4000 Ind. Eng. Chem. Res.

2004, 43, 4000-4011

Simplified Design of Batch Reactive Distillation Columns

Maria E. Huerta-Garrido and Vicente Rico-Ramirez*
Departamento de Ingenieria Quimica, Instituto Tecnologico de Celaya, Av. Tecnologico y Garcia Cubas S/N,
Celaya, Gto., CP 38010, Mexico

Salvador Hernandez-Castro
Facultad de Ciencias Quimicas, Universidad de Guanajuato, Col. Noria Alta S/N, Guanajuato, Gto.,
CP 36050, Mexico

This work proposes a simplified methodology for the analysis and design of reactive batch
distillation columns based on the McCabe-Thiele method for reactive continuous columns and
on the concept of a reactive difference point. To extend the application of the concept of a reactive
difference point for reactive batch distillation columns, expressions for the McCabe-Thiele
operating line and for the dynamics of the reboiler in the reactive case have been derived; two
cases are considered depending upon the phase in which reactions occur (i.e., liquid or vapor).
We also provide an approach to the derivation of an expression to calculate the molar turnover
flow rate by considering each reactive distillation plate as a combined system of a conventional
equilibrium stage linked to a chemical reactor (phenomena decomposition). Furthermore, we
present our derivation of the Underwood equations (minimum reflux) for continuous and batch
reactive distillation columns. Finally, five illustrative examples allow us to show that our results
present reasonable agreement with those obtained through BatchFrac of AspenPlus.

1. Introduction Despite the extensive body of literature reported on

Reactive distillation has recently emerged as a prom-
ising technology because of its integrated functionality
of separation and reaction. The general advantages of
reactive distillation are1 (1) it can achieve higher
conversion rates for an equilibrium-limited reaction
because of the continuous remotion of products being
formed and (2) the heat of reaction can reduce the heat
load of condensers or reboilers. Its most serious limita-
tion, however, is that the temperature of the reaction
must coincide with the distillation range.2 Despite this
weakness, potential savings in terms of investment and
operation costs of this synergistic unit operation have
motivated considerable research effort aimed to gener-
ate efficient design strategies.
Barbosa and Doherty3,4 developed reactive residue
curves in transformed coordinates and then proposed
an algorithm to calculate the minimum reflux on
reactive distillation columns by using transformed
variables. Espinosa et al.5 developed Ponchon-Savarit
diagrams in a transformed enthalpy-composition space,
and Perez-Cisneros6 proposed McCabe-Thiele diagrams
for reactive distillation columns based on the element
balance approach. Following these initial attempts,
Westerberg’s group at Carnegie Mellon University
developed the concept of the reactive difference point7
and used this concept to provide simplified design
strategies and visual and graphical insights for reactive
distillation columns.8-12 This reactive difference point
is similar to the difference point for extractive distilla-
tion columns and can be used as a basis for performing
numerical calculations and geometric visualizations of
reactive columns.
* To whom correspondence should be addressed. Tel.: +52-
(461)-6117575 ext. 156. Fax: +52-(461)-6117744. E-mail:
vicente@iqcelaya.itc.mx.
10.1021/ie030658w CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/08/2004
the topic of reactive distillation, much work remains to
be done. As yet, there are few works concerning the
design of reactive batch distillation columns.13 Given the
current applications of batch distillation in small-scale
industries producing high-value-added specialty chemi-
cals (pharmaceutical industry, fertilizers, etc.), attention
should also be focused on that direction. Furthermore,
very few reports provide results with respect to the
theoretical limiting conditions of reactive distillation
columns (such as minimum reflux, minimum number
of plates, etc.). This paper intends to contribute to both
of the topics mentioned above.
First, we provide a simplified methodology for the
analysis and design of reactive batch distillation col-
umns based on the McCabe-Thiele method and on the
concept of the reactive difference point. To extend the
applications of the reactive difference point for reactive
batch distillation columns, we propose a simplified
approach to the calculation of the molar turnover flow
rate. By using the idea of phenomena decomposition,
we consider each reactive distillation stage as a com-
bined system of a conventional distillation plate linked
to a chemical reactor. Also, expressions for the dynamics
of the reboiler and the McCabe-Thiele operating line
(quasi-steady-state assumed) have been rederived for
reactive batch distillation columns.
With respect to the limiting operation conditions of
reactive distillation columns, we have derived the
Underwood equations (minimum reflux) for the reactive
case (for both continuous and batch distillation).
The paper has been divided into six sections. Section
2 presents some previous work relevant to our ap-
proach: (1) it briefly explains the graphical design of a
continuous reactive distillation column using the Mc-
Cabe-Thiele method9 and (2) it describes the McCabe-
Thiele method for batch distillation columns for the
nonreactive case.13 The contributions of the paper are

Figure 1. McCabe-Thiele diagram for reactive distillation in the
rectifying section.
presented in sections 3-5. Section 3 explains the
proposed approach to the analysis and design of reactive
batch distillation columns using the McCabe-Thiele
method. It also shows how we have derived expressions
for the dynamics of the reboiler, McCabe-Thiele operat-
ing lines, and the extent of the reaction so that the
concept of the reactive difference point can still be
applied. Section 4 presents our derivations for the
Underwood equations for reactive distillation columns.
Section 5 shows the results of the approach for several
illustrative examples as well as a comparison to the
results obtained through BatchFrac of AspenPlus. Fi-
nally, section 6 concludes the paper.
2. Previous Work
This section summarizes the concepts that serve as
a basis for the development of our approach to the
analysis and design of reactive batch distillation col-
umns.
2.1. McCabe-Thiele Method for Reactive Con-
tinuous Distillation Columns.2,9 Hauan et al.7 de-
veloped the idea of reactive fixed points arising from
collinearity of reaction, separation, and mixing as
individual phenomena; the authors also derived the
concept of the reaction difference point characterizing
the flow generated by reaction. Hence, by combination
of the concept of a reactive difference point with the
concept of a pseudofeed,12 reactive operating lines can
be defined and used to construct McCabe-Thiele dia-
grams for reactive distillation columns. For example,
for the case of an isomerization reaction taking place
in the rectifying section of a column (so that 1 mol of
heavy reactant R1 converts into 1 mol of light product
P1), the expression for the operating line is given by
L L ξn
V V(
yn+1 ) xn + 1 - xD -
V ) (1)
where V and L are the vapor and liquid interstage flow
rates, respectively, and ξn is the accumulated sum of
the reaction molar turnover flow rates until the nth
stage from the top. Equation 1 represents several
operating lines parallel to each other because, for the
same slope, the y intercept is changing in terms of the
accumulated sum of the reaction molar turnover flow
rates. Consider the McCabe-Thiele diagram shown in
Figure 1. Starting from the top at the distillate composi-
tion, xD, the first operating line intersects the 45° line
Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4001
to the left of the distillate composition for a given
reaction molar flow rate. Then, as we move down the
column, the accumulated sum of the reaction molar
turnover flow rates increases and the intersection point
also moves further to the left. These intersection points
are the reactive difference points and can be calculated
from eq 2.
ξn
xn ) xD - (2)
D
Lee et al.2 show the derivation of the operating line
for the stripping section and the derivation for the q
line and present an analysis of the performance of
reactive columns depending upon where the reaction
zone is located. In a related paper,9 the authors analyze
the cases where changes in molar flow rates occur
because of reaction; an analysis based on either mass
(rather than molar) balance equations or changing-slope
operating lines is suggested in that situation to con-
struct McCabe-Thiele diagrams. A generalization of the
use of the difference points in reactive and extractive
cascades has also been reported.11,12
An important aspect of this approach to the design of
reactive distillation is the knowledge of (or the ability
to calculate) the molar turnover flow rate, ξ. As we
explain later, an approach to the calculation of ξ based
on phenomena decomposition is proposed in this paper.
2.2. McCabe-Thiele Method for Batch Distilla-
tion Columns.13 The unsteady-state nature of batch
distillation implies solutionof a set of differential equa-
tions. Diwekar13 describes the two main operation
policies for batch distillation: constant reflux and
constant distillate composition. For any of them, the
McCabe-Thiele method can be applied by considering
only the reboiler and condenser dynamics and assuming
a quasi steady state on the plates. The solution proce-
dure involves an iterative scheme for the simultaneous
determination of x(k)D (distillate composition of compo-
nent k) and x(k)B (still composition of component k) for
each time interval until the stopping criterion is met.
Typical stopping criteria include reaching a specified
average distillate composition, obtaining a given amount
of distillate, or operating the column for a specified
batch time. For a binary system, the McCabe-Thiele
operating line for batch distillation columns presents
the same basic form as that of continuous distillation,
but it has to be applied for each time step:
R 1
yn+1 ) xn + x (3)
R+1 R+1 D
where the reflux ratio, R, is defined as R ) L0/D. Figure
2 shows the McCabe-Thiele diagram for two time steps
in a column (three equilibrium stages) undergoing
constant reflux operation. Initially, the still composition
xB0 is known, and the composition of the distillate xD0
can be found iteratively from the specified number of
stages and from the given slope of the operating line
(constant reflux ratio). After the distillate compositions
are calculated, the differential equations representing
the dynamics of the reboiler can be integrated to obtain
the amount of mixture remaining in the still (B1), the
distillate product (D1), and xB1. Then, the McCabe-
Thiele diagram is used again to calculate xD1 iteratively.
This procedure continues for the following time steps
in a similar way until the stopping criterion is met.
4002 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004

Figure 2. McCabe-Thiele diagram for batch distillation under

constant reflux policy.

3. Simplified Method for Analyzing and

Designing Reactive Batch Distillation Columns
Figure 3. Reactive batch distillation column.
This section provides the derivation of the expressions
needed to simulate the performance and/or to design overall and component (i) balance equations around
reactive batch distillation columns using a simplified section 1 of Figure 3 are
method. The solution strategy can be directly used for
binary systems, but an approximation is also proposed Lj D νi ξk,j
for the case of multicomponent systems (see section 5.3). yi,j+1 ) xi,j + xi,D - (4)
V V -νk V
Our approach is based on the McCabe-Thiele method
for reactive columns and on the concepts of the reactive
difference point and molar turnover flow rate. We
V ) Lj + D - νTξk,j (5)
consider separately the cases in which reaction occurs
either in the liquid phase or in the vapor phase, where ν represents the stoichiometric coefficients of
although the analysis could be integrated. As a simpli- reaction (negative for reactant k and positive for product
fied approach, the following are the assumptions made i), νT is the total sum of stoichiometric coefficients, and
through our derivations for kinetically controlled reac- (νi/-νk)ξk,j represents the production of i due to reaction
tive batch columns: of k on stage j. The last of the terms in eq 5 represents
1. Heat of mixing, stage heat losses, and sensible heat the overall change in the number of moles due to
changes of both liquid and vapor are negligible. reaction. Notice that, although we are using a binary
2. The pressure on the column remains constant system as the basis for our derivations here, eqs 4 and
through the operation. 5 can actually be generally applied, and that is the basis
3. Startup conditions will not be considered. for the extension of the approach to multicomponent
4. The stages of the column will be considered in quasi systems.
steady state. Because for this case the reaction is taking place in
5. Reaction takes place on all of the stages but the the liquid phase, the vapor flow rate can be assumed
reboiler and condenser. as constant, but the liquid flow rate might change
6. Reaction is irreversible because of the continuous depending on the stoichiometric coefficients. Changes
removal of the product. in the liquid flow rate could be calculated as
If assumption 1 holds, then the molar flow rate of the Lj ) Lj-1 + νT(ξk,j - ξk,j-1) (6)
phase in which reaction does not occur can be considered
as a constant. Seeking simplicity, in the following
Observe that if νi ) -νk, then νT ) 0 and Lj ) Lj-1, so
derivations we will obviate most of the algebraic steps
that the assumption of constant molar flow will also hold
and provide only the main results. The analysis consid-
for the liquid phase. Equations 4-6 can be used to
ers two cases depending upon the phase in which the
obtain the McCabe-Thiele operating line for reactive
reactions occur. The derivations for the liquid-phase
batch distillation:
reactions are presented first.
3.1. Reactive Batch Distillation Column: Reac- Lj νi ξk,j
1
tion in the Liquid Phase. Consider the batch reactive yi,j+1 ) xi,j + xi,D - (7)
distillation column represented in Figure 3. ξk,j repre- V R+1 -νk V
sents the sum of the molar turnover flow rate for
component k (reactant defined as the base component) and for the case in which there is no change in the liquid
in the stage j, the distillate product is represented as flow rate:
D, and the reflux ratio as R ) L0/D. The subtractions
indicated in Figure 3 are used to emphasize the contri- R 1 νi ξk,j
yi,j+1 ) xi,j + xi,D - (8)
butions of reaction on each stage because ξk,j is an R+1 R+1 -νk V
accumulated sum. For a binary system involving com-
ponents k (heavy reactant) and i (light product), the Also note that, if there is no change in the liquid flow
 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4003

Figure 5. Stage on a reactive batch distillation column: reaction

in the liquid phase.

can be considered as a separation cascade linked to a

chemical reactor having an equivalent conversion; such
an approach is known as phenomena decomposition and
has been explained in detail.7,11 Basically, Hauan et al.7
show that the phenomena occurring in some combined
systems of separation and reaction (mixing, separation,
Figure 4. Mass balance for the dynamics of the reboiler.
and reaction) can be separated and analyzed indepen-
dently from each other. Moreover, they show that, for
rate, νi ) -νk, eq 8 is basically the same as the operating the case of reactive cascades, given the extent of the
line obtained for continuous distillation (eq 1). Further- reaction, the decomposition does not affect the mass
more, by comparing eqs 3 and 8 (nonreactive and balance equations.11
reactive batch distillation), we see that the contribution In a similar way, to derive an expression for the
of reaction is given through the term -(νi/-νk)(ξk,j/V), calculation of the molar turnover flow rate ξk,j, in this
or -(ξk,j/V) if there is no change in the number of moles. paper we assume that each separation stage of a
3.1.1. Dynamics of the Reboiler. To derive the reactive batch distillation column can be considered as
dynamics of the reboiler, consider the overall and a nonreactive equilibrium separation stage linked to a
component balance for section 2 of Figure 4: continuous stirred tank reactor (CSTR; see Figure 5).
If we were able to know a priori the exact value of the
νTξk,T - D ) dB/dt (9) molar turnover flow rate for each stage, then the mass
balance equations obtained through the phenomena
νi d decomposition assumption would hold. However, the
ξ - Dxi,D ) (Bxi,B) (10) sequential approach (reaction-separation) applied here
-νk k,T dt is, in fact, used for the calculation of such a value of
the extent of the reaction. Hence, it is evident that in
where ξk,T is the total molar turnover flow rate (k being this case a sequential approach will not exactly repre-
the base component). The overall mass balance for the sent a simultaneous phenomenon in nature and that
condenser is the assumptions made, such as representing the reac-
tion volume as a CSTR, are approximations that may
V - L0 - D (11) lead to error. A CSTR is used because we are consider-
ing perfect mixing in the liquid and vapor phases. Also,
By combining eqs 9-11, one can show that the the CSTR is placed above the separation stage just
differential equations representing the behavior in the because of numerical implications in the solution scheme.
reboiler and condenser are The component mass balance equation for the reactor
of Figure 5 is given by
dB V
) νTξk,T - (12)
dt 1+R υ(rk,j) ) Lj-1xk,j-1 - L′jx′k,j (15)
V
D) (13) where υ is the reaction volume (liquid holdup), rk,j is
1+R the rate of reaction of component k in stage j, L is the

{ [ ] }
liquid flow rate, and x is the liquid composition. In
dxi,B 1 V νi principle, the calculation of υ would require the use of
) (xi,B - xi,D) + - νTxi,B ξk,T (14)
dt B 1+R -νk column hydraulic analysis, which could provide a rela-
tionship between Lj-1 and υ.
Observe again that, when compared to the nonreactive The reactor outlet liquid stream, L′j, can be ex-
case for batch distillation, eqs 12 and 14 include an extra pressed in terms of the molar conversion fraction of the
term to account for changes due to reaction. Further, reactant, Cj:
notice that in eq 14 the separate effects of reaction and
separation are well defined. L′jx′k,j ) Lj-1xk,j-1(1 - Cj) (16)
3.1.2. Extent of the Reaction: Molar Turnover
Flow Rate. Hauan et al.7,11 provided a generalization so that eq 15 becomes
of the concept of a difference point for reactive cascades.
The authors assume that a reactive separation cascade υ(rk,j) ) Lj-1xk,j-1Cj (17)
4004 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004

V1 R V1 1 νi ξk,j
yi,j+1 ) xi,j + xi,D -
Vj+1 R + 1 Vj+1 R + 1 -νk Vj+1
(22)
where changes in the vapor flow rate due to reaction
are given by

Vj+1 ) Vj + νT(ξk,j - ξk,j-1) (23)

If there are no changes in the vapor flow rates, then eq

22 reduces to eq 8.
3.2.1. Dynamics of the Reboiler. The overall and
component mass balances for section 2 of Figure 6
allow the derivation of the differential equations that
represent the dynamics of the reboiler as described
earlier:

dB V1
) νTξk,T -
dt 1+R

Figure 6. Derivation of expressions for the case of reaction in

dxi,B 1 V1
dt
)
B 1+R {
(xi,B - xi,D) +
νi
-νk
- νTξi,B ξk,T [ ] }
the vapor phase.
3.2.2. Extent of the Reaction: Molar Turnover
Assuming an elemental irreversible reaction, νrR f νpP, Flow Rate. Our approach to calculate the molar
the rate of reaction can be represented by an expression turnover flow rate is based again on phenomena de-
such as composition as represented in Figure 7. Calculations in
the reactor are performed before the calculations on the

( )
L′jx′k,j equilibrium stage. The consideration of having a sepa-
νk
rk,j ) kj (18) ration stage connected to a CSTR in the case of reaction
υ0
in the vapor phase could seem inappropriate; however,
more than the need of a CSTR, our approach works by
where the term inside the parentheses represents the assuming that the compositions of reactive and nonre-
molar concentration of the reactant in the reactor and active streams are homogeneous as if the mixing on
kj is the kinetics parameter given by the Arrhenius them was perfect. A derivation similar to that of section
equation. υ0 is the volumetric flow rate entering the 3.1.2 results in the following expressions:
stage. υ0 can be calculated from

( Cj
)
n
υ0 ) Lj-1/F (19) ξk,j ) ∑
j)1
V′jy′k,j
1-C
(24)
j
where F is the density of the liquid stream. Knowing υ0
would also allow the evaluation of the residence time, where the conversion fraction of the reactant can be
τj ) υ/υ0; hence, if the liquid holdup is known or can be obtained from the implicit eq 25:

[ ]
evaluated, the use of υ0 or τj is equivalent.
When eqs 16-18 are combined, an implicit equation V′jy′k,j νk

for the molar conversion of the reactant can be obtained: V′jy′k,jCj ) υkj (1 - Cj) (25)
υ0

[
Lj-1xk,j-1(1 - Cj)
]
νk
3.3. Solution Approach. The resulting model is a
Lj-1xk,j-1Cj ) υkj (20) well-posed differential-algebraic system of equations
υ0
(DAE). Table 1 presents a summary of the model
Once eq 20 is solved to obtain Cj (analytically or specifications and the equations used for the calcula-
numerically for νk greater than 2), one can finally tions of the variables involved in each stage. The
calculate the molar turnover flow rate through the solution procedure for each time step of a reactive batch
expression distillation column is similar to the procedure for solving
the rectifying section of a continuous reactive column.
n The equations involved in the calculation could be solved
ξk,j ) ∑
j)1
(Lj-1xk,j-1Cj) (21) either simultaneously with an appropriate numerical
method or sequentially by using a method such as the
direct substitution method. We describe next the se-
3.2. Reactive Batch Distillation Columns: Reac- quential procedure for the case in which reaction occurs
tion in the Vapor Phase. If the reaction takes place in the liquid phase (constant molar flow in the vapor
in the vapor phase, derivations similar to the ones phase) in all of the stages but the reboiler; an iterative
presented in the previous subsection can be obtained. procedure for the calculation of the distillate composi-
Hence, the component and overall mass balances for tions has to be completed.
section 1 of the column presented in Figure 6 result in Considering a constant reflux policy, we assume that
the operating line for reactive batch distillation columns the number of stages (N), the reflux ratio (R), and the
(quasi-steady-state approximation): initial conditions (feed load and still compositions) are

Figure 7. Extent of the reaction: reaction in the vapor phase.
Table 1. Degrees of Freedom Analysis: Specifications
and Computations on Stage j
variable specified/calculated from
N, R, V, B0, xB specified
υ0, υ specified
L0 eq 5
Lj eq 6
Cj eq 20
ξk,j eq 21
xk,j equilibrium (relative volatility)
yk,j+1 eq 8
x′k,jL’j eq 16 (plus summation
of compositions)
xD iteratively from independent
equations used to calculate xB
given. Also, a typical specification in this case is the
vapor boilup flow rate (V), which will remain constant
through the column. As one of the main limitations of
our approach, assumed values of the liquid holdup, υ,
and entering volumetric flow rate, υ0 (or residence time,
τ), are used in this work (see section 5 for an explana-
tion).
Hence, we start by assuming the values of the dis-
tillate compositions. Then, by using a bubble-point cal-
culation, the temperature of the distillate can be com-
puted. When the temperatures of the reboiler (which
can also be computed through a bubble-point calculation
because the compositions in the reboiler are known) and
the condenser are known, a linear temperature profile
is assumed. The temperature of each stage is required
because the computations of the kinetics parameter and
the relative volatility of the mixture depend on it. Then,
a mass balance in the condenser allows the calculation
of L0; for the condenser ξk,0 ) 0 (no reaction in the
condenser) and eq 5 reduces to V ) L0 + D, which is
equivalent to L0 ) V[R/(R + 1)]. Also notice that the
distillate compositions are equal to the compositions of
the vapor flow entering the condenser (yk,1).With that,
we proceed to perform the calculation on stage 1.
Equations 20 and 21 are used for the calculation of C1
and the molar turnover flow rate, ξk,1, respectively. The
liquid molar flow rate on stage 1, L1, is obtained from
eq 6. Equation 16 and the summation equation for the
compositions are used to find the values of the liquid
flow (L′1) and the compositions (x′k,l) entering the equi-
librium separation stage of Figure 5. Then, the equi-
librium curve (equilibrium in terms of relative volatility)
and the operating line (eq 8) allow the calculation of
the rest of the compositions for stage 1 (xk,1 and yk,2).
The procedure continues for the rest of the stages
moving down the column until we evaluate the composi-
tions in the reboiler. Those values provide the conver-
gence criteria: If the computed values of the reboiler
Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4005
Figure 8. Reactive distillation column with an infinite number
of stages.
compositions are equal to the known values, then we
proceed to the next time step; otherwise, we modify our
guess for the distillate compositions and repeat the cal-
culations in the column. Notice that, with respect to the
number of degrees of freedom, the model is square be-
cause the distillate compositions can be indirectly found
from the independent equations used to calculate the
still compositions (stage-by-stage procedure). Before one
moves on to the next time step, integration of eqs 12-
14 is needed to find the values of the amount of mixture
in the still, the distillate collected, and the bottom com-
positions for the following time step. N, R, and V remain
as constants so that the simulation continues for the
next time steps and ends when a specified stopping
criterion is met.
4. Limiting Conditions for Reactive Distillation
Columns
In this section we derive the expressions to calculate
the minimum reflux (Underwood equations) for continu-
ous and batch reactive distillation columns; further-
more, a discussion regarding the Fenske equation (mini-
mum number of stages) for continuous reactive distil-
lation columns is also provided.
4.1. Underwood Equations. To derive the expres-
sion for the minimum reflux in the case of continuous
reactive distillation columns, a system such as the one
shown in Figure 8 is assumed. Our approach is based
on the derivation for the nonreactive case presented by
King.14 The section with an infinite number of stages
is placed in the rectifying section above the feed plate.
A further assumption in our derivation is that there is
no reaction in the section with an infinite number of
plates (to avoid depletion of the reactant).
The mass balance equation for component i around
section 1 of Figure 8 is
 [ ]
4006 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004

Vyi,∞ ) L∞xi,∞ + Dxi,D -

νi
ξ
-νk k,T
(26)

V-V
h )
NC

∑
(
Ri,∞ Dxi,D -
-νk
νi
ξk,T + Bxi,B
) (34)
where the index ∞ has been assigned to the streams i)1 Ri,∞ - φ
coming from the section with an infinite number of
plates. The overall mass balance for the condenser is Finally, by introducing the definition of q

V ) L0 + D (27) V-V
h ) F(1 - q)

It is also considered that the liquid-vapor equilibrium and the component mass balance equation for the whole
on the last stage of section 1 is given by column

xi,∞ ) yi,∞/Ki,∞ (28) νi

Fzi,F ) Dxi,D - ξ + Bxi,B
-νk k,T
When eq 28 is substituted into eq 26 and with rear-
rangement: one can get

[ ]
Ri,∞zi,F
NC
νi ξk,T
V -νk D
xi,D - 1-q) ∑
i)1 R -φ
(35)
yi,∞ ) (29) i,∞
D 1 L∞
1- which is the second of the Underwood equations. Equa-
Ki,∞ V
tion 35 can be used for calculating φ and eq 32 for
calculating Rmin for continuous reactive distillation
When the definition of relative volatility (with respect columns.
to the key component r) is incorporated: 4.1.1. Extension of the Underwood Equations to

( )
Reactive Batch Distillation Columns. A direct ex-
νi ξk,T tension to the Underwood equations derived above can
Ri,∞ xi,D -
V -νk D be done for the case of reactive batch distillation
yi,∞ ) (30) columns. An approach similar to the one proposed by
D 1 L∞ Diwekar13 serves that purpose (Figure 9).
Ri,∞ -
Kr,∞ V In Figure 9, a reactive batch distillation column is
represented as a continuous column where the feed
Here a new variable, φ ) (1/Kr,∞)(L∞/V), called the enters the column at the bottom stage with a temper-
absorption factor, is introduced. Also, because the ature equal to its bubble point and with a composition
summation of the compositions in the vapor stream equal to xi,B. Such a representation allows rewriting of
going into the section with an infinite number of stages eqs 32 and 35 as

[ ]
has to be 1, eq 30 reduces to eq 31. where NC is the

[ ]
NC Ri,∞xi,B

( )
νi ξk,T ∑
i)1 R -φ
)0 (36)

[ ]
Ri,∞ xi,D - i,∞

( )
V NC -νk D
D
) ∑
i)1 Ri,∞ - φ
(31)
Ri,∞ xi,D -
νi ξk,T
NC -νk D
number of components. Finally, the substitution of eq
Rmin + 1 ) ∑
i)1 Ri,∞ - φ
(37)
27 and the definition of the reflux ratio in eq 31 result
in

[ ]
which correspond to the Underwood equations for

( )
reactive batch distillation columns. Observe that the
νi ξk,T minimum reflux computation not only depends on the
Ri,∞ xi,D - distillate and bottom compositions, as it does for a
NC -νk D nonreactive column, but also depends on the extent of
Rmin + 1 ∑
i)1 Ri,∞ - φ
(32) the reaction. Therefore, a value of the extent of the
reaction has to be given in order to make eq 37 useful
in practical terms. It might be difficult to provide an
which is the first of the Underwood equations for approximation to the extent of the reaction a priori, and
calculating the minimum reflux. Following a similar a parametric search might be necessary to obtain a
procedure for section 2 (nonreactive stripping section) feasible value. For a specific reaction-separation sys-
of Figure 8, one can obtain tem, a reasonable value of the extent of the reaction can

[ ]
be estimated, for instance, by assuming that the molar
h
V NC R′i,∞xi,B turnover flow rate is equally distributed among the
-
B
) ∑
i)1 R′ - φ′
(33) reactive stages of the column and by defining the
i,∞ amount of product obtained through the reaction (using
a value of the molar conversion fraction based on the
Combining eqs 31 and 33 and taking into account that kinetics of the reaction involved and the amounts of the
φ ) φ′ and Ri,∞ ) R′i,∞ result in reactants initially fed to the column).

Figure 9. Reactive batch column as a continuous column.
4.2. Comments on the Fenske Equation for
Reactive Distillation. The derivation of the Fenske
equation for nonreactive continuous columns assumes
operation at total reflux. Interesting conclusions can be
drawn with respect to the corresponding derivation in
the reactive case. Let us assume that an irreversible
isomerization reaction (binary mixture) is taking place
in the column and that the product of the reaction is
the most volatile component.
The case of total reflux is then the first one that we
analyzed for the reactive case, as shown in Figure 10a.
A problem arises, however, in such a scheme. Because
the reaction takes place regardless of whether products
are being obtained or not, as time and the reaction
progress, the reactant will get depleted and the column
behaves just like a chemical reactor. Hence, the mini-
mum number of stages in a reactive distillation column
does not necessarily correspond to total reflux operation.
An outlet product stream, such as the distillate stream
in Figure 10b, makes the problem worse because the
light product will be continuously removed and the
column will become empty if no inlet stream is incor-
porated; a feed to the column is therefore required.
Figure 10c shows a column similar to the scheme
considered for reactive batch distillation columns in the
derivation of the Underwood equations because the feed
enters the column just above the reboiler. We believe
that such a configuration could be used for obtaining
the Fenske equation in reactive distillation. However,
our experience of using the methodologies for the
derivation of the Fenske equation reported by King,14
Henley and Seader,15 and Hohmann16 is that the
appearance of the molar turnover flow rate and the
reflux ratio makes the equation more complicated as we
move down the column. Also, most of the reasonable
assumptions used to simplify it introduce significant
errors in the numerical calculation. Moreover, the
summations involved do not seem to correspond to a
converging series of any kind. This topic should be the
subject of further investigation. Sundmacher and Kien-
le17 provide a simple expression for calculating the
minimum number of stages for the case of a reaction
taking place in the reboiler of the column.
Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4007
5. Numerical Examples and Analysis of the
Results
This section describes the numerical examples per-
formed to illustrate the application of the proposed
methodology for reactive batch distillation columns.
Because of the dynamic nature of batch columns, the
compositions of the distillate product change with
respect to time for a constant reflux operation policy.
Hence, the results of the simulations are reported in
terms of the average distillate composition profiles of
the key component versus time. The average distillate
composition xji,D is calculated through integration as
follows:
∫0tDxi,D dt
xji,D(t) ) (38)
∫0tD dt
When possible, the results were compared to those
obtained through the use of BatchFrac from AspenPlus.
The Antoine parameters (for the vapor-liquid equilib-
rium) were taken from Reid et al.18 To keep the design
method simple enough, we did not include column
hydraulic equations in our approach; that means that
values for the liquid holdup have to be assumed.
Furthermore, the kinetic parameters (frequency factor
and activation energy) were provided and adjusted to
achieve an accumulated value of the extent of the
reaction equal to the one obtained through AspenPlus
simulations. Note that our goal in this work was not to
perform realistic calculations but to show that our
simulation results present reasonable agreement with
those of the state of the art process simulators; as a
matter of fact, the assumed values for the liquid holdup
and the kinetic parameters were the same as the ones
used in BatchFrac. Finally, we also assumed a constant
value of the volumetric flow rate υ0; however, such a
simplification can easily be removed by evaluating the
liquid density on each stage as a function of temperature
and composition and then using eq 19.
5.1. Reaction Causes No Change in the Number
of Moles. For a scenario in which the assumption of
constant molar flow holds for both the liquid and vapor
phases, two cases were solved. In the first one, the
reaction takes place in the liquid phase; in the second
example, the reaction is assumed to take place only in
the vapor phase.
5.1.1. Reaction in the Liquid Phase. The example
corresponds to an isomerization reaction in the liquid
phase: o-xylene (C8H10) f ethylbenzene (C8H10). The
lightest component is ethylbenzene. The data used for
this example are shown in Table 2.
The McCabe-Thiele diagram for the initial time step
of this example is shown in Figure 11. As expected, the
contribution of the reaction is greater for stages closer
to the reboiler (larger reactant concentrations). Figure
11 does not show the last of the operating lines because
the difference point is negative. Figure 12 presents three
instances of the calculation of the average distillate
composition by changing the value of the reflux ratio.
Because the reaction shows high conversion values, the
effect of the reflux ratio is not significant. Observe also
that, because of reaction, the average distillate composi-
tion increases with time; this result is contrary to the
behavior observed in nonreactive batch distillation
columns. This effect can be explained by looking at the
4008 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004

Figure 10. Fenske equation for reactive distillation.

Figure 12. Average distillate composition profiles of ethylbenzene

in example 1.

Figure 11. McCabe-Thiele diagram for the initial step in

example 1.

Table 2. Data for the Reaction-Separation System

o-Xylene-Ethylbenzene
parameter value
no. of stages 4 + reboiler
feed 100 kmol
feed composition of ethylbenzene 0.1
vapor boilup flow rate 140 kmol h-1
column pressure 1 atm
batch time 1.4 h
order of reaction 1.0
activation energy 30 000 kJ kmol-1
frequency factor 1.6 × 109 h-1 Figure 13. Our results as compared to those of BatchFrac for
volumetric flow rate 2 m3 h-1 ethylbenzene.
liquid holdup 4 × 10-4 m3
5.1.2. Reaction in the Vapor Phase. The isomer-
right-hand side of eq 14. Because xB < xD, the first term ization reaction n-butane (C4H10) f isobutane (C4H10)
is always negative; the still composition (and, therefore, takes place in the vapor phase; isobutane is the lightest
the distillate composition) will only increase if the component. Table 3 shows the parameters used in the
second term (reaction) of eq 14 is positive and larger simulation for this example. The McCabe-Thiele dia-
than the first one (separation). Finally, Figure 13 shows gram for a simulation time of 0.6 h is shown in Figure
a comparison between the results of our approach and 14. Once again, the last of the difference points is
the results obtained through BatchFrac of AspenPlus negative, and the last of the operating lines has not been
for a reflux ratio equal to 2 and a production of 73.83 drawn. The diagram corresponds to a reflux ratio equal
mol of ethylbenzene. An excellent agreement is ob- to 2. Figure 15 shows the behavior of the average
served. distillate composition of isobutane; the trend is similar
 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4009

Figure 14. McCabe-Thiele diagram for example 2. Figure 16. McCabe-Thiele diagram for example 3.

Figure 17. Average distillate composition for isobutyraldehyde

Figure 15. Average distillate composition profiles for isobutane in example 3.
in example 2.
Table 4. Data for the Reaction-Separation System
Table 3. Data for the Reaction-Separation System Isobutyl Isobutyrate-Isobutyraldehyde
n-Butane-Isobutane
parameter value
parameter value
no. of stages 3 + reboiler
no. of stages 4 + reboiler feed 100 kmol
feed 100 kmol feed composition of isobutyraldehyde 0.1
feed composition of n-butane 0.1 vapor boilup flow rate 140 kmol h-1
vapor boilup flow rate 140 kmol h-1 column pressure 1 atm
column pressure 1 atm batch time 1.4 h
batch time 1.4 h order of reaction 1.0
order of reaction 1.0 activation energy 30 000 kJ kmol-1
activation energy 40 000 kJ kmol-1 frequency factor 1 × 103 h-1
frequency factor 2 × 103 h-1 volumetric flow rate 2 m3 h-1
volumetric flow rate 2 m3 h-1 liquid holdup 4 × 10-4 m3
reaction volume 4 × 10-4 m3
operating lines. Observe that the movement from one
to the one on the previous example because the average difference point to another is very notorious as we move
distillate composition increases with time because of to the left from stage 2 to stage 3. Figure 17 shows the
reaction. Also observe in Figure 15 that the reflux ratio average distillate composition profiles for three values
has very little effect on the average product composition. of the reflux ratio; because the liquid flow rates are
Comparison of this case to BatchFrac was not possible changing from one stage to another, the reflux ratio has
because BatchFrac does not support the case where a significant effect in the composition. Also, in this
reaction occurs in the vapor phase in a kinetically example separation predominates over reaction and the
controlled column. average distillate composition of isobutyraldehyde de-
5.2. Reaction Causes a Change in the Number creases with time. Finally, Figure 18 compares our
of Moles. This situation is illustrated with the system results to those obtained through BatchFrac for a reflux
involving the reaction isobutyl-isobutyrate (C8H16O2) ratio of 2.
f 2-isobutyraldehyde (C4H8O) in the liquid phase. The 5.3. McCabe-Thiele Method for Multicompo-
lightest component is isobutyraldehyde. Kinetics and nent Mixtures. The McCabe-Thiele method as de-
equilibrium data are shown in Table 4. Figure 16 shows scribed in section 3 of this paper can also be applied for
the McCabe-Thiele diagram for the operation time of multicomponent mixtures (NC components) because the
0.6 h. The distillate composition is very close to 1. equations developed for the reaction either on the liquid
Changes in the number of moles present an impact on phase or the vapor phase remain valid. To solve the
the difference points as well as on the slope of the problem for multicomponent mixtures, a procedure
4010 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004
Figure 18. Comparison in example 3 for the composition of
isobutyraldehyde.
Table 5. Data for the Reaction-Separation of the
Multicomponent Mixture of Example 4
parameter value
no. of stages 2 + reboiler
feed 100 kmol
feed composition of benzene 0.006
feed composition of o-xylene 0.485
vapor boilup flow rate 140 kmol h-1
column pressure 1 atm
batch time 1h
order of reaction 1.0
activation energy 30 000 kJ kmol-1
frequency factor 8 × 102 h-1
volumetric flow rate 2 m3 h-1
liquid holdup 4 × 10-4 m3
consisting of the simultaneous calculation of NC - 1
components is needed. A further assumption is that the
rate of reaction can be expressed in terms of the
concentration of just one of the reactants (if more than
one). Hence, the molar turnover flow rate for the rest
of the components in terms of the base component is
given by a stoichiometric relationship
νi
ξi,j ) ξ (39)
νk k,j
Also, equilibrium can be calculated in terms of the
equilibrium constant instead of relative volatilities as
follows.
xi,j ) Ki,jyi,j
An example for the reaction-separation of multicom-
ponent mixtures is illustrated with the system involving
the reaction (no change in the number of moles) in the
liquid phase: 2-toluene (C7H8) f benzene (C6H6) +
o-xylene (C8H10), where the order in relative volatility
is benzene > toluene > o-xylene. The data used for this
case are shown in Table 5.
The McCabe-Thiele solution approach was used for
benzene and toluene. Figure 19 shows the average
distillate composition of the three components when the
reflux ratio is equal to 2. This is an interesting case
because reaction presents a higher contribution than
separation for benzene and o-xylene, so that their
distillate compositions increase with time. However, for
the case of toluene, the trend is different and the
composition decreases with time.
5.4. Minimum Reflux Calculation. The calculation
of the minimum reflux ratio by using the Underwood
equations derived in this work (eqs 32 and 35) for
Figure 19. Average distillate composition for a reflux ratio equal
to 2 in example 4.
continuous reactive distillation columns was tested for
the case of the isomerization reaction isobutane f
n-butane. The system considered is a column with nine
stages where the feed enters the column as a saturated
liquid in stage number 8. The column pressure is 1 atm.
The feed is 1000 kmol h-1 with a composition of 0.04 of
n-butane; the distillate composition of n-butane is 0.98.
It is assumed that 380 kmol h-1 of n-butane are
produced in the column and that such a molar turnover
flow rate is equally distributed in the stages of the
column. Solving eqs 32 and 35 results in Rmin equal to
0.518. After the solution approach using the McCabe-
Thiele method is used for a range of values of the reflux
ratio, a value of 0.51 was found for the minimum value
of the reflux ratio that allows the reaction and separa-
tion specified. Such a result indicates that the Under-
wood equations derived in this work present a reason-
able agreement with the simulations.
6. Concluding Remarks
This paper provides the mathematical derivations
needed for the simplified analysis and design of reactive
batch distillation columns. In our opinion, the main
contributions of the paper are as follows: (1) The
development of the theoretical and mathematical tools
that allow the use of a McCabe-Thiele strategy for
reactive batch distillation columns. This includes the
derivation for the dynamics of the reboiler and the
operating line under the assumption of quasi steady
(40) state in the plates. Furthermore, an approach to the
computation of the molar turnover flow rate of reactive
distillation stages has been proposed. Such an approach
is based on phenomena decomposition and is needed in
order to apply the concept of the reactive difference point
to the case of batch distillation. (2) The derivation of
the Underwood equations for continuous and batch
reactive distillation columns.
The many assumptions considered in this work have
been extensively explained, and we expect that our
numerical examples involving various reactive systems
show the scope and confirm the usefulness of our
approach. Through our analysis and numerical ex-
amples we have (1) shown that our results present a
reasonable agreement with those of the state of the art
process simulators for reactive batch distillation col-
umns, (2) emphasized the advantages of the combina-
tion of separation and reaction for batch distillation,
where the product purity can even be improved as time
progresses, and finally (3) proved that the results
obtained for Rmin by the derived Underwood equations

for reactive columns are approximated enough to the
results obtained through parametric search.
Acknowledgment
M.A.H.-G. and V.R.-R. are thankful for the financial
support provided by the Consejo del Sistema Nacional
de Educacion Tecnologica (CoSNET) and by the Consejo
Nacional de Ciencia y Tecnologia (CONACYT). V.R.-R.
and S.H.-C. also thank the Consejo de Ciencia y Tec-
nologia del Estado de Guanajuato (CONCyTEG).
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Received for review August 11, 2003
Revised manuscript received May 5, 2004
Accepted May 5, 2004
IE030658W