Ind. Eng. Chem. Res.

2007, 46, 3255-3264 3255

‘Feasible Products for Double-Feed Reactive Distillation Columns†

Sagar B. Gadewar
Gas Reaction Technologies (GRT), Inc., 861 Ward Dr., Santa Barbara, California 93111

Michael F. Malone
Department of Chemical Engineering, UniVersity of Massachusetts, Amherst, Massachusetts 01003

Michael F. Doherty*
Department of Chemical Engineering, UniVersity of California, Santa Barbara, California 93106

We have developed a quick and effective method to predict the feasible products from a double-feed reactive
distillation column. The method relies on the prediction of the pinch point for the middle section, using a
cross-flow arrangement of vapor-liquid continuously stirred tank reactors (CSTRs). The cross-flow model
substantially simplifies the prediction of the compositions at both ends of the middle section of a two-feed
column, which are then used to predict the feasible distillate and bottoms compositions, using existing methods.
The cross-flow arrangement can also be used to predict minimum and maximum flows for double-feed reactive
distillation columns.

Introduction curve maps for simple reactive distillation). Barbosa and

Separation accompanied by chemical reaction, has been a
constant theme of research throughout M. M. Sharma’s career.
His first published paper, coauthored with his doctoral thesis
advisor, P. V. Danckwerts, on absorption with chemical reaction1
remains a classic in the field. During the 1980s and 1990s, he
published many papers on the themes of “separations through
reactions” (for example, see Gaikar and Sharma2) and reactive
distillation.3 The theme continued into the new century with
his encyclopedic description of potential applications of reactive
distillation in practice, which was coauthored by Mahajani.4
Many of these applications are practiced in two-feed, counter-
current cascade reactive distillation columns, which are notori-
ously difficult to design. In particular, it is difficult to rapidly
assess the feasible products that can be obtained from such
devices. In this paper, we develop an approximate, but accurate,
solution to the feasibility problem.
Double-feed columns are often used in extractive distillation.
Knapp and Doherty5 published an approach based on bifurcation
theory to determine minimum entrainer flows for double-feed
extractive distillation columns. They found that, in addition to
a minimum reflux, every extractive distillation exhibits a
maximum reflux, above which the desired separation is impos-
sible, and a minimum entrainer flow rate, below which the
separation is also impossible. Petlyuk and Danilov6 described
a study of the fixed points in the middle section of a double-
feed column. They also developed a method to determine the
minimum entrainer flow rate and the minimum reflux ratio.
A double-feed reactive distillation column is used to achieve
good contact between light-boiling reactants and heavy-boiling
reactants. A heuristic by Bessling et al.7 suggests that a double-
feed column is desirable when one or both products are saddles
in the concentration profile (usually determined from residue
* To whom correspondence should be addressed. Tel.: (805) 893-
5309. Fax: (805) 893-4731. E-mail address: mfd@engineering.ucsb.edu.
†
This paper is dedicated to Professor M. M. Sharma, in recognition
of his many outstanding contributions to chemical engineering research,
education, and practice.
10.1021/ie060867r CCC: $37.00 © 2007 American Chemical Society
Published on Web 03/08/2007
Doherty8 described a method for calculating minimum reflux
ratios for double-feed reactive distillation columns in the limit
of phase and reaction equilibrium. Methods for double-feed
nonreactive distillation columns were adapted for reactive
distillation columns, using reaction invariant compositions. Chin
and Lee9 published a method for the design of double-feed
reactive distillation columns to determine feasible reflux ratios
and entrainer flow rates for a specified reaction extent and
product purity.
A method to determine feasible product compositions from
a single-feed reactive distillation column was developed by
Chadda et al.10 They determined that the product composition
region, at finite rates of reaction, are bounded by the limits of
minimum reflux on one side of the region and minimum number
of stages at the other. They exemplified the methodology on a
ternary reaction mixture undergoing a single reversible reaction.
Although such an approach is useful for mapping the feasible
products for a double-feed reactive distillation column, the
methodology is cumbersome and difficult to extend to more
than three components or to multiple reactions. A feasibility
method described by Lee11 determines if pure products can be
achieved in a double-feed reactive distillation column.
A bifurcation-based approach can be used to track the sharp
split products from a single-feed reactive distillation column.12
The approach is based on the hypothesis that the compositions
achieved in an isobaric flash cascade lie in the feasible product
regions for continuous reactive distillation. The fixed points for
an isobaric flash cascade are hypothesized to correspond to the
products from a single-feed reactive distillation column. This
method is applicable to multiple reactions with many compo-
nents. Another important advantage of the method is the non-
iterative calculations needed to find the feasible products. A
model that calculates the profile for the middle section of a
two-feed reactive distillation column was published by Gadewar
et al.13 Chadda et al.14 extended the isobaric flash cascade
approach to double-feed reactive distillation columns, and also
to hybrid reactive distillation columns (consisting intermixed
sections of reaction and no-reaction within the column), using
3256 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
Figure 1. Schematic of a double-feed reactive distillation column.
Figure 2. Schematic of a counter-current cascade of two-phase continuously
stirred tank reactors (CSTRs).
a counter-current cascade of vapor-liquid continuously stirred
tank reactors (CSTRs) to represent the middle section of a
double-feed column and isobaric flash cascade to represent the
stripping and rectifying sections. Unlike the isobaric flash
cascade, which requires sequential stage-to-stage calculation,
the counter-current cascade equations must be solved simulta-
neously, making it difficult to converge to solutions.13 Therefore,
there is a need to develop a simple configuration that represents
the middle section of a double-feed column.
The objective of this article is to describe a cross-flow
arrangement that simplifies the determination of feasible
products from a counter-current cascade of vapor-liquid
CSTRs. The method described here can be used to predict
feasible splits for continuous double-feed reactive distillation
that is not limited by the number of reactions or components.
The method uses minimal information on the phase equilibrium
between the components in the mixture, reaction kinetics, and
feed specification.
Middle Section of a Double-Feed Column
A schematic for a double-feed column is shown in Figure 1.
The middle section is equivalent to a counter-current cascade
of vapor-liquid CSTRs, as shown in Figure 2. The model
equations for a constant molar overflow counter-current cascade
are given by Gadewar et al.,13 which, at steady state, for any
stage j, are given as
kf
xi,j-1 - xi,j + φ(yi,j+1 - yi,j) + Da (ν - νTxi)r(xj) ) 0
kf,ref i
(for i ) 1, ..., c - 1; j ) 1, ..., N) (1)
At a pinch point in the cascade, (xi,j-1 - xi,j) f 0 as j f ∞,
which implies that (yi,j-1 - yi,j) f 0, and, in turn, means that
(yi,j - yi,j+1) f 0. At a fixed point x̂, therefore, eq 1 gives
Da(νi - νTx̂i)r(x̂) ) 0 (for i ) 1, ... , c - 1) (2)
From eq 2, for all 0 < Da < ∞, one of the fixed points (the
pinch point, if it is on the profile) always lies at the pole point
x̂i ) νi/νT (for i ) 1, ..., c - 1). All other fixed points (or pinch
points) lie on the reaction equilibrium surface:
r(x̂) ) 0 (3)
This means that the pinch point is independent of the Damköhler
number (Da) and lies on the equilibrium surface, even when
the cascade operates in the kinetic regime. The trajectory, of
course, will be dependent on the specific value of Da.
Equation 1 can be formulated in terms of reaction invariants.
For example, consider the reaction A + B h C + D. Choosing
C as the reference component, the reaction invariant liquid mole
fractions are X1 ) xA + xC and X2 ) xB + xC. Using eq 1, we
get the following:
Xi,j-1 - Xi,j + φ(Yi,j+1 - Yi,j) ) 0 (for i ) 1, ..., c - 2) (4)
Writing overall material balances for the cascade between the
first stage and the stage where the pinch point occurs (as shown
by the bounding box in Figure 3a), we get
Xi,0 - φYi,1 ) X̂i - φŶi (for i ) 1, ..., c - 2) (5)
Now, writing overall material balances for the cascade between
the stage where the pinch point occurs and the last stage of the
cascade (as shown by the bounding box in Figure 3b), we get
Xi,N - φYi,0 ) X̂i - φŶi (for i ) 1, ..., c - 2) (6)
From eqs 5 and 6, we write
Xi,0 - φYi,1 ) Xi,N - φYi,0 ) X̂i - φŶi
(for i ) 1, ..., c - 2) (7)
Equation 7 shows how the pinch point composition is related
to the liquid and vapor product composition for the cascade. If
the pinch point composition is known, the reaction-invariant
product compositions can be determined for given feed com-
positions.
Pinch point calculations for nonreactive distillation require
solving a set of algebraic equations, as described by Julka and
Doherty.15 These methods require product specifications and
the objective is to find minimum flows (e.g., minimum reflux
ratio). In feasibility studies, however, the product specifications
are not known and the purpose of the study is to determine
these product specifications. To determine the pinch points in
a counter-current cascade, the model (eq 1) must be solved for
a large number of stages (N > 50). The solutions to eq 1 are
time-consuming and often do not converge. Therefore, we need
a simple device configuration that can predict the pinch point
compositions by sequential calculation from stage to stage,
 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3257

Figure 3. Schematic diagrams for (a) the section of counter-current cascade between the top stage and the pinch point and (b) the section of counter-current
cascade between the pinch point and the bottom stage.

and the temperature is equal to the boiling point of the mixture.

The overall mass balance for the jth stage is
Lj ) Lj-1 (8)

The material balance for the ith component on the jth stage is

Ljxi,j ) Lj-1xi,j-1 + V′j(yi,0 - yi,j) + νikfHjr(xj)

(for i ) 1, ..., c - 1; j ) 1, ..., N) (9)
where L and V′ are liquid and vapor molar flows; xi and yi are
the liquid and vapor mole fractions for component i; νi is the
stoichiometric coefficient for component i; kf is the forward rate
constant with the dimensions of reciprocal time; Hj is the molar
liquid holdup in the jth stage; and r(x) is the reaction driving
force:

Figure 4. Schematic of the cross-flow arrangement.

r(x) )
( ∏
reactants
a-ν
i
i -
1
∏
K products
eq
aνi i
) (10)

where Keq is the chemical equilibrium constant and ai is the

without solving the rigorous counter-current cascade model for activity for component i. For liquid-phase reactions, activities
all stages simultaneously. are represented by the product of the activity coefficient γi and
the liquid-phase composition xi: ai ) γixi. Substituting eq 8 in
Cross-flow Arrangement eq 9, we get

We use the cross-flow arrangement shown in Figure 4 to

estimate the products from the middle section of a two-feed
column. The heavy reactant is the liquid feed to the first
xi,j ) xi,j-1 + φ′j(yi,0 - yi,j) + νi ( )
kf
kf,ref
Dajr(xj)

(i ) 1, ..., c - 1; j ) 1, ..., N) (11)

stage in the cross-flow device. The light reactant is added
to each stage of the device to achieve contact between the
reactants. The objective of this device is to predict the pinch
point in the middle section. The underlying assumption
of the analysis is that the pinch point for the device in
Figure 4 is an estimate of the pinch point in a counter-current
cascade.
Each flash device in Figure 4 is a two-phase CSTR with a
liquid inlet and a vapor inlet; the reaction occurs only in the
liquid phase. We consider a single reaction with equimolar
chemistry and steady-state conditions, therefore, a vapor stream
is removed from each stage at the same rate as the vapor inlet.
The vapor inlet composition for each stage in the cross-flow
device has the same composition (y0) and each stage is isobaric
We have defined two dimensionless parameters:
(i) φ′j ) V′j/Lj-1), which is the ratio of the vapor feed to the
liquid feed in the jth stage.
(ii) Daj ) [(Hj/Lj-1)/(1/kf,ref)], which is the Damkohler number
for stage j. This is the ratio of the characteristic liquid residence
time to a characteristic reaction time; kf,ref is the forward rate
constant at a reference temperature Tref. No reaction occurs in
the limit of Daj f 0, and reaction equilibrium is achieved as
Daj f ∞. At intermediate values of Daj, the stage operates in
the kinetically controlled regime.
Assuming that each stage has the same residence time,
Da1 ) Da2 ) ... ) Daj ) ... ) DaN ) Da (12)
3258 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

The liquid feed composition to the cross-flow scheme is the Example 1: Production of Isopropyl Acetate
same as the composition of the liquid feed to the corresponding
Isopropyl acetate can be produced by the esterification of
counter-current cascade. We use a vapor feed composition on
acetic acid with isopropanol. The reaction is
the reaction equilibrium surface, because the pinch point that
we want to estimate lies on the equilibrium surface (according acetic acid (HOAc) + isopropanol
to eq 3). The same vapor feed composition is specified for each
(IPOH) h isopropyl acetate (IPOAc) + water (H2O) (15)
stage in the cross-flow device. A convenient choice is to specify
the vapor feed based on the feed to the corresponding counter-
The thermodynamic equilibrium constant has a value of Keq )
current cascade. We choose the vapor feed in the cross-flow
8.7 in the boiling temperature range of interest.16 The kinetic
device to have the dew-point composition of a liquid mixture
model was taken from Manning17 for experiments performed
at reaction equilibrium that corresponds to the overall feed (of
on a heterogeneous catalyst (Amberlyst 15W, Rohm and Haas
the corresponding counter-current cascade). For example, if the
Company). A heterogeneous Langmuir-Hinshelwood/Hougen-
liquid feed of the counter-current cascade is acetic acid and the
Watson kinetic model used by Manning17 is
vapor feed is isopropanol with equal flow rates (i.e., φ ) 1),
the vapor feed for the cross-flow device is in phase equilibrium R ) Wk′s(aHOAcaIPOH - aIPOAcaH2O/Keq)/(1 + KHOAcaHOAc +
with a liquid mixture obtained by reacting a mixture of 50 mol
% acetic acid and 50 mol % isopropanol without vapor removal KIPOHaIPOH + KIPOAcaIPOAc + KH2OaH2O)2 (16)
until it reaches reaction equilibrium (for instance, in a plug-
flow reactor (PFR)). where k′s is the apparent forward rate constant, given by
An important decision in this configuration is the vapor
addition policy. It is desirable that the total amount of vapor 8253.6
ln k′s ) 23.81 - (17)
added in the cross-flow device be equal to that for the T
corresponding counter-current cascade (given that the liquid flow
rate is the same in both devices). Vapor addition policies can Here, T is the temperature (given in Kelvin), k′s has units of
be constructed such that (1) vapor addition rate increases with moles reacted per mole of H+ ions per minute, W is the catalyst
the stage number, (2) vapor addition rate is constant with concentration (given in moles of H+ per mole of liquid mixture),
increasing stage number, and (3) vapor addition rate decreases and the adsorption equilibrium constants are assumed to be
with increasing stage number. The cross-flow arrangement is independent of temperature:
solved until a fixed point is reached; therefore, the number of KHOAc ) 0.1976 (18a)
stages is not known a priori. If a constant value of vapor feed
flow rate per stage is used in the model, it will correspond to a KIPOH ) 0.2396 (18b)
very large total vapor feed, which is unrealistic, compared to
the counter-current cascade with a finite vapor feed rate. KIPOAc ) 0.147 (18c)
Furthermore, for a large number of stages, the pinch point for KH2O ) 0.5079 (18d)
the cross-flow device will have a composition that is identical
to the vapor feed composition. For the same reasons, a increasing
The vapor-liquid equilibrium (VLE) is modeled using the
vapor rate policy cannot be used. Therefore, only the decreasing
Antoine vapor-pressure equation, the nonrandom two-liquid
vapor rate policy can be used. To construct a decreasing vapor
(NRTL) equation for activity coefficients, and including vapor-
addition policy, it must be dependent on the stage number. We
phase dimerization of acetic acid. The physical property models
use a decreasing vapor rate policy, according to the following
are given by Gadewar et al.13
relation:
Consider a counter-current cascade (Figure 2) with pure acetic
j acid as the liquid feed and pure isopropanol as the vapor feed.
φ′j ) (φ +φ 1) (for j ) 1, ..., N) (13) If the vapor feed rate is equal to the liquid feed rate, φ ) 1.
Our intention is to use the cross-flow device to predict the
product compositions from such a counter-current cascade,
Here, φ is the ratio of the molar vapor feed rate to the molar
because the pinch point in the cross-flow device is hypothesized
liquid feed rate in the corresponding counter-current cascade
to be an estimate of the pinch point in the counter-current
of vapor-liquid CSTRs. The vapor flow rate decreases with
cascade. The liquid feed to the cross-flow device is pure acetic
stage number, because φ/(φ + 1) < 1. Adding the vapor feed
acid, and the vapor feed has a composition at phase equilibrium
using this policy in the cross-flow device gives
with a equimolar mixture of acetic acid and isopropanol reacted
∞
until it reaches reaction equilibrium. Using φ′j ) (0.5)j and Da
) 10, we solve eq 11 to a pinch point, as shown in Figure 5.
∑
j)1
φ′j ) φ (14)
Because the pinch point is at reaction equilibrium, we use
reaction-invariant compositions using the transformations pub-
This policy ensures that the amount of vapor feed is equivalent lished by Ung and Doherty:18
to the corresponding counter-current cascade. The cross-flow X1 ) xHOAc + xIPOAc (19a)
device calculations are sequential, compared to the simultaneous
calculations for a counter-current cascade. The iterative calcula- X2 ) xIPA + xIPOAc (19b)
tions for a counter-current cascade are time-consuming and often
difficult to converge for a large number of stages. A single From eqs 5 and 6, the corresponding vapor and liquid product
calculation for either the cross-flow device or the corresponding compositions are calculated as shown in Figure 5. Although
counter-current cascade gives a pinch point that is independent the product compositions are dependent on the value of Da,
of Da. It is useful to predict the product compositions for a their projection in the reaction invariant composition space is
range of Da values, as shown in the following example. independent of Da. We use this projection to simplify the view

Figure 5. (4) Predicted pinch point, (b) predicted liquid products, (O)
predicted vapor products, and (×) a calculated trajectory for a counter-
current cascade in the reaction invariant space for the isopropyl acetate
system (Da ) 1, φ ) 1, and N ) 50).
of the composition profile. The pinch point is also independent
of the Damköhler number Da, and, therefore, the same pinch
point is obtained by solving eqs 11 for any finite value of Da.
A liquid composition profile for a counter-current cascade with
50 stages, φ ) 1, and Da ) 1, with acetic acid as the liquid
feed and isopropanol as the vapor feed, is shown in Figure 5.
The product compositions predicted from the cross-flow model
give a very good estimate of the calculated values.
There is a one-to-one correspondence between the reaction
invariant space (X1-X2) and the mole fraction space at reaction
equilibrium. However, this is not the case in the kinetic regime;
therefore, we use the three-dimensional space given by X1, X2,
and xIPOAc, which is equivalent to the three-dimensional mole
fraction space. The liquid product composition and vapor
product composition in the reaction invariant space are given
by XL and YV, respectively. A range of xIPOAc values that satisfies
the reaction invariant product compositions XL and YV, respec-
tively, is determined using a simple linear model that satisfies
the following equations and constraints:
0 e xi,L e 1 (for i ) 1, ..., c -1) (20)
c The liquid feed is pure acetic acid, and the vapor feed is pure
∑ xi,L ) 1 (21)
i)1
xHOAc,L + xIPOAc,L ) X1,L (22)
xIPOH,L + xIPOAc,L ) X2,L (23)
One way to solve this model is to use a linear programming
method (e.g., Simplex method). In the solution procedure, a
guess value for xIPOAc,L is chosen, and the values for xHOAc,L
and xIPOH,L are varied until the equations and constraints (eqs
20-23) are satisfied. We can choose the difference between
the right-hand side and the left-hand side of eq 22 as the
objective function and minimize it in a linear program. If the
equations and constraints are not satisfied, the guessed value
of xIPOAc is considered infeasible. An equivalent linear model
can be arranged for the vapor product composition, YV. The
range of compositions that solve the aforementioned linear
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3259
Figure 6. Predicted liquid and vapor products for the middle section in
the X1-X2-xIPOAc space for the isopropyl acetate system.
Figure 7. Calculated counter-current cascade trajectory at Da ) 1 and
φ ) 1 for the isopropyl acetate system.
program is shown in Figure 6; the liquid products and vapor
products each lie in a straight line in the X1-X2-xIPOAc
composite space.
We now check how well our predictions match with the
calculations for a counter-current cascade with a large number
of stages. Figure 7 shows a liquid composition profile for a
counter-current cascade with 50 stages, φ ) 1, and Da ) 1.
isopropanol. Figure 7 shows that the liquid product from a
counter-current cascade lies very close to the predicted value.
Although the predicted vapor composition lies very close to
the calculated value, it cannot be clearly observed in Figure 7
(the projection in Figure 5 gives a better view). Figure 8 shows
the liquid composition profile and the liquid and vapor product
compositions for a counter-current cascade for Da ) 100; all
other parameters are the same as mentioned previously. The
calculated products lie very close to the predicted compositions.
Figures 7 and 8 also show that the predicted products are swept
out by a counter-current cascade as Da varies between the limits
of no reaction (Da ) 0) and reaction at equilibrium (Da ) ∞).
However, note that the predicted products cannot be directly
linked to a specific value of Da. Therefore, we must pick product
compositions from the predicted feasible range without exactly
knowing the Da value for the middle section that produced those
products.
3260 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

Table 1. Thermodynamic Data for the Methyl Acetate Examplea

Antoine Equation
b b
ln(Psat) ) a +
T+c
Psat in Pa and T in K.

Antoine Coefficients
molar normal
volume boiling
component (cm3/g-mol) point (°C) a b c
acetic acid (1) 57.24 118.0 22.1001 -3654.62 -45.392
methanol (2) 40.50 64.7 23.499 -3643.31 -33.434
methyl 79.31 57.08 21.1520 -2662.78 -53.460
acetate (3)
water (4) 18.051 100.1 23.2256 -3835.18 -45.343

( )
Wilson Equationc
j)n k)n xkAki
Figure 8. Calculated counter-current cascade trajectory at Da ) 100 and
ln(γi) ) 1.0 - ln ∑ xA - ∑
j ij
j)n

∑x A
j)1 k)1
φ ) 1 for the isopropyl acetate system.
j kj
j)1
where

Aij )
Vj
Vi
exp (
aij + bijT
RT )
Binary Interaction Parameters, Aij (cal/g-mol)
A11 ) 0.0 A21 ) -547.5248 A31 ) -696.5031 A41 ) 658.0266
A12 ) 2535.2019 A22 ) 0.0 A32 ) -31.1932 A42 ) 469.5509
A13 ) 1123.1444 A23 ) 813.1843 A33 ) 0.0 A43 ) 1918.232
A14 ) 237.5248 A24 ) 107.3832 A34 ) 645.7225 A44 ) 0.0
Dimerization in the Vapor Phased

kij )
( ){
Zij 1
Zi Zj P
exp[BFijP/(RT)]
exp[BFiiP/(RT)] exp[BFjjP/(RT)] }
-BDij (2 - δij)
kij )
RT

a Data taken from ref 18. b Saturation pressure Psat given in units of Pa

and temperature T given in Kelvin. c Dimerization of acetic acid in the vapor

phase is also included. In this equation, γi is the activity coefficient of
component i, n is the number of components, aij is the non-temperature-
dependent energy parameter between components i and j (cal/g-mol), bij is
the temperature-dependent energy parameter between components i and j
(cal/g-mol), and Vi is the molar volume of pure liquid component i (L/g-
mol). d In this equation, Z represents the true mole fractions of the species
in phase equilibrium, P is the system pressure, and kij is the dimerization
reaction equilibrium constant for acetic acid (kij ) 10.0-12.5454+(3166/T)). Also,
δij ) 0 if i * j, and δij ) 1 if i ) j, BF is the contribution to the second
virial coefficient from physical forces, and BDij is the contribution of
dimerization to the second virial coefficient.

Figure 9. Nonreactive stripping and rectifying cascade trajectories,

starting from the predicted products for the middle section of a double-
feed hybrid column: (a) trajectories in the X1-X2-xIPOAc space and (b)
projection in the reaction invariant space.
To determine the feasibility of a double-feed column, the
vapor product from the counter-current cascade (middle section),
V, is fed to an isobaric flash cascade that represents the
rectifying section, and the liquid product, L, is fed to an isobaric
flash cascade that represents the stripping section.12 These
rectifying and stripping sections can be reactive or non-
reactive, as desired. The cross-flow device predicts the
products from the middle section; however, the composition
profile for the middle section cannot be predicted. Because
the objective of this feasibility analysis is to determine the
product splits from a double-feed column, the profile for the
middle section need not be known. We choose a set of
compositions from the predicted (using the cross-flow device)
range of feasible products as a feed to the isobaric flash cascade,
and the feasible splits for a double-feed column are then
determined. Figure 9a shows the feasible product splits for a
double-feed column with nonreactive stripping and rectifying
sections. A projection of the feasible products splits in the
reaction invariant space is shown in Figure 9b. Pure acetic acid
can be obtained as a bottoms product, whereas isopropyl
acetate cannot be obtained as a pure product from a double-
feed hybrid reactive distillation column. The stripping and
rectifying cascade trajectories are used to select the feasible
distillate and bottoms composition from a double-feed column,
such that the overall material balances between feed and
products are satisfied.

Figure 10. (4) Predicted pinch point, (b) predicted liquid products, (O)
predicted vapor products, and (×) a calculated trajectory for a counter-
current cascade in the reaction invariant space for the methyl acetate system
(Da ) 1, φ ) 1, and N ) 50).
Figure 11. Calculated counter-current cascade trajectory at Da ) 1 and
φ ) 1 for the methyl acetate system.
Algorithm for Feasible Splits
The following algorithm determines the feasible splits for a
double-feed reactive distillation column.
(i) For a given reaction chemistry and column pressure,
choose the heavy reactant as the upper feed and the light reactant
as the lower feed.
(ii) Based on the reaction stoichiometry, determine the upper
feed and lower feed flow rates (e.g., equal flow rates for a heavy
acetic acid upper feed and the light isopropanol lower feed in
the case of producing isopropyl acetate).
(iii) Use the cross-flow arrangement shown in Figure 4 to
predict the pinch point in the middle section. Based on the lower
feed to upper feed ratio in step (ii), determine the vapor addition
policy for the cross-flow device using eq 13.
(iv) Determine the reaction invariants for the liquid and vapor
products from the middle section using eq 7.
(v) Determine the range of reference components for the
liquid and vapor product compositions in a three-dimensional
(3-D) composition space (consisting of the reaction invariant
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3261
Figure 12. Nonreactive stripping and rectifying cascade trajectories starting
from the predicted products for the middle section of a double-feed hybrid
column: (a) trajectories in the X1-X2-xMeOAc space and (b) projection in
the reaction invariant space.
space plus the reference component mole fraction composition),
using a linear model equivalent to eqs 20-23.
(vi) Choose a liquid and a vapor composition from the product
compositions in the 3-D composition space and determine the
corresponding compositions in the mole fraction space (using
transformations for reaction invariant compositions).
(vii) The liquid product composition from the middle section
is the feed to the stripping section and the vapor product
composition is the feed to the rectifying section.
(viii) Use isobaric flash cascade method12 to determine both
reactive and nonreactive stripping and rectifying cascade
profiles.
(ix) Choose a desirable composition on the rectifying cascade
trajectory (potential distillate) and calculate the corresponding
composition on the stripping cascade trajectory (potential
bottoms) by solving the overall mole balances for the column.
Alternatively, the potential bottoms product can be chosen and
the potential distillate is calculated using mole balances.
Example 2: Production of Methyl Acetate
Methyl acetate is produced via the esterification of methanol
with acetic acid. The reaction is given as
acetic acid (HOAc) + methanol (MeOH) h methyl acetate
(MeOAc) + water (H2O) (24)
A pseudo-homogeneous rate model is given as
( )
aMeOAcaH2O
r ) kf aHOAcaMeOH - (25)
Keq
3262 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007

The reaction equilibrium constant and the rate constant are

given as19

Keq ) 2.32 exp(782.98

T )
(26)

-6287.7
) ) 9.732 × 10 exp(
T )
kf (h-1 8
(27)

where T is given in Kelvin. The rate constant was obtained by

fitting the pseudo-homogeneous rate equation to predictions
from a more-complex heterogeneous rate model.20 The heat of
reaction is -3.01 kJ/mol, which is slightly exothermic. We
neglect heat effects in this example; however, in some examples
where the heat of reaction is large, heat effects must be
considered. Therefore, the liquid and vapor flow rates are
constant from stage to stage. The liquid-phase activity coef-
ficients are well-represented by the Wilson equation, using the
parameters listed in Table 1.
For a counter-current cascade with a liquid feed of acetic
acid and a vapor feed of methanol, the pinch point at φ ) 1 is
estimated using the cross-flow device. The cross-flow device
follows the vapor rate policy in eq 13. The predicted pinch point
and the corresponding liquid and vapor products in a reaction
invariant space are shown in Figure 10. A reaction invariant
liquid composition profile for a counter-current cascade with
50 stages, φ ) 1, and Da ) 1, with acetic acid as the liquid
feed and methanol as the vapor feed, is also shown in Figure
10. A linear program equivalent to eqs 20-23 determines the
predicted product compositions in the X1-X2-xMeOAc space, as
shown in Figure 11. A liquid composition profile for the counter-
current cascade in Figure 11 shows that the predictions are very
similar to the calculated values of the product compositions.
We choose a composition predicted from the cross-flow
device as a feed to the isobaric flash cascade to determine
feasible splits for a double-feed column. Figure 12a shows the
splits for a double-feed column with nonreactive stripping and
rectifying sections. A projection of the feasible products splits
in the reaction invariant space is shown in Figure 12b. The figure
shows that pure methyl acetate can be obtained as a distillate
and pure water can be obtained as a bottoms product from a
double-feed hybrid reactive distillation column. The double-
feed column configuration described here does not have a
distinct nonreactive extractive section at the top of the reactive
zone. Chadda et al.14 have shown, using column simulations,
that such a configuration is indeed feasible.

Effect of Vapor Rate on the Middle Section

The cross-flow arrangement predicts the pinch point in the
middle section. The vapor addition policy for the cross-flow
device is related to the ratio of the lower feed to the upper feed
by eq 13. Extractive distillation columns are known to exhibit
minimum entrainer flows (or a minimum ratio of upper feed
flow rate to lower feed flow rate), below which the desired
products cannot be obtained, even in a column with an infinite
number of stages. Therefore, double-feed reactive distillation
columns can be expected to exhibit such a minimum ratio.
The predictions for the liquid products from the middle
section in the reaction invariant space at different values of the
ratio of lower feed rate to the upper feed rate are shown in Figure
13a. For a value of φ > 1.3, the cross-flow device predicts
product compositions that lie outside the feasible mole fraction
space (although the predicted pinch point lies in the positive
mole fraction space at all values of φ). The vapor products in
the reaction invariant space are shown in Figure 13b. Figure
Figure 13. (a) Predicted liquid products and (b) predicted vapor products,
each at varying feed ratios in the reaction invariant space.
13b shows that, for φ < 0.6, the cross-flow arrangement predicts
vapor products that do not lie in the positive mole fraction space.
Comparing these results with the calculations for a counter-
current cascade with 50 stages for different feed ratios, we
observe that, for φ > 1.5, the liquid product from the counter-
current cascade (middle section) consists of pure isopropanol
(lower feed). Therefore, even by adding a stripping section, the
reactant isopropanol will emerge as a bottoms product. Also,
from the counter-current cascade calculations, we observe that,
for φ < 0.5, the vapor product from the counter-current cascade
(middle section) consists of pure acetic acid. Hence, even after
adding a rectifying section, the reactant acetic acid will emerge
as a distillate in a double-feed column. This happens because
the pinch occurs at the lower feed stage for φ > 1.5 (the upper
feed flow is possibly below the minimum feasible value), and

Figure 14. Calculated counter-current cascade trajectory at Da ) 1 and φ
) 1 for the methyl acetate system. Predicted products for the vapor addition
policy given by eq 28.
at the upper feed stage for φ < 0.5 (the lower feed flow is
possibly below the minimum feasible value). An important
utility of the cross-flow arrangement is to estimate the upper
and lower limits of the feed ratio for a desirable double-feed
column, because it is usually not desirable to get pure reactants
as a distillate or bottoms.
Vapor Addition Policy
The vapor feed addition policy in the cross-flow device
follows a geometric series given by eq 13. This is not the only
vapor addition policy that can be used to predict the pinch point
in the middle section. For example, an alternative vapor addition
policy is given as
4φ
φ′j ) (28)
3j(j + 2)
Using this policy, eq 14 is satisfied; therefore, the net vapor
added to the cross-flow device is equal to that in the corre-
sponding counter-current cascade. Figure 14 shows a liquid
composition profile for a counter-current cascade with acetic
acid as the liquid feed and methanol as the vapor feed, Da ) 4,
and φ ) 1. The figure shows that the calculated product
compositions lie very close to the feasible products predicted
by the cross-flow device using eq 28. In fact, the policy in eq
28 gives a slightly better prediction of the products, compared
to the policy in eq 13, and also gives a better estimate of the
vapor-to-liquid ratios at which the pinch moves to either end
of the middle section. However, a simpler policy (eq 13) is
desirable at the expense of a small amount of inaccuracy in the
predictions. Other policies can be devised for the vapor feed
addition policy; however, we know of no simpler expression
than eq 13.
Conclusions
We have developed a method that does not require repetitive
simulations to determine feasible products from a double-feed
reactive distillation column. The tool developed in this work
complements the method for single-feed reactive distillation
columns described by Chadda et al.12 A cross-flow arrangement
is used to predict the pinch point for the middle section of a
double-feed column. Use of a cross-flow device simplifies the
calculations for the middle section. Knowledge of the pinch
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3263
point composition allows the prediction of the composition of
liquid and vapor products from a counter-current cascade using
material balances. Also, a single calculation coupled with a
simple linear model predicts the range of product compositions
for different Damköhler number (Da) values. These product
compositions are used as feed compositions to an isobaric flash
cascade model that represents the stripping and rectifying
sections. We find that a double-feed reactive distillation column
cannot give isopropyl acetate as a pure product; however, methyl
acetate can be obtained as a pure product in a double-feed hybrid
reactive distillation column.
Nomenclature
A, B, C ) generic chemical species
ai ) activity of component i
c ) total number of reacting and inert components
Da ) Damköhler number
H ) liquid-phase molar holdup (mol)
Hj ) liquid-phase molar holdup on stage j (mol)
kf ) forward reaction rate constant (1/time)
kf,ref ) forward reaction rate constant at the reference temper-
ature (1/time)
Lj ) liquid molar flow rate from stage j (mol/s)
N ) number of two-phase CSTRs in the cascade
r(x) ) mole fraction based on the rate of reaction (1/time)
Tref ) reference temperature (K)
V′ ) vapor flow rate (mol/s)
Vj ) vapor molar flow rate from stage j (mol/s)
x ) column vector of c mole fractions
xi,j ) mole fraction of component i in the liquid phase for the
jth stage
x̂ ) vector of liquid mole fractions at the pinch point
Xi,j ) reaction invariant liquid mole fraction of component i in
stage j
XL ) vector of reaction invariant compositions of the liquid
product from the middle section of a double-feed column
yi,j ) mole fraction of component i in the vapor phase for the
jth stage
Yi,j ) reaction invariant vapor mole fraction of component i in
stage j
YV ) vector of reaction invariant compositions of the vapor
product from the middle section of a double-feed column
Greek Symbols
νi,r ) stoichiometric coefficient of component i in reaction r
νTj ) sum of stoichiometric coefficients of reaction j
φ ) ratio of the vapor rate to the liquid inlet rate (dimensionless)
φj ) ratio of the vapor rate to the liquid inlet rate for stage j
(dimensionless)
φ′j ) ratio of the vapor rate to the liquid inlet rate for stage j in
the cross-flow arrangement (dimensionless)
Subscripts, Superscripts, and Accents
0 ) initial
i ) component i
Ref ) indicates reference components
T ) total
∧ ) pinch
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ReceiVed for reView July 5, 2006
ReVised manuscript receiVed January 4, 2007
Accepted January 9, 2007
IE060867R