U.S. patent application number 11/839958 was filed with the patent office on 2008-02-21 for catalytic converter configuration and method for desulfurizing a nox storage catalytic converter.
This patent application is currently assigned to VOLKSWAGEN AG. Invention is credited to Achim Freitag, Martina Kosters.
Application Number | 20080041038 11/839958 |
Document ID | / |
Family ID | 38973200 |
Filed Date | 2008-02-21 |
United States Patent
Application |
20080041038 |
Kind Code |
A1 |
Freitag; Achim ; et
al. |
February 21, 2008 |
Catalytic Converter Configuration and Method for Desulfurizing a
NOx Storage Catalytic Converter
Abstract
A catalytic converter configuration for an internal combustion
engine that is capable of running lean has an exhaust gas duct and
a NO.sub.x storage catalytic converter arranged in the exhaust gas
duct. A novel method allows desulfurizing the NO.sub.x storage
catalytic converter. An H.sub.2S storage catalytic converter is
provided. This catalytic converter is capable of storing hydrogen
sulfide under a rich or stoichiometric exhaust gas atmosphere with
lambda.ltoreq.1 and oxidizing hydrogen sulfide under a lean exhaust
gas atmosphere with lambda>1.
Inventors: |
Freitag; Achim;
(Wolfenbuttel, DE) ; Kosters; Martina; (Hannover,
DE) |
Correspondence
Address: |
LERNER GREENBERG STEMER LLP
P O BOX 2480
HOLLYWOOD
FL
33022-2480
US
|
Assignee: |
VOLKSWAGEN AG
Wolfsburg
DE
|
Family ID: |
38973200 |
Appl. No.: |
11/839958 |
Filed: |
August 16, 2007 |
Current U.S.
Class: |
60/287 ; 60/295;
60/299 |
Current CPC
Class: |
F01N 3/0842 20130101;
F01N 3/0864 20130101; Y02T 10/22 20130101; F01N 3/0814 20130101;
F01N 2510/0684 20130101; F01N 2570/04 20130101; F01N 2510/06
20130101; F01N 13/0097 20140603; F01N 3/0885 20130101; F01N 13/009
20140601; Y02T 10/12 20130101 |
Class at
Publication: |
60/287 ; 60/295;
60/299 |
International
Class: |
F01N 3/20 20060101
F01N003/20 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 16, 2006 |
DE |
10 2006 038 367.2 |
Claims
1. A catalytic converter configuration for an internal combustion
engine that is capable of running lean, comprising: an exhaust gas
duct connected with the internal combustion engine; a NO.sub.x
storage catalytic converter disposed in said exhaust gas duct; and
an H.sub.2S storage catalytic converter configured to store
hydrogen sulfide under a rich or stoichiometric exhaust gas
atmosphere with lambda.ltoreq.1 and to release the hydrogen sulfide
under a lean exhaust gas atmosphere with lambda>1.
2. The catalytic converter configuration according to claim 1,
wherein said H.sub.2S storage catalytic converter is disposed
downstream and at a spacing distance from said NO.sub.x storage
catalytic converter.
3. The catalytic converter configuration according to claim 1,
wherein said H.sub.2S storage catalytic converter is disposed
downstream and adjoining said NO.sub.x storage catalytic
converter.
4. The catalytic converter configuration according to claim 1,
wherein said H.sub.2S storage catalytic converter is integrated in
said NO.sub.x storage catalytic converter.
5. The catalytic converter configuration according to claim 1,
wherein said H.sub.2S storage catalytic converter contains at least
one metal component suitable for binding H.sub.2S as a metal
sulfide under a rich or stoichiometric exhaust gas atmosphere with
lambda.ltoreq.1.
6. The catalytic converter configuration according to claim 5,
wherein said metal component includes at least one metal of
subgroups I, II and/or VIII of the table of elements.
7. The catalytic converter configuration according to claim 5,
wherein said metal component includes at least one component
selected from the group consisting of Ag, Zn, Cd, Fe, Co, and
Ni.
8. The catalytic converter configuration according to claim 5,
wherein a specific loading of said H.sub.2S catalytic converter
with said at least one metal component amounts to at least 0.2
grams per liter.
9. The catalytic converter configuration according to claim 5,
wherein a specific loading of said H.sub.2S catalytic converter
with said at least one metal component amounts to at least 0.5
grams per liter.
10. The catalytic converter configuration according to claim 1,
wherein said H.sub.2S storage catalytic converter additionally has
an oxidation catalytic component or a three-way catalytic
component.
11. The catalytic converter configuration according to claim 5,
wherein said H.sub.2S storage catalytic converter contains at least
one noble metal component.
12. The catalytic converter configuration according to claim 11,
wherein said noble metal component is selected from the group
consisting of platinum, palladium, and rhodium.
13. The catalytic converter configuration according to claim 1,
which further comprises a component for storing oxygen disposed
downstream of said NO.sub.x storage catalytic converter and/or of
said H.sub.2S storage catalytic converter.
14. The catalytic converter configuration according to claim 1,
which comprises an oxygen-sensitive gas sensor disposed downstream
of said NO.sub.x storage catalytic converter and/or of said
H.sub.2S storage catalytic converter.
15. The catalytic converter configuration according to claim 14,
wherein said oxygen-sensitive gas sensor is a lambda probe or a
NO.sub.x sensor.
16. A method of desulfurizing a NO.sub.x storage catalytic
converter disposed in an exhaust gas duct of an internal combustion
engine that is capable of running lean, which comprises: exposing
the NO.sub.x storage catalytic converter at least temporarily to a
rich or stoichiometric exhaust gas atmosphere with lambda.ltoreq.1
at a desulfurization temperature of the NO.sub.x storage catalytic
converter; and storing hydrogen sulfide released from the NO.sub.x
storage catalytic converter in an H.sub.2S storage catalytic
converter; and releasing the hydrogen sulfide in a lean exhaust gas
atmosphere with lambda>1.
17. The method according to claim 16, which comprises, during
desulfurization, alternately exposing the NO.sub.x storage
catalytic converter to rich intervals with a rich or stoichiometric
exhaust gas atmosphere with lambda.ltoreq.1 and in lean intervals
to a lean exhaust gas atmosphere with lambda>1.
18. The method according to claim 16, which comprises regenerating
the H.sub.2S storage catalytic converter by an oxidation product of
H.sub.2S.
19. The method according to claim 16, which comprises regenerating
the H.sub.2S storage catalytic converter by regeneration of
SO.sub.2 by exposure of the H2S storage catalytic converter to a
lean exhaust gas atmosphere and a minimum temperature.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority, under 35 U.S.C.
.sctn.119, of German patent application DE 10 2006 038 367.2, filed
Aug. 16, 2006; the prior application is herewith incorporated by
reference in its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The invention relates to a catalytic converter configuration
for internal combustion engines capable of running lean and having
a NO.sub.x storage catalytic converter arranged in their exhaust
gas duct. The invention also relates to a method for desulfurizing
the NO.sub.x storage catalytic converter.
[0003] In internal combustion engines which are operated with a
lean fuel-air mixture, traditional three-way catalytic converters
are not sufficient for quantitative conversion of all exhaust gas
constituents, in particular nitrogen oxides NO.sub.x. Therefore,
the arrangement of so-called NO.sub.x storage catalytic converters
in the exhaust gas ducts of such internal combustion engines is
known. NO.sub.x storage catalytic converters have a NO.sub.x
storage component which stores NO.sub.x under a lean exhaust gas
atmosphere. NO.sub.x regeneration is performed through short rich
intervals during which the stored NO.sub.x is desorbed and
converted to N.sub.2 and O.sub.2 by means of a catalytic component
of the NO.sub.x storage catalytic converter. The use of NO.sub.x
storage catalytic converters is known in both diesel engines and
lean mix gasoline engines.
[0004] Due to the sulfur that is present in the fuel, the NO.sub.x
storage catalytic converter loses activity over its surface life.
This is referred to as sulfur poisoning. The sulfur is deposited in
the form of sulfate on the storage components of the catalytic
converter, thereby blocking the NO.sub.x storage sites of the
storage catalytic converter so they are no longer available for
storing NO.sub.x. If a lower limit of NO.sub.x storage capacity of
the NO.sub.x storage catalytic converter is reached, it must be
desulfurized (desulfated). This is performed at high exhaust gas
temperatures of at least 500.degree. C. by exposing the storage
catalytic converter to a rich exhaust gas atmosphere (lambda<1).
At these temperatures, the stored sulfur is desorbed and reduced to
SO.sub.2 by the reducing exhaust gas atmosphere while also being
reduced to hydrogen sulfide H.sub.2S. The richer the exhaust gas
conditions during desulfurization, the faster the desorption and
reduction of sulfur take place, which has positive effects on
thermal aging of the storage catalytic converter, but is associated
with an increase in the unwanted formation of H.sub.2S.
[0005] It is known that to perform desulfurization, the engine is
operated alternately in rich operation with lambda<1 and in lean
operation with lambda>1 for short intervals of time, i.e., in
so-called wobble operation. This promotes the heating of the
catalytic converter to the required desulfurization temperature and
maintaining same. Furthermore, due to the alternating exposure of
the storage catalytic converter to rich and lean exhaust gas,
production of H.sub.2S is decreased because in the lean intervals
oxygen is incorporated into the catalytic converter, thereby
ensuring oxidation of H.sub.2S, which is formed as an intermediate,
to SO.sub.2. However, it has been found that complete
desulfurization of a storage catalytic converter in wobble
operation is also associated with a certain production of H.sub.2S,
the concentration of which may result in exceeding limit
values.
SUMMARY OF THE INVENTION
[0006] It is accordingly an object of the invention to provide a
catalytic converter configuration and a method for desulfurizing a
NO.sub.x storage catalyst which overcomes the above-mentioned
disadvantages of the heretofore-known devices and methods of this
general type and which allows desulfurizing the NO.sub.x storage
catalyst in such a way that it protects the catalytic converter and
in which production of H.sub.2S is minimized. It is a concomitant
object to provide for a catalytic converter configuration that is
suitable for implementing the novel method.
[0007] With the foregoing and other objects in view there is
provided, in accordance with the invention, a catalytic converter
configuration for an internal combustion engine that is capable of
running lean, comprising:
[0008] an exhaust gas duct connected with the internal combustion
engine;
[0009] a NO.sub.x storage catalytic converter disposed in said
exhaust gas duct; and
[0010] an H.sub.2S storage catalytic converter configured to store
hydrogen sulfide under a rich or stoichiometric exhaust gas
atmosphere with lambda.ltoreq.1 and to release the hydrogen sulfide
under a lean exhaust gas atmosphere with lambda>1.
[0011] In other words, the objects of the invention are achieved by
a catalytic converter configuration that includes an H.sub.2S
storage catalytic converter that is suitable for storing hydrogen
sulfide H.sub.2S under rich or stoichiometric exhaust gas
atmosphere, i.e., with an air/fuel ratio of lambda.ltoreq.1 and
then releasing it in a lean exhaust gas atmosphere, with
lambda>1, in particular essentially as sulfur dioxide SO.sub.2.
Through the inventive arrangement of the H.sub.2S storage catalytic
converter it is possible to desulfurize the NO.sub.x storage
catalytic converter under constantly rich exhaust gas conditions
and thus at relatively low temperatures, thereby delaying its
thermal aging. At the same time unwanted H.sub.2S emissions are
greatly reduced or even prevented entirely.
[0012] According to an advantageous embodiment of the invention,
the H.sub.2S storage catalytic converter is connected downstream
from the NO.sub.x storage catalytic converter in the direction of
flow of the exhaust gas, the H2S storage catalytic converter being
arranged directly adjacent to the NO.sub.x storage catalytic
converter or at a distance therefrom. As an alternative the
H.sub.2S storage catalytic converter may also be integrated into
the NO.sub.x storage catalytic converter, i.e., there may be a
mixed coating of H.sub.2S and NO.sub.x storage catalytic converter
components on a common support for the catalytic converter. All
these requirements ensure that the H.sub.2S released from the
NO.sub.x storage catalytic converter is stored and converted in the
H.sub.2S storage catalytic converter.
[0013] As the H.sub.2S storage component of the H.sub.2S storage
catalytic converter, it preferably contains a metal component which
is suitable for binding H.sub.2S as metal sulfide in particular
under rich or stoichiometric exhaust gas atmosphere. The
prerequisite for selecting the suitable metal component is its
suitability for entering into a metal-sulfur compound in the rich
exhaust gas and releasing the sulfur, preferably in the form of
SO.sub.2, under lean conditions. Metals of subgroups I, II and/or
VIII of the periodic system of elements are especially suitable for
this purpose, preferably using silver (Ag), zinc (Zn), cadmium
(Cd), iron (Fe), cobalt (Co) and/or nickel (Ni). The loading of the
H.sub.2S storage catalytic converter with the metal component
depends on the desired H.sub.2S storage capacity of the H.sub.2S
storage catalytic converter, in particular after typical sulfur
loading of the NO.sub.x storage catalytic converter to be removed
at the time of its desulfurization. In typical cases, a specific
metal loading of at least 0.2 g/l has proven advantageous, in
particular at least 0.3 g/L, especially preferably at least 0.5
g/l.
[0014] Furthermore it is preferably also provided that the H.sub.2S
storage catalytic converter may additionally have an oxidation
catalytic component or a three-way catalytic component under a lean
exhaust gas atmosphere, i.e., it catalyzes oxidation of carbon
moNOxide CO and/or hydrocarbons HC and--in the case of a three-way
catalytic effect--additionally supports reduction of nitrogen
oxides NO.sub.x. To do so, the catalytic converter may additionally
contain at least one noble metal, e.g., platinum (Pt), palladium
(Pd) and/or rhodium (Rh).
[0015] Another advantageous embodiment according to the invention,
the catalytic converter configuration also has an oxygen-storing
component downstream from the NO.sub.x storage catalytic converter
and/or the H.sub.2S storage catalytic converter, this
oxygen-storing component being capable of storing oxygen in a lean
exhaust gas atmosphere and releasing oxygen under a rich exhaust
gas atmosphere, so that H.sub.2S desorbed from the NO.sub.x storage
catalytic converter is oxidized to SO.sub.2. Such oxygen-storing
components (OSC for oxygen storage component) are known in the
state of the art and therefore will not be explained further here.
In addition with the help of the oxygen stored in the OSC, the
components CO and HC can also be converted and thus emissions in
rich operation can be reduced.
[0016] The present invention also relates to a method for
desulfurizing a NO.sub.x storage catalytic converter in which
hydrogen sulfide coming from the NO.sub.x storage catalytic
converter is stored in an H.sub.2S storage catalytic converter and
is released again, preferably as SO.sub.2 under a lean exhaust gas
atmosphere having a lambda>1 in particular above a certain
catalytic converter temperature. The release temperature in the
H.sub.2S storage catalytic converter may be induced by an upstream
particle filter reaction, for example (by way of PF
regeneration).
[0017] It is especially advantageous to alternately treat the
NO.sub.x storage catalytic converter in so-called wobble operation
during desulfurization, i.e., with rich intervals with
lambda.ltoreq.1 and lean intervals with lambda>1. However, the
desulfurization may also essentially be performed in continuous
rich operation of the internal combustion engine using the
catalytic converter configuration described above.
[0018] Other features which are considered as characteristic for
the invention are set forth in the appended claims.
[0019] Although the invention is illustrated and described herein
as embodied in catalytic converter configuration and method for
desulfurizing a NO.sub.x storage catalytic converter, it is
nevertheless not intended to be limited to the details shown, since
various modifications and structural changes may be made therein
without departing from the spirit of the invention and within the
scope and range of equivalents of the claims.
[0020] The construction and method of operation of the invention,
however, together with additional objects and advantages thereof
will be best understood from the following description of specific
embodiments when read in connection with the accompanying
drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0021] FIG. 1 shows an internal combustion engine having a
downstream catalytic converter configuration according to a first
embodiment of the invention;
[0022] FIG. 2 shows an internal combustion engine having a
downstream catalytic converter configuration according to a second
embodiment of the invention;
[0023] FIG. 3 shows an internal combustion engine having a
downstream catalytic converter configuration according to a third
embodiment of the invention;
[0024] FIG. 4 shows curves of the lambda value as a function of
time, measured upstream and downstream from the NO.sub.x storage
catalytic converter as well as the SO.sub.2 and H.sub.2S
concentrations after the NO.sub.x storage catalytic converter
during desulfurization of the NO.sub.x storage catalytic converter
in the catalytic converter configuration according to FIG. 1;
and
[0025] FIG. 5 shows curves of the SO.sub.2 and H.sub.2S
concentrations downstream from the NO.sub.x storage catalytic
converter according to the present invention and the state of the
art as a function of time.
DETAILED DESCRIPTION OF THE INVENTION
[0026] Referring now to the figures of the drawing in detail and
first, particularly, to FIG. 1 thereof, there is illustrated an
internal combustion engine 10 which can be operated with a lean
air-fuel mixture. This may be a diesel engine or a gasoline engine
capable of running lean.
[0027] According to a first advantageous embodiment of the present
invention, a catalytic converter configuration 12 is connected
downstream from the internal combustion engine 10. Exhaust gas
emanating from the internal combustion engine 10 is directed into
the catalytic converter configuration, where it is after-treated.
The catalytic converter configuration 12 comprises an exhaust gas
duct 14 in which various catalytic converters are arranged.
According to the embodiment depicted here, an oxidation catalytic
converter or a three-way catalytic converter that acts as a
precatalytic converter 16 is arranged in a position near the
internal combustion engine 10. Alternatively or in addition to the
precatalytic converter 16 a particulate filter (not shown here) may
also be arranged near the engine for storing soot (carbon black)
particles and may optionally also be combined with the oxidative or
three-way precatalytic converter 16 on a common support.
[0028] Downstream from the precatalytic converter 16 (and/or the
particle filter provided as an alternative or in addition), a
NO.sub.x storage catalytic converter 18 is provided in the exhaust
gas duct 14. The NO.sub.x storage catalytic converter 18 has a
NO.sub.x storage component which stores NO.sub.x under a lean
exhaust gas atmosphere and releases it again in the intermediate
regeneration intervals during which the internal combustion engine
10 is operated with a stoichiometric or rich air-fuel mixture. An
oxidation component or three-way component integrated into the
NO.sub.x storage catalytic converter 18 catalyzes the reaction of
the desorbed nitrogen oxides N.sub.2 and oxygen O.sub.2 during the
NO.sub.x regeneration.
[0029] In addition to NO.sub.x storage, incorporation of sulfur
present in the fuel also takes place in the form of sulfate in the
NO.sub.x storage catalytic converter 18 in an unwanted manner.
Since the sulfur is not removed from the NO.sub.x storage catalytic
converter 18 during the usual NO.sub.x regeneration thereof, it
therefore accumulates in the storage catalytic converter 18 and
leads to increasing blockage of the NO.sub.x storage sites. To
ensure an adequate NO.sub.x storage activity, desulfurization is
performed at greater intervals. To do so, the NO.sub.x storage
catalytic converter 18 is heated to a desulfurization temperature
of 550.degree. C. or more, for example, through engine-related
measures, and is at least temporarily exposed to a rich or
stoichiometric exhaust gas atmosphere having a lambda<1. Under
these conditions, sulfur is desorbed and released mainly in the
form of sulfur dioxide SO.sub.2. However, a portion of the sulfur
is released in the form of hydrogen sulfide H.sub.2S during the
desulfurization, which is also unwanted because of the toxicity of
H.sub.2S and its odor problem. The formation of H.sub.2S is even
more intense, the richer the air-fuel mixture and the longer the
NO.sub.x storage catalytic converter 18 is exposed to the rich
exhaust gas. On the other hand, complete desulfurization of the
NO.sub.x storage catalytic converter 18 cannot be achieved with an
air-fuel mixture that is only slightly rich and/or desulfurization
must be performed at higher catalytic converter temperatures, which
is associated with a thermal burden on the NO.sub.x storage
catalytic converter 18 and an increased fuel consumption.
[0030] To avoid this problem, the catalytic converter configuration
12 according to this invention has an H.sub.2S storage catalytic
converter 20 which is arranged downstream from the NO.sub.x storage
catalytic converter 18 and directly adjacent thereto in the example
shown in FIG. 1. The H.sub.2S storage catalytic converter 20 is
designed to store H.sub.2S in the form of a metal sulfide in
particular under rich exhaust gas conditions and to release and
oxidize it to SO.sub.2 under lean exhaust gas conditions. For
example, a coating comprising a transition metal, e.g., nickel that
binds H.sub.2S as nickel sulfide is suitable for this. The H.sub.2S
storage catalytic converter 20 advantageously also has a three-way
catalytic component that is responsible for the reaction of HC, CO
and NO.sub.x during lean operation of the internal combustion
engine 10, so that the H.sub.2S storage catalytic converter 20
supports the precatalytic converter 16 or may even replace it. In
comparison with conventional three-way catalytic converters, the
coating of the H.sub.2S storage catalytic converter 20 has a much
greater loading with the transition metal. The transition metal
loading of the H.sub.2S storage catalytic converter 20 depends on
the sulfur load typically preventing in desulfurization of the
NO.sub.x storage catalytic converter 18, amounting to at least 0.2
g per liter catalytic converter volume, for example. The
arrangement of the H.sub.2S storage catalytic converter 20 allows
desulfurization of the NO.sub.x storage catalytic converter 18 to
be performed at relatively low temperatures and low lambda values
without having to accept undesirable H.sub.2S emissions. Due to the
low desulfurization temperatures, a thermal burden on the NO.sub.x
storage catalytic converter 18 and thus a shortening of its
lifetime are prevented. According to the example illustrated in
FIG. 1, the NO.sub.x and the H.sub.2S storage catalytic converters
18, 20 may be designed as spatially separate zones on one and the
same catalytic converter support or on a separate catalytic
converter support directly adjacent to one another.
[0031] The exhaust gas duct also contains various gas sensors.
Upstream from the precatalytic converter 16 (and/or the particulate
filter) there is an oxygen-sensitive gas sensor 22, in particular a
lambda probe which regulates the lambda regulation [sic; enables
lambda regulation] of the air-fuel mixture of the internal
combustion engine 10 in a known way. Another oxygen-sensitive gas
sensor 24 is arranged downstream from the H.sub.2S storage
catalytic converter 20. This may also be a lambda probe or a
NO.sub.x sensor, which supplies an oxygen-dependent signal.
Additional gas sensors and/or temperature sensors may also be
additionally installed in the exhaust gas duct 14.
[0032] The internal combustion engine 10 is supplied with air
through an air intake duct 26 in which there is an adjustable
throttle valve 28. An electronic engine control unit 30 which is
provided for controlling the internal combustion engine 10 receives
the signals of the gas sensors 22 and 24, any other gas and/or
temperature sensors that might be present as well as various
operating parameters of the internal combustion engine 10, e.g.,
rotational speed, the driver's intended torque, etc. Depending on
this data, the engine control unit 30 executes the control using
stored characteristic lines and/or engine characteristics maps, to
which end the control unit influences parameters, e.g., the
quantity the fuel, the injection point in time, the firing angle
(in gasoline engines), the exhaust gas recirculation EGR rate, air
mass, etc. The engine control unit 30 in particular also contains a
program algorithm for operating the exhaust gas system 12, in
particular for performing the desulfurization of the NO.sub.x
storage catalytic converter 18.
[0033] FIGS. 2 and 3 show other embodiments of the inventive
catalytic converter configuration 12, whereby corresponding
elements are labeled with the same reference numerals as those
shown in FIG. 1. For the sake of simplicity, the signal lines and
the engine control unit are not shown in FIGS. 2 and 3.
[0034] The system shown in FIG. 2 differs from that in FIG. 1 in
that the NO.sub.x storage catalytic converter 18 and the H.sub.2S
storage catalytic converter 20 are not installed adjacent to one
another but instead are installed with a distance between them in
the exhaust gas duct 14. In this constellation, the
oxygen-sensitive gas sensor 24 is preferably arranged between the
storage catalytic converters 18 and 20.
[0035] In the embodiment shown in FIG. 3, the NO.sub.x storage
catalytic converter 18 and the H.sub.2S storage catalytic converter
20 are present as a mixed coating on the same catalytic converter
support, i.e., no local separation of the two functions is provided
here.
[0036] Performance of a method for desulfurizing a NO.sub.x storage
catalytic converter in a system according to FIG. 1 but without the
H.sub.2S storage catalytic converter 20 is illustrated in a typical
embodiment on the basis of the curve of various exhaust gas
parameters as a function of time in FIG. 4. The NO.sub.x storage
catalytic converter used here has a total noble metal load of Pt,
Pd and Rh amounting to 110 g/ft.sup.3 as well as barium (Ba) and
cerium (Ce) as NO.sub.x storage components. In FIG. 4, curve 100
shows the lambda value measured with the lambda probe 22 upstream
from the NO.sub.x storage catalytic converter 18 during its
desulfurization, while curve 102 shows the lambda value measured
with the lambda probe 24 downstream from the NO.sub.x storage
catalytic converter 18. Curves 104 and 106 show the emissions of
sulfur dioxide SO.sub.2 and/or hydrogen sulfide H.sub.2S measured
at the exhaust outlet downstream from the NO.sub.x storage
catalytic converter. Except for the H.sub.2S curve (curve 106), the
execution of the inventive method for desulfurizing the NO.sub.x
storage catalytic converter 18, i.e., using an H.sub.2S storage
catalytic converter 20, corresponds in principle to that
illustrated in FIG. 4.
[0037] First, starting from a leaner exhaust gas atmosphere with
lambda.apprxeq.1.01 a rich exhaust gas atmosphere with
lambda.apprxeq.0.98 is adjusted for heated the NO.sub.x storage
catalytic converter 18 and for initiating its desulfurization. As
soon as the rich exhaust gas reaches the NO.sub.x storage catalytic
converter 18, it leads to an intense release of SO.sub.2 (curve
104, point in time 176000). However, release of SO.sub.2 drops
again very rapidly in favor of an increase in the H.sub.2S
emissions (curve 106). Starting approximately at the point in time
192000, so-called wobble operation is begun, in which the internal
combustion 10 is operated alternately with a lean air-fuel mixture
with lambda.apprxeq.1.01 and a rich air-fuel mixture with
lambda.apprxeq.0.98. The lambda curve 102 measured downstream from
the NO.sub.x storage catalytic converter 18 follows this change
with a certain delay and with reduced amplitudes, which is caused
first by the exhaust gas running time and secondly by the
consumption of oxygen in the exhaust gas to reduce the sulfur.
Switching between lean and rich intervals is regulated by the
lambda probe 24 downstream from the NO.sub.x storage catalytic
converter 18. The switch from lean to rich is made as soon as the
probe detects a lean exhaust gas. Conversely, the switch from rich
to lean is made as soon as the lambda probe 24 records the
breakthrough of rich exhaust gas. In each rich interval, an
increase in SO.sub.2 emission 104 downstream from the NO.sub.x
storage catalytic converter 18 can be observed, declining toward
the end of the rich interval--with increasing consumption of the
oxygen incorporated in the lean intervals--in favor of the H.sub.2S
emission 106.
[0038] FIG. 5 shows comparatively the H.sub.2S emissions according
to the state of the art (see FIG. 4) and according to the present
invention for the entire duration of desulfurization. Curve 108
shows the measured final H.sub.2S emission at the exhaust gas
outlet of an exhaust gas system according to the state of the art
without a downstream H.sub.2S storage catalytic converter. Curve
110 however shows the corresponding curve with an exhaust gas
arrangement having an H.sub.2S storage catalytic converter 20
according to FIG. 1. In both cases a NO.sub.x storage catalytic
converter having a total noble metal load of 110 g/ft.sup.3 Pt, Pd
and Rh plus barium (Ba) and cerium (Ce) as NO.sub.x storage
components was used. In the inventive curve as represented by curve
110, an H.sub.2S storage catalytic converter 20 having a nickel
load of >0.5 g/L was additionally used. It can be seen clearly
here that the total H.sub.2S emissions according to the present
invention are reduced to a fraction in comparison with the state of
the art. To achieve a regeneration of the H.sub.2S storage
catalytic converter 20 following the desulfurization and thus to
restore the H.sub.2S storage function at the start of the next
desulfurization process, the catalytic converter is exposed to a
lean exhaust gas atmosphere at an elevated exhaust gas temperature.
In doing so, the sulfur is oxidized to SO.sub.2 and removed from
the surface of the catalytic converter 20. For regeneration of the
H.sub.2S storage catalytic converter, standard operating situations
of the internal combustion engine 10 may be utilized. For example,
regeneration may be performed during the heating phase for
desulfurization of the NO.sub.x storage catalytic converter 18
or--in a diesel vehicle--during a heating phase of particulate
filter regeneration. In addition, it may also be performed in
driving situations of moderate load, in which there is an increase
in temperature of the exhaust gas in a lean exhaust gas atmosphere.
With all the aforementioned modes of operation of the internal
combustion engine 10, formation of SO.sub.2 is facilitated by the
high exhaust gas temperature and the oxygen excess of the exhaust
gas.
* * * * *