Chemical Engineering and Processing 42 (2003) 365
/371

www.elsevier.com/locate/cep

Kinetic analysis of selective catalytic NOx reduction (SCR) in a

catalytic filter
G. Schaub a,*, D. Unruh a, J. Wang a, T. Turek b
a
Engler-Bunte-Institut der Universität Karlsruhe, Engler-Bunte-Ring 1, 76131 Karlsruhe, Germany
b
Institut für Chemische Verfahrenstechnik der Universität Karlsruhe, D-76128 Karlsruhe, Germany

Received 10 October 2001; received in revised form 26 April 2002; accepted 26 April 2002

Abstract

A multifunctional reactor allows substitution of two or more process units with a single reactor, where all the operations of
interest are executed simultaneously. For example, when ceramic filter materials, used in flue gas cleaning, are doped with
compounds of transition metals, high efficiencies in particulate separation and catalytic activity for the removal of NOx, CO and
CHx are obtained. The present study addresses a kinetic analysis of NOx reduction occurring in the catalytic filter material,
including experimental data reported in the literature. A numerical model, based on available knowledge of SCR kinetics, is
developed, validated with catalytic filter data and with honeycomb profiles, and finally used for case studies regarding design
variables (GHSV, inlet concentration). The results indicate that NOx conversion typically required is possible on time scales of gas
flow through a catalytic filter medium in the temperature range 250
/350 8C, with strong temperature effects due to the competition
of the desired SCR reaction and NH3 oxidation with O2. Application of the model and parameter values derived from the catalytic
filter analysis to a SCR honeycomb situation constitutes a sort of indirect validation.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Selective catalytic NOx reduction; Multifunctional reactor; Ceramic filter; Honeycomb reactor; Flue gas cleaning; Environmental
catalysis; Vanadium-oxide catalyst

1. Introduction interest are executed simultaneously. As an example in

The removal of particles and gaseous pollutants from
high-temperature gases is often required in thermal
power plants and waste incineration. Particles are
commonly removed in electrostatic precipitators or
filters, gaseous pollutants by sorptive or-as in the case
of NOx-catalytic processes. Here, NOx is selectively
reduced by NH3 in a solid-catalyzed reaction, typically
in low pressure drop honeycomb V2O5/TiO2 structures.
A new type of reactor has been suggested for savings
in energy, space and cost that is capable of carrying out,
besides the chemical reaction, other functions, such as
separation or heat exchange. The resulting multifunc-
tional reactor allows substitution of two or more process
units with a single reactor, where all the operations of
gas cleaning, catalytic filters for flue gases have been
suggested, either for fossil fuel power plants [1
/3] or for
biomass and waste incineration [4
/6]. When ceramic
filter materials are doped with compounds of transition
metals, high efficiency for particulate separation (to dust
concentration below 1 mg m 3) and catalytic activity
for the removal of NOx, CO and CHx are obtained.
Once activated with a suitable catalytic species, the
obtained filter must separate fly ashes (by formation of a
dust cake, periodically removed by a counter current jet-
pulse) and, at the same time, catalytically convert
gaseous pollutants passing through the inner structure
of the filter material.
NO reduction can be seen to occur according to Eq.
(1), at the same time the extent of a parallel oxidation of
NH3 with O2 (Eq. (2)) has to be minimized.

* Corresponding author. Tel.: /49-721-608-4238; fax: /49-721- 4NO4NH3 O2 0 4N2 6H2 O (1)
606-172
E-mail address: georg.schaub@ciw.uni-karlsruhe.de (G. Schaub). 4NH3 3O2 0 2N2 6H2 O (2)

0255-2701/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 5 - 2 7 0 1 ( 0 2 ) 0 0 0 5 6 - 9
366 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371

Experiments in laboratory and pilot scale reactors

with a rigid ceramic filter medium activated with V2O5/
TiO2 are reported in connection with the treatment of
flue gases from coal-fired burners [2]. Here, character-
istic NO conversion versus temperature curves were
measured, similar to the data in Fig. 2.

3. Kinetic model and parameter values

An isothermal pseudo-homogeneous model is devel-

oped in the following, leading to differential equations
based on steady state continuity equations.
The observed NO conversion-temperature behavior in
Fig. 2 is represented by the two parallel reactions Eq. (1)
and Eq. (2) with different temperature-dependencies and
Fig. 1. Sketch of a honeycomb reactor (left) and an idealized catalytic rate Eqs. (3)
/(6). Selection of these rate equations is
filter (right), with geometric definitions used in Table 1. inspired by earlier studies regarding intrinsic SCR-
kinetics [10,15].
The situations in an idealized catalytic filter and in a
honeycomb DeNOx reactor as commonly used today acNH3
r1  k1 cNO (3)
are shown in Fig. 1, characteristic features of both and 1  acNH3
data are collected in Table 1.
r2  k2 cNH3 (4)
Limited experimental data are reported in the litera-


ture. The present study addresses a kinetic analysis of E
kj kj0 exp  j (5)
the chemical reactions occurring in the catalytic filter RT
material. A numerical model, based on available knowl-

edge of SCR kinetics, is developed, validated with A
a a0 exp  (6)
published catalytic filter data and with honeycomb RT
profiles. It subsequently helps in case studies regarding
design variables (GHSV, inlet concentration). The catalytic filter medium is treated as a plug flow
reactor with continuity equations for NO and NH3 Eqs.
(7)
/(9), treated as isothermal, given the small tempera-
ture effects due to the small amounts of NO converted.
2. Experimental database Underlying assumptions include steady state, ideal plug
flow in z-direction, axial dispersion slow compared with
Experiments with a filter medium made from ceramic convective transport, uniform concentrations in radial
fibers (alumina
/silica [14]) were carried out by Hübner direction.
et al. [11] on laboratory and bench scale, using model
dci X
flue gases and a real flue gas from fuel oil combustion. 0 ueff  nij rj (7)
Filter candles were used, impregnated with various SCR dz j
catalysts (vanadium-oxide and others), with technical dcNO acNH3
data given in Table 2. Impregnation was done by a wet 0 ueff k1 cNO (8)
dz 1  acNH3
method followed by drying and calcination. The experi-
mental data in Fig. 2 originate from experiments with a dcNH3 acNH3
0 ueff k1 cNO k2 cNH3 (9)
real flue gas and a V-based catalyst and constitute the dz 1  acNH3
basis for the present modeling study (curves calculated
with rate equations resulting from model validation). Among the parameters in the equations, two para-
The same type of catalytic filter material was used in a meter values (E1, E2) are taken from published kinetic
pilot filter placed in the bypass of a waste incineration information [9,10], k10 is estimated from low tempera-
plant [4]. Here, a NOx conversion of 75% was achieved ture NO conversion data by assuming that below 593 K,
at 240 8C and a gas velocity of up to 3 cm s 1. Catalyst ammonia oxidation is negligible. The values of the other
deactivation due to the fly ash from waste incineration three parameters are estimated by minimizing an error
was not observed to be a limiting factor in these function F. Catalyst geometry and structural data used
experiments. are given in Tables 1 and 2.
 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371 367

Table 1
Comparison of catalytic reactors (honeycomb and filter) for NO-reduction in flue gases

SCR honeycomb Catalytic filter (rigid or fibre material)

Geometry
Filter medium thickness m 0.7f
/1.4f
/3g 0.009d
/0.02e,i
dchan mm 3
/12f 0.015c
dcat mm 0.5
/1.5f (wall thickness) 0.001c (layer thickness)
Catalyst properties
Catalyst V2O5/TiO2porous homogeneous solid V2O5other components impregnated support
V2O5 content wt.% 1
/3.45b 0.5c
/10.4c
Void fraction honeycomb vol.% 65g
Material porosity vol.% 50g
Porosity o vol.% 64a
/82.5f 25c
/8h
/95d
Catalyst mass fraction
In solid wt.% 80f
/100g 0.5f
/20f
V2O5 wt.% 1f
/5.5f
TiO2 wt.% 94.5f
/99f
Support wt.% 20f
Cat volume fraction vol.% 0.14g 0.00025g
/0.005g
/0.01g
Relative factor
/ 10
/100 1
Tortuosity V
/ 6b 3c
Specific surface m2 m 3 300c
/350c
Area a m2 g 1 30a
/200a 200c
/300c
Density r kg m 3 500g 180d
Operating conditions
T 8C 100b
/300b 160d
/420d
GHSVj h 1 5000b
/15 000g
/30 000b 3000d
/5400e,i
/11 000d
Ueff m s 1 0.2a
/4g 0.047d
/0.073d
Dp mbar 5g
/15g 12g
/15g
Inlet concentration NOk cNO in ppm 100
/1000b 170e
/350d
Catalyst efficiency factors l
h NO red
/ 51 1
h SO2 ox
/ 1 1
h SO2 ox/h NO red
/ ]1 1

Sources: various publications, own calculations and estimates. [9].

a
[7].
b
[8].
c
[10] (rigid material).
d
[11] (fibre material).
e
[4] (fibre material).
f
[12].
g
Own estimate or assumption.
h
[13].
i
[14].
j
Vgas, n /Vreac (n : 0 8C, 1 bar).
k
Inlet concentration of NH3 equimolar to NO.
l
Conclusion from intrinsic rates.advantage of catalytic filter for NOx reduction.

4. Numerical solution and model validation X

The continuity equations for NH3 and NO Eqs. (8)
and (9) are solved numerically with a MATLAB routine
(ODE 23, Runge-Kutta algorithm). A non-linear least
square algorithm (FMINS, simplex search) minimizes
the sum of the squares of the vertical differences
between the calculated curve and the experimental
data (Eq. (10)). Ammonia conversion is not included
in the minimization criterion as it was not measured in
the experiments (Fig. 2).
n
2
F (XNO calc m XNO exp m ) (10)
m1
The results of the fitting procedure are shown in Fig. 2
and Table 3. Calculated values of NO conversion agree
well with the experimental values. Values for E1 and E2
were set in the ranges of published values (48
/65 and
83
/87 kJ mol 1, respectively, both in [9,10]). Although
the number of experimental data points does not allow
discrimination of rate equations, the parameter values
obtained together with the kind of rate equation
368 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371

Table 2
Technical data of ceramic fibre filter element used in published
experiments [11]

Outer diameter mm 60
Inner diameter mm 42
Length of element mm 985
Mass per area g m 2 1600
Mass of element kg 0.300
Thickness of filter medium mm 9
Density g cm 3 0.18
Air permeability (200 Pa) l dm 2 min 120
Porosity % 95
Tortuosity
/ n.a.
Area/element m2 0.19

Fig. 3. Calculated values of reaction rates r1 and r2 for inlet

concentration values, conditions: see Fig. 2.

example, from the structure of rate Eqs. (3)
/(6),

parameter A can be seen as something like a Gibbs
free energy of adsorption for ammonia. Its value
appears high compared with the activation energies
found. However, the limited number of experimental
data precludes further physical interpretation. In addi-
tion, model discrimination regarding the flow behavior
inside the porous filter medium presently is not possible.
Calculations with the continuity equations according to
a perfectly mixed flow reactor (PMFR) have shown that
the experimental data can also be described by a PMFR
model.
Fig. 2. Results of fitting procedure in model validation, experimental
data from catalytic filter candle experiments using ceramic material in
a bench-scale test facility (extracted from published curves, yNO in /
yNH in /350 ppm, yO in /7.6 vol.%, GHSV/11000 1 h 1, ueff /
3 2
0.047
/0.073 m s 1 [11]).
5. Case studies

Table 3
Parameter values in rate equations, constant values (left) and results of
model validation (right)
Constant parameters
E1  60 kJ mol1
k10  1 106 1 s 1
E2  85 kJ mol1
The effect of gas hourly space velocity (GHSV) is
shown in Fig. 4 for constant gas inlet concentrations,
calculated with parameter values from model validation.
Conversion curves shift towards lower temperatures at
Optimal parameters
lower GHSV values (4000 vs. 12 000 h 1) and higher
k20  6.8 107 1 s 1
A 243 kJ mol 1
a0  2.68 10 17 m3 mol 1
F 2.63 10 2

assumed provide a reasonable fit for the conditions

investigated.Values for the reaction rates according to
Eqs. (3) and (4), calculated for inlet concentration
values, are shown in Fig. 3. The maximum in r1 reflects
the fact that above 380 8C the NH3 term (associated
with adsorption of NH3 on the catalyst surface) begins
to decrease considerably.
Given the limited data base available, in particular the
lack of data with variations in residence time, the
resulting parameter values are linked to the kind of
Fig. 4. Case study: effect of space velocity GHSV, conditions: yNO
model applied (plug flow). They have only limited in /yNH in /350 ppm, yO in /7.6 vol.%, parameter values: see Table
3 2
physical meaning in terms of intrinsic kinetics. For 3.
 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371
NO conversion can be achieved. Variations in GHSV
represent either variations in the thickness of the filter
element or variations in gas volume flow, or linear gas
velocity, respectively. For the values of filter medium
thickness reported in the literature (9 and 20 mm, see
Table 1) the corresponding effective gas velocities are in
the range 1.7
/16.4 cm s 1.
A second case study shows the effect of inlet NO
concentrations, varying for example with the kind of
combustion feedstock or process technology. The calcu-
lated results show that with lower NO inlet concentra-
tion, lower conversions are achieved above 350 8C. For
the boundary conditions considered in this study
(yNH3 in /yNO in), the NH3 term in r1 leads to an
apparent reaction order for NO greater than 1.
The two case studies include the operating conditions
reported for the catalytic pilot filter placed in the bypass
of a waste incineration plant ([4]: T /240 8C, GHSV 5/
5400 h1, filter element thickness /2 cm, ueff 5/5.6 cm
s 1, yNO in /170 ppm). The reported NO conversion
value of 75% is close to the calculated values shown in
Figs. 4 and 5.
6. Application of kinetic parameters to a honeycomb
reactor
The kinetic parameter values determined in the
catalytic filter analysis were subsequently applied to a
honeycomb reactor. This may yield an indirect proof of
the validity of the model and its parameter values
because the honeycomb situation is understood quite
well after numerous investigations in the past (see [7],
[15] and others). An available mathematical model [9]
was used to calculate NO and NH3 concentration
profiles in the catalyst walls of a honeycomb structure
and the efficiency factors in the catalyst, as varying with
temperature. Main underlying assumptions in this
Fig. 5. Case study: effect of inlet concentrations, conditions: see Fig. 2
and Table 2.
369
model are (a) steady-state prevails, (b) no concentration
gradients exist in the gas phase, (c) diffusion in the
catalyst pores is described by Fick’s law with the same
diffusion coefficient for every reactant, (d) catalyst wall
is isothermal.
Continuity equations for NO and NH3 inside the
catalyst wall include diffusive transport terms and
chemical reaction rates (Eqs. (11) and (12)). Effective
diffusion coefficients are calculated including gas diffu-
sion and Knudsen diffusion, both estimates based on
structural parameters of the filter medium (Table 1) and
on binary diffusion parameters. Wall thickness dcat is
assumed to be 1 mm, De to be 0.035 cm2 s 1 for 350 8C.
d2 cNO acNH3
0 De k1 cNO (11)
dx2 1  acNH3
 
d2 cNH3 acNH3
0 De  k1 cNO k2 cNH3 (12)
dx2 1  acNH3
d2 cNO acNH3
0 De
/ k1 cNO /
dx2 1  acNH3
The NO and NH3 concentration profiles obtained for
the wall thickness assumed (1 mm) and for the
maximum reaction temperature considered (T /
420 8C) are shown in Fig. 6. The full curves shown
are calculated with a value of the catalyst volume
fraction tenfold greater than that in the catalytic filter
studied, the dotted curves with a value hundredfold
greater than that in the catalytic filter. Comparing the
concentration trends, it results that a higher catalyst
volume fraction obviously leads to a faster chemical
reaction and thus to a sharper profile in the catalyst
wall. The reaction in the very inner part of the catalyst
cannot take place because NH3 reacts completely in the
catalyst near the surface.
Fig. 6. Calculated NO and NH3 concentration profiles in a honey-
comb catalyst wall of 1 mm thickness, volume catalyst fraction tenfold
( */) or hundredfold (
/.
/.
/) higher than in catalytic filter; */, k10 /
1/107 1 s 1, k20 /6.8/108 1 s 1;
/.
/.
/, k10 /1/108 1 s 1, k20 /
6.8 /109 1 s 1, other parameter values, see Table 3, conditions, T/
420 8C, yNO in /yNH in /350 ppm.
3
370 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371

Using the calculated profiles, average rates of both
reactions in the catalyst wall were obtained by numerical
integration over the wall segments. According to the
definition of the efficiency factor (Eq. (13)), reaction
rates are related to the maximum possible rates achiev-
able for uniform maximum concentration over the entire
porous catalyst.
results of which were indirectly confirmed by experi-
mental measurements. Comparison of the results in-
dicates that the trends of the efficiency factors in both
cases are qualitatively the same. Differences can be
attributed to the different characteristics of the catalysts
used, as well as the different conditions and assumptions
made.

g r (c (x); T(x)) dV
V
j i
7. Conclusions
h
j (13)
g r (c ; T ) dV
V
j is s The present kinetic study based on published experi-
mental data with a ceramic fibre filter leads to the
following conclusions: (a) according to the calculated
For temperatures in the range 150
/420 8C, efficiency
results, NO conversion of 60
/85% is possible on time
factors were calculated for bulk gas NO and NH3
scales of gas flow through the catalytic filter medium for
concentrations of 350 ppm (typical value reactor inlet)
temperatures around 250 8C and higher, (b) a strong
and 35 ppm (typical value reactor outlet, assuming 90%
temperature effect can be explained by means of a
conversion). Results are shown in Fig. 7 for 350 ppm,
competition of two NH3-consuming reactions, the
calculations for 35 ppm indicate no significant effect of
desired SCR reaction and the undesired NH3 oxidation
bulk gas concentration. From the calculated curves it
with O2, (c) modeling catalytic filter kinetics agrees with
clearly appears that the efficiency factor is depending
the actual understanding of SCR honeycomb kinetics,
only weakly on NO and NH3 inlet concentrations.
application of the model and parameter values consti-
However, the strong effect of temperature is evident.
tutes a sort of indirect validation, (d) loading of porous
By increasing temperature, the efficiency factors mark-
filter medium structures with a catalyst without exces-
edly decrease since diffusion becomes significant and the
sive reduction of porosity (toward plugging, pressure
inner structure of the catalyst wall is not available for
drop increase) as a crucial aspect for filtration remains a
chemical reaction. The increase of the catalyst volume
point to be investigated in more detail. Many activities
fraction leads to a decrease of the amount of the
in this direction are, therefore, ongoing.
reactant molecules that reach the active site in the inner
structure of the catalyst. Consequently the efficiency
factors have lower values for a given temperature.
Acknowledgements
The calculated results for concentration profiles and
efficiency factors in the catalyst wall exhibit the same
The presented work was funded in part by the
trends as results reported in the literature [8]. Buza-
European Commission within the JOULE III Pro-
nowsky and Yang developed a theoretical procedure to
gramme, contract number JOR 3-CT98-0250. Partners
predict the concentration profile in the honeycomb
were: Universität Karlsruhe IMVM and EBI, USF
catalyst wall analogous to that used in the present
Schumacher, Solvay S.A., EC-JRC and CIEMAT.
study. They derived a simplified analytical solution the
Assistance from Camilla Grati in numerical calculations
is gratefully acknowledged.

Appendix A: Nomenclature

A exponential factor, (kJ mol 1)

a factor in rate equation r1, (m3 mol 1)
a0 preexponential factor, (m3 mol 1)
ci concentration, gas component i, (mol m 3)
dcat thickness of catalyst wall or layer, (mm)
dchanopening in honeycomb structure or in filter
material, (mm)
De diffusion coefficient in honeycomb wall pore
structure, (cm2 s 1)
Fig. 7. Calculated efficiency factors for reaction 1 (h1) and reaction 2
(h2) in a catalyst wall of 1 mm thickness, catalyst volume fraction
Ej activation energy reaction j, (kJ mol1)
tenfold ( */) or hundredfold (
/.
/.
/) higher than in catalytic filter, yNO GHSV gaseous hourly space velocity, (h 1)
and yNH3 at outer catalyst surface: 350 ppm. kj rate constant reaction j, (s 1)
 G. Schaub et al. / Chemical Engineering and Processing 42 (2003) 365
/371 371

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n number of experimental data points, (/)
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/
R gas constant, (83 143 J mol 1 K 1) 73.
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