Ind. Eng. Chem. Res.

2010, 49, 3275–3285 3275

Optimal Design of Staged Three-Phase Reactive Distillation Columns Using

Nonequilibrium and Orthogonal Collocation Models
Theodoros Damartzis† and Panos Seferlis*,†,‡
Chemical Process Engineering Research Institute, Centre for Research and TechnologysHellas,
P.O. Box 60361, 57001 Thermi-Thessaloniki, and Department of Mechanical Engineering, Aristotle UniVersity
of Thessaloniki, P.O. Box 484, 54124 Thessaloniki, Greece

Reactive distillation with potential liquid-phase split and subsequent formation of a third phase is a highly
complex process system nevertheless quite common in the production of useful solvents and biofuels through
esterification. The optimal design of such process systems requires the development and solution of reliable
and accurate process models that lead to a computationally demanding mathematical problem. In this work,
a nonequilibrium (NEQ) model coupled with the orthogonal collocation on finite elements (OCFE) technique
is developed for the simulation and optimal design of three-phase reactive distillation systems. The resulting
NEQ/OCFE model combines the predictive accuracy of the NEQ model as well as the model reduction and
approximation capabilities of the OCFE formulation. Therefore, an accurate but compact in size and thus
easier to solve model that accounts for all the physical phenomena, the interactions among the multiple phases,
and the occurring chemical reactions becomes available. The NEQ/OCFE model is enriched with an accurate
prediction procedure for the identification and tracking of the phase transition boundaries (point of transition
for a single liquid phase to two liquid-phase regimes and vice versa) inside the column for varying operating
conditions. The model is validated using experimental results and utilized in the optimal design and the
dynamic simulation of a staged reactive distillation column for the production of butyl acetate via the
esterification reaction of butanol with acetic acid. The optimal column configuration defined by the number
of stages in each column section, the feed strategy (single feed or multiple feed points), the location of the
feed stages, and the operating conditions are calculated through a rigorous design optimization procedure for
tight production purity specifications. At optimal conditions the specific column appears to have both two-
and three-phase regions that are separated by the feed stage.

1. Introduction component in the reactive mixture aims to create such thermo-

Reactive distillation (RD) is a relatively new and attractive
enhancement of the classical distillation processes. The incor-
poration of chemical reactions and product separation into one
single process may result in significant economical benefits due
to a drastic reduction of investment costs and higher product
yields when compared to conventional reaction distillation
processes especially for chemical equilibrium controlled reac-
tions with substantial volatility differences among reactants and
products. Reactive distillation has been mainly used for the
industrial production of ether and acetate solvents such as
TAME (tert-amyl methyl ether), MTBE (methyl tert-butyl
ether), and esters such as methyl, ethyl, and butyl acetate.
The achieved process intensification results in higher overall
efficiency, but in the meantime process complexity increases
significantly. Indeed, reactive distillation is a complex unit
operation, where simultaneous mass and energy transfer, coupled
with phase equilibrium and reactive phenomena, occurs. The
reactive separation system becomes even more perplexed when
the formation of a second liquid phase is favored by thermo-
dynamics in some sections of the distillation column. The
splitting of a single liquid phase into two distinct liquid phases
is a phenomenon that cannot be neglected in design, simulation,
and control of the reactive separation system as it may greatly
affect the product stream quality and subsequently the overall
column performance. On several occasions, the addition of a
* To whom correspondence should be addressed. Tel.: +30 2310
994229. E-mail: seferlis@auth.gr.
†
Centre for Research and TechnologysHellas.
‡
Aristotle University of Thessaloniki.
10.1021/ie901260b  2010 American Chemical Society
Published on Web 03/04/2010
dynamic conditions that favor the formation of a second liquid
phase for the efficient separation of azeotropic mixtures.
Phase transition phenomena greatly complicate the associated
process modeling equations due to the higher degree of
nonlinearity that is introduced. Furthermore, phase transition
causes discontinuities in the model due to the spontaneous
appearance and disappearance of the second liquid phase, thus
increasing model complexity and consequently solution effort.
Another challenge relates to the fact that the boundaries between
the two-phase and three-phase regions in the column are not
known a priori as these are solely determined by the prevailing
conditions within the column that become available only after
a solution has been obtained. This implies that an alternation
of modeling relations that correspond to two- and three-phase
regimes for successive column sections may be required.
Several researchers have studied extensively the optimal
design of three-phase reactive distillation systems. More specif-
ically, Venimadhavan et al.1 and Steinigeweg and Gmehling2
using simplified process models proposed optimal column
configurations and operating conditions for a high-purity butyl
acetate column. Steyer et al.3 proposed a novel reactive
distillation process for the production of cyclohexanol from
cyclohexene and water taking into consideration liquid-phase
splitting. Khaledi and Bishnoi4 and Khaledi and Bishnoi5 used
an equilibrium model to describe three-phase reactive distillation
and examined various reactive systems. Shyamsundar and
Rangaiah6 used an equilibrium model coupled with a fictitious
parameter (τ method) that enabled the tractability of phase
transition boundaries through suitable model structure adjust-
ments. Bruggemann et al.7 and Radulescu et al.8 investigated
3276 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010
the dynamic features of three-phase reactive distillation systems
using equilibrium models. In addition to modeling, design
optimization has also been examined for reactive distillation
columns using equilibrium models. Gangadwala et al.9 and
Gangadwala and Kienle10 examined various column configura-
tions and case studies for the optimal design of butyl acetate
production via catalytic two-phase reactive distillation using
mixed-integer nonlinear programming.
However, in the aforementioned modeling and design at-
tempts equilibrium models have been employed that require all
phases present in a column tray to be in thermodynamic
equilibrium. While the equilibrium model provides greater
simplicity, it does not provide a realistic representation of the
phenomena occurring during reactive distillation, leading to
discrepancies between simulated predictions and experimental
data. Such a process can be described in a more accurate way
by introducing a nonequilibrium (NEQ) or rate-based model.11,12
Lao and Taylor11 developed an NEQ model for a single
distillation stage which was later expanded for an entire column
by Higler et al.12 Higler et al.12 provide the most comprehensive
NEQ model for conventional three-phase distillation, which was
tested for its accuracy of predictions in a number of relevant
separation systems. While these two works consider the general
case of rate-based mass and energy transfer among all three
phases, Eckert and Vanek13 used an NEQ model assuming that
the two liquid phases are in equilibrium with each other. This
last assumption is an interesting physical and mathematical
simplification that applies in cases where strong agitation of
the liquid phases is present.
Evidently, the employment of NEQ models further increases
the complexity and size of the resulting process model.
Unfortunately, such highly complex models consist of a very
large set of nonlinear differential algebraic equations (DAEs)
that require significant computational effort usually forbidding
real time applications. In addition, it is necessary to develop a
technique that would enable the identification of the phase
transition boundaries and also trace the phase discontinuities
inside the column as the operating conditions change in design
optimization problems or dynamic simulations. Such require-
ments necessitate that the developed process model possesses
the flexibility to adapt in terms of model structure as phase
transition points emerge or disappear within the column domain.
Approximating techniques such as orthogonal collocation on
finite elements (OCFE) provide a solid solution to the significant
reduction in terms of the total number of modeling equations
without compromising the resolution of modeling details. OCFE
is a technique that transforms the column in a continuous
analogue, thus eliminating the need for integer design variables
associated with the existence of column trays, thus tackling the
discrete character of staged distillation columns. The OCFE
formulation approximates the temperature and composition
profiles in staged or packed columns by continuous polynomial
functions of position inside the column. Consequently, the OCFE
formulation uses a smaller set of equations, proportional to the
degree of the approximating polynomials, to describe the
reactive distillation process than other conventional modeling
methods and in this way reduces the computational effort for
the solution of the model. Moreover, the approximation of the
concentration and temperature profiles as continuous functions
of position in the column for the OCFE formulation eliminates
the need for the use of integer variables for the representation
of stages as column size becomes a continuously varying
variable. Therefore, the optimal design of staged separation units
can be formulated as a conventional nonlinear program, thus
enormously facilitating the solution effort.
In this work, the NEQ/OCFE model developed by Dalaouti
and Seferlis14 for the optimal design of two-phase columns is
expanded to efficiently model three-phase reactive distillation
units. The model combines the accuracy and validity of a rate-
based model with the approximating properties of the OCFE
formulation. Phase boundaries are predicted and traced by
adaptively placing a finite element breakpoint at the phase
transition points as proposed by Swartz and Stewart.15 Phase
splitting is monitored through liquid-liquid (L-L) flash
calculations for the liquid phases. The model is then employed
for the optimal design and process optimization of a tray reactive
distillation column for the production of butyl acetate.
2. Model Formulation
The NEQ model for a distillation column as presented by
Higler et al.12 involves the description of simultaneous mass
and heat transfer among the existing phases, phase equilibrium
at the interface, and chemical reactions. For the description of
mass transfer near the phase interfaces, the thin film model is
used. According to the latter, the resistance to the mass transfer
is solely located in two thin films adjacent to each interface.
Thermodynamic equilibrium occurs only at the interface, while
the bulk of the phases are in contact only with the corresponding
films. Mass transfer through the thin films is modeled with the
use of the Maxwell-Stefan equations for multicomponent
mixtures. Hydrodynamic conditions determine the interfacial
areas, film thickness, and mass transfer coefficients.
In its most general case, three-phase distillation involves one
gaseous phase and two liquid phases in contact with each other,
leading to three interfaces and six thin films (two for each
interface). According to Higler et al.,12 the second liquid phase
can be considered either as immiscible with or dispersed in the
other liquid phase. In the present work it is assumed that the
second liquid phase is formed as a dispersed phase inside the
bulk of the continuous liquid phase. Therefore, the second liquid
phase is not in direct contact with the gaseous phase, and thus,
only two interfaces are distinct; they are gas-liquid I and liquid
I-liquid II. Possible contact of the gaseous and dispersed liquid
phases would be incidental, and the influence it may have on
the overall column behavior can be considered negligible due
to the short contact time.13
The NEQ model has been proved to be more rigorous and
accurate in the prediction of the column behavior than the
conventional equilibrium model.12,16 The coupling of the NEQ
model with the OCFE formulation creates an NEQ/OCFE model
which combines the accuracy of the rate-based NEQ model with
the model reduction properties of the OCFE formulation. In this
work the generic OCFE formulation developed by Seferlis and
Hrymak17 and Seferlis and Grievink,18 extended for NEQ
modeling relations by Dalaouti and Seferlis,14 and finally
adapted to accommodate the effect of a third phase (dispersed
liquid phase) and equipped with a robust algorithm for the
tracking of the phase transition boundary has been employed.
Following the work of Dalaouti and Seferlis,14 the distillation
column is divided into sections defined as the regions between
two streams entering or leaving the column. Each section is
divided into finite elements (FEs) of variable size, with each
element including a specified number of collocation points (CPs)
determined by the degree of polynomial approximation. The
mass and energy balances are satisfied exactly only at the
position of the designated CP. The collocation points are selected
as the roots of discrete Hahn family orthogonal polynomials.19
 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 3277
the following form for the liquid and gaseous phases:

n
s - sk
WLj (s) ) ∏ s - sk
j ) 0, ..., n (1)
k)0,k*j j

n+1
s - sk
WGj (s) ) ∏ s - sk
j ) 1, ..., n + 1 (2)
k)1,k*j j

Considering the thin film model which assumes that mass and
heat transfer is concentrated in thin films adjacent to the phase
interface, the model representation of each collocation point or
discrete stage for a three-phase system is shown in Figure 2.
Consequently, the mass balances for each phase are as follows:

liquid I phase
Figure 1. Schematic of the NEQ/OCFE formulation in a reactive distillation
column. dmLI
i (sj)
) L̃Ii (sj - 1) - L̃Ii (sj) + (φLI(sj) RLIb
i (sj) +
dt
Hahn orthogonal polynomials would place a collocation point
NGLb
i (sj)aGL - NLLIb
i (sj)aLL)Acol∆h (3)
at the exact location of a column tray in the limiting case that
the number of collocation points equals the number of actual i ) 1, ..., NC j ) 1, ..., n
trays in the column, so that the full-order tray-by-tray model is
recovered. Streams entering or leaving the column are modeled liquid II (dispersed liquid) phase
as discrete stages to isolate discontinuities in the concentration
and temperature profiles. The column condenser, the reboiler, dmLII
i (sj)
and the decanter are also modeled as separate equilibrium stages. ) L̃IIi (sj - 1) - L̃IIi (sj) + (φLII(sj) RLIIb
i (sj) +
dt
In the general case, where the number of collocation points is
much smaller than the number of column trays, the latter can NLIIb LL col
i (sj)a )A ∆h (4)
be extracted by the means of calculating the lengths of the finite
elements in the column. The element length is a design variable i ) 1, ..., NC j ) 1, ..., n
that represents the number of stages that the element accounts gas phase
for. In this way, the total number of stages in the column equals
the sum of the employed element lengths including the discrete dmGi (sj)
stages such as feed stages, the reboiler, and the condenser. A ) G̃i(sj - 1) - G̃i(sj) + (φG(sj) RGb
i (sj) -
schematic representation of the distillation column with one side dt
feed stream and a decanter at the top is depicted in Figure 1.
Gb
Ni (sj)aGL)Acol∆h (5)
The following assumptions are made for the development of
the process model: (1) one-dimensional mass and heat transport i ) 1, ..., NC j ) 1, ..., n
across phase interfaces, (2) thermodynamic equilibrium at phase In the dynamic mass balances above, mi is the component molar
interfaces, (3) no axial dispersion along the distillation column, accumulation which is computed from the relations
(4) no entrainment of the liquid phases in the vapor phase, (5)
complete mixing of bulk phases, (6) no contact between the
gas and dispersed liquid phase, (7) negligible heat transfer LIi (sj)
i (sj) ) φ (sj) d (sj)
mLI LI LI
through the films, (8) negligible pressure drop inside the column. Acol∆h (6)
LIt (sj)
Component molar flow rates and stream molar enthalpies are
approximated by Lagrange interpolating polynomials that take i ) 1, ..., NC j ) 1, ..., n

Figure 2. Schematic stage/collocation point representation of the NEQ/OCFE model.

3278 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010

LIIi (sj) ∂cGLf

i (sj) ∂NGLf
i (sj)
i (sj) ) φ (sj) d (sj)
mLII + - RGLf
i (sj) ) 0
LII LII
Acol∆h (7) (16)
LIIt (sj) ∂t ∂ηGLf

i ) 1, ..., NC j ) 1, ..., n i ) 1, ..., NC j ) 1, ..., n 0 < ηGLf e δGLf(sj)

Gi(sj) col
mGi (sj) ) φG(sj) dG(sj) A ∆h (8) boundary conditions
Gt(sj)
i ) 1, ..., NC j ) 1, ..., n i (sj) ) Ni (sj)
NLIb GLf
|ηGLf)δGLf(sj)
i (sj) ) xi (sj)
xLIb GLf
|ηGLf)δGLf(sj)
where φ stands for the phase volumetric holdup fraction and d (17)
stands for the phase molar density at each collocation point.
The total molar flow rates and molar fractions for each phase i ) 1, ..., NC j ) 1, ..., n
are computed from the component flow rates as follows:
L-L interface, liquid I side film
NC
LIi (sj)
∑ L (s ) ) L (s )
I
i j
I
t j i (sj) )
xI,Lb
LIIt (sj)
(9) ∂cLLIf
i (sj)
+
∂NLLIf
i (sj)
- RLLIf (sj) ) 0 (18)
i)1 i
∂t LLIf
∂η
i ) 1, ..., NC j ) 1, ..., n
i ) 1, ..., NC j ) 1, ..., n 0 < ηLLIf e δLLIf(sj)
NC
LIIi (sj)
∑ L (s ) ) L (s )
II
i j
II
t j xII,Lb
i (sj) )
LIIt (sj)
(10) boundary conditions
i)1

NC
i ) 1, ..., NC j ) 1, ..., n
i (sj) ) Ni
NLIb LLIIf
(sj) |ηLLIIf)0
i (sj) ) xi
xLIb LLIf
(sj) | ηLLIf)0
Gi(sj)
∑ G (s ) ) G (s )
(19)
i j t j i (sj) )
yGb (11)
i)1
Gt(sj)
i ) 1, ..., NC j ) 1, ..., n
i ) 1, ..., NC j ) 1, ..., n
L-L interface, liquid II side film
Under the assumption of negligible heat transfer through the
films, the dynamic energy balance attains the form ∂cLLIIf
i (sj) ∂NLLIIf
i (sj)
+ LLIIf
- RLLIIf
i (sj) ) 0 (20)
∂t ∂η
dU(sj)
) L̃It (sj - 1) H̃LI(sj - 1) + L̃IIt (sj - 1) H̃LII(sj - 1) +
dt i ) 1, ..., NC j ) 1, ..., n 0 < ηLLIIf e δLLIIf(sj)
G̃t(sj + 1) H̃G(sj + 1) - L̃It (sj) H̃LI(sj) - L̃IIt (sj) H̃LII(sj) -
G̃t(sj) H̃G(sj) + Q(sj) (12) boundary conditions

j ) 1, ..., n
In eq 12 Q(sj) denotes the net heat rate exchanged between the
i (sj) ) Ni
NLIIb LLIIf
(sj) | ηLLIIf)δLLII(sj)
i (sj) ) xi
xLIIb LLIIf
(sj) |ηLLIIf)δLLIIf(sj)

column and its surroundings, H̃ the stream molar enthalpy, and (21)
U(sj) the total molar energy accumulation, which is calculated
from the relation i ) 1, ..., NC j ) 1, ..., n
NC Thermodynamic equilibrium is valid at the phase interfaces
U(sj) ) ∑ i (sj) ui (sj) + mi (sj) ui (sj) + mi (sj) ui (sj)}
{mLI LI LII LII G G (G-LI and LI-LII) and is described by the following equations:
i)1
(13)
i (sj) ) Ki (sj) xi (sj)
yGL i ) 1, ..., NC j ) 1, ..., n
GL GL
j ) 1, ..., n (22)
The dynamic mass balances in the gas and liquid films at the
two possible interfaces (G-LI and LI-LII) along with the
boundary conditions are as follows: xI,LL (sj) ) KLL II,LL
i ) 1, ..., NC j ) 1, ..., n
i i (sj) xi (sj)
G-L interface, gas side film (23)
∂cGf
i (sj) ∂NGf
i (sj)
+ - RGf(sj) ) 0 (14) In eqs 22 and 23, xI,LL and xII,LL represent the molar fractions
∂t ∂ηGf i i
of the first and second liquid phases on the L-L interface,
i ) 1, ..., NC j ) 1, ..., n 0 < ηGf e δGf(sj) respectively. The boundary conditions that arise from the
equilibrium equations at the interfaces are
boundary conditions
i (sj) ) Ni (sj)| ηGf)0
NGb i (sj) ) yi (sj)| ηGf)0
Gf
yGb Gf
(15)
i (sj)| ηGf)δGf(sj) ) Ni (sj) ) Ni (sj)| ηGLf)0
NGf GL GLf
(24)
i ) 1, ..., NC j ) 1, ..., n
G-L interface, liquid side film i ) 1, ..., NC j ) 1, ..., n
 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 3279

yGf
i (sj)| ηGf)δGf(sj) ) yGL
i (sj) xGL
i (sj) ) xGLf
i (sj)| ηGLf)0
(25)
Γi,k(sj) ) δi,k + xi(sj)
∂ ln γi(sj)
∂xk(sj) |T̃(sj),P(sj),xk(sj),k*i)1,...,NC-1

i ) 1, ..., NC j ) 1, ..., n (33)

NLLIf
i (sj)| ηLLIf)δLLIf(sj) ) NLL
i (sj) ) Ni
LLIIf
(sj)| ηLLIIf)0 (26)
Equations 1-33 form the NEQ/OCFE model for an element
i ) 1, ..., NC j ) 1, ..., n where three phases are present. An element with two phases
would involve only balances without the terms associated with
xLLIf
i (sj)| ηLLIf)δLLIF(sj) ) xI,LL
i (sj) xII,LL
i (sj) ) xLLIIf
i (sj)| ηLLIIf)0 the third phase. Connecting equations between successive
(27) elements or between an element and a discrete stage (e.g., feed
stage) are reported elsewhere.14,17,18
i ) 1, ..., NC j ) 1, ..., n
One major feature of three-phase distillation units is that the
liquid-phase split regions (i.e., regions in which two liquid
The reaction terms Ri used in the above equations represent the
phases are present) are not known before a solution of the
total rate of reaction per component i and are computed from
the following equation: modeling equations is obtained. Unless the correct set of
modeling equations corresponding to two- or three-phase
NR regimes is used, the simulated results will not represent
Ri(sj) ) ∑ν i,rrr(sj) i ) 1, ..., NC j ) 1, ..., n accurately the column behavior and occasionally fail to reach a
feasible solution. The NEQ/OCFE model formulation is there-
r
(28) fore properly modified to automatically detect the presence of
a second liquid phase and use a suitable set of modeling
rr are the rates of the reactions taking place, and νi,r are the equations for the column sections. The point of appearance or
corresponding stoichiometric coefficients. disappearance of the second liquid phase causes a discontinuity
The component molar flux terms Ni at the collocation points in the concentration profiles that would otherwise jeopardize
are calculated through the multicomponent Maxwell-Stefan the accuracy of the approximating interpolation polynomials.
equations. Considering one-dimensional transport normal to each Such a situation requires the proper adaptation of the set of the
interface, the Maxwell-Stefan equations are applied at each modeling equations to account for changes in the phase
collocation point as follows: distribution. According to the proposed methodology,15 an
element breakpoint is adaptively placed at the phase transition
gas phase boundary. The identification of the discontinuity point (liquid-
phase split or complete mixing of two liquid phases) is
∂yGf k (sj) Ni (sj) - yi (sj) Nk (sj)
yGf
NC Gf Gf Gf
i (sj)

∂ηGf
)- ∑ (P(sj)/RTGf(sj))ÐGik
performed with the aid of L-L flash calculations applied at
k)1,k*i the prevailing conditions of the liquid phase at the element
(29) breakpoint. The L-L flash calculations determine whether the
formation of the second liquid phase is feasible and subsequently
i ) 1, ..., NC j ) 1, ..., n 0 < ηGf e δGf(sj) specify whether the element breakpoint is a phase transition
boundary. As the element breakpoint may be set free to move
liquid phases in the OCFE model formulation, the determination of the exact
NC-1
∂xGLf location of the breakpoint inside the column is achieved through
i (sj)
∑Γ i,k(sj)
∂ηGLf
) the satisfaction of the bubble point calculation for the appearing
k)1 second liquid phase. Similarly, in the case of disappearance of
k (sj) Ni (sj) - xi (sj) Nk (sj)
xGLf
NC GLf GLf GLf a liquid phase the element breakpoint is placed at the bubble
- ∑ ct(sj)ÐLik
(30) point of the liquid-liquid equilibrium. The L-L flash calcula-
k)1,k*i tions involve the following equations:
i ) 1, ..., NC j ) 1, ..., n 0 < ηGLf e δGLf(sj)
i (s0) + (1 - Φ(s0))xi (s0) ) xi(s0)
Φ(s0) xLIb LIIb

NC-1
∂xLLIf (sj) i ) 1, ..., NC (34)
∑ Γi,k(sj)
i
LLIf
∂η
)
k)1
NC
(sj) - xLLIf
xLLIf
∑ (x
LLIf
NC
k (sj) Ni (sj) NLLIf
k (sj)
∑ - xLIIb
i (s0)) ) 0 i ) 1, ..., NC
LIb
i (s0) (35)
i
- (31)
k)1,k*i ct(sj)ÐLik i)1

i ) 1, ..., NC j ) 1, ..., n 0 < ηLLIf e δLLIf(sj)

i xi (s0) ) γi xi (s0)
γLIb i ) 1, ..., NC
LIb LIIb LIIb
(36)
NC-1
∂xLLIIf (sj)
∑ Γi,k(sj)
i
LLIIf
∂η
) where γi is the activity coefficient of each component and Φ is
k)1 the phase split fraction (Φ ) 1 implies a single liquid phase,
NC
xLLIIf(sj) NLLIIf (sj) - xLLIIf (sj) NLLIIf(sj) whereas 0 < Φ < 1 implies two liquid phases). The L-L flash
- ∑ k i i

ct(sj)ÐLik
k
(32) calculations are performed at the top of the finite element (s0
k)1,k*i
corresponds to the interpolation point for the liquid phase at
i ) 1, ..., NC j ) 1, ..., n 0 < ηLLIIf e δLLIIf(sj) the top of each element). Element breakpoints are therefore
placed at suitable positions so that the condition Φ(s0) ) 1.0
where holds.
3280 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010
3. Optimal Design Problem: Solution Algorithm
3.1. Optimal Design Problem Definition. For staged sepa-
ration processes such as reactive distillation, the problem of
optimal design involves the determination of the column
configuration which can be expressed through the location of
the feed stages, the number of stages in each column section,
and the stage holdups or catalyst loads and the operating
conditions such as condenser and reboiler heat duties and feed
stream policy (ratio of reactants) that optimize a criterion relative
to the economic feasibility of the process while satisfying the
process operational and safety constraints and product specifica-
tions. The most common economic criterion is the minimization
of the total annualized cost of the column that includes the
process investment and operating costs. The problem statement
for the optimal design of a staged reactive distillation column
can therefore be formulated as follows: Given (1) a set of
components and chemical reactions, (2) a flowsheet configu-
ration, (3) the condition of the fresh feed streams, (4) a set of
product specifications as well as safety and operating constraints,
and (5) economic data (prices for products and reactants,
investment cost data), calculate (1) the total number of stages
for each column section, (2) the location of the feed stages, (3)
the stage liquid-phase holdups or catalyst load for every column
section, and (4) the column operating conditions that minimize
the annualized process investment and operating costs subject
to the steady-state NEQ/OCFE process model.
The process design as derived by the above formulation
ensures that all safety regulations as well as all operating,
product, environmental, and economical constraints are satisfied
by the optimal design under nominal model parameter values.
The formulation of the design optimization problem enables the
performance of extensive sensitivity analysis of the optimal
solution under model or process uncertainty.18
3.2. Model Solution Algorithm. The numerical solution of
the mathematical model for a three-phase distillation column
is a highly demanding task, not only because of the possible
phase transition along the column that results in a varying model
structure but also because of the complexity caused by the large
set of nonlinear differential algebraic equations. Attaining an
accurate solution by solving such a large and complex set
requires consistent initial values that satisfy both the differential
and algebraic equations. However, as the model is formulated
in a time-varying fashion the steady-state solutions can be easily
obtained by integration using a consistent initial point.
Moreover, as discussed in section 2, the phase splitting
distribution along the column length is generally not known a
priori. As a result, modeling the entire column as a three-phase
column could lead to an infeasible solution as there may be
sections within the column where the second liquid phase is
not thermodynamically stable. To ensure that a feasible solution
will be attained, the column is first modeled as a two-phase
column. Liquid-liquid flash calculations are then performed
in an offline fashion at the conditions obtained from the solution
of the two-phase model at each collocation point. The
liquid-liquid flash calculations clearly indicate whether a second
liquid phase is present without interfering with the column
balance equations of the two-phase model. Consequently, the
sections with two or three phases are determined and finite
elements with two- or three-phase modeling equations, respec-
tively, are employed accordingly for an overall accurate
representation. The predictions of the offline L-L flash calcula-
tions are utilized as starting values for the two liquid-phase
concentrations in the three-phase model equations. The exact
location of the phase transition inside the column is then
Table 1. Reaction Kinetic Parameters2
reaction k0 (mol s-1) E (kJ mol-1)
esterification 6.1084 × 104 56.67
hydrolysis 9.8420 × 104 67.66
determined through the adaptive element length selection
performed during the solution of the modeling equations. The
main aim in the solution procedure is to provide sufficient
flexibility to the overall model through the selection of an
appropriate model structural combination of two- or three-phase
finite elements for an accurate representation of the distillation
column. In conclusion, the solution algorithm can be sum-
marized in the following steps:
Step 1. Model the column entirely as a two-phase column.
Step 2. Employ the LL flash equations at the element
boundaries to determine whether the formation of the
third phase is possible. If the LL flash calculations
are in agreement with the modeling assumption
regarding the phase split, then STOP. Otherwise,
proceed to Step 3.
Step 3. Model those elements with potential phase split (0
< Φ(sj) < 1) as three phase elements/sections.
Step 4. Determine the phase transition boundaries through
adaptive placement of the element breakpoints be-
tween two successive elements with alternating two/
three phase modeling equations (condition Φ(s0) )
1.0) and simultaneously solve the optimal design
problem. Go to Step 2.
The exact satisfaction of the condition Φ(s0) ) 1.0 can be
relaxed to |Φ(s0)| e ε, where ε denotes a desired tolerance, to
facilitate convergence. The solution of the dynamic model
equations is performed using gPROMS,20 an efficient modeling
environment that enables a fast and reliable convergence
provided that a feasible initial point that satisfies the modeling
equations is available.
4. Design Case Study: Butyl Acetate Production via
Reactive Distillation
4.1. Process Description. Butyl acetate is an organic com-
pound used mainly in the lacquer and color industries as a
solvent and in the food industry as a synthetic food flavoring
and is produced by the esterification reaction of butanol with
acetic acid. The design of a tray reactive distillation column
for the simultaneous production and separation of n-butyl acetate
(BuAc) is investigated. 1-Butanol (BuOH) and acetic acid
(AcOOH) are fed into the column at a ratio to be determined
by the design optimization problem. The esterification-hydrolysis
reactions take place in the liquid phase within the column
according to the following scheme:
BuOH + AcOOH T BuAc + H2O
The reaction requires a strongly acidic catalyst. Homogenous
acidic catalysts however have been proven to be less attractive
as the corrosion problems in the column arising from their use
and the formation of the poisonous side product dibutyl ether
(DBE) need to be taken into consideration.9 More recent
studies2,9 favor heterogeneous catalysts in the form of ion
exchange resins such as Amberlyst-15. The resins are loaded
in the column inside the catalytic reaction zone at the beginning
of the process. The reaction constants of both reactions are
considered to be Arrhenius type, following the basic form
k ) k0e-E/RT (37)

Figure 3. Experimental validation of the model.
The values of k0 and E have been taken from Steinigeweg and
Gmehling2 for both esterification and hydrolysis reactions and
are given in Table 1. Reaction and separation proceed simul-
taneously inside the column, separating the products from the
reactants and driving the esterification reaction to the right-hand
side, thus leading to higher product yields. An equilibrium
reboiler ensures the recycling of the gaseous phase back into
the column, while a total condenser coupled with a decanter
condenses and separates the two liquid phases of the top product
stream.
The overhead stream leaving the condenser is composed by
water as well as butyl acetate. In the decanter this stream is
separated into an aqueous phase and an organic phase due to
the large miscibility gap between butyl acetate and water.8 The
aqueous phase is driven away, while the organic one, composed
primarily of butyl acetate, is recycled back to the top of the
column. The bottom stream is almost pure butyl acetate with
small traces of water, and unreacted acetic acid and butanol.
The binary diffusion coefficients used in the multicomponent
Maxwell-Stefan equations have been calculated using the
Chapman-Enskog-Wilke-Lee model21 for the gaseous phase,
while the liquid diffusion coefficients have been estimated using
the method proposed by Siddiqi and Lucas.22 Thermodynamic
properties, such as molar enthalpies, vapor pressures, and
activity coefficients, for each component have been estimated
using the UNIFAC23,24 property method, a quite reasonable
choice as reported elsewhere.2
4.2. Experimental Model Validation. The proposed process
model has been validated with experimental data reported in
the work of Steinigeweg and Gmehling.2 In this work, the
production of butyl acetate is performed in a laboratory scale
packed reactive distillation column. The reactants are fed into
the column at two different stages. The reactive zone utilized a
strongly acidic ion exchange resin (Amberlyst-15) as the
catalyst. The experimental conditions have been utilized for the
NEQ/OCFE simulations. According to the experimental data
and the simulated results there is no appearance of a second
liquid phase within the column except the decanter at the top
of the column. The column is simulated with 28 stages as
indicated by Steinigeweg and Gmehling.2 Figure 3 compares
the experimental data2 for the liquid composition with the
simulation results obtained from the NEQ/OCFE model along
the entire column. A total number of 11 collocation points
distributed among 5 finite elements have been utilized in the
process model. The symbols on the simulation lines correspond
to the location of the collocation points and discrete stages in
Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 3281
the NEQ/OCFE model along the column. The agreement of the
experimental data and the simulated results at the two ends of
the column is very good, with some discrepancies in the
concentration profiles present in the reactive zone between the
two feeds. However, similar deviations are also reported by
Steinigeweg and Gmehling2 when comparing the experimental
data to the simulation results from an equilibrium stage-by-
stage model, indicating that the simulated points are within the
bounds of the experimental error. Therefore, a satisfactory match
of the NEQ/OCFE process model has been obtained.
4.3. Design Optimization. The column is divided into two
sections as shown in Figure 1, namely, the rectifying and
stripping sections, which represent the section above the feed
stage up to the condenser and the section below the feed stage
down to the reboiler, respectively. The feed stage location is
indirectly determined from the calculation of the sizes of the
rectifying and stripping sections. For the particular column under
study, one finite element is used in the rectifying section and
four finite elements are used in the stripping section. Four
collocation points are placed within each finite element. The
liquid holdups along the column are assumed to be varying
between sections but maintaining a constant value per section
due to construction constraints. The vapor-phase holdups as well
as the pressure drop inside the column and gas phase reactions
are considered negligible. The NEQ/OCFE model is employed
in the rectifying and stripping sections, while the feed stage is
modeled as a discrete nonequilibrium stage. The condenser, the
reboiler, and the decanter are modeled as single equilibrium
stages. The decanter separates the liquid phase into an organic-
rich phase that is recycled back into the column and an aqueous-
rich phase that is removed as the top product. The partial
differential equations referring to the mass transfer between the
boundary films have been discretized using orthogonal colloca-
tion on finite elements. Specifically, an approximating scheme
with four finite elements and second-order polynomials has been
selected for the balance equations in the liquid and gas boundary
films (eqs 14-33).
Optimization (design) variables in this process are the number
of stages per section, as represented by the lengths of the
associated elements in each section, and the column operating
conditions such as the condenser and reboiler duties, BuOH to
AcOOH feed flow rate ratio, and liquid holdups per section.
The problem has been formulated into the gPROMS optimizer
along with given constraints such as the desirable purity of the
product streams and an objective function representing the total
annual cost for the process. The objective function consists of
three terms representing the capital cost25 for the shell, the trays,
the condenser, and the reboiler, the energy cost,25 and the
material loss cost represented as the differential cost26 for useful
product and reactant lost in the overhead stream as shown in
the following relation: Ltop top
BuAc and LBuOH represent the liquid molar
flow rates (mol/h) of BuAc and BuOH in the top water-rich
product stream, respectively, while D and H are the column
diameter and height. The last term in eq 39 represents the cost
due to the loss of some amounts of products (BuAc) and raw
materials (BuOH) in the distillate stream with the coefficients
chosen in such a way to enforce a high conversion of reactants.
The column diameter obeys the following flooding constraint:25
3282 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010

[( )( ]
NC 0.5 0.5 Table 2. Optimization Results
∑
)
yiMwiRgTr two-phase
i)1 4Grtot model three-phase NEQ/OCFE NEQ/OCFE
De (39)
Pr 3.14 × 1.5 × 3600
column diameter (m) 1.317 1.213
total no. of stages 60 43
where Tr, Pr, and Grtot
denote the reboiler temperature, pressure, feed stage 10 4
and total gas streamflow, respectively. condenser duty (kW) -1559 -1368
According to the solution algorithm presented in section 3.2, reboiler duty (kW) 1420 1142
feed ratio (BuOH/AcOOH) 1.005 1.004
the column is initially modeled using a two-phase model. After bottom flow (kmol/h) 51.46 42.43
convergence to an optimal design point, an L-L flash is bottom composition 0.0035/0.0015/0.98/0.015 0.007/0/0.98/0.013
performed at the condition of all collocation in the column to (mole fraction),
BuOH/AcOOH/BuAc/H2O
identify possible three-phase regions in the column. On the basis top composition 0/0.002/0.001/0.997 0/0.006/0.001/0.993
of the L-L flash results, the rich in water rectifying section (mole fraction),
BuOH/AcOOH/BuAc/H2O
exhibited liquid-phase splitting, and therefore, the three-phase total annual cost ($) 1617.64K 1240.01K
NEQ/OCFE model is utilized in that section. The solution to
the optimal design problem is then obtained for the hybrid three/ Table 3. Design Conditions for the Butyl Acetate Reactive
two-phase model. In this case, the element size in the rectifying Distillation Column
section not only defines the number of stages in the respective feed stream
section but also designates the boundary between the three- temperature (K) 291
phase rectifying section and the two-phase feed stage. The flow rate (kmol/h), BuOH/AcOOH 34.992/34.809 (BuOH/
AcOOH ) 1.005)
optimal design results for solely two-phase and hybrid two/ length of elements in rectifying/ 8.541/12
three-phase models are summarized in Table 2. stripping section
Optimization results show that there are some significant liquid holdups (m3)
differences in the optimal column configurations obtained by condenser 0.676
rectifying section 0.040
the two models. With reference to the same BuAc purity at the feed stage 0.250
bottom stream, the solely two-phase model predicts a smaller stripping section 0.197
column in both diameter and number of stages and a lower reboiler 0.593
bottom flow rate than the hybrid two/three-phase model. The reflux ratio 5.52
minimization of acetic acid in the top stream is directly involved reboil ratio 2.52
in the objective function, and according to the results, the hybrid
two/three-phase model predicts a 3 times lower concentration stripping section due to the combined effect of the esterification
than the solely two-phase model. It is therefore evident that the reaction and the separation process. The concentration of BuAc
inclusion of the third phase formation in the mathematical model drops drastically near the top of the column as the water
not only alters the model structure, but also results in significant concentration increases, but then it rises sharply shortly after
changes in the model predictions and optimal column design as the water-rich phase is removed in the decanter and the reflux
configurations. Such an observation implies that failure to trace stream enters at the top of the rectifying section. The BuAc
and properly model the three-phase regions in the column as and water compositions reach the lowest level at the feed stage
these spontaneously form due to the prevailing operating (stage 10). The profile for AcOOH has been omitted as it is
conditions in the column would result in erroneous column almost identical to the BuOH profile. The rectifying section also
design solutions and unreliable model predictions. The remain- contains the third phase (water-rich liquid phase), which is
ing design parameters for the separation system such as the feed composed almost entirely of H2O. The maximum attainable
stage location, column section liquid holdups, reflux and reboil product purity with this NEQ/OCFE model was 98% BuAc as
ratios, condenser and reboiler heat duties, alcohol to acid feed the bottom product and almost pure water (99.7%) as the top
ratio, and total column stages as resulted from the solution of product.
the design optimization problem are shown in Table 3. Figures 5 and 6 depict the temperature and reaction rate
Simulation results show that at the optimum operating (esterification) profiles throughout the column, respectively. The
conditions the column has both two- and three-phase regions.
In particular, the rectifying section is entirely a three-phase
section, while the stripping section has only two phases. In this
way, the phase transition boundary is determined by the location
of the feed stage, which in place has been determined by the
adaptive placement of the rectifying section breakpoint. Ther-
modynamic conditions indicate that the third phase appears
because of the miscibility gap between butyl acetate and water.
It has been noted from the simulation results that the three-
phase region tends to disappear near the feed stage due to the
elevated concentrations of the incoming through the feed stream
1-butanol and acetic acid. The second, water-rich liquid phase
is hence formed when a certain composition ratio between butyl
acetate and water is reached near the top section where the
reactant concentrations are low.
The column composition profiles at the optimal operating
point are shown in Figure 4. Stage 1 represents the column
condenser, while the last stage represents the reboiler. The butyl
acetate concentration maintains an increasing trend in the Figure 4. Component composition profiles along the column.
 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 3283

Figure 5. Temperature profile along the column.

Figure 7. Liquid flow rate profile.

Table 4. Comparison of Design Optimization Results between

Single- and Double-Feed-Stage Configurations
configuration single feed double feed
column diameter (m) 1.317 1.180
total no. of stages 60 58
feed stage location 10 4 (AcOOH)/9 (BuOH)
finite element lengths 8.541/12/12/12/ 12 2/3.177/16/16/16
condenser duty (kW) -1559 -1344
reboiler duty (kW) 1,420 931.9
feed ratio (BuOH/AcOOH) 1.005 1.058
bottom flow (kmol/h) 51.46 52.15
bottom composition 0.0035/0.0015/0.98/0.015 0.002/0.005/0.98/0.013
(mole fraction),
BuOH/AcOOH/BuAc/H2O
top composition 0/0.002/0.001/0.997 0/0.003/0.001/0.996
(mole fraction),
BuOH/AcOOH/BuAc/H2O
total annual cost ($) 1617.64K 1409.54K
configuration with two feed stages, where butanol is fed at the
Figure 6. Reaction rate profile along the column. lower feed location and acetic acid is fed at the upper feed
location. Butanol is lighter than acetic acid and prefers the vapor
first temperature peak around the feed stage can be attributed phase, which is a disadvantage since the reaction takes place
to the esterification reaction exothermal nature and the increased primarily in the liquid phase. However, feeding at different
reaction rate due to the high composition of BuOH and AcOOH stages distributes the reactants in a larger section of the column,
near the feed stage region. The temperature profile remains thus enhancing the reaction rates. The two-feed-stage config-
almost uniform in the stripping section before reaching another uration is optimized in a fashion similar to that of the single-
peak at the reboiler. The reaction rates exhibit a sharp peak at feed configuration without however considering the additional
the feed stage due to the introduction of the reactants into the investment cost of the second feed stage in the objective function
column followed by a large decrease and an almost steady value (e.g., piping and fitting costs). Five finite elements are
profile for the largest part of the stripping section. The aqueous- used for the column representation, one for the section above
phase reaction rates on the other hand remain low because of the upper feed stage, one for the section between the two feed
the very low concentrations of reactants in the rectifying section stages, and three for the section below the lower feed stage.
(three-phase region). The results from the design optimization are shown in Table 4
The liquid flow rate profile for both liquid phases inside the and compared to the single-feed configuration.
column is shown in Figure 7. As can be observed, the water- The optimization results reveal that the rectifying section is
rich liquid phase completely disappears after the feed stage. At a three-phase region whereas the sections below the upper feed
the left side of the graph (rectifying section) three phases exist stage (acetic acid feed) as well as the feed stages themselves
in the column, while at the right side (stripping section) only are two-phase regions in the double-feed-stage configuration.
two phases are stable. The phase boundary is decided through The results show that although the total number of stages is
the optimization process by means of determining the section almost the same, the column’s diameter and the necessary
boundaries and therefore the sizes (lengths) of the finite reboiler duty are smaller in this case due to the larger product
elements. The addition of a second decanter aiming at removing bottom stream, which leads to a smaller total annualized cost
the water-rich phase through a side stream in the rectifying for this column. In conclusion, the maximization of butyl acetate
section does not improve the economics of the design, and production is favored by a double-feed configuration and a
therefore, it has not been further investigated. placement of the feed stages near the top of the column.
4.4. Double-Feed-Stage Configuration. Another column 4.5. Dynamic Simulation Studies. Modeling eqs 1-33 for
configuration involves the feeding of the reactants at different the reactive three-phase column include the dynamic compo-
stages. Therefore, a scenario has been formulated using a column nents, thus allowing the investigation of the dynamic behavior
3284 Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010
Figure 8. Dynamic response to a 6% decrease in the feed AcOOH
concentration.
Figure 9. Dynamic response to a 5% increase in the feed H2O concentration.
of the column around the optimal operating point. During the
dynamic simulation studies, the same assumptions regarding the
negligible pressure drop and vapor holdups apply in the column.
The design parameters for the staged column such as the
condenser and reboiler duties, section liquid holdups, feed stage
location, and number of stages per column section are taken
from the design optimization problem (Tables 2 and 3). The
liquid holdup per stage indicates the volume of the reacting
mixture for a fixed catalyst density per volume of stage capacity
that also considers the porosity of the catalyst substrate. Dynamic
simulations enable the study of the influence of disturbances in
the product specifications. During dynamic transition the phase
boundary may migrate within the column. Figures 8 and 9 show
the dynamic behavior of the process for a 6% decrease in the
acetic acid flow rate in the feed stream and a 5% increase in
the water content of the feed stream, respectively. In Figure 8,
the butyl acetate product purity (BuAc mole fraction) gradually
decreases before it reaches a final steady state of 0.964. Such
behavior is attributed to the decrease in the esterification reaction
rate due to the reduced amount of acetic acid in the feed. In the
second case, the water entering the column acts as a hindrance
for the process as the final product purity is decreased by 0.8%.
An increased amount of water in the column would drive the
reaction to the left (hydrolysis), reducing the effectiveness of
the process for butyl acetate production. In both cases the
column exhibits three phases in the section above the feed stage
and two phases in the section below the feed stage. L-L flash
calculations have been performed at the collocation point
prevailing conditions to ensure the utilization of the correct
modeling structure (three-phase vs two-phase systems) along
the column. Obviously, the element breakpoints have been kept
fixed during the dynamic transition. However, the adaptive
placement of the element breakpoints to follow possible phase
boundary drift during dynamic transition still remains a chal-
lenging research problem.
5. Conclusions
In this work, a model for the steady-state optimal design of
a reactive distillation column with possible liquid-phase splitting
is developed. The model is a combination of rate-based NEQ
balance equations and the OCFE formulation that also includes
a liquid-liquid flash at the element breakpoints that aims to
adaptively place the element breakpoints at the exact location
of the phase transition point. The model takes into consideration
all the mass and energy transfer phenomena as well as
thermodynamic equilibrium and chemical reactions while main-
taining a compact structure that facilitates the solution of the
mathematical program.
The model has first been validated against experimental
results from the literature and then employed for the design
optimization of a tray reactive distillation column for the
production of butyl acetate. At the optimal design, the column
appears to have three phases in the rectifying section whereas
the stripping section is an entirely two-phase region. In that
case, the phase transition boundary is determined by the adaptive
placement of the rectifying section element breakpoint. As
design variables for the process optimization, the number of
stages per column section, the feed tray location, the reactant
feed ratio, the condenser and reboiler heat duties, and the liquid
molar holdups per column section have been selected. Moreover,
the influence of the column feed strategy (single-feed vs double-
feed configuration) on the optimal solution is investigated. A
98% butyl acetate stream has been achieved as the bottom
product, while the top stream consists of 99.7% water.
The column design obtained using a process model that
ignores the formation of a second liquid phase fails to meet the
purity constraints and product specifications of the actual three-
phase system. Therefore, the modeling of the second liquid
phase is imperative in providing an accurate representation of
the column steady-state and dynamic behavior. Furthermore,
OCFE formulation successfully manages to reduce the model
size, remove the need for integer-valued design variables, and
provide a flexible model structure that can efficiently handle
the discontinuous nature of three-phase systems while maintain-
ing a detailed representation of the column phenomena using
NEQ modeling equations. Application of the NEQ/OCFE model
formulation in the study of the dynamic behavior of a three-
phase system with an automatic phase transition monitoring
scheme remains however a challenging field of research.
Nomenclature
aint ) specific interfacial area (m2/m3)
Acol ) column stage cross section (m2)
c ) molar concentration (kmol/m3)
d ) molar density (kg/m3)
D ) column diameter (m)
Ð ) Maxwell-Stefan diffusion coefficient (m2/s)
E ) reaction activation energy (J/kmol)
G ) gas molar flow rate (kmol/h)
h ) column height (m)

H ) stream molar enthalpy (J/kmol)
k0 ) pre-exponential kinetic parameter
k ) kinetic constant (kmol/s)
K ) equilibrium K value
L ) liquid molar flow rate (kmol/h)
m ) component molar holdup (kmol)
Mw ) component molecular weight
n ) number of collocation points in a finite element
N ) molar flux (kmol/(m2 s))
NC ) number of components
NE ) number of finite elements in a column section
NR ) number of chemical reactions
P ) pressure (Pa)
Q ) rate of heat loss/heat duty (J/s)
r ) rate of reaction (kmol/(m3 s))
R ) component rate of reaction (kmol/(m3 s))
Rg ) ideal gas constant (8.314 J/(mol K))
s ) column position coordinate
t ) time (h)
T ) temperature (K)
u ) component internal energy (J)
U ) stream internal energy (J)
Vb ) component molar volume (m3/kmol)
W ) Langrange interpolating polynomial
x ) liquid-phase mole fraction
y ) gas-phase mole fraction
Greek Letters
γ ) activity coefficient
Γ ) thermodynamic factor
δ ) film thickness (m)
δi,k ) Kronecker δ, 1 if i ) k, 0 if i * k
∆h ) stage height (m)
η ) film coordinate
µ ) component dynamic viscosity (Pa s)
ν ) stoichiometric coefficient
σ ) characteristic molecule diameter (Å)
φ ) phase volumetric holdup fraction (m3(phase)/m3(stage))
Φ ) phase split fraction
Ω ) collision integral
Subscripts
t ) total
Superscripts
G ) gas phase
Gb ) gas bulk region
Gf ) gas film in gas-liquid I interface
GL ) gas-liquid interface
GLf ) liquid film in gas-liquid I interface
LI ) first liquid phase (continuous)
LIb ) first liquid phase (continuous) bulk region
LLIf ) liquid I film in liquid-liquid interface
LII ) second liquid phase (dispersed)
LIIb ) second liquid phase (dispersed) bulk region
LLIIf ) liquid II film in liquid-liquid interface
LL ) liquid-liquid interface
Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 3285
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ReceiVed for reView August 10, 2009
ReVised manuscript receiVed January 24, 2010
Accepted February 4, 2010
IE901260B