Reactions and Separations

Modeling

Effective modeling of reactive absorption

Eugeny Kenig
Univ. of Paderborn enhances system design, improves
experiment planning for parameter
Panos Seferlis
Aristotle Univ. of Thessaloniki estimation, and facilitates process
operation and control decisions.

R
eactive absorption i.e., the absorption of gases in
liquid solutions accompanied by chemical reactions
is an important industrial operation for the produc-
tion of basic chemicals (e.g., sulfuric or nitric acid) and for the
removal of harmful substances (e.g., H2S) from gas streams.
In recent decades, this process has become especially impor-
tant for the purification of gases to high purities. Unlike physi-
cal absorption (without reactions), reactive absorption is able
to provide high throughput at moderate partial pressures and
without requiring large amounts of solvent.
The advantages of combining chemical reactions with
absorption are realized only in the region of low gas-phase
concentrations due to the liquid-load limitations imposed
by the reaction stoichiometry or equilibrium. Other factors
that may limit the efficiency of reactive absorption are the
heat liberated by exothermal reactions and the difficulty of
solvent regeneration. Most reactive absorption processes
are steady-state operations involving reactions in the liquid
phase, although some applications involve both liquid-
phase and gas-phase reactions.
Reactive absorption is a complex rate-controlled process
that occurs far from thermodynamic equilibrium. Therefore,
the equilibrium concept is often insufficient to describe it,
and instead, accurate and reliable models involving the
process kinetics (rate-based models) are required. The effec-
tiveness of online model-based applications, such as process
control and optimization, depends strongly on the quality of
the available model predictions.
Equilibrium stage model
Modeling and design of reactive absorption processes
are usually based on the equilibrium stage model, which
assumes that each gas stream leaving a tray or a packing
segment (stage) is in thermodynamic equilibrium with the
corresponding liquid stream leaving the same tray or seg-
ment. For reactive absorption, the chemical reaction must
also be taken into account.
With very fast reactions, the reactive separation
process can be satisfactorily described assuming reaction
equilibrium. A proper modeling approach is based on the
nonreactive equilibrium stage model, which is extended
by simultaneously considering the chemical equilibrium
relationship and the tray or stage efficiency. If the reac-
tion rate is slower than the mass-transfer rate, the influ-
ence of the reaction kinetics increases and becomes a
dominating factor. This tendency is taken into account by
integrating the reaction kinetics into the mass and energy
balances. This approach is widely used today.
In real reactive absorption processes, thermodynamic
equilibrium is seldom reached. Therefore, correlation
parameters such as tray efficiencies or height equivalent to
a theoretical stage (HETS) values are introduced to adjust
the equilibrium-based theoretical description to real column
conditions. However, reactive absorption occurs in multi-
component mixtures, for which this simplified concept
often fails (1).
The acceleration of mass transfer due to chemical reac-

CEP January 2009 www.aiche.org/cep 65

Reactions and Separations

Two-Film Model

Stage 1 Film Interface Film A similar equation can be written

for the gas phase. Thus, the gas-liq-
yiB yiI uid mass transfer is modeled as a
Stage S combination of the film model
xi I
xiB
presentation and the Maxwell-
Stefan diffusion description. In this
Gas Phase Liquid Phase
stage model, equilibrium is
y x
Stage N assumed at the interface only.
Packed Tray The film thickness represents a
Column Column model parameter that can be esti-
mated using the mass-transfer
Figure 1. The column discretization and the two-film model for the stage description.
coefficient correlations governing
the mass transport dependence on
tions in the interfacial region is often accounted for via so- physical properties and process hydrodynamics. These
called enhancement factors (2, 3). These are either obtained correlations are usually obtained experimentally and are
by fitting experimental results or derived theoretically available from the literature. Another important parameter
based on simplified model assumptions. However, it is not of the film model is the specific contact (interfacial) area,
possible to derive the enhancement factors properly from which is also estimated from experimental data.
data on binary experiments, and a theoretical description of Balance equations. The component mass-balance equa-
reversible, parallel or consecutive reactions is based on tions of the rate-based models are written separately for
rough simplifications. each phase, and, due to the presence of chemical reactions,
include the reaction source terms (6). Considering the
Rate-based stage model process dynamics, these equations become:
A more physically consistent way to describe a column mLi B

stage is the rate-based approach (4). This approach directly
t
=
l
( ) (
LxiB + N Li B I
)
a + rLiB L Ac i = 1 n (2)
considers actual rates of multicomponent mass and heat
transfer and chemical reactions. mGi B

Mass transfer at the gas-liquid interface can be described
t
=
l
( ) (
GyiB N Gi B I
)
a rGiB G Ac i = 1 n (3)
using different theoretical concepts (1, 5). Usually, the two-
film model or the penetration/surface-renewal model are Equations 2 and 3 are valid for continuous systems
used, and the model parameters are estimated via empirical (packed columns). For discrete systems (tray columns),
correlations. The advantage of the two-film model is that the differential terms on the right-hand side become finite
there is a broad spectrum of correlations available in the lit- differences and the balances are reduced to ordinary dif-
erature for all types of column internals. ferential equations (5).
In the two-film model (Figure 1), it is assumed that the If chemical reactions take place in the liquid phase only
resistance to mass transfer is concentrated entirely in thin (which is true for most reactive absorption processes), the
films adjacent to the phase interface, and that mass transfer reaction term in Eq. 3 is omitted.
occurs within these films by steady-state molecular diffu- Equations 2 and 3 are supplemented by the summation
sion alone. Outside the films, in the fluid bulk phases, the equation for the liquid and gas bulk mole fractions:
level of mixing is assumed to be sufficiently high so that n n
there is no composition gradient i.e., one-dimensional xi
B
= 1 yiB = 1 (4)
diffusion transport normal to the interface takes place. i = 1 i = 1

Multicomponent diffusion in the films can be described The volumetric liquid hold-up, L, depends on the gas
by the Maxwell-Stefan equations that relate components and liquid flowrates in the column and is calculated by
diffusion fluxes to their chemical potential gradients. In a empirical correlations. To determine axial temperature pro-
generalized form, the Maxwell-Stefan equations can be files, differential energy balances that include the product
used for the description of real gases and liquids (1). For of the liquid molar hold-up and the specific enthalpy as
the liquid phase: energy capacity are formulated. The energy balances for
n x N x N continuous systems are:
xi d i
=
i Lj j Li
di = i =1 n (1) U LB
RT dz j =1 cLt Dij
t
=
l
( ) ( )
LhLB + QLB a I Ac - qLloss (5)

66 www.aiche.org/cep January 2009 CEP

UGB
t
=
l
( ) ( )
GhGB QGB a I Ac - qGloss (6)
aI
Nomenclature
= specific contact area, m2/m3
Ac = cross-sectional column area, m2
Mass transfer and reaction coupling in the fluid film. c = molar concentration, kmol/m3
The component fluxes, NiB, in Eqs. 2 and 3 are determined d = mass-transport driving force, m-1
based on the mass transport in the film region. The descrip- D = Maxwell-Stefan diffusivity, m2/s
tion of the film phenomena is usually reduced to a steady- F = Faradays constant = 9.65104 C/mol
state problem (6). The key assumptions of the film model G = gas-phase stream molar flowrate, kmol/s
h = molar enthalpy, kJ/kmol
result in one-dimensional mass transport normal to the
l = axial coordinate, m
interface, and the differential component-balance equations L = liquid-phase stream molar flowrate, kmol/s
including simultaneous mass transfer and reaction in the m = length-specific molar hold-up, kmol/m
film are: n = number of components, dimensionless
dN Li N = molar flux, kmol/(m2-s)
rLi = 0 i =1 n (7) P = pressure, Pa
dz qloss = length-specific heat loss, kJ/(m-s)
Q = heat flux, kW/m2
Equation 7 is generally valid for both liquid and gas
r = reaction rate, kmol/(m3-s)
phases if reactions take place in both phases. It represents R = universal gas constant = 8.3144 kJ/(kmol-K)
the differential mass balance for the film region including t = time, s
the source term due to the reaction. The component fluxes T = temperature, K
are expressed in terms of concentrations using Eq. 1, U = length-specific energy hold-up, kJ/m
whereas the source terms result from the reaction kinetics x = mole fraction of component in liquid phase
description and usually represent nonlinear dependencies y = mole fraction of component in gas phase
z = normal coordinate, m
on the mixture composition and temperature of the corre-
zi = ionic charge, dimensionless
sponding phase.
The boundary conditions for Eq. 7 are those typical for Greek Letters
the film model and specify the values of the mixture com- = film thickness, m
= volumetric hold-up, m3/m3
position at both film boundaries. They are applicable to = electrical potential, V
both phases; for the liquid phase they are: = film coordinate, dimensionless
xi ( z = 0 ) = xiI xi ( z = L ) = xiB i =1 n (8) = chemical potential, kJ/kmol
Subscripts
Combining Eqs. 7 and 8 results in a set of vector-type G = gas phase
boundary value problems that permits the component con- i, j = component or reaction index
centration profiles to be obtained as functions of the film L = liquid phase
coordinate. These concentration profiles allow the compo- t = mixture property
nent fluxes to be determined. Thus, the boundary value Superscripts
problems describing the film phenomena have to be solved B = bulk phase
in conjunction with all other model equations. I = interface
An analytical solution of this boundary value problem in
a closed matrix form can be obtained (5) if some further equations is completed with the continuity equations for
assumptions concerning the linearization of the diffusion and the mass and energy fluxes at the phase interface.
reaction terms are made. On the other hand, the boundary
values need to be determined from the total system of equa- Handling electrolyte systems
tions describing the process. The bulk values in both phases Reactive absorption processes occur mostly in aque-
are found from the balance relationships, Eqs. 2 and 3. The ous systems, with both molecular and electrolyte species.
interfacial liquid-phase concentrations are related to the rele- These systems demonstrate substantially nonideal behav-
vant gas-phase concentrations, yiI, by the thermodynamic ior. Two basic models are employed for the thermody-
equilibrium relationships and by the continuity condition for namic description of electrolyte-containing mixtures, the
the molar fluxes at the interface (1, 5). Electrolyte NRTL model and the Pitzer model. The
Due to the chemical conversion in the liquid film, the Electrolyte NRTL model is able to estimate the activity
molar fluxes at the interface and at the boundary between coefficients for both ionic and molecular species in aque-
the film and the bulk of the phase differ. The system of ous and mixed-solvent electrolyte systems based on the

CEP January 2009 www.aiche.org/cep 67

Reactions and Separations
binary pair parameters (7). The Pitzer model (8, 9) can
be used for aqueous electrolyte systems up to 6 mol/kg
ionic strength. The models require different parameters,
such as pure-component dielectric constants of nonaque-
ous solvents, Born radii of ionic species, and binary and
(for the Pitzer model) ternary interaction parameters.
The electrolyte solution chemistry involves a variety
of chemical reactions in the liquid phase. These reactions
occur very rapidly, so chemical equilibrium conditions
are often assumed. Therefore, chemical equilibrium cal-
culations are of special importance for electrolyte sys-
tems. Concentration or activity-based reaction equilibri-
um constants as functions of temperature can be found in
the literature.
The presence of electrolyte species makes calculation
of relevant diffusion coefficients crucial. The effective
diffusion coefficients for electrolyte components can be
obtained from the Nernst-Hartley equation for dilute solu-
tions and from the Gordon equation for higher electrolyte
concentrations (10). The driving force due to electrical
potential difference also needs to be taken into account
(1), which is done by introducing the electrical potential
gradient into the generalized driving force di:
x 1 d i F 1 d
di = i + xi zi i =1 n (9)
RT L d RT L d greatest advantage is that the form of the balance equations
In dilute electrolyte systems, the diffusional interactions
can usually be neglected, and the generalized Maxwell-
Stefan equations are reduced to the Nernst-Planck equa-
tions (1). In all cases, the electroneutrality condition must
be met at each point of the liquid phase:
n as discrete stages, thus isolating abrupt and sharp changes
xi zi = 0 (10)
i =1
Reducing the size of the model
The models described in the previous sections, when
applied to a tray or packed absorption column (Figure 1),
will eventually result in a large set of complex and highly
coupled nonlinear equations whose solution may become
quite tedious. Several online applications, such as operator
training, and process control and optimization, require the
solution within a reliably defined timeframe. This can be
achieved by formulating the rate-based model in a compact
form, for example by using the orthogonal collocation on
finite elements (OCFE) model. The OCFE formulation
reduces the overall size of the reactive absorption process
model (in terms of the total number of equations) while
preserving the models structure and accuracy.
The basic concept behind this efficient approximating
technique (mathematical details can be found in Refs.
68 www.aiche.org/cep January 2009 CEP
Rate-Based/OCFE Model Rate-Based/Staged Model
Rate-Based
Interface
Gas Gas Liquid Liquid
Bulk Film Film Bulk
Materials Streams
Energy Streams
Figure 2. Schematic of the OCFE and the full column model
formulation for a configuration with multiple feed and recycle
streams (blue lines) and heat-transfer streams (orange lines).
1115) is that the stagewise domain within a column section,
defined as the part of the column between two consecutive
streams entering or leaving the column, is considered to be a
continuous analog. Subsequently, molar and enthalpy
flowrate profiles within such a column section are treated as
continuous functions of the longitudinal coordinate in the
column. The approximating power of the OCFE model lies
in the fact that the behavior within a specific column section
can be accurately approximated by fewer balance equations
(applied only at selected points namely the collocation
points) than a traditional stage-by-stage formulation. The
at the selected collocation points is entirely preserved; hence,
the rate-based model formulation as previously described is
fully maintained.
An important feature of the OCFE approximation model
shown schematically in Figure 2 is that stages at which
feed or side-draw material streams are attached are treated
in the concentration and temperature profiles in the column
approximating scheme. The extent to which the model
order is reduced is dictated by the shape of the approxi-
mated concentration and temperature profiles along a given
column section. Consequently, column sections with steep
temperature and concentration profiles generally require a
denser pattern of collocation points than column regions
with relatively flat profiles.
In design optimization, the decision variables involve
the overall column configuration (e.g., the number of
stages in each column section, the locations of material
and energy feed and side-draw streams, etc.) and the col-
umn operating conditions (e.g., solvent flowrate, stage
cooling/heating, recycle scheme, etc.). The OCFE model
formulation transforms the otherwise discrete decision
problem (e.g., calculation of the optimal number of dis-
crete stages in the column) to a continuous design opti-
mization problem, where the size of the column sections
becomes a continuous degree of freedom, thus facilitating
solution of the problem. Rounding up to the next-highest
integer value leads to the optimal number of stages. This
is of particular interest in synthesis problems where the
optimal interconnectivity of multiple sequential separa-
tions is sought (16) as the overall number of required inte-
ger decision variables is significantly reduced.
Enhancing the predictive power
of a reactive absorption model
Liquid- and gas-side film thicknesses depend strongly
on the flow pattern in the column, the type of column
internals, and gas and liquid physical properties, such as
surface tension, diffusivity and viscosity. Similarly, spe-
cific contact area, which, in general, differs from the
geometric surface area of the column internals, strongly
depends on the flow pattern and physical properties of
the fluids. In simple packed beds (e.g., packed with
rings or saddles), it is possible that, at moderate liquid
loads, the packing surface is not completely covered, so
the mass transfer occurs through a smaller area than the
geometric surface area. The opposite situation, in which
the phase interface is larger than the geometric surface
area, is also possible.
Values of film thicknesses, specific contact area, and
mass transfer coefficients are most often determined by
empirical correlations, which allow scale-up to different
operating states. The liquid- and gas-phase mass-transfer
coefficients are usually related to Sherwood number (Sh);
the latter is represented as a function of Reynolds number
(Re), Schmidt number (Sc) and other dimensionless
process characteristics (17, 18). It is important that the
correlations are applied to conditions within their range
of validity.
Additional parameters related to the empirical correla-
tions are the liquid hold-up on the relevant column inter-
nals and the pressure drop caused by the flow resistance in
the column. The liquid hold-up is necessary both for the
liquid-phase reaction description and for the estimation of
the gas-phase hold-up in the case of gas-phase reactions.
The pressure drop can influence primarily the phase equi-
librium and hold-up. These parameters also depend on the
operating conditions, column internals type, and physical
properties. In some cases, hold-up and pressure drop are
coupled and cannot be calculated explicitly, so they are
determined iteratively (18). The range of application for
each correlation depends on the actual column loads, as
both hold-up and pressure drop strongly depend on hydro-
dynamic interactions.
Selecting the proper correlation is mostly a question of
column operating regime and user experience. Mass-
transfer correlations must be compared and validated with
experimental data generated through experiments in the
reactive absorption column. During the experimental runs
(planned using statistical design of experiments tech-
niques (19)), one or more input process variables to the
reactive absorption column are changed deliberately in
order to record the effect these changes have on the out-
put process variables (responses).
The accuracy of model parameter estimates is
improved by centering the joint confidence region (JCR)
of the model parameter estimates on their true values, and
their precision is subsequently increased by reducing the
volume of the multi-dimensional JCR. Statistical correla-
tion of model parameter estimates provides a measure of
the degree to which two or more parameters co-vary
under certain experimental conditions, and is mainly char-
acterized by the orientation of the JCR. In general, a
small (with respect to volume) and spherical JCR cen-
tered at the true values of the model parameters is the
most desirable situation.
To satisfy (all or a subset of) the aforementioned objec-
tives, the inputs to the process system should be selected in
such a way that the system response becomes sensitive to
its major model parameters. Reactive absorption process
models can then be utilized in the calculation of optimal
experimental runs. Several techniques are available (19)
based on a variety of objective functions that are intended
to improve the quality of parameter estimates. Key deci-
sions in designing new steady-state and dynamic experi-
ments involve the choice and characteristics of the input
variables to the system (usually these are the manipulated
variables of the control system), the selection of a suitable
set of measured variables (e.g., stages with temperature
sensors or composition analyzers), and the sampling rate.
The duration of an experimental run depends on the system
dynamics and the time it takes to reach the final steady
state (which is proportional to the dominant system time
constant). Combining all these elements within a unified
optimal experimental-design framework that utilizes the
rate-based model provides a well-defined context for
improving the predictive power of the model for reactive
absorption columns.
NOx absorption example
Absorption of nitrous gases is an important operation in
the chemical process industries, used mainly in the produc-
tion of nitric acid and in the purification of exhaust gas
streams. It is a highly complex process due to the interac-
tion of several components and chemical reactions in both
the liquid and gas phases. This example demonstrates the
ability of the rate-based modeling approach to accurately
predict the steady-state and dynamic column behavior of
CEP January 2009 www.aiche.org/cep 69
Reactions and Separations

Table 1. Nitric acid is produced Table 2. Design parameters for

through a series of reactions. the industrial sieve tray column.
Gas-Phase Column Diameter 3.8 m
RR1 2 NO + O2 2 NO2 Number of Trays 20
RR2 2 NO2 N2O4 Plate Spacing 0.9 m
RR3 3 NO2 + H2O 2 HNO3 + NO Weir Height 0.25 m
RR4 NO + NO2 N2O3 Weir Length 3.015 m
RR5 NO + NO2 + H2O 2 HNO2 Flow Path 2.3 m
Number of Holes 54,000
Liquid-Phase Hole Diameter 2.2 mm
RR6 N2O4 + H2O HNO2 + HNO3 Distance between
RR7 3 HNO2 HNO3 + H2O +2 NO Holes (Pitch) 13 mm
RR8 N2O3 + H2O 2 HNO2 Hole Diameter 2.2 mm
RR9 2 NO2 + H2O HNO2 + HNO3

industrial and experimental columns.
Chemical reactions are important in NOx absorption
because they enhance the absorption of components that
are otherwise insoluble in water (e.g., NO) through their
chemical transformation to more soluble components (e.g.,
NO2). Nitric acid is produced through the complex reaction
mechanism detailed in Table 1 (2022). The oxidation of
NO to NO2 (RR1) is the slowest reaction, and thus is the
limiting step (21). Diffusion coefficients in the gas phase
were estimated using the Chapman-Enskog-Wilke-Lee
model (7) and in the liquid phase using the method pro-
posed in Ref. 23. The liquid-phase activity coefficients
were calculated using the NRTL activity model, and all
other necessary thermodynamic calculations were based on
the Soave-Redlich-Kwong equation of state.
Validation for a packed column. The model was imple-
mented using the commercial simulator Aspen Custom
Modeler (www.aspentech.com), which utilizes Aspen
Properties to calculate the required physical properties.
Validation was performed by comparing simulation
results with experimental data for three pilot-scale
columns connected countercurrently (22). Simulations for
two of these columns are presented here.
The simulated units have a simple configuration, with
one liquid inlet stream at the top and one gas inlet
stream at the bottom. Both columns have a diameter of
0.254 m and are filled with a random packing (16-mm
steel Pall rings) to a packing height of 6 m. In Column
1, a gas stream containing 20 mol% nitrogen oxides is
absorbed by an aqueous solution containing 5 mol%
nitric acid. The inlet gas stream of Column 2 contains
10.2 mol% nitrogen oxides and is treated by an aqueous
solution containing 2.65 mol% nitric acid.
Figure 3 compares the simulated axial profiles of the
total NOx concentration in the gas phase for Columns 1
and 2 with reported experimental measurements (shown
with 5% error bars). For Column 1, the calculated total
NOx concentration at the top of the column shows good
agreement with the experiments, as the maximum deviation
is less than 5%. Figure 4 presents the simulated axial pro-
files of the liquid-phase temperature and measured values
for both columns. The liquid temperature profiles reveal a
maximum in the lower section of each column, which is
typical for NOx absorption processes (24). The absolute
deviation between the simulated and measured liquid tem-
peratures is 4.5C for Column 1 and 3.8C for Column 2,
which can be attributed to heat losses through the column
wall because the experimental column was not insulated.
Validation for a tray column. The design details of a
tray column are given in Table 2. A gas stream containing
0.77 mol% nitrogen oxides is treated with an aqueous solu-
tion containing 0.68 mol% nitric acid. To maintain a fairly
constant temperature profile, seven trays in the lower part
5
Column 1
Simulation
4 Experiment
Packing Height, m

5 Column 2
Simulation
Column 1 3
Experiment
Packing Height, m

4 NOx, Simulation
NOx, Experiment
3 2
Column 2
2 NOx, Simulation
1
NOx, Experiment
1
0
0 20 25 30 35 40 45 50 55
0.04 0.06 0.08 0.10 0.12 0.14 0.18 0.22
Molar Fraction Temperature, C

Figure 3. An axial profile of the total gas-phase NOx Figure 4. An axial profile of the liquid temperature of
concentration of Columns 1 and 2 and their measured values. Columns 1 and 2 and their measured values.

70 www.aiche.org/cep January 2009 CEP

 18 Table 3. Stream data for the
NOx, Simulation NOx absorption column shown in Figure 6.
16
HNO3, Simulation
14 NOx, Experiment
Gas Inlet Stream (Bottom) Liquid Inlet Stream (Top)
Column Height, m

HNO3, Experiment
12
10 NO 21.83 mol/s H2O 4.55 mol/s
8 NO2 58.08 mol/s T 293 K
6
N2O4 20.11 mol/s
O2 82.74 mol/s Side Feed Stream
4
N2 1016.44 mol/s
2 H2O 34.62 mol/s
T 332 K
0 HNO3 6.02 mol/s
P 5.6 bar
0.00 0.01 0.1 1 NO2 0.41 mol/s
Molar Fraction T 306 K

Figure 5. An axial profile of the total NOx concentration in
the gas phase, the nitric acid concentration in the liquid phase,
and the measured values.
of the column are equipped with cooling coils fed with
152 m3/h water at an average temperature of 23.6C.
The resulting rate-based model was solved using
gPROMS, an integrated process modeling environment
(www.psenterprise.com). Figure 5 shows the calculated
axial profiles of the total NOx concentration in the gas
phase and the nitric acid concentration in the liquid phase,
as well as the measured inlet and outlet values (with a
measurement error of 15%). The experimental and simulat-
ed values of the total NOx reveal a maximum deviation of
8.5%, and the deviation of the simulated HNO3 concentra-
tion from the experimental value is within 10%. Thus, the
agreement is good, as all deviations lie within the measure-
ment error margins. The simulated outlet temperature of
the cooling water is 24.8C. This agrees very well with the
measured value of 24.9C (deviation <1%). From the
results of both pilot plant and industrial applications, it can
be concluded that the suggested model demonstrates good
accuracy for the highly complex NOx absorption process.
Improving column operation through design optimiza-
tion and control. A similar example involves an industrial
column that comprises 44 trays with an internal diameter of
3.6 m. Tray spacing is 0.9 m, except at the bottom of the
column. The oxidation reaction (RR1) takes place mainly
Recycle Stream Flowrate 4.55 mol/s
for better control of the HNO3 concentration in the product
stream, which is subject to quality constraints. Similarly,
the concentration of NOx components in the gas stream at
the top of the column is subject to composition constraints
due to environmental regulations. Inlet stream data for the
column are provided in Table 3.
Applying the OCFE model formulation, the absorption
column is partitioned into three sections with boundaries
defined by the location of the side feed and draw streams
attached to the column (15). Each column section is further
partitioned into a number of finite elements. However, the
six oxidation stages at the bottom of the column are treated
as discrete stages. The resulting model is only one-third the
size of the respective tray-by-tray model.
Control of the total NOx composition in the fluegas
stream is achieved by adjusting the temperature profile in
the column. Three PID controllers use temperature meas-
urements at selected stages, which act as inferential vari-
ables of NOx
composition at H2 O
the effluent gas
AC
stream, to Fluegas
NOx Specifications
manipulate the
cooling water
flowrate in the
stage coils. Cooling System

over the bottom six trays, where larger spacing is used for Another PID H2O, HNO3
TC
higher gas-phase hold-up to enhance the NO oxidation. controller
Three independent water-cooling systems control the col- directly controls
TC
umn temperature. In general, low column temperatures the NOx compo-
favor both the NO oxidation reaction and the absorption of sition at the
NO2 in water. Empirical correlations were used for pres- fluegas stream TC
sure drop, liquid-phase hold-up, film thickness, and stage through the
interfacial area for sieve plate calculations (15). manipulation of LC
In the column configuration shown in Figure 6, a gas the solvent
stream with a high concentration of NOx enters the bottom (water) flowrate Air, NOx
of the reactive absorption column, a liquid water stream at the top of the
enters at the top, and a weak solution of nitric acid enters column.
as a side feed stream. The bottom liquid stream, an aque- Dynamic simu- Figure 6. A schematic representation
of a NO absorption column with its
ous nitric acid solution, is partially recycled in the column lation runs using control xsystem.

CEP January 2009 www.aiche.org/cep 71

Reactions and Separations

0.015 Table 4. Column design configuration

NO2 Composition, Molar Fraction

at different operating conditions.

0.0145
Case B
0.014 (Operation
Case A and Column
0.0135
(Operation Configuration
Optimization) Optimization)
0.013
Column Specifications
0.012
NOx in Gas Outlet* < 0.0125 < 0.0125
0.0125 HNO3 in Liquid Product* > 0.32 > 0.32
0 0.5 1 1.5 2 2.5 3
Time, h Number of Stages
Top Section 19 10
Middle Section 18 27
Figure 7. Fluegas composition closed-loop response to a step
change in the NOx composition of the inlet gas stream. Liquid Feed Stream Flowrates
Solvent (Top), mol/s 25 25
gPROMS, shown in Figure 7, demonstrate the ability of Side Stream, mol/s 44.93 42.67
the control system to successfully compensate for the
effects of disturbances in the NOx concentration of the Cooling Water Flowrates
Side Stream Feed Stage, mol/s 10 10
inlet gas stream. Middle Section, mol/s 247.47 247.09
A viable alternative for improving the operation of the Bottom Section, mol/s 100 100
NOx absorption column (25) involves determining a suit-
able column configuration at different operating modes. Outlet Stream Concentrations
NOx in Gas Outlet* 0.0117 0.0115
Absorption columns are often equipped with piping to sup- 0.3222 0.3216
HNO3 in Liquid Product*
ply the feed streams at multiple locations. Design optimiza- 72,634 69,074
Total Cost, $/yr
tion determines the best location and distribution of the side
feed and recycle streams at different operating conditions *molar fraction
(e.g., variable feed gas composition and/or variable fluegas
and product stream specifications). Table 4 shows that a stages (the six stages from column bottom) were selected
4.9% improvement in operating costs can be achieved as input variables in order to obtain the necessary informa-
through a suitable column configuration (calculation of the tion for parameter estimation. Temperature and the compo-
optimal position of the side feed streams to the column), sition of the liquid and gas bulk phases at the bottom oxi-
solvent flowrates, and cooling policy in the entire column. dation stages were selected as feasible measured variables.
Experimental design for improved parameter estimation. The optimal steady-state experimental conditions (as
An experimental design was performed for the NOx dictated by the cooling water flowrates) were calculated by
absorption column described to estimate the kinetic param- minimizing the volume of the joint confidence region for
eters in reactions RR1 and RR3 (Table 1). Since the rates the kinetic parameter estimates (19). The experimental
of reactions RR1 and RR3 are strongly affected by temper- design capabilities of gPROMS were used to solve the
ature, the cooling water flowrates at the column oxidation resulting optimization problem using the rate-based/OCFE
model of the absorption column.
Figure 8 shows the surface reduction of the JCR for the
Arbitrary Design two kinetic parameters. The dashed contour corresponds to
1.1 Optimal Design
the JCR of the kinetic parameter estimates for two arbi-
Kinetic Parameter for RR3

1.05 trarily selected steady-state experiments. The solid contour

represents the JCR for the kinetic parameters achieved
1 with the addition of an optimally designed experiment. In
the optimally designed experimental run, the bottom three
0.95 stages are operated at higher temperatures and stages four
through six at lower temperatures. In both cases, model
0.9
parameters have been scaled to unity at the nominal oper-
0.85 ating point to enable good numerical conditioning.
0.986 0.988 0.99 0.992 0.994 0.996 0.998 1 1.002 1.004
Kinetic Parameter for RR1 Final thoughts
Detailed and accurate models are essential for numerous
Figure 8. Joint confidence region for the kinetic parameter
estimates for RR1 and RR3. online and offline reactive absorption column applications,

72 www.aiche.org/cep January 2009 CEP

including control performance evaluation, operator train-
ing, design optimization, and steady-state operation opti-
mization. Rate-based models using the two-film theory and
adapted to the particular features of reactive absorption
units provide a reliable modeling framework. OCFE tech-
niques allow for significant reduction of model size (in
terms of the number of modeling equations) without com-
promising the accuracy of the model predictions. Hence,
the predictive power of rate-based models has been effi-
ciently combined with the systematic and adaptable
approximating properties of the OCFE technique.
Examples given in this article demonstrate the accuracy
of the models and the successful implementation in design
and control applications. CEP
Acknowledgements
The experimental data for industrial-scale one-pass sieve tray column in the
NOx absorption example were provided in the context of research funded
by the European Commission, Project OPT-ABSO (G1RD-CT-2001-00649).
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CEP January 2009 www.aiche.org/cep 73