EP1301698A1

EP1301698A1 - Method for desulphurising at least one nox storage catalyst located in the exhaust gas channel of an internal combustion engine

Info

Publication number: EP1301698A1
Application number: EP01949366A
Authority: EP
Inventors: Ekkehard Pott
Original assignee: Volkswagen AG
Current assignee: Volkswagen AG
Priority date: 2000-07-05
Filing date: 2001-05-29
Publication date: 2003-04-16
Anticipated expiration: 2021-05-29
Also published as: WO2002002921A1; EP1301698B1; DE10032561A1; DE50112377D1

Abstract

The invention relates to a method for desulphurising at least one NOx storage catalyst located in the exhaust gas channel of an internal combustion engine. According to the inventive method, at least one gas sensor is located downstream from the NOX storage catalyst. When desulphurising is required, a minimum temperature of the NOx storage catalyst and a rich working mode of the internal combustion engine with λ < 1 is adjusted by at least temporarily influencing at least one working parameter of the internal combustion engine. The invention is characterised in that a) the internal combustion engine (14) is operated in a first phase (t1) when a need for desulphurising has been established, in the presence of a minimum temperature, initially according to a lean working mode with λ > 1 until a first threshold value (Sm) for lambda is reached in the gas sensor (21), b) the internal combustion engine (14), is operated in a second phase (t2) in a rich working mode with λ < 1 once the first threshold value (Sm) has been reached until a second threshold value (Sf) for lambda is reached in the gas sensor (21) or a measured or calculated H2S concentration downstream from the NOx storage catalyst reaches a threshold (Ss), c) the first phase (t1) and the following second phase (t2) are repeated until a measurable degree of sulphurisation is reached.

Description

METHOD FOR DESULFURING AT LEAST ONE NO X STORAGE CATALYST, SITUATED IN AN EXHAUST GAS CHANNEL OF AN INTERNAL COMBUSTION ENGINE

The invention relates to a method for desulfurization of at least one NO _x storage catalytic converter arranged in an exhaust gas duct of an internal combustion engine with the features mentioned in the preamble of claim 1.

Processes for the desulfurization of NO _x storage catalysts are known. So-called regeneration parameters, such as a minimum temperature at the NO _x storage catalytic converter and a working mode of the internal combustion engine, must be set with λ <1 during the desulfurization.

Under a working mode of the internal combustion engine with λ <1 (rich atmosphere), a proportion of reducing gas components, such as CO, HC or H ₂ , predominates, a proportion of oxygen in the exhaust gas. At λ> 1 (lean atmosphere) the oxygen concentration is dominant and the NO _x reduction is hindered. In addition, SO _{2 is} formed during combustion of the internal combustion engine in a lean atmosphere by combustion of changing sulfur components in the fuel. Like the NO ebenso, this is absorbed by the NO _x storage catalytic converter in a lean atmosphere. The SO ₂ absorption reduces _NOx - storage capacity of the NO _x storage catalyst and leads to the formation of local inhomogeneities due to rapid sulfate grain formation. Such inhomogeneities offer a point of attack for corrosive processes which can result in permanent damage to the NO _x storage catalytic converter.

It is therefore known to initiate the desulfurization in recurring cycles, it being possible to determine a need for desulfurization on the basis of a predeterminable degree of sulfurization of the NO _x storage catalytic converter. Such a degree of sulphurization can, for example, using a _NOx conversion determine in which a ratio of a concentration of NO _x before the NO _x - storage catalyst and after the NO _x storage catalytic converter is formed. After determining the need for desulfurization, suitable measures are then taken seized, for example a late ignition or a post-injection, in order to set the regeneration parameters.

A desulfurization time depends on the one hand on the level of the temperature, which can of course also be above a minimum temperature, and on the other hand on a position of the lambda value. The desulfurization time is shortened with rising temperatures and / or falling lambda values. However, H ₂ S is predominantly formed at very low lambda values, while SO ₂ is predominantly formed at lambda values just below 1. The formation of H ₂ S should be suppressed if possible, since this is odor-intensive. In addition, complete conversion of the reducing gas components at very low lambda values is no longer possible, so that a breakthrough of pollutants cannot be avoided.

It is known to suppress the formation of H ₂ S by periodically applying lean and rich exhaust gas to the NO _x storage catalytic converter. Since the SO ₂ formation is kinetically preferred over the H ₂ S formation, the H ₂ S formation can be largely suppressed by choosing a sufficiently high lambda wobble frequency. The disadvantage here is that the desulfurization time is extended significantly and that a constantly changing catalyst state is not taken into account. Thus, signs of aging, such as a decrease in the ability to store oxygen, cannot be taken into account.

The object of the process according to the invention is to carry out the desulfurization taking account of time-varying catalyst states. On the one hand, the formation of H ₂ S should be largely suppressed and, on the other hand, the desulfurization time should be kept as short as possible, so that additional fuel consumption due to desulfurization can be reduced.

According to the invention, this object is achieved by the method for desulfurization with the features mentioned in claim 1. As a result of that

(a) the internal combustion engine in a first phase after determining the need for desulfurization and when the minimum temperature is present initially operated under a lean working mode with λ> 1 until a first threshold value for lambda is reached at the gas sensor,

(b) the internal combustion engine is operated in a second phase after reaching the first threshold value in the rich working mode with λ <1 until a second threshold value for lambda or a measured or calculated H ₂ S concentration downstream of the NO _x storage catalytic converter occurs at the gas sensor Threshold (S _s ) reached,

(c) the first phase and then the second phase) are repeated until a predeterminable degree of sulfurization is reached,

the desulfurization can be carried out with very short desulfurization times and with monitoring of the H ₂ S emission. In contrast to the conventional methods, the phases of rich and lean exposure to the NO _x storage catalytic converter are controlled or regulated, so that a very precise adaptation to the actual catalytic converter conditions and conditions during the desulfurization can take place in this way.

In a preferred embodiment of the method, the threshold value for the H ₂ S concentration is set to a value <100 ppm, preferably <50 ppm, in particular <10 pprn. The H ₂ S concentration can be determined with the aid of a sulfur-sensitive measuring device arranged downstream of the NO _x storage catalytic converter based on a signal for a content of a sulfur-containing component in the exhaust gas. Electrochemical cells can be used as the sensor element of such a sulfur-containing measuring device, in which an electromotive force is detected as a function of a sulfur concentration in the vicinity of the measuring electrodes. Systems are also conceivable in which resistances of the sensor element or its conductivity, which depend on the sulfur concentration, are measured via resistance cells. Such sensor elements are known for example from DE 31 122 18 and EP 0 700 517 B1. Accordingly, a calculated or measured value for the H ₂ S concentration can be used to determine an end of the time phase. It is also preferred to redefine the setpoints and / or the threshold values in each new desulfurization cycle (first and second phase). These can then be varied in particular as a function of a currently stored sulfur mass, a sulfur mass at the beginning of the desulfurization, a catalyst temperature, an oxygen storage capacity or a duration of the first and second phases. It is also conceivable to vary the temperature during the desulfurization. The measures shown allow the desulfurization to be adapted much more dynamically to the current state of the catalyst.

Further preferred embodiments of the invention result from the other features mentioned in the subclaims.

The invention is explained in more detail below in exemplary embodiments with reference to the associated drawings. Show it:

Figure 1 shows an arrangement of a catalyst system in an exhaust duct of an internal combustion engine and

FIG. 2 shows a course of lambda in front of and behind a NO _x .

Storage catalyst and an H ₂ S concentration during desulfurization.

An arrangement of a catalytic converter system 10 in an exhaust duct 12 of an internal combustion engine 14 is shown schematically in FIG. The catalytic converter system 10 comprises a NO _x storage catalytic converter 16 and a pre-catalytic converter 18 as well as various temperature sensors 22. Furthermore, there are gas sensors 19, 20, 21 in the exhaust gas duct 12, which are used to detect at least one gas component of an exhaust gas of the internal combustion engine and a signal corresponding to a content provide the gas component on the exhaust gas. Such gas sensors 19, 20, 21 are known and can be, for example, NO _x sensors or lambda sensors.

Furthermore, a sulfur-sensitive measuring device 23 can be arranged downstream of the NO _x storage catalytic converter 16 in the exhaust gas duct 12 of the internal combustion engine 14 his. The measuring device 23 enables a concentration determination of a sulfur-containing component, such as sulfur dioxide SO ₂ . Based on the resistance or the conductivity of a sensor element of such a measuring device 23, the concentration of the sulfur-containing component can be deduced by comparison with a stored characteristic curve. The H ₂ S concentration can also be determined on the basis of empirical values with operating parameters of the internal combustion engine 14, such as, for example, the lambda value detected by the gas sensor 21. With a corresponding design of the measuring device 23, it is also conceivable to directly record the H ₂ S concentration. The measured or calculated H ₂ S concentration is then used for the further regulation of the desulfurization process shown here.

A working mode of the internal combustion engine 14 can be regulated by means of an engine control unit 24. If, for example, a working mode with λ <1 (rich atmosphere) is desired, an oxygen concentration in an intake manifold 26 must be reduced before a fuel-air mixture is combusted. This increases the proportion of reducing gas components in the exhaust gas compared to a proportion of oxygen. For example, such a working mode can take place by reducing a volume flow of intake air by means of a throttle valve 28 and by simultaneously supplying low-oxygen exhaust gas via an exhaust gas reflux valve 30.

In a working mode with λ> 1 (lean atmosphere), in addition to NO _x , SO _{2 is} also absorbed in the NO _x storage catalytic converter 16, while the small proportions of reducing gas components are converted almost completely in the precatalyst 18, at least at low space velocities. Depending on a NO _x storage capacity and a desorption temperature of the NO _x storage catalytic converter 16, the internal combustion engine 14 must be operated with λ <1 for regeneration. In such a working mode, the previously absorbed NO _{x is} reduced on a catalytically active surface of the NO _x storage catalytic converter 16.

Likewise absorbed SO ₂ is stored in the form of sulfate in the NO _x storage catalytic converter 16, although reversibility of this storage process, in contrast to the storage of NO _x, requires significantly higher temperatures. A minimum desulfurization temperature and a lambda value <1 must therefore be available for desulfurization (regeneration parameters).

A desulfurization requirement arises from the efficiency of the NO _x storage catalytic converter 16 for a conversion reaction of NO _x . The efficiency can be detected with the aid of the gas sensor 21, which measures a NO _x concentration behind the NO _x storage catalytic converter 16. Based on empirical values or by measuring the NO _x concentration upstream of the NO _x storage catalytic converter 16 - for example with at least one of the gas sensors 19, 20 - the NO storage efficiency can be determined in this way and a conclusion can be drawn about a degree of sulfurization. A current temperature (catalyst temperature) on the NO _x storage catalytic converter 16 can be detected via the temperature sensors 22, while the current lambda value upstream of the NO _x storage catalytic converter 16 can in turn be determined via at least one of the gas sensors 19 and / or 20.

A desulfurization time depends on the temperature at the NO _x storage catalytic converter 16 and the position of the lambda value. The desulfurization time decreases as the temperature rises and the lambda value falls. The temperature can be significantly higher than the minimum temperature and can also be changed during the desulfurization according to a temperature model.

At very low lambda values, the desulfurization predominantly leads to H ₂ S, while at lambda values just below 1, predominantly SO _{2 is} formed. Since H ₂ S is odor-intensive, its formation in the process according to the invention should be largely suppressed. Another disadvantage is that at very low lambda values a complete conversion of the reducing gas components is no longer possible and so-called pollutant breakthroughs occur. Since the H ₂ S formation is kinetically inhibited compared to the SO ₂ formation, the H ₂ S formation can be suppressed by periodically changing the working mode of the internal combustion engine.

FIG. 2 shows a course of a lambda value in front of and behind the NO _x storage catalytic converter 16 as an example. Furthermore, FIG. 2 shows a course of the H ₂ S concentration as it is measured with the aid of the measuring device 23 downstream of the NO _x Storage catalyst 16 is detectable. The course of the lambda value in front of the NO _x storage catalytic converter 16 (solid line) can be monitored with the gas sensor 20, while the gas sensor 21 shows a course of the lambda value behind the NO _x storage catalytic converter 16 (dashed line). If the need for desulfurization is determined at a time To and, for example, the minimum temperature has not yet been reached, an exhaust gas temperature can be increased in a heating phase to by at least temporarily influencing at least one operating parameter of the internal combustion engine 14. For this purpose, it is usually switched to a working mode with λ = 1, since the exhaust gas here has a higher temperature, the pollutant emissions are low and the fuel consumption does not increase excessively. Such a procedure is known and is therefore not explained in more detail.

After reaching the minimum temperature at a time T- _| the internal combustion engine 14 is regulated during the phase t-] in such a way that a lambda value corresponding to a predefinable target value W _{m is} established in front of the NO _x storage catalytic converter 16. The target value W _m should be in a lambda range of 1.01 to 4.00, preferably 1.02 to 1.7, in particular 1.03 to 1.1.

A change in the lambda value behind the NO _x storage catalytic converter 16 takes place with a time delay. This time delay is based not only on a dead volume of the NO _x storage catalytic converter 16, but is also dependent on the removal and storage of the oxygen in the NO _x storage catalytic converter 16. In a region 40, the lambda value behind the NO _x storage catalytic converter increases 16 steeply, the steepness of the increase being determinable by the height of the setpoint W _m . The higher W _m is, the steeper the region 40 rises. From a time T ₂ , the lambda value behind the NO _x storage catalytic converter 16 reaches a first threshold value S _m , whereupon the internal combustion engine 14 is set to the rich working mode. A target value Wf for lambda is again determined in front of the NO _x storage catalytic converter 16. The setpoint Wf is in a range from λ = 0.995 to 0.65, preferably 0.99 to 0.75, in particular 0.98 to 0.85.

After the change of the working mode from the time T ₂ , the NO _x storage catalytic converter 16 is charged with the rich atmosphere for a phase t _{2 in} accordance with the desired value Wf. Shortly after the threshold value S _{m is reached} , the Lambda value in a region 42 is still briefly on, since the change of the working mode occurs only behind the NO _x storage catalytic converter 16 with a time delay. In an area 44, the lambda value behind the NO _x storage catalytic converter 16 drops steeply to a lambda value = 1 (area 46). The value remains close to λ = 1 in the region 46 until the oxygen stored in the NO _x storage catalytic converter 16 and the at least partially overlapped released SO _x are reduced from a point in time T ₃ until the lambda signal gradually moves in the direction of the Setpoint Wf drifts (area 50).

As already mentioned, the lower part of FIG. 2 shows a curve of the H ₂ S concentration downstream of the NO _x storage catalytic converter 16. In phases of stoichiometric or lean operation, the H ₂ S concentration is close to zero. The H ₂ S concentration gradually increases (range 60) only when the change to rich operation begins (time T ₂ ). The increase is generally not linear, but exponential, as the kinetic factors in H ₂ S formation fade into the background with increasing duration of the second phase t ₂ .

A renewed change of the working mode can now be triggered by either the lambda value downstream of the NO _x storage catalytic converter 16 reaching a rich threshold value S _f or - as shown here - the H ₂ S concentration exceeding a threshold value S _s (time T ₄ ) , The threshold value S _s is usually set to a value of <100 ppm, preferably <50 ppm, in particular <10 ppm.

After the threshold value S _{s has been reached} , the internal combustion engine 14 is again operated under a lean atmosphere, in accordance with the desired value W _m . Due to the volume, the lambda value falls behind the NO _x storage catalytic converter 16 for a short time in an area 52, and then subsequently increases again in an area 54. Conversely, the H ₂ S concentration rises briefly (area 62), only to then drop again very quickly to very low emission values (area 64). A steepness of the increase in the area 54 is determined not only by the position of the setpoint W _m , but also by an additional oxygen storage in the NO _x storage catalytic converter 16. From a point in time T ₅ , an oxygen storage capacity is exhausted and therefore the lambda value rises adjoining area 58 is steeper. After the threshold value S _m has been reached again, the phase t ₂ follows again, that is to say a change to a rich atmosphere is initiated (time T ₆ ). Phase t-] and phase t ₂ repeat until a predeterminable degree of sulfurization is reached and then the internal combustion engine 14 is switched back to normal operation. The setpoints W and / or the threshold values S _f , S _m , S _s can be redefined in each new cycle of desulfurization (phases ti and t ₂ ) depending on the catalyst state parameters. As

Catalyst state parameters come into consideration here, such as a currently stored sulfur mass, a sulfur mass at the beginning of desulfurization, a catalyst temperature, an oxygen storage capacity or a duration of the preceding phases ti and t ₂ . The redefinition enables an optimal compromise to be found between the shortest possible desulfurization time on the one hand and the lowest possible pollutant emissions during the desulfurization on the other.

LIST OF REFERENCE NUMBERS

10 catalyst system

12 exhaust duct

14 internal combustion engine

16 NO _x storage catalytic converter

18 pre-catalytic converter

19 gas sensor

20 gas sensor

21 gas sensor

22 temperature sensors

23 sulfur sensitive measuring device

24 Engine control unit 26 Intake pipe

28 throttle valve

30 exhaust gas reflux valve

40, 42, 44, 46, 50, 52, 54, 58 selected areas of the course of the lambda signal behind the NO _x storage catalytic converter 60, 62, 64 selected areas of the course of the H ₂ S

Concentration W _m lean target value W _f fat setpoint S _m lean threshold value S _f fat threshold value S _s threshold for the H ₂ S concentration T instants tj periods lambda value λ

Claims

PATE N TAN SPEECH

1. A method for desulfurization of at least one NO _x storage catalytic converter arranged in an exhaust gas duct of an internal combustion engine, at least one gas sensor being arranged downstream of the NO _x storage catalytic converter, and in which a minimum temperature on the NO _x storage catalytic converter and a rich working mode are determined after a need for desulfurization has been determined the internal combustion engine is set with λ <1 by at least temporarily influencing at least one operating parameter of the internal combustion engine, characterized in that

(a) the internal combustion engine (14) is operated in a first phase (t- |) after determining the need for desulfurization and when the minimum temperature is present, under a lean working mode with λ> 1 until a first threshold value is reached at the gas sensor (21) (S _m ) for lambda is reached

(b) the internal combustion engine (14) is operated in a second phase (t ₂ ) after reaching the first threshold value (S _m ) in the rich working mode with λ <1 until a second threshold value (Sf) for lambda at the gas sensor (21) or a measured or calculated H ₂ S concentration downstream of the NO _x storage catalytic converter reaches a threshold value (S _s ),

(c) the first phase (ti) and then the second phase (t ₂ ) are repeated until a predeterminable degree of sulfurization is reached.

2. The method according to claim 1, characterized in that the threshold value (S _s ) of the H ₂ S concentration is set to a value <100 ppm, preferably <50 ppm, in particular <10 ppm.

3. The method according to claim 2, characterized in that arranged by a downstream of the NO _x storage catalyst (16) sensitive to sulfur Measuring device (23) detects a signal for a content of a sulfur-containing component in the exhaust gas and from this the H S concentration is determined.

4. The method according to any one of claims 1 to 3, characterized in that the internal combustion engine (14) during the first phase (t- |) is set to a lean working mode corresponding to at least one target value (W _m ) and during the second phase (t ₂ ) the internal combustion engine (14) is set in a rich working mode in accordance with at least one target value (Wf) (target values W).

5. The method according to claim 4, characterized in that the target value (Wf) is in a range from λ = 0.65 to 0.995, preferably 0.75 to 0.99, in particular 0.85 to 0.98.

6. The method according to claim 4, characterized in that the target value (W _m ) is in a range from λ = 1.01 to 4, preferably 1.02 to 1.7, in particular 1.03 to 1.1.

7. The method according to any one of the preceding claims, characterized in that the target values (W) and / or the threshold values (Sf, S _m , S _s ) in each new cycle of desulfurization (phases t- _| and t ₂ ) as a function of the catalyst state parameters.

8. The method according to claim 7, characterized in that a currently stored sulfur mass, a sulfur mass at the beginning of desulfurization, a catalyst temperature, an oxygen storage capacity, a duration of the phases (ti and t ₂ ) or a combination thereof are used as the catalyst state parameters.