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

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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

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Reactions and Separations

Rate-Based/OCFE Model Rate-Based/Staged Model

binary pair parameters (7). The Pitzer model (8, 9) can


be used for aqueous electrolyte systems up to 6 mol/kg Rate-Based
ionic strength. The models require different parameters, Interface
such as pure-component dielectric constants of nonaque- Gas Gas Liquid Liquid
ous solvents, Born radii of ionic species, and binary and Bulk Film Film Bulk
(for the Pitzer model) ternary interaction parameters.
The electrolyte solution chemistry involves a variety Materials Streams
Energy Streams
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- Figure 2. Schematic of the OCFE and the full column model
formulation for a configuration with multiple feed and recycle
tems. Concentration or activity-based reaction equilibri- streams (blue lines) and heat-transfer streams (orange lines).
um constants as functions of temperature can be found in
the literature. 1115) is that the stagewise domain within a column section,
The presence of electrolyte species makes calculation defined as the part of the column between two consecutive
of relevant diffusion coefficients crucial. The effective streams entering or leaving the column, is considered to be a
diffusion coefficients for electrolyte components can be continuous analog. Subsequently, molar and enthalpy
obtained from the Nernst-Hartley equation for dilute solu- flowrate profiles within such a column section are treated as
tions and from the Gordon equation for higher electrolyte continuous functions of the longitudinal coordinate in the
concentrations (10). The driving force due to electrical column. The approximating power of the OCFE model lies
potential difference also needs to be taken into account in the fact that the behavior within a specific column section
(1), which is done by introducing the electrical potential can be accurately approximated by fewer balance equations
gradient into the generalized driving force di: (applied only at selected points namely the collocation
x 1 d i F 1 d points) than a traditional stage-by-stage formulation. The
di = i + xi zi i =1 n (9)
RT L d RT L d greatest advantage is that the form of the balance equations
at the selected collocation points is entirely preserved; hence,
In dilute electrolyte systems, the diffusional interactions the rate-based model formulation as previously described is
can usually be neglected, and the generalized Maxwell- fully maintained.
Stefan equations are reduced to the Nernst-Planck equa- An important feature of the OCFE approximation model
tions (1). In all cases, the electroneutrality condition must shown schematically in Figure 2 is that stages at which
be met at each point of the liquid phase: feed or side-draw material streams are attached are treated
n as discrete stages, thus isolating abrupt and sharp changes
xi zi = 0 (10) in the concentration and temperature profiles in the column
i =1 approximating scheme. The extent to which the model
order is reduced is dictated by the shape of the approxi-
Reducing the size of the model mated concentration and temperature profiles along a given
The models described in the previous sections, when column section. Consequently, column sections with steep
applied to a tray or packed absorption column (Figure 1), temperature and concentration profiles generally require a
will eventually result in a large set of complex and highly denser pattern of collocation points than column regions
coupled nonlinear equations whose solution may become with relatively flat profiles.
quite tedious. Several online applications, such as operator In design optimization, the decision variables involve
training, and process control and optimization, require the the overall column configuration (e.g., the number of
solution within a reliably defined timeframe. This can be stages in each column section, the locations of material
achieved by formulating the rate-based model in a compact and energy feed and side-draw streams, etc.) and the col-
form, for example by using the orthogonal collocation on umn operating conditions (e.g., solvent flowrate, stage
finite elements (OCFE) model. The OCFE formulation cooling/heating, recycle scheme, etc.). The OCFE model
reduces the overall size of the reactive absorption process formulation transforms the otherwise discrete decision
model (in terms of the total number of equations) while problem (e.g., calculation of the optimal number of dis-
preserving the models structure and accuracy. crete stages in the column) to a continuous design opti-
The basic concept behind this efficient approximating mization problem, where the size of the column sections
technique (mathematical details can be found in Refs. becomes a continuous degree of freedom, thus facilitating

68 www.aiche.org/cep January 2009 CEP


solution of the problem. Rounding up to the next-highest experimental data generated through experiments in the
integer value leads to the optimal number of stages. This reactive absorption column. During the experimental runs
is of particular interest in synthesis problems where the (planned using statistical design of experiments tech-
optimal interconnectivity of multiple sequential separa- niques (19)), one or more input process variables to the
tions is sought (16) as the overall number of required inte- reactive absorption column are changed deliberately in
ger decision variables is significantly reduced. order to record the effect these changes have on the out-
put process variables (responses).
Enhancing the predictive power The accuracy of model parameter estimates is
of a reactive absorption model improved by centering the joint confidence region (JCR)
Liquid- and gas-side film thicknesses depend strongly of the model parameter estimates on their true values, and
on the flow pattern in the column, the type of column their precision is subsequently increased by reducing the
internals, and gas and liquid physical properties, such as volume of the multi-dimensional JCR. Statistical correla-
surface tension, diffusivity and viscosity. Similarly, spe- tion of model parameter estimates provides a measure of
cific contact area, which, in general, differs from the the degree to which two or more parameters co-vary
geometric surface area of the column internals, strongly under certain experimental conditions, and is mainly char-
depends on the flow pattern and physical properties of acterized by the orientation of the JCR. In general, a
the fluids. In simple packed beds (e.g., packed with small (with respect to volume) and spherical JCR cen-
rings or saddles), it is possible that, at moderate liquid tered at the true values of the model parameters is the
loads, the packing surface is not completely covered, so most desirable situation.
the mass transfer occurs through a smaller area than the To satisfy (all or a subset of) the aforementioned objec-
geometric surface area. The opposite situation, in which tives, the inputs to the process system should be selected in
the phase interface is larger than the geometric surface such a way that the system response becomes sensitive to
area, is also possible. its major model parameters. Reactive absorption process
Values of film thicknesses, specific contact area, and models can then be utilized in the calculation of optimal
mass transfer coefficients are most often determined by experimental runs. Several techniques are available (19)
empirical correlations, which allow scale-up to different based on a variety of objective functions that are intended
operating states. The liquid- and gas-phase mass-transfer to improve the quality of parameter estimates. Key deci-
coefficients are usually related to Sherwood number (Sh); sions in designing new steady-state and dynamic experi-
the latter is represented as a function of Reynolds number ments involve the choice and characteristics of the input
(Re), Schmidt number (Sc) and other dimensionless variables to the system (usually these are the manipulated
process characteristics (17, 18). It is important that the variables of the control system), the selection of a suitable
correlations are applied to conditions within their range set of measured variables (e.g., stages with temperature
of validity. sensors or composition analyzers), and the sampling rate.
Additional parameters related to the empirical correla- The duration of an experimental run depends on the system
tions are the liquid hold-up on the relevant column inter- dynamics and the time it takes to reach the final steady
nals and the pressure drop caused by the flow resistance in state (which is proportional to the dominant system time
the column. The liquid hold-up is necessary both for the constant). Combining all these elements within a unified
liquid-phase reaction description and for the estimation of optimal experimental-design framework that utilizes the
the gas-phase hold-up in the case of gas-phase reactions. rate-based model provides a well-defined context for
The pressure drop can influence primarily the phase equi- improving the predictive power of the model for reactive
librium and hold-up. These parameters also depend on the absorption columns.
operating conditions, column internals type, and physical
properties. In some cases, hold-up and pressure drop are NOx absorption example
coupled and cannot be calculated explicitly, so they are Absorption of nitrous gases is an important operation in
determined iteratively (18). The range of application for the chemical process industries, used mainly in the produc-
each correlation depends on the actual column loads, as tion of nitric acid and in the purification of exhaust gas
both hold-up and pressure drop strongly depend on hydro- streams. It is a highly complex process due to the interac-
dynamic interactions. tion of several components and chemical reactions in both
Selecting the proper correlation is mostly a question of the liquid and gas phases. This example demonstrates the
column operating regime and user experience. Mass- ability of the rate-based modeling approach to accurately
transfer correlations must be compared and validated with predict the steady-state and dynamic column behavior of

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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. 1, a gas stream containing 20 mol% nitrogen oxides is
Chemical reactions are important in NOx absorption absorbed by an aqueous solution containing 5 mol%
because they enhance the absorption of components that nitric acid. The inlet gas stream of Column 2 contains
are otherwise insoluble in water (e.g., NO) through their 10.2 mol% nitrogen oxides and is treated by an aqueous
chemical transformation to more soluble components (e.g., solution containing 2.65 mol% nitric acid.
NO2). Nitric acid is produced through the complex reaction Figure 3 compares the simulated axial profiles of the
mechanism detailed in Table 1 (2022). The oxidation of total NOx concentration in the gas phase for Columns 1
NO to NO2 (RR1) is the slowest reaction, and thus is the and 2 with reported experimental measurements (shown
limiting step (21). Diffusion coefficients in the gas phase with 5% error bars). For Column 1, the calculated total
were estimated using the Chapman-Enskog-Wilke-Lee NOx concentration at the top of the column shows good
model (7) and in the liquid phase using the method pro- agreement with the experiments, as the maximum deviation
posed in Ref. 23. The liquid-phase activity coefficients is less than 5%. Figure 4 presents the simulated axial pro-
were calculated using the NRTL activity model, and all files of the liquid-phase temperature and measured values
other necessary thermodynamic calculations were based on for both columns. The liquid temperature profiles reveal a
the Soave-Redlich-Kwong equation of state. maximum in the lower section of each column, which is
Validation for a packed column. The model was imple- typical for NOx absorption processes (24). The absolute
mented using the commercial simulator Aspen Custom deviation between the simulated and measured liquid tem-
Modeler (www.aspentech.com), which utilizes Aspen peratures is 4.5C for Column 1 and 3.8C for Column 2,
Properties to calculate the required physical properties. which can be attributed to heat losses through the column
Validation was performed by comparing simulation wall because the experimental column was not insulated.
results with experimental data for three pilot-scale Validation for a tray column. The design details of a
columns connected countercurrently (22). Simulations for tray column are given in Table 2. A gas stream containing
two of these columns are presented here. 0.77 mol% nitrogen oxides is treated with an aqueous solu-
The simulated units have a simple configuration, with tion containing 0.68 mol% nitric acid. To maintain a fairly
one liquid inlet stream at the top and one gas inlet constant temperature profile, seven trays in the lower part
stream at the bottom. Both columns have a diameter of
0.254 m and are filled with a random packing (16-mm
5
steel Pall rings) to a packing height of 6 m. In Column 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 Recycle Stream Flowrate 4.55 mol/s
the gas phase, the nitric acid concentration in the liquid phase,
and the measured values. for better control of the HNO3 concentration in the product
stream, which is subject to quality constraints. Similarly,
of the column are equipped with cooling coils fed with the concentration of NOx components in the gas stream at
152 m3/h water at an average temperature of 23.6C. the top of the column is subject to composition constraints
The resulting rate-based model was solved using due to environmental regulations. Inlet stream data for the
gPROMS, an integrated process modeling environment column are provided in Table 3.
(www.psenterprise.com). Figure 5 shows the calculated Applying the OCFE model formulation, the absorption
axial profiles of the total NOx concentration in the gas column is partitioned into three sections with boundaries
phase and the nitric acid concentration in the liquid phase, defined by the location of the side feed and draw streams
as well as the measured inlet and outlet values (with a attached to the column (15). Each column section is further
measurement error of 15%). The experimental and simulat- partitioned into a number of finite elements. However, the
ed values of the total NOx reveal a maximum deviation of six oxidation stages at the bottom of the column are treated
8.5%, and the deviation of the simulated HNO3 concentra- as discrete stages. The resulting model is only one-third the
tion from the experimental value is within 10%. Thus, the size of the respective tray-by-tray model.
agreement is good, as all deviations lie within the measure- Control of the total NOx composition in the fluegas
ment error margins. The simulated outlet temperature of stream is achieved by adjusting the temperature profile in
the cooling water is 24.8C. This agrees very well with the the column. Three PID controllers use temperature meas-
measured value of 24.9C (deviation <1%). From the urements at selected stages, which act as inferential vari-
results of both pilot plant and industrial applications, it can ables of NOx
be concluded that the suggested model demonstrates good composition at H2 O
accuracy for the highly complex NOx absorption process. the effluent gas
AC
Improving column operation through design optimiza- stream, to Fluegas
NOx Specifications
tion and control. A similar example involves an industrial manipulate the
column that comprises 44 trays with an internal diameter of cooling water
3.6 m. Tray spacing is 0.9 m, except at the bottom of the flowrate in the
column. The oxidation reaction (RR1) takes place mainly 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.

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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- EUGENY KENIG, PhD, is professor and chair of the Fluid Process Engineering in
ing, design optimization, and steady-state operation opti- the Mechanical Engineering Dept. at the Univ. of Paderborn (Pohlweg 55,
33098 Paderborn, Germany; Phone: +49 5251 60 2408; E-mail:
mization. Rate-based models using the two-film theory and eugeny.kenig@upb.de). He worked for the Russian Academy of Sciences, and
adapted to the particular features of reactive absorption later became a postdoctoral fellow at the Univ. of Dortmund. He also worked
units provide a reliable modeling framework. OCFE tech- for BASF AG in Ludwigshafen, Germany, before returning to Dortmund as a
professor. His main expertise is in the mathematical modeling and simulation
niques allow for significant reduction of model size (in of complex process systems (reactive and hybrid separations,
terms of the number of modeling equations) without com- microseparations, design and optimization of column internals). He has
authored more than 200 publications and has participated in the research
promising the accuracy of the model predictions. Hence, and coordination activities of several large European and joint national
the predictive power of rate-based models has been effi- projects. A member of DECHEMA, Kenig holds an MS in applied mathematics
ciently combined with the systematic and adaptable from the Moscow Univ. of Oil and Gas, a PhD in chemical engineering from
the Russian Academy of Sciences, and a DSci and a Venia Legendi from the
approximating properties of the OCFE technique. Univ. of Dortmund.
Examples given in this article demonstrate the accuracy PANOS SEFERLIS, PhD, is an assistant professor in the Dept. of Mechanical
of the models and the successful implementation in design Engineering at Aristotle Univ. of Thessaloniki (AUTh) and a collaborating
researcher in the Chemical Process Engineering Research Institute (CPERI) at
and control applications. CEP the Centre for Research and Technology Hellas (CERTH) (P.O. Box 484, 54124,
Thessaloniki, Greece; Phone: +30 2310 99 4229; E-mail: seferlis@auth.gr). His
interests are in the areas of automatic control of process and mechanical
systems, integrated process design and control, and optimization. Prior to
coming to AUTh in 2006, he worked for CPERI for six years, he was a
Acknowledgements
postdoctoral fellow at Delft Univ. of Technology, the Netherlands, and he
The experimental data for industrial-scale one-pass sieve tray column in the worked for Honeywell Hi-Spec Solutions in Canada. He has authored more
NOx absorption example were provided in the context of research funded than 50 publications and is a member of AIChE and the Society for Industrial
by the European Commission, Project OPT-ABSO (G1RD-CT-2001-00649). and Applied Mathematics (SIAM). He has a BS in chemical engineering from
AUTh and a PhD in chemical engineering from McMaster Univ. in Canada.

Literature Cited
1. Taylor, R., and R. Krishna, Multicomponent Mass 14. Huss, R. S., and A. W. Westerberg, Collocation Methods
Transfer, Wiley, Hoboken, NJ (1993). for Distillation Design. 1. Model Description and Testing,
2. Doraiswamy, L. L., and M. M. Sharma, Heterogeneous Ind. Eng. Chem. Res., 35 (5), pp. 16031610 (1996).
Reactions: Analysis, Examples and Reactor Design, Wiley, 15. Dalaouti, N., and P. Seferlis, A Unified Modeling
Hoboken, NJ (1984). Framework for the Optimal Design and Dynamic Simulation
3. Danckwerts, P. V., Gas-Liquid Reactions, McGraw-Hill, of Staged Reactive Separation Processes, Comput. Chem.
New York, NY (1970). Eng., 30, pp. 12641277 (2006).
4. Seader, J. D., The Rate-Based Approach for Modeling 16. Algusane, T. Y., et al., A Framework for the Synthesis of
Staged Separations, Chem. Eng. Progress, 85 (10), Reactive Absorption Columns, Chem. Eng. and Process., 45
pp. 4149 (1989). (4), pp. 276290 (2006).
5. Kenig, E. Y., Modeling of Multicomponent Mass Transfer in 17. Sherwood, T. K., and R. L. Pigford, Absorption and
Separation of Fluid Mixtures, VDI-Verlag, Dsseldorf, Extraction, McGraw-Hill, New York, NY (1952).
Germany (2000). 18. Billet, R., and M. Schultes, Prediction of Mass Transfer
6. Kenig, E. Y., et al., Rigorous Dynamic Modeling of Columns with Dumped and Arranged Packings, Trans.
Complex Reactive Absorption Processes, Chem. Eng. Sci., IChemE, 77 A, pp. 498504 (1999).
54, pp. 51955203 (1999). 19. Atkinson A. C., and A. N. Donev, Optimum Experimental
7. Reid, R., et al., The Properties of Gases and Liquids, Designs, Oxford Univ. Press, Oxford, U.K. (1992).
McGraw-Hill, New York, NY (1987). 20. Joshi, J. B., et al., Absorption of NOx Gases. Chem. Eng.
8. Pitzer, K. S., and G. Mayorga, Thermodynamics of Comm., 33, pp. 192 (1985).
Electrolytes. II. Activity and Osmotic Coefficients for Strong 21. Emig, G., et al., Absorption with Simultaneous Complex
Electrolytes with One or Both Ions Equivalent, J. Phys. Reactions in Both Phases, Demonstrated by the Modeling and
Chem., 77, pp. 23002308 (1973). Calculation of a Counter-Current Flow Column for the
9. Pitzer, K. S., Thermodynamics of Electrolytes. I. Production of Nitric Acid, Comput. Chem Eng., 3,
Theoretical Basis and General Equations, J. Phys. Chem., pp. 143150 (1979).
77, pp. 268277 (1973). 22. Suchak, N. J., et al., Modeling and Simulation of NOx
10. Horvath, A. L., Handbook of Aqueous Electrolyte Absorption in Pilot-Scale Packed Columns, AIChE J., 37,
Solutions, Ellis Horwood, Chichester, U.K. (1985). pp. 323339 (1991).
11. Stewart, W. E., et al., Simulation of Fractionation by 23. Siddiqi, M. A., and K. Lucas, Correlations for Prediction of
Orthogonal Collocation, Chem. Eng. Sci., 40 (3), pp. 409421 Diffusion in Liquids, Canad. J. Chem. Eng., 64 (5),
(1985). pp. 839843 (1986).
12. Swartz, C. L. E., and W. E. Stewart, A Collocation 24. Hpen, B., and E. Y. Kenig, Rigorous Modelling of NOx
Approach to Distillation Column Design, AIChE J., 32 (11), Absorption in Tray and Packed Columns, Chem. Eng. Sci.,
pp. 18321838 (1986). 60, pp. 64626471 (2005).
13. Seferlis, P., and A. N. Hrymak, Optimization of Distillation 25. Dalaouti, N., and P. Seferlis, Design Sensitivity of Reactive
Units Using Collocation Models, AIChE J., 40, pp. 813825 Absorption Units for Improved Dynamic Performance and
(1994). Cleaner Production: The NOx Removal Process, J. of Cleaner
Production, 13, pp. 14611470 (2005).

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