Topics in Catalysis Vols. 16/17, Nos.

1–4, 2001 319

Automotive exhaust gas conversion: from elementary step kinetics

to prediction of emission dynamics
J.H.B.J. Hoebink a,∗ , J.M.A. Harmsen a , M. Balenovic b , A.C.P.M. Backx b and J.C. Schouten a
a Laboratory of Chemical Reactor Engineering, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands
E-mail: j.h.b.j.hoebink@tue.nl
b Systems Measurement and Control Group, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

Elementary step based kinetics show a high added value to describe the performance of catalytic exhaust gas converters under dynamic
conditions, as demonstrated with a Euro test cycle. Combination of such kinetic models for individual global reactions covers the mutual
interactions via common adsorbates. Feed composition modulation as a transient kinetic technique provides detailed information about
elementary steps and their rate parameters.
KEY WORDS: automotive converter modeling; transient kinetics; elementary step kinetics; feed composition cycling; Euro test cycle
prediction

1. Introduction for reasons of oxygen storage in ceria, oxidation and re-

The conversion of harmful components in an automotive
exhaust gas is a highly dynamic process, which shows var-
ious transients, that may arise from at least three sources.
One of them is the car driver’s behaviour, which is usu-
ally expressed by prescribed driving schedules as the FTP
or Euro cycles for testing catalytic converters. It affects the
converter performance via the space velocity and the exhaust
gas temperature. Another cause of dynamic features is the
lambda sensor based control system. Due to a time lag, the
controller induces periodic changes in the composition of the
flow, that leaves the engine and enters the converter. Such os-
cillations, often referred to as cycling of the feed, are known
to influence the reactor performance as well. Transients also
occur after a cold engine start, when the converter gradu-
ally starts functioning as its temperature rises because of heat
transfer from the hot engine gas. This warming-up period is
important notably for three-way converters, since during this
period the largest contribution to the emissions by Otto en-
gines is released. All these transients lead to the demand that
one and the same exhaust gas reactor should operate prop-
erly under a wide variety of conditions. This is a remarkable
difference with other chemical reactors, that usually oper-
ate in a steady state at predefined conditions within a rather
narrow window [1].
Many studies on automotive converter modelling use
steady state kinetic rate equations. In particular the classi-
cal work of Voltz et al. [2] is often applied, which should
be considered as empirical, since not based upon a mech-
anism [3,4]. The unsteady state aspect, however, of auto-
motive converter operation is important for reactor simu-
lation and design as far as the choice of kinetic models is
concerned. The assumption, whether steady state reaction
kinetics can be used in the transient state, is questionable
∗ To whom correspondence should be addressed.
duction of rhodium, reversible poisoning, and transient sur-
face phenomena in general [5]. Unsteady state operation in-
volves accumulation terms in a reactor model, both for gas
phase components and for surface species. This requires
reaction kinetics based upon elementary steps, because the
classical steps of a catalytic reaction, e.g., adsorption, sur-
face reaction, desorption, do not proceed at the same rate.
Approximations via Langmuir–Hinshelwood or Eley–Rideal
type of rate equations could be applied in case of one rate-
determining step. Such an approach, however, may fail even
in a steady state, since different steps may become rate con-
trolling if concentrations change considerably from reactor
inlet to outlet, as to be expected for zero-emission vehicles.
CO oxidation over noble metals is a well-known example of
a reaction with an order +1 in CO at low CO concentration,
but −1 for high concentrations [6]. Different rate determin-
ing steps may also arise if operating temperatures change
considerably [3], because adsorption usually is not an ac-
tivated process, while surface reaction and desorption rates
often obey Arrhenius behaviour. Such behaviour may occur
along the reactor axis, because temperature differences of
150 K between reactor inlet and outlet are not exceptional.
After a cold engine start, reactor temperatures may rise from
below room temperature up to 700 K and more.
The foregoing pleads for kinetic modeling on the basis
of elementary steps because of the larger impact of such
models. An even more important advantage of elementary
step modeling is that a model can be determined experimen-
tally for one global reaction, but applied in a combination of
elementary step kinetics for other global reactions. In this
way mutual interactions between different global reactions,
as may happen because of common gas phase or surface
species, can be simply accounted for. An automotive ex-
haust gas is an example of such a complicated reacting mix-
ture, where many competing reactions occur simultaneously.

1022-5528/01/0900-0319$19.50/0  2001 Plenum Publishing Corporation

320 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics
Oxygen adatoms may arise from gaseous oxygen or nitric
oxide, and may be consumed by hydrogen, carbon monox-
ide, or many hydrocarbons with different affinities for oxy-
gen. Elementary step kinetics may incorporate the effects of
distinct hydrocarbons, as they include steps for the reduction
of NO by hydrocarbons. Modeling via elementary steps also
allows to adapt the kinetic model when the catalyst formula-
tion is changed in order to introduce new catalytic functions.
A typical example is the introduction of ceria into the three-
way catalyst, which takes care of the so-called bifunctional
reaction path between carbon monoxide on the noble metal
surface and oxygen adatoms from the ceria lattice. This path
has been proven important at high CO and low O2 concen-
trations [6,7].
Kinetic modeling on the basis of elementary steps ex-
ploits the law of mass action, which is the best possible rate
equation. It is sometimes argued that elementary step ki-
netics contain so many parameters that any description of
experimental data becomes within reach. It should be re-
alised, however, that each step preferably is proven relevant
on the basis of experimental evidence, and quite often such
relevance has already been reported in the literature from
studies that applied completely different techniques. More-
over, the rate parameters should have significant values from
a statistical point of view, as to be obtained from multi-
response non-linear regression, and these values should be
consistent with well-established theories. Elementary step
kinetics have already been proven very effective in model-
ing gas phase chain reactions, whether or not catalytically
initiated, like hydrogen [8] or methane [9] oxidation, or ox-
idative coupling of methane [10].
Steady state kinetic studies may provide limited infor-
mation on the rate coefficients of the underlying mechanis-
tic steps, as those coefficients can get lumped if some step
should be considered as rate determining or instantaneous.
During kinetic measurements under transient conditions, re-
actor outlet responses to perturbations at the reactor inlet are
observed in real time. In principle, such experiments con-
tain more information on individual reaction steps [11], as
all steps may proceed at different rates after imposing the
perturbation, and each step may temporarily become domi-
nant during the relaxation process. Transient kinetic meth-
ods apply pulse type of perturbations, as in temporal analysis
of products (TAP) [12], or stepwise perturbations, which is
well-known as cycling of the feed [13]. A special stepwise
perturbation concerns steady state isotopic transient kinetic
analysis (SSITKA) [14]. A reactant in the feed is replaced by
an isotopic variant, which allows the reactor to be operated in
a chemical steady state, while the interaction of the reactant
with the catalyst can be monitored via mass-spectrometry at
the reactor outlet.
To illustrate the power of elementary step kinetics, some
simulation results for a monolithic converter are men-
tioned [15,16], that were obtained under application of a
kinetic model, constructed from various literature sources.
These kinetics included oxidation of CO and the hydro-
carbons ethylene and acetylene, as well as reduction of
Figure 1. Effects of the air/fuel ratio on the steady state conversion (drawn
lines) and on the conversion during 1 Hz feed composition cycling (dotted
curves) at 485 K, as simulated for a monolith reactor with elementary step
kinetics. (♦) C2 H2 , (◦) C2 H4 , () NO, (+) CO.
NO [15]. Although, propene usually is considered as repre-
sentative for most hydrocarbons, C2 H2 and C2 H4 were cho-
sen instead because of their relative abundance in an exhaust
gas, while C3 H6 mostly is a minor fraction of all hydrocar-
bons [17]. Moreover, acetylene was reported as an inhibitor
for all exhaust gas reactions after a cold engine start, and
ethylene may react like exhaust components benzene and
toluene [18]. The reactor was essentially modeled as a one
channel monolith under transient conditions, including the
typical 1 Hz feed oscillations, that are induced by the lambda
sensor based control system [19]. Figure 1 shows the simu-
lated conversion of the various reactants versus the air/fuel
ratio, where drawn curves refer to a real steady state and
dotted curves to a situation with imposed feed oscillations.
The steady state results are in qualitative agreement with the
general observation that all conversions are highest around
stoichiometric conditions. At high air/fuel ratio the con-
version is high for the oxidation reactions, but low for NO
reduction, while the opposite holds for rich feed mixtures.
With feed oscillations present, the results are in line with the
observation [19,20] that cycling of the feed is beneficial at
low conversion, but detrimental at high conversion. Quali-
tative agreement was also obtained for light-off curves and
cold start simulations [15]. Using a similar kinetic model,
but with propene and hydrogen instead of acetylene and eth-
ylene, a NO conversion maximum in light-off curves was
qualitatively predicted [16]. It should be recognised, how-
ever, that such a maximum also has been predicted for en-
gine bench tests on the basis of steady state kinetics [5].
A major drawback of transient kinetic studies concerns
time and costs involved, due to the more complicated char-
acter of the experimental set-up, the experiments themselves
and their interpretation. In fact, these studies should be per-
formed only for the major fast processes involved in exhaust
gas conversion, while slow processes can be added to con-
verter models via a quasi-steady state approach. Because
of the large number of parameters involved, full transient
models might be simplified on the true basis of a sensitivity
analysis, for verification with other catalysts. Such model
simplifications could be implemented in more sophisticated
control strategies. As on-board computational capabilities
 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics 321

continue to increase, self-diagnostic features will be incor-

porated in the control system to compensate for catalyst ag-
ing and sensor response characteristics [21].

2. Scope

This paper focusses on dynamic modeling of automotive

exhaust gas reactions at Eindhoven University of Technol-
ogy over a single catalyst Pt/Rh/CeO2 /γ -Al2 O3 . The work
intends to settle a kinetic model on the basis of elementary
steps with quantification of rate parameters, specifically at
low temperatures, as major emissions by Otto engines oc-
cur after a cold engine start. The model can be applied in
the design/optimisation of catalytic converters and for de-
velopment of a new converter control strategy [22]. Such
a kinetic model can be extended by adding new elementary
steps, accounting for new catalytic functions of improved
formulations, or new effects that are considered as relevant
for similar catalysts.

3. Experimental

The experimental set-up and procedures for studying

transient kinetics of automotive exhaust gas reactions have
been described before [23,24]. The set-up operates accord-
ing to the principle of feed cycling. Two sets of mass flow
controllers provide two feeds. Reactants are diluted with
helium, up to concentration levels relevant for automotive
catalysis. The reactor, shown schematically in figure 2, is
a fixed-bed laboratory reactor. Actual switching between
the feeds is performed with specially designed valves, sit-
uated very close to the catalyst bed which allows feed cy-
cling at frequencies up to 10 Hz. The upper frequency in
fact is limited by the sampling rate of a quadrupole mass-
spectrometer, which is used for monitoring in real time re-
actor outlet responses of both reactants and products [24].
In practice, lower frequencies are applied to avoid effects of
diffusion limitation and to assure isothermal operation. Wa-
ter cannot be detected. Recently, the quadrupole apparatus
was replaced by a Jeol JMS-GCmate magnetic sector mass-
spectrometer. This machine enables real time observations
at high mass resolution, which allows distinction to be made
between CO, C2 H4 and N2 , and between N2 O and CO2 dur-
ing NO reduction studies.
The commercial Pt/Rh/CeO2 /γ -Al2 O3 catalyst was pro-
vided by dmc2 , Degussa Metals Catalysts Cerdec AG, in a
powder form as used for coating monoliths. For reference
purposes, dmc2 also supplied alumina based model cata-
lysts, containing one and two of the components in the com-
mercial one. The powder is pressed into pellets, which are
crushed and sieved to obtain a suitable pellet size. This pro-
cedure does not affect the catalyst’s microstructure. Kinetic
experiments are carried out at intrinsic conditions, which
means that the data are free from heat and mass transport
limitations. Therefore the kinetic results can be applied for
any type of reactor if the proper reactor model in the form
Figure 2. Schematic view of the fixed-bed laboratory reactor.
of continuity and energy equations is added to the kinetic
model.
Kinetic rate parameters are obtained via non-linear multi-
response regression of the data with a kinetic model [23].
4. Results and discussion
4.1. Carbon monoxide oxidation
The oxidation of carbon monoxide by oxygen has been
studied [23,24] with alternating feeds of CO in helium and
O2 in helium. The effect of ceria on the CO conversion was
observed from catalysts with and without ceria. Typical re-
action temperatures were in the range 373–433 K. For Pt/
γ -Al2 O3 the reaction mechanism is shown in table 1(a), the
rate parameters were published elsewhere [24]. The steps of
reversible CO adsorption and associative O2 adsorption with
instantaneous dissociation are all well-known from the lit-
erature. A Langmuir–Hinshelwood type of surface reaction
between adsorbed CO and O, and an Eley–Rideal-like step
between CO in the gas phase and adsorbed oxygen adatoms
have been proposed as well, but are combined here in one
mechanism, which appears necessary for a proper descrip-
tion of the data. Carbon dioxide shows reversible adsorption
on the alumina support, and the corresponding rate parame-
ters were determined from independent experiments.
For the catalyst Pt/Rh/CeO2 /γ -Al2 O3 , the very same
mechanism of table 1(a) could be applied [23] for the so-
322 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics

Table 1 Table 2
Elementary steps in CO oxidation over Pt/Rh/CeO2 /Al2 O3 .a Elementary steps in C2 H2 oxidation over Pt/Rh/CeO2 /Al2 O3 .a

(a) Monofunctional path f

k
1
k
f 1 C2 H2 (g) + ∗  C2 H2 ∗
1 kb
1 CO + ∗  CO ∗ 1
kb k
f
1 2
k
f 2 C2 H2 ∗ + 2∗  C2 H2 ∗∗∗
2 kb
2 O2 + ∗ → O2 ∗ 2
f f
k3 k3
3 O2 + ∗ → 2O∗ 3 C2 H2 ∗ + 3O∗ → 2CO∗ + H2 O + 2∗
f
k4
4 CO∗ + O∗ → CO2 + 2∗ f
k
f 4
k
5 4 C2 H2 ∗∗∗ + 3O∗ → 2CO∗ + H2 O + 4∗
5 CO + O∗  OCO∗ f
k5
kb
5 5 C2 H2 (g) + O∗  C2 H2 O∗
f k5b
k6
6 OCO∗ → CO2 + ∗ f
k
6
6 C2 H2 O∗ + 2O∗ → 2CO∗ + H2 O + ∗
(b) Bifunctional path f
k7
f
k7
7 C2 H2 ∗ + 3Os →2CO∗ + H2 O + 3s
7 O2 + s → O2 s
a The mechanism holds in combination with the mechanisms of
f
k
8
8 O2 s + s → 2Os table 1.
f
k
9
9 CO∗ + Os → CO2 + ∗ + s
f
k
10 tion and dissociation steps for acetylene oxidation should be
10 CO2 + γ  CO2 γ
b k
10
the same as for the CO oxidation model, in line with the
principle of elementary steps. The corresponding rate pa-
a ∗ is an active site on noble metal, s an oxygen storage site on
rameters should be the same as well. Comparative experi-
ceria and γ denotes a support site.
ments over Pt/Al2 O3 and Pt/Rh/CeO2 /γ -Al2 O3 showed that
CeO2 has a distinct influence on the oxidation rate in the
called monofunctional path, which involves the noble metals
only. The mechanism shown in table 1(b) describes the bi- form of a bifunctional path. The elementary steps for oxi-
functional path [6,7] of the reaction at the noble metal/ceria dation of C2 H2 to adsorbed CO over Pt/Rh/CeO2 /γ -Al2 O3
interface. This path contains steps for oxygen adsorption and catalyst are presented in table 2 [26]. Acetylene adsorption is
dissociation, that are similar as in the monofunctional path. a reversible process. In line with various literature data [27],
At low oxygen concentrations, ceria provides oxygen for CO different adsorbed acetylene species exist, which have a dif-
oxidation, while at high oxygen concentrations this contri- ferent reactivity with oxygen and which can be converted
bution becomes neglectable in comparison to the monofunc- reversibly one into the other. The experiments gave clear
tional path. When the mechanisms of table 1 (a) and (b) are evidence that gaseous C2 H2 , like CO, can adsorb on noble
added, transient CO oxidation over Pt/Rh/CeO2 /γ -Al2 O3 is metal sites covered with O adatoms. Adsorbed C2 H2 species
predicted quite well [23]. react with O adatoms to adsorbed CO and H2 O. These reac-
tion steps as shown are not elementary, but it is generally ac-
4.2. Acetylene oxidation cepted that oxygen assisted abstraction of the first hydrogen
atom determines the rate [28]. The same has been assumed
The oxidation of acetylene was studied in a way similar to for the corresponding bifunctional reaction. The combined
CO oxidation. Feeds of C2 H2 /He and O2 /He were alternated model of tables 1 and 2 with the rate parameters belong-
over the reactor. Reactor temperatures were in the range ing to table 1 (a) and (b) has been used to estimate the rate
503–543 K. No conversion was observed at lower temper- parameters of table 2 with regression analysis [26]. Acety-
atures, which is ascribed to strong adsorption of acetylene. lene adsorption, however, was based on reported sticking
Therefore, acetylene inhibits the conversion of other com- coefficients of unity. An observed large CO2 peak during
ponents like CO, and increases the automotive converter’s the lean half-cycle and small one during the rich counter-
light-off temperature after a cold start [15,18]. part could not be explained by the stoichiometry of the re-
During transient experiments CO was observed only in action alone. Deposition of carbonaceous species during the
very small amounts. Preliminary steady state experiments first hours time-on-stream covered part of the noble metal
showed that the only primary product of the oxidation reac- surface, which was still accessible for adsorption of acety-
tion is carbon monoxide, which consecutively reacts to car- lene, but not for oxygen adsorption. Similar effects were
bon dioxide [25]. It therefore was concluded that a kinetic observed during oxidation of ethylene [29]. Figure 3 shows
model should describe the oxidation of C2 H2 to adsorbed the results of a validation experiment with alternating feeds
CO, and that the description of the consecutive reaction to of C2 H2 /CO/He and O2 /He, and predictions with the model
CO2 should be covered by the CO oxidation model of the of tables 1 and 2 and the corresponding parameters. The
preceding paragraph. Moreover, oxygen adsorption, desorp- comparison is adequate.
 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics 323

Figure 4. Simultaneous oxidation of C2 H4 and CO by O2 via cycling of

Figure 3. Simultaneous oxidation of C2 H2 and CO by O2 via cycling of the feed at 433 K and 0.1 Hz. Catalyst Pt/Rh/CeO2 /Al2 O3 . Comparison
the feed at 523 K and 0.1 Hz. Catalyst Pt/Rh/CeO2 /Al2 O3 . Comparison of experiment (data points) with model predictions (curves). Above C2 H4 ,
of experiment (data points) with model predictions (curves). Above C2 H2 , CO and O2 ; below CO2 (for H2 O, predictions only).
CO and O2 ; below CO2 .

Table 3
Elementary steps in C2 H4 oxidation over Pt/Rh/CeO2 /Al2 O3 . tion, as CeO2 /Al2 O3 showed neglectable conversion at these
f
temperatures [31], while results obtained over Pt/Al2 O3 and
k1
1 C2 H4 + 2∗  C2 H4 ∗∗ over Pt/Rh/CeO2 /Al2 O3 were quite similar [30]. The kinetic
kb scheme is shown in table 3 [29]. Ethylene is reversibly ad-
1
f
k
2 sorbed. Two types of ethylene species with different reac-
2 C2 H4 ∗∗  C2 H4 ∗ + ∗
kb
tivity exist on the catalyst surface. Moreover, ethylene may
2
f
k3
adsorb on sites, covered with oxygen. All adsorbed hydro-
3 C2 H4 ∗∗ + 6O∗ → 2CO2 + 2H2 O + 8∗ carbon species are converted to carbon dioxide and water;
the corresponding steps are considered as oxygen assisted
f
k
4
4
C2 H4 ∗ + 6O∗ → 2CO2 + 2H2 O + 7∗
hydrogen abstraction, as for acetylene oxidation. The rate
f parameters were obtained from regression analysis [29], but
k5
5 C2 H4 + O∗  C2 H4 O∗ those of the dissociative oxygen adsorption were taken from
kb the CO oxidation model. As in acetylene oxydation, the CO2
5
f
6
k
6
C2 H4 O∗ + 5O∗ → 2CO2 + 2H2 O + 7∗
peaks during the rich and lean part of a period could not be
explained from stoichiometry, and a similar selective deac-
tivation for oxygen had to be assumed in order to describe
4.3. Ethylene oxidation the data with one model. From element analysis it was no-
ticed that the catalyst contained carbon after a short period
The oxidation of ethylene was studied at temperatures of time-on-stream. Moreover, a LEIS (low-energy ion scat-
between 393 and 443 K, comparable to temperatures ap- tering) analysis showed that a used catalyst had a smaller
plied for CO oxidation, but significantly lower than acety- noble metal surface area [29]. An earlier description of eth-
lene oxidation temperatures. The latter illustrates that C2 H4 ylene oxidation required two kinetic models, one for rich
can be more easily oxidized than C2 H2 . During both tran- conditions and one for lean conditions [31]. An experiment
sient [29,30] and steady state [31] experiments, carbon with alternating feeds of C2 H4 /CO/He and O2 /He has been
monoxide was not detected at all, and carbon dioxide was the predicted with the kinetic schemes of tables 1 and 3. The
only observed product. Ceria did not contribute to the reac- comparison, shown in figure 4, is satisfactory.
324 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics
Figure 5. Experimental reactor outlet responses when switching at
523 K and 0.05 Hz between feeds of CO and NO/O2 . Catalyst Pt/Rh/
CeO2 /Al2 O3 . Above O2 , CO and CO2 ; below NO, N2 , N2 O and NO2 .
4.4. Qualitative results on NO reduction by CO under net
oxidizing conditions
On the way to settling a dynamic mechanism for the re-
action NO + CO + O2 , composition modulation was per-
formed over the commercial catalyst and the model cata-
lysts [33]. Light-off behaviour of these catalysts was al-
ready reported by Leclercq et al. [34]. Alternating feeds
at 0.1 Hz of NO/He and He over the alumina support with
and without ceria made clear that at 523 K NO does not ad-
sorb on Al2 O3 , but does adsorb reversibly on CeO2 /Al2 O3
in considerable amounts. Both observations confirm litera-
ture [35–37]. The NO signals at the reactor outlet were the
same after a pretreatment of CeO2 /Al2 O3 with hydrogen or
oxygen, followed by flushing with helium. Decomposition
reactions of NO were not significant, although formation of
N2 O and nitrite has been reported on the basis of XPS stud-
ies at 90 K [36].
Figure 5 shows data for the Pt/Rh/CeO2 /Al2 O3 catalyst
when switching between NO/O2 /He and CO/He at 523 K
and 0.05 Hz cycling frequency, measured with the Jeol mass-
spectrometer. A considerable ad- and desorption of NO is
observed, but the conversion to N2 and N2 O is small, espe-
cially if gaseous oxygen is present [34].
Figure 6. Experimental reactor outlet responses when switching at 523 K
and 0.05 Hz, between feeds of CO and NO/O2 . Catalyst Pt/Rh/Al2 O3 .
Above O2 , CO and CO2 ; below NO, N2 , N2 O and NO2 .
At the end of the lean part of a period, say at 21 s, the
catalyst is probably covered with both O adatoms and NO,
since other gas phase concentrations are zero, CO2 excepted.
Immediately after switching to CO, a huge CO2 production
starts in combination with NO desorption. The concentra-
tion of NO exceeds the feed concentration of the preceding
half-cycle for a while, which could be caused by competi-
tive adsorption between NO and CO. CO2 formation from
reaction between gaseous or adsorbed CO and O adatoms
makes free sites, which enables some NO dissociation on
the surface and the temporarily formation of N2 and N2 O.
NO2 is observed as well. The CO concentration is zero for
a short while after the switch, as observed during CO oxida-
tion with O2 alone over the same catalyst [23]. The inflexion
point is an artefact. Then CO relaxes toward the inlet value
of 0.44 vol%, which is not yet reached at the end of the half-
cycle. At that moment the CO2 production is still going on.
In view of the large CO2 peak area it is obvious that oxygen
from ceria is involved via the bifunctional path [34]. It is
likely that the noble metal is mostly covered with adsorbed
CO at the end of the rich half-cycle.
After switching to lean conditions at about 31 s, there
is an immediate production of CO2 and a complete oxygen
consumption for a short while. Both should initially be as-
cribed to the bifunctional path, as oxygen cannot adsorb on
CO covered sites, but gradually the Langmuir–Hinshelwood
type of surface reaction will take over [23]. CO desorption
at this temperature will cause some vacant sites on the noble
metal after the switch. The immediate, although marginal
amounts of N2 , N2 O and NO2 in the gas phase indicate that
these vacant sites are occupied by NO. Major amounts of
NO, however, are likely to adsorb on ceria. At the end of
the half-cycle the NO concentration is still below the reactor
inlet concentration.
Figure 6 shows the same experiment at the same condi-
tions over a Pt/Rh/Al2 O3 catalyst for comparison. At the end
 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics
of the lean half-cycle the reactor outlet shows O2 and NO,
more or less at inlet concentration levels, and some NO2 .
Switching to CO shows for CO and CO2 similar behaviour
as observed with Pt/Rh/CeO2 /Al2 O3 , but the total CO con-
sumption and CO2 production during the rich half-cycle are
much smaller due to the absence of ceria. The NO concen-
tration does not increase initially after the switch from lean
to rich, as it did for Pt/Rh/CeO2 /Al2 O3 , probably because
ceria, hence NO desorption from ceria, is absent in this cata-
lyst. NO desorption from Pt/Rh/Al2 O3 takes more time than
from Pt/Rh/CeO2 /Al2 O3 . A substantial amount of NO2 is
observed, and very small amounts of N2 and N2 O, even less
when compared to the ceria-containing catalyst. When the
lean half-cycle is entered again after about 30 s, all phenom-
ena occur very fast. There is a small break-through peak of
oxygen [23,24], followed by a sharp CO2 peak, that is con-
siderably smaller than during the preceding half-cycle. In
the same short time interval, a complete consumption of NO
causes small peaks in the sequence N2 , N2 O and NO2 . The
oxygen concentration reaches subsequently its inlet value
relatively fast. The NO concentration, however, passes a
temporary maximum, probably because the reactions have
decayed, and then increases gradually during the rest of the
lean period. The NO2 concentration increases as well at a
lower level. An explanation might be that NO is able to ad-
sorb on oxygen covered surface sites. In some way, an extra
amount of O adatoms must be supplied to the catalyst during
the lean half-cycle, which causes the larger CO2 peak during
the rich counterpart.
Data for Pt/Al2 O3 catalyst are not shown, as they are es-
sentially the same as for Pt/Rh/Al2 O3 . An exception is the
NO concentration after the switch from lean to rich. It ex-
ceeds the former inlet level for a while, as was also observed
for Pt/Rh/CeO2 /Al2 O3 . The addition of rhodium was re-
ported as less unfavorable for NO adsorption than for O2
adsorption [34].
5. Emission prediction during a test cycle
The implementation of the kinetics in a catalytic con-
verter model can be used to optimise the design of the con-
verter, as well as to investigate new control strategies, with-
out the need for extensive testing [22]. A convenient test for
the converter model accuracy is its ability to predict exhaust
emission during a standard emission test cycle. Experimen-
tal data of a European test procedure have been used in this
study.
The dynamic converter model accounts for the accumu-
lation of mass in the bulk gas phase, in the pores of the
washcoat and on the catalytic surface, as well as for the
energy accumulation in the gas and solid phase. The reac-
tor is considered to operate adiabatically with uniform flow
distribution over the channels and with constant heat and
mass transfer coefficients. With these conditions satisfied
only one channel has to be modeled as representative for
the whole monolith. Detailed model equations were already
published [15,22].
325
Table 4
Converter parameters used in the Euro test cycle
validation.
Substrate length 6 inch
Substrate diameter 4 inch
Cell density 400 cpsi
Wall thickness 6.5 × 10−3 inch
Washcoat loading 250 g/l
Catalyst aging strongly aged
The kinetic models for CO, C2 H2 and C2 H4 oxidation,
described previously, have been applied directly in the con-
verter model. All rate parameters were used as published
except the adsorption rate coefficient of CO on O adatoms.
For NO reduction the kinetic model of Oh et al. [38] was
applied, which also was used in previous modeling stud-
ies [15,16,22]. This model includes dissociation of adsorbed
NO, and two reaction paths toward N2 via the recombination
of N adatoms and via reaction between adsorbed NO and N.
The NO reduction kinetics were obtained on Rh catalyst. In-
teraction with ceria was not taken into account, but known to
influence the kinetic rate parameters [39]. The parameters of
the NO reduction have therefore been adapted to get a better
agreement with measured test cycle data. Other adapted pa-
rameters were the monolith thermal capacity, the noble metal
dispersion and the oxygen storage capacity. The fraction of
the noble metal sites covered by carbonaceous species, see
the section on acetylene oxidation, was set to 0.3 [26,29].
The model has been validated using catalytic converter
input–output data recorded during a European test cycle on
a 4 cylinder 1.8 l Audi A4 vehicle with a strongly aged cat-
alyst. The physical parameters of the converter used in the
test are given in table 4. The inputs that have been measured
and fed into the converter model are: exhaust gas mass flow,
exhaust gas temperature, concentrations of carbon monox-
ide, oxygen, carbon dioxide, nitric oxide and hydrocarbons.
The model outputs have been compared with the measured
carbon monoxide, nitric oxide and hydrocarbons concentra-
tions, as well as the gas temperature behind the converter.
Hydrogen, which has neither been measured nor modeled,
has been accounted for by increasing the amount of energy
released during the CO oxidation by 30%. Note that the
measured concentrations do not give a completely correct
information on the fast dynamics of the catalytic converter
due to response lags of the analyzers. The influence of slow
analysers was already reported before [5]. These measure-
ments can therefore reveal only slower dynamics of the con-
verter, i.e., filtered concentrations of the measured compo-
nents with a low-pass filter. Consequences of the air/fuel ra-
tio control system are oscillations of the inlet concentrations.
These oscillations typically have a frequency between 0.5
and 2 Hz and amplitude around 2% (expressed in lambda).
This phenomenon cannot be seen in the data measured by
“slow” analyzers, but has quite a large effect on the conver-
sion of the catalytic converter [15,19,20,22]. To account for
this effect, oscillations have been superimposed on the meas-
ured inlet oxygen signal to create lambda oscillations with
amplitude around 2% and a frequency of 0.66 Hz. Acetylene
326 J.H.B.J. Hoebink et al. / Automotive converter modeling with elementary step kinetics
Figure 7. Comparison of Euro test cycle data at the inlet and outlet of a
monolith reactor with model predicted output. Dashed curve: reactor input;
thin curve: measured reactor output; thick curve: model predicted reactor
output.
is set to represent 30% of total hydrocarbons, while ethylene
represents the remaining 70%.
Figure 7 compares the measured converter output data
with output of the model during the warming up phase of
the test (first 150 s), which includes the converter light-off.
The model outputs have been filtered for the lambda oscil-
lations, i.e., only low frequency components have been re-
tained, for better comparison with the measured outputs. As
the vast majority of emissions occur at low temperatures,
prediction of the converter light-off becomes crucial. It is
clear from figure 7 that the light-off of all components is
well predicted. The output temperature of the model is also
in good agreement with the measurements. Perfect quanti-
tative agreement, however, is not obtained during the whole
test. The model predicted conversion of carbon monoxide
is somewhat higher then the measured one. The higher in-
let concentration of nitric oxide during the time interval be-
tween 120 and 145 s results in larger amounts of N and NO
adatoms on the noble metal surface, thus inhibiting the con-
version of ethylene. The hydrocarbon conversion predicted
by the model during this interval is too low. The overall
model prediction, however, is quite satisfactory. It is to be
expected that NO reduction kinetics, which account for ef-
fects of ceria, will lead to a significant improvement of the
existing model accuracy and a more complete description of
the dynamic processes taking place inside the catalytic con-
verter.
6. Conclusions
The dynamic behaviour of automotive exhaust gas con-
verters asks for unsteady state reactor modeling with incor-
poration of kinetic models on the basis of elementary steps.
Such models for individual global reactions can be combined
to cover their mutual interactions, and show a high potential
to describe various converter characteristics. Detailed infor-
mation about the rate parameters of elementary steps can be
obtained from transient kinetic studies, notably cycling of
the feed.
Acknowledgement
Professor Guy B. Marin, now at the university of Gent,
Belgium, is greatfully acknowledged as the initiator and
stimulator of research on transient kinetics and automo-
tive catalysis during his Eindhoven period. E. Lox and
J.A.A. van den Tillaart from dmc2 , Degussa Metals Cata-
lysts Cerdec AG, and J.C. Leenmans and W. van der Velden
from NedCar, Netherlands Car BV are acknowledged for
their interest and support. Financial support was provided
by the Dutch Technology Foundation STW.
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