International Journal of Automotive Technology, Vol. 9, No. 6, pp.

641−647 (2008) Copyright © 2008 KSAE

DOI 10.1007/s12239−008−0076−8 1229−9138/2008/043−01

PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE

CATALYTIC EFFICIENCY OF A DIESEL OXIDATION CATALYST:
PARAMETERS INFLUENCING THE EFFICIENCY OF A DIESEL
CATALYST

E. ZERVAS*
Department of Environmental Engineering, Democritus University of Thrace, Vas. Sofias 12, 67100 Xanthi, Greece

(Received 22 October 2007; Revised 25 March 2008)

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

1. INTRODUCTION 1996; Wu et al., 2007; Yashnik et al., 2007), but also on

Current European regulations of Diesel exhaust gas are
satisfied using a Diesel Oxidation Catalyst (DOC), which
oxidizes engine-out HC and CO to CO2. The parameters of
this catalyst (volume, load of precious metals, etc.) are
optimized for each vehicle. As one of the main problems is
the oxidation of HC and CO in the beginning of the New
European Driving Cycle (NEDC) when the catalyst is still
cold, zeolithes can be added in the wash-coat of this
catalyst to improve the catalytic activity (Kamijo et al.,
2001). These zeolithes adsorb HC at low temperatures,
when catalyst is not activated, and desorb them at higher
temperatures when catalyst is activated, leading to lower
tail-pipe emissions.
Catalyst position is a very significant parameter (Zervas,
2008a) and is often imposed from engine architecture and
available space. Catalyst position influences CO and HC
tail-pipe emissions because of the different temperature of
exhaust gases influencing catalytic activity and thus CO
and HC conversion.
The tail-pipe emissions of CO and HC depend on the
type of catalyst used, such as load on precious metals, type
of wash-coat and zeolithes used, etc. (Hosoya and Shimoda,
*Corresponding author. e-mail: ezervas@env.duth.gr
some parameters external of the catalyst, as CO and CH
engine-out emissions and temperature of exhaust gas. The
current work studies the impact of five parameters on the
tail-pipe emissions of HC and CO: CO and HC engine-out
emissions, space velocity, average value of exhaust temper-
ature on the urban part (ECE) of the NEDC and profile of
this temperature. In the first part, reactor experiments were
used to specify this impact, while tests on the NEDC were
used on the second part.
2. EXPERIMENTAL SECTION
The first type of tests is conducted in a reactor using a
commercial catalyst of 10 g Pt/ft3, 400 cpsi, aged on an
engine test bench. This ageing procedure is carefully selected
to correspond to an ageing on vehicle of 80,000 km. Similar
procedures can be found in the literature (Anderson, 2007).
The impact of mileage, and thus of catalyst aging, on the
exhaust emissions is studied in a previous work (Bikas and
Zervas, 2007). The dimensions of the catalyst are 1 inch
diameter and 3 inches length. The standard operation
conditions use a feed gas of 1500 ppm CO, 100 ppm NO,
430 ppm HC (in ppm C1), 14% O2, 4% CO2 and 4% H2O.
The HC used was a mixture of four hydrocarbons (the
percentages are expressed in C1): 47% decane, 28% pro-
pene, 18% toluene and 7% methane. This gas contains no

641
642 E. ZERVAS

sulfur. The temperature increase rate was 20oC/min from

80oC to 400oC and the gas flow was 35 l/min (correspond-
ing to a space velocity of 55,000 h−1).
To study the impact of initial CO concentration on the
CO and HC conversion, five values of CO concentration
were used: 500, 1000, 1500, 2000 and 2500 ppm. To study
the impact of the HC initial concentration, four concen-
trations of HC were used: 215, 430, 645 and 860 ppm. In
both cases, the concentration of the other gas remains the
same as in the case of standard operation conditions. In the
case of the study of the impact of space velocity four values
were used: 38000 h−1 (corresponding to a total flow of 24.5
L/min), 55000 h−1 (35 L/min), 80000 h−1 (51.5 L/min) and
110000 h−1 (70 L/min), while the other conditions remain
the same to the standard operation ones.
The second type of tests is conducted on a passenger car
equipped with a Euro4 Diesel engine of 1.6 L using Euro4
fuel with 50 ppm of sulfur. The standard New European
Driving Cycle (NEDC) is used for these tests, following
the regulatory European procedure (European Directive 70/
220). To study the impact of space velocity, three catalysts
with a volume of 0.5, 1.25 and 2 L were used. To study the
impact of gas temperature, the catalyst were put at different
positions of the exhaust line to obtain an average temper-
ature during the urban part of NEDC of 160oC, 170oC and
180oC. The impact of the temperature shape is studied Figure 1. CO (upper curves) and HC (lower curves)
using a smoother temperature profile. Different HC and conversion as a function of temperature, for different initial
CO engine-out emissions were obtained by changing the concentrations of CO.
engine-out emissions using different engine calibrations.
These calibrations are mainly based on different fuel injec- CO initial concentration on the conversion of both CO and
tion parameters (timing, fuel quantity,…). As expected, HC. For both HC and CO oxidation, light-off temperature
fuel consumption (or CO2 emissions) and NOx and PM (T50, where a conversion of 50% is achieved) increases
emissions are completely different from the original engine about 7oC in average for every 500 ppm of CO added.
tuning; however, these emissions have no impact on the Another study also show this tendency, although the ex-
oxidation catalyst. As, for technical reasons, it was not perimental conditions were different (Salomons et al., 2006).
possible to study experimentally all these configurations, However, this increase is higher at lower initial concen-
four of these points were approached using a model, which trations of CO (for example, from 500 to 1000 ppm of CO).
gives very good results. This model is presented in another CO initial concentration does not influence the adsorption
work (Zervas, 2008b). These four points are: V=1.25 L for capacities of HC from 80 to 150oC, neither desorption of
all four points, T=180oC, CO=1.15 g/km and HC=0.15 g/ adsorbed HC at 150~180oC. However, at temperatures higher
km for point 1, T=180oC, CO=1.15 g/km and HC=0.3 g/km than 180oC, HC conversion decreases at high CO initial
for point 2, T=160oC, CO=0.8 g/km and HC=0.15 g/km for concentrations, indicating that CO is favorably oxidized on
point 3 and T=160oC, CO=0.8 g/km and HC=0.3 g/km for the catalyst than HC, while HC desorbing continues up to
point 4. 210oC, before the beginning of complete oxidation.
As no NOx and PM (IOF) after-treatment device were As in the case of CO conversion, there is a significant
used, NOx and PM tail-pipe emissions are very similar to effect of HC initial concentration on the conversion of both
the engine-out emissions and are not presented here. CO and HC (Figure 2). Light-off temperature increases 4oC
in average for every 200 ppm of HC added for both HC and
3. RESULTS AND DISCUSSION CO. This increase is higher at lower initial concentrations
of HC in the case of HC conversion, while there is no
3.1. Impact of CO and HC Initial Concentrations on DOC difference in the case of CO oxidation, indicating that HC
Efficiency initial concentration influences more HC conversion than
Figures 1 and 2 show the CO and HC conversion as a that of CO. As in the case of CO, the initial concentration
function of temperature for different initial concentrations of HC does not influence the adsorption capacities of HC
of CO and HC, in the case of laboratory experiments. from 80 to 150oC, neither desorption of adsorbed HC at
Figure 1 shows clearly that there is a significant effect of 150~180oC. However, at temperatures higher than 180oC,
 PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE CATALYTIC EFFICIENCY 643

Figure 3. CO (upper curves) and HC (lower curves) con-

version as a function of temperature, for different space
Figure 2. CO (upper curves) and HC (lower curves) con- velocities.
version as a function of temperature, for different initial
concentrations of HC.

HC conversion decreases at high HC initial concentrations,

because the adsorbed quantity of HC is too high and the
desorbed rate is higher than the oxidation one.

3.2. Impact of Space Velocity on DOC Efficiency

The impact of space velocity on CO and HC conversion as
a function of temperature is shown in Figure 3. CO conver-
sion is influenced from space velocity, as T50 increases
10oC when space velocity increase three times (from
38,000 to 110,000 h−1). However, the main impact of space
velocity is observed in the case of HC conversion. Space
velocity is the only parameter from those studied here that
influences HC adsorption. HC adsorption decreases with
space velocity due to the decrease of residence time, and
thus the contact time of HC in the catalyst. There is no
linear relation between adsorption rate and space velocity
due to diffusion phenomena, which are not linear. HC light-
off temperature (T50) increases 22oC when space velocity
increases from 38,000 to 110,000 h−1. This increase is
enhanced at lower space velocities (9oC from a change of
space velocity from 38,000 to 55,000 h−1.
While HC conversion is not influenced by HC or CO
initial concentration at temperatures higher than 250oC
(Figures 1 and 2), space velocity decreases HC conversion
almost proportionally at this temperature region. This is
due to the decrease of residence time and thus the decrease
of contact time of HC with the oxidation catalyst.
Figure 4. Typical shape of cumulative engine-out and tail-
pipe CO and HC emissions on the NEDC of a typical
Euro3 Diesel passenger car.
3.3. Impact of CO and HC Engine-Out Emissions on CO
and HC Conversion Efficiency on the NEDC
Figures 1~3 show that CO conversion is always 100% at
exhaust temperature above 250oC, while the conversion of
HC is about 90%. The temperature of exhaust gas at the
Extra-Urban Driving Cycle (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 the Cycle (ECE), where the majority of CO and HC tail-
pipe emissions are produced.
Figure 4 shows a typical shape of cumulative engine-out
644 E. ZERVAS
Figure 5. CO tail-pipe emissions and conversion efficiency
as a function of engine-out CO (upper curves) and HC
(lower curves), for different exhaust temperatures and
DOC volume used.
and tail pipe CO and HC exhaust emissions of a Euro3
Diesel passenger car. It is clearly shown that even cumu-
lative engine-out emissions increase until the end of NEDC,
tail-pipe emissions reach an upper value (particularly in the
case of CO) and then remain constant quite early, even
before the beginning of EUDC.
Figure 5 shows the CO tail-pipe emissions and conver-
sion efficiency on the NEDC as a function of CO and HC
engine-out emissions, for different average exhaust temper-
atures on the urban part of NEDC and different volumes of
oxidation catalyst used. It is clearly shown that CO conver-
sion efficiency slightly increases with engine-out CO and
HC. The reason must be the increased temperature on the
catalyst because of the increased rate of reactions due to
increased initial concentrations.
However, for constant engine-out HC missions, even if
conversion efficiency increases, tail-pipe CO emissions
increase with CO engine-out emissions. This increase is
due to the higher increase of engine-out CO emissions
comparing to the increase of the corresponding CO con-
version due to the increased exothermicity. For constant
engine-out CO, tail-pipe CO slightly decreases with the
increase of engine-out HC emissions.
Figure 6. HC tail-pipe emissions and conversion efficiency
as a function of engine-out CO (upper curves) and HC
(lower curves), for different exhaust temperatures and
DOC volume used.
The decrease of CO conversion with increased HC
initial concentration is also shown in Figure 2. The reason
must be the searched at the increased competition between
CO and HC to occupy the active centres of the oxidation
catalyst. Even if CO is adsorbed better than HC, the
increased HC concentration decreases the available active
centres for the CO adsoption. The decrease of tail-pipe CO
is a balance between the increased rate of oxidation due to
the increased exothermicity and the decreased number of
active centres because they are occupied from HC. The
curves of CO conversion efficiency have the same slop for
all catalyst volumes and ECE average temperatures tested,
showing that CO and HC engine-out emissions are more
important than catalyst volume and exhaust temperature for
CO oxidation efficiency.
Figure 6 shows the HC tail-pipe emissions and conver-
sion efficiency on the NEDC as a function of CO and HC
engine-out emissions, for different average ECE exhaust
temperatures and volumes of oxidation catalyst used.
This figure shows that HC conversion efficiency slightly
increases with engine-out CO and HC emissions and this
increase is higher in the case of lower ECE temperature
(160oC than 180oC) and lower engine-out emissions, for the
 PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE CATALYTIC EFFICIENCY
same reasons as in the case of CO oxidation efficiency. In
the case of high engine-out HC and CO emissions, big
catalytic volume and high ECE temperature, HC conver-
sion efficiency remains constant after having reached its
upper limits (around 86~87%). The CO adsorption on the
oxidation catalyst is much better than the HC adsorption
and thus a decrease of the tail-pipe HC would occur in the
case of increased CO engine-out emissions. However, for
temperatures lower than 180oC, CO adsorption does not
influences significantly HC conversion efficiency, as shown
in Figure 1, and thus HC tail-pipe emissions remain rela-
tively constant with increased CO engine-out emissions.
For constant engine-out CO missions, tail-pipe HC emi-
ssions increase with HC engine-out emissions (Tanaka,
2005), even if conversion efficiency slightly increases,
because engine-out HC emissions are much higher than the
increase of the corresponding conversion. For constant
engine-out HC emissions, HC oxidation is very little influ-
enced by CO, as tail-pipe HC emissions remain practically
constant with engine out CO emissions.
3.4. Impact of Average Exhaust Temperature and DOC
Volume on CO and HC Conversion on the NEDC
Figure 7. CO (upper curves) and HC (lower curves) tail-
pipe emissions as a function of exhaust temperature (aver-
age value on the ECE), for different engine-out HC and CO
emissions and different volumes of oxidation catalyst.
645
CO and HC tail-pipe emissions and conversion efficiency
on the NEDC as a function of average temperature on the
ECE, for different CO and HC engine-out emissions and
catalytic volumes used, are shown in Figure 7. It is clearly
shown that CO conversion efficiency is, for all cases
studied, strongly dependent on exhaust temperature and
increases almost linearly.
Figure 7 shows that an increase of ECE average temper-
ature of 20oC increases CO conversion efficiency by about
15 percentage units. Consequently, CO tail-pipe emissions,
decrease significantly with temperature. HC conversion
efficiency also increases with temperature (Tanaka et al.,
2005); however, the slope of conversion curves decreases
at higher temperatures, indicating that there is an upper
limit for this increase (Tanaka et al., 2005). HC tail-pipe
emissions also decrease with temperature; however, the
slope is lower than in the case of CO, indicating that
temperature is more important in the case of CO oxidation
than on the case of HC oxidation, as shown in Figures 1
and 2.
Figure 8 shows CO and HC tail-pipe emissions and con-
version efficiency on the NEDC as a function of the cata-
lytic volume used, for different CO and HC engine-out
Figure 8. CO (upper curves) and HC (lower curves) tail-
pipe emissions as a function of DOC volume, for different
engine-out HC and CO emissions and different values of
exhaust temperature (average value on the ECE).
646 E. ZERVAS
emissions and different average ECE temperatures of ex-
haust gas. For both CO and HC, their conversion efficiency
increases with the catalytic volume as the residence time
within the catalyst decreases. The slope of the conversion
curves is quite high in the case of lower catalytic volumes;
however it decreases at higher catalytic volumes indicating
that there is a lower limit at the residence time which
influences CO and HC oxidation. Figure 3 shows that there
is a significant impact of space velocity on HC conversion;
however, this impact is lower at high space velocities.
Apparently, the space velocity of the NEDC tests used is
quite high to have a significant impact on HC emissions.
For this reason, HC tail-pipe emissions of Figure 8 seem
not to be so dependent on space velocity as in Figure 3.
3.5. Impact of Exhaust Temperature Shape
The previous results show that the average ECE temper-
ature influences CO and HC conversion efficiency; however,
the shape of the temperature curve also influences these
conversions. Figure 9 shows two different shapes of ex-
haust temperature: the initial one and one modified, which
is smoother.
Figure 9. ECE initial and modified exhaust gas temperature
(upper curves) and CO and HC tail-pipe emissions and
conversion efficiency of these two tests (lower bars).
Ti=initial temperature, Tm=modified temperature, in the
case of two Diesel oxidation catalysts of 1.1 L and 1.3 L.
The two shapes have the same average value on the
ECE. Right bars show that CO and HC conversion effici-
ency is lower in the case of the smoother exhaust temper-
ature. When exhaust temperature is low, the difference on
CO and HC conversions between the two curves is not
significant. However, CO and HC conversions are much
higher in the four peaks with increased temperature than at
the peaks of the smoother one, leading to a higher global
conversion efficiency. As CO conversion efficiency depends
more on temperature than the conversion efficiency of HC,
the difference between the conversion of the initial and
smoother exhaust temperature is higher in the case of CO.
These results show that an engine tuning with some, even
small, parts of the NEDC with increased exhaust temper-
ature helps to increase significantly the total CO and HC
conversion efficiency.
4. CONCLUSIONS
This work studies the impact of CO and HC engine-out
emissions, space velocity and exhaust temperature (aver-
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
with the increase of engine-out HC emissions due to the
increased catalyst temperature. For constant engine-out CO
missions, tail-pipe HC emissions increase with HC engine-
out emissions, because engine-out HC emissions are much
higher than the increase of the corresponding conversion.
 PARAMETRIC STUDY OF THE MAIN PARAMETERS INFLUENCING THE CATALYTIC EFFICIENCY
For constant engine-out HC emissions, HC oxidation is
very little influenced by CO.
CO conversion efficiency is strongly dependent on ex-
haust temperature and increases almost linearly. HC con-
version efficiency also increases with temperature; however,
the slope of conversion curves decreases at higher temper-
atures indicating that there is an upper limit for this
increase. For both CO and HC, the conversion efficiency
increases with the catalytic volume as the residence time
within the catalyst decreases. 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, because CO and HC
conversions are much higher in the parts of the cycle of
increased temperature leading to a higher global conver-
sion efficiency.
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