Topics in Catalysis Vol. 28, Nos.

1–4, April 2004 (
2004) 99

Lean-burn catalysts from the perspective of a car manufacturer. Early

work at Volkswagen Research
Axel Königa,*, Wolfgang Heldb, and Thomas Richterc
a
Galgenkamp 13, D-38448 Wolfsburg, Germany
b
Wilhelmstrase 1, D-38448 Wolfsburg, Germany
c
Advanced Gasoline Engines, Letter Box 1685, Volkswagen AG, D-38436 Wolfsburg, Germany

Lean burn engines offer significantly better fuel economy and also lower engine out emissions of gaseous pollutants than
engines tuned to stoichiometric air-fuel ratio. However, the high oxygen excess in the exhaust prohibits the use of the 3-way-
catalyst technology for further NOx reduction. New catalytic processes and catalyst materials had to be developed for NOx
aftertreatment, to ensure that diesel engines and lean burn DI gasoline engines can comply with very stringent exhaust emissions
standards. The paper describes the start and some aspects of the history of that development, from the viewpoint of a car
company.
KEY WORDS: nitrogen oxides; NOx catalysis; zeolite catalysts; Cu-ZSM5 catalyst; exhaust after treatment; learn burn
engines

1. Background used indirect injection prechamber or swirl chamber

engines. Injection systems were mechanical, with very
For a car company, exhaust aftertreatment is not an
limited variability of injection parameters. First direct
end in itself, because it normally does not add directly
injection engines for passenger cars were in develop-
additional benefit to its customers. The research for lean
ment, but had hardly entered the market. The truck
NOx aftertreatment processes, beginning in the early
market was dominated by DI-diesel propulsion, as is the
eighties was targeted at an indirect benefit for car
case also today.
customers and society: the synthesis of low tail pipe
emissions and exceptionally good fuel economy. At that
time, the world economy had suffered from two oil crises,
2. The project
but crude oil was again available in unlimited quantities
and oil prices had come down again. Smog formation At Volkswagen Research, where a programme on
and forest damages by acid rain and ozone were high on NOx catalysis under lean exhaust conditions was initi-
the environmental agenda, so the main emphasis in ated in 1984, several potential applications had been
future powerplant development was on exhaust emis- envisaged:
sions. Nevertheless, people were still aware of the • The most important issue was NOx reduction for
vulnerability of oil supply, and a few people already
diesel engines, because these engines became more
saw that global warming and CO2 emissions would
and more important for the Volkswagen Group, due
become a main challenge in the foreseeable future.
to its favourable fuel economy. Swirl chamber en-
In the United States and Japan gasoline engines with
gines were still able to meet the existing standards for
port fuel injection, stoichiometric engine setting and
gaseous exhaust components all over the world
exhaust aftertreatment with three-way-catalyst systems
without additional exhaust treatment. DI diesel
were standard for passenger cars. In Europe, the vast
engines fulfilled the NOx requirements with the
majority of passenger cars had carburated gasoline help of EGR. Further reductions of NOx limits,
engines, tuned to the most fuel efficient setting, that
however, could mean a threat to the future of the
means slightly lean. Discussions on the introduction of
diesel engine.
catalytic exhaust aftertreatment with three way catalysts
• Extension of the lean operating range of three way
in Europe, too, had started, but there was still a strong
catalyst aftertreatment systems, to enable lean part
opposition because of the resulting increase in fuel
load operation of conventional port fuel injection
consumption, and lead free gasoline was not available
gasoline engines, thus improving their part load
yet. Passenger cars with diesel engines nearly exclusively
efficiency.
• NOx reduction for a lean operating DI gasoline en-
* To whom correspondence should be addressed. gine, which was in preparation as powerplant for the
E-mail: aekoenig@t-online.de Volkswagen research vehicle ‘‘Futura’’ [1].

1022-5528/04/0400–0099/0
2004 Plenum Publishing Corporation

100
The project started with a literature search and a look to
other processes and other industries where NOx was
formed and had to be aftertreated. Existing NOx
treatment systems were analyzed with respect to their
applicability for lean NOx catalysis in vehicle exhaust,
especially under the boundary conditions of diesel
exhaust. It became obvious that a nonselective catalytic
process with noble metal catalysts, like the three way
process, did not have any potential for a diesel engine,
due to the high oxygen excess even at full load. Selective
noncatalytic processes with ammonia, urea or other N-
containing reducing agents, which were used for NOx
control during combustion in furnaces could not be
applied because of their high operating temperature and
low reaction rate. Therefore, the research work was
concentrated from the very beginning on selective
catalytic processes, with different reducing agents.
The first attempts to find partners from industry for
catalyst development and supply and from academia for
scientific evaluation of the problem and for catalyst
screening on laboratory level did not show much pros-
pect. Suppliers of standard exhaust catalysts, although
interested in the topic, were rather sceptical about the
success of the project, and the only research institute that
claimed to be able to reduce NOx under oxygen excess
could do this only on a single platinum crystal under
ultrahigh vacuum. In the end, a working group was
formed, together with the research division of Bayer AG
and the Institute of Fuel Chemistry and Chemical
Technology at RWTH Aachen, Prof. Hammer.
3. First results
Catalysts for the project were initially taken from
three groups, which had already shown potential for
SCR with ammonia: titania vanadia catalysts, zeolites
2500
2000
Concentration (ppm)
1500
1000
500
0 0
0 5000
Figure 1. Catalyst temperature and gas concentrations versus time for a copper-exchanged mordenite catalyst. Reduction agent C2H4.
A. König et al./Lean-burn Catalysts
and activated carbon. The highest priority for reducing
agents of course was given to the hydrocarbon fuel on
board the vehicle or components which could be easily
produced from fuel. However, there were no absolute
restrictions on reducing agents in the beginning. First
tests with titania vanadia catalysts revealed that these
catalysts did not show any prospect for SCR with
hydrocarbons. Their potential for SCR with ammonia
was well known, but ammonia was not seen as a realistic
feature on an automobile, because of its high safety
risks. Activated carbon, in particular when doped with
some base metal catalysts showed some NOx reduction
during SCR with hydrocarbons. This was, however,
more of interest for mechanistic studies and not so much
for a practical application, because of the risk of
uncontrolled combustion in a lean exhaust environment.
Moreover, pellets of activated carbon were rather
brittle, and the application of activated carbon onto
monoliths, which are much better suited for use in an
automobile, seemed to be rather difficult. The investi-
gations were therefore more and more concentrated on
zeolite catalysts.
In autumn 1985, after a couple of months of
experimental work with different catalysts and reducing
agents showing only low NOx conversion rates with
hydrocarbons, a breakthrough was achieved. When a
copper exchanged mordenite catalyst was heated in a
gas stream, containing nitrogen oxide, a hydrocarbon
(methane, ethene, propene, or butane), oxygen, and
nitrogen as balance, a distinct reduction of nitrogen
oxide concentration was detected in a temperature range
between 200 and 400 C, accompanied by the formation
of CO and a decline of HC concentration. At higher
temperatures, both the rate of NO reduction and the
concentration of CO in the product gas went down
again and carbon dioxide was the only product of
hydrocarbon oxidation (figure 1). The NO reduction in
700
600
500
Temperature (˚C)
O2 (x10)
400 CO2
CO
300 NOx
Temp.
200
100
10000 15000 20000 25000
Time (s)
 A. König et al./Lean-burn Catalysts
the respective temperature interval was obviously attrib-
uted to a kind of incomplete HC oxidation, and the first
idea was that the intermediately produced CO was the
reducing agent for NO. However, the addition of CO to
the reactant feed in a subsequent experiment did not
lead to increased NO reduction. So it became clear that
other intermediates of HC oxidation were responsible
for the remarkable effect.
The first sets of experiments were conducted with
zeolite catalysts of the types X, Y and mordenite.
Cations exchanged into the catalysts included copper,
chromium, iron, manganese, vanadium, cobalt, nickel
and silver. The highest NO conversion rates of 66%
were achieved with copper exchanged mordenite, in a
temperature range of 150–230 C, which seemed to be
very favourable for the application on a diesel engine.
However, these first experiments were carried out
under laboratory conditions that differed considerably
from conditions in real exhaust gas. The most severe
shortcoming was the absence of water vapor in the
reactant feed. When water was added in subsequent
experiments, a severe decline of the NO conversion rate
on Cu-mordenite was observed. Therefore, the next set
of catalysts produced by Bayer for evaluation at RWTH
Aachen were of a more hydrophobic nature. Copper
exchanged ZSM-5 catalysts showed distinct overall
advantages in wet gas mixtures compared to Cu-
mordenite, although the maximum NO conversion rate
was somewhat lower and was achieved in a higher
temperature interval around 350 C. Figure 2 shows a
comparison of the catalyst performance of Cu-morde-
nite and Cu-ZSM-5 at 350C and different water content
in the reactant. It is obvious that water vapor inhibits
the NO conversion on Cu-mordenite to a much higher
degree, especially in the concentration range around
10% water vapor, which is most relevant for exhaust
aftertreatment of lean burn engines.
Further tests using ZSM-5 catalysts exchanged with
other transition metals (nickel, chromium, cobalt, man-
ganese and iron) gave inferior results in comparison to
copper exchanged catalysts. Catalysts exchanged with
60
50
NOx Conversion (%)
40
30
20
10
0
0 10
Water Vapour (%)
Figure 2. Comparison of the performance of mordenite and Cu-ZSM-5 catalysts in gas mixtures containing increasing amounts of water.
101
noble metals (platinum, rhodium, iridium) showed only
low NOx conversion rates in a rather narrow temper-
ature range, accompanied by a distinct formation of
NO2. The best results in this set of experiments were
achieved on iridium containing catalysts, however,
iridium catalysts were not seen as a realistic alternative
for automotive application at that time, due to its
limited availability, high cost and the comparably high
vapor pressure at elevated temperature.
With Cu-ZSM-5 catalysts first tests under real engine
conditions were carried out. For these experiments the
active catalyst material was coated onto conventional
cordierite exhaust gas monoliths. For the experiments
with a lean burn gasoline engine (1.8l displacement) on
an engine test bench, two catalyst converters (4¢¢ diam-
eter, 6¢¢ length) were arranged in parallel in the exhaust
system. Engine speed, load and air/fuel ratio were
selected to obtain a catalyst temperature of around
400 C and a space velocity of approximately 15,000/h
in each converter. The results showed that NO conver-
sion was strongly dependent on the ratio of nitrogen
oxide and hydrocarbon concentration in the exhaust
(figure 3). For HC concentrations higher than NO
concentrations, conversion rates of more than 45%
could be achieved.
Vehicle tests on a roller test bench with the same
engine and a conventional exhaust system with only one
Cu–ZSM-5 catalyst brick , using the FTP test procedure
gave the following results: For the cold start and warm-
up phase of the test (bag 1), a NOx conversion rate of
only 15% could be achieved, due to the rather long
period of time that the catalyst needed to achieve its
optimum operating temperature of around 350 C, and
the higher space velocity, compared to the tests on the
engine test bench. During the hot start phase (bag 3), an
overall NOx conversion rate of 30% was found. A
general drawback of the principle of lean NOx conver-
sion with hydrocarbons on the engine in use resulted
from the emission characteristics of that engine. During
acceleration periods, where NOx concentrations in the
exhaust went up, hydrocarbon emissions went down, and
Cu - ZSM5
Cu - Mordenite
16
102
1000
NOx / HC (ppm)
500
0 0
RPM (min-1) 2000
Load (Nm) 17
Air/fuel ratio 1.30
Figure 3. NOx reduction at different part load conditions for a DI gasoline engine.
of course exhaust volume and respectively, space velocity
on the catalyst went up. This effect limited the potential
of the process during the most critical phases of the test.
For use on a diesel engine, the low concentration of
hydrocarbons in the exhaust means a general limitation.
Moreover, due to the normally unthrottled operation of
the diesel engine, exhaust gas volume is generally higher
than on gasoline engines, and at part load oxygen
concentration is high and exhaust gas temperature is
low. All these boundary conditions restrict the efficient
use of Cu–ZSM-5 catalysts on diesel engines with
hydrocarbons as the reductant. Initial tests on an engine
test bench with a diesel engine only showed significant
NOx conversions when additional hydrocarbons were
injected into the exhaust system, and even under these
conditions not more than 20% conversion could be
achieved. For later tests a diesel engine was modified to
obtain higher exhaust gas temperature and higher
hydrocarbon concentrations in the raw exhaust gas, at
the expense of fuel efficiency. This engine was used in a
vehicle for tests on a roller test bench. However, NOx
conversion rates above 20% could not be achieved.
The same set of catalysts that was used for engine
tests, was also investigated in respect to their hydro-
thermal stability. Monolithic catalyst samples were
heated in a furnace for 4 h to 600, 700, 800 and
850 C, respectively, in an oxidizing, wet atmosphere
(2% of O2 and 10% water vapor in nitrogen). Subse-
quently the NOx conversion behaviour was measured in
a laboratory device at 350 and 400 C at different air–
fuel ratios, characteristic for a lean burn gasoline engine.
It turned out that aging at 600 C already increased the
optimum operating temperature of the catalyst by 50 to
400 C. Aging at 700 C reduced the maximum obtain-
able NOx conversion rate to about 25%, and to 10%
after aging at 800 C. The catalyst sample aged at
850 C showed no activity at all. Structural analysis of
the spent catalysts revealed that the crystallite structure
of the catalyst had not been altered during aging,
therefore the reason for the thermal deactivitation
should result from the status of the copper ion.
In the following period of time the work was
concentrated on improvements of the catalyst material
A. König et al./Lean-burn Catalysts
100
NOx conversion (%)
50
NOx inlet concentration
HC inlet concentration
NOx conversion
2000 2000
10 17
1.20 1.20
to overcome the main shortcomings of temperature
window of optimum operation, the comparably low
activity and the insufficient aging resistance. The main
influencing factors under investigation were Si/Al-mod-
ule, catalyst loading, and different procedures of catalyst
preparation. Moreover, catalysts with an additional
content of rare earths (cerium, lanthanium) were inves-
tigated on catalyst conversion efficiency and hydrother-
mal stability. Unfortunately, only limited progress was
achieved and it was not possible to exploit the remark-
able scientific findings for a product of technical
significance.
With this in mind it was decided to publish some of
the results and, later on, to bring the acquired knowl-
edge into a joint European research project, in order to
broaden the work basis. A first presentation of results
was given on the occasion of a conference on ‘‘The
future of the diesel engine’’ in late 1988, at Wolfsburg,
Germany [2] and a second one at the SAE conference in
March 1990 at Detroit [3]. At the same time it become
obvious that a group at Hokkaido University, led by
Prof. Iwamoto, had found similar results at around the
same time [4]. A (friendly, but not too serious) dispute
arose, about who really had found for the first time that
Cu-exchanged catalysts were able to selectively reduce
nitrogen oxides under net oxidizing gas conditions. This
‘‘dispute’’ was never really decided.
4. Subsequent work
In late 1991 Volkswagen Research started to initiate a
project called ‘‘Nitrogen oxide removal from diesel and
lean otto engine exhaust (Lea NOx) in the framework of
the European Brite EuRam program, which finally
started officially in November 1992. Seven European car
manufacturers and seven research institutes were in-
volved in the project, and six partners from the catalyst
industry were associated to the project for catalyst
supply. The project included a broad range of basic
investigations, material development and application
oriented test work. It must be stated, however, that the
outcome from that project and also from subsequent
 A. König et al./Lean-burn Catalysts
similar projects added more to basic knowledge and
understanding than to real exploitable results on a
technical level.
The proprietary work at Volkswagen Research on
zeolite catalysts was shifted away from lean NOx
conversion with hydrocarbons to two other topics:
• Lean NOx conversion on diesel engines with urea,
which showed from the very beginning more poten-
tial for higher conversion rates under the given
boundary conditions, of course at the expense of
additional technical and logistic effort during prac-
tical use.
• Application of zeolite based catalysts for particulate
reduction [5].
Later on, when NOx storage catalysts came up [6], the
work was focused on these catalysts for application on
the newly developed DI gasoline engines with flexible
air–fuel ratio, and on diesel engines.
The process of direct NOx reduction with hydrocar-
bons as reducing agent has been applied only to a very
limited extent to DI gasoline engines, using iridium-
containing catalysts [7]. Selective catalytic reduction
with urea on titania vanadia catalysts has been devel-
oped for serial application, mainly for the use on trucks
[8]. The technical potential of zeolite-based catalysts for
this purpose still remains to be evaluated. Zeolite
components in noble metal oxidation catalysts for
particulate conversion are a standard feature today.
Their main purpose is the improvement of catalyst cold
start behaviour.
The progress on injection technology and, above all,
on engine and injection control, together with its
inherent advantages concerning overall conversion effi-
103
ciency gave a strong push to the application of NOx
storage catalysts. These catalysts are now in serial use on
DI gasoline engines, and they could also be used for
diesel engines, provided that low sulfur diesel fuel would
be available [8]. The technical effort and the cost for
exhaust aftertreatment with NOx storage catalysts is,
however, considerable. Therefore, the search for catalyst
materials and processes for NOx dissociation or a simple
direct NOx reduction with hydrocarbons remains an
important challenge.
References
[1] K.D. Emmenthal, H.J. Grabe, W. Oppermann and H. Schäper-
töns, Engine with gasoline direct injection and evaporation cooling
for the VW research vehicle IRVW-Futura (in german). Motor-
technische Zeitschrift 50 (1989), Heft 9.
[2] A. König, W. Held, T. Richter and L. Puppe, Catalytic reduction
of nitrogen oxides for diesel engines (in german). VDI Berichte,
714, 1988.
[3] W. Held, A. König, T. Richter and L. Puppe, Catalytic NOx
reduction in net oxidizing exhaust gas SAE 900496.
[4] M. Iwamoto, Metal ion-exchanged zeolites as highly active
materials for removal of nitrogen monoxide by catalytic decom-
position, selective catalytic reduction or adsorption. Proc. of
Meeting of Catalytic Technology for Removal of Nitrogen Monox-
ide, (Tokyo 1990).
[5] Volkswagen, A.G. and Bayer, A.G., German Patent DE 4105534
(1991).
[6] N. Miyoshi, T. Tanizawa, S. Takeshima, N. Takahashi and K.
Kasahara, Development of NOx storage-reduction 3-way catalyst
for lean-burn engines Toyota Technical Review, Vol. 44 (1995)
[7] Mitsubishi Heavy Ind. Ltd, Japan Patent JP 07060067 (1995).
[8] E. Pott, G. Splisteser, R. Bosse, A. König, F.-J. Quissek and
I. Kutschera, Potential of NOx-trap catalyst application for DI-
diesel engines (in german). 20, Wiener Motorensymposium, (Wien
1999).