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Computers and Chemical Engineering 32 (2008) 2243–2255

Non-equilibrium stage modeling and non-linear dynamic effects in the

synthesis of TAME by reactive distillation
Amit M. Katariya, Ravindra S. Kamath, Kannan M. Moudgalya, Sanjay M. Mahajani ∗
Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai 400076, India
Received 29 November 2006; received in revised form 28 October 2007; accepted 4 November 2007
Available online 19 November 2007

Abstract
Tertiary-amyl methyl ether (TAME) is a potential gasoline additive that can be advantageously synthesized using the reactive distillation (RD)
technology. This work emphasizes on non-linear effects in dynamic simulations of reactive distillation column. For certain configurations, dynamic
simulation with equilibrium stage (EQ) model leads to sustained oscillations (limit cycles) which have been reported in our earlier work [Katariya,
A. M., Moudgalya, K. M., & Mahajani, S. M. (2006). Nonlinear dynamic effects in reactive distillation for synthesis of TAME. Industrial and
Engineering Chemistry Research, 45 (12), 4233–4242]. Feed condition and Damkohler number are the important parameters that influence the
existence of these effects. To confirm the authenticity of the observed non-linear behaviors, a more realistic and rigorous dynamic NEQ model for
a packed column is developed which uses a consistent hardware design. The steady state behavior of the NEQ model is examined by varying the
number of segments and the column height. The dynamic simulation and the bifurcation study with stability analysis indicate that the parameter
space, in which oscillations may be observed, is shifted in the case of NEQ model.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Reactive distillation; Dynamic simulation; Continuation analysis; Non-equilibrium model; Hopf bifurcation; Oscillations

1. Introduction dealing with departures from equilibrium in multistage towers

Computer-aided design and simulation of multi-component
multistage separation processes such as distillation, gas absorp-
tion and reactive distillation are important aspects of modern
chemical engineering. Currently, such simulations are based
on the well-known equilibrium stage model. The EQ model
assumes that the vapor and liquid leaving a stage are in equi-
librium. Equilibrium stage simulations are frequently termed
rigorous, but this appellation is not entirely justified because in
actual operation, columns rarely, if ever, operate at equilibrium.
The degree of separation is, in fact, determined as much by
mass and energy transfer between the phases being contacted
on a tray or within sections of a packed column, as it is by
thermodynamic equilibrium considerations. The usual way of
Abbreviations: RD, reactive distillation; EQ, equilibrium stage modeling;
NEQ, non-equilibrium stage modeling; MeOH, methanol; 2M1B, 2-methyl 1-
butene; 2M2B, 2-methyl 2-butene; TAME, tertiary-amyl methyl ether; i-PENT,
iso-pentane; Da, Damkohler number; DAE, differential algebraic equation.
∗ Corresponding author. Tel.: +91 22 25767246; fax: +91 22 25726895.
E-mail address: sanjaym@che.iitb.ac.in (S.M. Mahajani).
is through the use of stage and/or overall efficiencies or use of
height equivalent to a theoretical plate (HETP) in case of packed
towers. Though, this may be a useful approach for simulating
an existing column for which there is a good deal of data avail-
able, it may not be possible to predict safely how the column
will perform under quite different operating conditions (Baur,
Higler, Taylor, & Krishna, 2000). Furthermore, it is difficult to
use this approach to simulate new processes in the design stage
for which no plant data exists.
It is advantageous to use NEQ model over the EQ model due
to some of the following reasons. It eliminates the need for effi-
ciencies and HETPs. The operating strategies for the influence
of chemical reactions on separations can be accounted in a bet-
ter way. The over-design or under-design can also be avoided
as the tray and packed columns are modeled with greater accu-
racy thereby reducing the capital and operating costs. Also, as
mentioned before the NEQ model is more realistic as compared
to the EQ model and represents a more accurate modeling of
reactive systems.
The non-equilibrium (NEQ) model assumes that the
vapor–liquid equilibrium is established only at the interface

0098-1354/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2007.11.009
2244 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255

between the bulk liquid and vapor phases, and employs a

Nomenclature transport-based approach to predict the flux of mass and energy
across the interface. Various authors have presented steady state
ai activity coefficient of ith component
non-equilibrium stage models for tray (Baur, Higler, et al., 2000;
Ac interfacial area for vapor–liquid mass transfer
Baur, Krishna, & Taylor, 2003; Baur, Taylor, & Krishna, 2000;
(m2 )
L L Higler, Taylor, & Krishna, 1999;) as well as packed (Asprion,
Ctk , Ctk total concentration of liquid and vapor phase on
2006; Jakobsson, Hasanen, & Aittamaa, 2004; Peng, Lextrait,
k th stage (mol/m3 )
Edgar, & Eldridge, 2002; Sundmacher & Hoffmann, 1996) reac-
D, B molar flow rates of distillate and bottom
tive distillation columns. For the purpose of design, optimal
EkL , EkV liquid and vapor energy holdup of k th stage (J)
operation, and the control of the reactive distillation process,
hLtk , hV
tk liquid and vapor side heat transfer coefficients for a rigorous theoretical dynamic model is required. The modeling
k th stage (W/m2 K)
and simulation with NEQ model is a computationally rigor-
Hk , hk , hfk molar enthalpy of vapor, liquid and feed for k
ous activity as it involves large number of highly non-linear
th stage (J/mol)
L , H̃ V partial molar enthalpy liquid and vapor for ith equations like pressure drop correlations, packing holdup corre-
H̃i,k i,k lations, etc. Hence, there are very few publications on dynamic
component and k th stage (J/mol)
simulation of tray (Baur, Taylor, & Krishna, 2001; Schenk,
kfm forward rate constant of m th reaction
Gani, Bogle, & Pistikopoulos, 1999) and packed (Kreul, Gorak,
(mol/equiv. s)
Dittrich, & Barton, 1998; Noeres, Dadhe, Gesthuisen, Engell,
kL , kV liquid and vapor mass transfer coefficient matri-
& Grak, 2004; Peng, Edgar, & Eldridge, 2003; Xu, Flora, &
ces (m/s)
Rempel, 2005) reactive distillation columns using NEQ model.
Kam equilibrium constant of m th reaction
They differ in the way the mass and heat transfer resistances
KIi,k interface vapor–liquid equilibrium constant of ith
are incorporated in the model. The main differences are (1)
component and k th stage
the use of driving force for the mass transfer: some use con-
MkL , MkV liquid and Vapor molar holdup of k th stage (mol)
centration gradient, whereas others use the correct gradients of
NLk , NV k vectors of liquid and vapor mass transfer fluxes chemical potentials and fugacities; (2) the diffusivity models:
of the order, C − 1 (mol/m2 s) Fick’s law or Stefan–Maxwell approach; (3) number of phases
L V
Ni,k , Ni,k liquid and vapor mass transfer fluxes for ith involved: two phase or pseudo homogeneous model and three
component and k th stage (mol/m2 s) phase heterogeneous model.
Qk heat loss from k th stage (J/s) TAME, a popular fuel additive, is commercially produced
Qr , Qc reboiler and condenser duty (J/s) by reactive distillation through the reaction of methanol with
R reflux ratio isoamylene coming from C5-stream of the refinery. It is a widely
Rm,k rate of m th reaction and k th stage (mol/s) studied model system to understand the complex behavior of
SkV , SkL molar flow of vapor and liquid side streams of k reactive distillation. A few case studies of TAME synthesis in
th stage (mol/s) RD using both EQ and NEQ models have appeared in the liter-
T L , T V , T I liquid, vapor and interface temperatures (K) ature (Baur, Taylor, et al., 2000; Baur et al., 2003; Katariya,
Vk , Lk , Fk molar flow rates of vapor, liquid and feed of k Kamath, Moudgalya, & Mahajani, 2006; Mohl et al., 1999;
th stage, respectively (mol/s) Ouni, Jakobsson, Pyhalahti, & Aittamaa, 2004; Peng et al., 2003;
W weight of the catalyst (kg or equiv.) Subawalla & Fair, 1999). Most of these except that by Peng et al.
xD , xB mole fraction of distillate and bottom (2003) are restricted to steady state analysis. Peng et al. (2003)
xfi,k , yfi,k liquid and vapor feed mole fraction of ith com- have compared the dynamic rate-based and equilibrium models
ponent and k th stage for a packed reactive distillation column for the production of
xi,k , yi,k liquid and vapor mole fractions of ith component tert-amyl methyl ether (TAME) and proposed a new approach
and k th stage to simplify the dynamic rate-based model by assuming the mass
xIi,k , yIi,k interphase liquid and vapor mole fractions of ith transfer coefficients to be time invariant. It can reduce the num-
component and k th stage ber of equations by up to two-third and still accurately predict
the dynamic behavior. A high-index problem in the models may
Greek letters arise if the pressure drop is not related to vapor and liquid flow
δ dirac-delta function rates (Kreul et al., 1998).
k volume or weight of the catalyst for k th stage Synthesis of TAME by reactive distillation is known to exhibit
γi activity coefficient of ith component non-linear dynamic effects such as multiple steady states and
γi,m stoichiometric coefficient of ith component and m relevant literature is reviewed in our earlier work (Katariya,
th reaction Moudgalya, & Mahajani, 2006). We showed for the first time
that under certain conditions, the EQ model based dynamic sim-
ulation of the reactive distillation column exhibits another type
of non-linear effect, i.e. sustained oscillations or limit cycles
(Katariya, Moudgalya, et al., 2006). In order to further examine
the authenticity of this observed non-linear dynamic effect, here
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
we present a rigorous dynamic non-equilibrium model for the
synthesis of TAME in packed RD columns. The model includes
all the essential dynamic terms comprising vapor and liquid
holdups. Since the TAME synthesis is carried out at high pres-
sure (4.5 bar), it is important to consider the vapor mass and
energy holdups in the modeling equations, which are otherwise
neglected in the earlier studies due to index issues (Peng et al.,
2003) and low pressure operations (Noeres et al., 2004). Also,
time variant mass and heat transfer coefficients are considered in
our model, which are made time invariant in the earlier studies
due to computational difficulties and simulation time. We also
present a comparative study of steady state and dynamic simu-
lations using both EQ and NEQ models. Detailed index analysis
of the NEQ model is carried out and the variables responsible
for the higher index in each case are identified and accord-
ingly, model simplifications are made without compromising
on essential dynamic terms. The work by Reepmeyer, Repke,
and Wozny (2004) may be referred to understand and handle
some of the numerical issues involved in the dynamic simula-
tions. Also to systematically investigate the non-linear dynamics
of the system, bifurcation behavior of the simplified NEQ
model with stability analysis has been carried out in some cases
which, to the best of our knowledge, has not been reported till
date.
2. Model description and hardware specification
A rigorous NEQ model has been developed to examine the
effect of column hardware and heat and mass transfer resistances
on the non-linear behavior of the RD column. The purpose is to
compare the performance and behavior with that obtained by
the EQ model in our earlier studies (Katariya, Moudgalya, et
al., 2006). We refer to Powers, Vickery, Arehole, and Taylor
(1988) for detailed model implementation and computational
aspects. In case of NEQ models, the specification of hardware
Fig. 1. The conceptual column configuration used for EQ and NEQ simulations along with the hardware design derived from it.
2245
design information such as column diameter, tray or packing
type and geometry, etc., is mandatory. A packed column has
been selected for the NEQ simulations. Each continuous section
of the packed column is divided into a number of segments,
each of which acts as a non-equilibrium stage. The packing
selected for the reactive and non-reactive rectifying and strip-
ping sections are KATAPAK-S and Sulzer-BX, respectively. The
hydraulic and mass transfer correlations for the selected pack-
ing are obtained from Kolodziej, Jaroszynski, and Bylica (2004)
and Rocha, Bravo, and Fair (1993, 1996), respectively, and are
given in Appendix A.
The preliminary column design for the NEQ model is derived
from the steady state results of the EQ model. The column diame-
ter is estimated by applying the fractional approach to flooding.
The height of each packed section is calculated by multiply-
ing the HETP with the corresponding number of theoretical
stages. The hardware design for the selected conceptual column
configuration is shown in Fig. 1.
2.1. Kinetics and thermodynamics
The following three reactions have been considered while
modeling the process for the synthesis of TAME, which includes
two synthesis reactions for TAME from the isomers of isoamy-
lene and one isomerization reaction. The side reactions such
as dimerization of methanol and formation of TAA have been
neglected. The rate equations are as given below. The tempera-
ture dependent rate constants and the equilibrium constants for
the reactions are obtained from Rihko and Krause (1995) and
Faisal, Syed, and Datta (2000).
MeOH + 2M1B ⇔ TAME,
 
a2M1B 1 aTAME
R1 = kf 1 − 2
aMeOH Ka1 aMeOH
2246 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255

MeOH + 2M2B ⇔ TAME, and liquid streams are not identical. Condenser and reboiler are
  treated as equilibrium stages.
a2M2B 1 aTAME Total material balance equation for the NEQ stage are as
R2 = kf 2 − 2
aMeOH Ka2 aMeOH
dMkL  C
= Lk−1 + FkL − (Lk + SkL ) + Ac Ni,k
L
  dt
a2M1B 1 a2M2B i=1
2M1B ⇔ 2M2B, R3 = kf 3 −
aMeOH Ka3 aMeOH 
r 
C
+ γi,m Rm,k k (1)
As the system consists of mixture of polar and non-polar
m=1 i=1
components, it is highly non-ideal and the use of activity based
kinetics and thermodynamics is justifiable. The UNIQUAC dMkV  C

model has been used for describing non-ideality of the liquid = Vk+1 + FkV − (Vk + SkV ) − Ac Ni,k
V
(2)
dt
i=1
phase, with binary interaction parameters taken from HYSYS.
All the thermodynamic and kinetic parameters used in the Component material balance equation are written as
study have been also reported in our earlier work (Katariya,
dMkL xi,k
Moudgalya, et al., 2006). The process design of the column and = Lk−1 xi,k−1 + FkL xfi,k − (Lk + SkL )xi,k + Ac Ni,k
L
the input conditions have been obtained from Subawalla and Fair dt
(1999). Fig. 1 shows the column configuration along with oper- r

ating and design parameters used for the study. Here, methanol + γi,m Rm,k k (3)
is fed in excess, which is required to form a minimum boiling m=1
azeotrope with inerts (e.g. isopentane) and separate them effi- dMkV yi,k
= Vk+1 yi,k+1 + FkV yfi,k − (Vk + SkV )yi,k − Ac Ni,k
V
ciently from the top of the column. Escess methanol also helps dt
to maintain the desired temperature (330–350 K) in the reactive (4)
section of the column. Also, Subawalla and Fair (1999) have
observed in their analysis that if the methanol used is less than where Ac is the interfacial area for vapor–liquid mass trans-
V and N L are vapor and liquid mass transfer fluxes
fer and Ni,k
the amount required to form an azeotrope then the conversion i,k
of amylene and the purity of the TAME are adversely affected. respectively. Only (C − 1) component material balance equa-
tions are independent, summation constraint on vapor and liquid
phase compositions is used to get the composition of the remain-
2.2. Model equations
ing components.
Energy balance equation:
A schematic representation of the NEQ stage is shown in
Fig. 2. This NEQ stage may represent a tray or a cross-section dEkL
of a packed column. The stage equations are the traditional equa- = Lk−1 hk−1 + FkL hfk − (Lk + SkL )hk − Qk
dt
tions for mass and energy balances for individual phase, in which  
mass and heat transfer rates are also included. Bulk variables C
+ Ac htk (Tk − Tk ) +
L I L L L
Ni,k H̃i,k (5)
(compositions, flow rates, molar fluxes, energy fluxes and tem-
i=1
peratures) are different from the interface variables. Equilibrium
is assumed to be only at the interface and temperatures of vapor dEkV
= Vk+1 Hk+1 + FkV Hfk − (Vk + SkV )Hk
dt
 
C
− Ac htk (Tk − Tk ) +
V V I V V
Ni,k H̃i,k (6)
i=1
V and H̃ V are partial molar enthalpies of vapor and
where H̃i,k i,k
liquid. Vapor–liquid equilibrium at interface can be as given
below.
yIi,k = KIi,k xIi,k (7)
Mass and energy conservation equations for interface can be
written as below. It is assumed that reaction does not take place
in the liquid film.
V
Ni,k = Ni,k
L
(8)

C 
C
hLtk (TkI − TkL ) + L
Ni,k L
H̃i,k = hV
tk (Tk − Tk ) +
V I V V
Ni,k H̃i,k
i=1 i=1
(9)
Fig. 2. The typical NEQ stage representing tray or section of packed column.
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255 2247

Summation constraints for the mole fractions in bulk vapor given in Appendix A. Binary diffusion coefficients in the corre-
and liquid as well as at the interface are written as lations are calculated using method given by Wilke and Chang
(1955) for liquid phase and correlation given by Fuller, Schettler,

C
and Diddings (1966) for gas phase. Maxwell–Stefan diffusivi-
xi,k = 1.0 (10)
ties are derived from these infinite dilution diffusivities (Dijo )
i=1
using Eq. (20).

C
yi,k = 1.0 (11) Dij = (Dijo )(1+xj −xi )/2 (Dji
o (1+xi −xj )/2
) (20)
i=1
The matrix of the thermodynamic factor, [Γ ] is calculated using

C following relation:
xIi,k = 1.0 (12)
∂ ln γi
i=1 Γi,j = δi,j + xi (21)
∂xj

C
yIi,k = 1.0 (13) Damkohler number is a key parameter which is the ratio of
i=1 characteristic residence time to characteristic reaction time. In
the present work Damkohler number is defined based on the total
Fick’s law approach described earlier (Peng et al., 2003) is
feed to the column and total amount of the catalyst used in the
used to calculate the mass transfer fluxes.
column. Boiling point of the lowest boiling component is used

C as the reference temperature.
NLk = CtjL kV (xIk − xk ) + xk L
Ni,k (14)
WT kf ,ref
i=1 Da = (22)
Ftotal

C

k = Ctj k (yk − yIk ) + yk

NV V L V
Ni,k (15) 2.3. Steady state analysis
i=1

where NLk and NV Steady state simulations with the help of developed NEQ
k are the vectors of mass transfer fluxes of
the order (C − 1) for each stage. Only (C − 1) mass fluxes are model are carried out for the design and operating parameters
independent, summation equation of the interface mole fractions given in Fig. 1. This step is mandatory for getting the initial
are used to find the mass flux of the last component. kL and kV steady state required for carrying out the dynamic simulations.
are the mass transfer matrices of order (C − 1) × (C − 1) for Same design and operating parameters as in EQ stage simu-
each stage. lations (Katariya, Moudgalya, et al., 2006) have been used to
We used a method suggested by Krishna and Standart (1976) compare the behavior (P = 4.5 bar, Qreb = 20.5 MW, R =
which involves relating [k∗ ] to the binary pairs of mass transfer 1.5). Pure methanol is fed at the bottom of the reactive zone
coefficients through solution of Maxwell–Stefan equations for whereas the pre-reacted feed was supplied at the midpoint of
film model. Matrices are calculated using following relations non-reactive stripping section.
with assumption that the matrices accounting the influence of The NEQ model equations are implemented in large scale
mass transfer rates on the mass transfer coefficients are identity. equation oriented simulator DIVA (Kroner, Holl, Marquardt, &
Gilles, 1990). DIVA uses the equation-oriented approach for
−1
[kV ] = [BV ] (16) solving all the differential and algebraic equations simultane-
ously. This comes with an inbuilt package for continuation and
L −1
[kV ] = [B ] [Γ L ] (17) stability analysis for the DAEs systems.
Initially the column height in NEQ model was divided in the
The elements of the matrix [B] have been calculated using same number of slices as the number of equilibrium stages, i.e.
the following equations. 33 (4 slices in non-reactive rectifying, 19 slices in reactive sec-
 C tion and 10 slices in non-reactive stripping section). Following
zi zk
Bii = + (18) attempts have been made to arrive at the initial steady state of
κi,C κi,k the NEQ simulations which is required for starting the dynamic
k=1
simulation.
k = i
  1. Steady state simulation of NEQ model: the results from
1 1
Bij = zi − (19) equilibrium stage model were used as initial guesses to the
κi,j κi,C
non-linear algebraic equation solver. The guess values for
where zi is the mole fraction of vapor or liquid phase and κi,j is bulk and interface variables were assumed to be same. Con-
the mass transfer coefficient of the binary pair in an appropriate vergence failed in this case.
phase. The packing selected for the non-reactive and the reactive 2. Steady state simulation of NEQ model with infinite mass and
sections are Suzler-BX and KATAPAK-S, respectively. Corre- heat transfer coefficients: the model when solved with infi-
lations for calculating the binary mass transfer coefficients are nite mass and heat transfer coefficients, is equivalent to the
2248 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
EQ model. This model with the initial guesses same as in an
attempt one above is used for the simulation and a continua-
tion approach was used to reach the finite values of mass and
heat transfer coefficients. In this case also the convergence
could not be obtained due to the non-linearity and interaction
of the pressure drop and holdup equations.
3. Dynamic simulation of rigorous NEQ model: the integration
of the rigorous dynamic model for relatively large time to
arrive at the steady state has been carried out. This attempt
was also failed due to large number of stiff DAEs.
4. Dynamic simulation of constant holdup NEQ model: the
dynamic model was simplified with certain assumptions
like constant molar holdup of liquid and negligible vapor
and energy holdup on each segment of the column and the
required steady state was obtained. This steady state was
then used in further simulations. This approach was found
to work well in most of the cases. The number of segments
in each section of the column was increased such that there
was no further change in the column profiles, conversion of
isoamylene and purity of the TAME in the bottom.
2.4. Influence of number of segments
The effect of the number of segments in the packed sections of
the RD column on the steady state results using the NEQ model
is shown in Fig. 3. When the number of segments in a particular
section is chosen to be same as the number of corresponding
theoretical stages in the EQ model, a significant difference in
the composition profile predicted by the two models is seen but
only in the stripping section. As the number of segments in the
Fig. 3. Comparison of the steady state composition and temperature profiles along the height of the column for the EQ model and NEQ model with various number
of total segments.
stripping section increases, the NEQ profile in the stripping sec-
tion moves in the direction towards the EQ profile, crosses it
and continues to move away from it. Finally a stage is reached
when a further increase in the number of segments does not sig-
nificantly influence the composition profiles. Peng et al. (2002)
have correlated the effect of NEQ segments with the extent of
back-mixing. At very large number of segments, back-mixing in
liquid and vapor phases is virtually absent and there is no effect
of further change in the number of segments. Thus Fig. 3 shows
that the number of slices, i.e. the extent of back-mixing in the
packed columns strongly influences the composition profile. In
real columns, back-mixing and other non-ideal conditions can-
not be eliminated and hence an appropriate number of segments
should be used. However, this number cannot be determined a
priori. For steady state simulations it was observed that for the
number of segments greater than 189 the composition profiles
do not change significantly.
As discussed before, the objective of the present work is to
confirm whether the oscillations observed in the EQ model pre-
dictions still persist in the case of NEQ simulations. In other
words, we examine whether the consideration of mass and heat
transfer limitations would influence the presence of non-linear
dynamic behavior. The oscillations being a non-linear dynamic
effect, may originate from the nonlinearity in the vapor–liquid
equilibrium relation, reaction kinetics or the functional depen-
dence of the physical properties on the compositions and/or
temperature (Kienle & Marquardt, 2003). Hence, the probabil-
ity of realizing oscillations with NEQ model will be more if we
work in the same region of composition and temperature space
for which the oscillations were observed in the case of the EQ
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
model predictions. As mentioned before, in the case of NEQ
predictions, the composition profiles, conversion of isoamylene
and TAME purity in the bottom are significantly different from
that obtained by the EQ model and are very sensitive to the
change in column height and number of segments. Hence, we
present here two different column designs as mentioned below.
Further we perform dynamic simulations and the bifurcation
analysis in some cases, to explore the possibility of the presence
of oscillations.
• In the first case, we vary the column height, especially that of
the stripping section, such that the composition and temper-
ature profiles and isoamylene conversion/TAME purity are
close to the EQ predictions. The number of segments used
here is such that the back mixing is absent (i.e. 189 segments)
and there is no further change in the composition profile with
increase in number of segments.
• In the second case, the number of segments, which repre-
sent the extent of back-mixing in vapor and liquid phases, is
varied such that composition and temperature profiles of EQ
and NEQ model match reasonably well. This is the case with
partial back-mixing.
3. Case 1: NEQ model without back-mixing
3.1. Influence of height of the stripping section
The steady state result using the NEQ model, with total num-
ber of slices 189, showed a much lower isoamylene conversion
(67.6%) compared to 84.6% obtained in the EQ model. Since
the primary objective was to compare the non-linear dynamic
effects of EQ and NEQ models, getting similar conversions
and end compositions is essential. So, an attempt was made
to change the hardware design (diameter and heights of sec-
tions) estimated from the EQ model to a new design such that
EQ and NEQ models give similar results, and the composition
and temperature profiles roughly lie in the same domain. From
the previous analysis, it is clear that the stripping zone plays
a crucial role in the column behavior. The effect of height of
the stripping section on isoamylene conversion was investigated
using continuation analysis and is shown in Fig. 4. Surprisingly,
conversion of isoamylene increases with decrease in height of
the column. This is clearly a counter-intuitive effect since we
expect that a larger packed height should result in a better
separation and as per the principles of RD, a better separa-
tion of the product TAME from the reactants should result in
enhanced amylene conversion. However, an optimum in conver-
sion was observed beyond which conversion of amylene again
decreases as height is decreased. This is because an increase
in the number of stages in the stripping section results in bet-
ter separation of not only TAME but C5 olefins also, which
are the reactants. C5-olefins under otherwise similar conditions
find the way out from the bottom thereby causing a reduc-
tion in their concentrations in the reactive zone. Hence, the
overall isoamylene conversion decreases with an increase in
the height of the stripping section. This particular effect has
also been confirmed through EQ stage simulations as well.
2249
Fig. 4. Effect of height of the stripping section on the isoamylene conversion.
The optimum stripping height in this case was found to be
about 1.62 m. A height of 1.98 m was selected for the new
design since it not only gives a conversion of isoamylene close
to the optimum but also the conversion and end composition
are very similar to that given by the earlier design with EQ
model.
The steady state composition and temperature profiles of the
NEQ model using this new design are plotted along with that of
the EQ model in Fig. 5. Even though the top and bottom com-
positions and temperature profiles are similar, certain sections
of the stripping zone show different compositions.
3.2. Dynamic simulation
For the NEQ model, the liquid and vapor flow rates in the
packed sections are not responsible for the higher index as alge-
braic equations for these variables in terms of pressure drop and
holdup correlations are incorporated in the model. However,
the liquid and vapor flows associated with the condenser and
the reboiler can pose high-index problems as those are mod-
eled using equilibrium assumptions. One will arrive at index
two DAEs when the equations for the holdup as a function
of vapor and/or liquid flows, e.g. controller equations are not
explicitly considered in the model. If these equations are not
available (open loop column) then some of the differential equa-
tions need to be converted to algebraic equations by neglecting
the dynamics to eliminate the index problem. It can be proved
with the help of a detailed index analysis that at least the fol-
lowing differential equations need to be converted to algebraic
equations:
1. Energy balance for the condenser: this is because condenser
load does not appear in any other algebraic equation.
2. Energy balance for the reboiler: this is to account for reboiler
duty, bottom flow rate or vapor flow from the reboiler depend-
ing upon the bottom specification.
3. Total material balance for the reboiler and condenser: this
is to account for either vapor or liquid flow.
2250 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
Fig. 5. Comparison of composition and temperature profile for the EQ and the NEQ model with the new design.
Apart from this rigorous model, we define constant holdups
dynamic NEQ model as the one in which differential equations
for all the total material and energy balances are converted to
algebraic equations, as was done in the case of the EQ model
(Katariya, Moudgalya, et al., 2006). Starting from a steady state
with the same operating conditions, the dynamics of EQ model,
rigorous NEQ model and the constant holdups NEQ model for a
2% step increase in the pre-reacted feed flow rate have been stud-
ied. As seen from Fig. 6, both the NEQ models show a slightly
different dynamics but reach the same steady state while the
EQ model reaches a different steady state as expected. Both
Fig. 6. Dynamic response of EQ, rigorous and ‘constant holdups’ NEQ model
for a 2% step change in feed flow.
the NEQ models take almost equal computation times since the
total number of equations (differential and algebraic) is the same.
However, the rigorous NEQ model was much more difficult to
converge for larger step changes because of the stiffness issues.
The convergence properties of the constant holdups NEQ model
were very similar to that of the EQ model with almost no conver-
gence problem up to ±5% step changes in operating parameters.
The computation time for the NEQ models was observed to be
almost 15 times higher than that of the EQ model.
Fig. 7 shows the response of the average values of liquid and
vapor side heat and mass transfer coefficients to a step increase
in the pre-reacted feed flow rate using rigorous NEQ model. It
has been seen that for very small changes in the feed there are
significant changes in the heat and mass transfer coefficients.
This justifies the fact that time variant heat and mass transfer
coefficients have to be considered while simulating the NEQ
model for reactive distillation.
To confirm the authenticity of the sustained oscillations
observed in the dynamic EQ model, similar analysis was
repeated with constant holdup NEQ model using the new hard-
ware design (i.e. 189 total number of segments, stripping section
height =2.43 m, reactive section height =8.41 m and rectifying
section height =2.98 m). As seen in Fig. 8, unlike the EQ model,
oscillations were not observed and the system always reaches the
corresponding steady state. Thus, the oscillatory behavior that
existed in the EQ model disappears in the NEQ model for the
desired isoamylene conversion and TAME purity in the bottom.
However, it must be noted that the parameter space wherein the
non-linear dynamic effects are observed in EQ model, is likely
to shift in the case of NEQ model simulations. Such a possibility
can be ascertained only by studying the bifurcation behavior with
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
Fig. 7. Dynamic response of (a) mass transfer coefficient and (b) heat transfer coefficients, in the rigorous NEQ model to a 2% step change in feed flow.
Fig. 8. Dynamic response for change in amylene feed composition for Da = 3.0
using the NEQ model with new design.
respect to all possible parameters and their combinations, using
continuation method coupled with stability analysis, which is
computationally an intensive task.
The presence of non-ideality in terms of the partial back-
mixing may also influence the column performance. Hence the
model with partial back-mixing has been considered in the next
section for the realistic comparison of non-linear dynamics.
4. Case 2: NEQ model with partial back-mixing
As mentioned earlier, it is difficult to perform the bifurcation
and stability analysis of the model with 189 NEQ segments. Also
to have a realistic comparison of non-linear behavior observed
in the EQ stage simulations (Katariya, Moudgalya, et al., 2006),
NEQ model with partial back-mixing is considered. For studying
the detailed bifurcation behavior with stability analysis, simu-
lations were carried out with reduced number of segments such
that the steady state column profiles with both EQ and NEQ
2251
models are close to each other, with approximately same con-
version of isoamylene and the purity of TAME in the bottom.
Fig. 9 shows the steady state composition and temperature pro-
files when the column is divided in 47 segments (6 segments in
non-reactive rectifying section in 2.43 m height, 23 segments
in reactive section in 8.41 m height, and 18 segments in non-
reactive stripping section in 3.4 m height), with almost same
conversion of isoamylene and TAME purity in the bottoms. A
very good match with the base case EQ profiles is observed.
The response of the rigorous NEQ model with partial back-
mixing, constant holdups NEQ model with partial back-mixing
and constant holdup EQ model, to a change in 2-methyl-1-butene
concentration can be seen in Fig. 10. Significant differences
are observed in the responses. As mentioned before, sustained
oscillations are realized only in the case of EQ model. Whereas
oscillations disappear in both the NEQ models under similar
operating conditions.
4.1. Bifurcation analysis of NEQ model with partial
back-mixing
Comparison of the bifurcation diagrams for EQ and NEQ
models is shown in Fig. 11. Both the curves almost overlap
quantitatively but they have different stability behaviors. The
EQ model shows unstable solution branch with the presence of
Hopf bifurcation whereas NEQ model under similar condition
shows the stable solution. This comparison shows that modeling
assumptions have a significant impact on the observed oscilla-
tions in case of EQ model. The difference in the stability of the
two curves in Fig. 11 does not imply that the oscillations have
disappeared in NEQ model. Fig. 12 shows the bifurcation dia-
gram with reboiler duty as a parameter. The presence of the Hopf
bifurcation point is realized in this case. This probably implies
that the parameter space wherein the oscillations were observed
in the case of EQ model has been shifted while dealing with the
NEQ model. Hopf bifurcation is observed at higher reboiler duty.
Fig. 13 shows the bifurcation diagram with respect to Damkohler
number at the corresponding higher reboiler duty. Upto certain
value of the Da (= 4.39), stable steady state is observed, which
then converts to unstable steady state with possible oscillations.
2252 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255

Fig. 9. Steady state composition and temperature profiles: comparison of EQ and NEQ model with partial back-mixing. Da = 3.0Q = 20.5 MW, R = 1.5, P =
4.5 bar. Amylene conversion (EQ) = 0.8457; (NEQ) = 0.8461. TAME purity in bottom (EQ) = 0.8782; (NEQ) = 0.8776.

This behavior is qualitatively similar to that of the EQ model
reported earlier (Katariya, Moudgalya, et al., 2006).
From the foregoing discussion, it is clear that the oscillations
observed in the EQ model are not because of ignoring the trans-
port processes. To understand the cause behind this effect, it may
be useful to study separately each of the modeling entities, such
as column stages, condenser and reboiler. Methanol–isopentane
mixture, which is realized as a distillate, has been observed to
exhibit phase splitting under certain conditions. Also the work by
Zayer, Kulkarni, Kienle, Kumar, and Pushpavanam (2007) iden-
tifies the role of energy balance formulation in the dynamics of
CSTR and reactive flash. This work may be extended to the mul-

Fig. 10. Comparison of the step (10% increase) response in 2M1B concentration
in feed for EQ, rigorous NEQ and constant holdup NEQ models: plot of TAME Fig. 11. Comparison of the bifurcation diagrams of EQ and NEQ models: plot of
purity in bottom vs. time (operating and design parameters: Da = 3.0, Q = bottom temperature vs. Damkohler number as continuation parameter (operating
20.5 MW, R = 1.5, P = 4.5 bar.) and design parameters: Q = 20.5 MW, R = 1.5, P = 4.5 bar).
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
Fig. 12. Bifurcation diagrams of NEQ models: plot of bottom temperature vs. re-
boiler duty as continuation parameter (operating and design parameters: Da =
3.0, R = 1.5, P = 4.5 bar).
Fig. 13. Bifurcation diagrams of NEQ models: plot of bottom temperature vs.
Damkohler number as continuation parameter (operating and design parameters:
Q = 20.82 MW, R = 1.5, P = 4.5 bar).
tistage columns and more specifically to TAME synthesis. It has
been noticed that the assumption of pseudo-steady state energy
balance, especially for the condenser and reboiler, strongly in-
fluences the dynamic behavior, often resulting in oscillations.
A detailed investigation on these aspects is expected to give a
better insight into the nonlinear dynamics of TAME synthesis
in reactive distillation. A preliminary study of these topics is
available in Katariya (2007).
5. Conclusion
A rigorous dynamic NEQ stage model has been formulated
and solved for the synthesis of TAME by reactive distillation.
The results of steady state and dynamic simulations using both
EQ model and NEQ models with and without partial back-
mixing are compared. From the steady state analysis of NEQ
2253
model, it is found that the number of segments (extent of
back-mixing) in the stripping section strongly influences the
performance of the NEQ results. A counter-intuitive behavior in
the form of isoamylene conversion increasing with decrease in
the height of the stripping section is observed. Also the dynamic
response of time variant mass and heat transfer coefficients show
significant variation when small disturbances are introduced.
This implies that consideration of time variant mass and heat
transfer coefficient is important. Synthesis of TAME in RD may
be associated with non-linear dynamic effects like limit cycles,
which are confirmed by dynamic simulation using an EQ model
in our earlier studies. However, NEQ model simulations in the
same parameter space and operating region do not reveal such
phenomena. The oscillatory behavior that existed in the EQ
model has been shifted to a new parametric space in the case
of NEQ model that considers partial back-mixing.
To summarize, in order to explain the oscillations observed
in a simple EQ model, we have studied in detail a complex and
computationally rigorous NEQ model that incorporates concen-
tration dependent heat and mass transfer coefficients. Steady
state and dynamic simulations, along with bifurcations studies,
have confirmed the existence of oscillations in the NEQ model
as well. We believe that the effect of possible liquid phase split-
ting and dynamic energy balance may provide an explanation to
this phenomenon.
Acknowledgement
Authors would like to acknowledge Max Planck Institute for
Dynamics of Complex Technical Systems, Magdeburg, Sand-
torstr.1, 39106, Germany for providing the DIVA simulation
environment which has been used for bifurcation analysis in the
present work.
Appendix A. Calculation of mass transfer coefficients
A.1. Non-reactive SULZER BX packing (Rocha et al., 1993,
1996)
Void fraction:  = 0.9; packing area (m2 /m3 ): a = 492; chan-
nel flow angle: θ = 60; channel side (mm): 8.9.
• Gas phase calculations:
   
kg S (Uge + ULe )ρg S 0.8 μg 0.33
= 0.054 (23)
Dg μg D g ρg
Ugs
Uge = (24)
(1 − hL ) sin θ
ULs
ULe = (25)
hL sin θ
where Uge and ULe is the effective gas and liquid velocity in
m/s, respectively, Ugs and ULs the superficial gas and liquid
velocity in m/s, respectively, kg the mass transfer coefficient
in m/s (for binary pair), S the characteristic length, i.e. side
dimension of the corrugation crass-section (m), hL the frac-
2254 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255

tional liquid holdup, μg and μL the gas and liquid viscosity in crimp height (mm): 11.5; crimp wavelength (mm): 21.8; thick-
Pa s and Dg and DL are the gas and liquid diffusion coefficient ness of single sandwich (mm) =21.8.
in m2 /s (for binary pair).
• Liquid phase calculations: • Mass transfer coefficient: for ReL = 13 − 320
 
DL CE ULe 0.5 ShL = 3.846 × 10−3 Re0.667
L ScL0.5 ,
kL (m/s) = 2 (26)
πS for 630 < Reg < 2181 (39)
where CE is the factor slightly less than unity to account for
those part of the packed bed that do not encourage the rapid ShL = 9.457 × 10−5 Re0.667
L Re0.482
g ScL0.5 ,
surface renewal (CE = 0.9) for 2181 < Reg < 5900 (40)
• Hydraulic calculations:
   1/3 Shg = 0.0476 Re0.736 Re0.229 Scg0.33 ,
Ft 2/3 3μL ULs g L
hL = 4 (27)
S ρL sin θgeff for ReL = 15.2 − 360 and Reg = 610 − 5920 (41)

Ft = 29.12(WeL FRL )0.15

μg μL kg de
Scg = , ScL = , Shg = ,
S 0.359 ρg D g ρg D L Dg
× 0.2 (28)
ReL 0.6 (1 − 0.93 cos γ)(sin θ)0.3 kL ν 2 gog de goL de
ShL = , Reg = , ReL = ,


DL μg μL
ρL − ρg (P/z)
geff = g 1− (29) gog deK
ρl (P/z)flood RegK = , deK = 4K/a,
μg
2 ρ S
ULs L  1/3
WeL = (30) 1 mu2L
σ K= and ν2 =
2
1 + (4/ap D) ρL2 g
ULs
FRL = (31) where de = 4/ap is the hydraulic packing diameter (m) for
Sg
mass transfer.
ULs SρL • Hydraulic calculations:
ReL = (32)
μL
 
5 ReL = 7.3 − 530 and RegK = 620 − 5900
P Pd 1
= (33)
z z 1 − K 2 hL
  hd = 0.0273 Re0.331
L (42)
Pd
= AUgs2
+ BUgs (34)   0.5
z 4Fs 2σ(1 − cos γ)
hstat = (43)
0.177ρg S gρL (1 − ρg /ρL ) sin θ
A= (35)
S2 (sin θ)2 • Pressure drop calculations:
Limited to 70% of the flooding point, i.e. for given liquid
88.774μg load, gas velocity does not exceed 70% of its value corre-
B= (36)
S 2  sin θ sponding to flooding.
K2 = 0.614 + 71.35S (37) P Pdry
⎛ = , ReL < 94 (44)
 0.111 ⎞ H H
ae U 2
β= = ⎝1 − 1.203 Ls ⎠ (38) P Pdry
ap Sg = 0.716 exp(0.00357 ReL ), 94 ≤ ReL ≤ 264
H H
where ae is the effective interfacial area (m2 /m3 ), ap the area (45)
of packing (m2 /m3 ), σ the surface tension (N/m), cos γ =
P Pdry
0.9 for σ < 0.055, cos γ = 5.211.1016.835σ for σ > 0.055 and = 0.443 exp(0.00539 ReL ),
P/z is the pressure drop per unit section height (Pa/m). H H
264 < ReL < 630 (46)
A.2. Reactive KATAPAK packing (Kolodziej et al., 2004)

Void fraction (m3 /m3 ):  = 0.622; packing area or specific Pdry ψaρg w2og
= (47)
surface area (m2 /m3 ): a = 128.2; corrugation angle: θ = 45; H 83 K
 A.M. Katariya et al. / Computers and Chemical Engineering 32 (2008) 2243–2255
ψ = 6.275 Re−0.293
gK , 550 < RegK < 1550,
ψ = 6.561 Re−0.171
gK , 1550 ≤ RegK < 6000 (48)
where wog is the superficial velocity (m/s) of gas and Fs =
0.018.
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