Applied Thermal Engineering 50 (2013) 152e158

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Modeling the selective catalytic reduction of NOx by ammonia over

a Vanadia-based catalyst from heavy duty diesel exhaust gases
Byoung Kyu Yun, Man Young Kim*
Department of Aerospace Engineering, Chonbuk National University, 664-14 Duckjin-Dong, Duckjin-Gu, Jeonju, Chonbuk 561-756, South Korea

h i g h l i g h t s

< To find the reaction parameters for LH mechanism over a commercial V2O5 catalyst.
< To investigate the effects of various parameters on the SCR NOX conversion.
< To present benchmark solutions on SCR behavior with diesel exhaust environments.

a r t i c l e i n f o a b s t r a c t

Article history: A numerical simulation for prediction of NOX conversion over a commercial V2O5 catalyst with NH3 as
Received 30 July 2011 a reductant was performed for a heavy duty diesel engine applications. The chemical behaviors of the
Accepted 30 May 2012 SCR reactor are described by using the global NOX kinetics including standard, fast, and NH3 oxidation
Available online 15 June 2012
reactions with the LangmuireHinshelwood (LH) mechanism incorporated into the commercial Boost
code. After introducing mathematical models for the SCR reaction with specific reaction parameters, the
Keywords:
effects of various parameters such as space velocities, the O2, H2O, NO2, and NH3 concentrations on the
NOx
NOx conversion are thoroughly studied and validated by comparing with the experimental data available
Selective catalytic reduction (SCR)
DeNOx
in the literature. It is found that NOX conversion increases with decreasing space velocity, H2O
Ammonia concentration, and NH3/NOX ratio, and increasing O2 concentration and NO2/NOX ratio. The study shows
Diesel exhaust gas that not only is the present approach adopted is flexible in treating performance of the commercial V2O5
based SCR catalyst, it is also accurate and efficient for the prediction of NOX conversion in diesel exhaust
environments.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction performance increases with increasing exhaust gas temperature. At

Due to growing concerns about protecting the environment and
human health, the NOx emission standards from heavy duty diesel
engines have been continuously tightened over the years
throughout the world [1]. Stringent NOx emission standards for
heavy duty diesel engines necessitate clean diesel technology and
the application of highly efficient exhaust gas aftertreatment
systems [2]. Several approaches seem to be technically feasible,
such as cooled EGR, common rail fuel injection, LNT, LNC, and SCR
DeNOx systems. Among others, the SCR system with urea or NH3 as
a reductant is seen as one of the most promising technologies for
adhering to the Euro V and VI NOx emission standards for heavy
duty diesel engines [3e9].
At low temperature (<250
C), the SCR reaction, such as stan-
dard, fast and slow SCR reaction, dominate over Pt SCR, SCR DeNOx
* Corresponding author. Tel.: þ82 63 270 2473; fax: þ82 63 270 2472.
E-mail address: manykim@jbnu.ac.kr (M.Y. Kim).
about 225e250
C, the oxidation of NH3 to NOx and H2O becomes
dominant. To utilize the Pt SCR catalyst, one must control the
process gas temperature to be above approximately 200
C to avoid
NH4NO3 formation, but not to exceed about 225
C, where the
catalyst loses its selectivity toward the NOx reduction reaction.
Consequently, the use of Pt SCR technology has been rather limited
[10]. In addition, Fe zeolite SCR catalysts which are commercially
available for stationary applications is known to be operated at
temperatures up to 600
C. When NOx is present, this catalyst does
not oxidize NH3 to NOx. Fe zeolite SCR may be prone to stability
problems when exposed to high temperatures in the presence of
H2O. At exposure temperatures above 600
C, in a high H2O
concentration process stream, zeolites SCR tend to deactivate by
de-alumination whereby the Alþ3 ion in the SiO2eAl2O3 framework
migrates out of the structure. This leads to permanent deactivation
and, in extreme cases, collapse of the crystalline structure. A
different type of a low temperature zeolite SCR has been developed
for mobile diesel engine applications. When used as an SCR

1359-4311/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.applthermaleng.2012.05.039
 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158 153

catalyst, the Cu/ZSM-5 was active in reducing NOx within the H2O concentrations, and NO2/NOX and NH3/NOX ratios on the NOX
temperature window of about 200e400
C, but its thermal dura- conversion efficiency. Thereby, benchmarking solutions regarding
bility was insufficient [10]. NOX conversion and its behavior over a commercial V2O5 SCR
Medium temperature V2O5 SCR catalysts operate best in the catalyst with diesel exhaust environments are generated for
temperature range between 260 and 450
C [10e13]. V2O5/WO3/ development of SCR catalyst. In the following, the mathematical
TiO2 SCR technology became a very common SCR catalyst for formulation and the corresponding reaction pathways are intro-
stationary engine. Vanadia is reported to be responsible for both duced with the LH mechanism, and then parametric studies such as
NOX reduction and for the undesired SO2 oxidation. WO3, which space velocities, the O2, H2O, NO2, and NH3 concentrations are
improves the durability and also increases the acidity of the SCR performed to identify the DeNOx behavior over a V2O5 catalyst
catalyst, is used at about 10%. Catalyst temperatures depend on from heavy duty diesel engine exhaust gases. Finally, some
several factors such as (1) the exhaust gas temperatures, (2) the concluding remarks are presented.
distance of the catalyst from the exhaust manifold, and (3) the
presence of an upstream particulate filter that could produce exo-
2. Mathematical models for an SCR reaction
therms during regeneration. V2O5/TiO2 SCR technology, therefore,
could be widely used on Euro IV/V engines without filters. Due to
2.1. Governing equations
their resistance to sulfur poisoning, V2O5 based formulations can be
also the preferred SCR catalyst choice for applications with diesel
Under the assumption that radial transport effects of a honey-
fuels, such as diesel SCR systems in emerging markets [10].
comb-type catalyst are small compared to the heat transport in
SCR systems can selectively reduce NO and NO2 even in envi-
axial direction, the entire converter can be represented by one single
ronments with excess O2, as is usually encountered in diesel
channel. The effects taking place are convective, diffusive and
exhaust gases. However, tuning these SCR systems into a practical
conductive transport in the gas phase, mass and energy transfer
application requires the optimization of a number of such different
through the boundary layer, diffusion and catalyst in the washcoat,
parameters as the SCR catalyst position, the space velocity, the urea
and conduction in the solid phase. Neglecting radial gradients in the
injection strategy, and the interaction between the engine setup
channel, transient and 1D (in axial direction) conservation equation
and the aftertreatment systems.
suffice to describe the thermo- and fluid dynamic. The differential
A large number of investigations have been performed or are now
conservation equations for mass momentum and energy of a single
in progress to improve the SCR DeNOx performance by using urea/
channel can be written as shown in the following section [18,19].
NH3 as a reductant. Winkler et al. [11] developed a one-dimensional
The gas phase continuity equation is
numerical model for chemical reactions to describe the DeNOx
behavior of a current commercial SCR catalyst by considering both vrg vrg ,vg
the standard and fast SCR reactions with the oxidation of NH3. ¼ (1)
vt vz
Winkler et al. [11] also carried out the parametric study by changing
the concentrations of various components such as NO, NO2, N2O, where rg is the density of the gas phase, t is the time, vg is the
NH3, H2O, O2 and HNO3 to find the effects on SCR performance using interstitial gas velocity and z is the spatial coordinate in axial
FTIR spectrometry and computational investigation. The heteroge- direction.
neous chemical reactions taking place on the catalytic surface are The momentum conservation equation is given by the steady-
also taken into account based on the LangmuireHinshelwood (LH) state Darcy equation.
mechanism, while the NH3 storage phenomena are adopted through
vpg
the Dubinin-Radushkevich adsorption isotherm [12]. ¼ AD ,vg (2)
Meanwhile, it is well known that the SCR performance largely vz
depends on the NO2/NOx ratio, especially at temperatures lower where pg is the pressure of the system. The Darcy constant AD can
than 300 +C [12]. To evaluate the DeNOx performance, Gieshoff be described as
et al. [13] carried out studies varying such parameters as the NH3/
vg rg
NOx and the NO2/NOx ratios over a V2O5 SCR catalyst. In an effort to AD ¼ 4 , ,z (3)
improve the NOx conversion efficiency, several investigations have 2 dhyd
been performed using the common diesel engine parameters, such
dhyd is the hydraulic channel diameter and z is a friction coef-
as space velocity, the temperature of the SCR catalyst, and the
ficient. The factor 4 is called Fanning friction factor and takes into
volume of the oxidation catalyst, at different raw NOx emission
account deviations from round channel cross sections. The friction
levels [14]. Also, the dynamic investigations for a V2O5 SCR catalyst
factor z is typically described as a function of the Reynolds Number
have been successfully performed using a kinetic model, which is
Re and changes depending on the flow regime (laminar, transition
supportive of an Eley-Rideal (ER) mechanism for the SCR reactions
or turbulent):
as developed by Lietti et al. [15]. Following Lietti et al. [15] per-
formed the numerical investigations to determine the DeNOx Re  Relam for z ¼ zlam (4a)
behavior over a V2O5 SCR catalyst by changing such various
parameters as the NH3 concentration, the temperature of the SCR
Returb  Re for z ¼ zturb (4b)
catalyst, and the NH3/NO ratio. Recently, Nova et al. [16,17] con-
ducted the kinetic modeling of the SCR reactions over a V based
catalysts for heavy duty Diesel applications. Relab  Re  Returb for z



Even though there exist some researches in the field of SCR Re  Relam Re  Relam
DeNOx performance, there have been relatively restricted ¼ zlam 1  þ ztrub
Retrub  Relam Retrub  Relam
modeling studies on the reaction parameters for the NH3 oxidation
(4c)
in comprehensive parametric studies. The objectives of this present
study, therefore, are to find the workable reaction parameters for where Relam ¼ 2300 and Returb ¼ 5000. In the turbulent region, zturb
practical use for a commercial V2O5 SCR catalyst and to investigate is considered as a constant input value. In the laminar region zlam is
the effects of such various parameters as the space velocity, O2 and given by
154 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158

zlam ¼ a,Reb (5)   X

I  
atrans ,kk;m cLk ck;g ¼ r_ cLk ; Ts (9)
where a and b are 64 and -1, respectively, and therse two param- i
eters are described by Hagen-Poisseuille-Law for laminar tube flow.
where ck,g is the molar concentration of species of the k in the bulk
The species conservation equation is given by
gas, and kk,m is the mass transfer coefficient of the individual


vrg ,wk;g vrg ,wk;g ,vg v vw species [18].
3g ¼ 3g þ 3g rg ,Deff , k;g
vt vz vz vz
XI  
2.2. SCR reaction modeling
þ MGk;g , vi;k ,r_ cLk ; Ts (6)
i
It is well known that Eqs. (10) and (11) are the reactions that
where wk,g is the mass fraction of species k and Deff is an effective reduce NOx to N2, while the third reaction (12) is an undesirable
diffusion coefficient. r_ ðcLk ; Ts Þ represent molecular reaction rate of oxidation process in which the reductant NH3 is unproductively
the catalyst surface reaction with their stoichiometric coefficient consumed and NO is generated.
vi,k. Also, assuming that viscous dissipation can be neglected, the
energy equation of gas phase is written 4NH3 þ 4NO þ O2 /4N2 þ 6H2 O (10)
! !
v X
K
v X
K
4NH3 þ 2NO þ 2NO2 /4N2 þ 6H2 O (11)
3g rg , wk;g ,hk ¼ 3g, rg , wk;g ,hk ,vg
vt vt
k k

 4NH3 þ5O2 /4NO þ 6H2 O (12)
v vT
þ3 g , lg , g
vz vz Eq. (10) is the standard SCR reaction and is known to be the

 dominant NOx reduction process [19]. Here, it is noted that the
P
K v vw  
þ 3g, r ,D , k;g ,hk þ atrans ,kh , Ts  Tg stoichiometric NH3/NO ratio in this reaction is 1. This reaction is
k vz g eff vz useful when the temperature ranges from 250 to 450 +C, typical for
P
I   diesel exhaust gases. At temperatures lower than 200 +C, however,
 Dhi ,r_ cLk ; Ts the SCR DeNOx performance of this reaction is too low for use in
i
practical applications to reduce the diesel NOx. Therefore, in order
(7) to increase the SCR reaction rate it has been proposed to take
where Tg represent gas temperature and hk total enthalpy of the advantage of the fact that the reaction rate of an equimolar mixture
component k. Conductive heat transport in gas phase is modeled by of NO and NO2 is much higher than a reaction involving only NO.
Fourier’s Law using the thermal conductivity lg. Conductive heat This process is called a fast SCR reaction and is shown in Eq. (11).
transport effect is usually small compared to convection but This second reaction includes reductions of both NO and NO2 and
becomes important for small Pe of heat transfer. kh is the heat dominates an NO/NO2 ratio up to 1. This reaction requires an
transfer coefficient between the gas phase and the solid walls, and equimolar mixture of NO and NO2 to allow for a higher NOx
atrans represents the total channel surface area per unit of substrate conversion, and the effect is most pronounced at temperatures
volume. The heat of reaction of the catalytic surface reactions is below 300 +C. At temperatures higher than 500 +C the undesirable
represented by Dhi This heat is released in the solid phase and oxidizing properties of the SCR catalysts become pronounced as
convected into the gas phase. Thus, the heat of reaction that is shown in Eq. (12), which represents the NH3 oxidation reaction
implicitly taken into account by the combined solution of the gas converting NH3 to NO [12]. Although several reactions involving
species and energy conservation equations has to be deduced from NH3 oxidation have been reported in various studies, it is assumed
the gas phase and subsequently added to the solid phase energy that the proposed reaction scheme accounts for all of the NH3
balance equation. oxidation to NO in order to facilitate the model validation [12].
The solid phase energy balance equation can be described by Following the works of Tsinoglou and Koltsakis [12] the LH
mechanism is adopted in this work to describe the mild inhibitory
 
 influence of NO as well as effect of NO2 on NOX conversion. The rate
  v cp;s ,Ts   v vT expressions for the two SCR reactions, i.e., Eqs. (10) and (11), and for
1  3 g ,rs , ¼ 1  3g , ls , s
vt vz vz the NH3 oxidation, Eq. (12), are summarized in Table 1. The term G
 
 atrans ,kh Ts  Tg in the denominator in Table 1 accounts for the inhibition effects of
the surface coverage of the species, and is expressed by the
X
I  
þ Dhi ,r_ cLk ; Ts þ q_ Rad (8) following forms [12] :
i

Table 1
where Ts is the temperature of the catalyst wall, ls is its thermal Chemical reactions and rate expressions for the SCR reactions and the NH3 oxidation
conductivity, and q_ Rad represents a heat loss to the surrounding. [11].
Thermal radiation is not taken into account in the energy conser-
Reaction Rate expression
vation equation due to the low temperature range. Thus, radiation
4NH3þ4NO þ O2/4N2þ6H2O A01 expðE10 =RTÞCNH3 CNO CO2
does not significantly affect the exit conversion and ignition/ R1 ¼
G1
extinction bounds. A02 expðE10 =RTÞCNH3 CNO CNO2
Balance equation for the individual species fractions at the solid 4NH3þ2NOþ2NO2/4N2þ6H2O R2 ¼
G2
surface are formulated to take into account the different case of
A03 expðE30 =RTÞCNH3 CNO2
chemical and mass transfer limitation. Under the assumption of 4NH3þ5O2/4NOþ6H2O R3 ¼
G3
quasi steady-state conditions, the molar surface concentration cLj
component of j can be evaluated using
 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158 155

 2  2  2
G1 ¼ T 1 þ K1 CNO þ K2 CH2 O 1 þ K3 CNH3 1 þ K4 CO2
 2  2
G2 ¼ T 1 þ K1 CNO þ K2 CH2 O 1 þ K3 CNH3
G3 ¼ G1
where T and Ci are the temperature and the concentration of the gas
phase of the i th species, respectively. Ki is given by the following
Arrhenius-type expression :
Ki ¼ Ai expð  Ei =RTÞ
where Ai and Ei are the pre-exponential factor and the activation
energy of the gas phase species of i, respectively, and R is the gas
constant. The kinetic constants of Ki used in this work are listed in
Table 2 following the work of Tsinglou and Koltsakis [12].
In order to numerically investigate the DeNOx behavior over the
vanadium-based catalyst, the commercial one-dimensional BOOST
(AVL List) code [18], as part of the gas exchange and cycle simula-
tion, was adopted in this work with the optimized reaction
constants as shown in Table 2.
3. Results and discussion
The kinetic analysis for the individual SCR rate approaches was
performed for a variety of exhaust conditions corresponding to the
experimental investigations described by Winkler et al. [11]. A 1
inch sample with a 1 inch diameter and a 1 inch length including
a 400/4 [cpsi/mil] substrate coated with a vanadium-based wash-
coat was used for all of the calculations presented below. In the
following, a comprehensive analysis is performed to determine the
effects of such various parameters as space velocities, and the O2,
H2O, NO2, and NH3 concentrations on the NOx conversion effi-
ciency over an SCR DeNOx catalyst with the heavy duty diesel
exhaust gases.
3.1. Effect of space velocity
For the heterogeneous fixed-bed catalysis typically used in
automobile aftertreatment, the residence time of the exhaust gases
is defined in terms of the volumetric flow rate and the volume of
the catalyst. By dividing the volumetric gas flow rate at STP by the
total volume of the catalyst, the space velocity can be obtained as
follows, i.e.,
GHSV ¼ V_ exhaust =Vcatalyst
where GHSV is the gas hourly space velocity in [1/h], Vexhaust is the
volumetric flow rate of the exhaust gas in [m3/h], and Vcatalyst is the
the exhaust gas increases, but it may also lead to various problems
with the layout of the vehicle installation and may increase costs
(13) due to the increased volume of the catalyst. Therefore, to investi-
gate the effect of space velocity on the SCR DeNOx performance,
(14) a computational experiment has been conducted for space veloci-
ties from 10,000 to 100,000 [1/h], typical in real heavy duty diesel
engines.
(15)
Fig. 1 shows the effect of space velocity on the NOx conversion in
a composite exhaust gas containing 5% O2, 5% H2O, 500 ppm NO,
and 500 ppm NH3. Here, the symbols represent the experimental
results [11], and the lines show the results of the present compu-
tation. As can be seen in Fig, 1, the SCR DeNOx performance
(16) depends strongly on the space velocity. In particular, the light off
temperature (LOT), in which the SCR DeNOx performance achieves
a 50% conversion rate, increases from 220 to 370 +C as the space
velocity increases from 10,000 to 100,000 [1/h]. It also can be seen
that NOx conversions increase as lowering the space velocities. This
is because the residence time of the exhaust gas over the surface of
the catalyst decreases as the space velocity increases [23,26].
Furthermore, note that at temperatures higher than 500 +C, the
oxidizing property of NH3 becomes more pronounced, so that the
SCR DeNOx performance decreases slightly. In the meantime, there
is some inconsistency between the experimental and computa-
tional investigations at higher space velocities and temperatures.
Such inconsistencies are usually attributed to two-dimensional
flow and heat transfer effects [12]. In general, however, good
agreements between experimental and computational results can
be found in Fig. 1.
3.2. Effect of O2 concentration
Diesel exhaust gases generally contain O2, ranging from 2 to 17%
by volume, which does not react with the fuel in the combustion
chamber. This O2 is steadily consumed in the exhaust systems such
as such as the DOC, which is usually located in front of the SCR unit.
Fig. 2 shows the NOx conversion efficiency at different O2 concen-
trations varying from 0.05 to 10% with the other exhaust gas
conditions of 0% H2O, 500 ppm NO, 500 ppm NH3, and a space
velocity of 20,000 [1/h]. As can be seen, the NOx conversion effi-
ciency increases with temperature and reaches nearly 100% in the
range of 350 and 450 +C, above which the efficiency decreases
slightly because of the oxidizing property of NH3, as described in
120
(17)
-1
100 SV=10,000 hr
20,000
NOx Conversion (%)

30,000
volume of the catalyst in [m3]. Lowering the space velocity can 80 40,000
improve the SCR DeNOx performance because the residence time of
60 60,000
80,000
Table 2
Constants of the SCR reaction, NH3 oxidation and inhibition terms [12].
100,000
40
Constant Ai [molK/m3s] Ei [J/mol]
SCR Reaction and NH3 Oxidation, Eqs. (10)e(12) 20 symbols : Exp. (Winkler et al., 2003)
Standard 1.5  1017 8.8  104 lines : present predictions
Fast 7.0  1027 1.57  105
NH3 oxidation 8.8  1024 3.0  105 0
Inhibition Terms, Eqs. (13)e(15) [12] 100 200 300 400 500 600
K1 20 7.9  103 Temperature (oC)
K2 1.5 7.9  103
K3 107 3.1  104 Fig. 1. Effect of space velocity on the NOx conversion. The exhaust gas contains 5% O2,
K4 20 0 5% H2O, 500 ppm NO, and 500 ppm NH3, while the space velocity varies from 10,000 to
100,000 [1/h].
156 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158

120 120
symbols : Exp. (Winkler et al., 2003)
lines : present predictions
100 100
0% H2O
NOx Conversion (%)

NOx Conversion (%)

10% O2
80 0.2% O2 80

2% O2 5% H2O
60 5% O2 0.1% O2 60

10% H2O
40 40
0.05% O2
20 20 symbols : Exp. (Winkler et al., 2003)
lines : present predictions

0 0
100 200 300 400 500 600 100 200 300 400 500 600
o
Temperature ( C) Temperature (oC)
Fig. 2. Effect of O2 on the SCR NOx conversion. The exhaust gas containing 0% H2O, Fig. 3. Effect of H2O on the NOx conversion. The exhaust gas containing 2% O2,
500 ppm NO, and 500 ppm NH3 is fed at a space velocity of 20,000 [1/h], while the O2 500 ppm NO, and 500 ppm NH3 is fed to the SCR converter at the space velocity of
concentrations vary from 0.05 to 10%. 20,000 [1/h], while the H2O concentration varies from 0 to 10%.

Eq. (3). However, note that the O2 concentrations greater than 2%
have no significant effects on the NOx conversion throughout the
temperature range considered here. Therefore, in real diesel
exhaust gases, it can be concluded that the effect of O2 concen-
tration is not an important factor in the standard SCR reaction
expressed in Eq. (10). However, in cases in which the O2 concen-
trations are lower than 2%, the NOx conversion can be dramatically
decreased because the standard SCR reaction fails to convert the NO
[11]. Fig. 2 also shows that there is very good agreement between
the experimental and computational investigations for the given
environments.
3.3. Effect of H2O concentration
It is well known that the presence of H2O inhibits some of the
reactions in the SCR process [20]. Although this effect of H2O is not
directly related to the SCR DeNOx performance, the heat released in
the exothermic adsorption process, and consequently the heat
absorbed in the desorption phase, may significantly affect the SCR
catalyst. In order to determine the effect of H2O on the SCR
performance, therefore, the NOx conversion is investigated at
various H2O concentrations and temperatures, as shown in Fig. 4.
For this simulation, it is assumed that the exhaust gas containing 2%
O2, 500 ppm NO, and 500 ppm NH3 is fed into the SCR converter at
the space velocity of 20,000 [1/h]. In Fig. 3, the experimental
investigations [11] are represented by symbols, and the present
computational results are illustrated by lines. Here, it can be seen
that the NOx conversion decreases as the H2O concentration
assumed that the exhaust gas mixture contains 0% H2O, 5% O2, and
500 ppm NH3, and its space velocity is set to 20,000 [1/h], while
the NO2/NOx ratio is varied from 0 to 0.5. From Fig. 4, it can be
seen that as the NO2/NOx ratio increases from 0 to 0.5, the NOx
conversion efficiency and the temperature window also increase,
although the entering total NOx remains the same at 500 ppm.
This is due to the fast SCR reaction, where NO2 is also converted to
N2 via a reaction with NH3, as seen in Eq. (11) [25]. Meanwhile, it
has been reported that the SCR DeNOx performance decreases if
the NO2/NOx ratio increases above 0.5, since the slow SCR reaction
plays a role in that range [12]. Therefore, the highest NOx
conversion efficiency is obtained for the case of an equimolar
mixture of diesel NO and NO2. Although the NO2 can be converted
from NO through the oxidation process by the oxidation catalyst,
the activity of the oxidation catalyst may not be sufficient to
provide a significant oxidation of NO to NO2, especially at lower
temperatures below 150 +C [13]. In this case, an increase in the
volume of the oxidation catalyst can increase the NO2 in the
exhaust systems since the residence time of the exhaust gas over
the surface of the catalyst is increased. Therefore, the volume of
the oxidation catalyst that oxidizes NO to NO2 and the
120
NO2/NOx=0.5
100
NOx Conversion (%)

increases. At an exhaust gas temperature of 200 +C, the NOx 80

NO2/NOx=0.3
conversion efficiencies are 32, 15, and 8% for the H2O concentra-
tions of 0, 5, and 10%, respectively, while the LOT has values of 220,
60
260, and 292 +C for 0, 5, and 10% H2O concentrations, respectively.
NO2/NOx=0
This inhibiting effect of H2O is due to the effect of the competition
reaction of H2O with NH3 on the reaction sites of the catalyst 40
[21e24].
20 symbols : Exp. (Winkler et al., 2003)
3.4. Effect of the NO2/NOx ratio lines : present predictions

0
In general, the majority of NOx emitted from the diesel engine 100 200 300 400 500 600
is in the form of NO (>95%), with a smaller amount being in the Temperature (oC)
form of NO2 (<5%). However, because NO2 is generated in the Fig. 4. Effect of NO2 on the NOx conversion. The exhaust gas mixture contains 0% H2O,
exhaust systems due to the use of oxidation catalyst, the effects of 5% O2, and 500 ppm NH3, and its space velocity is set to 20,000 [1/h], while the NO2/
the NO2/NOx ratio are examined in this section. Here, it is NOx ratio is varied from 0 to 0.5. The total NOx is set to 500 ppm.
 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158
temperature of the exhaust gas are both key factors in the after-
treatment system design in order to possibly avoid conversions of
NO to NO2 to a degree that the level of NO2 becomes more than
50% of the total NOx in the SCR system.
3.5. Effect of the NH3/NOx ratio
The NH3 emitted to the ambient air can react with sulfuric acid
and nitric acid to form ammonium sulfate and ammonium nitrate
salts, which are important constituents of undesirable particulate
matter [23], and also have an unpleasant odor. Therefore, the
quantity of NH3 that is emitted is normally required to be less than
5e10 ppm. In order to determine the optimum level of NH3 and to
find the roles of the standard and fast SCR reactions in the NH3
emission, the effects of the NH3 injection rates on the NOx
conversion are investigated in this section. Here, the NH3/NOx ratio
is changed from 0.5 to 2. In real vehicles, however, urea is used as
the reductant instead of NH3. In practice, therefore, conditions such
as inadequate urea spraying, the inefficient mixing of urea and
exhaust gases, and the transient driving mode cause non-
stoichiometric conditions to occur locally. Here, the test exhaust
gas is assumed to contain 5% H2O and 5% O2 and has a 20,000 [1/h]
space velocity. The total NOx is set to 500 ppm for both cases in
Figs. 5 and 6.
Fig. 5 shows the effects of the NH3/NOx ratio on the NOx
conversion when there is no NO2 (i.e., only the standard SCR
reaction is considered). When the NH3/NOx ratio is 0.5, the
maximum NOx conversion remains at 50% since the reductant NH3
is not sufficient to convert the exhaust NO to N2 via the standard
reaction, Eq. (10). As the NH3/NOx ratio increases from 1 to 2, the
conversion rate of NOx into N2 reaches 100%. Note that a higher LOT
can be observed as the NH3/NOx ratio increases. This is because of
the NH3 oxidation in Eq. (12) as well as NH3 inhabitation term in the
denominators G1 and G2 in Eqs. (15) and (16). This results in a lower
efficiency when the exhaust temperature is low. To find the effects
of NO2, i.e., the fast SCR reaction in Eq. (11), on the NOx conversion,
equal quantities of NO and NO2 in the exhaust gases are considered,
as shown in Fig. 6. The NH3/NOx ratio is also set as 0.5, 1.0, 1.5, and
2.0. Here, although the trends are similar to those in Fig. 5, as can be
seen in Fig. 6, it is noted that a more rapid conversion is observed in
the presence of NO2 because of the fast SCR reaction. In both Figs. 5
and 6, it can be seen that the present results are in good agreement
with those of Winkler et al. [11].
120
NO2/NOx=0
100
NOx Conversion (%)
80 NH3/NOx=1.5
NH3/NOx=1.0
NH3/NOx=2.0
60
NH3/NOx=0.5
40
20 symbols : Exp. (Winkler et al., 2003)
lines : present predictions
0
100 200 300 400
o
500
Temperature ( C)
Fig. 5. Effect of NH3 on the NOx conversion through the standard SCR reaction for the
case of NO2/NOx ¼ 0. The exhaust gas is assumed to contain 5% H2O and 5% O2, with
a 20,000 [1/h] space velocity. The total NOx is set to 500 ppm.
157
120
NO2/NOx=0.5
100 NH3/NOx=1.0
NOx Conversion (%)
80 NH3/NOx=1.5
NH3/NOx=2.0
60
NH3/NOx=0.5
40
20 symbols : Exp. (Winkler et al., 2003)
lines : present predictions
0
100 200 300 400 500 600
Temperature (oC)
Fig. 6. Effect of NH3 on the NOx conversion through the fast SCR reaction for the case
of NO2/NOx ¼ 0.5. The exhaust gas is assumed to contain 5% H2O and 5% O2, with
a 20,000 [1/h] space velocity. The total NOx is set to 500 ppm.
4. Conclusions
In this work, a computational investigation has been conducted
to investigate the characteristics of the SCR DeNOx performance by
changing such various parameters as space velocity and the O2,
H2O, NO2, and NH3 concentrations. After introducing the SCR model
descriptions with kinetic parameters available, numerical study on
the extensive range of parameters are performed in view of the
development of SCR catalysts in Diesel exhaust environments. The
following conclusions can be drawn from this work.
(1) An increase in the space velocity decreases the SCR DeNOx
performance since the residence time of the exhaust gas over
the surface of the catalyst is decreased. Also, at temperature
higher than 500 +C the NOx conversion decreases since the
oxidizing properties of the SCR reactions become pronounced.
(2) The O2 concentrations greater than 2% have no significant
effects on the NOX conversion, however, in cases where O2
concentrations are lower than 2% NOX conversion dramatically
decreases.
(3) As the H2O concentration increases, the SCR DeNOx perfor-
mance decreases. This hindering effect of H2O has been inter-
preted as a product of the competition between H2O and NH3
on the sites of the V2O5 catalyst.
(4) The NOx conversion efficiency increases with an increasing
NO2 fraction from 0 to 50% of the total NOx quantity because an
increasing amount of NO2 reacts with NH3 through the fast SCR
reaction.
(5) The SCR DeNOx performance increases as the NH3/NOx ratio
goes up from 0 to 1 since the fast SCR reaction also participates
in the NOx conversion reaction. When the NH3/NOx ratio
exceeds 1, however, the NOx conversion decreases because of
NH3 inhabitation and oxidation effects.
Acknowledgements
This paper was supported by the selection of research-oriented
600 professor of Chonbuk National University in 2011, also this research
was partially supported by Leading Foreign Research Institute
Recruitment Program (2011) through the National Research Foun-
dation of Korea funded by the Ministry of Education, Science and
Technology.
158 B.K. Yun, M.Y. Kim / Applied Thermal Engineering 50 (2013) 152e158

References [14] J.G. Nam, Static characteristics of a urea-SCR system for NOx reduction in
diesel engines, International Journal Automotive Technology 8 (2007)
283e288.
[1] P. Gilot, M. Guyon, B.R. Stanmore, A review of NOx reduction on zeolite
[15] L. Lietti, I. Nova, S. Camurri, E. Tronconi, P. Frozatti, Dynamics of the SCR-
catalysts under diesel exhaust conditions, Fuel 76 (1997) 507e515.
DeNOx reduction by transient-response method, AIChE Journal 43 (1997)
[2] P. Soltic, D. Edenhauser, T. Thurnheer, D. Schreiber, A. Sankowski, Experi-
2559e2570.
mental investigation of mineral diesel fuel, GTL fuel, RME and neat soybean
[16] I. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee, M. Weibel, Unifying Redox
and rapeseed oil combustion in a heavy duty on-road engine with exhaust gas
kinetics for standard and fast NH3-SCR over a V2O5-WO3/TiO2 catalyst,
after treatment, Fuel 88 (2009) 1e8.
AIChE Journal 52 (2009) 1514e1529.
[3] M. Koebel, M. Elsener, M. Kleemann, Urea-SCR: a promising technique to
[17] I. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee, M. Weibel, NH3eSCR of NO
reduce NOx emissions from automotive diesel engines, Catalysis Today 59
over a V-based catalyst: low-T Redox kinetics with NH3 inhibition, AIChE
(2000) 335e345.
Journal 52 (2006) 3222e3233.
[4] G. Schaub, D. Unruh, J. Wang, T. Turek, Kinetic analysis of selective catalytic
[18] J.C. Wurzenberger, P. Wanker, Multi-scale SCR Modeling, 1D Kinetic Analysis
NOx reduction (SCR) in a catalytic filter, Chemical Engineering and Processing
and 3D System Simulation, SAE, 2005, 2005-01-0948.
42 (2003) 365e371.
[19] AVL BOOST, Aftertreatment (2006).
[5] M. Calatayud, B. Mguig, C. Minot, Modeling catalytic reduction of NO by
[20] R. Willi, B. Roduit, R.A. Koeppel, A. Wokaun, A. Baiker, Selective reduction
ammonia over V2O5, Surface Science Reports 55 (2004) 169e236.
of NO by NH3 over Vanadia based commercial catalyst: parametric sensi-
[6] C.S. Sluder, J.M.E. Storey, S.A. Lewis, L.A. Lewis, Low Temperature Urea
tivity and kinetic modeling, Chemical Engineering Science. 51 (1996)
Decomposition and SCR Performance, SAE, 2005, 2005-01-1858.
2897e2902.
[7] J.F. Kelly, M. Stanciulescu, J.P. Charland, Evaluation of amines for the selective
[21] G. Busca, L. Lietti, G. Ramis, F. Berti, Chemical and mechanistic aspects of the
catalyst reduction (SCR) of NOx from diesel engine exhaust, Fuel 85 (2006)
selective catalytic reduction of NOx by ammonia over oxide catalystst:
1772e1780.
a review, Applied Catalysis B: Environmental 18 (1998) 1e36.
[8] C. Ciardelli, I. Nova, E. Tronconi, D. Chatterjee, T. Burkhardt, M. Weibel, NH3
[22] M. Magnusson, E. Fridell, H.H. Ingelsten, The influence of sulfur dioxide and
SCR of NOx for diesel exhausts aftertreatment: role on NO2 in catalytic
water on the performance of a marine SCR catalyst, Applied Catalyst B:
mechanism, unsteady kinetics and monolith converter modeling, Chemical
Environmental 111-112 (2012) 20e26.
Engineering Science 62 (2007) 5001e5006.
[23] T.T. Yang, H.T. Bi, X. Cheng, Effect of O2, Co2, and H2O on NO adsorption and
[9] C. Ciardelli, I. Nova, E. Tronconi, D. Chatterjee, B. Bandl-Konrad, M. Weibel,
selective catalytic reduction over Fe/ZSM-5, Applied Catalyst B: Envir-
B. Krutzsch, Reactivity of NO/NO2 -NH3 SCR system for diesel exhaust after-
ionmental 102 (2011) 163e171.
treatment: identification of the reaction network as a function of temperature
[24] M. Chen, S. Williams, Modelling and Optimization of SCR-exhaust After-
and NO2 feed content, Applied Catalysis B: Environmental 70 (2007) 80e90.
treatment System, SAE, 2005, 2005-01-0969.
[10] http://www.dieselnet.com/tech/cat_scr.php.
[25] P.S. Metkar, N. Salazar, R. Muncrief, V. Balakotaiah, M.P. Harold, Selective
[11] C. Winkler, P. Florchinger, M.D. Patil, J. Gieshoff, P. Spurk, M. Pfeifer, Modeling
catalytic reduction of NO with NH3 on iron zeolite monolith monolithic
of SCR DeNOx Catalyst e Looking at the Impact of Substrate Attributes, SAE,
catalysts: steady-state and transient kiniecs, Applied Catalyst B: Environ-
2003, 2003-01-0845.
mental 104 (2011) 110e126.
[12] D. Tsinoglou, G. Koltsakis, Modelling of the selective catalytic NOx reduction
[26] F. Liu, H. He, C. Zhang, F. Zhang, L. Zhang, Y. Xie, T. Hu, Selective catalytic
in diesel exhaust including ammonia storage, Proceedings of the IMechE Part
reduction of NO with NH3 over iron titanate catalyst: catalytic performance
D: Journal Automobile Engineering 221 (2007) 117e133.
and characterization, Applied Catalyst B: Environmental 96 (2010)
[13] J. Gieshoff, A. Schafer-Sindlinger, P.C. Spurk, J.A.A. Van Den Tillaart, G. Garr,
408e420.
Improved SCR System for Heavy Duty Applications, SAE, 2000, 2000-01-0189.