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Modeling and Simulation of Automotive Catalytic Converters

Tariq Shamirn
Deppartment ofMechmical Engineering, Universfy of Michigan, Dearborn, M 481 28, USA
This paper describes the development of LI
comprehensive ma fhema fical and numerical model f or
simulating the performunce of automotive three-way
catalytic convertem, which are employed to reduce
enigine exhaust emisfions. The model simulates the
emissiori sysrem behavior by using an exhaust system
heat consen~ahm and catalvsf chemical kinetic sub-
model. The resitlting governing equations are solved
nzunericolly. Good agreements were found between
the nrtmerical predictiotzs and e,qxrimental
nwu~i t i ~ement s under both steaaIy state and transient
conditions. The developed model is employed to
invesligule the converter dynumic wsponse during
tr-onseni driving conditions. The transient conditions
are simiilaied by considering modulutions in the air-
fidel ratio.
gas phase concentration of speciesj, 1noiim
surface concentration of speciesj, mo1i1n3
specific heat of gas, J/kgK
specific heat of substrate, J/kg.K
empirical constant for oxygen storage eaction
activation energy, ~a- m~/g- mol
empirica! constant for reaction rates
geometric surface area, m2/m3
heat of reaction of species k, J imol
heat transfer coefficient between flow and
substrate, J /mZ.s.K
heat transfer coefficient between substrate
and atmosphere, J /m2.s.K
empirical constant for oxygen storage
reaction rates
mass transfer coefficient for species j , m/s
reaction rate ofkth reaction, mol/m2,s
external surface to volume area ratio, in2/m3
time, s
ambient temperature, K
gas temperature, K
substrate temperature, K
gas flow velocity, m/s
mole fraction of species i in substrate
coordinate along catalyst axis, m
hydrogen-to-carbon ratio in the fuel
void volume fraction [value ranging from
zero (for no void) to one]
thermal conductivity of substrate, J /m.s.K
gas density, kgim3
substrate density, kgim
I. Tntroduction
Emissions from engines are major sources of
urban air pollution. The engine exhaust gases contain
oxidcs of nitrogen (NO,)? carbon monoxide (CO), and
partially burned or unburned hydrocarbons (HC).
These pollutants have hazardous effects on
environmcnt and living beings. They may cause acid
rain, smog, and several respiratory diseases.
Accordingly, they are being subjected to stringent
regulations worldwide. I n gasoline engine
applications, thcse pollutants can be removed from the
exhaust gases by employing catalytic converters.
Catalytic converters have been used in
automobiles for several years and various types of
them are available. They can reduce engine emissions
by more than 90%. However, due to progressively
stricter emission regulations, the catalytic converter
design and performance need to be continuously
improved. The design improvement efforts require
broadening of fundamental understanding of various
physiochemical processes that occur in a catalytic
In the past, much of the design and engineering
process to optimize various components of engine
emission systems has involved the prototype testing.
The complexity of modern systems and the resulting
flow dynamics and thermal and chemical mechanisms
havc increased the difficulty in assessing and
optimizing system operation. Due to overall
complexity and increased costs associated with these
factors, modeling continues to be pursued as a method
of obtaining valuable information supporting the
0-7803-8680-9/04/$20.00 02004 IEEE. INMIC 2004
Exhaust 3
- A tn tailninp
Inlet diffuser Catalyst Outlet diffuser Cel lichannel
Side view of catalyst assembly Front view of catalyst brick
Figure 1. Schematic of a three-way catalytic converter
design and development process associated with
the exhaust emission system optimization.
Due to its various advantages, the use of modeling
in designing and optimizing the catalytic converter
systcm i s now becoming a c o n" practice. The
modeling can particularly be beneficial in
understanding the catalyst response under realistic
transient driving conditions since the catalyst behavior
under steady state conditions is very different from
that under transient conditions. The catalyst behavior
under dynamic conditions has a great deal of practical
interest, and therefore has been investigated by many
researchers [I-SI. Several of these studies report the
enhancement of cataIyst's activity or selectivity.
The present study employs a single channel based
1 -D inodcling approach to simulate the catalyst
performance during the US driving test cyctes. The
modcl incl tides the transient heat transfer sub-model,
coupled with a transient catalyst chemical kinetic
mechanism. The modcl is used to investigate the
catalyst performance under transient driving
condi tions.
2. Mathematical Formulation
Figure 1 shows a schematic of the catalytic
converter. The governing equations were developed
by considering the conservation of mass, energy and
chemical species. Using the assumptions and
notations listed elsewhere [9], the governing
conservation equations for a typical single channel
may be written as foollows:
The gas phase energy equalion.
r T
The gas phase species equations f or 7 species}:
The superscript j in species equations varies from
1 to 7, representing the following species: CO, NO,
NH?, 02, C3H,, H2 and C3Hs. The heat and mass
transfer coefficients in the above equations are
calculated from thc conventional correlations of
Nusselt and Sherwood numbers [lo]. The
heterogeneous surface chemistry and the oxygen
storage capacity are modeled by using respectively 13
and 9-step chemical mechanisms [9]. Thew chemical
reactions represent thc so far most inclusive reaction
scheme for automotive catalyst. The reaction rate
expressions used in the present study were similar to
those used in Ref. [9]. The conservation equation for
the surface oxygen storage mechanism is represented
by the surface species equation excluding the
convective mass transport tenn. The governing
equations were discretized by using a non-uniform
grid and employing the control volume approach with
the central implicit difference scheme in the spatial
direction. A standard tridiagonal matrix algorithm
with an iterative successive line under relaxation
method was used to solve the finite difference
equations. The spatial node size rangjiig from 0.1693
min to 19.32 mm and the time stcp of 0.001 second
were employed. The grid insensitivity of results was
ensured by performing a sensitivity study. Details of
I * I
Redox Rat l o
Figure 2 Comparison of model prediction and
experimental measurements at steady state
the solution procedure are described elsewhere [SI.
3, Results and Discussion
3.1. Model Validation
The numerical model was validated using
experimental measurements under both steady and
transient conditions. The model's predictions under
steady state conditions were compared with the
experimental measurements of Montreuil et al. [ 131.
For this case, all transient terms in the governing
equations werc set to be zcro. The catalyst used for
the steady-state validation was palladium-based and
had a length of 3.81 cm, cross-sectional area of 5.067
tin', cell density of62 cells/cm2, and wall thickness of
0.188 min. The space velocity was 50000 hr' and the
species mole fractions werc: CO I %, CH4 0 ppm,
C3H6 1000 ppm (C3), C3H8 500 ppm (C3), and NO
1000 ppm, The stoichiometric value of air-to-fuel
ratio ( N F ) was 14.51 and the feed gas temperature
was 3 7 1 "C.
Figure 2 shows the comparison of the converter
pollutant conversion efficiencies as determined by the
model and experimental measurements. The
conversion efficiencies are plotted as a function of
redox ratio. The figure depicts that the numerical
model results are in good agreement with the
experimental measurements at the typical engine air-
fuel ratio regions. NO conversion efficiency is
particularly well predicted by the model over a wide
redox ratio range. The discrepancies in the predictions
of CO and HC at higher redox ratios is due to
inaccuracies in chemical kinetic data, which are
obtained for conditions dose to redox ratio of unity.
Hence, the model predicts the performance of catalytic
converters under steady state and typical opcrating
conditions very well.
The model's performance under transient
conditions were assessed by using expcrimental
measurements across the front catalyst brick from a
4.6L 2V Lincoln Towncar as it was driven during the
US Federal Test Procedure (FTP-72) cycle. The
converter was a palladium-based catalyst, with a
length of 8 cm, cross-sectional area of 86.0254 cm2,
cell density of 62 cells/cm2, and wall thickness of
0.1905 mm. The boundary conditions for the model
were obtaiiied from the experimental measurements,
which included the mass flow rates of CO, HC, NOx
and the total gases at the catalyst inlet during the FTP.
The air-fuel ratio of engine's fresh charge was
calculated based on the measured airflow and fucl
supply rates. The ambient temperature for the
measurements and simulation was 297 K. The
ineasurements were made at an interval of 1 second;
therefore, thcre were 1372 incasurcd data for FTP-72.
Figure 3 shows the comparison of cumulative
emissions as determined by the model and
experimental measurements during the first 600
seconds of the FTP. The results show good agreement
as the difference between the computational results
and the experimental measurements are within 2.4%
during this 600 second period. The results show that
the model underestimates thc NO emissions during the
legislated cycle. The model accuracy for CO and NO
is not as good as in the case of HC prediction,
however, the difference between the numcrical
predictions and thc expcrimental measurements is
within the variability caused by the dynamic
measurement of AfF ratio, which strongly influences
modeling results [26].
Table 1 Comparison of total conversion
efficiencies between model predictions and
experimental measurements during the
federal test procedure (FTP)
Efficiency(%) CO NO HC
Experimental 91.53 92.03 95.88
Model prediction 88.69 95.93 94.84
Difference ("A) 3.1 4.24 1.08
Figure 3 Comparison of pollutant emissions between model predictions and experimental
measurements during the federal test procedure (FTP) (a) CO emissions; (h) HC emissions; (c) NO
The pollutant conversion efficiencies as
determined by the model and experimental
ineasurements during the total FTP-72 test cycle are
listed i n Table 1. The table shows a difference of less
than 5% between the conversion efficiencies predicted
by the numerical model and those determined
experimentally. These results clearly show the
adequacy of the numerical niodel in simulating the
performance of three-way catalytic converter.
3.2. Catalyst Dynamic Behavior
The catalyst dynamic behavior was investigated
by subjecting the catalyst to modulations in air-fuel
ratio ( AI F) . The catalyst used for this study was
palladium-based and had a length of 3 cm, cross-
sectional area of 86.0254 an2, cell density of 62
cellsicm', arid wall thickness of 0,1905 nun. The gas
mass flow rate was 1.417~10'~ kgis with 9.9205xIO-'
kgis CO, 8.0834 xlO-* kgis total HC, and 1.0282~10"~
kg/s NO. The feed gas temperature was 297C.
These results were obtained by considering the
catalyst, which was initially at steady state conditions
and was suddenly subjected to sinusoidal modulations
iii NF. During these modulations, other inlet
condrtions and the concentrations af CO, HC and NO
remained unchanged. Thc A/F was varied by
changing the oxygen concentration. Figures 4 shows
the CO, HC, and NO conversion efficiencies as a
function of imposed fluctuation time period. The AR,
iiiitially set at 14.8 (stoichiometric valuc of AiF is
14.5 I ) , is varied sinusoidally with a frequency of 1 Hz
and amplitude of 5%. The AIF ranges between 14.06
and 15.54, and the catalyst undcrgoes a transition
between rich and lean operating conditions during
each fluctuation time period. The catalyst responds to
Ai F modulations with a time delay.
Figure 4(a) shows the CO conversion efficicncy
as a function of the fluctuation time period. The initial
CO conversion efficiency, due to lean operating
conditions, is very high. The results show that, with
the imposed fluctuations in AIF and the corresponding
transition to the rich zone, the CO conversion
decreases. Tt starts increasing again after reaching a
minimum value. Interestingly, the CO conversion
efficiency drops much lower than the steady state
value corresponding to the lower value of AIF. Near
the stoichiometric conditions, the CO conversion
performance exhibits a discontinuous behavior and a
sharp decrease in the efficiency. The efficicncy
increases again as the AIF increases beyond
stoichiometric value. The catalyst response i s
unsteady periodic during thc initial time periods, and
becomes steady periodic after a long time.
Figure 4(b) depicts the HC conversion efficiency
as a hnction of the fluctuation time period. The
results show that the HC conversion efficiency of the
catalyst responds to the sinusoidal modulations in A/F
in a periodic manner. However, the response is not
truly sinusoidal. The increase in A/F increases the HC
conversion efficiency. The conversion efficiency
reaches a maxiinum value (- 93%) corresponding to
the maximum value of AIF. After reaching the
maximum value, the HC conversion decreases. This
decrease in HC convcrsion continues in the rich zone
RS the AIF crosses the stoichiometric value. The HC
conversion efficiency attains a minimum value (-
76%) before the A/F reaches its minimum value. The
conversion efficiency then increases. The increase is
g o
0 80
; 15.2
I I t
a 2 4 6 B
Ti me Peri od
Figure 4 Catalyst response to sinusoidal
modulations in air-fuel ratio near
stoichiometric operating conditions (Mean A/F
=14.8, Frequency =1 Hz, Amplitude =5%)
relatively sharp near the stoichiometric AIF. Beyond
the stoichiometric value, the HC conversion efficiency
continues to increase until the maximum value is
attained. After the first cycle, the catalyst HC
response exhibits a cyclic pattern Similar to CO
response, the result shows a drop in the mean value
around which the conversion efficiency oscillates.
This indicates that, near the stoichiometric point, the
AIF modulation causes a reduction in CO and HC
Figure 4(c) shows the NO conversion efficiency
as a fknction of Iluctuation time period. Compared to
HC conversion efficiency, the responsc of NO
conversion to the sinusoidal fluctuations is relatively
more sinusoidal and more substantial. The initial
steady state NO conversion efficiency corrcsponding
to initial NF of 14.8 is approximately 66.8%. The NO
conversion responds to the change in AIF with a slight
time delay. The conversion efficiency decreases due
to an increase i n the AIF. The efficiency attains a
minimum value (- 27%) corresponding to the
maximum value of MF, following which it starts
increasing again. Thc conversion efficiency increases
sharply with a decrease in the AIF near the
stoichiometric conditions in the rich zone. As
NO 1
y 12A
11.6 '
I . I .
4 6 8
Time Period
Figure 5 Catalyst response to sinusoidal
modulations in AIF near rich operating
conditions (Mean A/F =12.5, Frequency =1
Hz, Amplitude =5%)
expected, in most of the rich region, the NO
conversion efticieiicy is very high and is close to
100%. The conversion efficiency remains high even
when the A/F is increased beyond the stoichiometric
value and into the lean zonc. The efficiency starts
decreasing after the A/F is increased further in the lean
zone. The catalyst's periodic response continues as
long as the fluctuating AIF field is maintained.
Contrary to the CO and HC cases, the AIF modulation
has positive impact on NO conversion, which is
improved from a steady state value of 66.8% to
The effects of sinusoidal fluctuations in rich and
lean zones away from the stoichiometric value are
presented next. The rich zone results, as shown in
Figure 5, were obtained by initially setting the A/F at
12.5. The catalyst is subjected to sinusoidal
modulations in the A/F with a 1 Hz frequency and 5%
amplitude. The resulting N F ranges between 11.88
and 13.13. The effect of fluctuation on the CO
conversion is found to be insignificantly small. The
HC conversion, on the other hand, is found to be
relatively more affected. Due to rich conditions
throughout, the initial HC conversion efficiency is
very small (- 2.1%). The results show that, in contrast
67. 3 3%.
to the casc of transition zone, thc conversion response
is truly sinusoidal. There is no delay in catalyst
response to AIF variations. Owing to rich conditions
tliraughout the fluctuation periods, the NO conversion
remains very high and is not influcliced by the
imposed modulations. The lean zone results, not
shown here, depict no influence on CO conversion and
insignificantly small influence on HC conversion. The
NO conversion efficiency shows relatively larger
influence of NF modulations. These rcsults clearly
show that the effects of A/F modulations are different
under different operating conditions.
4. Conclusions
A numerical simulation code for predicting the
catalytic converter performance has been
developed. This code includes the transient
teims in the governing equations so that it can be
used tu predict the catalytic converter
perfonnance during transient operating
conditions such as US FTP regulated driving
The compiitational results show good agreement
with the experimental mensurcinznts at both
steady state and transient operating conditions.
The model predicts the pollutant conversion
efficiencics within 5% of the experiinentaI
mcasurements for the FTP.
9 The numerical model is used to clucidatc the
catdyst dynamic behavior which is very different
fi-omthat under the steady state conditions. The
behavior is intluenccd by the operating
conditions and chemical kinetics. Near
stoichiometric conditions, the A/F modulation
decreases the CO and HC conversion and
improves the NO conversion. The effect QR HC
conversion is relatively small. For these
conditions, the tcsponse of conversion
efficiencies is not truly sinusoidal to sinusoidal
modulations. At higher inodulation frequencies,
however, the rcsponse bccoines sinusoidal.
Under lean and rich conditions, the A/F
modulations have rclatively insignificant effects
on the catalyst conversion performance.
5. Acknowledgments
6. References
[ I ]
Mcrz, R. K., Dynamic Rchavior of Automotivc Thrcc-
Way Emission Control System, Cutnl~vsis und
Aufonzotive Pollulion Conlrol, Elsevier, Amsterdam.
1957, pp. 427-444.
[2] Hcrz, K. K., Dynamic Bchavior of Automotivc
Catalysts: 1. Catalyst Oxidation and Reduction,
Induslrial and Engineering Chemistry hodi r c t
Research arid DeiJelopmen!. Vol. 20, 1981, pp. 481-
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pp. 175- 195.
[4] Silveston, P. L., Automotive Exhaust Catalysis: Is
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[8] Matsunga, S . 4, Yokota, K., Muraki, H. and Fujitani,
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[9] Shamim, T., Shen, H., Sengupta, S., Son, S., aiid
Adamczyk, A. A., A Comprchensivc Modcl to Prcdict
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[IO] Montrcuil, C. N., Wi l hns, S. C., and Adamczyk,
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Thc financial support from the Oak Ridge
National Laboratory, Ford Scientific Research
Laboratory and the Center for Engineering Education
and Practice (CEEP) of the University of Michigan-
Dearborn is greatly appreciated.