JP2005042734A - Exhaust emission control device of internal combustion engine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To detect the degree of thermal deterioration of a storage/reduction type NOx catalyst. <P>SOLUTION: In this exhaust emission control device of an internal combustion engine in which the storage/reduction type NOx catalyst 17 is installed in the exhaust tube 16 of the internal combustion engine allowing lean burn, an input gas SOx sensor 23 is installed on the upstream side of the NOx catalyst 17, and an output gas SOx sensor 24 and an air-fuel ratio sensor 27 are installed on the downstream side. An SOx poisoning recovering treatment is applied to the NOx catalyst 17, and immediately after the poisoning is generally completely recovered, a saturated NOx release treatment is applied to the NOx catalyst 17. Then, a rich changeover time is measured, the measured value is compared with the rich changeover time of the NOx catalyst 17 in a fresh state, and based on the compared value, the degree of the thermal deterioration is determined or the NOx clean-up rate of the NOx catalyst is measured to determine the degree of the thermal deterioration. When the degree of the thermal deterioration exceeds a predetermined level, a thermal deterioration suppressing means is operated to suppress the thermal deterioration thereafter. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an exhaust gas purification apparatus capable of purifying nitrogen oxide (NOx) from exhaust gas exhausted from a lean burnable internal combustion engine, and more particularly to an apparatus capable of detecting thermal deterioration of a NOx catalyst.

As an exhaust purification device that purifies NOx from exhaust gas discharged from a lean burnable internal combustion engine, there is an NOx storage reduction catalyst. The NOx storage reduction catalyst (hereinafter sometimes simply referred to as catalyst or NOx catalyst) absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean (ie, in an oxygen-excess atmosphere), and the oxygen concentration of the inflowing exhaust gas It is a catalyst that releases absorbed NOx and reduces it to N ₂ when NO decreases.

The structure of the NOx catalyst and the mechanism of NOx purification will be briefly explained. The NOx catalyst carries a catalyst substance such as platinum (Pt) and a NOx storage agent such as barium (Ba) on a support such as alumina. (In the following description, an example of a NOx catalyst in which Pt and Ba are supported) will be described. When a lean air-fuel ratio exhaust gas flows into the NOx catalyst, NOx in the exhaust gas is oxidized on the surface of Pt. becomes NO ₂ Te, the NO ₂ is absorbed in the Ba combined with BaO, it is absorbed in the form of nitrate ions NO ₃ over. This NOx absorption is performed at the interface between Ba and Pt. On the other hand, when stoichiometric (theoretical air / fuel ratio) or rich air / fuel ratio exhaust gas flows into the NOx catalyst and the oxygen concentration decreases, the NO ₃₋ absorbed in the NOx catalyst is released in the form of NO ₂ or NO. It reacts with HC and CO in the exhaust gas and is reduced to N ₂ .

  Therefore, when this NOx catalyst is disposed in the exhaust passage of an internal combustion engine capable of lean combustion, and the lean air-fuel ratio exhaust gas and the stoichiometric or rich air-fuel ratio exhaust gas are alternately flowed, the NOx in the exhaust gas is purified. Can do.

  It has been known that when this NOx catalyst is used for exhaust gas purification for a long time, the NOx catalyst deteriorates with time, and the NOx purification ability decreases as shown in FIG. This deterioration is considered to be caused by (a) sulfur in the fuel and (b) heat. The deterioration caused by sulfur in the fuel is called sulfur poisoning deterioration, and the deterioration caused by heat is called heat deterioration. Sometimes they are distinguished. In addition, although sulfur poisoning deterioration may be expressed as S poisoning deterioration or SOx poisoning deterioration, in the following description, it unifies with the expression SOx poisoning deterioration.

Explaining the SOx poisoning deterioration, the fuel of the internal combustion engine generally contains a sulfur content. When the fuel is burned in the internal combustion engine, the sulfur content in the fuel is combusted to oxidize sulfur such as SO ₂ and SO _3. Things (SOx) are generated. The NOx storage reduction catalyst absorbs SOx in the exhaust gas by the same mechanism that absorbs NOx. Therefore, if a NOx catalyst is arranged in the exhaust passage of the internal combustion engine, the NOx catalyst can contain only NOx. SOx is also absorbed.

  However, SOx absorbed by the NOx catalyst forms a stable sulfate with the passage of time, so that it is difficult to be decomposed and released and tends to accumulate in the catalyst. The accumulation of sulfate on the NOx catalyst is called SOx poisoning. When SOx poisoning progresses and the amount of SOx accumulated in the NOx catalyst increases, the NOx absorption capacity of the catalyst decreases and the NOx purification rate decreases. . This is SOx poisoning deterioration.

Explaining thermal degradation, as described above, NOx absorption in the NOx catalyst is carried out at the interface between Pt (catalyst substance) and Ba (NOx absorbent), but Pt undergoes sintering and grows due to heat. It is known that the particle size increases. In the purification of exhaust gas discharged from a vehicle internal combustion engine, the heat load applied to the NOx catalyst is large, and Pt sintering cannot be avoided. Thus, when Pt causes sintering, the contact area between Pt and Ba decreases, that is, the interface between Pt and Ba decreases. As a result, the NOx absorption capability of the NOx catalyst is reduced, and the NOx purification capability is reduced. This is thermal degradation.

FIG. 12 shows the influence of the sintering of the catalyst material (catalyst material particle size growth) on the NOx purification performance, and when the catalyst material sintering does not proceed (that is, when the particle size is small). The NOx purification performance is high, and the NOx purification performance decreases as the sintering progresses (that is, as the particle size increases).
Japanese Patent No. 2745985

By the way, as for the SOx poisoning deterioration, as disclosed in the patent publication of No. 2745985, etc., by performing a predetermined recovery process, SOx absorbed in the NOx catalyst is released to SO ₂ . Since it can be reduced, it is possible to recover the NOx catalyst from SOx poisoning.

  On the other hand, it is impossible to return Pt once sintered to the state before sintering, and therefore it is impossible to recover the NOx catalyst from thermal deterioration. Therefore, in managing the NOx catalyst, it is important to detect the degree of thermal degradation (thermal degradation level) of the NOx catalyst.

  However, at present, a technique for detecting the degree of thermal deterioration has not been established, and development of a technique for detecting the degree of thermal deterioration is eagerly desired. The present invention has been made in view of such problems of the prior art, and the problem to be solved by the present invention is to establish an internal combustion engine by establishing a technology for detecting the degree of thermal degradation of a NOx storage reduction catalyst. The purpose is to improve engine exhaust gas purification technology.

The present invention employs the following means in order to solve the above problems. An exhaust gas purification apparatus for an internal combustion engine according to a first aspect of the present invention includes (a) an exhaust gas that is provided in an exhaust passage of a lean burnable internal combustion engine and absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean. Whether or not it is time to execute a NOx storage reduction catalyst that releases NOx absorbed when the oxygen concentration of the catalyst is low and reduces it to N ₂ , and (b) a SOx poisoning recovery process that releases SOx from the NOx storage reduction catalyst A poisoning recovery execution time determination means for determining whether or not (c) the poisoning recovery execution time determination means determines that it is the execution time; A poisoning recovery means for releasing the total amount to recover the NOx storage reduction catalyst from SOx poisoning; (d) a storage capacity detection means for detecting the NOx storage capacity of the NOx storage reduction catalyst; By poisoning recovery means The NOx storage capacity of the NOx storage reduction catalyst detected by the storage capacity detection means after executing the SOx poisoning recovery process is compared with the reference NOx storage capacity, and the storage reduction type is based on the comparison value. And a heat deterioration determining means for determining the degree of heat deterioration of the NOx catalyst.

In this exhaust gas purification apparatus for an internal combustion engine, when the poisoning recovery execution time determining means determines that it is time to execute the SOx poisoning recovery process for the NOx storage reduction catalyst, the poison recovery means performs the storage reduction. The SOx poisoning recovery process for the NOx catalyst is executed, and the SOx stored in the NOx storage reduction catalyst is almost completely released. Immediately after the completion of the SOx poisoning recovery process, the storage capacity detecting means detects the NOx storage capacity of the NOx storage reduction catalyst. Thereafter, the thermal deterioration determination means compares the NOx storage capacity detected by the storage capacity detection means with the reference NOx storage capacity, and determines the degree of thermal deterioration of the NOx storage reduction catalyst based on the comparison value. .

  The principle for determining the degree of thermal degradation is as follows. The deterioration of the NOx storage reduction catalyst includes SOx poisoning deterioration caused by sulfur in the fuel and heat deterioration caused by heat. The SOx poisoning deterioration is recovered by executing a predetermined poisoning recovery process. In contrast, once thermal degradation occurs, it cannot be recovered. Therefore, even if the SOx poisoning recovery process is executed, the portion where the performance cannot be recovered can be regarded as being due to thermal degradation. This is the principle of determining the degree of thermal deterioration in the present invention.

  In the exhaust gas purification apparatus for an internal combustion engine according to the first aspect of the present invention, the NOx occlusion ability used as a reference by the thermal deterioration determination means is NOx of a new NOx storage reduction catalyst that has not undergone both SOx poisoning deterioration and heat deterioration. It can be the storage capacity.

  The comparison value obtained by comparing the NOx storage capacity of the NOx storage reduction catalyst detected by the storage capacity detection means and the reference NOx storage capacity by the thermal degradation determination means may be the difference between the two. The quotient may be obtained by dividing one by the other.

An exhaust gas purification apparatus for an internal combustion engine according to a second aspect of the invention is (i) an exhaust gas that is provided in an exhaust passage of a lean burnable internal combustion engine and that absorbs NOx and flows in when the air-fuel ratio of the inflowing exhaust gas is lean. Is it time to execute a NOx storage reduction catalyst that releases NOx absorbed when the gas oxygen concentration is low and reduces it to N ₂ and (b) a SOx poisoning recovery process that releases SOx from the NOx storage reduction catalyst? A poisoning recovery execution time determining means for determining whether or not (c) when the poisoning recovery execution time determining means determines that it is the execution time, the amount of SOx accumulated on the NOx storage reduction catalyst (D) a purification rate measuring means for measuring a NOx purification rate of the NOx storage reduction catalyst; According to the poisoning recovery means After performing the SOx poisoning recovery process, the NOx purification rate that is the NOx purification rate standard of the NOx storage reduction catalyst measured by the purification rate measurement is compared, and based on the comparison value, the NOx purification rate of the NOx storage reduction catalyst is compared. And a heat deterioration determination means for determining the degree of heat deterioration.

  In the second invention, the NOx purification rate measuring means is based on the NOx amount in the exhaust gas flowing into the NOx catalyst and the NOx amount in the exhaust gas by the NOx detecting means installed downstream of the NOx catalyst. Can be measured. In the exhaust gas purification apparatus for an internal combustion engine according to the second aspect of the invention, when the poisoning recovery execution time determining means determines that it is time to execute the SOx poisoning recovery processing for the NOx storage reduction catalyst, the poison recovery means However, the SOx poisoning recovery process for the NOx storage reduction catalyst is executed, and the SOx stored in the NOx storage reduction catalyst is almost completely released. Immediately after the completion of the SOx poisoning recovery process, the purification rate measuring means measures the NOx purification rate of the NOx storage reduction catalyst. Thereafter, the thermal deterioration determining means compares the NOx purification rate measured by the purification rate measuring means with the reference NOx purification rate, and determines the degree of thermal degradation of the NOx storage reduction catalyst based on the comparison value. .

  The principle for determining the degree of thermal degradation is as follows. The deterioration of the NOx storage reduction catalyst includes SOx poisoning deterioration caused by sulfur in the fuel and heat deterioration caused by heat. The SOx poisoning deterioration is recovered by executing a predetermined poisoning recovery process. In contrast, once thermal degradation occurs, it cannot be recovered. Therefore, even if the SOx poisoning recovery process is executed, the portion where the performance cannot be recovered can be regarded as being due to thermal degradation. This is the principle of determining the degree of thermal deterioration in the present invention.

In the exhaust gas purification apparatus for an internal combustion engine according to the second aspect of the present invention, the NOx purification rate based on the thermal deterioration determining means is the NOx of a new NOx storage reduction catalyst that has not undergone both SOx poisoning deterioration and thermal deterioration. It can be a purification rate.

  The comparison value obtained by the thermal degradation determination means by comparing the NOx purification rate of the NOx storage reduction catalyst measured by the purification rate measuring means with the reference NOx purification rate may be the difference between the two. The quotient may be obtained by dividing one by the other.

  As the lean burnable internal combustion engine in the first and second inventions (hereinafter referred to as the present invention), an in-cylinder direct injection type lean burn gasoline engine or diesel engine can be exemplified. The air-fuel ratio of exhaust gas refers to the ratio of air and fuel (hydrocarbon) supplied into the exhaust passage upstream of the engine intake passage and the NOx storage reduction catalyst.

  When the internal combustion engine is a lean burn gasoline engine, the exhaust air / fuel ratio control means can control the air / fuel ratio of the exhaust gas by controlling the air / fuel ratio of the air-fuel mixture supplied to the combustion chamber. When the internal combustion engine is a diesel engine, the reducing agent is supplied by so-called sub-injection in which fuel is injected in the intake stroke, expansion stroke or exhaust stroke, or in the exhaust passage upstream of the NOx storage reduction catalyst. As a result, the air-fuel ratio of the exhaust gas can be controlled.

The NOx storage reduction catalyst is a catalyst that absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean, releases the absorbed NOx when the oxygen concentration in the inflowing exhaust gas decreases, and reduces it to N _2. . This NOx storage reduction catalyst uses, for example, alumina as a carrier, and an alkali metal such as potassium K, sodium Na, lithium Li and cesium Cs, an alkaline earth such as barium Ba and calcium Ca, and lanthanum La. And at least one selected from rare earths such as yttrium Y and a noble metal such as platinum Pt are supported.

  Further, the storage capacity detecting means maintains the rich air-fuel ratio of the exhaust gas flowing into the NOx storage reduction catalyst from lean to rich after saturating the NOx storage state of the NOx storage reduction catalyst, The time required from when the air-fuel ratio is switched to when the air-fuel ratio of the exhaust gas at the outlet of the NOx storage reduction catalyst becomes rich can be detected as a barometer of NOx storage capacity.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, the poisoning recovery execution timing determination means is configured to detect when the NOx storage capacity of the NOx storage reduction catalyst detected by the storage capacity detection means falls below a predetermined lower limit value. It can be determined that it is time to execute the SOx poisoning recovery process. In this case, for example, it is preferable to detect the NOx storage capacity of the NOx storage reduction catalyst by the storage capacity detection means for every fixed fuel consumption or every fixed travel distance.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, when it is provided with the input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, it is detected by the input gas SOx concentration detection means. The amount of SOx flowing into the NOx storage reduction catalyst is calculated based on the SOx concentration and the intake air amount of the internal combustion engine, and when the amount of SOx flowing into the NOx storage reduction catalyst exceeds a predetermined amount, The poisoning recovery execution time determination means can determine that it is the execution time of the SOx poisoning recovery process.

In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, when it further comprises an input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, the detection is performed by the input gas SOx concentration detection means. The amount of SOx flowing into the NOx storage reduction catalyst is calculated based on the sulfur concentration of the fuel of the internal combustion engine estimated from the measured SOx concentration and the fuel consumption or travel distance, and the NOx storage reduction catalyst When the amount of SOx flowing into the exhaust gas exceeds a predetermined amount, the poisoning recovery execution time determination means can determine that it is the execution time of the SOx poisoning recovery process.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, the input gas SOx concentration detecting means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, and the SOx of the exhaust gas flowing out from the NOx storage reduction catalyst An output gas SOx concentration detection means for detecting a concentration; and a concentration difference between the SOx concentration detected by the input gas SOx concentration detection means and the SOx concentration detected by the output gas SOx concentration detection means; The SOx occlusion amount is estimated based on the intake air amount or the exhaust gas amount of the internal combustion engine, and when the SOx occlusion amount exceeds a predetermined amount, the poisoning recovery execution timing determination means It can be determined that it is time to execute the recovery process. This is because when the SOx concentration upstream of the NOx storage reduction catalyst is higher than the SOx concentration downstream of the NOx storage reduction catalyst, it can be considered that the concentration difference is absorbed by the NOx storage reduction catalyst.

  Input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, and output gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing out of the NOx storage reduction catalyst And the poisoning recovery execution timing determination means, when the SOx concentration detected by the output gas SOx concentration detection means approaches a predetermined level with respect to the SOx concentration detected by the input gas SOx concentration detection means, It can be determined that it is time to execute the SOx poisoning recovery process. This is because as the SOx accumulation amount of the NOx storage reduction catalyst approaches the saturated state, the SOx concentration downstream of the NOx storage reduction catalyst approaches the SOx concentration upstream of the NOx storage reduction catalyst.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, when the input gas SOx concentration detection means and the output gas SOx concentration detection means are provided, the SOx poisoning recovery process is executed by the poisoning recovery means. The difference in concentration between the SOx concentration detected by the output gas SOx concentration detection means and the SOx concentration detected by the input gas SOx concentration detection means, and the intake air amount or exhaust gas amount of the internal combustion engine. Based on this, the amount of released SOx released from the NOx storage reduction catalyst is estimated, and the amount of released SOx is subtracted from the amount of SOx stored estimated to be stored in the NOx storage reduction catalyst, thereby storing the storage. The remaining amount of SOx remaining in the reduced NOx catalyst is estimated, and when the remaining amount of SOx is reduced to a predetermined amount, the SOx poisoning recovery process by the poisoning recovery means is terminated. It can be. If the SOx concentration downstream of the NOx storage reduction catalyst is larger than the SOx concentration upstream of the NOx storage reduction catalyst, the difference in concentration can be considered as SOx released from the NOx storage reduction catalyst, and the intake air This is because the released SOx amount can be calculated and estimated based on the amount or the exhaust gas amount.

  The exhaust gas purification apparatus for an internal combustion engine according to the present invention includes a heat deterioration suppressing means for suppressing the heat deterioration of the NOx storage reduction catalyst, and the heat deterioration suppressing means is the heat deterioration determined by the heat deterioration determining means. It is not activated when the degree is below a predetermined level, but can be activated when the degree exceeds the predetermined level. Thereby, it can suppress that thermal deterioration progresses more than that, and can suppress the fall of the NOx occlusion capability of a NOx storage reduction catalyst.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, the thermal deterioration suppressing means may be a fuel cut prohibition control that prohibits a fuel cut in a high temperature operation region of the internal combustion engine. When fuel cut is performed in the high temperature operating range, exhaust gas with high oxygen concentration flows when the high temperature storage reduction type NOx catalyst is in a high temperature state, which promotes sintering of the catalyst material that causes thermal degradation. End up. This can be prevented by prohibiting fuel cut in the high temperature operation region.

  In the exhaust gas purification apparatus for an internal combustion engine according to the present invention, the thermal deterioration suppressing means may be a lean operation region reduction control for reducing a lean operation region in a high temperature operation region of the internal combustion engine. By reducing the lean operation region in the high temperature operation region, it is possible to reduce the flow of exhaust gas with high oxygen concentration to the NOx storage reduction catalyst in the high temperature operation region, and as a result, thermal degradation of the NOx storage reduction catalyst Can be suppressed. Further, the thermal degradation suppressing means increases the amount of rich or stoichiometric exhaust gas flowing into the NOx catalyst according to the degree of thermal degradation, and / or shortens the period during which the rich or stoichiometric exhaust gas flows into the NOx catalyst. Rich spike control can be performed. In this way, it is possible to increase the amount of reducing agent for releasing and reducing NOx according to the degree of thermal deterioration, and to suppress a decrease in action due to thermal deterioration of the NOx storage reduction catalyst.

  According to the exhaust gas purification apparatus for an internal combustion engine according to the present invention, it is possible to determine the degree of thermal deterioration of the NOx storage reduction catalyst by including the thermal deterioration determining means for determining the degree of thermal deterioration of the NOx storage reduction catalyst. . Therefore, it is possible to know that the NOx purification performance is deteriorated and cannot be recovered, and it is possible to avoid a situation where NOx in the exhaust gas is not purified by replacing the catalyst.

  The exhaust gas purification apparatus for an internal combustion engine according to the present invention further includes a heat deterioration suppressing means for suppressing the heat deterioration of the NOx storage reduction catalyst, and the heat deterioration suppressing means is the heat deterioration determined by the heat deterioration determining means. When the degree of thermal degradation of the NOx storage reduction catalyst reaches the predetermined level, the thermal degradation progresses after the degree of thermal degradation of the NOx storage reduction catalyst reaches the predetermined level. Can be suppressed.

  Embodiments of an exhaust gas purification apparatus for an internal combustion engine according to the present invention will be described below with reference to the drawings of FIGS.

  FIG. 1 is a diagram showing a schematic configuration when the present invention is applied to a vehicle gasoline engine capable of lean combustion. In this figure, reference numeral 1 is an engine body, reference numeral 2 is a piston, reference numeral 3 is a combustion chamber, reference numeral 4 is a spark plug, reference numeral 5 is an intake valve, reference numeral 6 is an intake port, reference numeral 7 is an exhaust valve, and reference numeral 8 is an exhaust port. Respectively.

  The intake port 6 is connected to a surge tank 10 via a corresponding branch pipe 9, and a fuel injection valve 11 for injecting fuel into the intake port 6 is attached to each branch pipe 9. The surge tank 10 is connected to an air cleaner 13 via an intake duct 12 and an air flow meter 21, and a throttle valve 14 is disposed in the intake duct 12.

  On the other hand, the exhaust port 8 is connected via an exhaust manifold 15 and an exhaust pipe 16 to a casing 18 containing an NOx storage reduction catalyst 17 (in the following description, sometimes abbreviated as NOx catalyst). A muffler (not shown) is connected via 19.

  An electronic control unit (ECU) 30 for engine control is composed of a digital computer, and is connected to each other by a bidirectional bus 31. A ROM (Read Only Memory) 32, a RAM (Random Access Memory) 33, and a CPU (Central Processor Unit) 34 are connected to each other. An input port 35 and an output port 36. The air flow meter 21 generates an output voltage proportional to the amount of intake air, and this output voltage is input to the input port 35 via the AD converter 38.

  The exhaust pipe 16 upstream of the casing 18 has an input gas SOx sensor (input gas SOx concentration detection means) that generates an output voltage proportional to the SOx concentration of exhaust gas flowing into the NOx catalyst 17 (hereinafter referred to as input gas). ) 23 is provided. On the other hand, in the exhaust pipe 19 downstream of the casing 18, an output gas SOx sensor (output gas SOx concentration) that generates an output voltage proportional to the SOx concentration of exhaust gas flowing out from the NOx catalyst 17 (hereinafter referred to as output gas). Detection means) 24, a temperature sensor 25 for generating an output voltage proportional to the temperature of the output gas, and an air-fuel ratio sensor 27 for generating an output voltage representing the air-fuel ratio of the output gas are attached. The output voltages of the SOx sensors 23 and 24, the temperature sensor 25, and the air-fuel ratio sensor 27 are input to the input port 35 via corresponding AD converters 38, respectively.

  The input port 35 is connected to a rotational speed sensor 26 that generates an output pulse representing the engine rotational speed. The output port 36 is connected to the spark plug 4 and the fuel injection valve 11 via a corresponding drive circuit 39, respectively.

In this gasoline engine, the fuel injection time TAU is calculated based on the following equation, for example. TAU = TP ・ K
Here, TP indicates the basic fuel injection time, and K indicates a correction coefficient. The basic fuel injection time TP indicates the fuel injection time required to make the air-fuel ratio of the air-fuel mixture supplied into the engine cylinder the stoichiometric air-fuel ratio. This basic fuel injection time TP is obtained in advance by experiments, and is previously stored in the ROM 32 in the form of a map as shown in FIG. 2 as a function of the engine load Q / N (intake air amount Q / engine speed N) and the engine speed N. Is remembered. The correction coefficient K is a coefficient for controlling the air-fuel ratio of the air-fuel mixture supplied into the engine cylinder. If K = 1.0, the air-fuel mixture supplied into the engine cylinder becomes the stoichiometric air-fuel ratio. On the other hand, when K <1.0, the air-fuel ratio of the air-fuel mixture supplied into the engine cylinder becomes larger than the stoichiometric air-fuel ratio, that is, lean, and when K> 1.0, the air-fuel ratio is supplied into the engine cylinder. The air-fuel ratio of the air-fuel mixture is smaller than the stoichiometric air-fuel ratio, that is, becomes rich.

  In the gasoline engine of this embodiment, the value of the correction coefficient K is set to a value smaller than 1.0 in the engine low and medium load operation region, and lean air-fuel ratio control is performed. During warm-up operation, acceleration, and high-speed constant speed operation, the value of the correction coefficient K is set to 1.0 and the stoichiometric control is performed. In the engine full load operation region, the value of the correction coefficient K is from 1.0. Is set to a large value so that rich air-fuel ratio control is performed.

  The internal combustion engine is usually most frequently operated at low and medium loads. Therefore, the value of the correction coefficient K is made smaller than 1.0 during most of the operation period, and the lean air-fuel mixture is combusted.

FIG. 3 schematically shows the concentrations of typical components in the exhaust gas discharged from the combustion chamber 3. As can be seen from this figure, the concentration of unburned HC and CO in the exhaust gas discharged from the combustion chamber 3 increases as the air-fuel ratio of the air-fuel mixture supplied into the combustion chamber 3 becomes richer. The concentration of oxygen O ₂ in the exhaust gas discharged increases as the air-fuel ratio of the air-fuel mixture supplied into the combustion chamber 3 becomes leaner.

  The NOx catalyst (occlusion reduction type NOx catalyst) 17 accommodated in the casing 18 uses, for example, alumina as a carrier, and an alkali metal such as potassium K, sodium Na, lithium Li, cesium Cs, barium Ba, etc. on this carrier. At least one selected from alkaline earths such as calcium Ca, lanthanum La, and rare earths such as yttrium Y, and a noble metal such as platinum Pt are supported.

When this NOx catalyst 17 is disposed in the exhaust passage of the engine, the NOx catalyst 17 absorbs NOx when the air-fuel ratio of the inflowing exhaust gas (hereinafter sometimes referred to as exhaust air-fuel ratio) is lean, and the NOx catalyst 17 in the inflowing exhaust gas When the oxygen concentration is lowered, NOx is absorbed and released to release the absorbed NOx. Here, the exhaust air-fuel ratio refers to the ratio of air and fuel (hydrocarbon) supplied into the engine intake passage and the exhaust passage upstream of the NOx catalyst 17.

  When fuel (hydrocarbon) or air is not supplied into the exhaust passage upstream of the NOx catalyst 17, the exhaust air-fuel ratio matches the air-fuel ratio of the air-fuel mixture supplied into the combustion chamber 3. Therefore, in this case The NOx catalyst 17 absorbs NOx when the air-fuel ratio of the air-fuel mixture supplied into the combustion chamber 3 is lean, and absorbs NOx when the oxygen concentration in the air-fuel mixture supplied into the combustion chamber 3 decreases. Will be released.

  It is considered that the NOx absorption / release action by the NOx catalyst 17 is performed by the mechanism shown in FIG. Hereinafter, this mechanism will be described by taking as an example the case where platinum Pt and barium Ba are supported on the support, but the same mechanism can be obtained by using other noble metals, alkali metals, alkaline earths, and rare earths.

First, when the inflowing exhaust gas becomes considerably leaner, the oxygen concentration in the inflowing exhaust gas greatly increases, and as shown in FIG. 4 (A), oxygen O ₂ becomes platinum Pt in the form of O ₂ ⁻ or O ^2−. Adhere to the surface. On the other hand, NO contained in the inflowing exhaust gas reacts with O ₂ ⁻ or O ²⁻ on the surface of platinum Pt to become NO ₂ (2NO + O ₂ → 2NO ₂ ).

Next, a part of the generated NO ₂ is oxidized on platinum Pt while being absorbed in Ba and combined with barium oxide BaO, and as shown in FIG. 4 (A), the form of nitrate ions NO ₃ ⁻ is formed. To diffuse into Ba. In this way, NOx is absorbed into the NOx catalyst 17.

As long as the oxygen concentration in the inflowing exhaust gas is high, NO ₂ is generated on the surface of platinum Pt, and as long as the NOx absorption capacity of the NOx catalyst 17 is not saturated, NO ₂ is absorbed in the NOx catalyst 17 and nitrate ions NO ₃ ⁻ are generated. Generated.

In contrast, when the oxygen concentration in the inflowing exhaust gas decreases and the amount of NO ₂ produced decreases, the reaction proceeds in the reverse direction (NO ₃ ⁻ → NO ₂ ), and nitrate ions NO ₃ ^{− in} Ba are converted to NO _2. Or released from Ba in the form of NO. That is, when the oxygen concentration in the inflowing exhaust gas decreases, NOx is released from the NOx catalyst 17. As shown in FIG. 3, if the lean degree of the inflowing exhaust gas is lowered, the oxygen concentration in the inflowing exhaust gas is lowered. Therefore, if the lean degree of the inflowing exhaust gas is lowered, NOx is released from the NOx catalyst 17. The Rukoto.

On the other hand, when the air-fuel mixture supplied into the combustion chamber 3 at this time becomes a stoichiometric or rich air-fuel ratio, a large amount of unburned HC and CO are discharged from the engine as shown in FIG. CO is oxidized by reacting with oxygen O ₂ ⁻ or O ²⁻ on platinum Pt.

Further, when the exhaust air-fuel ratio becomes the stoichiometric air-fuel ratio or the rich air-fuel ratio, the oxygen concentration in the inflowing exhaust gas extremely decreases, so that NO ₂ or NO is released from the NOx catalyst 17, and this NO ₂ or NO is shown in FIG. As shown in (B), it reacts with unburned HC and CO and is reduced to N ₂ .

That, HC in the inflowing exhaust gas, CO, first platinum Pt on the oxygen O ₂ in ^- or O ^2- immediately be reacted with oxidized and then the oxygen O ₂ on the platinum Pt ^- is or O ^2- is consumed even yet HC, any remaining CO is the HC, NOx of NOx and the inflow exhaust gas discharged from the NOx catalyst 17 by the CO is made to reduction to N _2.

When NO ₂ or NO no longer exists on the surface of platinum Pt in this manner, NO ₂ or NO is released from the NOx catalyst 17 to the next, and further reduced to N ₂ . Therefore, when the exhaust air-fuel ratio is made the stoichiometric air-fuel ratio or rich, NOx is released from the NOx catalyst 17 within a short time.

Thus, NOx when the exhaust air-fuel ratio becomes lean is absorbed in the NOx catalyst 17, NOx when the exhaust air-fuel ratio to the stoichiometric air-fuel ratio or rich is released in a short time from the NOx catalyst 17 is reduced to N ₂ The Accordingly, NOx emission into the atmosphere can be prevented.

  By the way, in this embodiment, as described above, the air-fuel mixture supplied into the combustion chamber 3 is made rich at the time of full load operation, and the air-fuel mixture is made to be the stoichiometric air-fuel ratio at the time of high load operation, etc. Since the air-fuel mixture is made lean during operation, NOx in the exhaust gas is absorbed by the NOx catalyst 17 during low and medium load operation, and NOx is released and reduced from the NOx catalyst 17 during full load operation and high load operation. Will be. However, if the frequency of full load operation or high load operation is low, the frequency of low and medium load operations is high and the operation time is long, NOx release / reduction will not be in time, and the NOx absorption capacity of the NOx catalyst 17 will be saturated. This makes it impossible to absorb NOx.

  Therefore, in this embodiment, when the lean air-fuel mixture is being burned, that is, when the medium / low load operation is being performed, the combustion of the stoichiometric or rich air-fuel mixture is performed in a spike manner (short time) in a relatively short cycle. The air-fuel ratio of the air-fuel mixture is controlled so that NOx is released and reduced in a short cycle. In this way, in order to absorb and release NOx, the exhaust air-fuel ratio (air-fuel ratio of the air-fuel mixture in this embodiment) is “lean” and “spike-like stoichiometric or rich air-fuel ratio (rich spike) in a relatively short cycle. ) "Is controlled to be repeated alternately, which is referred to as lean / rich spike control. In this application, the lean / rich spike control is included in the lean air-fuel ratio control.

On the other hand, the fuel contains sulfur (S), and when sulfur in the fuel burns, sulfur oxides (SOx) such as SO2 and SO3 are generated, and the NOx catalyst 17 also absorbs these SOx in the exhaust gas. . The SOx absorption mechanism of the NOx catalyst 17 is considered to be the same as the NOx absorption mechanism. That is, the case where platinum Pt and barium Ba are supported on the carrier as in the description of the NOx absorption mechanism will be described as an example. As described above, when the exhaust air-fuel ratio is lean, oxygen O ₂ is It adheres to the surface of the platinum Pt of the NOx catalyst 17 in the form of O ₂ ⁻ or O ²⁻ , and SOx (for example, SO ₂ ) in the inflowing exhaust gas is oxidized on the surface of the platinum Pt to become SO ₃ .

Thereafter, the generated SO ₃ is further oxidized on the surface of platinum Pt, absorbed into Ba, and combined with barium oxide BaO, and diffused into Ba in the form of sulfate ions SO ₄ ²⁻ to form sulfate BaSO ₄ . Form. Since BaSO ₄ is easy to coarsen crystals and is relatively stable, once it is produced, it is difficult to decompose and release. When the amount of BaSO ₄ produced in the NOx catalyst 17 increases, the amount of BaO that can participate in the absorption of the NOx catalyst 17 decreases, and the NOx absorption capacity decreases. This is SOx poisoning. Therefore, in order to maintain the NOx absorption capacity of the NOx catalyst 17 high, it is necessary to execute an SOx poisoning recovery process for releasing SOx absorbed by the NOx catalyst 17 at an appropriate timing.

  In order to release SOx from the NOx catalyst 17, the air-fuel ratio of the inflowing exhaust gas needs to be the stoichiometric or rich air-fuel ratio, and it is found that the higher the catalyst temperature of the NOx catalyst 17, the easier it is to release. ing. Therefore, in the SOx poisoning recovery process, the catalyst temperature of the NOx catalyst 17 is set to a predetermined high temperature at which SOx is easily released (hereinafter referred to as the SOx release temperature), and the exhaust gas having a stoichiometric or rich air-fuel ratio is converted to the NOx catalyst 17. Execute by flowing to.

  In this embodiment, even when the air-fuel ratio of the exhaust gas is set to the stoichiometric air-fuel ratio or the rich air-fuel ratio for SOx poisoning recovery processing, the amount of fuel injected from the fuel injection valve 11 is controlled by the ECU 30 and burned. This is performed by controlling the air-fuel ratio of the air-fuel mixture supplied to the chamber 3 to the stoichiometric air-fuel ratio or the rich air-fuel ratio. Therefore, the ECU 30 and the fuel injection valve 11 constitute part of the poisoning recovery means.

  Next, a method for detecting the degree of thermal deterioration of the NOx catalyst 17 of the exhaust purification system in this embodiment will be described. FIG. 5 shows that every time the SOx poisoning of the NOx catalyst 17 reaches a predetermined level, the SOx poisoning recovery process is executed until the SOx stored in the NOx catalyst 17 is completely released, and immediately after the SOx poisoning recovery. 3 is a graph showing a result of an experiment in which the NOx purification performance of the NOx catalyst 17 is measured. The NOx purification performance of the NOx catalyst 17 decreases every time the SOx poisoning recovery process is executed.

  As described above, the SOx poisoning deterioration of the NOx catalyst 17 can be recovered by executing the SOx poisoning recovery process. However, since the NOx catalyst 17 cannot be recovered from the heat deterioration, the SOx poisoning recovery is impossible. It can be said that the performance recovery portion immediately after the poisoning recovery process is a performance decrease due to SOx poisoning, and the portion where the performance recovery is impossible is a performance decrease due to thermal deterioration.

  Therefore, if the NOx storage capability of the NOx catalyst 17 when it is new and the NOx storage capability of the NOx catalyst 17 immediately after the SOx poisoning recovery process can be detected, the degree of thermal deterioration is detected from the difference between these NOx storage capabilities. be able to.

  In this embodiment, the NOx storage capacity is detected as follows. First, a lean air-fuel ratio exhaust gas is continuously supplied to the NOx catalyst 17 to saturate the NOx storage capacity of the NOx catalyst 17 so that no more NOx can be stored. Next, the exhaust gas flowing into the NOx catalyst 17, that is, the air-fuel ratio of the input gas is switched from lean to rich, and the rich air-fuel ratio exhaust gas continues to flow through the NOx catalyst 17, so that the NOx stored in the NOx catalyst 17 is stored. Release and reduce the entire amount. At this time, even if the air-fuel ratio of the input gas is switched from lean to rich, the exhaust gas at the outlet of the NOx catalyst 17, that is, the air-fuel ratio of the output gas, does not immediately switch to rich, but remains close to the theoretical air-fuel ratio for a while. . This is because HC and CO in the input gas are consumed as a reducing agent for the reduction of NOx stored in the NOx catalyst 17. When all of the NOx stored in the NOx catalyst 17 is released and reduced and HC and CO in the input gas are no longer consumed as a reducing agent, the air-fuel ratio of the output gas changes to rich.

  Therefore, after the NOx occlusion capacity of the NOx catalyst 17 is saturated in this way, a NOx release / reduction process (hereinafter referred to as a saturated NOx release process) is executed, and the air-fuel ratio of the output gas at that time is determined. The time that is detected by the air-fuel ratio sensor 27 and the saturated NOx releasing process is started, and the time during which the air-fuel ratio of the output gas maintains the stoichiometric air-fuel ratio, in other words, the time until the air-fuel ratio of the output gas switches from the stoichiometric air-fuel ratio to rich , The required time (hereinafter, this required time is referred to as a rich switching time) becomes a barometer representing the NOx storage capacity of the NOx catalyst 17, that is, a barometer of the purification performance of the NOx catalyst 17.

  FIG. 6 shows an example of the temporal change in the air-fuel ratio of the incoming gas and the air-fuel ratio of the outgoing gas during the saturated NOx release process. In the new NOx catalyst 17, the rich switching time is t1. The rich switching time of the NOx catalyst 17 in which the thermal deterioration has progressed to some extent is t2, which is shorter than t1.

In this embodiment, the determination of the timing for executing the SOx poisoning recovery process for the NOx catalyst 17 is also performed using the rich switching time. More specifically, in the exhaust emission control device of this embodiment, the saturated NOx release process is executed on the NOx catalyst 17 at an appropriate timing, for example, every fixed traveling distance or every fixed fuel consumption, and the rich at that time Measure the switching time. When the measured rich switching time becomes shorter than the predetermined time t3 shown in FIG. 6, it can be considered that the NOx purification performance of the NOx catalyst 17 has decreased to a predetermined level. It is determined that it is time to execute the poison recovery process.

  Further, in the exhaust purification apparatus of this embodiment, after the SOx poisoning recovery process is completed, the saturated NOx release process is executed to measure the rich switching time, and the rich switching time t2 measured and the new NOx catalyst 17 are richly switched. When the difference from the time t1 is calculated and the difference is longer than the predetermined time t4, it is determined that the thermal deterioration of the NOx catalyst 17 has progressed to a predetermined degree, and the thermal deterioration suppressing means is to suppress the thermal deterioration. Actuate. The rich switching time t1 of the new NOx catalyst 17 is experimentally obtained in advance and stored in the ROM 32 of the ECU 30, and a threshold t4 for determining that the thermal deterioration suppressing means should be operated is also set in advance. It memorize | stores in ROM of ECU30.

  Next, a method for suppressing thermal degradation will be described. For example, in general, when an engine is decelerated, fuel cut is executed, but when thermal degradation has progressed to a predetermined level, the engine is in a high temperature operating range. When the vehicle is decelerated, it is possible to suppress thermal degradation by prohibiting fuel cut. This is because when the engine is in the high temperature operation region, the NOx catalyst 17 is also in a high temperature state, and if fuel cut is performed at this time, exhaust gas having a high oxygen concentration flows into the NOx catalyst 17. It is known that the sintering of the catalyst material (Pt) in the NOx catalyst 17 is faster as the oxygen concentration is higher when the catalyst temperature is the same. Therefore, if fuel cut is performed during deceleration in the high temperature operation region, exhaust gas with a high oxygen concentration flows when the catalyst temperature is high, which promotes sintering. Therefore, if the fuel cut is prohibited when the deceleration operation is performed in the high temperature operation region, sintering of the NOx catalyst 17 can be suppressed and thermal degradation can be suppressed. In this case, the fuel cut prohibition control that prohibits the fuel cut in the high temperature operation region constitutes the thermal deterioration suppressing means.

  Further, as another method for suppressing thermal degradation, when the thermal degradation has progressed to a predetermined degree, the leanness in the high temperature operation region of the engine is higher than before that (that is, when the thermal degradation has not progressed to the predetermined degree). There is a way to reduce the operating range. This is also the same reason as described above, and when the catalyst temperature of the NOx catalyst 17 is high, the thermal deterioration of the NOx catalyst 17 can be suppressed by lowering the oxygen concentration of the input gas. As a specific control method, a part or all of the high temperature operation region and the lean operation region before the heat deterioration has progressed to a predetermined degree may be stoichiometric ( Change to the stoichiometric air-fuel ratio) operating range. In this case, the lean operation region reduction control for reducing the lean operation region in the high temperature operation region constitutes the thermal deterioration suppressing means.

  Next, a routine for determining the thermal deterioration of the NOx catalyst 17 in this embodiment will be described with reference to FIG. A flowchart including the steps constituting the control routine is stored in the ROM 32 of the ECU 30, and the control routine is executed by the CPU 34 at regular intervals.

  <Step 101> First, in step 101, the ECU 100 determines whether it is time to execute the SOx poisoning recovery process on the NOx catalyst 17. As described above, in this embodiment, the determination as to whether or not the SOx poisoning recovery process execution time is performed is performed by performing a saturated NOx release process every predetermined period, and the rich switching time measured at that time becomes smaller than the threshold value t3. It is determined that it is time to execute the SOx poisoning recovery process. If a negative determination is made in step 101, the ECU 30 once ends the execution of this routine.

  <Step 102> If an affirmative determination is made in step 101, the ECU 30 proceeds to step 102 and executes SOx poisoning recovery processing. In the SOx poisoning recovery process, when the NOx catalyst 17 has not reached the SOx release temperature, a predetermined temperature increase process is executed to make the catalyst temperature of the NOx catalyst 17 equal to or higher than the SOx release temperature, and the NOx catalyst 17 This is done by making the air-fuel ratio of the input gas slightly richer than stoichiometric.

  <Step 103> Next, the ECU 30 proceeds to Step 103 and determines whether or not the SOx poisoning recovery process is completed. Here, the SOx poisoning recovery process is executed until the SOx absorbed in the NOx catalyst 17 is almost completely released. The determination of the completion of the SOx poisoning recovery process will be described later. If a negative determination is made in step 103, the ECU 30 returns to step 102 and continues execution of the SOx poisoning recovery process.

  <Steps 104 and 105> When an affirmative determination is made in Step 103, the ECU 30 proceeds to Step 104, executes a saturated NOx release process, and further proceeds to Step 105 to measure the rich switching time t.

  <Step 106> Next, the ECU 30 proceeds to step 106 and calculates the difference between the rich switching time t1 of the new NOx catalyst 17 stored in advance in the ROM 32 of the ECU 30 and the rich switching time t measured in step 105. To do. That is, the current degree of thermal deterioration of the NOx catalyst 17 is calculated.

  <Step 107> Next, the ECU 30 proceeds to step 107 and determines whether or not the rich switching time difference (degree of thermal deterioration) calculated in step 106 is greater than or equal to a preset threshold value t4. If a negative determination is made in step 107, the ECU 30 once ends the execution of this routine.

  <Step 108> If an affirmative determination is made in Step 107, it is determined that the degree of thermal deterioration of the NOx catalyst 17 has reached a predetermined level, and the ECU 30 proceeds to Step 108 to operate the thermal deterioration suppressing means, and this routine The execution of is temporarily terminated. By the operation of the thermal deterioration suppression means, that is, the execution of the fuel cut prohibition control in the high temperature operation region or the lean operation region decrease control in the high temperature operation region, the subsequent progress of the thermal deterioration of the NOx catalyst 17 is suppressed. Is done.

  In this embodiment, the ECU 30 executes step 101 in the thermal deterioration determination processing routine, thereby realizing the poisoning recovery execution time determination means in the present invention. The poisoning recovery means in the present invention is realized, and the ECU 30 executes Step 104 and Step 105, thereby realizing the storage capacity detecting means in the present invention. The ECU 30 executes Step 106 and Step 107, thereby The thermal deterioration determination means in the invention is realized.

  Next, the SOx poisoning recovery process in this embodiment will be described with reference to FIG. FIG. 8 shows the air-fuel ratio of the input gas of the NOx catalyst 17 during the SOx poisoning recovery process in this embodiment, the SOx concentration of the input gas detected by the input gas SOx sensor 23, and the output gas SOx sensor 24. It is the figure which showed the time-dependent change of SOx density | concentration of the emitted gas. It is assumed that the catalyst temperature of the NOx catalyst 17 is equal to or higher than the SOx release temperature during the execution period of the SOx poisoning recovery process.

First, the air-fuel ratio of the input gas is changed from the lean air-fuel ratio to the stoichiometric air-fuel ratio according to the SOx poisoning recovery process execution command, and the richness of the air-fuel ratio of the input gas is gradually increased. When the output gas SOx concentration detected by the output gas SOx sensor 24 matches the input gas SOx concentration detected by the input gas SOx sensor 23, the air-fuel ratio of the input gas becomes constant at the rich air-fuel ratio. Hold. After the output gas SOx concentration coincides with the input gas SOx concentration, SOx is substantially released from the NOx catalyst 17, so the output gas SOx concentration becomes larger than the input gas SOx concentration, and the output gas is discharged at a predetermined concentration. The SOx concentration becomes almost constant. Further, if SOx release from the NOx catalyst 17 continues thereafter, the amount of SOx released from the NOx catalyst 17 decreases, so that the concentration of the outgas SOx decreases, and when there is no SOx remaining in the NOx catalyst 17, The gas SOx concentration becomes lower than the input gas SOx concentration. Therefore, if the SOx poisoning recovery process is continued until the output gas SOx concentration is lower than the input gas SOx concentration by a predetermined value, it can be considered that the NOx catalyst 17 has been almost completely recovered from the SOx poisoning. In this embodiment, the SOx poisoning recovery process is continued until the outgas SOx concentration becomes lower than the poisoning recovery completion level in FIG.

  In this embodiment, a case will be described in which the degree of thermal deterioration of the NOx catalyst 17 of the exhaust purification device is detected based on a change in the NOx purification rate of the NOx catalyst. FIG. 13 is a schematic view of the exhaust emission control device in this embodiment. The engine body 40 is provided with four cylinders 41, and a fuel injection valve 42 is attached to an intake port connected to each cylinder 41. . The intake manifold 43 is connected to an air cleaner 45 via an intake duct 44. A throttle valve 46 is provided in the intake duct 44.

  On the other hand, the exhaust gas is connected to a casing 49 containing the NOx storage reduction catalyst 50 via an exhaust manifold 47 and an exhaust pipe 48, and the casing 49 is connected to a muffler (not shown) via an exhaust pipe 51. The other components such as the ECU 30 and the NOx catalyst 17 are the same as those in the exhaust gas purification apparatus according to the first embodiment, and thus the same reference numerals are given and the description thereof is omitted.

  An output gas NOx sensor 50 that generates an output voltage proportional to the NOx concentration of the output gas flowing out from the NOx catalyst 17 is provided downstream of the casing 49, and this output voltage is input to the input port 35 of the ECU 30. FIG. 14 is a diagram showing an example of the NOx purification rate by the NOx catalyst 17. Here, the input NOx indicates the NOx concentration per unit time in the exhaust gas flowing into the NOx catalyst 17, and the output NOx indicates the NOx concentration per unit time in the exhaust gas flowing out from the NOx catalyst 17. Here, when the NOx concentration per unit time in the exhaust gas discharged from the NOx catalyst 17 reaches the threshold value X, the exhaust gas is stoichiometric or rich, and NOx stored in the NOx catalyst 17 is released and reduced to reduce NOx. The NOx storage capacity of the catalyst 17 is recovered. However, when the operation with the exhaust gas lean is continued and NOx in the exhaust gas is occluded by the NOx catalyst 17, the saturation state is reached again, and the concentration of the output NOx reaches the threshold value X. Therefore, NOx is released and reduced by executing rich spike again.

  However, if this process is repeated, as detailed in the first embodiment, the SOx poisoning of the NOx catalyst 17 reaches a predetermined level, so that the SOx poisoning recovery process is executed. The SOx poisoning of the NOx catalyst 17 can be recovered by executing the SOx poisoning recovery process. However, since the thermal deterioration of the NOx catalyst 17 cannot be recovered, the performance unrecoverable part immediately after the SOx poisoning recovery process. May be a performance degradation due to thermal degradation.

Therefore, if the NOx purification rate of the NOx catalyst 17 when it is new and the NOx purification rate immediately after the SOx poisoning recovery process are measured and compared, the degree of thermal deterioration can be known from the difference in the NOx purification performance. . Here, the NOx purification rate is based on the NOx amount (incoming NOx amount) in the exhaust gas flowing into the NOx catalyst and the NOx amount (outgoing NOx amount) in the exhaust gas by the NOx detection means installed downstream of the NOx catalyst. Is required. At this time, the amount of the input NOx can be calculated from the integrated value of the NOx concentration per unit time and the exhaust gas amount from the output value by attaching a NOx sensor to the exhaust passage upstream of the NOx catalyst 17. The amount of input NOx can also be obtained by the following method.

  That is, when the lean air-fuel mixture is combusting, the amount of NOx discharged from the engine per unit time increases as the engine load increases, and the amount of NOx discharged from the engine per unit time increases as the engine speed increases. Increase. Therefore, the NOx amount per unit time is a function of the engine load and the engine speed. In this case, since the engine load can be represented by the absolute pressure in the surge tank, the amount NOXA of the output NOx per unit time is a function of the absolute pressure PM in the surge tank and the engine speed N. Therefore, in this embodiment, the amount of NOx per unit time is obtained beforehand by experiment as a function of the absolute pressure PM and the engine speed N, and this is stored in the RAM of the ECU 30 in the form of a map as shown in FIG. .

  On the other hand, by attaching a NOx sensor to the exhaust passage downstream of the NOx catalyst 17, the NOx concentration per unit time is detected from the output value, so the amount of output NOx is the integrated value of this NOx concentration and the amount of exhaust gas. Can be calculated based on In this way, the NOx purification rate of the NOx catalyst 17 is measured, and this is compared with the purification rate or required purification rate in the case of an initial new article, so that the timing of SOx poisoning regeneration can be determined.

  If the NOx purification rate of the NOx catalyst 17 when it is new and the NOx purification rate of the NOx catalyst 17 immediately after the SOx poisoning recovery process can be detected and compared, the NOx catalyst 17 can be calculated from the difference between the purification rates. The degree of thermal degradation of can be detected. The NOx purification rate and the necessary purification rate of the new NOx catalyst 17 are experimentally obtained in advance and stored in the ROM 32 of the ECU 30, and the necessary purification rate when it is determined that the thermal deterioration suppressing means should be operated. Are preset and stored in the ROM of the ECU 30.

  In this embodiment, the NOx purification performance is detected as follows. First, a lean air-fuel ratio exhaust gas is continuously supplied to the NOx catalyst 17 to saturate the NOx storage capacity of the NOx catalyst 17 so that no more NOx can be stored. At this time, the purification performance of the NOx catalyst is measured in consideration of the temperature window.

  Next, the exhaust gas flowing into the NOx catalyst 17, that is, the air-fuel ratio of the input gas is switched from lean to rich, and the rich air-fuel ratio exhaust gas continues to flow through the NOx catalyst 17, so that the NOx stored in the NOx catalyst 17 is stored. Release and reduce the entire amount. At this time, even if the air-fuel ratio of the input gas is switched from lean to rich, the exhaust gas at the outlet of the NOx catalyst 17, that is, the air-fuel ratio of the output gas, does not immediately switch to rich, but remains close to the theoretical air-fuel ratio for a while. . This is because HC and CO in the input gas are consumed as a reducing agent for the reduction of NOx stored in the NOx catalyst 17. When all of the NOx stored in the NOx catalyst 17 is released and reduced, and HC and CO in the input gas are no longer consumed as a reducing agent, the air-fuel ratio of the output gas changes to rich.

  Further, in this embodiment, the timing for executing the SOx poisoning recovery process for the NOx catalyst 17 is determined by whether or not the NOx purification rate has become a predetermined value or less. More specifically, in the exhaust gas purification apparatus of this embodiment, the saturated NOx release process is performed on the NOx catalyst 17 at an appropriate timing, for example, every fixed travel distance or every fixed fuel consumption, and the NOx at that time Measure the purification rate. In this measurement, the purification performance of the NOx catalyst under each load and temperature condition is grasped by the output side NOx sensor 50.

  And when the measured NOx purification rate falls below the threshold value x shown in FIG. 14, it is considered that the NOx purification performance of the NOx catalyst 17 has fallen to a predetermined level. Further, this time is determined to be the time when the SOx poisoning recovery process should be executed.

  When the SOx poisoning recovery process is completed, the NOx purification rate is measured to determine whether the performance of the NOx catalyst has been recovered. As shown in FIG. 15, this is determined by whether or not the NOx purification rate exceeds the required purification rate within a predetermined temperature range (for example, about 300 ° C. to 420 ° C.). In FIG. 15, (1) shows the NOx purification rate when the NOx catalyst is new, and (2) shows the NOx purification rate when SOx is poisoned. In the state (2), SOx poisoning recovery is necessary, and (3) shows the purification rate after SOx poisoning recovery.

  If the required purification rate is not secured, next, a rich spike is executed according to the degree of thermal deterioration of the NOx catalyst. This is because when the lean mixture is burned in the internal combustion engine, that is, when the medium / low load operation is being performed, the combustion of the stoichiometric or rich mixture is performed in a spike-like (short time) with a relatively short cycle. As described above, the air-fuel ratio of the air-fuel mixture is controlled to release and reduce NOx in a short cycle. However, if the recovery from the performance deterioration is insufficient, the rich spike is increased. This includes both increasing the amount of rich spikes, or increasing the number of rich spikes, i.e. shortening the cycle of rich spikes, and either or both are performed in proportion to the degree of thermal degradation. .

  Next, in the exhaust purification system of this embodiment, after performing the rich spike control, the NOx purification rate is measured, and when the purification rate is below a predetermined level, the thermal deterioration of the NOx catalyst 17 does not restore performance. It is judged that the process has progressed to the extent possible, and the thermal deterioration suppressing means is operated to suppress the thermal deterioration. That is, even when such control is performed, a sufficient NOx purification rate cannot be ensured.

  First, lean operation is prohibited in a temperature range where performance is insufficient. This is to suppress the thermal deterioration of the NOx catalyst 17 by reducing the lean operation region and lowering the incoming gas oxygen concentration of the NOx catalyst 17 than when the thermal deterioration has not progressed to a predetermined degree. Specifically, as shown in FIG. 15, the lean operation is prohibited and the stoichiometric operation region is changed in the temperature region where the NOx catalyst performance is below the required purification rate (the region that does not return even if recovered). Is.

  Next, as another thermal degradation suppression method or a thermal degradation suppression method executed in conjunction with the above, as described in the first embodiment, when the engine is in a high temperature operation range, Even when it becomes, thermal degradation is suppressed by prohibiting fuel cut. Further, as a method for suppressing the thermal deterioration, a method is adopted in which the lean operation region in the high temperature operation region of the engine is reduced as compared with the case where the heat deterioration has not progressed to a predetermined degree. This overlaps the above-described range of prohibition of lean operation in a temperature range where performance is insufficient, but prohibits lean operation in all high temperature operation regions above a predetermined temperature.

  Hereinafter, the routine for determining the thermal deterioration of the NOx catalyst 17 in this embodiment will be described with reference to FIG. A flowchart including the steps constituting the control routine is stored in the ROM 32 of the ECU 30, and the control routine is executed by the CPU 34 at regular intervals.

  <Step 201> First, in step 201, the ECU 100 determines whether it is time to execute the SOx poisoning recovery process for the NOx catalyst 17. To determine whether it is time to execute the SOx poisoning recovery process, a saturated NOx release process is performed every predetermined period, and the NOx purification rate is measured after the release process is completed. This is calculated based on the output value of the outgoing NOx sensor 50. When this value becomes lower than the required purification rate, it is determined that it is time to execute the SOx poisoning recovery process. If a negative determination is made in step 201, the ECU 30 once terminates execution of this routine.

  <Step 202> If the determination in step 201 is affirmative, the ECU 30 proceeds to step 202 and executes SOx poisoning recovery processing. In the SOx poisoning recovery process, when the NOx catalyst 17 has not reached the SOx release temperature, a predetermined temperature increase process is executed to make the catalyst temperature of the NOx catalyst 17 equal to or higher than the SOx release temperature, and the NOx catalyst 17 This is done by making the air-fuel ratio of the input gas slightly richer than stoichiometric.

  <Step 203> Next, the ECU 30 proceeds to step 203 and determines whether or not the SOx poisoning recovery process is completed. Here, the SOx poisoning recovery process is executed until the SOx absorbed in the NOx catalyst 17 is almost completely released. If a negative determination is made in step 203, the ECU 30 returns to step 202 and continues execution of the SOx poisoning recovery process.

  <Step 204> If the determination in step 203 is affirmative, the ECU 30 proceeds to step 204 to execute a saturated NOx release process, and further proceeds to step 205 to measure the NOx purification rate.

  <Step 205> Next, the ECU 30 proceeds to step 205 and measures the NOx purification rate of the NOx catalyst 17.

  <Step 206> Proceeding to step 206, the ECU 30 determines whether or not the NOx purification rate measured in step 206 is equal to or greater than a preset required purification rate and the NOx catalyst function has been restored. If the determination in step 206 is affirmative, the ECU 30 once ends the execution of this routine.

  <Step 207> If a negative determination is made in step 206, rich spike control is executed to try the performance of the NOx catalyst 17.

  <Step 208> It is determined whether or not the NOx purification rate of the NOx catalyst has been recovered by the rich spike control executed in Step 207. This is determined by whether or not the NOx purification rate in a predetermined temperature range is lower than the required purification rate. If the purification rate is equal to or higher than the necessary purification rate, the ECU 30 once terminates execution of this routine.

  <Step 209> If the NOx purification rate is less than or equal to the required purification rate in step 208, lean operation in a temperature region where performance is insufficient is prohibited. When the NOx purification rate is less than or equal to the required purification rate, performance recovery is impossible and it is determined that thermal degradation is large.

  <Step 210> Further thermal deterioration suppression control is performed. This is a control for reducing the lean operation region in the high temperature operation region and prohibiting the fail cut in the high temperature operation region. As a result, the subsequent thermal deterioration of the NOx catalyst 17 is suppressed.

  In this embodiment, the ECU 30 executes step 201 in the thermal deterioration determination processing routine, thereby realizing the poisoning recovery execution time determination means in the second invention, and the ECU 30 executes step 202. Thus, the poisoning recovery means is realized, and the NOx purification rate measuring means is realized when the ECU 30 executes step 204 and step 205.

  Further, in this embodiment, when the NOx purification rate is not ensured by the rich spike control, it can be determined that the thermal deterioration of the NOx catalyst 17 is large, and the replacement of the catalyst can be promoted.

[Other Embodiments] The completion of the SOx poisoning recovery process execution can be determined by whether or not the execution time of the SOx poisoning recovery process exceeds a predetermined time. In this case, the poisoning recovery processing time necessary for almost completely releasing the SOx stored in the NOx catalyst 17 is experimentally obtained in advance, and this is stored in the ROM 32 of the ECU 30.

  Whether or not it is the SOx poisoning recovery processing execution time is determined as the SOx poisoning recovery processing execution time when the amount of sulfur passing through the NOx catalyst 17 exceeds a predetermined amount (hereinafter referred to as the allowable sulfur amount). May be.

  In that case, the sulfur concentration in the fuel is estimated from the SOx concentration of the input gas detected by the input gas SOx sensor 23, and the fuel consumption or travel distance corresponding to the allowable sulfur amount based on the estimated sulfur concentration in the fuel. And the time when the fuel consumption amount or travel distance is reached can be determined as the SOx poisoning recovery processing execution timing. Further, in this case, the estimated sulfur concentration in the fuel may be displayed on a panel or the like in front of the driver's seat so that the frequency of the SOx poisoning recovery process can be roughly determined.

  Alternatively, the amount of SOx flowing into the NOx catalyst 17 is calculated based on the SOx concentration of the input gas detected by the input gas SOx sensor 23 and the intake air amount of the engine, and when the integrated value exceeds a predetermined amount, It can be determined that it is time to execute the SOx poisoning recovery process.

  In this way, when the amount of sulfur passing through the NOx catalyst 17 exceeds the allowable sulfur amount, it is determined that the SOx poisoning recovery processing execution timing is reached, and the determination of the completion of the SOx poisoning recovery processing is performed as described above. In the case of performing the poison recovery processing execution time, the outgas SOx sensor 24 can be omitted.

  Whether or not it is the SOx poisoning recovery process execution time is estimated by estimating the SOx amount occluded in the NOx catalyst 17, and when the estimated stored SOx amount exceeds a predetermined amount, the SOx poisoning recovery process execution time is reached. You may determine that there is. The amount of occluded SOx is estimated as shown in FIG. 9 in which the concentration difference between the SOx concentration of the inlet gas detected by the inlet gas SOx sensor 23 and the SOx concentration of the outlet gas detected by the outlet gas SOx sensor 24 is NOx. As what is occluded by the catalyst 17, it can be calculated based on this SOx concentration difference (incoming gas SOx concentration−outgoing gas SOx concentration) and the intake air amount of the engine. Then, the storage SOx amount calculated and estimated in this way is integrated by the SOx deposition counter, and when the count value of the SOx deposition counter exceeds a predetermined value, it can be determined that the SOx poisoning recovery processing execution timing is reached. .

  In addition, when the SOx accumulation counter is provided as described above, the completion of the SOx poisoning recovery process can be determined as follows. In the period during which the SOx poisoning recovery process is executed and the output gas SOx concentration is greater than the input gas SOx concentration, the concentration difference between the output gas SOx concentration and the input gas SOx concentration is SOx released from the NOx catalyst 17. Since it can be estimated, the SOx amount released from the NOx catalyst 17 is calculated based on this SOx concentration difference (outgoing gas SOx concentration−inlet gas SOx concentration) and the intake air amount of the engine, and the calculated estimated SOx emission amount Is subtracted by the SOx deposition counter, and the SOx poisoning recovery process is completed when the count value of the SOx deposition counter decreases to a predetermined value (poisoning recovery completion level) as shown in FIG. Execution of the recovery process can be terminated.

Further, the determination as to whether or not it is the SOx poisoning recovery process execution time may be determined as the SOx poisoning recovery process execution time when the SOx concentration of the output gas approaches the SOx concentration of the input gas to a predetermined level. . As shown in FIG. 11, the SOx concentration of the output gas of the NOx catalyst 17 approaches the SOx concentration of the input gas as SOx poisoning proceeds. Therefore, it can be said that the degree of approach of the SOx concentration of the output gas to the SOx concentration of the input gas corresponds to the degree of SOx poisoning. Therefore, it is set in advance to what extent the SOx concentration of the output gas approaches the SOx concentration of the input gas, and the SOx poisoning recovery process is set, and the SOx of the output gas detected by the output gas SOx sensor 24 is set. When the concentration exceeds the set SOx concentration, it can be determined that the SOx poisoning recovery processing execution time is reached.

  In each of the above-described embodiments, the input gas SOx sensor 23 is provided upstream of the NOx catalyst 17, and the SOx concentration of the exhaust gas flowing into the NOx catalyst 17 is detected by the input gas SOx sensor 23. Since the SOx concentration of the exhaust gas flowing in depends on the sulfur concentration in the fuel, the fuel amount, and the exhaust gas amount, if the sulfur concentration in the fuel is known, the engine operating state (fuel injection amount, air-fuel ratio, intake air) It can be estimated from the air amount, engine speed, etc. Therefore, in that case, instead of providing the input gas SOx sensor 23, the ECU 30 may calculate and estimate the SOx concentration of the catalyst input gas from the engine operating state.

  In the above-described embodiments, the present invention has been described as being applied to a gasoline engine. However, it is needless to say that the present invention can be applied to a diesel engine. In the case of a diesel engine, combustion in the combustion chamber is performed in a much leaner region than stoichiometric, so that the air-fuel ratio of the exhaust gas flowing into the NOx catalyst 17 is very lean under normal engine operation conditions, and NOx and Although SOx is absorbed, NOx and SOx are hardly released.

  In the case of a gasoline engine, as described above, the air-fuel ratio supplied to the combustion chamber 3 is stoichiometric or rich, so that the exhaust air-fuel ratio is stoichiometric or rich, and the oxygen concentration in the exhaust gas is reduced. NOx and SOx absorbed by the catalyst 17 can be released. However, in the case of a diesel engine, if the air-fuel mixture supplied to the combustion chamber is stoichiometric or rich, soot is generated during combustion. Yes, it cannot be adopted.

  Therefore, when the present invention is applied to a diesel engine, in order to make the exhaust air-fuel ratio stoichiometric or rich, a reducing agent (for example, light oil as a fuel) is used in addition to burning the fuel to obtain engine output. It is necessary to supply the exhaust gas. The reducing agent can be supplied to the exhaust gas by sub-injecting fuel into the cylinder during the intake stroke, the expansion stroke, or the exhaust stroke, or the reducing agent can be supplied into the exhaust passage upstream of the NOx catalyst 17. It is also possible to supply.

  In addition, even if it is a diesel engine, when it has an exhaust gas recirculation device (so-called EGR device), a large amount of exhaust gas recirculation gas is introduced into the combustion chamber, so that the air fuel ratio of the exhaust gas is the stoichiometric air fuel ratio. Or it is possible to make it a rich air-fuel ratio.

1 is a schematic configuration diagram of an exhaust gas purification apparatus for an internal combustion engine according to a first embodiment of the present invention. It is a figure which shows an example of the map of basic fuel injection time. It is a diagram which shows roughly the density | concentration of unburned HC, CO, and oxygen in the exhaust gas discharged | emitted from an engine. It is a figure for demonstrating the NOx absorption / release action of a NOx storage reduction catalyst. It is a figure which shows the progress of deterioration of the NOx storage reduction catalyst. It is a figure which shows the time-dependent change of the air fuel ratio of the output gas at the time of saturated NOx discharge | release process in Example 1 of this invention. It is a flowchart which shows the thermal deterioration determination processing routine in Example 1 of this invention. It is a figure which shows the time-dependent change of the air fuel ratio of input gas at the time of the SOx poisoning recovery process in Example 1 of this invention, and SOx density | concentration of output gas. It is a figure explaining the method to determine the execution time of the SOx poisoning recovery process in the exhaust gas purification apparatus of the internal combustion engine concerning the Example of this invention. It is a figure explaining the method to determine completion of the SOx poisoning recovery process in the exhaust gas purification apparatus of the internal combustion engine concerning the Example of this invention. It is a figure explaining the method to determine the execution time of the SOx poisoning recovery process in the exhaust gas purification apparatus of the internal combustion engine concerning the Example of this invention. It is a figure which shows the relationship between the sintering of a catalyst substance, and the NOx purification performance of a NOx storage reduction catalyst. It is the schematic of the exhaust gas purification apparatus of the internal combustion engine concerning Example 2 of this invention. It is a figure which shows the change of the NOx purification rate in the exhaust gas purification apparatus of the internal combustion engine concerning the Example of this invention. It is a figure for demonstrating the SOx poisoning recovery | restoration process of the NOx storage reduction catalyst in the exhaust gas purification apparatus of the internal combustion engine concerning the Example of this invention. It is a figure which shows the numerical value table used for determination of the amount of input NOx. It is a flowchart which shows the thermal deterioration determination processing routine in Example 2 of this invention.

Explanation of symbols

1, 40 ... Engine body (internal combustion engine)
3 ... Combustion chamber 4 ... Spark plug 11, 42 ... Fuel injection valve (poisoning recovery means)
16, 48 .. Exhaust pipe (exhaust passage)
17. NOx storage reduction catalyst 18, 49. Casing 19, 51. Exhaust pipe (exhaust passage)
21, 45 .. Air flow meter 23 .. Inlet gas SOx sensor (inlet gas SOx concentration detection means)
24 .. Outgas SOx sensor (Outgas SOx concentration detection means)
25..Temperature sensor 27..Air-fuel ratio sensor 30..ECU
50. ・ Outgas NOx sensor (Outgas NOx concentration detection means)

Claims (5)

(B) provided in the exhaust passage of a lean burnable internal combustion engine, which absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean and releases the absorbed NOx when the oxygen concentration of the inflowing exhaust gas is low, and N a NOx storage reduction catalyst for reducing the _2, and (ii) the storage-reduction type NOx catalyst timing to perform the SOx poisoning recovery process for releasing SOx from whether poisoning recovery execution timing determining determination means, ( C) When it is determined by the poisoning recovery execution time determination means that it is the execution time, almost all of the SOx deposited on the NOx storage reduction catalyst is released, and the NOx storage reduction catalyst is made to be SOx covered. A poisoning recovery means for recovering from poison, (d) a storage capacity detecting means for detecting the NOx storage capacity of the NOx storage reduction catalyst, and (e) after executing the SOx poisoning recovery process by the poisoning recovery means. The storage capacity Thermal degradation determination for comparing the NOx storage capability of the NOx storage reduction catalyst detected by the detection means with the reference NOx storage capability, and determining the degree of thermal degradation of the NOx storage reduction catalyst based on the comparison value And an input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, and the SOx concentration detected by the input gas SOx concentration detection means and the intake of the internal combustion engine Based on the amount of air, the amount of SOx flowing into the NOx storage reduction catalyst is calculated, and when the amount of SOx flowing into the NOx storage reduction catalyst exceeds a predetermined amount, the poisoning recovery execution timing determining means An exhaust gas purification apparatus for an internal combustion engine, characterized in that it is determined that it is time to execute the SOx poisoning recovery process. (B) provided in the exhaust passage of a lean burnable internal combustion engine, which absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean and releases the absorbed NOx when the oxygen concentration of the inflowing exhaust gas is low, and N a NOx storage reduction catalyst for reducing the _2, and (ii) the storage-reduction type NOx catalyst timing to perform the SOx poisoning recovery process for releasing SOx from whether poisoning recovery execution timing determining determination means, ( C) When it is determined by the poisoning recovery execution time determination means that it is the execution time, almost all of the SOx deposited on the NOx storage reduction catalyst is released, and the NOx storage reduction catalyst is made to be SOx covered. A poisoning recovery means for recovering from poison, (d) a storage capacity detecting means for detecting the NOx storage capacity of the NOx storage reduction catalyst, and (e) after executing the SOx poisoning recovery process by the poisoning recovery means. The storage capacity Thermal degradation determination for comparing the NOx storage capability of the NOx storage reduction catalyst detected by the detection means with the reference NOx storage capability, and determining the degree of thermal degradation of the NOx storage reduction catalyst based on the comparison value The internal combustion engine estimated from the SOx concentration detected by the input gas SOx concentration detection means, and an input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst The amount of SOx flowing into the NOx storage reduction catalyst is calculated based on the sulfur concentration of the fuel and the fuel consumption or travel distance, and the amount of SOx flowing into the NOx storage reduction catalyst exceeds a predetermined amount. The exhaust gas purification apparatus for an internal combustion engine, wherein the poisoning recovery execution time determination means determines that it is the execution time of the SOx poisoning recovery process. (B) provided in the exhaust passage of a lean burnable internal combustion engine, which absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean and releases the absorbed NOx when the oxygen concentration of the inflowing exhaust gas is low, and N a NOx storage reduction catalyst for reducing the _2, and (ii) the storage-reduction type NOx catalyst timing to perform the SOx poisoning recovery process for releasing SOx from whether poisoning recovery execution timing determining determination means, ( C) When it is determined by the poisoning recovery execution time determination means that it is the execution time, almost all of the SOx deposited on the NOx storage reduction catalyst is released, and the NOx storage reduction catalyst is made to be SOx covered. A poisoning recovery means for recovering from poison, (d) a storage capacity detecting means for detecting the NOx storage capacity of the NOx storage reduction catalyst, and (e) after executing the SOx poisoning recovery process by the poisoning recovery means. The storage capacity Thermal degradation determination for comparing the NOx storage capability of the NOx storage reduction catalyst detected by the detection means with the reference NOx storage capability, and determining the degree of thermal degradation of the NOx storage reduction catalyst based on the comparison value Means, input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, and output gas SOx concentration detection for detecting the SOx concentration of the exhaust gas flowing out of the NOx storage reduction catalyst And a difference in concentration between the SOx concentration detected by the input gas SOx concentration detection means and the SOx concentration detected by the output gas SOx concentration detection means, and an intake air amount or an exhaust gas amount of the internal combustion engine The SOx occlusion amount is estimated on the basis of the above, and when the SOx occlusion amount exceeds a predetermined amount, the poisoning recovery execution time determination means determines the execution time of the SOx poisoning recovery process. Exhaust purification system of an internal combustion engine, characterized in that to determine that. (B) provided in the exhaust passage of a lean burnable internal combustion engine, which absorbs NOx when the air-fuel ratio of the inflowing exhaust gas is lean and releases the absorbed NOx when the oxygen concentration of the inflowing exhaust gas is low, and N a NOx storage reduction catalyst for reducing the _2, and (ii) the storage-reduction type NOx catalyst timing to perform the SOx poisoning recovery process for releasing SOx from whether poisoning recovery execution timing determining determination means, ( C) When it is determined by the poisoning recovery execution time determination means that it is the execution time, almost all of the SOx deposited on the NOx storage reduction catalyst is released, and the NOx storage reduction catalyst is made to be SOx covered. A poisoning recovery means for recovering from poison, (d) a storage capacity detecting means for detecting the NOx storage capacity of the NOx storage reduction catalyst, and (e) after executing the SOx poisoning recovery process by the poisoning recovery means. The storage capacity Thermal degradation determination for comparing the NOx storage capability of the NOx storage reduction catalyst detected by the detection means with the reference NOx storage capability, and determining the degree of thermal degradation of the NOx storage reduction catalyst based on the comparison value Means, input gas SOx concentration detection means for detecting the SOx concentration of the exhaust gas flowing into the NOx storage reduction catalyst, and output gas SOx concentration detection for detecting the SOx concentration of the exhaust gas flowing out of the NOx storage reduction catalyst And the poisoning recovery execution time determining means approaches the SOx concentration detected by the outgas SOx concentration detecting means to a predetermined level with respect to the SOx concentration detected by the input gas SOx concentration detecting means. An exhaust purification device for an internal combustion engine, characterized in that it is determined that it is time to execute the SOx poisoning recovery process. The concentration difference between the SOx concentration detected by the outgas SOx concentration detection means and the SOx concentration detected by the input gas SOx concentration detection means when the SOx poisoning recovery processing is executed by the poisoning recovery means. And the amount of released SOx released from the NOx storage reduction catalyst based on the intake air amount or exhaust gas amount of the internal combustion engine, and this released SOx amount is stored in the NOx storage reduction catalyst. The remaining amount of SOx remaining in the NOx storage reduction catalyst is estimated by subtracting from the estimated amount of stored SOx, and when the remaining amount of SOx is reduced to a predetermined amount, SOx by the poisoning recovery means is estimated. The exhaust gas purification apparatus for an internal combustion engine according to claim 3, wherein the poisoning recovery process is terminated.

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