On the other hand, as shown in FIG. 6B, if the produced reducing intermediate is surrounded by the hydrocarbons HC, the reducing intermediate is blocked by the hydrocarbons HC and the reaction will not proceed any further. In this case, if the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is lowered and thereby the oxygen concentration becomes higher, the hydrocarbons around the reducing intermediate will be oxidized. As a result, as shown in FIG. 6A, the reducing intermediate and the active NOx* will react. At this time, the active NOx* reacts with the reducing intermediate R—NCO or R—NH2 to form N2, CO2, and H2O and consequently the NOx is removed.
In this way, in the exhaust purification catalyst 13, by making the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 higher, a reducing intermediate is produced. By making the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 lower and raising the oxygen concentration, the active NOx* reacts with the reducing intermediate and the NOx is removed. That is, in order for the exhaust purification catalyst 13 to remove the NOx, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 has to be periodically changed.
Of course, in this case, it is necessary to raise the concentration of hydrocarbons to a concentration sufficiently high for producing the reducing intermediate and it is necessary to lower the concentration of hydrocarbons to a concentration sufficiently low for making the produced reducing intermediate react with the active NOx*. That is, it is necessary to make the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 vibrate by within a predetermined range of amplitude. Note that, in this case, it is necessary to hold a sufficient amount of reducing intermediate R—NCO or R—NH2 on the basic layer 53, that is, the basic exhaust gas flow surface part 54, until the produced reducing intermediate reacts with the active NOx*. For this reason, the basic exhaust gas flow surface part 54 is provided.
On the other hand, if lengthening the feed period of the hydrocarbons, the time in which the oxygen concentration becomes higher becomes longer in the period after the hydrocarbons are fed until the hydrocarbons are next fed. Therefore, the majority of the active NOx* is absorbed in the basic layer 53 in the form of nitrates without producing a reducing intermediate. To avoid this, it is necessary to make the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 vibrate by within a predetermined range of period.
Therefore, in an embodiment of the present invention, to make the NOx contained in the exhaust gas and the reformed hydrocarbons react and produce the reducing intermediate R—NCO or R—NH2 containing nitrogen and hydrocarbons, precious metal catalysts 51 and 52 are carried on the exhaust gas flow surface of the exhaust purification catalyst 13. To hold the produced reducing intermediate R—NCO or R—NH2 inside the exhaust purification catalyst 13, a basic exhaust gas flow surface part 54 is formed around the precious metal catalysts 51 and 52. NOx is reduced by the reducing action of the reducing intermediate R—NCO or R—NH2 held on the basic exhaust gas flow surface part 54, and the vibration period of the hydrocarbon concentration is made the vibration period required for continuation of the production of the reducing intermediate R—NCO or R—NH2. Incidentally, in the example shown in FIG. 4, the injection interval is made 3 seconds.
If the vibration period of the hydrocarbon concentration, that is, the feed period of the hydrocarbons HC, is made longer than the above predetermined range of period, the reducing intermediate R—NCO or R—NH2 disappears from the surface of the basic layer 53. At this time, the active NOx* which was produced on the platinum Pt 51, as shown in FIG. 7A, diffuses in the basic layer 53 in the form of nitrate ions NO3− and becomes nitrates. That is, at this time, the NOx in the exhaust gas is absorbed in the form of nitrates inside of the basic layer 53.
On the other hand, FIG. 7B shows the case where the air-fuel ratio of the exhaust gas which flows into the exhaust purification catalyst 13 is made the stoichiometric air-fuel ratio or rich when the NOx is absorbed in the form of nitrates inside of the basic layer 53. In this case, the oxygen concentration in the exhaust gas falls, so the reaction proceeds in the opposite direction (NO3−→NO2), and consequently the nitrates absorbed in the basic layer 53 become nitrate ions NO3− one by one and, as shown in FIG. 7B, are released from the basic layer 53 in the form of NO2. Next, the released NO2 is reduced by the hydrocarbons HC and CO contained in the exhaust gas.
FIG. 8 shows the case of making the air-fuel ratio (A/F) in of the exhaust gas which flows into the exhaust purification catalyst 13 temporarily rich slightly before the NOx absorption ability of the basic layer 53 becomes saturated. Note that, in the example shown in FIG. 8, the time interval of this rich control is 1 minute or more. In this case, the NOx which was absorbed in the basic layer 53 when the air-fuel ratio (A/F) in of the exhaust gas was lean is released all at once from the basic layer 53 and reduced when the air-fuel ratio (A/F) in of the exhaust gas is made temporarily rich. Therefore, in this case, the basic layer 53 plays the role of an absorbent for temporarily absorbing NOx.
Note that, at this time, sometimes the basic layer 53 temporarily adsorbs the NOx. Therefore, if using term of storage as a term including both absorption and adsorption, at this time, the basic layer 53 performs the role of an NOx storage agent for temporarily storing the NOx. That is, in this case, if referring to the ratio of the air and fuel (hydrocarbons) which are supplied into the engine intake passage, combustion chambers 2, and exhaust passage upstream of the exhaust purification catalyst 13 as the air-fuel ratio of the exhaust gas, the exhaust purification catalyst 13 functions as an NOx storage catalyst which stores the NOx when the air-fuel ratio of the exhaust gas is lean and releases the stored NOx when the oxygen concentration in the exhaust gas falls.
FIG. 9 shows the NOx purification rate when making the exhaust purification catalyst 13 function as an NOx storage catalyst in this way. Note that, the abscissa of the FIG. 9 shows the catalyst temperature TC of the exhaust purification catalyst 13. When making the exhaust purification catalyst 13 function as an NOx storage catalyst, as shown in FIG. 9, when the catalyst temperature TC is 300° C. to 400° C., an extremely high NOx purification rate is obtained, but when the catalyst temperature TC becomes a 400° C. or higher high temperature, the NOx purification rate falls.
In this way, when the catalyst temperature TC becomes 400° C. or more, the NOx purification rate falls because if the catalyst temperature TC becomes 400° C. or more, the nitrates break down by heat and are released in the form of NO2 from the exhaust purification catalyst 13. That is, so long as storing NOx in the form of nitrates, when the catalyst temperature TC is high, it is difficult to obtain a high NOx purification rate. However, in the new NOx purification method shown from FIG. 4 to FIGS. 6A and 6B, as will be understood from FIGS. 6A and 6B, nitrates are not formed or even if formed are extremely fine in amount, consequently, as shown in FIG. 5, even when the catalyst temperature TC is high, a high NOx purification rate is obtained.
Therefore, in the present invention, an exhaust purification catalyst 13 for reacting NOx contained in exhaust gas and reformed hydrocarbons is arranged inside of an engine exhaust passage, precious metal catalysts 51 and 52 are carried on the exhaust gas flow surface of the exhaust purification catalyst 13, a basic exhaust gas flow surface part 54 is formed around the precious metal catalysts 51 and 52, the exhaust purification catalyst 13 has the property of reducing the NOx which is contained in exhaust gas if the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is made to vibrate within a predetermined range of amplitude and within a predetermined range of period and has the property of being increased in storage amount of NOx which is contained in exhaust gas if the vibration period of the hydrocarbon concentration is made longer than this predetermined range, and, at the time of engine operation, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is made to vibrate within the predetermined range of amplitude and within the predetermined range of period to thereby reduce the NOx which is contained in the exhaust gas in the exhaust purification catalyst 13.
That is, the NOx purification method which is shown from FIG. 4 to FIGS. 6A and 6B can be said to be a new NOx purification method designed to remove NOx without forming almost any nitrates in the case of using an exhaust purification catalyst which carries a precious metal catalyst and forms a basic layer which can absorb NOx. In actuality, when using this new NOx purification method, the nitrates which are detected from the basic layer 53 become much smaller in amount compared with the case where making the exhaust purification catalyst 13 function as an NOx storage catalyst. Note that, this new NOx purification method will be referred to below as the first NOx purification method.
Next, referring to FIG. 10 to FIG. 15, this first NOx purification method will be explained in a bit more detail.
FIG. 10 shows enlarged the change in the air-fuel ratio (A/F) in shown in FIG. 4. Note that, as explained above, the change in the air-fuel ratio (A/F) in of the exhaust gas flowing into this exhaust purification catalyst 13 simultaneously shows the change in concentration of the hydrocarbons which flow into the exhaust purification catalyst 13. Note that, in FIG. 10, ΔH shows the amplitude of the change in concentration of hydrocarbons HC which flow into the exhaust purification catalyst 13, while ΔT shows the vibration period of the concentration of the hydrocarbons which flow into the exhaust purification catalyst 13.
Furthermore, in FIG. 10, (A/F) b shows the base air-fuel ratio which shows the air-fuel ratio of the combustion gas for generating the engine output. In other words, this base air-fuel ratio (A/F) b shows the air-fuel ratio of the exhaust gas which flows into the exhaust purification catalyst 13 when stopping the feed of hydrocarbons. On the other hand, in FIG. 10, X shows the upper limit of the air-fuel ratio (A/F) in used for producing the reducing intermediate without the produced active NOx* being stored in the form of nitrates inside the basic layer 53 much at all. To make the active NOx* and the modified hydrocarbons react to produce a reducing intermediate, the air-fuel ratio (A/F) in has to be made lower than this upper limit X of the air-fuel ratio.
In other words, in FIG. 10, X shows the lower limit of the concentration of hydrocarbons required for making the active NOx* and reformed hydrocarbon react to produce a reducing intermediate. To produce the reducing intermediate, the concentration of hydrocarbons has to be made higher than this lower limit X. In this case, whether the reducing intermediate is produced is determined by the ratio of the oxygen concentration and hydrocarbon concentration around the active NOx*, that is, the air-fuel ratio (A/F) in. The upper limit X of the air-fuel ratio required for producing the reducing intermediate will below be called the demanded minimum air-fuel ratio.
In the example shown in FIG. 10, the demanded minimum air-fuel ratio X is rich, therefore, in this case, to form the reducing intermediate, the air-fuel ratio (A/F) in is instantaneously made the demanded minimum air-fuel ratio X or less, that is, rich. As opposed to this, in the example shown in FIG. 11, the demanded minimum air-fuel ratio X is lean. In this case, the air-fuel ratio (A/F) in is maintained lean while periodically reducing the air-fuel ratio (A/F) in so as to form the reducing intermediate.
In this case, whether the demanded minimum air-fuel ratio X becomes rich or becomes lean depends on the oxidizing strength of the exhaust purification catalyst 13. In this case, the exhaust purification catalyst 13, for example, becomes stronger in oxidizing strength if increasing the carried amount of the precious metal 51 and becomes stronger in oxidizing strength if strengthening the acidity. Therefore, the oxidizing strength of the exhaust purification catalyst 13 changes due to the carried amount of the precious metal 51 or the strength of the acidity.
Now, when using an exhaust purification catalyst 13 with a strong oxidizing strength, if the air-fuel ratio (A/F) in is periodically lowered while maintaining the air-fuel ratio (A/F) in lean as shown in FIG. 11, the hydrocarbons are completely oxidized when the air-fuel ratio (A/F) in is lowered. As a result, the reducing intermediate cannot be produced. As opposed to this, when using an exhaust purification catalyst 13 with a strong oxidizing strength, if the air-fuel ratio (A/F) in is periodically made rich as shown in FIG 10, the hydrocarbons are partially oxidized, when the air-fuel ratio (A/F) in is made rich. As a result, the reducing intermediate is produced. Therefore, when using an exhaust purification catalyst 13 with a strong oxidizing strength, the demanded minimum air-fuel ratio X has to be made rich as shown in FIG. 10.
On the other hand, when using an exhaust purification catalyst 13 with a weak oxidizing strength, if the air-fuel ratio (A/F) in is periodically lowered while maintaining the air-fuel ratio (A/F) in lean as shown in FIG. 11, the hydrocarbons will be partially oxidized and consequently the reducing intermediate is produced. As opposed to this, when using an exhaust purification catalyst 13 with a weak oxidizing strength, if the air-fuel ratio (A/F) in is periodically made rich as shown in FIG. 10, a large amount of hydrocarbons are exhausted from the exhaust purification catalyst 13. Therefore, when using an exhaust purification catalyst 13 with a weak oxidizing strength, the demanded minimum air-fuel ratio X has to be made lean as shown in FIG. 11.
That is, it is learned that the demanded minimum air-fuel ratio X, as shown in FIG. 12, has to be reduced the stronger the oxidizing strength of the exhaust purification catalyst 13. In this way the demanded minimum air-fuel ratio X becomes lean or rich due to the oxidizing strength of the exhaust purification catalyst 13. Below, taking as an example the case where the demanded minimum air-fuel ratio X is rich, the amplitude of the change in concentration of hydrocarbons flowing into the exhaust purification catalyst 13 and the vibration period of the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 will be explained.
Now, if the base air-fuel ratio (A/F) b becomes larger, that is, if the oxygen concentration in the exhaust gas before the hydrocarbons are fed becomes higher, the feed amount of hydrocarbons required for making the air-fuel ratio (A/F) in the demanded minimum air-fuel ratio X or less increases and along with this the excess amount of hydrocarbons which did not contribute to the production of the reducing intermediate also increases. In this case, to remove the NOx well, as explained above, it is necessary to make the excess hydrocarbons oxidize. Therefore, to remove the NOx well, the larger the amount of excess hydrocarbons, the larger the amount of oxygen which is required.
In this case, if raising the oxygen concentration in the exhaust gas, the amount of oxygen can be increased. Therefore, to remove the NOx well, when the oxygen concentration in the exhaust gas before the hydrocarbons are fed is high, it is necessary to raise the oxygen concentration in the exhaust gas after feeding the hydrocarbons. That is, the higher the oxygen concentration in the exhaust gas before the hydrocarbons are fed, the larger the amplitude of the hydrocarbon concentration has to be made.
FIG. 13 shows the relationship between the oxygen concentration in the exhaust gas before the hydrocarbons are fed and the amplitude ΔH of the hydrocarbon concentration when the same NOx purification rate is obtained. From FIG. 13, it is learned that, to obtain the same NOx purification rate the higher the oxygen concentration in the exhaust gas before the hydrocarbons are fed, the greater the amplitude ΔH of the hydrocarbon concentration has to be made. That is, to obtain the same NOx purification rate, the higher the base air-fuel ratio (A/F) b, the greater the amplitude ΔT of the hydrocarbon concentration has to be made. In other words, to remove the NOx well, the lower the base air-fuel ratio (A/F) b, the more the amplitude ΔH of the hydrocarbon concentration can be reduced.
In this regard, the base air-fuel ratio (A/F) b becomes the lowest at the time of an acceleration operation. At this time, if the amplitude ΔH of the hydrocarbon concentration is about 200 ppm, it is possible to remove the NOx well. The base air-fuel ratio (A/F) b is normally larger than the time of acceleration operation. Therefore, as shown in FIG. 14, if the amplitude ΔH of the hydrocarbon concentration is 200 ppm or more, an excellent NOx purification rate can be obtained.
On the other hand, it is learned that when the base air-fuel ratio (A/F) b is the highest, if making the amplitude ΔH of the hydrocarbon concentration 10000 ppm or so, an excellent NOx purification rate is obtained. Therefore, in the present invention, the predetermined range of the amplitude of the hydrocarbon concentration is made 200 ppm to 10000 ppm.
Further, if the vibration period ΔT of the hydrocarbon concentration becomes longer, the oxygen concentration around the active NOx* becomes higher in the time after the hydrocarbons are fed to when the hydrocarbons are next fed. In this case, if the vibration period ΔT of the hydrocarbon concentration becomes longer than about 5 seconds, the majority of the active NOx* starts to be absorbed in the form of nitrates inside the basic layer 53. Therefore, as shown in FIG. 15, if the vibration period ΔT of the hydrocarbon concentration becomes longer than about 5 seconds, the NOx purification rate falls. Therefore, the vibration period ΔT of the hydrocarbon concentration has to be made 5 seconds or less.
On the other hand, if the vibration period ΔT of the hydrocarbon concentration becomes about 0.3 second or less, the fed hydrocarbons start to build up on the exhaust gas flow surface of the exhaust purification catalyst 13, therefore, as shown in FIG. 15, if the vibration period ΔT of the hydrocarbon concentration becomes about 0.3 second or less, the NOx purification rate falls. Therefore, in the present invention, the vibration period of the hydrocarbon concentration is made from 0.3 second to 5 seconds.
Now, in the present invention, by changing the hydrocarbon feed amount and injection timing from the hydrocarbon feed valve 15, the amplitude ΔH and vibration period ΔT of the hydrocarbons concentration is controlled so as to become the optimum values in accordance with the engine operating state. In this case, in this embodiment of the present invention, the hydrocarbon feed amount W able to give the optimum amplitude ΔH of the hydrocarbon concentration is stored as a function of the injection amount Q from the fuel injector 3 and engine speed N in the form of a map such as shown in FIG. 16 in advance in the ROM 32. Further, the optimum vibration period ΔT of the hydrocarbon concentration, that is, the injection period ΔT of the hydrocarbons is similarly stored as a function of the injection amount Q and engine speed N in the form of a map in advance in the ROM 32.
Next, referring to FIG. 17 to FIG. 20, an NOx purification method in the case when making the exhaust purification catalyst 13 function as an NOx storage catalyst will be explained in detail. The NOx purification method in the case when making the exhaust purification catalyst 13 function as an NOx storage catalyst in this way will be referred to below as the second NOx purification method.
In this second NOx purification method, as shown in FIG. 17, when the stored NOx amount ΣNOX of NOx which is stored in the basic layer 53 exceeds a predetermined allowable amount MAX, the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13 is temporarily made rich. If the air-fuel ratio (A/F) in of the exhaust gas is made rich, the NOx which was stored in the basic layer 53 when the air-fuel ratio (A/F) in of the exhaust gas was lean is released from the basic layer 53 all at once and reduced. Due to this, the NOx is removed.
The stored NOx amount ΣNOX is, for example, calculated from the amount of NOx which is exhausted from the engine. In this embodiment according to the present invention, the exhausted NOx amount NOXA of NOx which is exhausted from the engine per unit time is stored as a function of the injection amount Q and engine speed N in the form of a map such as shown in FIG. 18 in advance in the ROM 32. The stored NOx amount ΣNOX is calculated from exhausted NOx amount NOXA. In this case, as explained before, the period in which the air-fuel ratio (A/F) in of the exhaust gas is made rich is usually 1 minute or more.
In this second NOx purification method, as shown in FIG. 19, the fuel injector 3 injects additional fuel WR into the combustion chamber 2 in addition to the combustion-use fuel Q so that the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13 is made rich. Note that, in FIG. 19, the abscissa indicates the crank angle. This additional fuel WR is injected at a timing at which it will burn, but will not appear as engine output, that is, slightly before ATDC90° after compression top dead center. This fuel amount WR is stored as a function of the injection amount Q and engine speed N in the form of a map such as shown in FIG. 20 in advance in the ROM 32. Of course, in this case, it is also possible to make the amount of feed of hydrocarbons from the hydrocarbon feed valve 15 increase so as to make the air-fuel ratio (A/F) in of the exhaust gas rich.
In this regard, to use the first NOx purification method to remove NOx, even when the NOx concentration in the exhaust gas is low, at least a certain amount of hydrocarbons has to be fed in a short period. Therefore, when the NOx concentration of the exhaust gas is low, the NOx purification efficiency becomes poor. As opposed to this, in the second NOx purification method, when the NOx concentration in the exhaust gas is low, the time until the stored NOx amount ΣNOX reaches the allowable value MAX becomes longer, so the period for making the air-fuel ratio (A/F) in of the exhaust gas rich just becomes longer, and accordingly, NOx purification efficiency does not particularly become worse. Therefore, when the NOx concentration in the exhaust gas is low, use of the second NOx purification method rather than the first NOx purification method can be said to be preferable. That is, which of the first NOx purification method and second NOx purification method should be used changes in the engine operating state.
Now, as explained before, when the second NOx purification method is used, NOx is stored in the form of nitrate ions NO3− inside the basic layer 53. Further, even when the first NOx purification method is used, while actually small in amount, NOx, as shown in FIG. 6A, is stored in the form of nitrate ions NO3− inside the basic layer 53. Therefore, as explained before, when the first NOx purification method is being used, nitrates are detected, though small in amount, from the basic layer 53. In this regard, in this way, if the NOx is stored inside the basic layer 53, the amount of production of the reducing intermediate is reduced and the NOx purification rate ends up falling.
If explaining this with reference to the case where the basic layer 53 is formed from the alkaline earth metal barium Ba as an example, first the active NOx* which is produced when the NOx purification method is being performed is attracted by the barium Ba and held on the basic layer 53 then becomes a reducing intermediate. However, if the active NOx* is pulled into the basic layer 53 and becomes the nitrate Ba(NO3)2, the force of the barium attracting the active NOx* ends up disappearing, that is, the base sites end up disappearing. Therefore, if the amount of the active NOx* which is stored inside the basic layer 53 increases, the amount of active NOx* itself is reduced, so not only is the amount of production of the reducing intermediate decreased, but also the force holding the active NOx* on the basic layer 53 becomes weaker, so the amount of production of the reducing intermediate is decreased.
If the amount of production of the reducing intermediate is decreased in this way, the NOx purification rate falls. That is, if the amount of the active NOx* which is stored inside the basic layer 53 is increased, the NOx purification rate falls. Note that, the NOx which is stored in the basic layer 53 is desorbed and forms the reducing intermediate if the temperature of the exhaust purification catalyst 13 becomes higher. That is, when the temperature of the exhaust purification catalyst 13 is high, a high NOx purification rate is secured without the NOx storage action being performed. The NOx storage action is performed and the NOx purification rate falls when the temperature of the exhaust purification catalyst 13 is low.
FIG. 21 shows the changes in the amount of feed of hydrocarbons from the hydrocarbon feed valve 15, the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13, the amount of active NOx* which is held on the basic layer 53, and the stored NOx amount SNOX which is stored inside the basic layer 53 when the NOx purification action by the first NOx purification method is being performed in the state where the temperature of the exhaust purification catalyst 13 is relatively low. As will be understood from FIG. 21, the active NOx* which is held on the basic layer 53 is used for producing a reducing intermediate when hydrocarbons are fed and the air-fuel ratio (A/F) in of the exhaust gas falls. Therefore, at this time, the active NOx* temporarily disappears from the basic layer 53. Next, if the air-fuel ratio (A/F) in of the exhaust gas becomes higher, the amount of active NOx* gradually increases.
On the other hand, as shown in FIG. 21, the stored NOx amount SNOX increases along with the elapse of time. If the stored NOx amount SNOX increases, as shown in FIG. 21, the amount of active NOx* decreases, therefore the amount of production of the reducing intermediate decreases. Therefore, if the stored NOx amount SNOX increases, the NOx purification rate falls. In this case, the allowable drop in the NOx purification rate is predetermined, and if the NOx purification rate falls to this allowable drop, the NOx purification rate has to be restored.
In this case, if making the NOx which is stored in the basic layer 53 desorb from the basic layer 53, the NOx purification rate is restored. On the other hand, when the NOx purification action is being performed by the first NOx purification method, if the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is made to temporarily increase, NOx is desorbed from the basic layer 53. The desorbed NOx becomes a reducing intermediate. Therefore, in the present invention, when the NOx purification rate falls to the allowable drop, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is made to temporarily increase whereby the NOx purification rate is restored.
In this case, in the present invention, the amount NX of the stored NOx amount SNOX which causes such an allowable amount of drop in the NOx purification rate is predetermined. When the NOx purification action is being performed by the first NOx purification method, if this predetermined amount NX or more of NOx is stored in the exhaust purification catalyst 13 or can be stored in it, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is temporarily increased for making the NOx which was stored at the exhaust purification catalyst 13 desorb from it.
Note that, in this way, the air-fuel ratio (A/F) in of the exhaust gas when the concentration of hydrocarbons is temporarily increased is made rich and smaller than the air-fuel ratio (A/F) in of the exhaust gas when the NOx purification action is being performed by the first NOx purification method. That is, in other words, when the NOx purification action is being performed by the first NOx purification method, the concentration of hydrocarbons is made to vibrate by within the predetermined range of amplitude ΔH. The air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13 when the concentration of hydrocarbons is temporarily increased is made rich and smaller than the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13 when the concentration of hydrocarbons is made to vibrate by within the predetermined range of amplitude ΔH.
Next, explaining the present invention in a bit more detail, in the first embodiment of the present invention, when the NOx purification action is being performed by the first NOx purification method, the stored NOx amount SNOX which is stored in the exhaust purification catalyst 13 is calculated. When the calculated stored NOx amount SNOX exceeds the predetermined amount NX, as shown in FIG. 21, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is temporarily increased.
Next, referring to FIG. 22, the method of calculation of the stored NOx amount SNOX will be explained.
In FIG. 22, the storage rate SR shows the ratio of the NOx which is stored in the basic layer 53 to the NOx which is contained in the exhaust gas when the NOx purification action is being performed by the first NOx purification method. The NOx which is contained in the exhaust gas matches with the exhausted NOx amount NOXA shown in FIG. 18, so the NOx amount which is stored in the basic layer 53 is expressed by the SR·NOXA. As shown in FIG. 22, the storage rate SR decreases as the temperature TC of the exhaust purification catalyst 13 rises. Therefore, the NOx amount (=SR·NOXA) which is stored in the basic layer 53 becomes smaller the higher the temperature TC of the exhaust purification catalyst 13.
On the other hand, in FIG. 22, the desorption rate DR shows the ratio of the NOx which is desorbed to the stored NOx amount SNOX which is stored in the basic layer when the NOx purification action is being performed by the first NOx purification method. Therefore, the amount of NOx which is desorbed from the basic layer 53 is expressed by DR·SNOX. As shown in FIG. 22, the desorption rate DR rapidly rises if the temperature TC of the exhaust purification catalyst 13 exceeds an NOx desorption start temperature TK determined by the exhaust purification catalyst 13. This NOx desorption start temperature TK is for example, 400° C. In this embodiment according to the present invention, the stored NOx amount SNOX is calculated by using these storage rate SR and desorption amount DR.
Next, referring to FIG. 23, the NOx purification control according to the present invention as a whole will be explained. Note that, FIG. 23 shows a time chart for the time when, after engine startup, the temperature of the exhaust purification catalyst 13 gradually rises and thereby the second NOx purification method is switched to the first NOx purification method. Further, FIG. 23 shows the changes in the injection amount WR of the additional fuel, the amount of feed W of hydrocarbons, and the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13, the change in the stored NOx amount ΣNOX of the NOx which is stored in the exhaust purification catalyst 13 when the second NO purification method is being used, and the change in the stored NOx amount SNOX of the NOx which is stored in the basic layer 53 when the first NOx purification method is being used.
As shown in FIG. 23, when the second NOx purification method is being performed, if the stored NOx amount ΣNOX exceeds the allowable amount MAX, additional fuel WR is injected and the air-fuel ratio (A/F) in of the exhaust gas is made rich. Due to this, the NOx is released from the exhaust purification catalyst 13. On the other hand, when switched from the second NOx purification method to first NOx purification method, additional fuel WR is fed to make the stored NOx amount ΣNOX zero, and the air-fuel ratio (A/F) in of the exhaust gas is made temporarily rich. After this, the NOx purification treatment by the first NOx purification method is started.
Right after the NOx purification treatment by the first NOx purification method is started, the temperature of the exhaust purification catalyst 13 does not become that high, therefore, at this time, the stored NOx amount SNOX is gradually increased. Next, if the stored NOx amount SNOX exceeds the predetermined amount NX, the feed amount W of hydrocarbons is increased and the air-fuel ratio (A/F) in of the exhaust gas is made rich. At this time, the NOx which is stored in the basic layer 53 is desorbed, and the desorbed NOx is used so as to form the reducing intermediate.
On the other hand, if, a little after the NOx purification treatment by the first NOx purification method is started, the temperature of the exhaust purification catalyst 13 rises, the NOx will no longer be stored in the basic layer 53 and the stored NOx will just be desorbed from the basic layer 53. Therefore, at this time, the stored NOx amount SNOX will not exceed the predetermined amount NX, so the concentration of hydrocarbons will never be temporarily increased and a good NOx purification action is continued by the first NOx purification method.
Note that, in FIG. 23, the allowable amount MAX expresses the NOx storage ability of the exhaust purification catalyst 13. AS opposed to this, the predetermined amount NX expresses an amount far smaller than the NOx storage ability of the exhaust purification catalyst 13. Therefore, as will be understood from FIG. 23, this predetermined amount NX is a far smaller amount than the allowable amount MAX.
FIG. 24 shows the NOx purification control routine for working this first embodiment. Note that, this routine is executed by interruption every predetermined time.
Referring to FIG. 24, first, at step 60, it is judged if the temperature TC of the exhaust purification catalyst 13 is higher than the activation temperature TC shown in FIG. 5. When TC≦TX, that is, when the NOx purification treatment cannot be performed well by the first NOx purification method, the routine proceeds to step 61 where the second NOx purification method is performed.
That is, at step 61, the NOx amount NOXA stored per unit time is calculated from the map shown in FIG. 18. Next, at step 62, the next formula is used as the basis to calculate the NOx amount ΣNOX stored in the exhaust purification catalyst 14 during the NOx purification action by the second NOx purification method:

ΣNOX←ΣNOX+NOXA−NOXD

Next, at step 63, it is judged if the stored NOx amount ΣNOX exceeds the allowable value MAX. When ΣNOX>MAX, the routine proceeds to step 64 where the additional fuel amount WR is calculated from the map shown in FIG. 20 and the additional fuel injection action is performed. Next, at step 65, ΣNOX is cleared.
On the other hand, when it is determined at step 60 that TC>TX, the routine proceeds to step 66, where it is determined that at the time of the current interruption, TC>TX stands. When it is determined that now TC>TX, to release the residual stored NOx, the routine proceeds to step 64 where additional fuel WR is injected. As opposed to this, when it is judged at step 66 that at the time of the current interruption, TC>TX does not currently stand, meaning that TC>TX has been previously determined to stand in step 66, and thus TC>TX already stands, the routine proceeds to step 67 where the first NOx purification method is performed.
That is, first, at step 67, the NOx amount NOXA of the NOx which is exhausted per unit time is calculated from the map shown in FIG. 18. Next, at step 68, the output signal of the temperature sensor 23 is used as the basis to calculate the storage rate SR from the relationship shown in FIG. 22. Next, at step 69, the output signal of the temperature sensor 23 is used as the basis to calculate the desorption rate DR from the relationship shown in FIG. 22. Next, at step 70, the following formula is used as the basis to update the stored. NOx amount SNOX of the NOx which is stored in the basic layer 53.

SNOX←SNOX+SR·NOXA−DR·SNOX

Next, at step 71, it is judged if the stored NOx amount SNOX exceeds the predetermined amount NX. When SNOX≦NX, the routine proceeds to step 72 where the feed amount W of hydrocarbons is calculated from the map shown in FIG. 16, and the amount W of hydrocarbons is fed from the hydrocarbon feed valve 15 by the period ΔT calculated from the map. At this time, the NOx purification action is being performed by the first NOx purification method. As opposed to this, when it is judged at step 71 that SNOX>NX. the routine proceeds to step 73 where the feed amount of hydrocarbons for making NOx desorb from the basic layer 53 is increased. Next, at step 74, the NOx storage amount SNOX is cleared.
Next, a second embodiment according to the present invention will be explained. In this second embodiment, when the NOx purification action is being performed by the first NOx purification method, the NOx storage operation state where the NOx is stored in the exhaust purification catalyst 13 is found in advance. As an example of this NOx storage operation state, the case where a low speed operation is continued for a constant time or more may be mentioned. In such a case, a predetermined amount NX or more of NOx can be stored in the exhaust purification catalyst 13. Therefore, in this case, to make the NOx which is stored in the NOx exhaust purification catalyst 13 desorb, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is temporarily increased by a predetermined period.
That is, in this second embodiment, when the NOx purification action is being performed by the first NOx purification method, the concentration of hydrocarbons is made to vibrate with the predetermined range of period ΔT. When the engine operating state is the above NOx storage operation state, the concentration of hydrocarbons flowing into the exhaust purification catalyst 13 is temporarily increased by a period longer than this predetermined range of period ΔT. Due to this, the NOx which was stored in the basic layer 53 can be periodically desorbed and therefore a high NOx purification rate can be secured.
Further, in this second embodiment, as will be understood from FIG. 22, when the temperature TC of the exhaust purification catalyst 13 is lower than the NOx desorption start temperature TK, the exhaust purification catalyst 13 stores NOx. Therefore, a temperature region lower than the NOx desorption start temperature TK becomes the NOx storage temperature region. In this case, if the temperature TC of the exhaust purification catalyst 13 is within this NOx storage temperature region, a predetermined amount NX or more of NOx may be stored in the exhaust purification catalyst 13. Therefore, in this case, to desorb the NOx which is stored in the exhaust purification catalyst, the concentration of hydrocarbons flowing into the exhaust purification catalyst is temporarily increased by a predetermined period.
That is, in this case, when the first NOx purification method is used for the NOx purification action, if the temperature TC of the exhaust purification catalyst 13 is in the NOx storage temperature region, it is judged that the engine operating state is in the above NOx storage operation state.
FIG. 25 shows the NOx purification control routine for executing this embodiment. Note that, this routine is also executed by interruption every certain time.
Referring to FIG. 25, first, at step 80, it is judged if the temperature TC of the exhaust purification catalyst 13 is higher than the activation temperature TC shown in FIG. 5. When TC≦TX, that is, when the NOx purification treatment cannot be performed well by the first NOx purification method, the routine proceeds to step 81 where the second NOx purification method is executed.
That is, at step 81, the NOx amount NOXA stored per unit time is calculated from the map shown in FIG. 18.
Next, at step 82, the next formula is used as the basis to calculate the NOx amount ΣNOX which is stored in the exhaust purification catalyst 14 for the NOx purification action by the second NOx purification method.

ΣNOX←ΣNOX+NOXA−NOXD

Next, at step 83, it is judged if the stored NOx amount ΣNOX exceeds the allowable value MAX. When ΣNOX>MAX, the routine proceeds to step 84 where the additional fuel amount WR is calculated from the map shown in FIG. 20 and an injection action of additional fuel is performed. Next, at step 85, ΣNOX is cleared.
On the other hand, when it is determined at step 80 that TC>TX, the routine proceeds to step 86, where it is determined that, at the time of the current interruption, TC>TX. When it is determined that now TC>TX, to release the residual stored NOx, the routine proceeds to step 84 where additional fuel WR is injected. As opposed to this, when it is determined at step 86 that at the time of the current interruption, TC>TX does not currently stand, meaning that TC>TX has been previously determined to stand in step 86, and thus TC>TX already stands, the routine proceeds to step 87 where the first NOx purification method is performed.
That is, first, at step 87, it is judged if the temperature TC of the exhaust purification catalyst 13 is higher than the NOx desorption start temperature TK. When TC>TK, the routine proceeds to step 88 where the feed amount W of hydrocarbons is calculated from the map shown in FIG. 16, and the amount W of hydrocarbons is fed from the hydrocarbon feed valve 15 by the calculated period ΔT. At this time, the NOx purification action is being performed by the first NOx purification method. As opposed to this, when it is judged at step 87 that TC≦TK, the routine proceeds to step 89 where when the NOx purification action is being performed by the first NOx purification method, the feed amount of hydrocarbons for making NOx desorb from the basic layer 53 is temporarily increased by the predetermined period. That is, at this time, the air-fuel ratio (A/F) in of the exhaust gas flowing into the exhaust purification catalyst 13 is made temporarily rich by the predetermined period.
Note that, as another embodiment, in the engine exhaust passage upstream of the exhaust purification catalyst 13, an oxidation catalyst for reforming the hydrocarbons can be arranged.
REFERENCE SIGNS LIST
4 . . . intake manifold
5 . . . exhaust manifold
7 . . . exhaust turbocharger
12 . . . exhaust pipe
13 . . . exhaust purification catalyst
14 . . . particulate filter
15 . . . hydrocarbon feed valve

## Claims

1. An exhaust purification system of an internal combustion engine, the exhaust purification system comprising:
an exhaust purification catalyst for reacting NOx contained in exhaust gas and reformed hydrocarbons arranged inside of an engine exhaust passage;
a precious metal catalyst carried on an exhaust gas flow surface of the exhaust purification catalyst;
a basic exhaust gas flow surface part formed around the precious metal catalyst; and
an electronic control unit that is at least configured to control a vibration of a concentration of hydrocarbons flowing into the exhaust purification catalyst within a predetermined range of amplitude and within a predetermined range of period, wherein
when the electronic control unit controls the vibration of the concentration of hydrocarbons within the predetermined range of amplitude and within the predetermined range of period, a reducing intermediate containing nitrogen and hydrocarbons is produced on the precious metal catalyst and held on the basic exhaust gas flow surface part, the NOx contained in the exhaust gas catalyst is chemically reduced by a reducing action of the reducing intermediate held on the basic exhaust gas flow surface part, the exhaust purification catalyst has a property of chemically reducing the NOx that is contained in the exhaust gas without storing a substantial amount of nitrates in the basic exhaust gas flow surface part, and when a first predetermined amount or more of nitrates are stored at, or when the first predetermined amount or more of nitrates are estimated to be stored at, the exhaust purification catalyst, the concentration of hydrocarbons flowing into the exhaust purification catalyst is temporarily increased to desorb the nitrates that are stored at the exhaust purification catalyst.

2. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein an air-fuel ratio of the exhaust gas flowing into the exhaust purification catalyst when the concentration of hydrocarbons is temporarily increased is made rich and smaller than an air-fuel ratio of the exhaust gas flowing into the exhaust purification catalyst when the concentration of hydrocarbons is made to vibrate within said predetermined range of amplitude.

3. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein an amount of nitrates that is stored in the exhaust purification catalyst is calculated when the concentration of hydrocarbons flowing into the exhaust purification catalyst is made to vibrate within said predetermined range of amplitude and said predetermined range of period and wherein the concentration of hydrocarbons flowing into the exhaust purification catalyst is temporarily increased when the calculated stored nitrate amount exceeds said first predetermined amount.

4. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein a nitrate storage operation state where nitrates are stored in the exhaust purification catalyst when the concentration of hydrocarbons flowing into the exhaust purification catalyst is made to vibrate within said predetermined range of amplitude and within said predetermined range of period is found in advance and, when an engine operating state is said nitrate storage operation state, the concentration of hydrocarbons flowing into the exhaust purification catalyst is temporarily increased by a period longer than the predetermined range of period.

5. An exhaust purification system of an internal combustion engine as claimed in claim 4, wherein when a temperature of the exhaust purification catalyst is in a nitrate storage temperature region of the exhaust purification catalyst when the concentration of hydrocarbons flowing into the exhaust purification catalyst is made to vibrate within said predetermined range of amplitude and within said predetermined range of period, the electronic control unit determines that an engine operating state is in said nitrate storage operation state.

6. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein the predetermined vibration period of the hydrocarbon concentration is the vibration period necessary for continued production of the reducing intermediate.

7. An exhaust purification system of an internal combustion engine as claimed in claim 6, wherein said vibration period of the hydrocarbon concentration is 0.3 second to 5 seconds.

8. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein said precious metal catalyst is comprised of platinum Pt and at least one of rhodium Rh and palladium Pd.

9. An exhaust purification system of an internal combustion engine as claimed in claim 1, wherein a basic layer containing an alkali metal, an alkaline earth metal, a rare earth metal, or a metal which can donate electrons to NOx is formed on the exhaust gas flow surface of the exhaust purification catalyst and wherein a surface of said basic layer forms said basic exhaust gas flow surface part.