J. Phys. Chem.

C 2009, 113, 1393–1405 1393

Detailed Kinetic Modeling of NH3 and H2O Adsorption, and NH3 Oxidation over Cu-ZSM-5

Hanna Sjövall,† Richard J. Blint,‡ and Louise Olsson*,†

Competence Centre for Catalysis, Chemical Reaction Engineering, Chalmers UniVersity of Technology,
412 96 Göteborg, Sweden, and Chemical and EnVironmental Sciences Laboratory, General Motors R&D
Center, 30500 Mound Road, Warren, Michigan 48090-9055
ReceiVed: March 20, 2008; ReVised Manuscript ReceiVed: NoVember 25, 2008

The NH3 and H2O adsorption and desorption, and the NH3 oxidation was studied using detailed kinetic modeling
and flow reactor experiments. Ammonia storage and ammonia oxidation are important for the NH3 SCR
application. In this study, both ammonia storage and oxidation are investigated, with and without the presence
of water. Four sites were included in the model. On each copper atom was one active site introduced, denoted
S1a, where NH3, H2O, NO2 and O2 can adsorb. However, electron paramagnetic resonance studies (EPR) and
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also DFT calculations in the literature suggest that [Cu(NH3)4]2+complex are formed in copper zeolites. We
therefore introduced three additional sites (S1b) that ammonia can adsorb on in order to add up to the four
ammonia adsorbed per copper atom. It was important to separate between S1a and S1b since it is not possible
for four NO2 to adsorb per copper and also in order to describe the ammonia TPD and SCR reactions
simultaneously. The Cu-ZSM-5 catalyst also contains Brönsted acid sites (S2), and in order to account for
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the large amount stored at ambient temperature, sites for weakly bound species (S3) were included as well.
The Brönsted sites were investigated using NH3 and H2O TPD experiments on H-ZSM-5. Water and ammonia
TPD experiments on Cu-ZSM-5 were also used in the model development and the model was able to describe
the experiment well. An NH3 TPD experiment with storage performed in the presence of water was used for
model validation, and the model was able to predict the experimental results adequately. The model was then
extended to include steps for oxygen adsorption, desorption, dissociation, recombination and two summary
steps for ammonia oxidation. Ammonia oxidation in both the presence and absence of water was used in the
model development. The resulting model was able to predict ammonia storage, desorption and oxidation
accurately, both in the presence and absence of water.

1. Introduction The SCR activity is influenced by the ammonia concentration

in the feed, and varies with both temperature and relative amount
Nitrogen oxides are formed during the combustion of fossil
in comparison to nitrogen oxides. An inhibiting effect of
fuels. There are several possible approaches to reducing nitrogen
ammonia has been observed over various catalyst formulations,
oxides in the presence of excess oxygen, and one efficient
including ZSM-5 and V-based catalysts.13,25,26 Stevenson et al.27
approach for the reduction of NOx to N2 is the selective catalytic
observed an inhibiting effect over H-ZSM-5, which decreased
reduction (SCR) with urea or ammonia. The reaction between
with increasing temperature. They found that the effect was most
NH3 and NOx occurs continuously on the surface of a catalyst
likely due to competitive adsorption, with ammonia blocking
and there are several catalysts investigated for this application.
sites needed for the SCR reaction to take place. A similar
Catalysts composed of vandia supported on titania are com-
inhibition was observed by Eng and Bartholomew,28 who
monly used especially for stationary-source emissions control,1-7
suggested that gas phase NH3 may prevent NOx diffusion to
but several zeolites exchanged with metal ions, such as
the active adsorbed NH3 species. Wallin et al.26 also investigated
Fe-ZSM-5 and Cu-ZSM-5, have also been tested for ammonia
the ammonia blocking effect and concluded that the NO
SCR application.8-17 The Cu-ZSM-5 has been widely studied,
oxidation is hindered by adsorbed NH4+ ions. They also found
not only for SCR with ammonia, but also for applications such
that physisorbed or weakly adsorbed NH3 is likely to be of
as NO decomposition and selective catalytic reduction by
importance. Information about the adsorption and desorption
hydrocarbons.18-21
of ammonia is thus important for the understanding of the SCR
The typical NOx conversion in the presence of excess oxygen
activity. In addition, in order to simulate transient experiments
over a Cu-ZSM-5 catalyst initially increases with temperature,
it is crucial to have a good description of the ammonia storage
reaches a maximum between 200 and 400 °C, and then
and release characteristics which play an important role in
declines.9-11,22 The declining activity at high temperature is due
determining the transient performance of SCR catalysts. Also,
to the competition between ammonia oxidation and NOx
since ammonia oxidation causes a decreased NOx reduction
reduction, since the oxidation of ammonia results in a smaller
activity at high temperatures, it is important to further investigate
amount of ammonia available for the NOx reduction.8,11,22-24
the ammonia oxidation.
* Corresponding author. Telephone: +46-31 772 4390. Fax: +46-31 772 Reaction steps that describe the storage and oxidation of
3035. E-mail: louise.olsson@chalmers.se.
†
ammonia are often included in SCR modeling. Global models
Competence Centre for Catalysis, Chemical Reaction Engineering, that describe steady-state conditions have been developed for
Chalmers University of Technology.
‡
Chemical and Environmental Sciences Laboratory, General Motors various catalyst formations2,4,27,29-31 and such models do not
R&D Center. need a detailed description of the ammonia storage. Other
10.1021/jp802449s CCC: $40.75  2009 American Chemical Society
Published on Web 01/07/2009
1394 J. Phys. Chem. C, Vol. 113, No. 4, 2009
TABLE 1: Weight and Ion-Exchange Level of the Catalyst
Samples
weight weight
SiO2/ alumina zeolite Cu ion-exchange
Al2O3 layer layer loading level
sample ratio (mg) (mg) (wt-%)12 (Cu/2 Al)12
H-ZSM512 27 92 1002
Cu-ZSM-5-a12 27 73 1038 2.03 0.70
Cu-ZSM-5-b 27 78 1010 2.03 0.70
authors include one adsorption and desorption reaction in order
to account for transient conditions. A step for ammonia
adsorption and desorption has been included in kinetic models
for ammonia SCR over several catalysts such as Cu-ZSM-5,32
Fe-exchanged zeolites33 and vandia based catalysts.34-36 How-
ever, there are no detailed kinetic models that describe the
adsorption and desorption of ammonia on the different sites
which are available for ammonia storage on copper zeolites.
The objective with this study is to perform experiments and
develop a detailed kinetic model that describes the ammonia
storage as well as the competition between ammonia and water
for storage sites. The ammonia oxidation is also investigated,
both with and without water in the feed.
2. Experimental Section
2.1. Catalyst Preparation. The catalysts were prepared using
H-ZSM-5 powder with silica to alumina ratio of 27 obtained
from Alsi-Penta. The Cu-ZSM-5 powder was ion-exchanged
in two steps. The H-ZSM-5 powder was initially ion exchanged
using a NaNO3 solution at ambient temperature. The ion
exchange to sodium was performed twice before the Na-ZSM-5
obtained was placed in an oven and dried. The copper was
introduced into the zeolite by exchange in a Cu(CH3COO)2
solution at ambient temperature. The slurry was stirred for
several hours, followed by two additional ion exchange steps.
After the last exchange, the powder was filtered and washed
with distilled water and then the Cu-ZSM-5 was placed in an
oven and dried. The aluminum and copper contents were
determined by using inductively coupled plasma and atomic
emission spectrometry (ICP-AES).
The zeolite powder was added to the cordierite monoliths
using incipient wetness technique. The monoliths had a cell
density of 400 cpsi. Each slurry mixture was composed of a
liquid phase containing distilled water and ethanol and a solid
phase containing the binder boehmite and Cu-ZSM-5 (or HZSM-
5). A thin layer of alumina was coated on the catalyst to generate
an improved surface for the zeolite attachment. The sample was
then calcined before introducing the zeolite layer. The monolith
was coated with the zeolite slurry by immersing the monolith
in the slurry, blowing away the excess slurry, and drying and
heating in air. This procedure was repeated until the monolith
was coated with the desired amount of washcoat, followed by
the final calcination of the catalyst. Two Cu-ZSM-5 monoliths
were prepared at the same time, using the same slurries. They
are denoted Cu-ZSM-5-a and Cu-ZSM-5-b.The length and the
diameter of the samples were 30 mm and 22 mm, respectively.
Details about the ion-exchange and the monolith coating can
be found in.12 The catalysts weight and the ion-exchange level
are shown in Table 1.
2.2. Flow Reactor Experiments. A flow reactor was used
for the storage experiments and the activity experiments. The
feed gas composition was controlled by an Environics 2000 gas
mixer and the flow reactor consisted of a horizontal quartz tube
supplied with a heating coil and insulation. A thermocouple was
Sjövall et al.
placed in front of the catalyst to measure the gas phase
temperature; a second thermocouple was placed inside the
sample to measure the catalyst temperature. A Bio-Rad FTS
3000 Excalibur FTIR spectrometer was used to measure the
concentration of NH3 and H2O. The gas flow rate and the
corresponding space velocity were 3500 mL/min and 18 400
h-1, respectively, in all experiments. Prior to each experiment,
the catalyst was exposed to 8% O2 in argon for 20 min at 500
°C and cooled in Ar. All experiments were performed at
atmospheric pressure and the inert balance was argon. A detailed
description of the reactor setup is available elsewhere.12
Temperature programmed desorption (TPD) experiments were
carried out using both the H-ZSM-5 and the Cu-ZSM-5-b
catalyst. The samples were exposed to either 500 ppm NH3 or
5% H2O for 60 min, followed by 80 min of argon only and a
temperature ramp (10 °C/min) in argon. Ammonia was stored
at two temperatures, 27 and 150 °C, but water was stored at
150 °C only. A corresponding experiment was made exposing
the catalyst to 500 ppm NH3 and 5% H2O simultaneously at
150 °C, followed by a 63 min period of argon only and a
temperature ramp (10 °C/min) in argon. Prior to the introduction
of ammonia was the catalyst exposed to water for 10 min.
Ammonia oxidation experiments were made using the Cu-
ZSM-5-a sample and a feed composition of 500 ppm NH3 and
8% O2, with or without 5% H2O. The temperature was increased
stepwise from 100 to 400 °C. The temperature was held constant
at 100 °C for 50 min, at 150 °C for 20 min and for 10 min at
each of 200, 250, 300, 350, and 400 °C.
3. Catalyst Model
3.1. The Reactor Model. In the calculations presented in
this study, the monolith is described as a series of continuously
stirred tank reactors. The dispersion model in combination with
the tanks-in-series model37 were used to estimate the number
of tanks needed, which resulted in about 40. However, the
simulation time would be very long using 40 elements and the
model is only sensitive to changing the number of elements
when using few tanks. Ten elements were used by Westerberg
et al. 38 in the HC SCR model, instead of the theoretical number
of 40-140. We also chose to use 10 elements in this study.
The error between using 10 and 15 elements was less than 0.3%.
This control was conducted using 12 experiments, including
ammonia adsorption, water adsorption, ammonia oxidation and
SCR experiments. The assumptions made for the reactor model
are:
• No gas-phase accumulation
• No radial concentration gradients
• The energy balance is not solved, since only small difference
between inlet gas temperature and measured catalyst temperature
was observed. The catalyst bed temperature was used in the
simulations.
The mass-transfer in the washcoat has been studied experi-
mentally and the results indicated that there were no diffusion
limitations in a similar Cu-ZSM-5 catalyst,32 which is the reason
for not including it into the model. The film model is used to
describe the mass-transfer from the gas to the surface. The mass
balance for each gas component (i) in each tank (n) is
Fi,n-1 - Fi,n - kc,i,nAn(cg,i,n - cs,i,n) ) 0 (1)
and the surface balances are presented by reactions 2 and 3.
Detailed Kinetic Modeling J. Phys. Chem. C, Vol. 113, No. 4, 2009 1395

kc,i,nAn(cg,i,n - cs,i,n) ) ∑ νi,jrj,nmwc,n (2) TABLE 2: Number of Sites in the Model

j weak
Cu-sites, Cu-sites, Brönsted adsorption
∂Θi,n
Ncat
∂t
) ∑ νi,jrj,n (3)
sample
S1a S1b acid sites, sites, S3
(mol/kgzeolite) (mol/kgzeolite) S2 (mol/kgzeolite) (mol/kgzeolite)
j
H-ZSM5 0.928 1.227
The range for the coverage for each specie, Θi, is between 0 Cu-ZSM5-a 0.320 0.959 0.288 1.227
and 1, where a coverage of 1 means one molecule per site. Cu-ZSM5-b 0.320 0.959 0.288 1.227
3.2. The Surface Description. The amount of copper
TABLE 3: Reactions and Rate Expressions for NH3 and
exchanged into the zeolite was determined using ICP-AES. The H2O Adsorption on and Desorption from H-ZSM-5
result was used to calculate the theoretical number of Cu sites
(S1) in the zeolite. Williamson et al. 39,40 investigated ammonia reaction rate
reactions expressions
adsorption on CuY using infrared spectroscopy and Electron
paramagnetic resonance studies (EPR). On the basis of their rI,f ) kI,f cNH3θS2-vacant
rI,f
experimental findings, they suggest that [CuII(NH3)4]2+ ions are NH3 + S2 798 NH3-S2 rI,b ) kI,bθNH3-S2
formed. These results are supported by density functional theory rI,b

(DFT) calculations by Delabie et al.,41 who found [Cu(NH3)4]2+

complexes coordinated to oxygen atoms in the lattice after
saturation of CuY with ammonia. In addition, Komastu et al.8
propose that each copper ion can coordinate four ammonia
molecules in their mechanism of ammonia SCR. Based on these
experimental and theoretical findings four ammonia molecules
can bind to each copper in our model. NO2 temperature
programmed desorption experiments (TPD)42 showed that the
NO2 storage is much smaller than the ammonia storage on Cu-
ZSM-5. About one NOx adsorbed per copper atom fits the
experiments well.42 In the model we therefore use one active
site on each copper atom, denoted S1a. On this site can all the
molecules adsorb (NH3, O2, NO2, H2O) and the reaction always
occurs from this site. In order to add up to the four NH3
molecules per copper, which was suggested experimentally and
theoretically in the literature we add three additional sites per
copper (denoted S1b), where ammonia can adsorb. Also several
water molecules can bind to each copper, according to DFT
simulations.41 In the model is therefore also H2O allowed to
adsorb on S1b.
The silica to alumina ratio was 27 which was used to calculate
the number of acid sites (S2) in the HZSM-5 catalyst. For low
loading and low Si/Al ratio the copper atom (Cu2+) may replace
two hydrogen ions (H+), since the sites are sufficiently close.19
Since the ion exchange level is only 70% (Cu/2 Al) and the
Si/Al ratio is low (27) we assume that each copper ion in the
Cu-ZSM-5 catalyst replace two hydrogen ions, thus only 30%
of the initial number of Brönsted acid sites were present after
the ion exchange. This was used to calculate the number of S2
sites in the Cu-ZSM-5 catalysts.
Ammonia adsorbs very easily, and may adsorb at additional
positions in the catalyst. The ammonia TPD conducted at room
temperature revealed that the ammonia storage was much larger
than the theoretical number of sites. This is likely due to loosely
bound NH3, but can also be ammonia adsorbed on alumina, which
was used as a binder. A third site (S3), was introduced, which
could account for the additional bound ammonia. A site for
physisorbed molecules were also proposed by Grossale et al.,43 in
their study of NOx adsorption onto Fe zeolites. The total number
of sites (S1a + S1b + S2 + S3) was equal to the amount of
ammonia adsorbed at ambient temperature and this was used to
estimate the number of S3 sites. Since the same zeolite powder
was used for Cu-ZSM-5-a and Cu-ZSM-5-b they have the same
number of sites per wash-coat weight. These catalysts are prepared
using the same slurries and they contain very similar amounts of
Cu-ZSM-5, 1038 and 1010 mg, respectively. Further, they are
prepared the same time, and after the initial stabilization the samples
gave the same conversion (only about 5 ppm difference). The
rII,f ) kII,f cH2OθS2-vacant
rII,f
H2O + S2 798 H2O-S2 rII,b ) kII,bθH2O-S2
rII,b
rIII,f ) kIII,f cNH3θS3-vacant
rIII,f
NH3 + S3 798 NH3-S3 rIII,b ) kIII,bθNH3-S3
rIII,b
rIV,f ) kIV,f cH2OθS3-vacant
rIV,f
rIV,b ) kIV,bθH2O-S3
H2O + S3 798 H2O-S3
rIV,b
resulting numbers of S1a, S1b, S2, and S3 sites in the three catalysts
are shown in Table 2.
3.3. The Kinetic Model. 3.3.1. The Kinetic Model for NH3
and H2O Adsorption oWer H-ZSM-5. It was observed in a
previous study14 that ammonia is adsorbed on both Brönsted
and Lewis sites in the Cu-ZSM-5 catalyst. Since there are
residual Brönsted acid sites in the Cu-ZSM-5 catalyst, NH3 and
H2O TPD experiments over the H-ZSM-5 catalyst were
conducted in order to differentiate between copper sites and
Brönsted sites. In the model for the HZSM-5 catalyst we have
used S2 (Acid sites) and S3 (sites for physisorbed species). The
ammonia was adsorbed and desorbed from S2 and S3 and one
ammonia TPD experiment was used to investigate these steps.
In the same way, the water was adsorbed and desorbed from
the two sites and one H2O TPD was used to develop the model.
The reactions and reaction rates are presented in Table 3.
3.3.2. The Kinetic Model for NH3 and H2O Adsorption and
Desorption oWer Cu-ZSM-5. The model contains reactions steps
for adsorption on and desorption from all sites available. The
Cu-ZSM-5 catalysts are modeled using copper sites (S1a and
S1b), Brönsted acid sites (S2) and additional sites for weakly
bound species (S3). As described in section 3.2 four ammonia
can adsorb on each copper, according to EPR studies39,40 and
DFT calculations.41 This is the reason for the addition of
ammonia adsorption on both S1a and S1b (one mole S1a and
3 mol S1b per mole copper). It was important to divide the
copper sites into S1a and S1b, due to that much lower adsorption
of NOx compared to NH3 was observed. We also observed a
large ammonia adsorption on the acid sites (S2), which was
investigated using H-ZSM-5. Finally, ammonia adsorption on
S3 (loosely bound) is crucial at lower temperatures. Grossale
et al.43 also propose sites for physisorbed NOx species based
on NO2 TPD on Fe zeolites. Zeolites are known to adsorb a lot
of water, and DFT simulations41 showed that several water
1396 J. Phys. Chem. C, Vol. 113, No. 4, 2009 Sjövall et al.

TABLE 4: Reaction and Rate Expressions for NH3 and H2O stoichiometric coefficients to determine the reaction orders, and
Adsorption on and Desorption from Cu-ZSM-5 they were therefore put to the simplest form which is 1. The
reactions reaction rate expressions reaction order for ammonia was also set to 1 for NH3 oxidation
simulations on Cu-ZSM-5,32 HZSM-5,27 Fe ZSM-5,47 com-
r1,f ) k1,f cNH3θS1a-vacant
r1,f
r1,b ) k1,bθNH3-S1a mercial Fe zeolites48 and vanadia.49,50
NH3 + S1a 798 NH3-S1a Water was found to inhibit the NH3 oxidation to a quite small
r1,b
extent.12 However, water had a major impact on the NO
oxidation.12 Based on detailed kinetic simulations of NO
r2,f ) k2,f cNH3θS1b-vacant oxidation both with51 and without42 water present we propose
r2,f
NH3 + S1b 798 NH3-S1b r2,b ) k2,bθNH3-S1b that this inhibition is due to large formations of OH groups on
r2,b the copper. The OH groups are formed from a reaction between
oxygen and water on the copper sites and this reaction is showed
r3,f ) k3,f cNH3θS2-vacant in Table 5 (reaction 12). In order to simulate the poisoning of
r3,f
NH3 + S2 798 NH3-S2 r3,b ) k3,bθNH3-S2 the NO oxidation of water, large coverages of stable OH groups
r3,b are needed.51 However, the NH3 oxidation is only affected very
little by the OH groups and we therefore suggest that it is
r4,f ) k4,f cNH3θS3-vacant possible for the ammonia to react with these OH groups on the
r4,f surface and propose a second summary step where ammonia
NH3 + S3 798 NH3-S3 r4,b ) k4,bθNH3-S3
r4,b reacts with OH and oxygen to form nitrogen and water (Table
5, reaction 13).
In an earlier study we observed SCR activity on HZSM-5.12
r5,f ) k5,f cH2OθS1a-vacant At higher temperatures the consumption of NH3 was larger than
r5,f
H2O + S1a 798 H2O-S1a r5,b ) k5,bθH2O-S1a
NO implying NH3 oxidation activity.12 However, the activity
r5,b
was much smaller on H-ZSM-5 compared to Cu-ZSM-5. For
example at 350 °C we observed a conversion of 75% of NO
r6,f ) k6,f cH2OθS1b-vacant and 100% of NH3 on Cu-ZSM-5, but only 10% NO conversion
r6,f
H2O + S1b 798 H2O-S1b r6,b ) k6,bθH2O-S1b and 25% NH3 conversion on H-ZSM-5. Further, the ion
r6,b exchange level was 0.70 thus there are less acid sites available
compared to copper sites in the catalyst. In order to simplify
r7,f ) k7,f cH2OθS2-vacant the model we have therefore chosen not to add reaction steps
r7,f
H2O + S2 798 H2O-S2 r7,b ) k7,bθH2O-S2 for NH3 oxidation on S2.
r7,b 3.4. The Rate Parameters. The rate constants are described
by the Arrhenius expression
r8,f ) k8,f cH2OθS3-vacant
r8,f
H2O + S3 798 H2O - S3 r8,b ) k8,bθH2O-S3 kj ) Aje-Ea,j/RT (4)
r8,b
For reactions where both the pre-exponential factor and the
activation energy were fitted, a centered expression was used
to describe the rate constant. This expression was used to reduce
molecules can bind to each copper. Water was therefore chosen the correlation between the parameters. The reference temper-
to be able to adsorb on all sites available. The reaction rates ature, Tref was set to 600 K.
for adsorption and desorption of both ammonia and water are
presented in Table 4.
kj ) Aje-(Ea,j/R)(1/T-1/Tref) (5)
3.3.3. The Kinetic Model for Ammonia Oxidation. The
detailed mechanism for ammonia oxidation is not well-known. In the Results and Discussion section all parameters are given
It has been suggested that ammonia is oxidized directly to in the standard form of the Arrhenius expression, eq 4.
nitrogen.44 Some authors instead suggest that ammonia is first There is a very large storage at room temperature of ammonia
oxidized to NO, which subsequently reacts with additional and it increases when decreasing the temperature, which implies
ammonia to form nitrogen and water.23,45,46 However, we do that the storage of ammonia is nonactivated or has a very low
not observe NO production during NH3 oxidation and we value. Further, adsorption reactions are often nonactivated or
therefore produce nitrogen directly in our model. Further, in associated with low activation energies and the activation
our detailed model, the ammonia oxidation is represented by a energies for the adsorption reactions were therefore set to 0 kJ/
summary step, in order to introduce as few parameters as mol in this model. This was also done for ammonia SCR
possible (Table 5, reaction 11). The model also includes reaction simulations over Fe zeolites,48 Cu-ZSM-5,32 and vanadia.50
steps for adsorption and desorption of oxygen on copper sites Calorimetric measurements of ammonia adsorption on HZSM-5
(S1a). The oxygen is assumed to adsorb molecularly and then showed that the heat of adsorption for ammonia varied between
dissociate to oxygen atoms on the surface.42 The reaction steps 120-180 kJ/mol.52 According to Topsoe et al.53 and Hunger
for O2 adsorption, dissociation and desorption, and ammonia and Hoffman54 there are three adsorption states for ammonia
oxidation are shown in Table 5. Ammonia is available at four in HZSM-5 denoted R, β, and γ, with activation barriers of 87,
different sites, but the oxidation is modeled as a reaction between 97 and 163 kJ/mol, respectively.53 Martins et al.55 also propose
oxygen on S1a and ammonia on S1b. It is likely that a reaction three different Brönsted sites, based on FTIR and NH3 TPD.
will occur between species positioned nearby and, since S1a Thus it is not possible to model the ammonia adsorption on the
and S1b represents sites on the same copper, the model include Brönsted acid sites (S2) with a single value. In addition,
a reaction between species on these sites. Since the ammonia the ammonia TPD experiment over H-ZSM5 showed that the
oxidation is a summary step it was not possible to use the desorption peak was broad. In order to simplify the model we
Detailed Kinetic Modeling J. Phys. Chem. C, Vol. 113, No. 4, 2009 1397

TABLE 5: Reaction and Rate Expressions for O2 Adsorption, Dissociation, and Desorption,42 OH Production, and Ammonia
Oxidation
reactions reaction rate expressions
r9,f ) k9,f cO2θS1a-vacant r9,b ) k9,bθO2-S1a
r9,f
O2 + S1a 798 O2-S1a
r9,b

r10,f ) k10,f θO2-S1aθS1a-vacant r10,b ) k10,bθO-S1a2

r10,f
O2-S1a + S1a 798 2O-S1a
r10,b

r11 ) k11θNH3-S1bθO-S1a
r11
2NH3-S1b + 3O-S1a 98

N2(g) + 2H2O-S1b + H2O-S1a + 2S1a

r12,f ) k12,fθO-S1aθH2O-S1a r12,b ) k12,bθOH-S1a2

r12,f
H2O-S1a + O-S1a 9
7 8
r12,b

2OH-S1a

r13 ) k13θNH3-S1bθO-S1aθOH-S1a
r13
2NH3-S1b + 2O-S1a + 2OH-S1a 98

N2(g) + 2H2O-S1b + 2H2O-S1a + 2S1a

TABLE 6: Entropy Change (J/(mol K)) for Adsorption

d(ln(q))
(Calculated at 600 K) S ) R ln(q) + RT (8)
dT
component NH3 H2O O242
entropy loss, due to adsorption (J/(mol K)) -167.0 -166.8 -188.3 The partition function (q) for rotation and translation can be
calculated according to reactions 9-11.

use one site (S2) for the Brönsted acid sites and one for loosely (2πmkBT)3/2
bound species (S3) and use coverage dependent activation qtr,3D ) V (9)
energies: h3

Ea,j ) Ea,j(0)(1 - Ri,jθi) (6) 8π2√8π3IxIyIz(kBT)3/2

Also the high temperature peak, denoted γ, was by Hunger and
Hoffmann54 described with a coverage dependent activation
barrier. We also found it necessary to introduce, coverage
dependence for the desorption from the copper site (S1b) in
order to describe the broadness of the high temperature peak.
It is likely that there are different strengths of the sites in the
same way as for ammonia on the Brönsted acid sites. The same
strategy needed to be adopted also for ammonia on S3 and for
water adsorption in order to describe the broad peaks. The values
for the coverage constant Ri,j for all reactions are shown in
Tables 7-11.
The pre-exponential factors in most of the desorption rates
and surface reaction rates are fixed to 1013 s-1, to avoid
correlation between parameters. Since the channels in the zeolite
are narrow, the pre-exponential factors for adsorption were not
calculated according to the kinetic gas theory. Instead, an
estimated entropy change for adsorption was used.
qrot ) (non-linear molecule)
σrh3
(10)
2
(8π IxkBT)
qrot ) (linear molecule) (11)
σrh2
According to Sharma et al.56 ammonia adsorbed on H-ZSM-5 loses
the translational entropy and approximately one-third of the local
entropy (rotation and vibration). The compounds were assumed
to adsorb as localized species, and therefore lose all translational
entropy and, in addition, one-third of the rotational entropy. The
vibrational contribution to the entropy is much smaller compared
to the translational and rotational contribution. For example, for
ammonia in the gas phase the total entropy is 220.6 J/(mol K) at
600 K,57 and the translation part is 150.3 J/(mol K), the rotation
55.5 J/(mol K). The remaining entropy originates from the vibration
and this is only 14.8 J/(mol K). Further, according to Zhdanov58
the partition function for vibration can be neglected for adsorption

∆S ) R ln ( ) Aads
Ades
(7)
due to that it is close to unity and he gives one example of CO
which has a partition function for two-dimensional translation of
about 460, for rotation 180 and for vibration 1.0.58 The loss of
The entropy was calculated with the use of partition functions, q. vibrational entropy was therefore neglected in our estimation of
1398 J. Phys. Chem. C, Vol. 113, No. 4, 2009 Sjövall et al.

TABLE 7: Kinetic Parameters for NH3 Adsorption on and Desorption from H-ZSM-5
rate rate constants pre-exponential factor activation energy (kJ/mol) coverage dependence (R)
NH3 adsorption (S2 sites) kI,f 8.67 × 10 2 b,d
0
NH3 desorption (S2 sites) kI,b 9.28 × 1012 a,c 162.59 ( 1.39e -0.398 ( 0.0106 ( · θNH3-S2)e
NH3 adsorption (S3 sites) kII,f 1.15 × 103 b,d 0
NH3 desorption (S3 sites) kII,b 1.23 × 1013 a,c 117.92 ( 0.31e -0.638 ( 0.0100 ( · θNH3-S3)e
a
mol/(s kgzeolite). b m3/(s kgzeolite). c Fixed to 1013 s-1, values in table are given in mol/(s kgzeolite). d Calculated from entropy loss. e 13
experiments was used when fitting the parameters, including NH3 TPD at 150 °C on HZSM-5 and NH3 TPD at 30 and 150 °C, H2O TPD at
150 °C, NH3 oxidation with and without H2O, NO oxidation with water and six SCR experiments on Cu-ZSM-5.

TABLE 8: Kinetic Parameters for H2O Adsorption on and Desorption from H-ZSM-5
rate rate constants pre-exponential factor activation energy (kJ/mol) coverage dependence (R)
H2O adsorption (S2 sites) kII,f 8.90 × 10 2 b,d
0
H2O desorption (S2 sites) kII,b 9.28 × 1012 a,c 180.70 ( 3.50e -0.404 ( 0.013 ( · θH2O-S2)e
H2O adsorption (S3 sites) kIII,f 1.18 × 103 b,d 0
H2O desorption (S3 sites) kIII,b 1.23 × 1013 a,c 119.07 ( 1.87e -0.897 ( 0.067 ( · θH2O-S3)e
a
mol/(s kgzeolite). b m3/(s kgzeolite). c Fixed to 1013 s-1, values in table are given in mol/(s kgzeolite). d Calculated from entropy loss. e 13
experiments was used when fitting the parameters, including NH3 TPD at 150 °C on HZSM-5 and NH3 TPD at 30 and 150 °C, H2O TPD at
150 °C, NH3 oxidation with and without H2O, NO oxidation with water and five SCR experiments on Cu-ZSM-5.

TABLE 9: Kinetic Parameters for NH3 Adsorption on and Desorption from Cu-ZSM-5
rate rate constants pre-exponential factor activation energy (kJ/mol) coverage dependence (R)
NH3 adsorption (S1a) k1,f 2.99 × 10 2 b,d
0
NH3 desorption (S1a) k1,b 3.20 × 1012 a,c 97.78 ( 0.19e -0.133 ( 0.0062 ( · θNH3-S1a)e
NH3 adsorption (S1b) k2,f 8.96 × 102 b,d 0
NH3 desorption (S1b) k2,b 9.59 × 1012 a,c 229.69 ( 1.39e -0.907 ( 0.0188 ( · θNH3-S1b)e
NH3 adsorption (S2) k3,f 2.69 × 102 b,d 0
NH3 desorption (S2) k3,b 2.88 × 1012 a,c 162.59 ( 1.39e -0.398 ( 0.0106 ( · θNH3-S2)e
NH3 adsorption (S3) k4,f 1.15 × 103 b,d 0
NH3 desorption (S3) k4,b 1.23 × 1013 a,c 117.92 ( 0.31e -0.638 ( 0.0100 ( · θNH3-S3)e
a
mol/(s kgzeolite). b m3/(s kgzeolite). c Fixed to 1013 s-1, values in table are given in mol/(s kgzeolite). d Calculated from entropy loss. e 13
experiments was used when fitting the parameters, including NH3 TPD at 150 °C on HZSM-5 and NH3 TPD at 30 and 150 °C, H2O TPD at
150 °C, NH3 oxidation with and without H2O, NO oxidation with water and six SCR experiments on Cu-ZSM-5.

TABLE 10: Kinetic Parameters for H2O Adsorption on and Desorption from Cu-ZSM-5
rate rate constants pre-exponential factor activation energy (kJ/mol) coverage dependence (R)
H2O adsorption (S1a) k5,f 3.07 × 10 2 b,d
0
H2O desorption (S1a) k5,b 3.20 × 1012 a,c 67.70 ( 0.44f
H2O adsorption (S1b) k6,f 9.20 × 102 b,d 0
H2O desorption (S1b) k6,b 9.59 × 1012 a,c 184.61 ( 1.49f -0.638 ( 0.0070 (θH2O-S1b)f
H2O adsorption (S2) k7,f 2.04 × 103 b,d 0
H2O desorption (S2) k7,b 2.13 × 1013 a,c 180.70e -0.404 (θH2O-S2)e
H2O adsorption (S3) k8,f 1.18 × 103 b,d 0
H2O desorption (S3) k8,b 1.23 × 1013 a,c 119.07e -0.897 (θH2O-S3)e
a
mol/(s kgzeolite). b m3/(s kgzeolite). c Fixed to 1013 s-1, values in table are given in mol/(s kgzeolite). d Calculated from entropy loss. e Determined
from TPD over H-ZSM-5. f 13 experiments was used when fitting the parameters, including NH3 TPD at 150 °C on HZSM-5 and NH3 TPD at
30 and 150 °C, H2O TPD at 150 °C, NH3 oxidation with and without H2O, NO oxidation with water and six SCR experiments on Cu-ZSM-5.

the entropy loss due to adsorption. The calculated entropy changes
are shown in Table 6.
The parameters not fixed were then fitted to the experiments
using the least-squares method. The parameters for water
adsorption and desorption on S2 and S3 was fitted to the H2O
TPD on HZSM-5. It was important to fit the parameters for the
loosely ammonia species to the NH3 TPD at the lowest
temperature, which was 30 °C for the Cu-ZSM-5. Since S3 also
plays a role in the HZSM-5 catalyst the parameters for these
experiments needed to be fitted simultaneously. In addition,
when developing the SCR model the values for the ammonia
and water adsorption and desorption were crucial in order to
describe the activity and NH3 inhibition properly.51 Further, the
OH groups formed during water adsorption in the presence of
water were very important when simulating the inhibition effect
of water on the NO oxidation and NH3 oxidation. Therefore
was in total 13 experiments used when tuning the parameters.
The experiments used was NH3 TPD at 150 °C on HZSM-5,
NH3 TPD at 30 and 150 °C on Cu-ZSM-5, H2O TPD at 150 °C
on CuZSM-5, NH3 oxidation with and without water, NO
oxidation with water51 and six SCR experiments.51
4. Results and Discussion
4.1. The Kinetic Model for NH3 and H2O Adsorption on
and Desorption from H-ZSM-5. In order to differentiate
between the copper sites and the Brönsted acid sites in the Cu-
ZSM-5 catalysts, a TPD experiment was made using the
H-ZSM-5 catalyst. The catalyst was exposed to 500 ppm NH3
ammonia for 60 min at 150 °C, followed by a period of argon
flush, and finally a heating ramp 10 °C/min. The kinetic model
contains reaction steps for adsorption and desorption of ammonia
over S2 (Brönsted acid sites) and S3 (loosely bound species)
(Table 3). The result is shown in Figure 1. At the start of the
ammonia exposure there is a total uptake of ammonia for about
13 min, which the model describes well. The experimental TPD
peak is a combination of two peaks, one at 230 °C and a second
Detailed Kinetic Modeling J. Phys. Chem. C, Vol. 113, No. 4, 2009 1399

TABLE 11: Kinetic Parameters for O2 Adsorption, Dissociation and Desorption, and Ammonia oxidation.
rate rate constants pre-exponential factor activation energy (kJ/mol)
O2 adsorption k9,f 1.23 × 10 2 b,c
0
O2 desorption k9,b 3.20 × 1012 a,c 48.77c
O2 dissociation k10,f 3.21 × 1010 a,c 83.25c
O2 recombination k10,b 3.20 × 1012 a,c 161.39c
NH3 oxidation k11 4.10 × 105 ( 3.34× 104 a,d,e 97.36 ( 6.20e
OH production k12,f 3.20 × 1012 a 84.37 ( 0.45e
H2O production k12,b 3.20 × 1012 a 182.56 ( 0.43e
NH3 oxidation with OH and oxygen k13 3.52 × 109 ( 2.35× 108 a,d,e 103.93 ( 2.51e
a
mol/(s kgzeolite). b m3/(s kgzeolite). c Reference 42. d Fitted using a centered pre-exponent. e 13 experiments was used when fitting the
parameters, including NH3 TPD at 150 °C on HZSM-5 and NH3 TPD at 30 and 150 °C, H2O TPD at 150 °C, NH3 oxidation with and without
H2O, NO oxidation with water and six SCR experiments on Cu-ZSM-5.

Figure 1. (a) Measured and calculated concentrations during an ammonia TPD experiment using H-ZMS-5. Storage performed at 150 °C, the
temperature was raised 10 °C/min during the heating ramp. (b) Calculated mean coverage on the Brönsted acid sites.

peak at 350 °C. The peak at low temperature is small and may
be related to ammonia desorption from sites for weakly bound
ammonia, and the peak at the higher temperature, is likely
desorption from Brönsted acid sites. The model also predicts
two desorption peaks, but the first peak is larger in the simulation
and the second somewhat to small. However, the total amount
of stored and released ammonia agrees well between the
experiment and the model. Integration of the stored and released
ammonia in the experiment result in 1.2 and 1.1 mmol,
respectively. This shows that the ammonia stored on the
HZSM-5 catalyst is desorbed and there are no or very small
amounts of ammonia left on the surface. The difference of 0.1
mmol is within the error margins, when integrating over such
a long time period. The model also predicts ammonia coverages
close to zero at the end of the ramp. The kinetic parameters
and their linearized 95% confidence regions are shown in Table
7. The heat of adsorption for ammonia on H-ZSM-5 varied
between 120-180 kJ/mol52 according to calorimetric measure-
ments. Topsoe et al.53 and Hunger and Hoffman54 propose that
there are states for ammonia desorption in H-ZSM-5, which
were denoted R, β, and γ. The high temperature state (γ) had
a barrier of 163 kJ/mol according to Topsoe et al.53 and 159
kJ/mol for low coverages. We obtained 160 kJ/mol for zero
coverage, which is in good agreement with the reported literature
values. Further, we model the acid sites as one site using a
coverage dependent activation energy in order to simplify the
model. We obtain a range of 160 to 99 kJ/mol when changing
to coverage between 0 and 1. This is in the same range as the
values for the three desorption states, 87 kJ/mol (R), 97 kJ/mol
(β), and 163 kJ/mol (γ).
A similar experiment was carried out to investigate the
adsorption and desorption of water. In the same way as for the
ammonia, water was adsorbed and desorbed from both S2 and
sites for weakly bound species (S3). It was difficult in the
experiments to start the water feed precisely and this in
combination with the high water concentration (5%) made it
difficult to observe the storage of water. The release of water
during the temperature ramp was therefore used in the model
development The result is shown in Figure 2. It can be seen
that water desorb from the surface throughout the entire
temperature range. Some water is still left on the surface at the
end of the heating ramp. There are two desorption peaks
observed in both the model and the experiment. The first one
is in the model described by a release of water from both S2
and S3 and the second peak originates from water desorbing
from S3. There is a good agreement between the experiment
and the model. The kinetic parameters and their linearized 95%
confidence regions are shown in Table 8.
4.2. The Kinetic Model for NH3 and H2O Adsorption on
and Desorption from Cu-ZSM-5. Two TPD experiments were
carried out using the Cu-ZSM-5-b catalyst. Ammonia was stored
at 30 or 150 °C, followed by a period of argon flush and a
heating ramp. The result from the low temperature experiment
is shown in Figure 3 and the result from the high temperature
experiment is shown in Figure 4. A large amount of ammonia
is stored at 30 °C and there is a complete uptake of ammonia
for about 28 min, which the model describes adequately.
Thereafter, the outlet concentration increases slowly, and has
not reached the feed concentration level when ammonia is turned
off after 80 min. The reason might be that the adsorption of
1400 J. Phys. Chem. C, Vol. 113, No. 4, 2009
Figure 2. (a) Measured and calculated concentrations during water
TPD experiment using H-ZSM-5. Storage performed at 150 °C, the
temperature was raised 10 °C/min during the heating ramp. (b)
Calculated mean coverage on the Brönsted acid sites (S2) and sites for
weakly bound species (S3).
ammonia is hindered when the zeolite is close to saturation.
After ammonia is shut off, weakly bound ammonia desorbs
during the argon flush from the catalyst. As soon as the
temperature is raised, ammonia starts to desorb from the catalyst.
A large peak is observed at 150 °C, followed by several small
peaks at higher temperatures. The ammonia from S3 (loosely
bound site) starts to desorb at a low temperature and the release
is finalized at 300 °C. The desorption of ammonia at higher
temperatures occurs in the model from Brönsted acid sites (S2)
and copper sites (S1b), where the ammonia on the copper is
the one most strongly bound. However, the ammonia on the
active site S1a is desorbed at a quite low temperature. These
features are crucial in order to describe the ammonia TPD and
SCR activity simultaneously.51 The ammonia on S1b needed
to be strongly bound in order to describe the release of ammonia
at high temperatures in the ammonia TPD. However, if the same
parameters would have been applied on the S1a, which is the
site we use for reactions, there would have been a very much
too large ammonia blockage of the SCR reaction. Thus, since
a small blocking of ammonia is observed experimentally for
the SCR reaction12 it is important to have NH3 adsorbing on
S1a, but the ammonia must be bound quite loosely in order to
describe the experiments.51 The model is able to describe the
desorption well. There is still ammonia left on the surface after
the TPD. Thus some ammonia is very strongly bound. Integra-
tion of the amount of stored and released NH3 shows that 2.8
mmol ammonia is stored and 2.2 mmol desorbed. Also in the
model there are ammonia left on the copper (S1b) in the end of
the ramp.
The result from the experiment and simulation of the NH3
TPD conducted at 150 °C is presented in Figure 4. The catalyst
(Cu-ZSM-5-b) adsorbs ammonia completely for 15 min, which
is captured by the model. The amount of stored ammonia is
1.5 mmol and the released ammonia is 1.1 mmol. Thus, there
is ammonia left on the surface at the end of the ramp. In the
model, the NH3 storage is 1.4 mmol and in the desorption 1.2
mmol, which agrees very well with the experiment. The storage
of ammonia at 150 °C is about 50% of the storage at 30 °C,
which shows the importance of loosely bound species in order
to explain ammonia storage at low temperature. The adsorption
period is followed by an Ar only period, where ammonia is
released. During the proceeding temperature ramp there is
Sjövall et al.
ammonia desorption observed from multiple overlapping peaks.
The model can also describe the desorption of ammonia
adequately. The kinetic parameters and their linearized 95%
confidence regions are shown in Table 9. The activation barriers
we obtained for ammonia desorption on S1b and S1a were 219
and 99 kJ/mol, respectively, for zero coverage (both decreasing
when increasing the coverage). A high barrier for desorption
of ammonia from S1b was important in order to describe the
residues of ammonia at 500 °C. As discussed above it is central
to have a low value on S1a in order to describe the SCR
experiments and ammonia blockage adequately. In an earlier
more globalized model we obtained an activation barrier of 182
kJ/mol for the ammonia desorption.32
The storage of water on Cu-ZSM-5 was investigated using a
H2O TPD at 150 °C (Cu-ZSM-5-b), which results in a broad
peak, similar to the peak produced by desorption from H-ZSM-
5. This can be seen in Figure 5, where a comparison of the
water TPD over HZSM-5 and Cu-ZSM-5 is shown simulta-
neously. The result is shown in Figure 6. Two desorption peaks
are observed. In the model the first desorption peak origins from
S3 and S1b. The same amount of water adsorbed on Cu-ZSM-5
and H-ZSM-5, but there is much less Brönsted acid sites on
Cu-ZSM-5. Thus water needs to be adsorbed also on the copper
and we obtained large coverages on S1b. However, in the same
way as for the ammonia model, it is not possible to adopt the
same parameters for the water adsorption and desorption for
S1a, since that would block the actives sites needed for the SCR
reaction.51 The water on S1a is loosely bound, which results in
a low coverage in the TPD. However, the step must be
introduced since the water formed in the SCR reaction must be
able to desorb from the surface.51 The kinetic parameters and
their linearized 95% confidence regions are shown in Table 10.
4.2.1. Validation of the NH3 and H2O Adsorption on and
Desorption from Cu-ZSM-5. A validation experiment not
included in the fitting procedure was performed exposing the
catalyst (Cu-ZSM-5-b) to a mixture of H2O and NH3 at 150
°C, followed by a period of argon flush and a heating ramp.
The result can be seen in Figure 7. Prior to the introduction of
ammonia the catalyst was saturated with water (5%) for 10 min
and this procedure was also used in the simulations (not shown).
The ammonia in the inlet feed is completely stored the first 11
min, which is well captured by the model. The total uptake is
less when water is present, 11 min compared to 15 min without
water. This is due to that water blocks some sites for ammonia
adsorption. After the adsorptioin period the ammonia is shut
off and desorption of ammonia is observed. The peak during
the desorption is also lowered due to the smaller storage when
water is present. The release of ammonia decreases from 1.1 to
0.8 mmol when water is present. During the temperature a
release of ammonia is observed, which is slightly underestimated
in the model.
4.3. The Kinetic Model for Ammonia Oxidation. An
ammonia oxidation experiment was made exposing the Cu-
ZSM-5-a catalyst to 500 ppm NH3 and 8% O2, and increasing
the temperature in steps from 100 to 400 °C. The result is
shown in Figure 8. At 100 °C ammonia is totally stored for
20 min, which the model describes adequately by adsorption
of ammonia on copper, Brönsted acites and loosely bound
sites. The total adsorption corresponds to 1.9 mmol, which
is between the 2.8 and 1.5 mmol obtained for the ammonia
storage at 30 and 150 °C respectively. Desorption of ammonia
is observed at each temperature increase, and at 250 °C
ammonia starts to oxidize. All feed ammonia is converted
to N2 at 350 °C (N2 was not measured directly, but NO, NO2
Detailed Kinetic Modeling J. Phys. Chem. C, Vol. 113, No. 4, 2009 1401

Figure 3. (a) Measured and calculated concentrations during an ammonia TPD experiment using Cu-ZSM-5-b. Storage performed at 30 °C, the
temperature was raised 10 °C/min during the heating ramp. (b) Calculated mean coverage at each site.

Figure 4. (a) Measured and calculated concentrations during an ammonia TPD experiment using Cu-ZSM-5-b. Storage performed at 150 °C, the
temperature was raised 10 °C/min during the heating ramp. (b) Calculated mean coverage at each site.

Figure 5. Comparison between desorption of water from the H-ZSM-5

and the Cu-ZSM-5-b catalysts. The catalysts were heated 10 °C/min
in argon after water exposure.

and N2O could not be detected). A good agreement is found

between the measured and calculated concentrations. The
model predicts high initial coverage of ammonia and also
some oxygen on Cu-S1a. When the temperature is raised,
the surface coverage of ammonia deceases, freeing up vacant
sites for oxygen to adsorb and dissociate which results in an
increased coverage of S1a-O. As ammonia starts to oxidize,
water is formed and is observed on the surface. On the active
copper sites S1a the water reacts with oxygen to produce
OH groups on the S1a. At 400 °C the coverages of OH and
H2O starts to decrease since the desorption of water increases
Figure 6. (a) Measured and calculated concentrations during a water
TPD experiment using Cu-ZSM-5-b. Storage performed at 150 °C, the
temperature was raised 10 °C/min during the heating ramp. (b)
Calculated mean coverage at each site.
with the temperature. In the lower panel of Figure 8 the
coverages on the copper sites are plotted, since they are the
active sites in the model. Adsorption and desorption of
1402 J. Phys. Chem. C, Vol. 113, No. 4, 2009 Sjövall et al.

Figure 7. (a) Measured and calculated concentrations during an ammonia+water TPD experiment using Cu-ZSM-5-b (validation). Storage performed
at 150 °C, the temperature was raised 10 °C/min during the heating ramp. (b) Calculated mean coverage of ammonia. (c) Calculated mean coverage
of water.

Figure 8. (a) Measured and calculated concentrations during an ammonia oxidation experiment over Cu-ZSM-5-a. The temperature was raised
step-wised from 100 to 400 °C. (b) Calculated mean coverage of NH3, H2O, O and O2 on S1a and S1b.

ammonia and water on the S2 and S3 sites occur, but are
not shown in the figure.
One additional ammonia oxidation experiment in presence
of water was used to develop the model. This experiment
was conducted over the Cu-ZSM-5-a catalyst and the result
is displayed in Figure 9. There is a total uptake of ammonia
for about 14 min, which is significantly less than the 20 min
without the presence of water. The total storage decreases
from 1.9 to 1.4 mmol, which is due to water blocking some
of the storage sites for ammonia. Also the desorption of
ammonia when increasing the temperature is decreased. The
model predicts the reduced ammonia storage well, and also
the decreased release of ammonia at each temperature
increase. The reason is the competition for surface sites
between ammonia and water. The model predicts high initial
coverage of water due to high gas phase concentration (5%)
The ammonia competes and the coverages of ammonia are
increasing slowly, but the saturation level is lower compared
to in the dry experiment. Formation of large amount of OH
groups is also observed in the model. These are crucial in
order to describe the large poisoning effect that water has
on the NO oxidation.51 The coverage of OH groups in the
NH3 oxidation experiment in the presence of water is about
0.9 at 250 °C. This high coverage reduces the rate of reaction
11 very much. It was therefore crucial to add reaction 13
where NH3 can react with OH and O on the copper. At 300
°C the NH3 oxidation start (reaction 13) and the coverages
of OH drops and now also reaction 11 becomes important.
Detailed Kinetic Modeling
Figure 9. (a) Measured and calculated concentrations during an ammonia oxidation experiment over Cu-ZSM-5-a in presence of water. The
temperature was raised stepwise from 100 to 400 °C. (b) Calculated mean coverage of NH3, H2O, O and O2 on S1a and S1b.
The parameters and their linearized 95% confidence regions
are shown in Table 11. The parameters for oxygen adsorption,
desorption, dissociation and recombination are taken from
an earlier study by Olsson et al.42 There is a range of
activation energies reported in the literature. Baik et al. 30
obtained 166 kJ/mol for NH3 oxidation over Cu-ZSM-5 and
Williamson et al. 39 between 148-158 k/mol for Cu-Y,
Chatterjee et al. 48 178 kJ/mol for an commercial Fe zeolite
and Long and Yang47 88 kJ/mol for Fe-ZSM-5. The activation
barriers for the two NH3 oxidation reactions in our work were
93 and 115 kJ/mol for reaction 11 and 13, respectively. Thus
our values are close to the one reported by Long and Yang
for Fe-ZSM-5.47
5. Conclusions
The NH3 and H2O adsorption and desorption and the NH3
oxidation was studied using detailed kinetic modeling and flow
reactor experiments. The ammonia storage is important for the
NH3 SCR application, since minimum ammonia slip is desired.
Also, given the large storage of ammonia on the catalyst, it is
crucial to describe the ammonia adsorption well in order to
accurately simulate transient experiments. Also, ammonia
oxidation at high temperature may cause decreased NOx
reduction activity, and in this study, ammonia storage and
oxidation are investigated separately. The water adsorption and
desorption was also included in the study.
Electron paramagnetic resonance studies (EPR) and also
DFT calculations in the literature suggest that
[Cu(NH3)4]2+complex are formed in copper zeolites. In our
model we therefore use four sites on each copper for ammonia
adsorption. Further, in other experiments we found that the
adsorption of NO2 was significantly less than NH3 and it is
not possible to adsorb four NO2 on each copper. We therefore
introduce one S1a site per copper where both ammonia and
NOx adsorb. This is the active site, where the SCR reactions
occur. In addition, we also use three extra sites per copper
(S1b) for ammonia adsorption in order to add up to the four
ammonia adsorbed per copper. Also ammonia can be
adsorbed on the Brönsted acid sites and we denote them with
S2. These sites were investigated separately using a H-ZSM-5
catalyst. Finally, we observed a very large adsorption of
ammonia at 30 °C, which was much larger than the sum of
J. Phys. Chem. C, Vol. 113, No. 4, 2009 1403
S1a, S1b, and S2 sites, and we therefore introduced S3 sites
for loosely bound species.
One ammonia TPD experiment and one water TPD
experiment, both conducted at 150 °C, were modeled using
the H-ZSM-5 catalyst to get information about the ammonia
and water storage and release. The same experiments were
also conducted using the Cu-ZSM-5 catalyst in order to
describe the effect of copper on the adsorption and desorption
of ammonia and water. The same experiment were also
conducted over the Cu-ZSM-5 catalyst and was used to
describe the effect copper had on the adsorption and
desorption of ammonia and water. An ammonia TPD at 30
°C was also used. The model was able to describe the
experiments adequately. An NH3 TPD experiment with
storage performed in presence of water was used for model
validation. The water reduced the ammonia storage, due to
blocking of storage sites. The model was able to predict the
experimental result satisfactorily.
Elementary reaction steps for oxygen adsorption, desorp-
tion, dissociation and recombination were incorporated into
the model together with two summary steps for ammonia
oxidation. In the first step ammonia is reacting with oxygen
on the surface to produce N2 and this step is very important
for describing ammonia oxidation in dry conditions. When
water is present there is a large formation of OH groups that
blocks the surface, through a reaction between water and
oxygen. These OH groups are necessary in order to describe
the large decrease of NO oxidation in the presence of water.51
However, NH3 oxidation is only mildly affected by the
presence of water and therefore was a summary reaction
between ammonia oxygen and OH introduced. The model
was then able to predict ammonia storage, desorption and
oxidation well, both with and without water.
6. Nomenclature List
parameter description unit
An monolith wall area in each tank, m2
Aj pre-exponential factor for reaction j, depends on rate
expression
Aads pre-exponential factor for adsorption, used for cal-
culating ∆S, s-1
1404 J. Phys. Chem. C, Vol. 113, No. 4, 2009 Sjövall et al.

Ades pre-exponential factor for desorption used for cal- (5) Tronconi, E.; Nova, I.; Ciardelli, C.; Chatterjee, D.; Bandl-Konrad,
culating ∆S, s-1 B.; Burkhardt, T. Catal. Today 2005, 105, 529.
(6) Ciardelli, C.; Nova, I.; Tronconi, E.; Chatterjee, D.; Bandl-Konrad,
cg,i,n concentration in the gas phase of component i in tank B.; Weibel, M.; Krutzsch, B. Appl. Catal. B EnVironmental 2007, 70 (1-
number n, mol/m3 4), 80.
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