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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
2. Scope
3. Experimental
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
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
Table 4
of the lean half-cycle the reactor outlet shows O2 and NO,
Converter parameters used in the Euro test cycle
more or less at inlet concentration levels, and some NO2 . validation.
Switching to CO shows for CO and CO2 similar behaviour
Substrate length 6 inch
as observed with Pt/Rh/CeO2 /Al2 O3 , but the total CO con- Substrate diameter 4 inch
sumption and CO2 production during the rich half-cycle are Cell density 400 cpsi
much smaller due to the absence of ceria. The NO concen- Wall thickness 6.5 × 10−3 inch
tration does not increase initially after the switch from lean Washcoat loading 250 g/l
to rich, as it did for Pt/Rh/CeO2 /Al2 O3 , probably because Catalyst aging strongly aged
ceria, hence NO desorption from ceria, is absent in this cata-
lyst. NO desorption from Pt/Rh/Al2 O3 takes more time than The kinetic models for CO, C2 H2 and C2 H4 oxidation,
from Pt/Rh/CeO2 /Al2 O3 . A substantial amount of NO2 is described previously, have been applied directly in the con-
observed, and very small amounts of N2 and N2 O, even less verter model. All rate parameters were used as published
when compared to the ceria-containing catalyst. When the except the adsorption rate coefficient of CO on O adatoms.
lean half-cycle is entered again after about 30 s, all phenom- For NO reduction the kinetic model of Oh et al. [38] was
ena occur very fast. There is a small break-through peak of applied, which also was used in previous modeling stud-
oxygen [23,24], followed by a sharp CO2 peak, that is con- ies [15,16,22]. This model includes dissociation of adsorbed
siderably smaller than during the preceding half-cycle. In NO, and two reaction paths toward N2 via the recombination
the same short time interval, a complete consumption of NO of N adatoms and via reaction between adsorbed NO and N.
causes small peaks in the sequence N2 , N2 O and NO2 . The The NO reduction kinetics were obtained on Rh catalyst. In-
oxygen concentration reaches subsequently its inlet value teraction with ceria was not taken into account, but known to
relatively fast. The NO concentration, however, passes a influence the kinetic rate parameters [39]. The parameters of
temporary maximum, probably because the reactions have the NO reduction have therefore been adapted to get a better
decayed, and then increases gradually during the rest of the agreement with measured test cycle data. Other adapted pa-
lean period. The NO2 concentration increases as well at a rameters were the monolith thermal capacity, the noble metal
lower level. An explanation might be that NO is able to ad- dispersion and the oxygen storage capacity. The fraction of
sorb on oxygen covered surface sites. In some way, an extra the noble metal sites covered by carbonaceous species, see
amount of O adatoms must be supplied to the catalyst during the section on acetylene oxidation, was set to 0.3 [26,29].
the lean half-cycle, which causes the larger CO2 peak during The model has been validated using catalytic converter
the rich counterpart. input–output data recorded during a European test cycle on
Data for Pt/Al2 O3 catalyst are not shown, as they are es- a 4 cylinder 1.8 l Audi A4 vehicle with a strongly aged cat-
sentially the same as for Pt/Rh/Al2 O3 . An exception is the alyst. The physical parameters of the converter used in the
NO concentration after the switch from lean to rich. It ex- test are given in table 4. The inputs that have been measured
ceeds the former inlet level for a while, as was also observed and fed into the converter model are: exhaust gas mass flow,
for Pt/Rh/CeO2 /Al2 O3 . The addition of rhodium was re- exhaust gas temperature, concentrations of carbon monox-
ported as less unfavorable for NO adsorption than for O2 ide, oxygen, carbon dioxide, nitric oxide and hydrocarbons.
adsorption [34]. The model outputs have been compared with the measured
carbon monoxide, nitric oxide and hydrocarbons concentra-
5. Emission prediction during a test cycle tions, as well as the gas temperature behind the converter.
Hydrogen, which has neither been measured nor modeled,
The implementation of the kinetics in a catalytic con- has been accounted for by increasing the amount of energy
verter model can be used to optimise the design of the con- released during the CO oxidation by 30%. Note that the
verter, as well as to investigate new control strategies, with- measured concentrations do not give a completely correct
out the need for extensive testing [22]. A convenient test for information on the fast dynamics of the catalytic converter
the converter model accuracy is its ability to predict exhaust due to response lags of the analyzers. The influence of slow
emission during a standard emission test cycle. Experimen- analysers was already reported before [5]. These measure-
tal data of a European test procedure have been used in this ments can therefore reveal only slower dynamics of the con-
study. verter, i.e., filtered concentrations of the measured compo-
The dynamic converter model accounts for the accumu- nents with a low-pass filter. Consequences of the air/fuel ra-
lation of mass in the bulk gas phase, in the pores of the tio control system are oscillations of the inlet concentrations.
washcoat and on the catalytic surface, as well as for the These oscillations typically have a frequency between 0.5
energy accumulation in the gas and solid phase. The reac- and 2 Hz and amplitude around 2% (expressed in lambda).
tor is considered to operate adiabatically with uniform flow This phenomenon cannot be seen in the data measured by
distribution over the channels and with constant heat and “slow” analyzers, but has quite a large effect on the conver-
mass transfer coefficients. With these conditions satisfied sion of the catalytic converter [15,19,20,22]. To account for
only one channel has to be modeled as representative for this effect, oscillations have been superimposed on the meas-
the whole monolith. Detailed model equations were already ured inlet oxygen signal to create lambda oscillations with
published [15,22]. 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
6. Conclusions
Acknowledgement
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; References
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