Chemical Engineering Science 60 (2005) 6462 – 6471

www.elsevier.com/locate/ces

Rigorous modelling of NOx absorption in tray and packed columns

Bernhard Hüpen, Eugeny Y. Kenig∗
Department of Biochemical and Chemical Engineering, University of Dortmund, 44227 Dortmund, Germany

Received 15 November 2004; received in revised form 19 April 2005; accepted 19 April 2005
Available online 23 June 2005

Abstract
The absorption of NOx into pure water or nitric acid is usually a kinetically controlled operation in which complex reactions in both
gas and liquid phases are combined with multicomponent mass transfer. To be able to describe this process adequately, a rigorous general
rate-based model for the reactive absorption in tray and packed columns has been developed based on earlier works (see, e.g. [Kenig et
al., 2001. Chemical Engineering Science 56, 343–350; Kenig et al., 2003. Chemical Engineering and Technology 6, 631–646]). Heat and
multicomponent mass transfer in the film phases, chemical reactions and thermodynamic non-idealities are taken into account. Furthermore,
the influence of column internals and hydraulics is considered via relevant correlations. For tray columns, a special consideration of the
empty sections above the gas–liquid layer on a tray is included. The model is implemented into the simulation environment Aspen Custom
ModelerTM and validated by comparison with experimental data for a pilot scale packed column and an industrial sieve tray column
equipped with cooling coils. The simulation results obtained for both column types agree well with the experimental measurements. In
addition, the influence of cooling on the process behaviour is studied.
䉷 2005 Elsevier Ltd. All rights reserved.

Keywords: NOx absorption; Rate-based model; Cooling; Absorption; Simulation; Modelling; Transport processes

1. Introduction nitrogen oxides). A rigorous and reliable process description

Absorption of nitrous gases represents a widespread and
important operation in the chemical process industries. It is
mainly used in the production of nitric acid and in the purifi-
cation of exhaust gas streams, e.g. in the fertiliser industry.
One the other hand, it is a highly complex process due to
the interaction of several components (e.g. NO, NO2 , N2 O4 ,
HNO3 ), both in the liquid and gas phases, parallel and con-
secutive chemical reactions and simultaneous absorption and
desorption.
The design of columns for NOx absorption is mostly
based on experience and/or on usage of simplified models
which cannot reproduce the process behaviour with suffi-
cient accuracy. As a consequence, possible design errors can
lead to serious problems (e.g. exceeding emission limits for
∗ Corresponding author. Tel.: +49 231 755 2357; fax: +49 231 755 3035.
E-mail address: e.kenig@bci.uni-dortmund.de (E.Y. Kenig).
would help to avoid these difficulties.
Modelling and simulation of gas–liquid reactor units have
been usually based on the equilibrium stage concept in which
a unit is subdivided into several axial segments (stages). The
column profiles are determined assuming the equilibrium
state between the streams leaving each stage and by using
the HETP-values (Height Equivalent to a Theoretical Plate)
(Taylor and Krishna, 1993). However, the application of the
equilibrium stage concept is difficult for processes driven
by rate controlled phenomena. This is just the case with
reactive absorption operations, in which reaction kinetics
and mass and heat transfer resistances represent the key
issues (Schneider et al., 1999).
The rate-based approach is a more consistent modelling
method to consider reaction and transport kinetics. Here,
gas and liquid phases are balanced separately, whereas
the mass and heat fluxes across the interface are taken
into account directly (Taylor and Krishna, 1993). In ad-
dition, mutual influence of chemical reactions and mass

0009-2509/$ - see front matter 䉷 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.04.060
 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471
transfer can be properly taken into account (Kenig et al.,
2001).
Absorption of NOx is one of the most complex gas–liquid
reaction operations. This is the reason why various simpli-
fications reducing the accuracy and predictivity of the rate-
based approach have been made, e.g. consideration of mass
transport of the key components NO2 and N2 O4 only (Emig
et al., 1979; Greve and Bode, 1994; Wiegand et al., 1990),
assumption of equal component diffusivities (Emig et al.,
1979; Ramanand and Phaneswara Rao, 1996; Suchak et al.,
1991), application of enhancement factors (de Paiva and
Kachan, 2004), or neglecting the reactions in the gas film
(Patwardhan et al., 2002; Suchak et al., 1991).
The present work is free of such simplifications. We de-
veloped a general rate-based model which is valid for both
packed and tray columns and applicable for a broad spec-
trum of NOx absorption operations. The model is an exten-
sion of previous models (see Kenig et al., 1997, 2001, 2003;
Schneider et al., 1999) developed for the description of reac-
tive absorption in packed columns. The model involves the
film model equations combined with relevant reaction and
diffusion kinetics for all reactions and components, in both
the gas and liquid phases, and it is extended to include an
additional element—the so-called gas area—which consid-
ers the influence of the gas-phase reactions on the compo-
sition in the empty section above the gas–liquid layer on a
tray. Further, the model includes the description of cooling
effects through cooling coils installed in tray columns.
The model is realised with the help of the simulation en-
vironment Aspen Custom ModellerTM and successfully val-
idated with NOx absorption experimental data for columns
of both packed and tray type.
2. Process description
A typical simplified flow diagram of NOx absorption
process is shown in Fig. 1, with three columns connected
counter-currently. The inlet of the raw gas consisting of
nitrogen oxides and air is at the bottom of the first col-
umn. The solvent is fed at the top of the third column.
The nitrogen oxides are absorbed by the solvent flowing
Fig. 1. Simplified flow diagram of a NOx absorption process.
6463
counter-currently to the gas and form nitric acid which is
drawn off at the bottom of the first column. These columns
can be either of a packed or of a tray type. Tray columns
are often additionally equipped with cooling coils on trays
in order to achieve higher absorption rates via cooling.
The reaction network of the NOx system is extremely
complicated. Altogether, there are more than 40 reactions
known. For the simulation of the process, a relevant set of re-
actions was taken from Suchak et al. (1991). It contains five
gas-phase and four liquid-phase reactions presented below:
• gas-phase reactions
2NO + O2 → 2NO2 , (R1)
2NO2 ↔ N2 O4 , (R2)
NO + NO2 ↔ N2 O3 , (R3)
NO + NO2 + H2 O ↔ 2HNO2 , (R4)
3NO2 + H2 O ↔ 2HNO3 + NO; (R5)
• liquid-phase reactions
2NO2 + H2 O → HNO2 + HNO3 , (R6)
N2 O3 + H2 O → 2HNO2 , (R7)
N2 O4 + H2 O → HNO2 + HNO3 , (R8)
3HNO2 → HNO3 + H2 O + 2NO. (R9)
For the process performance, the oxidation of nitrogen
monoxide to nitrogen dioxide (R1) is especially significant,
because of the low solubility of nitrogen monoxide in water.
Compared to nitrogen monoxide, the solubility of nitrogen
dioxide is one order of magnitude higher. Reaction (R1)
is a kinetically controlled reaction and it is assumed to be
irreversible for temperatures below 350 ◦ C. In reactions
(R2)–(R5), nitrogen dioxides instantaneously react to in-
termediate products (e.g. N2 O3 or HNO2 ) whose solubility
increases with increasing molecular weight.
The liquid-phase reactions are kinetically controlled and
assumed to be irreversible at nitric acid concentrations below
35 wt% (Joshi et al., 1985). Via reactions (R6)–(R8) the
dissolved nitrogen oxides are transformed into nitric and
nitrous acids. NO produced in reaction (R9) is desorbed due
to its low solubility.
The instantaneous gas-phase reactions (R2)–(R5) are
taken into consideration by means of the mass action law

G
p,r
G p (yp P )
Kr =
G
e,r . (1)
e (ye P )
The chemical equilibrium constants Kr are given in Table 1.
The reaction rates of the irreversible, kinetically con-
trolled reactions are defined by the following
6464 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471

Table 1
Chemical equilibrium and forward reaction rate constants of reactions (R1)–(R9)

Reaction Equilibrium and rate constants Reference

ln k1 = 1468 −2 s−1 )
R1 T − 10.9043 (kPa Miller (1987)
R2 ln K2 = T − 25.865 (kPa−1 )
6893 Miller (1987)
ln K3 = 4869 −1
R3 T − 21.61 (kPa ) Hisatsune (1961)
R4 ln K4 = T2051.17 − 8.7385 (kPa−1 ) Joshi et al. (1985)
R5 ln K5 = T − 10.763 (kPa−1 )
2003.8 Joshi et al. (1985)
R6 log kc6 = 4.67209 (m2 mol−1 s−1 ) Lee and Schwartz (1981)
R7 log kc7 = 4.23044 (s−1 ) Corriveau (1971)
log kc8 = − 4139 −1
R8 T + 16.3415 (s ) Wendel and Pigford (1958)
R9 log kc9 = − 6200 + 20.1979 (atm 2 m 9 kmol−3 s−1 ) Wendel and Pigford (1958)
T

expressions:

rrG = kr,for
G
(yeG P )
e,r for (R1), (2)
e


e,r
rrL = kr,for
L
(xeL L
e) for (R6).(R9). (3)
e

The data on the forward reaction rate constants kr,for are

Fig. 2. Model structure of an axial segment for a tray column.
listed in Table 1. For reactions (R6)–(R9), these rate con-
stants are based on concentrations. During the simulation,
they are converted to activity-based constants.
time, the high liquid hold-up on the trays of the investigated
column due to a weir height of 250 mm. This leads to a
3. Rigorous rate-based model strong mixing of the liquid on trays and, therefore, to rela-
tively low concentration gradients over the liquid flow path.
In the investigated system, several components are present An important advantage of this model is that the hydrody-
in both phases. All components participate in complex gas- namics in the column can be directly involved using corre-
and liquid-phase consecutive and parallel reactions, which lations for hold-up, pressure drop, interfacial area and mass
lead to a coupling of multicomponent mass transfer and transfer coefficients (Schneider et al., 1999).
multiple reaction mechanism. As a consequence, a specially
developed rigorous mathematical model which considers the 3.1. Bulk-phase equations
reaction system and mass transfer resistances as well as the
column configuration is required (Kenig et al., 2003). In the liquid bulk balance equations, the axial change of
In Section 1, some previous studies of NOx absorption the total molar stream and the composition are considered
based on different simplifications are discussed. In this work,
we developed a more general model in which the above- j Lb
0= (x L) − nLb i a A
int col
− RiL Acol L ;
mentioned assumptions are not necessary. jz i
The model is based on a description of a single stage, i = 1, . . . , n. (4)
which is related either to a tray or to a packing segment of a
column unit. Gas and liquid phase are balanced separately, The differential heat balance of the liquid bulk is
whereas mass and heat transfer resistances are considered j
according to the film theory, by the direct account of the 0= (H Lb L) − q Lb a int Acol + QLb
loss . (5)
jz
interfacial fluxes. The film model equations are combined
with the relevant reaction and diffusion kinetics. The model
The term QLbloss is implemented into the heat balance to con-
is further extended in order to properly describe empty sec-
sider the heat effect achieved by cooling. In addition, the
tions in tray columns using the ideal plug flow reactor con-
summation condition for the molar fractions in the liquid
cept (see Emig et al., 1979). On each tray, such a section is
phase is valid
located above the gas–liquid layer (see Fig. 2). In the fol-
lowing, this empty section is called gas area. The gas–liquid n

layer is considered as homogeneously mixed. This is rea- xiLb = 1. (6)
sonable, because of the low liquid flow rate and, at the same i=1
 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471 6465

Similar equations can be applied for the gas bulk phase 3.3. Interface
j Gb
0=− (y G) + nGbi a A
int col
− RiG Acol Gb ; The thermodynamic equilibrium at the gas–liquid inter-
jz i face is usually calculated as follows:
i = 1, . . . , n, (7)
yiint = Ki xiint ; i = 1, . . . , n, (18)
j
0 = − (H Gb GGb ) + q Gb a int Acol + QGb
loss , (8)
jz where the distribution coefficient Ki comprises fugacities in
both phases and activity coefficients in the liquid phase. To
n
 determine Ki of very diluted systems, the Henry law for the
yiGb = 1. (9) dissolved components and the Raoult law for the solvent are
i=1 used.
Gas and liquid phases are connected by the following
3.2. Equations for the film region boundary conditions:
Gf
In the liquid film region, mass transfer and chemical re- ni |Gf =Gf = nLb
i |Lf =0 ; i = 1, . . . , n, (19)
action occur simultaneously. Therefore, a differential com-
ponent balance has to be considered q Gf |Gf =Gf = q Lf |Lf =0 . (20)
Lf
jni Lf
0= − Ri ; i = 1, . . . , n. (10) 3.4. Gas area equations
jLf
For the description of tray columns, some additional con-
In dilute systems, the diffusional interactions can usually
sideration is necessary to describe the gas area (cf. Fig.
be neglected, and the Maxwell–Stefan equations, generally
2). Whereas the gas–liquid layer is still described by Eqs.
applied for the description of mutlicomponent diffusion, are
(4)–(20), the gas area is covered in a different way.
replaced by the effective diffusivity description (Taylor and
The change of the gas composition in the gas area is
Krishna, 1993)
considered through the following differential equation:
Lf
Lf Lf jx i Lf Lf j Ga
ni = −ct Dieff + x i nt ; i = 1, . . . , n. (11) 0=− (y G) − RiG Acol Ga ; i = 1, . . . , n. (21)
jLf jz i
The differential energy balance of the liquid film is as fol- Further, the summation condition for the molar fractions has
lows: to be fulfilled
n
jq Lf 
0= . (12) yiGa = 1. (22)
jLf
i=1
The heat flux in the liquid film consists of a conductive and The energy balance of the gas area is
a convective term
j
n
jT Lf  Lf Lf 0=− (H Ga GGa ). (23)
q Lf
= − Lf
+ (ni Hi ); i = 1, . . . , n. (13) jz
jLf
i=1
Eqs. (21)–(23) are used in combination with the equations
Similar equations for the mass and heat transport are valid for the gas–liquid layer.
in the gas film:
3.5. Model parameters
Gf
jni Gf
0 = Gf − Ri ; i = 1, . . . , n, (14)
j For the determination of the mass transfer coefficients,
specific gas–liquid interfacial area and volumetric hold-up,
Gf
Gf Gf jyi Gf Gf empirical correlations are used, which govern the influence
ni = −ct Dieff Gf
+ y i nt ; i = 1, . . . , n, (15) of column internals and hydraulics. These correlations have
j
to be incorporated into the whole system of model equations.
jq Gf The relevant correlations are taken from Billet and Schultes
0= , (16) (1999) for packed columns and from Zuiderweg (1982) for
jGf
sieve tray columns. For the description of the hydraulics in
n
jT Gf  Gf Gf sieve tray columns, we included the equations for the spray
q Gf = −Gf + (ni Hi ). (17) and emulsion flow regime. The decision, which equation
jGf
i=1 should be used, is taken automatically during the simulation
6466 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471

Table 2
Physical property models according to Aspen Properties Manual (2001)

Property Gas phase Liquid phase

Enthalpy Via the heat capacity of an ideal gas Watson

Molar density Ideal gas Rackett
Dynamic viscosity Chapmann–Enskog–Brokaw Andrade
Thermal conductivity Mason–Saxena Sato–Riedel
Diffusion coefficients Chapmann–Enskog–Wilke–Lee Wilke–Chang
Surface tension — Hakim–Steinberg–Stiel
Activity coefficients — NRTL

Table 3
NRTL-parameters bij and bj i

Components Parameters Components Parameters

1 2 bij bj i 1 2 bij bj i

H2 O HNO3 0 0 HNO2 CO2 0 0

H2 O HNO2 0 0 NO NO2 128.8337 −114.7814
H2 O NO 751.8109 1892.6936 NO N 2 O3 0 0
H2 O NO2 751.8109 1892.6936 NO N 2 O4 128.8337 −114.7814
H2 O N2 O3 0 0 NO O2 448.7655 −345.7854
H2 O N2 O4 751.8109 1892.6936 NO N2 358.1516 −289.1752
H2 O O2 −101.8304 174.5380 NO CO2 −48.3459 125.2540
H2 O N2 −35.8278 142.4195 NO2 N2 O3 0 0
H2 O CO2 291.4104 177.4012 NO2 N2 O4 128.8337 −114.7814
HNO3 HNO2 0 0 NO2 O2 448.7655 −345.7854
HNO3 NO 0 0 NO2 N2 358.1516 −289.1752
HNO3 NO2 0 0 NO2 CO2 −48.3459 125.2540
HNO3 N2 O3 0 0 N 2 O3 N2 O4 0 0
HNO3 N2 O4 0 0 N 2 O3 O2 0 0
HNO3 O2 0 0 N 2 O3 N2 0 0
HNO3 N2 0 0 N 2 O3 CO2 0 0
HNO3 CO2 0 0 N 2 O4 O2 448.7655 −345.7854
HNO2 NO 0 0 N 2 O4 N2 358.1516 −289.1752
HNO2 NO2 0 0 N 2 O4 CO2 −48.3459 125.2540
HNO2 N2 O3 0 0 O2 N2 4.2683 −5.1213
HNO2 N2 O4 0 0 O2 CO2 246.3538 −132.3010
HNO2 O2 0 0 N2 CO2 179.4870 −91.2366
HNO2 N2 0 0

of the absorption process. It can be changed for each tray
within the same column and depends on the following ratio:
 
uL L 0.5
. (24)
uG G
In addition, pressure drop along the column is allowed for
via the relevant pressure drop correlations (see Zuiderweg,
1982; Billet and Schultes, 1999).
essary for the calculation of the physical properties. These
models are listed in Table 2.
The activity coefficients are calculated by the NRTL-
model for multicomponent mixtures. The NRTL-parameters
aij , aj i , dij , eij , ej i , fij and fj i for each binary pair are set
to the default value zero, whereas cij to the default value 0.3.
The estimated NRTL-parameters bij and bj i are collected
in Table 3.

3.6. Physical properties

The physical properties are calculated with the help of the
programme package Aspen PropertiesTM (Aspen Properties
Manual, 2001) which is directly linked to the simulation en-
vironment Aspen Custom ModellerTM , whereas the NRTL-
method is chosen as a basis method. According to the Aspen
PropertiesTM structure, this method specifies all models nec-
4. Model validation
4.1. Model implementation
In Kenig et al. (1997), an industrial NOx absorption prob-
lem was solved by splitting the rate-based equation set onto
parts describing film and bulk phenomena separately and by
 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471 6467

simplifying the film equations in order to obtain an analyt-

ically solvable matrix boundary value problem. Linearisa-
tion of the diffusion and reaction terms of the film equation
(cf. Eqs. (10) and (14)) allowed an analytical solution in a
closed matrix form (see Kenig and Górak, 1995; Kenig et
al., 1997). The composition boundary values need to be de-
termined from the total system of equations describing the
process.
In this work we applied a fully numerical algorithm which
does not require any additional linearisation. To obtain a
numerical solution of such problems, a discretisation in
regard to the axial and normal co-ordinates was performed
to yield an algebraic equation system. The number of
equations can reach up to 200,000 depending on the ax- Fig. 3. Axial profile of the total gas-phase NOx concentration of column
1 and measured values.
ial discretisation steps of the column. To solve this large
equation system, the model was implemented into the com-
mercial simulation environment Aspen Custom ModelerTM
(see http://www.aspentech.com/). The simulation tool offers
a direct link to the software package Aspen PropertiesTM
for the calculation of all required physical properties.

4.2. Validation for a packed column

The validation of the suggested model is performed by

comparison of simulation results with experimental data.
The data for the packed column is taken from Suchak et al.
(1991) where three pilot-scale columns connected counter-
currently are presented. We carried out simulations for two
of these columns. The simulated units have a simple config-
uration, with one liquid inlet stream at the top and one gas Fig. 4. Axial profile of the total gas-phase NOx concentration of column
inlet stream at the bottom. Both columns have a diameter 2 and measured values.
of 0.254 m and are filled with a random packing (Pall rings,
16 mm, steel), with a packing height of 6 m. In column 1,
a gas stream containing 20 mol% of nitrogen oxides is ab-
sorbed by an aqueous solution with 5 mol% of nitric acid.
The inlet gas stream of the column 2 contains 10.2 mol% of
nitrogen oxides and is treated by an aqueous solution con-
taining 2.65 mol% nitric acid.
Figs. 3 and 4 show the simulated axial profiles of the
total NOx concentration in the gas phase for columns 1 and
2. The outlet values are compared with the measurements.
To demonstrate the accuracy of the simulation results, the
experimental values are plotted with 5% error bars.
For column 1, the calculated total NOx concentration at
the top of the column show good agreement with the exper-
iments, the maximum deviation being less than 5%.
In Figs. 5 and 6, the simulated axial profiles of the liquid-
Fig. 5. Axial profile of the liquid temperature of column 1 and measured
phase temperature and measured values for both columns values.
are presented. Similar to Figs. 3 and 4, 5% error bars are
plotted to demonstrate the accuracy of the simulation results.
The liquid temperature profiles reveal a maximum in the the exothermic reactions are enhanced. In addition, the ab-
lower section of each column. This is typical for NOx ab- sorption rate of NOx is higher due to high NOx concentra-
sorption processes and can be explained as follows. The tion gradients. Both effects lead to an increase of the liquid
NOx concentration of the inlet gas stream is higher than in temperature. On the other hand, at the bottom of the col-
the upper part of the column. Therefore, in the lower part, umn, the liquid is cooled down again by the cold inlet gas
6468 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471
Fig. 6. Axial profile of the liquid temperature of column 2 and measured
values.
Table 4
Design parameters of the industrial sieve tray column
Column diameter
Number of trays
Plate spacing
Weir height
Weir length
Flow path
Number of holes
Hole diameter
Distance of holes (pitch)
Hole diameter
stream. These two opposite effects result in an extremum of
the axial temperature profile.
For both columns, the calculated liquid temperature at the
bottom differs from the measured value by more than 5%.
The absolute deviation is 4.5 ◦ C for column 1 and 3.8 ◦ C
for column 2. These deviations should be attributed to heat
losses through the column wall. Suchak et al. (1991) men-
tioned that their columns were not isolated, however they
did not quantify this phenomenon, and thus, it could not be
properly estimated in the calculations.
4.3. Validation for a tray column
The experimental data for an industrial scale one-
pass sieve tray column is provided by the Phosphoric
Fertilisers Industry (Greece) in the context of the Euro-
pean research project OPT-ABSO (G1RD-CT-2001-00649,
http://www.opt-abso.org). The design details of the tray col-
umn are given in Table 4. Each tray has a height of 0.9 m. In
the column, a gas stream containing 0.77 mol% of nitrogen
oxides is treated by an aqueous solution with 0.68 mol%
of nitric acid. To cool down the gas and liquid within the
column, it is equipped with cooling coils on 7 trays in the
lower part. The coils are fed with 152 m3 /h water, with an
average temperature of 23.6 ◦ C.
Fig. 7. Axial profile of the total NOx concentration in the gas phase and
the nitric acid concentration in the liquid phase and measured values.
Fig. 7 shows the calculated axial profiles of the total NOx
concentration in the gas phase and the nitric acid concen-
tration in the liquid phase. The inlet and outlet values deter-
3.8 m
20 mined with a measurement error of 15% are given, too. The
0.9 m agreement between the experimental and simulated values
0.25 m of the total NOx has a maximum deviation of 8.5%. The
3.015 m deviation of the simulated HNO3 concentration from the ex-
2.3 m
perimental value is in a range of 10%. Thus, the agreement
54,000
2.2 mm is good, as all deviations lie within the measurement error.
13 mm The simulated outlet temperature of the cooling water is
2.2 mm 24.8 ◦ C. This value agrees very well with the measured value
of 24.9 ◦ C, the deviation being less than 1%.
From the results of both pilot plant and industrial applica-
tions, it can be concluded that the suggested model demon-
strates a good accuracy for the highly complex NOx absorp-
tion processes studied.
5. Sensitivity analysis
5.1. Internals-related parameters
The validated model has been used to carry out compre-
hensive sensitivity studies for the packed columns in order
to investigate the influence of model parameters on the sim-
ulation results. The values of the internals-related parame-
ters, such as the mass transfer coefficients k L and k G , the
gas–liquid interfacial a int area and the liquid hold-up L ,
have been increased by 10%. The influence of these param-
eters is quantified by the change of the total absorption rate
of NO, NO2 , N2 O4 and total NOx .
The results presented in Fig. 8 show a substantial influence
of the interfacial area a int on the absorption rate of NO2 . An
increase of a int by 10% leads to a 7.2% higher absorption
rate. The influence of a int on the absorption rate of the other
components and the influence of the other model parameters
k L , k G and L is less significant. Changes by 10% lead to
deviations less than 3%.
 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471
Fig. 8. Influence of a 10% increase of the model parameters L , k L , k G
and a int on the absorption rate of NO, NO2 , N2 O4 and total NOx .
Fig. 9. Effect of cooling on the absorption rate of NOx in the industrial
sieve tray column.
5.2. Reaction rate
Further, the sensitivity of the reaction rate of the impor-
tant oxidation reaction (R1) on the simulation results for
the packed columns has been investigated. Simulations are
carried out based on rate constants obtained by four differ-
ent approaches (Sherwood et al., 1975; Emig et al., 1979;
Koukolik and Marek, 1968; Miller, 1987). The simulations
show a strong influence of the reaction rate. The different
approaches for this reaction lead to a variation of 12% of the
overall absorption rate of NOx . Similar analysis performed
for the other reactions lead to deviations less than 1%.
Thus, for both validation cases, the reaction rate constants
for (R1) and the gas–liquid interfacial area appear to be the
most significant model parameters, and hence, considerable
attention should be drawn to their proper determination.
5.3. Cooling
Finally, the effect of cooling on the process behaviour of
the industrial sieve tray column has been analysed. Fig. 9
6469
Fig. 10. Effect of cooling on the absorption rate of NOx for an increased
NOx inlet gas stream concentration.
shows the simulated absorption rate of NOx and the cooling
duty for different cooling water flows. A strong dependency
of the absorption rate of NOx on the cooling duty is visible.
Increasing heat duty leads to a growing absorption rate. The
increase of the cooling water flow up to 100 m3 /h leads to
an enhanced NOx absorption rate by 0.15% and to a cooling
duty of 0.18 MW. A further increase of the cooling water flow
does not have any significant influence on both parameters.
Despite the strong dependency on the cooling duty, the
absolute changes of the absorption rates caused by the cool-
ing are small. This effect can be understood if one bears in
mind the low NOx fraction in the inlet gas stream. A higher
NOx concentration in the inlet gas stream would result in
a more significant enhancement of the exothermic reactions
and thus to a temperature increase and to a drop of the ab-
sorption rate. In essence, the aim of gas and liquid cooling
is just to prevent these effects, and its efficiency should be
more clear at high inlet NOx concentrations. An example is
shown in Fig. 10 for an inlet gas stream containing 7.8 mol%
of NOx , which is about ten times more than in the previ-
ously considered industrial case.
6. Conclusions
In this work, a general rigorous rate-based model for the
NOx absorption in tray and packed columns has been devel-
oped. The model is based on the film theory and is able to
describe the strong interplay of the reaction, mass and heat
transport. This ability is based on the consideration of the
relevant reaction and diffusion kinetics for all reactions and
components in the film equations. An additional issue has
been the effect of the gas-phase reaction on the gas compo-
sition in the empty sections of a tray column. This effect is
described using the model of an ideal plug flow reactor. Fur-
thermore, the model of a tray unit includes the description
of cooling through cooling coils installed on trays.
The model is verified against experimental data of a pilot
scale packed column and of an industrial sieve tray column
6470 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471

equipped with cooling coils. Good agreement between ex-  density, kg/m3
perimental and simulated data is obtained for both processes.  volumetric hold-up, m3 /m3
This should be regarded as a success, since such processes
are usually difficult to describe adequately due to their ex- Subscripts
tremely high complexity. Thus, the suggested model can be
judged as accurate enough for the description of the NOx
absorption processes in tray columns and as both accurate c concentration-based
and predictive for the NOx absorption in packed columns. e reactant
A comprehensive parameter sensitivity study reveals that for forward reaction
the reaction rate constants of the oxidation reaction (R1) i component index
and the gas–liquid interfacial area have the most significant p product
influence on the process performance. Further, the investi- r reaction index
gation of the effect of column cooling on the process be- t total
haviour shows that there is a clear dependency between the
cooling duty and the NOx absorption rate. Superscripts
The application of the suggested model enables an ac-
curate design and operation of NOx absorption processes
and can be used for other relevant gas–liquid reaction b bulk
systems. f film
G gas phase
Ga gas area
int interface
Notation L liquid phase

a int specific gas–liquid interfacial area, m2 /m3

Acol column cross-section, m2 Acknowledgements
c molar concentration, mol/m3
Dieff effective diffusion coefficient, m2 /s The financial support of the European Commission in the
G total molar gas flow, mol/s context of the Project OPT-ABSO (Contract no. G1RD-CT-
H molar enthalpy, J/mol 2001-00649) is highly appreciated.
kr reaction rate constant of reaction r, diverse, depend-
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