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
Reactive distillation has recently emerged as a promising 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 limitation, 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 generate 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,
Westerbergs 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 distillation 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.

Despite the extensive body of literature reported on

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 chemicals (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 columns 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 combined 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 approach: (1) it briefly explains the graphical design of a
continuous reactive distillation column using the McCabe-Thiele method9 and (2) it describes the McCabeThiele method for batch distillation columns for the
nonreactive case.13 The contributions of the paper are

10.1021/ie030658w CCC: $27.50 2004 American Chemical Society

Published on Web 06/08/2004

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.

xn ) xD -

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 operating 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. Finally, 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 columns.
2.1. McCabe-Thiele Method for Reactive Continuous Distillation Columns.2,9 Hauan et al.7 developed 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 diagrams 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

n
L
L
yn+1 ) xn + 1 - xD V
V
V

(1)

where V and L are the vapor and liquid interstage flow

rates, respectively, and n 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 composition, xD, the first operating line intersects the 45 line

n
D

(2)

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 construct 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, . As we
explain later, an approach to the calculation of based
on phenomena decomposition is proposed in this paper.
2.2. McCabe-Thiele Method for Batch Distillation Columns.13 The unsteady-state nature of batch
distillation implies solutionof a set of differential equations. 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 procedure involves an iterative scheme for the simultaneous
determination of x(k)
D (distillate composition of component k) and x(k)
(still
composition of component k) for
B
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:

yn+1 )

R
1
xn +
x
R+1
R+1 D

(3)

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 McCabeThiele 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
This section provides the derivation of the expressions
needed to simulate the performance and/or to design
reactive batch distillation columns using a simplified
method. The solution strategy can be directly used for
binary systems, but an approximation is also proposed
for the case of multicomponent systems (see section 5.3).
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
consider separately the cases in which reaction occurs
either in the liquid phase or in the vapor phase,
although the analysis could be integrated. As a simplified approach, the following are the assumptions made
through our derivations for kinetically controlled reactive batch columns:
1. Heat of mixing, stage heat losses, and sensible heat
changes of both liquid and vapor are negligible.
2. The pressure on the column remains constant
through the operation.
3. Startup conditions will not be considered.
4. The stages of the column will be considered in quasi
steady state.
5. Reaction takes place on all of the stages but the
reboiler and condenser.
6. Reaction is irreversible because of the continuous
removal of the product.
If assumption 1 holds, then the molar flow rate of the
phase in which reaction does not occur can be considered
as a constant. Seeking simplicity, in the following
derivations we will obviate most of the algebraic steps
and provide only the main results. The analysis considers two cases depending upon the phase in which the
reactions occur. The derivations for the liquid-phase
reactions are presented first.
3.1. Reactive Batch Distillation Column: Reaction in the Liquid Phase. Consider the batch reactive
distillation column represented in Figure 3. k,j represents the sum of the molar turnover flow rate for
component k (reactant defined as the base component)
in the stage j, the distillate product is represented as
D, and the reflux ratio as R ) L0/D. The subtractions
indicated in Figure 3 are used to emphasize the contributions of reaction on each stage because k,j is an
accumulated sum. For a binary system involving components k (heavy reactant) and i (light product), the

Figure 3. Reactive batch distillation column.

overall and component (i) balance equations around

section 1 of Figure 3 are

yi,j+1 )

Lj
i k,j
D
xi,j + xi,D V
V
-k V

V ) Lj + D - Tk,j

(4)
(5)

where represents the stoichiometric coefficients of

reaction (negative for reactant k and positive for product
i), T is the total sum of stoichiometric coefficients, and
(i/-k)k,j represents the production of i due to reaction
of k on stage j. The last of the terms in eq 5 represents
the overall change in the number of moles due to
reaction. Notice that, although we are using a binary
system as the basis for our derivations here, eqs 4 and
5 can actually be generally applied, and that is the basis
for the extension of the approach to multicomponent
systems.
Because for this case the reaction is taking place in
the liquid phase, the vapor flow rate can be assumed
as constant, but the liquid flow rate might change
depending on the stoichiometric coefficients. Changes
in the liquid flow rate could be calculated as

Lj ) Lj-1 + T(k,j - k,j-1)

(6)

Observe that if i ) -k, then T ) 0 and Lj ) Lj-1, so

that the assumption of constant molar flow will also hold
for the liquid phase. Equations 4-6 can be used to
obtain the McCabe-Thiele operating line for reactive
batch distillation:

yi,j+1 )

Lj
i k,j
1
xi,j +
xi,D V
R+1
-k V

(7)

and for the case in which there is no change in the liquid

flow rate:

yi,j+1 )

i k,j
R
1
xi,j +
xi,D R+1
R+1
-k V

(8)

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.

Figure 4. Mass balance for the dynamics of the reboiler.

rate, i ) -k, eq 8 is basically the same as the operating

line obtained for continuous distillation (eq 1). Furthermore, by comparing eqs 3 and 8 (nonreactive and
reactive batch distillation), we see that the contribution
of reaction is given through the term -(i/-k)(k,j/V),
or -(k,j/V) if there is no change in the number of moles.
3.1.1. Dynamics of the Reboiler. To derive the
dynamics of the reboiler, consider the overall and
component balance for section 2 of Figure 4:

Tk,T - D ) dB/dt

(9)

i
d
- Dxi,D ) (Bxi,B)
-k k,T
dt

(10)

where k,T is the total molar turnover flow rate (k being

the base component). The overall mass balance for the
condenser is

V - L0 - D

(11)

By combining eqs 9-11, one can show that the

differential equations representing the behavior in the
reboiler and condenser are

dB
V
) Tk,T dt
1+R
D)

(12)

V
1+R

(13)

] }

i
dxi,B 1
V
)
(xi,B - xi,D) +
- Txi,B k,T
dt
B 1+R
-k

(14)

Observe again that, when compared to the nonreactive

case for batch distillation, eqs 12 and 14 include an extra
term to account for changes due to reaction. Further,
notice that in eq 14 the separate effects of reaction and
separation are well defined.
3.1.2. Extent of the Reaction: Molar Turnover
Flow Rate. Hauan et al.7,11 provided a generalization
of the concept of a difference point for reactive cascades.
The authors assume that a reactive separation cascade

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,
and reaction) can be separated and analyzed independently from each other. Moreover, they show that, for
the case of reactive cascades, given the extent of the
reaction, the decomposition does not affect the mass
balance equations.11
In a similar way, to derive an expression for the
calculation of the molar turnover flow rate k,j, in this
paper we assume that each separation stage of a
reactive batch distillation column can be considered as
a nonreactive equilibrium separation stage linked to a
continuous stirred tank reactor (CSTR; see Figure 5).
If we were able to know a priori the exact value of the
molar turnover flow rate for each stage, then the mass
balance equations obtained through the phenomena
decomposition assumption would hold. However, the
sequential approach (reaction-separation) applied here
is, in fact, used for the calculation of such a value of
the extent of the reaction. Hence, it is evident that in
this case a sequential approach will not exactly represent a simultaneous phenomenon in nature and that
the assumptions made, such as representing the reaction volume as a CSTR, are approximations that may
lead to error. A CSTR is used because we are considering perfect mixing in the liquid and vapor phases. Also,
the CSTR is placed above the separation stage just
because of numerical implications in the solution scheme.
The component mass balance equation for the reactor
of Figure 5 is given by

(rk,j) ) Lj-1xk,j-1 - Ljxk,j

(15)

where is the reaction volume (liquid holdup), rk,j is

the rate of reaction of component k in stage j, L is the
liquid flow rate, and x is the liquid composition. In
principle, the calculation of would require the use of
column hydraulic analysis, which could provide a relationship between Lj-1 and .
The reactor outlet liquid stream, Lj, can be expressed in terms of the molar conversion fraction of the
reactant, Cj:

Ljxk,j ) Lj-1xk,j-1(1 - Cj)

(16)

so that eq 15 becomes

(rk,j) ) Lj-1xk,j-1Cj

(17)

4004 Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004

yi,j+1 )

V1
V1
i k,j
R
1
xi,j +
xi,D Vj+1 R + 1
Vj+1 R + 1
-k Vj+1
(22)

where changes in the vapor flow rate due to reaction

are given by

Vj+1 ) Vj + T(k,j - k,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:

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

the vapor phase.

Assuming an elemental irreversible reaction, rR f pP,

the rate of reaction can be represented by an expression
such as

( )

rk,j ) kj

Ljxk,j
0

(18)

where the term inside the parentheses represents the

molar concentration of the reactant in the reactor and
kj is the kinetics parameter given by the Arrhenius
equation. 0 is the volumetric flow rate entering the
stage. 0 can be calculated from

(19)

where F is the density of the liquid stream. Knowing 0

would also allow the evaluation of the residence time,
j ) /0; hence, if the liquid holdup is known or can be
evaluated, the use of 0 or j is equivalent.
When eqs 16-18 are combined, an implicit equation
for the molar conversion of the reactant can be obtained:

Lj-1xk,j-1(1 - Cj)
0

(20)

Once eq 20 is solved to obtain Cj (analytically or

numerically for k greater than 2), one can finally
calculate the molar turnover flow rate through the
expression
n

k,j )

(Lj-1xk,j-1Cj)

j)1

(21)

3.2. Reactive Batch Distillation Columns: Reaction in the Vapor Phase. If the reaction takes place
in the vapor phase, derivations similar to the ones
presented in the previous subsection can be obtained.
Hence, the component and overall mass balances for
section 1 of the column presented in Figure 6 result in
the operating line for reactive batch distillation columns
(quasi-steady-state approximation):

] }

dxi,B 1 V1
i
- Ti,B k,T
)
(xi,B - xi,D) +
dt
B 1+R
-k

3.2.2. Extent of the Reaction: Molar Turnover

Flow Rate. Our approach to calculate the molar
turnover flow rate is based again on phenomena decomposition as represented in Figure 7. Calculations in
the reactor are performed before the calculations on the
equilibrium stage. The consideration of having a separation stage connected to a CSTR in the case of reaction
in the vapor phase could seem inappropriate; however,
more than the need of a CSTR, our approach works by
assuming that the compositions of reactive and nonreactive streams are homogeneous as if the mixing on
them was perfect. A derivation similar to that of section
3.1.2 results in the following expressions:
n

0 ) Lj-1/F

Lj-1xk,j-1Cj ) kj

V1
dB
) Tk,T dt
1+R

k,j )

Cj

Vjyk,j

1-C
j)1

(24)

where the conversion fraction of the reactant can be

obtained from the implicit eq 25:

[ ]

Vjyk,jCj ) kj

Vjyk,j
0

(1 - Cj)

(25)

3.3. Solution Approach. The resulting model is a

well-posed differential-algebraic system of equations
(DAE). Table 1 presents a summary of the model
specifications and the equations used for the calculations of the variables involved in each stage. The
solution procedure for each time step of a reactive batch
distillation column is similar to the procedure for solving
the rectifying section of a continuous reactive column.
The equations involved in the calculation could be solved
either simultaneously with an appropriate numerical
method or sequentially by using a method such as the
direct substitution method. We describe next the sequential procedure for the case in which reaction occurs
in the liquid phase (constant molar flow in the vapor
phase) in all of the stages but the reboiler; an iterative
procedure for the calculation of the distillate compositions has to be completed.
Considering a constant reflux policy, we assume that
the number of stages (N), the reflux ratio (R), and the
initial conditions (feed load and still compositions) are

Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4005

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
0,
L0
Lj
Cj
k,j
xk,j
yk,j+1
xk,jLj

specified
specified
eq 5
eq 6
eq 20
eq 21
equilibrium (relative volatility)
eq 8
eq 16 (plus summation
of compositions)
iteratively from independent
equations used to calculate xB

xD

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, ,
and entering volumetric flow rate, 0 (or residence time,
), are used in this work (see section 5 for an explanation).
Hence, we start by assuming the values of the distillate compositions. Then, by using a bubble-point calculation, the temperature of the distillate can be computed. 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 k,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, k,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 (L1) and the compositions (xk,l) entering the equilibrium separation stage of Figure 5. Then, the equilibrium 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 compositions in the reboiler. Those values provide the convergence criteria: If the computed values of the reboiler

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 calculations in the column. Notice that, with respect to the
number of degrees of freedom, the model is square because 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 1214 is needed to find the values of the amount of mixture
in the still, the distillate collected, and the bottom compositions 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 continuous and batch reactive distillation columns; furthermore, a discussion regarding the Fenske equation (minimum number of stages) for continuous reactive distillation columns is also provided.
4.1. Underwood Equations. To derive the expression 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, ) Lxi, + Dxi,D -

-k k,T

(26)
NC

where the index has been assigned to the streams

coming from the section with an infinite number of
plates. The overall mass balance for the condenser is

V ) L0 + D

xi, ) yi,/Ki,

i k,T
-k D
1 L
Ri, Kr, V

(30)

Here a new variable, ) (1/Kr,)(L/V), called the

absorption factor, is introduced. Also, because the
summation of the compositions in the vapor stream
going into the section with an infinite number of stages
has to be 1, eq 30 reduces to eq 31. where NC is the

i)1

Ri, xi,D -

i k,T
-k D

Ri, -

NC

Rmin + 1

i)1

-k D

Ri, -

(32)

V
h
B

NC

Ri,xi,B

i)1 R

i,

(33)

Combining eqs 31 and 33 and taking into account that

) and Ri, ) Ri, result in

(35)

which is the second of the Underwood equations. Equation 35 can be used for calculating and eq 32 for
calculating Rmin for continuous reactive distillation
columns.
4.1.1. Extension of the Underwood Equations to
Reactive Batch Distillation Columns. A direct extension to the Underwood equations derived above can
be done for the case of reactive batch distillation
columns. An approach similar to the one proposed by
Diwekar13 serves that purpose (Figure 9).
In Figure 9, a reactive batch distillation column is
represented as a continuous column where the feed
enters the column at the bottom stage with a temperature equal to its bubble point and with a composition
equal to xi,B. Such a representation allows rewriting of
eqs 32 and 35 as

[ ]
(

NC

Ri,xi,B

NC

which is the first of the Underwood equations for

calculating the minimum reflux. Following a similar
procedure for section 2 (nonreactive stripping section)
of Figure 8, one can obtain

i,

(31)

[ ]
Ri,zi,F

i)1 R

i,

i k,T

(34)

i
+ Bxi,B
-k k,T

one can get

i)1 R

number of components. Finally, the substitution of eq

27 and the definition of the reflux ratio in eq 31 result
in

Ri, xi,D -

Fzi,F ) Dxi,D -

(29)

Ri, xi,D -

and the component mass balance equation for the whole

column

1-q)

When the definition of relative volatility (with respect

to the key component r) is incorporated:

NC

Ri, -

NC

i k,T
-k D
V
yi, )
D
1 L
1Ki, V
xi,D -

k,T + Bxi,B
-k

V-V
h ) F(1 - q)

(28)

When eq 28 is substituted into eq 26 and with rearrangement:

i)1

Finally, by introducing the definition of q

(27)

It is also considered that the liquid-vapor equilibrium

on the last stage of section 1 is given by

V
yi, )
D

V-V
h )

Ri, Dxi,D -

Rmin + 1 )

i)1

)0

Ri, xi,D -

i k,T
-k D

Ri, -

(36)

(37)

which correspond to the Underwood equations for

reactive batch distillation columns. Observe that the
minimum reflux computation not only depends on the
distillate and bottom compositions, as it does for a
nonreactive column, but also depends on the extent of
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
approximation to the extent of the reaction a priori, and
a parametric search might be necessary to obtain a
feasible value. For a specific reaction-separation system, a reasonable value of the extent of the reaction can
be estimated, for instance, by assuming that the molar
turnover flow rate is equally distributed among the
reactive stages of the column and by defining the
amount of product obtained through the reaction (using
a value of the molar conversion fraction based on the
kinetics of the reaction involved and the amounts of the
reactants initially fed to 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 performed 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) )
0tD dt
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 minimum 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 incorporated; 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 Kienle17 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.

(38)

When possible, the results were compared to those

obtained through the use of BatchFrac from AspenPlus.
The Antoine parameters (for the vapor-liquid equilibrium) 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 0; 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 composition 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
feed
feed composition of ethylbenzene
vapor boilup flow rate
column pressure
batch time
order of reaction
activation energy
frequency factor
volumetric flow rate
liquid holdup

4 + reboiler
100 kmol
0.1
140 kmol h-1
1 atm
1.4 h
1.0
30 000 kJ kmol-1
1.6 109 h-1
2 m3 h-1
4 10-4 m3

right-hand side of eq 14. Because xB < xD, the first term

is always negative; the still composition (and, therefore,
the distillate composition) will only increase if the
second term (reaction) of eq 14 is positive and larger
than the first one (separation). Finally, Figure 13 shows
a comparison between the results of our approach and
the results obtained through BatchFrac of AspenPlus
for a reflux ratio equal to 2 and a production of 73.83
mol of ethylbenzene. An excellent agreement is observed.

Figure 13. Our results as compared to those of BatchFrac for

ethylbenzene.

5.1.2. Reaction in the Vapor Phase. The isomerization reaction n-butane (C4H10) f isobutane (C4H10)
takes place in the vapor phase; isobutane is the lightest
component. Table 3 shows the parameters used in the
simulation for this example. The McCabe-Thiele diagram for a simulation time of 0.6 h is shown in Figure
14. Once again, the last of the difference points is
negative, and the last of the operating lines has not been
drawn. The diagram corresponds to a reflux ratio equal
to 2. Figure 15 shows the behavior of the average
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 15. Average distillate composition profiles for isobutane

in example 2.
Table 3. Data for the Reaction-Separation System
n-Butane-Isobutane
parameter

value

no. of stages
feed
feed composition of n-butane
vapor boilup flow rate
column pressure
batch time
order of reaction
activation energy
frequency factor
volumetric flow rate
reaction volume

4 + reboiler
100 kmol
0.1
140 kmol h-1
1 atm
1.4 h
1.0
40 000 kJ kmol-1
2 103 h-1
2 m3 h-1
4 10-4 m3

to the one on the previous example because the average

distillate composition increases with time because of
reaction. Also observe in Figure 15 that the reflux ratio
has very little effect on the average product composition.
Comparison of this case to BatchFrac was not possible
because BatchFrac does not support the case where
reaction occurs in the vapor phase in a kinetically
controlled column.
5.2. Reaction Causes a Change in the Number
of Moles. This situation is illustrated with the system
involving the reaction isobutyl-isobutyrate (C8H16O2)
f 2-isobutyraldehyde (C4H8O) in the liquid phase. The
lightest component is isobutyraldehyde. Kinetics and
equilibrium data are shown in Table 4. Figure 16 shows
the McCabe-Thiele diagram for the operation time of
0.6 h. The distillate composition is very close to 1.
Changes in the number of moles present an impact on
the difference points as well as on the slope of the

Figure 16. McCabe-Thiele diagram for example 3.

Figure 17. Average distillate composition for isobutyraldehyde

in example 3.
Table 4. Data for the Reaction-Separation System
Isobutyl Isobutyrate-Isobutyraldehyde
parameter

value

no. of stages
feed
feed composition of isobutyraldehyde
vapor boilup flow rate
column pressure
batch time
order of reaction
activation energy
frequency factor
volumetric flow rate
liquid holdup

3 + reboiler
100 kmol
0.1
140 kmol h-1
1 atm
1.4 h
1.0
30 000 kJ kmol-1
1 103 h-1
2 m3 h-1
4 10-4 m3

operating lines. Observe that the movement from one

difference point to another is very notorious as we move
to the left from stage 2 to stage 3. Figure 17 shows the
average distillate composition profiles for three values
of the reflux ratio; because the liquid flow rates are
changing from one stage to another, the reflux ratio has
a significant effect in the composition. Also, in this
example separation predominates over reaction and the
average distillate composition of isobutyraldehyde decreases with time. Finally, Figure 18 compares our
results to those obtained through BatchFrac for a reflux
ratio of 2.
5.3. McCabe-Thiele Method for Multicomponent Mixtures. The McCabe-Thiele method as described in section 3 of this paper can also be applied for
multicomponent mixtures (NC components) because the
equations developed for the reaction either on the liquid
phase or the vapor phase remain valid. To solve 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
feed
feed composition of benzene
feed composition of o-xylene
vapor boilup flow rate
column pressure
batch time
order of reaction
activation energy
frequency factor
volumetric flow rate
liquid holdup

2 + reboiler
100 kmol
0.006
0.485
140 kmol h-1
1 atm
1h
1.0
30 000 kJ kmol-1
8 102 h-1
2 m3 h-1
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

i,j )

k k,j

(39)

Also, equilibrium can be calculated in terms of the

equilibrium constant instead of relative volatilities as
follows.

xi,j ) Ki,jyi,j

(40)

An example for the reaction-separation of multicomponent 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 McCabeThiele 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 separation specified. Such a result indicates that the Underwood equations derived in this work present a reasonable 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
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 examples 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 columns, (2) emphasized the advantages of the combination 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

Ind. Eng. Chem. Res., Vol. 43, No. 14, 2004 4011

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 Tecnologia del Estado de Guanajuato (CONCyTEG).
Literature Cited
(1) Lee, J. W.; Westerberg, A W. Visualization of Stage Calculations in Ternary Reacting Mixtures. Comput. Chem. Eng. 2000,
24, 639.
(2) Lee, J. W.; Hauan, S.; Westerberg A. W. Graphical Methods
for Reaction Distribution in a Reactive Distillation Column. AIChE
J. 2000, 46, 1218.
(3) Barbosa, D.; Doherty, M. F. A New Set of Composition
Variables for the Representation of Reactive Phase Diagrams.
Proc. R. Soc. London 1987, 413, 459.
(4) Barbosa, D.; Doherty, M. F. Design and Minimum-Reflux
Calculations for Single-Feed Multicomponent Reactive Distillation
Columns. Chem. Eng. Sci. 1988, 43, 1523.
(5) Espinosa, J.; Scenna, N.; Perez, G. Graphical Procedure for
Reactive Distillation Systems. Chem. Eng. Commun. 1993, 119,
109.
(6) Perez-Cisneros, E. S. Modelling, Designing and Analysis of
Reactive Separation Processes. Ph.D. Thesis, Technical University
of Denmark, Lyngby, Denmark, 1997.
(7) Hauan, S.; Westerberg, A. W.; Lien, K. M. Phenomena
Based Analysis of Fixed Points in Reactive Separation Systems.
Chem. Eng. Sci. 1999, 55, 1053.

(8) Lee, J. W.; Hauan, S.; Lien, K. M.; Westerberg, A. W. A

Graphical Method for Reaction Design Reactive Distillation
Columns. 1. The Ponchon-Savarit Method. Proc. R. Soc. London
2000, 456, 1953.
(9) Lee, J. W.; Hauan, S.; Lien, K. M.; Westerberg, A. W. A
Graphical Method for Reaction Design Reactive Distillation
Columns. 2. The McCabe-Thiele Method. Proc. R. Soc. London
2000, 456, 1965.
(10) Lee, J. W.; Hauan, S.; Westerberg, A. W. Circumventing
an Azeotrope in Reactive Distillation. Ind. Eng. Chem. Res. 2000,
39, 1061-1063.
(11) Hauan, S.; Ciric, A. R.; Westerberg, A. W.; Lien, K. M.
Difference Points in Extractive and Reactive Cascades. I. Basic
Properties and Analysis. Chem. Eng. Sci. 2000, 55, 3145.
(12) Lee, J. W.; Hauan, S.; Lien, K. M.; Westerberg, A. W.
Difference Points in Extractive and Reactive Cascades. II. Generating Designing Alternatives by the Lever Rule for Reactive
Systems. Chem. Eng. Sci. 2000, 55, 3161.
(13) Diwekar, U. M. Batch Distillation; Taylor and Francis:
Washington, DC, 1995.
(14) King, C. J. Separation Processes; McGraw-Hill: New York,
1980.
(15) Henley, E. J.; Seader, J. D. Equilibrium Stage Separation
Operations in Chemical Engineering; Wiley: New York, 1981.
(16) Hohmann, E. C. Analytical McCabe-Thiele Method (Smokers Equation). AIChE J. 1980, B1.8, 42.
(17) Sundmacher, K.; Kienle, A. Reactive Distillation; WileyVCH: Weinheim, Germany, 2003.
(18) Reid, R. C.; Prausnitz, J. M.; Poling, B. E. The Properties
of Gases and Liquids; McGraw-Hill: New York, 1987.

Received for review August 11, 2003

Revised manuscript received May 5, 2004
Accepted May 5, 2004
IE030658W