A method for purifying exhaust gas of an internal combustion engine

Abstract: According to the present invention, SO x in the exhaust gas of an internal combustion engine is absorbed by a sulfate absorbent which absorbs SO x in the exhaust gas when the temperature is lower than a releasing temperature and releases the absorbed SO x when the temperature becomes higher than the releasing temperature. When the exhaust gas temperature increases during the operation of the engine and reaches the releasing temperature, the temperature of the exhaust gas flowing into the sulfate absorbent is further raised to a predetermined temperature by supplying fuel to the exhaust gas passage upstream of the sulfate absorbent. The ratio of SO 3 in the SO x mixture released from the sulfate absorbent changes in accordance with the temperature, and takes the highest value at a certain temperature (i.e., a peak temperature). Therefore, when the exhaust gas temperature is raised above the peak temperature, the ratio of SO 3 in the SO x mixture released from the sulfate absorbent decreases as the temperature increases. In the present invention, the above-noted predetermined temperature is selected in such a manner that the ratio of SO 3 at this predetermined temperature becomes lower than the ratio of SO 3 at the releasing temperature. Therefore, when SO x is released from the sulfate absorbent, the amount of SO 3 , i.e., the amount of particulate matter released into the atmosphere can be maintained at a low level.

Description: The present invention relates to a method for purifying the exhaust gas of an internal combustion engine. More specifically, the present invention relates to a method for purifying the exhaust gas of an internal combustion engine which is capable of reducing the amount of SO 3 released into the atmosphere. In the exhaust gas from an internal combustion engine, especially from a diesel engine, particulate matter such as soot (carbon particles) and SOF (Soluble Organic Fractions) are contained. To prevent particulate matter in the exhaust gas from diffusing into the atmosphere, usually an oxidizing catalyst and a DPF (diesel particulate filter) are used. SOF in the exhaust gas is mainly composed of hydrocarbons, and can be oxidized to H 2 O and CO 2 by contacting the exhaust gas with an oxidizing catalyst. Soot can be collected by a DPF and removed from the exhaust gas. When an oxidizing catalyst and a DPF are disposed in the exhaust gas passage of an engine in this order from the upstream side, oxidation of SOF and the collection of soot can be performed at the same time. However, when SOF is oxidized by an oxidizing catalyst, a problem occurs. Usually, fuel for the engine, especially, diesel fuel, contains a sulfur component. This sulfur is burned in the engine and produces sulfur dioxide (SO 2 ) in the exhaust gas of the engine. When the exhaust gas is supplied to an oxidizing catalyst, SO 2 , as well as SOF, is oxidized by the oxidizing catalyst and forms sulfur trioxide (SO 3 ). Therefore, the exhaust gas flows out from the oxidizing catalyst contains SO 3 . SO 3 in the exhaust gas is not collected by the DPF, and released into the atmosphere. Since SO 3 is detected as particulate matter, the total amount of particulate matter in the exhaust gas increases in some cases due to SO 3 produced by the oxidizing catalyst even though SOF and soot are removed from the exhaust gas. Japanese Unexamined Patent Publication (Kokai) No. 53-38815 discloses a method for solving the above problem using a sulfate trap. The sulfate trap used in the '815 publication is capable of absorbing SO x (in this specification, sulfur oxide such as SO 2 and SO 3 are referred to as SO X in general) and holding it in the trap in the form of a sulfate. The device in the '815 publication disposes the sulfate trap in the exhaust gas passage of an internal combustion engine downstream of the oxidizing catalyst to absorb SO X in the exhaust gas. Thus, SO 2 passes through the oxidizing catalyst without being oxidized and SO 3 formed by the oxidation of SO 2 on the oxidizing catalyst are absorbed by the sulfate trap and, thereby, the amount of particulate matter released into the atmosphere can be kept small. However, sulfate formed in the sulfate trap starts to decompose when the temperature of the sulfate trap exceeds a certain value. In this case, since most of the sulfur oxide absorbed in the sulfate trap is released in the form of SO 3 , if the temperature of the sulfate trap exceeds the certain temperature, the amount of the particulate matter released into the atmosphere increases. In this specification, the temperature at which the releasing of the absorbed sulfur oxide occurs is referred to as the "releasing temperature". To prevent the releasing of SO 3 from occurring, the device in the '815 publication supplies cooling air to the sulfate trap to keep the temperature of the sulfate trap lower than the releasing temperature. However, problems may arise in the device of the '815 publication. Since sulfur oxide absorbed in the sulfate trap is never released in the device of the '815 publication, sulfur oxide continues to accumulate in the sulfate trap, and the sulfate trap is saturated with the absorbed sulfur oxide after the engine has operated for a long time. When the sulfate trap saturates with sulfur oxide, it cannot absorb SO X in the exhaust gas. Therefore, SO 3 produced by the oxidizing catalyst passes through the sulfate trap without being absorbed after the engine has operated for a certain period and, thereby, the amount of the particulate matter released into the atmosphere increases. In the device of the '815 publication, the accumulation of sulfur oxide in the sulfate trap can be prevented if the temperature of the sulfate trap is raised to the releasing temperature periodically before the sulfate trap is saturated with sulfur oxide. However, most of the absorbed sulfur oxide is released from the sulfate trap in the form of SO 3 near the releasing temperature. Therefore, if the temperature of the sulfate trap is raised to the releasing temperature to prevent the saturation thereof, most of the sulfur oxide absorbed during the engine operation is released in the form of SO 3 , and the total amount of the particulate matter released into the atmosphere increases. EP-A-0580389 discloses a method of combustion engine exhaust gas purification wherein a catalytic absorbent absorbs the SOx in the gas which is oxidised and stored in the absorbent as sulfates. The absorbent is regenerated by increasing the temperature to decompose the sulfates and to release SO 2 . According to EP-A-0580389 the SO x is released as SO 2 at 1100 °C in air, while at lower oxygen levels the release is obtainable at lower temperatures, i.e. 900 or 550 °C. Likewise for instance EP-A-0636770 and EP-A-0625633 disclose a process for catalytic purification of engine exhaust gas. The a catalytic absorbent absorbs SO X present in the gas when the air-fuel ratio is low (i.e. high oxygen level) whereby the SOx is oxidised and stored as BaSO 4 . The SOx is released from the material when the fuel-air ratio is made rich (i.e. under low oxygen conditions), and it is mentioned that increasing the temperature will promote the release of SOx. In view of the problems in the related art as set forth above, the object of the present invention is to provide a method for purifying the exhaust gas of an internal combustion engine which is capable of reducing the amount of SO 3 released into the atmosphere even after a long period of engine operation. This object is achieved by a method as defined in claim 1, which for instance comprises a step for contacting the exhaust gas of an internal combustion engine containing sulfur oxide with a sulfate absorbent at a temperature lower than a releasing temperature and a step for raising the temperature of the sulfate absorbent after it has absorbed sulfur oxide to a predetermined temperature higher than the releasing temperature to, thereby, cause the sulfate absorbent to release the absorbed sulfur oxide. The sulfate absorbent absorbs sulfur oxide in the exhaust gas when the temperature is lower than the releasing temperature and releases the absorbed sulfur oxide when the temperature becomes higher than the releasing temperature. The predetermined temperature to which the sulfate absorbent is heated is selected in such a manner that the ratio of the sulfur trioxide component in the sulfur oxide mixture released from the sulfate absorbent at this predetermined temperature is lower than the ratio of the sulfur trioxide in the sulfur oxide mixture released from the sulfate absorbent at the releasing temperature. According to the invention, the amount of SO 3 in the sulfur oxide mixture released from the sulfate absorbent is reduced by raising the temperature of the sulfate absorbent to a predetermined temperature higher than the releasing temperature. The ratio between the amounts of SO 3 and SO 2 in the sulfur oxide released from the sulfate absorbent is determined by the temperature of the sulfate absorbent provided the oxygen concentration is unchanged. The ratio of the SO 3 component in the sulfur oxide mixture released from the sulfate absorbent increases as the temperature of the sulfate increases from the releasing temperature, and reaches a peak value at a certain temperature ("a peak temperature") which is higher than the releasing temperature. If the temperature further increases from the peak temperature, the ratio of SO 3 decreases as the temperature increases. In the invention, the predetermined temperature to which the sulfate absorbent is heated to cause the releasing of sulfur oxide is higher than the peak temperature. Further, the predetermined temperature is selected in such a manner that the ratio of SO 3 in the sulfur mixture oxide released from sulfate absorbent at this temperature is smaller than the ratio of SO 3 in the sulfur oxide mixture released at the releasing temperature. Therefore, even if the releasing of sulfur oxide is required to prevent the saturation of the sulfate absorbent, the amount of SO 3 released from the sulfate absorbent can be reduced. According to the invention, there is provided a step for collecting soot in the exhaust gas of the internal combustion engine, a step for burning the collected soot, and a step for supplying the combustion exhaust gas generated by the combustion of the soot to the sulfate absorbent to cause the sulfate absorbent to release the absorbed sulfur oxide. The sulfate absorbent absorbs sulfur oxide in the exhaust gas when the temperature is lower than the releasing temperature and releases the absorbed sulfur oxide when the temperature becomes higher than the releasing temperature. The hot exhaust gas of low oxygen concentration produced by the combustion of the collected soot is supplied to the sulfate absorbent when releasing of the sulfur oxide from the sulfate absorbent is required. Since the hot exhaust gas is supplied to the sulfate absorbent, the sulfate absorbent is heated to its releasing temperature and, thereby the sulfur oxide is released from the sulfate absorbent. Further, since the concentration of oxygen in the combustion gas is low, the ratio of SO 3 in the released sulfur oxide becomes low. Therefore, the amount of particulate matter released into the atmosphere becomes low even though the releasing of sulfur oxide from the sulfate absorbent occurs. The present invention will be better understood from the description as set forth hereinafter, with reference to the accompanying drawings in which: Fig. 1 schematically illustrates an exhaust gas control system an internal combustion engine for an automobile; Fig. 2 is a diagram showing the change in the ratio of the SO 3 in the gas containing SO X mixture according to the change in the temperature and the concentration of oxygen in the gas; Fig. 3 is a diagram showing the change in the ratio of SO 3 in the SO X mixture contained in gas under the existence of an oxidizing catalyst in accordance with the change in the temperature; Fig. 4 is a diagram showing the change in the ratio of SO 3 in the SO X mixture contained in gas under the existence of an oxidizing catalyst in accordance with the change in the temperature and the concentration of oxygen; Fig. 5 schematically illustrates another embodiment of a device for conducting the method in the present invention; Fig. 6 is a flowchart showing an embodiment of the exhaust gas purifying method using the device in Fig. 5; Fig. 7 is a diagram showing the change in the ratio of SO 3 in the SO X released from the sulfate absorbent when the amount of secondary fuel supplied to the sulfate absorbent is changed; Fig. 8 is a diagram showing the change in the ratio of SO 3 in the SO x released from the sulfate absorbent caused by the combustion of soot on the DPF; Fig. 9 is a diagram showing the change in the ratio of SO 3 in the SO X released from the sulfate absorbent in accordance with the change in the concentration of carbon monoxide in the exhaust gas; Fig. 10 is a flowchart showing another embodiment of the exhaust gas purifying method according to the present invention; and Fig. 11 is a diagram showing the change in the ability of the sulfate absorbent for absorbing SO X with a lapse of time. Fig. 1 shows an embodiment of an exhaust gas purification device for applying the exhaust gas purifying method of the present invention to a diesel engine for an automobile. In Fig. 1, reference numeral 1 designates a diesel engine for an automobile. Though a multiple cylinder diesel engine is used in this embodiment, Fig. 1 shows one cylinder only. Numeral 2 is an intake air passage connected to the inlet port of the respective cylinder. Numeral 3 is an exhaust gas passage which is connected to the exhaust port of the respective cylinder via an exhaust manifold 3a. A fuel injection valve 4, which injects pressurized fuel into a combustion chamber, is provided on each of the cylinders. In this embodiment, an intake shutter valve 6 is disposed in the intake air passage 2. The intake shutter valve 6 is a type, such as a butterfly valve, which generates low flow resistance when open, and is normally used for throttling the intake air passage 2 to reduce the amount of intake air during an idle operation of the engine 1 to increase the stability of the engine operation. In Fig. 1, numeral 6a is an actuator of appropriate type, such as a vacuum actuator or solenoid actuator, which opens and closes the intake shutter valve 6 in accordance with a control signal stupplied by an ECU 20. In this embodiment, an EGR passage 13 which connects the exhaust manifold 3a and the intake air passage 2 is provided to feed a portion of exhaust gas discharged from the engine to the intake air passage 2. On the EGR passage 13, an EGR control valve 10 is disposed which controls the amount of the exhaust gas flowing through the EGR passage 13. The EGR control valve 10 is provided with an actuator 10a of appropriate type, such as a vacuum actuator, stepper motor, or solenoid actuator. The actuator 10a drives the EGR control valve 13 and adjusts the degree of opening of the valve 13 in response to a control signal from the ECU 20. In this embodiment, a secondary fuel supply unit 7 for injecting fuel into the exhaust gas passage 3 is provided. The secondary fuel supply unit 7 includes a injection nozzle 7a which injects pressurized fuel from an engine fuel supply pump (not shown) into the exhaust gas passage 3, and a flow control valve 7b for controlling the amount of fuel injected into the exhaust gas passage 3 in accordance with a control signal from the ECU 20. As explained later, the secondary fuel injection unit 7 injects fuel into the exhaust gas passage 13 to increase the exhaust gas temperature and to decrease the oxygen concentration by burning the injected fuel when it is required to cause a sulfate absorbent to release the absorbed sulfur oxide. Numeral 5 in Fig. 1 designates a sulfate absorbent disposed in the exhaust gas passage 3 downstream of the injection nozzle 7a. The sulfate absorbent 5 in this embodiment performs an absorbing and releasing operation of SO X . Namely, the sulfate absorbent 5 absorbs SO X in the exhaust gas and releases the absorbed SO X when conditions for releasing are fulfilled. The sulfate absorbent 5 will be explained later in detail. Numeral 20 in Fig. 1 is a control circuit or Electronic Control Unit (ECU) of the engine 1. The ECU 20 in this embodiment comprises, for example, a microcomputer of known type which has a CPU, RAM, ROM, and input and output ports all interconnected by a bidirectional bus. The ECU 20 performs fundamental control of engine such as fuel injection control, and, in addition to that, the ECU 20 in this embodiment performs SO X releasing control of the sulfate absorbent 5 in which SO X releasing operation of the sulfate absorbent is controlled. To perform the above-noted control, various signals are fed to the input port of the ECU 20. These signals are, for example, an engine speed signal from an engine speed sensor disposed near the crankshaft (not shown) of the engine, an accelerator signal from an accelerator sensor disposed near an accelerator pedal (not shown) which represents the amount of depression of the accelerator pedal by the driver, an exhaust gas temperature signal from a temperature sensor 8 disposed in the exhaust gas passage 3 downstream of the sulfate absorbent 5. The output port of the ECU 20 is connected to, for example, the fuel injection valve 4, the actuator 6a of the intake shutter valve 6, the actuator 10a of the EGR control valve 10 and the flow control valve 7b of the secondary fuel supply unit 7 via the respective drive circuit (not shown) in order to control the operations of these elements. The sulfate absorbent 5 uses a monolithic substrate made of cordierite which is similar to the substrate normally used for a conventional catalytic converter, and a layer made of a substance such as alumina (Al 2 O 3 ), silica (SiO 2 ) or titania (TiO 2 ) is formed on the surface of the substrate. In this embodiment, catalytic components of precious metal such as platinum (Pt) are carried by the layer. Therefore, the sulfate absorbent 5 in this embodiment also acts as an oxidizing catalyst which oxidizes SOF (hydrocarbons) and CO in the exhaust gas to H 2 O and CO 2 . When the engine is operated on a light load, the exhaust gas temperature is low, and the hydrocarbons (HC) and CO in the exhaust gas increases. However, in this embodiment, the HC and CO components in the exhaust gas are oxidized when the exhaust gas flows through the sulfate absorbent 5 and are converted to H 2 O and CO 2 by the catalytic components carried thereon. Therefore, HC and CO are not released into the atmosphere. Further, when the exhaust gas flows through the sulfate absorbent 5, an SO 2 component in the exhaust gas is also oxidized to SO 3 by the catalytic components. However, in this embodiment, the SO 3 produced by the oxidation of SO 2 is absorbed by the absorbent layer (such as made of alumina), and are not released into the atmosphere. Next, the mechanism of the absorbing and releasing operation of the sulfate absorbent 5 is explained taking the case in which alumina (Al 2 O 3 ) is used for the layer on the substrate, and platinum (Pt) is used as a catalyst, as an example. In this case, SO 2 and SO 3 in the exhaust gas are oxidized by O 2 - or O 2- attached on the surface of platinum and form sulfonic acid ions SO 4 2- . This sulfonic acid ions SO 4 2- diffuse into the alumina layer while combining with alumina (Al 2 O 3 ), and form sulfate Al 2 O 3 (SO 4 ) 3 . Thus, SO X such as SO 2 and SO 3 in the exhaust gas are absorbed by, and held in the sulfate absorbent 5. However, SO X held in the sulfate absorbent 5 in the form of sulfate Al 2 O 3 (SO 4 ) 3 is released from sulfate absorbent 5 when the temperature becomes high or oxygen concentration in the exhaust gas becomes low. For example, when the temperature of the sulfate absorbent 5 increases, the sulfate Al 2 O 3 (SO 4 ) 3 in the alumina layer is decomposed by heat, and sulfonic acid ions SO 4 2- are produced. Then, these sulfonic acid ions SO 4 2- form SO X when they are released from the sulfate absorbent 5. Thus, when the temperature of the sulfate absorbent 5 becomes high, SO X is released from the sulfate absorbent 5. Further, when the oxygen concentration in the exhaust gas becomes low, the amount of O 2 - and O 2- attached on the surface of Pt decreases. This causes reactions to proceed in the directions SO 4 2- → SO 3 and SO 4 2- → SO 2 on the surface of platinum. Therefore, SO X such as SO 3 and SO 2 are formed on the platinum (Pt), and sulfonic acid ions SO 4 2- are released from the sulfate absorbent in the form of SO X . The rate at which SO 4 2- ions are released from the absorbent is determined by the difference between the concentrations of SO 4 2- ions in the absorbent and on the surface of Pt. When the concentration of oxygen in the exhaust gas is low, the rate of the reactions in the directions SO 4 2- → SO 3 and SO 4 2- → SO 2 become larger and the concentration of SO 4 2- ions on the surface of Pt becomes low. Therefore, when the oxygen concentration in the exhaust gas becomes low, SO 4 2- ions are released from the absorbent even if the concentration of SO 4 2- ions in the absorbent (i.e., the amount of SO X absorbed by the absorbent) is low. Thus, when the oxygen concentration in the exhaust gas becomes lower, SO X is released from the sulfate absorbent 5. Further, similarly to this, since the rate of the reactions in the directions 50 4 2- → SO 3 and SO 4 2- → SO 2 becomes higher as the temperature of the sulfate absorbent becomes higher, SO X is released from the sulfate absorbent 5 when the temperature of the sulfate absorbent becomes high even though the oxygen concentration in the exhaust gas is high. Namely, whether the releasing of SO X from the sulfate absorbent occurs is determined by an equilibrium condition which is ruled by the temperature and the oxygen concentration. Further, the ratio between SO 2 and SO 3 in the SO X mixture released from the sulfate absorbent is determined by the temperature of the sulfate absorbent 5 and the oxygen concentration in the exhaust gas. Figs. 2 through 4 show the change in the ratio of SO 3 in the SO X mixture released from the sulfate absorbent 5 in the equilibrium condition according to the changes in the temperature and oxygen concentration. In Fig. 2, the vertical axis represents the ratio of SO 3 in the SO X mixture (the mixture of SO 2 and SO 3 ), and the horizontal axis represents the temperature of the sulfate absorbent. The curves A through D in Fig. 2 represent the ratio of SO 3 in the SO X mixture in the equilibrium conditions at various oxygen concentrations, and the curve A shows the case in which the oxygen concentration is highest and the oxygen concentration becomes lower in the order from A to D. In Fig. 2, the ratio of SO 2 in the SO X mixture can be calculated by subtracting the ratio of SO 3 from 100%. As illustrated in Fig. 2, in the equilibrium conditions, the ratio of SO 3 becomes lower as the temperature becomes higher if the oxygen concentration is kept constant. Further, if the temperature is kept constant, the ratio of SO 3 in SO X in the equilibrium condition becomes lower as the oxygen concentration becomes lower. However, in the actual operation of the engine, almost all of the SO X in the exhaust gas from the engine is composed of SO 2 , and the ratio of SO 3 in SO X is very low. Therefore, it takes a relatively long time to reach the equilibrium conditions shown in Fig. 2 in which the ratio of SO 3 is relatively high. When an oxidizing catalyst exists, since the oxidation of SO 2 is promoted, the time required for reaching the equilibrium conditions becomes shorter. However, the oxidizing ability of catalyst becomes larger as the temperature becomes higher. Therefore, when the temperature is relatively low, the ratio of SO 3 in the SO X mixture is determined by the oxidizing ability of the catalyst, and the ratio of SO 3 increases as the temperature becomes higher (i.e., the oxidizing ability of the catalyst becomes larger). In Fig. 3, the broken line represents the change in the ratio of SO 3 in the actual condition when an oxidizing catalyst exists. In this case, the oxygen concentration is kept constant (for example, at the concentration corresponding to the curve A in Fig. 2). The curve E in Fig. 3 shows the change in the oxidizing ability of the catalyst in accordance with the change in the temperature, and the curve A in Fig. 3 shows the ratio of SO 3 in the equilibrium condition (which is the same as the curve A in Fig. 2). As illustrated in Fig. 3, the ratio of SO 3 in the actual condition increases along the curve E (the oxidizing ability of the catalyst) as the temperature increases, and approaches the value determined by the equilibrium (the curve A). However, the ratio of SO 3 cannot become larger than the value determined by the equilibrium (i.e., the curve A in Fig. 3). Therefore, when the catalyst exists, the ratio of SO 3 (the dotted line) increases as the temperature becomes high, and reaches the value determined by the equilibrium at a certain temperature (i.e., T P in Fig. 3), and when the temperature exceeds this temperature (T P ), the ratio of SO 3 decreases along the equilibrium curve A as the temperature increases. Namely, when the catalyst exists, there is a peak temperature (T P in Fig. 3) at which the ratio of SO 3 in the SO x mixture becomes the highest value. Though Fig. 3 shows the case in which the oxygen concentration is maintained at constant value, the equilibrium curve itself changes in accordance with the oxygen concentration (for example, curves A through D in Fig. 2). Fig. 4 shows the ratio of SO 3 in the actual condition under the existence of the catalyst at various oxygen concentrations, and the curves A through D in Fig. 4 are the same curves as A through D in Fig. 2 which represent the ratio of SO 3 in equilibrium conditions at various oxygen concentrations. As illustrated in Fig. 4, the peak temperature (T P in Fig. 3) at which the ratio of SO 3 is the highest becomes lower as the oxygen concentration becomes lower, and the peak (the highest) value of the ratio of SO 3 also becomes smaller as the oxygen concentration becomes lower. As explained before, the amount of the particulate matter released into the atmosphere becomes smaller as the amount of SO 3 released from the sulfate absorbent becomes smaller. Therefore, if SO X is released from the sulfate absorbent in the conditions which minimize the ratio of SO 3 in the released SO X , the amount of the particulate matter can be reduced even if the total amount of SO X released from the sulfate absorbent is the same. In this embodiment, the amount of particulate matter is minimized by performing an SO X releasing control to minimize the ratio of SO 3 in the SO X released from the sulfate absorbent 5. Next, the SO x releasing control is explained. First, the case in which the oxygen concentration is kept constant is considered. In this case, the actual ratio of SO 3 in the released SO X is represented by the broken line in Fig. 3. Assuming that the releasing temperature is T D , the releasing of SO X starts when the exhaust gas temperature becomes higher than the temperature T D , for example, by the change in the operating conditions of the engine 1. Since the exhaust gas temperature is nearly the same as the temperature of the sulfate absorbent 5, the exhaust gas temperature is used instead of the temperature of the sulfate absorbent 5 in the following explanation. When SO X is released from the sulfate absorbent 5 at the releasing temperature T D , the ratio of SO 3 in the released SO X is R D as shown in Fig. 3. To reduce the ratio of SO 3 to a value smaller than R D , it is apparent that the exhaust gas temperature must be lowered below the releasing temperature T D , or the exhaust gas temperature must be raised above the peak temperature Tp so that the exhaust gas temperature exceeds the temperature T R in Fig. 3 at which the ratio of SO 3 becomes lower than R D . However, if the temperature is lowered to below the releasing temperature T D , the releasing of SO X does not occur in the actual operation. Therefore, when the exhaust gas temperature becomes high and reaches the releasing temperature T D , the exhaust gas temperature is further raised to the temperature T R by the method explained later to lower the ratio of SO 3 in the released SO X than the ratio R D at the releasing temperature T D . By doing so, the amount of SO 3 (the particulate matter) released from the sulfate absorbent 5 can be smaller than that when the SO X is released at the releasing temperature T D . Usually, the diesel engine is operated on a considerably lean air-fuel ratio (for example, an air-fuel ratio of about 30), and the oxygen concentration in the exhaust gas is high. In this condition, the releasing temperature T D of the sulfate absorbent 5 becomes relatively high (for example, 500 to 600°C) and, accordingly, the temperature T R also becomes high (for example, 700 to 800°C). However, the exhaust gas temperature of the diesel engine in the normal operation is relatively low, and the exhaust gas temperature at the sulfate absorbent 5 is normally in the range between 250 to 400°C, and at the highest 600°C (in a high load operation such as when ascending a slope). Therefore, in the practical operation of the diesel engine, the exhaust gas temperature is not likely to reach the temperature T R even though it may reach the releasing temperature T D . Fig. 11 illustrates a typical SO x absorbing characteristic of the sulfate absorbent. The vertical axis in Fig. 11 represents an SO x absorbing ratio α (ta) , and the horizontal axis represents the time ta lapsed since the sulfate absorbent starts to absorb SO x in the exhaust gas. The SO x absorbing ratio α (ta) in this embodiment is defined as a ratio of the amount of SO x absorbed by the sulfate absorbent to the amount of fuel burned by the engine. Since the amount of fuel burned by the engine is proportional to the amount of SO x produced by the engine, the SO x absorbing ratio α (ta) corresponds to the ratio of the amount of SO X absorbed by the sulfate absorbent to the amount of SO X in the exhaust gas flowing into the sulfate absorbent. As illustrated in Fig. 15, as the time ta passes, the SO X absorbing ratio α (ta) of the sulfate absorbent becomes low. The total amount of SO X absorbed by the sulfate absorbent in a given period (CS) can be calculated by cumulating the value obtained by multiplying the amount of fuel supplied to the engine per unit time by the SO X absorbing ratio α (ta) . Since the fuel injection amount FI represents the amount of fuel supplied to the engine per unit time, the total amount of SO X absorbed by the sulfate absorbent CS is calculated by cumulating the value FI × α (ta) (i.e., CS = E (FI. × α (ta) ) ) in this embodiment. Next, an embodiment of the present invention is explained with reference to Fig. 5. Fig. 5 is a drawing similar to Fig. 1 which illustrates an embodiment of a device for performing the method of the present invention. In Fig. 5, reference numerals the same as those in Fig. 1 represents similar elements. As shown in Fig. 5, the nozzle 7a of the secondary fuel supply unit 7, an oxidizing catalyst 91 and a DPF (diesel particulate filter) 7 are disposed in the exhaust gas passage 3 from the upstream side in this order. Further, a differential pressure sensor 95 which detects the pressure drop through the DPF 93 is provided. The oxidizing catalyst 91 uses a monolithic substrate made of cordierite, and catalytic components such as platinum (Pt), palladium (Pd) are attached to this substrate. The oxidizing catalyst 92 in this embodiment is used for oxidizing SOF in the exhaust gas during the normal operation, and also for burning the secondary fuel supplied to the exhaust gas passage 3 in order to initiate the combustion of soot collected by DPF 93 as explained later. The DPF 93 acts as a filter which collects soot (carbon particles) in the exhaust gas to prevent soot from being released into the atmosphere. Further, the DPF 93 in this embodiment is constructed so that it also acts as the sulfate absorbent 5 in the previous embodiments. DPF 93 is a honeycomb type porous filter made of, for example, cordierite. In the DPF 93, numerous exhaust gas passages are formed in parallel. Approximately half of the exhaust gas passages are plugged at the upstream ends thereof, and the rest of the passages are plugged at the downstream ends thereof. The exhaust gas passages plugged at the upstream ends and the exhaust gas passages plugged at the downstream ends are disposed in the DPF 93 alternately. The exhaust gas of the engine flows into the DPF 93 through the passages having open upstream ends, and flows into the exhaust gas passages having open downstream ends through porous walls separating the exhaust gas passages from each other, and flows out from the DPF 93 through the passages having open downstream ends. Therefore, particles such as soot (carbon particles) are collected by the porous walls of the DPF 93. In order to give the function of sulfate absorbent to the DPF 93, the wall of the surfaces of the exhaust gas passages in the DPF 93 in this embodiment is coated by the layer of alumina (Al 2 O 3 ), silica (SiO 2 ) or titania (TiO 2 ), and catalytic components such as platinum (Pt) are carried on this layer. During the normal operation of the diesel engine 1, the DPF 93 acts as a conventional particulate filter and collects particulate matter such as soot in the porous wall and, in addition to that, the DPF 93 also acts as a sulfate absorbent and absorbs SO x produced by the oxidizing catalyst 91 in the absorbent layer on the wall surface of the exhaust gas passages. When it is necessary to release the absorbed SO x (for example, when the exhaust gas temperature reaches the releasing temperature of the absorbent, and/or when the amount of the SO x absorbed by the absorbent reaches a predetermined value), or when the pressure drop through the DPF 93 increases due to accumulation of soot collected in the DPF 93, the ECU 20 supplies secondary fuel from the secondary fuel supply unit 7 to burn the soot on the DPF and to perform the releasing of SO X from the absorbent layer at the same time. When secondary fuel is supplied to the exhaust gas passage 3 upstream of the oxidizing catalyst 91, fuel is burned (oxidized) on the oxidizing catalyst 91. Therefore, the temperature of the exhaust gas flowing into the DPF 93 becomes high due to combustion of fuel on the oxidizing catalyst 91, and the soot (the carbon particles) collected by the DPF 93 starts to burn from the upstream side of the DPF 93. The hot exhaust gas flows into the DPF 93 is further heated by the combustion of soot in the DPF, and the oxygen concentration in the exhaust gas is lowered by the combustion of secondary fuel and soot. This causes the absorbent layer on the DPF 93 to release the absorbed SO X . The temperature of the exhaust gas increases, and the oxygen concentration thereof decreases as the exhaust gas flows down through the DPF 93 due to combustion of soot in the DPF. Therefore, both the highest temperature of the exhaust gas and the lowest oxygen concentration thereof are achieved at the downstream end of the DPF 93 at the same time. Since the ratio of SO 3 in the SO X released from the DPF 93 is determined by the temperature and the oxygen concentration at the outlet of the DPF 93, the ratio of SO 3 in the SO X released from the DPF 93 becomes extremely low. Thus, according to the present embodiment, both the carbon particles (soot) and other particulate matter (SO 3 ) released into the atmosphere can be largely reduced. Fig. 6 is a flowchart illustrating an embodiment of the routine for performing the SO X releasing control as explained above. This routine is performed by the ECU 20 at predetermined regular intervals. In the routine of Fig. 6, the burning of the soot on the DPF 93 and the releasing of the SO X from the absorbent layer in the DPF 93 are performed in the following manner Namely, in Fig. 6, at step 1003, the pressure drop ΔP is read from the differential pressure sensor 95, as well as the accelerator signal ACC, the engine speed NE and the exhaust gas temperature T EX . At steps 1005 and 1007, the releasing temperature T D of the absorbent, the target temperature T R , the amount CS of the SO X absorbed by the absorbent are calculated in the manner same as those in the previous embodiments. As explained before, the SO X releasing operation is performed by this routine when; (1) the exhaust gas temperature T EX reaches the releasing temperature T D (step 1009), (2) the amount CS of SO X absorbed by the absorbent reaches a predetermined value CS 0 (step 1011) and, in addition to that, (3) when the pressure drop ΔP through the DPF 93 reaches a predetermined value ΔP 0 (step 1012). If any of the above conditions (1), (2) and (3) is satisfied, the value of the releasing operation flag RX is set at 1 at step 1013, and the amount FI 2 of the secondary fuel is supplied to the exhaust gas passage 3 for a time period t 0 at steps 1015 through 1027. The soot on the DPF 93 is burned and the ratio of SO 3 in the released SO X is reduced at the same time. In the embodiments according to the invention, the ratio of SO 3 in the released SO X is reduced by increasing the temperature of the sulfate absorbent. It was found that if a substance having an affinity for oxygen greater than the affinity of SO 2 for oxygen is supplied to the sulfate absorbent when SO X is released, the ratio of SO 3 in the released SO X becomes low. As explained before, when SO X is released from the sulfate absorbent, SO 4 2- ions released from the sulfate absorbent react with O 2 - or O 2- on the surface of Pt and form SO 2 and SO 3 . In this case, if a substance having a greater affinity for oxygen than SO 2 , such as HC or CO exists, O 2 - and O 2- combine with these substance rather than with SO 4 2- ions. Therefore, O 2 - and O 2- on the surface of Pt are consumed by these substance, and the oxygen concentration on the surface of Pt. becomes low This makes the reaction SO 4 2- → SO 3 less likely to occur. Therefore, the reaction SO 4 2- → SO 2 becomes more likely to occur compared to the reaction SO 4 2- → SO 3 . Further, since the affinity of the substance for oxygen is greater than the affinity of SO 2 for oxygen, the reaction SO 2 + 1/2O 2 → SO 3 is not likely to occur and the SO 2 , even if it is produced, is not converted to SO 3 . Therefore, the ratio of SO 3 in the SO x mixture released from the sulfate absorbent can be lowered by supplying the substance having a larger affinity for oxygen than SO 2 to the sulfate absorbent during the SO X releasing operation. Fig. 7 is a diagram illustrating the change in the ratio of SO 3 in the SO X released from the sulfate absorbent in accordance with the change in the amount of secondary fuel (diesel fuel) supplied to the exhaust gas passage 3 which is measured using the device in Fig. 1. The vertical axis in Fig. 7 represents the ratio of SO 3 in the total amount of SO X at the outlet of the sulfate absorbent 5, the vertical axis represents the temperature of the sulfate absorbent 5 which is measured by a temperature sensor disposed on the substrate of the sulfate absorbent 5. The respective curves in Fig. 7 represent the change in the ratio of SO 3 in accordance with the change in the temperature of the substrate of the sulfate absorbent 5 when the engine is running at a same speed. The curve A in Fig. 7 shows the case in which secondary fuel is not supplied to the exhaust gas, and the temperature of the sulfate absorbent 5 is changed by adjusting the engine load. The curves B through D show the cases in which the engine load is maintained constant, and the temperature of the sulfate absorbent 5 is changed by adjusting the amount of secondary fuel supplied to the sulfate absorbent. While the engine load is maintained constant in the respective cases of the curves B through D, the engine load is becomes lower in the order of B, C, D (i.e., B > C > D). As shown by the curve A in Fig. 7 (the case in which no secondary fuel is supplied), the ratio of SO 3 at the outlet of the sulfate absorbent 5 changes in the same manner as shown by the broken line in Fig. 3. In this case, as explained before, the ratio of SO 3 is determined only by the temperature. In the curves B, C and D, the engine load is maintained constant and the temperature of the sulfate absorbent is adjusted by the amount of secondary fuel. Therefore, in the curves B, C and D, the amount of secondary fuel becomes larger as the temperature of the sulfate absorbent becomes higher. The temperature of the sulfate absorbent is determined by the exhaust gas temperature. Therefore, it is considered that the temperature of the sulfate absorbent changes in accordance with the ratio of the total amount of fuel supplied to the engine combustion chamber and the exhaust gas passage 3 to the amount of intake air. Further, since the engine speed is the same for all cases in Fig. 7, the amount of intake air is also the same for all cases in Fig. 7. Therefore, the points on the curves A through D of a same temperature represents the operating conditions in which the total amount of fuel supplied to the combustion chamber and to the exhaust gas passage is the same. Further, in this case, since the amount of intake air is the same in all the cases in Fig. 7, the air-fuel ratio of the exhaust gas flows into the sulfate absorbent becomes the same if the temperature of the sulfate absorbent is the same. In other words, the curve A represents the case in which all of the amount of fuel required to achieve a certain temperature of the sulfate absorbent is supplied to the combustion chamber of the engine, and the curves B, C and D represent the cases in which a part of fuel is supplied to the combustion chamber and the rest of fuel is supplied to the exhaust gas passage to achieve the same temperature as the curve A. Further, since the amount of fuel supplied to the combustion chamber of the engine becomes smaller as the engine load decreases, the amount of secondary fuel becomes larger as the engine load becomes smaller if the temperature of the sulfate absorbent is the same. Namely, when the points on curves A through D of the same temperature are compared, the amount of secondary fuel is largest at the curve D, and becomes smaller in the order of the curves C, B, A (i.e., D > C > B > A). As seen from Fig. 7, when the temperature of the sulfate absorbent is the same, the ratio of SO 3 in the released SO x is the largest in the case of the curve A (i.e., the amount of secondary fuel is 0), and is the smallest in the case of the curve D (i.e., the amount of secondary fuel is the largest). Since the air-fuel ratio of the exhaust gas, i.e., the oxygen concentration of the exhaust gas is the same when the temperature of the sulfate absorbent is the same, this means that the ratio of SO 3 becomes smaller as the amount of secondary fuel is larger even if the oxygen concentration of the exhaust gas is the same. The reason why the ratio of SO 3 decreases as the amount of secondary fuel increases even in the condition in which the temperature of the sulfate absorbent and the oxygen concentration in the exhaust gas are the same is explained as follows. When secondary fuel is supplied to the exhaust gas passage, it is oxidized (burned) by O 2 - and O 2- on the surface of the catalyst on the sulfate absorbent. This reduces the oxygen concentration on the catalyst surface and, at the same time, produces a relatively large amount of unburned HC and CO in the exhaust gas. Since HC and CO have a great affinity for oxygen, HC and CO further remove O 2 - and O 2- from the surface of the catalyst and the concentration of O 2 - and O 2- on the surface of the catalyst becomes very low. Therefore, SO 4 2- ions released from the absorbent cannot obtain a sufficient amount of O 2 - or O 2- to form SO 3 , and the reaction SO 4 2- → SO 3 becomes less likely to occur. This causes the ratio of SO 3 in the SO X released from the sulfate absorbent to become lower. Further, since the affinity of HC and CO for oxygen is greater than the affinity of SO 2 for oxygen, the reaction SO 2 + 1/2O 2 → SO 3 also becomes less likely to occur. Therefore, even if SO 2 is produced on the surface of the catalyst, SO 2 is not oxidized to SO 3 . Thus, by increasing the amount of secondary fuel, the ratio of SO 3 in the SO X released from the sulfate absorbent decreases. It is true that the fuel supplied to the combustion chamber also produces unburned HC and CO. However, the combustion in the combustion chamber of the diesel engine is performed under a large air-excess ratio, and the amount of HC and CO produced by the combustion is relatively small. Therefore, even if the total amount of the fuel is the same, the amount of HC and CO supplied to the sulfate absorbent increases as the amount of secondary fuel supplied to the exhaust gas passage increases. Though Fig. 7 shows the case in which HC and CO are supplied to the sulfate absorbent by secondary fuel, the ratio of SO 3 can be reduced by supplying the substance having a great affinity such as CO to the sulfate absorbent by other methods. Fig. 8 shows the case in which soot on the DPF 93 in Fig. 5 is burned by increasing exhaust gas temperature without supplying secondary fuel. In Fig. 8, the horizontal axis represents the temperature of the exhaust gas flowing into the DPF (sulfate absorbent) 93 and the vertical axis represents the ratio of SO 3 in the SO x released from the DPF and the concentration of CO in the exhaust gas. The curves A1 and A2 in Fig. 8 show the change in the ratio of SO 3 and the curves B1 and B2 show the change in the concentration of CO, respectively. Further, the curves A1 and B1 represent the case in which the amount of soot collected by the DPF 93 is large, and the curves A2 and B2 represent the case in which the amount of soot collected by DPF 93 is small. In Fig. 8, when the temperature of exhaust gas increases, the soot collected on the DPF 93 starts to burn at around 550°C. This causes the concentration of CO in the exhaust gas to increase. The concentration of CO in the exhaust gas increases as the exhaust gas temperature becomes higher. Further, the amount (concentration) of CO in the exhaust gas is large when the amount of soot collected by the DPF 93 is larger (the curve B1), and smaller when the amount of soot is small (the curve B2). When the temperature of the exhaust gas increases, SO X is released from the absorbent. However, the ratio of SO 3 in the released SO X is different when the amount of CO in the exhaust gas is different. Namely, when the amount of soot collected by the DPF 93 is small (the curve A2), the ratio of SO 3 in the released SO X changes in accordance with the temperature of the exhaust gas in the manner same as that represented by the broken line in Fig. 3. However, when the amount of soot collected by the DPF 93 is large (the curve Al), the ratio of SO 3 in the released SO X decreases more rapidly as the exhaust gas temperature increases (i.e., as the amount of CO in the exhaust gas increases). Fig. 9 is a diagram showing the change in the ratio of SO 3 shown in Fig. 8, but the horizontal axis thereof is re-drawn in terms of the concentration of CO in the exhaust gas. As shown in Fig. 9, the ratio of SO 3 in the released SO X decreases as the concentration of CO in the exhaust gas increases. This means that if CO is supplied to the sulfate absorbent when SO X is released, the ratio of SO 3 is reduced without supplying secondary fuel. Thus, it will be understood that if the substance having a greater affinity for oxygen than SO 2 is supplied to the sulfate absorbent when SO X is released, the ratio of SO 3 in the released SO X can be largely reduced. Such a substance may be HC and CO produced by secondary fuel supplied to the exhaust gas, or CO produced by the combustion of soot on the DPF. These methods for supplying the substance may be performed separately or in combination. Fig. 10 is a flowchart illustrating an SO X releasing control in which HC and CO are supplied to the sulfate absorbent.by using both methods (combustion of secondary fuel and soot) in combination in the device in Fig. 5 This routine is performed by the ECU 20 at a predetermined regular intervals. The flowchart in Fig. 10 is the same as the flowchart in Fig. 6 except that the target temperature TK in this embodiment (step 1419) is set at a constant value regardless of the oxygen concentration C R although the target temperature T R in Fig. 6 is determined in accordance with the releasing temperature T D and the oxygen concentration C R (step 1005 in Fig.6). The amount of secondary fuel FIK in this embodiment is calculated in accordance with the amount of intake air Q, the exhaust gas temperature T EX and the target temperature TK of fixed value. The target temperature TK is set at a temperature at which the concentration of CO is increased by the combustion of soot (Fig. 8) and the ratio of SO 3 is decreased by the supply of secondary fuel (Fig. 7). Namely, in case of Figs. 7 and 8, the target temperature TK is set at a temperature between 600 to 700°C. According to the embodiment in Fig. 10, since the substance (such as HC and CO) having a greater affinity for oxygen than the affinity of SO 2 for oxygen is supplied to the sulfate absorbent when SO X is released, the ratio of SO 3 in the released SO X is largely reduced. As explained above, according to the present invention, since the ratio of SO 3 in the SO X released from the sulfate absorbent is largely reduced, the amount of particulate matter released into the atmosphere can be maintained at low level even if the engine is operated for a long period.

Claims: Method of reducing the amount of SO 3 in the exhaust gas of an internal combustion engine wherein the gas contains sulfur oxide (SO X ) and soot, comprising the steps of a) collecting the soot in a filter; b) absorbing the SOx with a sulfate absorbent at a first temperature below a temperature Td below which no SO X is released during actual operation and above which the releasing of SO X starts, c) releasing the SO X from the absorbent by raising the temperature above a second temperature Tr at which the ratio of SO 3 in the SO X released is lower than at Td as determined at the same oxygen concentration in the exhaust gas characterized in that the temperature of the absorbent is raised by burning the collected soot and supplying the combustion gas thereof to the absorbent. Method according to claim 1, characterized in that said filter is a sulfate absorbent filter. Method according to claim 1 or 2, characterized in that the releasing of SO X is started when it is determined that the temperature of the sulfate absorbent has reached T D or when the amount of the sulfur oxide absorbed by the sulfate absorbent has reached a predetermined value or when the pressure drop through the filter has reached a predetermined value. A method according to any of claims 1 to 3, further comprising a step for supplying a substance having an affinity for oxygen greater than the affinity of sulfur dioxide for oxygen to the sulfate absorbent when the absorbed sulfur oxide is released from the sulfate absorbent.

Inventors: ARAKI YASUSHI, MIZUNO TATSUJI, TANAKA TOSHIAKI, ARAKI, YASUSHI, MIZUNO, TATSUJI, TANAKA, TOSHIAKI, Araki, Yasushi, c/o Toyota Jidosha K.K., MIZUNO, TATSUJI, C/O TOYOTA JIDOSHA K.K., TANAKA, TOSHIAKI, C/O TOYOTA JIDOSHA K.K.
Applicants: TOYOTA MOTOR CO LTD, TOYOTA JIDOSHA KABUSHIKI KAISHA
Application year: 1996
Main classification: B01D53
IPC codes: F01N3, B01D53, F02D41