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SAE TECHNICAL
PAPER SERIES 1999-01-0460

Modeling the Transient Characteristics

of a Three-Way Catalyst
James C. Peyton Jones, J. Brian Roberts, Jinfeng Pan and Richard A. Jackson
University of Sussex

Reprinted From: Gas Direct Injection Aftertreatment and Exhaust Aftertreatment Modeling
(SP-1455)

International Congress and Exposition

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March 1-4, 1999

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Modeling the Transient Characteristics of a Three-Way Catalyst
James C. Peyton Jones, J. Brian Roberts, Jinfeng Pan and Richard A. Jackson
Copyright © 1999 Society of Automotive Engineers, Inc.
ABSTRACT
The dynamic behavior of three-way catalysts has signifi-
cant impact on tailpipe emissions levels, but remains one
of the last unknowns in the overall vehicle emissions
model. A simple empirical model (appropriate for use in
real-time engine control and on-board diagnostic strate-
gies) has therefore been identified using fast response
input / output measurements of the actual process. The
model is able to characterize the (significant) dynamic
behavior which has recently been observed under rich
conditions, as well as the more well known dynamics
which arise from oxygen storage. The results therefore
compare well with measured responses over a wide
range of air / fuel ratio conditions.
INTRODUCTION
Three-way catalytic converters provide the most impor-
tant and now very common means for reducing the
tailpipe emissions of spark ignition gasoline engines. The
effectiveness of the converter depends critically on the
composition of exhaust gases produced by the engine,
with the optimum time averaged operating condition
occurring in a very narrow region around stoichiometric.
The goal of most current engine management systems is
therefore to maintain the air/fuel (A/F) ratio within this
window of operation, despite transient engine speed and
load disturbances, [1,2].
However tailpipe emissions depend not only on the time
averaged "steady state" exhaust conditions, but on the
dynamic behavior of the catalyst when subjected to tran-
sient disturbances in engine exhaust gas. A sufficiently
simple characterization of such behavior would allow the
catalyst dynamics to be integrated within a real-time,
model-based, engine control strategy. The complete
engine/catalyst system could then be optimized for both
performance and tailpipe emissions by actively manipu-
lating, (rather than merely passively regulating), the A/F
ratio operating condition. Such a model would also prove
useful in on-board diagnostic applications.
Many existing models used in catalyst design are based
on the underlying physical processes of heat transfer,
chemical kinetics, and fluid dynamics, but are unsuitable
for real-time control of catalytic operation because of the
1
1999-01-0460
University of Sussex
inherent computational complexity [3], and because the
dynamic effects are still not fully understood. A number
of authors have therefore sought to measure or identify
simpler, semi-empirical models for catalytic dynamics
based on input / output measurements of the actual pro-
cess, [4,5,6]. Though initial results are promising, recent
experimental results, [7], highlight some potential defi-
ciencies. In this paper a new catalyst model is developed
which captures many of the dominant features of this
data, though further work is needed to extend the
approach to operation at different engine speed and
loads.
CATALYST MODELS AND MODEL STRUCTURES
Engine exhaust is composed of many gas constituents,
and a complete mathematical model describing all possi-
ble reactions that then occur within a TWC is clearly very
difficult, if not impossible, to achieve. Even if it were pos-
sible to formulate such a model, it would be far too com-
plicated for use in the design and simulation of new
engine controllers and OBD systems.
In order to simplify the task, while retaining the dominant
dynamic behavior, it is common to consider only a small
number of key gas components and reactions, and to
approximate the spatially distributed nature of the cata-
lyst by a lumped parameter model. Within this frame-
work there are then two main approaches. The first is
based on the Arrhenius reaction kinetics of each individ-
ual gas component, together with the dynamics of gas
storage on the catalyst surface, while the second
assumes that the latter alone dominates catalyst
behavior.
KINETIC MODELING – One advantage of kinetic model-
ing is its direct relationship to the underlying chemistry,
and the global nature of the model which holds across
both rich and lean conditions, and different catalyst tem-
peratures. This avoids the use of temperature dependent
look-up tables, or discontinuous switches in model struc-
ture which are sometimes used to reflect the fueling con-
dition. The resulting system of coupled ODE's is still
potentially quite complex, and a variety of different model
structures have therefore been investigated.
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Aimard et al [4] for example modeled the kinetics of the
four gas components, HC, O2, CO, NOx, and their inter-
action with oxygen stored on the catalyst. They also pre-
sented a reduced order model which lumped all the
reducing and oxidation species together into two equiva-
lent components. Both models give good long-term time
cumulated results, though short-term dynamic responses
are only presented for upstream and downstream
exhaust gas oxygen (EGO), and CO sensors.
The model of Germann et al [5] is in some ways similar to
the reduced order model discussed above, since only two
components of the response, CO and O 2, are consid-
ered. In this case however the catalyst model is capable
of storing CO, (under rich conditions), as well as oxygen
when lean. The model also allows stored gas to be
released by desorption, rather than only by reaction with
the incoming exhaust. Initially this was applied only to
CO storage, but a small O2 desorption mechanism was
also added to resolve some numeric difficulties. The
stored oxygen level will therefore show a dynamic
response to lean region changes in A/F ratio, unlike the
Aimard model where no reduction in the stored oxygen
level can occur until the mixture returns rich once more.
Similar behavior, only relating to CO adsorption / desorp-
tion, would be observed in response to rich region
changes in A/F ratio.
STORAGE DOMINATED MODELING – An alternative
approach to modeling the catalyst chemical dynamics is
based on the observation that all the measured gas com-
ponents respond to input changes over a similar time-
scale. This suggests that the process is dominated by
the relatively slow dynamics of a single process such as
gas storage and release to / from the catalyst surface,
and that the other kinetics occur over a much shorter,
and less significant, time-scale. The conversion effi-
ciency of the catalyst can therefore be modeled using a
single nonlinear dynamic element to represent the stor-
age dynamics, (rather than the more complex coupled
dynamic equations of the kinetic approach), followed by a
more conventional static map of conversion efficiency.
The latter maps the effective A/F ratio after the absorp-
tion / desorption process, into individual tailpipe gas con-
centrations.
The model of Brandt et al, [6], has a structure of this kind,
and appears remarkably effective, though in some tests
the model predicted a response to one side of stoichiom-
etry, while the data actually deviated on the other. One
potential difficulty is that only oxygen storage dynamics
are considered. Under rich operating conditions, the
model would therefore yield a purely static response
once any oxygen on the surface had been depleted.
Another possible difficulty is that stored oxygen cannot
leave the surface if conditions remain lean, since the only
removal mechanism is by reaction with a rich input feed-
gas; the lack of a desorption mechanism means that the
catalyst model will again show no dynamic behavior once
the surface has become completely saturated.
2
EXPERIMENTAL DATA
In practice, the accuracy of many of the models intro-
duced above has been hard to assess because of the dif-
ficulties and costs inherent in obtaining transient
measurements of all the gas components of interest.
While upstream and downstream UEGO sensors do pro-
vide a low cost indication of transient catalyst behavior, it
should noted that such signals are sensitive to the pre-
cise gas composition as well as the A/F ratio itself, [8].
The sensor will therefore give different readings
upstream and downstream of the catalyst even under
static conditions.
Recently however a relatively complete set of transient
catalyst measurements have been obtained, as detailed
in a companion paper [7]. Fast response exhaust gas
analyzers were used to measure the gas concentrations
of CO, CO2, HC, and NOx upstream and downstream of
a demountable Pd:Rh catalyst, aged to 80 hours, 850o
lean spike. Thin sheathed thermocouples were also
used to measure upstream, downstream, and brick tem-
perature, and UEGO sensors were used to measure the
A/F ratio of the gas entering and leaving the catalyst.
The dynamic response of the catalyst was then mea-
sured in response to step changes in A/F ratio imposed
by the engine management system, first within the rich
region alone, then across stoichiometric, and finally in the
lean region alone. Though space precludes a full review,
some of the principal conclusions which relate to model-
ing are:
a. All gas components respond over a similar time-
scale, suggesting that catalyst behavior is dominated
by a single process, (probably the dynamics of gas
storage and release).
b. The time constant of this response generally
becomes shorter as the mean A/F ratio operating
point is moved further away from stoichiometric.
c. The catalyst response to transients performed within
the rich region still shows significant dynamic behav-
ior, and it is unlikely that this will be captured by mod-
els which include only oxygen storage mechanisms.
d. These dynamics may reflect adsorption and desorp-
tion of reductants to/from the catalytic surface as well
as the re-establishment of equilibria in the steam
reforming and water-gas shift reactions.
e. There appear to be two oxygen storage storage
mechanisms, with different rates of storage and
release; the more rapid involves formation of M-O
bonds at the surface, the slower probably involves
reversible oxidation of Ce2O3 to CeO2.
While a full discussion of the data is given in [7], some
evidence for conclusion c) can be seen in the post cata-
lyst responses to step changes of A/F ratio performed
entirely within the rich region. The “pre-“ and “post-“ plots
of Figure 5, for example, show a dynamic response to
step changes of l between 0.956 and 0.896, where,
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actual A / F ratio
λ= 5
stoichiometric A / F ratio NOx nox

Under such conditions any stored oxygen would have 4

been completely depleted, so the observed dynamic HC hc
response must be due to other processes such as those
1
suggested in d) above.
Delta 3
One possibility, for example, is that CO is being stored A/F in
Storage CO co
and released, as postulated in the model of Germann et Dynamics
al. In this case however one might expect a pulse of CO 2
generation on rich-to-lean transitions, as stored CO is 2
removed from the catalyst by reaction with excess oxy- CO2 co2
gen. In practice only a very slight increase in CO2 pro-
1
duction is observed, especially when compared to that
produced on lean-to-rich transitions, (see Figure 7b); Delta
A/F out
[The latter results from stored O2 being removed from the
surface by reaction with excess CO]. If reductants are
being stored, the dominant component is therefore more Figure 1. Storage dominated model structure
likely to be hydrogen, producing an (unmeasured) pulse
of H20 generation on rich-to-lean transitions. Alterna- Both upstream and effective A/F ratios are expressed in
tively, the observed dynamics could be the result of the terms of their difference, ∆λ , ∆ λ′
(respectively) from
equilibria in the steam reforming and water-gas shift stoichiometric, ( λ = 1 ). In this way the state of the cata-
reactions readjusting to the new conditions. Whatever lyst can be represented by a single integrator, with posi-
the physical cause, it is important that the dynamic tive values reflecting oxidized states, and negative values
behavior of the catalyst in its reduced state is in some the state under reduced conditions. Such an interpreta-
way characterized by the model. tion is however only implicit in the current model since the
state of the catalyst surface is not represented directly.
AN EMPIRICAL CATALYST MODEL Instead, the focus is on representing the relationship
between the input and effective A/F ratios in the simplest
None of the models introduced above are able to account way possible. This is both easier in terms of system iden-
for all the experimental observations, though each has tification, and more straightforward in terms of future con-
certain desirable properties. In this section an empirical trol objectives, since the lowest emissions are achieved if
catalyst model is developed in order to test the feasibility the effective A/F ratio is maintained at stoichiometric.
of an essentially storage dominated model structure, but The rich region step changes shown in Figure 5, for
one which captures the dynamic behavior observed in example, often give a response which rises sharply in a
the rich region tests as well as the more well known step-like manner, before continuing to change in a more
dynamics which arise from oxygen storage. The model exponential fashion. Such behavior is typical of a first
does not attempt to describe the effects of changing order system with a finite zero in addition to the usual
space velocities, or catalyst temperatures, though such pole. The system transfer function,
variables would not be difficult to incorporate in principle,
[5]. The slow secondary oxygen storage mechanism is b ( s + a)
also ignored for the present. G(s) = a>b (1)
a ( s + b)
The basic model structure, whereby transient responses
of HC, CO, CO2 and output A/F ratio are obtained from for example, can be implemented using a single integra-
the pre-catalyst A/F ratio input, is shown in Figure 1. The tor as shown in Figure 2, and gives the response shown
model assumes that the dominant dynamics can be rep- in Figure 3, for the values b = 1, a = 2.
resented by a single process, represented by the “stor-
age dynamics” element in the figure. This relates the b/a
upstream A/F ratio to the effective A/F ratio experienced
by the other reactions taking place on the catalyst. The +
1 + 1/s b + 1
latter are assumed to occur over a much shorter time- delta
-
Effective
Integrator
scale, and are therefore characterized by static maps of A/F Delta A/F
the tailpipe concentration levels for each gas component,
obtained from steady state tests. The model therefore
has a similar overall structure to that of Brandt et al,
though the underlying dynamics of the storage element
are radically different. Figure 2. First order storage model with finite zero

3
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Figure 3. Step Response of first order system with zero
In the case of the catalyst system, rough estimates for
the parameters a and b can be made by observation of
the initial step height and settling time from say the HC
response of Figure 5, [9]. This gives,
Ts ≈ 5 sec ≈ 4 / b ⇒ b ≈ 0.8
initial step
≈ 0.5 ≈ b / a ⇒ a ≈ 0.6
step amplitude
The response to step changes in the lean region how-
ever, shows much less of the dynamic exponential curve,
and more of a pure step change in the output. Such
behavior can still be obtained from the first order system,
(1), if the pole position b approaches that of the zero, a.
The parameter b (which determines the time constant of
the dynamics), therefore varies nonlinearly with the effec-
tive A/F ratio: if there is little gas storage / release, the
system time constant is fast, so b ª a; conversely, signifi-
cant gas storage / release effects moderate any changes
in effective A/F ratio, so a "slow" or small value of b
should be used.
These effects can be incorporated in the catalyst model
by introducing a lookup table to scale the value of b
according to the effective A/F ratio operating condition,
(see Figure 4). The resulting model is then nonlinear, but
is likely to perform better over a range of different fuelling
conditions. To assess its performance, the model was
driven with the measured A/F ratio input, and its
response to a variety of experimental tests compared to
the actual measured outputs.
The responses of Figure 5, for example, show the perfor-
mance of the model under step changes performed
entirely within the rich region. These are well character-
ized by the model, giving good agreement between mea-
sured and experimental data. However an exception is
seen in the prediction of downstream A/F ratio which
should normally follow the effective A/F ratio quite closely.
This is likely to be caused more by the commonly
observed inaccuracy in UEGO sensor measurements
under rich conditions, [8], rather than by any model defi-
ciency, especially since the other predictions, (which
depend entirely on the effective A/F ratio), are still quite
good.
lookup b/a
Gain3
+ 1
1 + * 1/s b +
- Delta
Delta
A/F in Gain1 A/F out
Figure 4. First order storage model with finite zero and a
nonlinearly varying time constant
The response of the model and catalyst to step changes
performed entirely within the lean region is shown in Fig-
ure 6. As one might expect the levels or CO and HC are
much lower than in the previous case, while the NOx lev-
els have risen. The dynamics of the response are also
much faster. In spite of these differences, the model still
provides a good fit to the data for all the gas components
considered, and even the measured and predicted A/F
(2) ratio signals are in good agreement.
Finally the behavior of the model and catalyst subjected
to step changes across stoichiometric is shown in the
responses of Figure 7. Once again the agreement
between the simulated and actual response of the down-
stream UEGO sensor, CO, and NOx measurements is
fairly good. The predicted effective A/F ratio in particular
accurately follows the classic plateau in the data near
stoichiometry, reflecting the mechanism whereby the
release of stored gas from the catalyst surface is able to
maintain stoichiometric conditions for a short period after
the upstream A/F ratio has switched.
Some discrepancies however can be seen in the CO 2
and HC results. In part this is believed to be due to the
secondary / slow release of stored oxygen under rich
conditions. The large pulse of CO2 production on lean to
rich transition is however due to the (much faster) initial
release of stored oxygen and its reaction with the CO rich
feed gas. To model this effect, the CO 2 output from the
static map in Figure 1 needs to be augmented by a quan-
tity proportional to the rate at which oxygen is released
from the catalyst surface. The latter can be approxi-
mated by the difference between the upstream and
downstream (ie. effective) A/F ratios,
O 2 release rate
= − K ( ∆λ − ∆λ ′) for − K ( ∆λ − ∆λ ′) > 0
where K is a constant of proportionality identified for the
data. If this extra component is added to the normal CO 2
output, then the improved results of Figure 7f are
obtained.
4
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Figure 5. Predicted, and measured, catalyst response to step changes within the rich region

5
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Figure 6. Predicted, and measured, catalyst response to step changes within the lean region

6
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Figure 7. Predicted, and measured, catalyst response to step changes across stoichiometric

7
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CONCLUSIONS
The feasibility of using a simple storage dominated model
for characterizing the dynamic behavior of a three-way
catalytic converter has been investigated. An empirical
model which is able to characterize the (significant)
dynamic behavior which has recently been observed
under rich conditions, as well as the more well known
dynamics which arise from oxygen storage, has therefore
been developed, giving results which compare well with
measured responses over a wide range of A/F ratio con-
ditions.
The effects of changing space velocities, catalyst temper-
ature and slow oxygen storage mechanisms, however,
have been ignored for the present. Further work is there-
fore necessary to extend the model for operation under
different speed and load conditions, and this is the sub-
ject of on-going research.
ACKNOWLEDGMENTS
The authors wish to acknowledge the financial and tech-
nical support of the following sponsors:
• Engineering and Physical Sciences Research Coun-
cil (EPSRC), UK
• Ford Motor Company Ltd, Advanced Vehicle Techon-
logies, UK
• Horiba Instruments Ltd, UK
• Johnson Matthey, Catalytic Systems Division, UK
• Ricardo Consulting Engineers Ltd, Vehicle Control
and Calibration
• Rover Group, Powertrain, Gaydon, UK
• SAGEM, Research and Development
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