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34 - 2008 - Int.-J.-Automot.-Technol. - Zervas-E. - Parametric-Study-Of-The-Main-Parameters-Influencing PDF
34 - 2008 - Int.-J.-Automot.-Technol. - Zervas-E. - Parametric-Study-Of-The-Main-Parameters-Influencing PDF
E. ZERVAS*
Department of Environmental Engineering, Democritus University of Thrace, Vas. Sofias 12, 67100 Xanthi, Greece
ABSTRACT−This work studies the impact of five parameters: CO and HC engine-out emissions, space velocity, average
value and profile of exhaust temperature, on Diesel CO and HC tail-pipe emissions. The first part of this work is conducted
on a reactor and shows that both HC and CO light-off temperature increases with CO and HC input concentration. CO and
HC initial concentration influence the adsorption/desorption capacities of HC only at high temperatures. Space velocity also
influences CO and HC conversion efficiency. The second part of this work studies the impact of different combinations of HC
and CO engine-out emissions on CO and HC conversion and tail-pipe emissions in the case of New European Driving Cycle.
This part proposes that a Diesel oxidation catalyst must be mainly studied at the Urban Part of NEDC, as the CO and HC
conversions are very high at the extra-urban part of NEDC. CO and HC conversion efficiencies are also dependent on exhaust
temperature and catalytic volume. In the case of two different profiles of exhaust temperature with the same average
temperature, CO and HC conversion efficiency is lower in the case of the smoother profile.
KEY WORDS : Diesel, Oxidation catalyst, CO, HC, Space velocity, Exhaust temperature, Emissions
641
642 E. ZERVAS
Figure 5. CO tail-pipe emissions and conversion efficiency Figure 6. HC tail-pipe emissions and conversion efficiency
as a function of engine-out CO (upper curves) and HC as a function of engine-out CO (upper curves) and HC
(lower curves), for different exhaust temperatures and (lower curves), for different exhaust temperatures and
DOC volume used. DOC volume used.
and tail pipe CO and HC exhaust emissions of a Euro3 The decrease of CO conversion with increased HC
Diesel passenger car. It is clearly shown that even cumu- initial concentration is also shown in Figure 2. The reason
lative engine-out emissions increase until the end of NEDC, must be the searched at the increased competition between
tail-pipe emissions reach an upper value (particularly in the CO and HC to occupy the active centres of the oxidation
case of CO) and then remain constant quite early, even catalyst. Even if CO is adsorbed better than HC, the
before the beginning of EUDC. increased HC concentration decreases the available active
Figure 5 shows the CO tail-pipe emissions and conver- centres for the CO adsoption. The decrease of tail-pipe CO
sion efficiency on the NEDC as a function of CO and HC is a balance between the increased rate of oxidation due to
engine-out emissions, for different average exhaust temper- the increased exothermicity and the decreased number of
atures on the urban part of NEDC and different volumes of active centres because they are occupied from HC. The
oxidation catalyst used. It is clearly shown that CO conver- curves of CO conversion efficiency have the same slop for
sion efficiency slightly increases with engine-out CO and all catalyst volumes and ECE average temperatures tested,
HC. The reason must be the increased temperature on the showing that CO and HC engine-out emissions are more
catalyst because of the increased rate of reactions due to important than catalyst volume and exhaust temperature for
increased initial concentrations. CO oxidation efficiency.
However, for constant engine-out HC missions, even if Figure 6 shows the HC tail-pipe emissions and conver-
conversion efficiency increases, tail-pipe CO emissions sion efficiency on the NEDC as a function of CO and HC
increase with CO engine-out emissions. This increase is engine-out emissions, for different average ECE exhaust
due to the higher increase of engine-out CO emissions temperatures and volumes of oxidation catalyst used.
comparing to the increase of the corresponding CO con- This figure shows that HC conversion efficiency slightly
version due to the increased exothermicity. For constant increases with engine-out CO and HC emissions and this
engine-out CO, tail-pipe CO slightly decreases with the increase is higher in the case of lower ECE temperature
increase of engine-out HC emissions. (160oC than 180oC) and lower engine-out emissions, for the
PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE CATALYTIC EFFICIENCY 645
same reasons as in the case of CO oxidation efficiency. In CO and HC tail-pipe emissions and conversion efficiency
the case of high engine-out HC and CO emissions, big on the NEDC as a function of average temperature on the
catalytic volume and high ECE temperature, HC conver- ECE, for different CO and HC engine-out emissions and
sion efficiency remains constant after having reached its catalytic volumes used, are shown in Figure 7. It is clearly
upper limits (around 86~87%). The CO adsorption on the shown that CO conversion efficiency is, for all cases
oxidation catalyst is much better than the HC adsorption studied, strongly dependent on exhaust temperature and
and thus a decrease of the tail-pipe HC would occur in the increases almost linearly.
case of increased CO engine-out emissions. However, for Figure 7 shows that an increase of ECE average temper-
temperatures lower than 180oC, CO adsorption does not ature of 20oC increases CO conversion efficiency by about
influences significantly HC conversion efficiency, as shown 15 percentage units. Consequently, CO tail-pipe emissions,
in Figure 1, and thus HC tail-pipe emissions remain rela- decrease significantly with temperature. HC conversion
tively constant with increased CO engine-out emissions. efficiency also increases with temperature (Tanaka et al.,
For constant engine-out CO missions, tail-pipe HC emi- 2005); however, the slope of conversion curves decreases
ssions increase with HC engine-out emissions (Tanaka, at higher temperatures, indicating that there is an upper
2005), even if conversion efficiency slightly increases, limit for this increase (Tanaka et al., 2005). HC tail-pipe
because engine-out HC emissions are much higher than the emissions also decrease with temperature; however, the
increase of the corresponding conversion. For constant slope is lower than in the case of CO, indicating that
engine-out HC emissions, HC oxidation is very little influ- temperature is more important in the case of CO oxidation
enced by CO, as tail-pipe HC emissions remain practically than on the case of HC oxidation, as shown in Figures 1
constant with engine out CO emissions. and 2.
Figure 8 shows CO and HC tail-pipe emissions and con-
3.4. Impact of Average Exhaust Temperature and DOC version efficiency on the NEDC as a function of the cata-
Volume on CO and HC Conversion on the NEDC lytic volume used, for different CO and HC engine-out
Figure 7. CO (upper curves) and HC (lower curves) tail- Figure 8. CO (upper curves) and HC (lower curves) tail-
pipe emissions as a function of exhaust temperature (aver- pipe emissions as a function of DOC volume, for different
age value on the ECE), for different engine-out HC and CO engine-out HC and CO emissions and different values of
emissions and different volumes of oxidation catalyst. exhaust temperature (average value on the ECE).
646 E. ZERVAS
emissions and different average ECE temperatures of ex- The two shapes have the same average value on the
haust gas. For both CO and HC, their conversion efficiency ECE. Right bars show that CO and HC conversion effici-
increases with the catalytic volume as the residence time ency is lower in the case of the smoother exhaust temper-
within the catalyst decreases. The slope of the conversion ature. When exhaust temperature is low, the difference on
curves is quite high in the case of lower catalytic volumes; CO and HC conversions between the two curves is not
however it decreases at higher catalytic volumes indicating significant. However, CO and HC conversions are much
that there is a lower limit at the residence time which higher in the four peaks with increased temperature than at
influences CO and HC oxidation. Figure 3 shows that there the peaks of the smoother one, leading to a higher global
is a significant impact of space velocity on HC conversion; conversion efficiency. As CO conversion efficiency depends
however, this impact is lower at high space velocities. more on temperature than the conversion efficiency of HC,
Apparently, the space velocity of the NEDC tests used is the difference between the conversion of the initial and
quite high to have a significant impact on HC emissions. smoother exhaust temperature is higher in the case of CO.
For this reason, HC tail-pipe emissions of Figure 8 seem These results show that an engine tuning with some, even
not to be so dependent on space velocity as in Figure 3. small, parts of the NEDC with increased exhaust temper-
ature helps to increase significantly the total CO and HC
3.5. Impact of Exhaust Temperature Shape conversion efficiency.
The previous results show that the average ECE temper-
ature influences CO and HC conversion efficiency; however, 4. CONCLUSIONS
the shape of the temperature curve also influences these
conversions. Figure 9 shows two different shapes of ex- This work studies the impact of CO and HC engine-out
haust temperature: the initial one and one modified, which emissions, space velocity and exhaust temperature (aver-
is smoother. age value and profile) on tail-pipe emissions.
Reactor experiments (first part of this work) show that
both HC and CO light-off temperature increases about 7oC
for every 500 ppm of CO added and about 4oC for every
200 ppm of HC added. CO and HC initial concentration
does not influence the adsorption/desorption capacities of
HC from 80 to 180oC; however, at temperatures higher
than 180oC, HC conversion decreases at high CO or HC
initial concentrations. The increase of space velocity influ-
ences significantly CO and HC conversion efficiency as
CO T50 increases 10oC and HC T50 increases 22oC when
space velocity increases three times (from 38,000 to 110,000
h−1). Space velocity has also a significant impact on HC
adsorption.
In the case of NEDC tests (second part of this work), CO
conversion is always 100% at exhaust temperature above
250oC, while the conversion of HC is about 90%. The
temperature of exhaust gas at EUDC is always high, lead-
ing to high CO and HC conversions and thus very low or
almost zero tail-pipe emissions. For this reason, a Diesel
oxidation catalyst must be mainly studied at the Urban Part
of NEDC.
CO and HC conversion efficiency slightly increases with
engine-out CO and HC, apparently due to increased cata-
lyst temperature due to increased engine-out emissions.
However, for constant engine-out HC emissions, tail-pipe
CO emissions increase with CO engine-out emissions,
because engine-out CO emissions increases more than the
increase of the CO conversion. From the other hand, for
constant engine-out CO, tail-pipe CO slightly decreases
Figure 9. ECE initial and modified exhaust gas temperature with the increase of engine-out HC emissions due to the
(upper curves) and CO and HC tail-pipe emissions and increased catalyst temperature. For constant engine-out CO
conversion efficiency of these two tests (lower bars). missions, tail-pipe HC emissions increase with HC engine-
Ti=initial temperature, Tm=modified temperature, in the out emissions, because engine-out HC emissions are much
case of two Diesel oxidation catalysts of 1.1 L and 1.3 L. higher than the increase of the corresponding conversion.
PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE CATALYTIC EFFICIENCY 647
For constant engine-out HC emissions, HC oxidation is Japan. Applied Catalysis B: Environmental, 10, 83−97.
very little influenced by CO. Kamijo, M., Kamikubo, M., Akama, H. and Matsushita, K.
CO conversion efficiency is strongly dependent on ex- (2001). Study of an oxidation catalyst system for diesel
haust temperature and increases almost linearly. HC con- emission control utilizing HC adsorption. JSAE Review,
version efficiency also increases with temperature; however, 22, 277–280.
the slope of conversion curves decreases at higher temper- Salomons, S., Votsmeier, M., Hayes, R. E., Drochner, A.,
atures indicating that there is an upper limit for this Vogel, H. and Gieshof, J. (2006). CO and H2 oxidation
increase. For both CO and HC, the conversion efficiency on a platinum monolith diesel oxidation catalyst. Catalysis
increases with the catalytic volume as the residence time Today, 117, 491−497.
within the catalyst decreases. In the case of two different Tanaka, Y., Hihara, T., Nagata, M., Azuma, N. and Ueno,
profiles of exhaust temperature with the same average A. (2005). Modeling of diesel oxidation catalyst. Ind.
temperature, CO and HC conversion efficiency is lower in Eng. Chem. Res., 44, 8205−8212.
the case of the smoother profile, because CO and HC Wu, X., Liang, Q., Weng, D., Fan, J. and Ran, R. (2007).
conversions are much higher in the parts of the cycle of Synthesis of CeO2–MnOx mixed oxides and catalytic
increased temperature leading to a higher global conver- performance under oxygen-rich condition. Catalysis
sion efficiency. Today, 126, 430−435.
Yashnik, S. A., Ismagilov, Z. R., Porsin, A. V., Denisov, S.
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