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3032

Ind. Eng. Chem. Res. 1997, 36, 3032-3042

Design of Processes with Reactive Distillation Line Diagrams


B. Bessling,*, G. Schembecker, and K. H. Simmrock
Engineering R&D, BASF Ludwigshafen, 67056 Ludwigshafen, Germany, and Technical Chemistry A,
Department of Chemical Engineering, University of Dortmund, D-44221 Dortmund, Germany

On the basis of the transformation of concentration coordinates, the concept of reactive distillation
lines is developed. It is applied to study the feasibility of a reactive distillation with an
equilibrium reaction on all trays of a distillation column. The singular points in the distillation
line diagrams are characterized in terms of nodes and saddles. Depending on the characterization
of the reactive distillation line diagrams, it can be decided whether a column with two feed
stages is required. On the basis of the reaction space concept, a procedure for the identification
of reactive distillation processes is developed, in which the reactive distillation column has to
be divided into reactive and nonreactive sections. This can be necessary to overcome the
limitations in separation which result from the chemical equilibrium. The concentration profile
of this combined reactive/nonreactive distillation column is estimated using combined reactive/
nonreactive distillation lines.
1. Introduction
In recent years many processes for basic and intermediate products were improved by a combination of
reaction and distillation in a reactive distillation column. The conventional process has to be compared with
the reactive distillation process to understand the
possible improvements; see Figures 1 and 2. The
conventional process consists of a reaction and a separation section. Two unitssusually connected by a recycle
streamsare necessary to produce and to separate the
products. In a reactive distillation column, it is possible
to combine two operations in one unit, so that synergistic effects between distillation and reaction occur; see
Figure 2.
Examples are as follows: (a) shift of the chemical
equilibrium by separation of the products and (b)
utilization of the reaction heat for the separation of
educts and products.
These synergistic effects cause benefits of a reactive
distillation process when compared to the conventional
design: (a) lower capital investment, (b) lower energy
consumption, and (c) higher product yields.
Because of these benefits it is necessary to check
during the development of a new process or during the
reengineering of an existing process whether the process
can be improved by reactive distillation. The obstacle
to the synthesis of a reactive distillation process is to
understand the interaction of reaction and distillation.
Consider, for example, that a first simple reactive
distillation process for methyl acetate was developed in
1921 by Backhaus (1921), but it took 60 years to reach
the level of the Eastman Kodak Process patented by
Agreda and Partin (1984).
To fill this gap, the interaction of reaction and
distillation has been a topic of intensive studies, for
example, by Barbosa and Doherty (1988a) and Ung and
Doherty (1995). This research, which is the basis for
the work presented here, focuses on the basic principles
of the interaction of reaction and distillation. Neverthe* To whom correspondence should be addressed. E-mail,
bernd.bessling@ze.basf-ag.de; telephone number, 0049/621/60/
55446; Fax, 0049/621/60/52411.
Dedicated to Prof. Gilbert Froment on the occasion of his
65th birthday.
BASF Ludwigshafen.
University of Dortmund.
S0888-5885(96)00727-0 CCC: $14.00

Figure 1. Block flow diagram for a conventional chemical process.

Figure 2. General structure of a reactive distillation process.

less a strategy for the design of reactive distillation


processes has not been published. We combine existing
knowledge and new aspects to a method which takes
into account important elements of an overall design
strategy. This method applies heuristic rules and
numeric routines.
2. Fundamentals
2.1. Reaction Spaces. Reactive distillation is usually applied to systems with equilibrium reactions. For
the following discussion, it is assumed that the system
is in chemical and physical equilibrium. Under this
assumption, the degrees of freedom (FG) of a system are
reduced by the number of independent chemical equilibrium reactions (Wales, 1985).

Gibbs phase rule:

FG ) 2 + n - - r

(1)

In Table 1 an overview is given about the systems


discussed in this paper. The following conditions were
varied: (a) type of reaction, (b) presence of inerts, (c)
number of components, and (d) type of phase equilibrium.
The number of degrees of freedom is identical to the
dimension of the concentration space in which the
1997 American Chemical Society

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3033

Figure 3. Reaction: A a B. In a binary system with two phases


at constant pressure or temperature the equilibrium is reached
only at one point (marked by a cross).

Figure 5. Reaction: A a B in the presence of the inert


components C an D. When another inert component D besides C
is assumed, the reaction space is stretched between equilibrium
concentration in the binary system AB and the inert components
C and D (K ) 1).

Figure 4. Reaction: A a B in the presence of the inert component


C. In the presence of one inert component the equilibrium is
located on a line between the equilibrium in the binary system
AB and the inert component C (K ) 1).
Table 1. Overview about the Systems Discussed in This
Paper

reaction
AaB
AaB
AaB
A+BaC
A+BaC
A+BaC+D
A+BaC+D
A+AaE
A+BaC
A+BaC+D

inerts

type of
phase
equilibrium

no. of
components

C
C,D
D

degrees of
freedom F
(P or T
constant)

2
3
4
3
4
4
5

VLE
VLE
VLE
VLE
VLE
VLE
VLE

0
1
2
1
2
2
2

3
4

VLLE
VLLE

0
1

equilibrium conditions are fulfilled. We define this part


of the concentration space as reaction space. The
reaction space is a subspace of the concentration space.
The geometrical shape of the reaction space depends on
the type of reaction, the position of the chemical
equilibrium, and the presence of inert components.
For the case study in Figures 3-10 it is assumed that
the chemical equilibrium can be described by the
following form of the mass action law:
nc

K)

xi

i)1

(2)

As examples some important types of reaction were


chosen. The reaction A a B is an example for isomerization (Figures 3-5), A + B a C for etherification
(Figures 6 and 7), and A + B a C + D for esterification
(Figure 8).
Figures 9 and 10 depict systems with a miscibility
gap, which reduces the reaction space.
2.2. Transformed Concentration Coordinates.
The reduction of the degrees of freedom allows us to

Figure 6. Reaction: A + B a C. Chemical equilibrium with


different equilibrium constants for an additive reaction.

Figure 7. Reaction: A + B a C in the presence of the inert


component D. When an inert component is added, the reaction
space is stretched between the chemical equilibrium in the reactive
ternary system A, B, C and the inert component D (K ) 1).

simplify the representation of reacting systems. To get


a structured representation of these systems, transformed concentration coordinates have been published
by Barbosa and Doherty (1988a) and Espinosa et al.
(1995a, 1995b). The chemical reaction is presented here
as the following:

AA + BB + ... a PP + QQ + ...
The transformed liquid and vapor coordinates for an
arbitrary component i are given by Espinosa et al.
(1995b):

3034 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 8. Reaction: A + B a C + D. The reaction space is


stretched between the nonreacting binary systems AC, AD, BC,
and BD (K ) 1).

Figure 9. Reaction: A + B a C (with two liquid phases). The


two liquid phases with the concentrations x und x are in chemical
and physical equilibrium. Within the miscibility gap the reaction
space has the dimension zero, outside the dimension one. An
example is the reaction of isobutene with water to tert-butyl alcohol
(Sakuth, 1995).

(3)

iyP
P
Yi )
TyP
1P

(4)

yi -

where P is the chosen reference component. When the


transformation is applied, the transformed liquid and
vapor mole fraction for component P is set to zero (i )
P; XP ) YP ) 0). The transformed composition coordinates fulfill the following contraints:
nc

nc

(5)

The stoichiometric coefficient T is defined as


nc

T )

i)1

Figure 11. Tranformation of the coordinates for the reaction A


+ B a C.

components being set to zero:

I ) 0

ixP
P
Xi )
TxP
1P
xi -

X i ) Yi ) 1

i)1
i)1

Figure 10. Reaction: A + B a C + D (with two liquid phases).


If the system AC has a miscibility gap, the reaction space will be
reduced. Within the miscibility gap, the reaction space has the
dimension one, outside the dimension two; see Table 1. An example
is the esterification of n-pentyl alcohol and acetic acid to pentyl
acetate and water.

(6)

Inert components can be included in that scheme,


simply by the stoichiometric coefficient I for inert

(7)

Consider, for example, a mixture of A, B, and C in


which the equilibrium reaction A + B a C takes place.
Using transformed concentration coordinates, we assume that C is completely decomposed to A and B and
only the transformed concentration of A or B has to be
specified; see Figure 11.
By the transformation the total number of moles
changes, if T * 0. Transformed concentration coordi-

N
h )N 1-

TxP
P

(8)

nates can be used to derive the lever rule and the


equations for the operating line for a reactive distillation
column; see the work of Barbosa and Doherty (1988b)
and Espinosa et al. (1995a).
The overall and the component molar balance for the
rectifying section of a reactive distillation column are
as follows:

G)D+L+R

(9)

GyGi ) DxDi + LxLi + Ri

(10)

Using transformed composition coordinates, eqs 9 and


10 can be rewritten:

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3035

In a similar way, transformed coordinates can be


applied to derive the equations for the rectifying and
stripping section of a reactive distillation column; see
Figure 13.
These equations are derived under the following
assumptions: (a) chemical and vapor-liquid equilibrium is achieved on all stages and (b) the column operates
at steady state. Using transformed flow rates and
concentration coordinates, the overall balance and
component balance for the rectifying section are as
follows:

Figure 12. Lever rule for reacting systems.

Gn-1 ) Ln + D
h

(17)

Gn-1Yn-1 ) LnXn + D
h XD

(18)

The local reflux ratio on stage n for the rectifying section


is defined as

(
(

)
)

TxnP
P
Ln
v)
)
D
h
TxDP
D 1P
Ln 1 -

(19)

Hence, the equation for the operating line in the


rectifying section changes to

Yn-1 )

v
1
X +
X
v+1 n v+1 D

(20)

Analogously the operating line for the stripping section


can be derived, using v* as the local reflux ratio on stage
m in the stripping section:
Figure 13. Material balance of a reactive distillation column.

G 1-

G yGi -

) (
) (

) (
) (

)
)

TyGP
TxDP
TxLP
)D 1+L 1P
P
P

(11)

iyGP
ixDP
ixLP
) D xDi + L xLi (12)
P
P
P

L/D )

( )

XDi - YGi
YGi - XLi

1-

(13)

)
)

TxmP
P
Lm
)
v* )
B
h
TxBP
B 1P
Ym-1 )

Rewriting eqs 11 and 12 gives the following:

TxDP
P
TxLP
1P

(
(

Lm 1 -

v*
1
X X
v* - 1 m v* - 1 B

(21)

(22)

2.3. The Concept of Reactive Distillation Lines.


Using transformed concentration coordinates and flow
rates, the equations for the operating lines and the lever
rule have the same structure as for systems without
reaction. For infinite reflux ratio (v f ), the operating
line can easily be calculated. The transformed liquid

The transformed flow rates are defined as the following:

(
(

)
)

TxLP
L
h )L 1P

(14)

TxDP
P

(15)

D
h )D 1-

Equation 12 can be rearranged with the help of eqs 14


and 15:

L
h /D
h )

XDi - YGi
YGi - XLi

(16)

This is the lever rule for systems with one equilibrium


reaction; see Figure 12.

Yn-1 ) Xn

(23)

Yn ) f(Xn,P)

(24)

composition X on stage n is identical to the transformed


vapor concentration Y arising from stage n - 1. The
vapor concentration is a function of the transformed
liquid concentration and the pressure.
Similar to nonreactive distillation (Stichlmair, 1988)
these lines can be called reactive distillation lines. Top
and bottom product for a reactive distillation column
at infinite reflux must be located on the reactive
distillation line and on the mass balance line; see Figure
14.

F
h XFi ) D
h XDi + B
h XBi

(25)

3036 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 14. Concept of reactive distillation lines. XD and XB are


located on a straight line that passes through the feed XF.

Figure 15. Reactive distillation lines for a system A + B a C in


the presence of the inert component D (relative volatilities A/B/
C/D, 4/2/1/8, equilibrium constant, K ) 0,1; pressure, P ) 1.013
bar).

The arrow on the distillation line points in the


direction of increasing low boiler concentrations and
decreasing temperatures. Only algebraic equations
have to be solved to calculate a distillation line. The
concentration and temperature profiles calculated by a
reactive distillation line can serve as a first estimate
for the rigorous simulation with an equilibrium stage
model. Using reactive distillation line diagrams, it is
possible to explore the feasibility of a specific reactive
distillation. The number of stages between the bottom
and the top product is the minimum number of stages
at infinite reflux.
3. Application of the Reactive Distillation Line
Concept
Applying the concept of reactive distillation lines, it
is possible to represent concentration profiles at infinite
reflux conditions in a reactive distillation column and
to discuss the feasibility of a specific reactive distillation
concept. In the following figures the influence of
volatilities and equilibrium constants for different ideal
systems will be studied. Then the discussion will be
extended to an industrially important system.
The presented simulations are based on the following
assumptions: (a) chemical and vapor-liquid equilibrium is achieved on all stages; (b) the column operates at
steady state; (c) the molar heat of vaporization for all
components is equal; (d) heat losses and the heat of
reaction are negligible; (e) the heat of mixing is negligible; (f) the sensible heat of the streams can be
neglected; (g) all streams are fed into the column as
saturated liquids.
3.1. Ideal Systems. One of the most important
areas of application for reactive distillation is the
etherification. Figure 15 presents the reactive distillation lines for a system with the reaction A + B a C
in the presence of an inert component, D. Relative

Figure 16. Reactive distillation lines for a system A + B a C in


the presence of the inert component D (relative volatilities A/B/
C/D, 4/2/1/8; equilibrium constant, K ) 10; pressure, P ) 1.013
bar).

volatilities and the equilibrium constant used in the


calculation are given in the figure. (The temperatures
correspond to parameters for the Antoine equation given
in the Appendix. Ideal gas and liquid phase were
assumed.)
In this diagram, the edges AD and BD represent the
binary nonreactive systems AD and BD. The edge AB
represents the reactive system AB in chemical equilibrium with the component C (compare Figures 6 and 7).
The concentration with the coordinates XB ) 0.5 and
XD ) 0 has the maximum concentration of C in equilibrium with A and B. Notice, there is no point
corresponding to the pure product C.
All distillation lines start at the high-boiling component B and end at the low-boiling inert component D.
Corresponding to the nonreactive distillation, we call
the starting and end points of reactive distillation lines
nodes and all other vertices saddles (Fien, 1994).
The distillation lines indicate that two different
reactive distillation designs are feasible. In design I,
the component C decomposes and B is separated from
A and D. Using design II, the component C is formed
and the inert component D is separated from a mixture
consisting of A and B in chemical equilibrium with C.
To purify C, a nonreactive distillation section must be
added. This nonreactive section purifies C and recycles
the educts A and B to the reactive distillation zone.
When the equilibrium constant is increased, a reactive azeotrope appears; see Figure 16. As defined by
Ung and Doherty (1995), a reactive azeotrope has
identical transformed vapor and liquid concentration
coordinates.

Xi ) Yi

(26)

The reactive azeotrope and the inert component D are


nodes; the components A and B are saddles. Corresponding to the normal nonreactive distillation, there
is no reactive distillation border (Stichlmair et al., 1989)
that divides the diagram into sections with different
start or end points of the reactive distillation lines. All
reactive distillation lines begin at that high-boiling
reactive azeotrope and end at the low-boiling inert
component D. Compared with Figure 15, it is not
possible to realize design I (decomposition of C). Only
design II (formation of C, separation D/A, B, C) is
feasible.
Another important type of reaction is the esterification. Many esterifications (Block, 1977) are carried out
in reactive distillation columns. In the following figures
the influence of the relative volatilities on the reactive
distillation for this type of reaction (A + B a C + D) is
studied.

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3037

Figure 17. Reactive distillation lines for a system A + B a C +


D (relative volatilities A/B/C/D, 4/2/8/1; equilibrium constant, K
) 10; pressure, P ) 1.013 bar).

Figure 18. Concentration profile of a reactive distillation with


20 stages for the properties given in Figure 17. The input data
for the simulation are molar ratio A/B ) 1:1; feed stage ) 10; reflux
ratio v ) 3:1; pressure, P ) 1.013 bar. The resulting conversion of
A is 99.7%.

For the representation of the quarternary system A,


B, C, D a square diagram is used. The edges are the
nonreactive binary systems. The diagonals AB and CD
are the reactive binary systems; see Figures 8 and 17.
An equilibrium constant of 10 is used in the calculation. In the first case (Figure 17), the educts A and B
are medium boilers and the products C and D are low
and high boilers, respectively. All distillation lines start
at the high-boiling product and end at the low-boiling
product. The products C and D are nodes in the
diagram shown in Figure 17, and the educts A and B
are saddles. From Figure 17 it can be seen that the
production of C and D in one reactive distillation column
is feasible.
The reactive distillation line diagram represents the
concentration profiles at infinite reflux. Figure 18
shows the concentration profile for the production of C
and D at a finite reflux. The column has 20 stages and
operates at a reflux ratio of 3:1. The equilibrium
reaction takes place on all stages. The molar ratio
distillate flow/bottom flow for the simulations with the
reaction A + B f C + D is 1:1.
Figure 19 illustrates the situation for the same system
except that product D is a medium-boiling component.
Then, product C, which is volatile, and educt B are
nodes whereas product D and educt A are saddles. In
that case, only with a large effort can a high conversion
and high-product purity be achieved at a stoichiometric
ratio of educts in one reactive distillation column.
To show some effects, Figures 20-22 depict the
concentration profiles of three simulations. In all cases
the columns are equipped with 120 stages on which
distillation and the equilibrium reaction take place. In
the first case (Figure 20), a conversion of 83% can be
achieved in a reactive distillation column with one feed
stage and a reflux ratio of 1.2:1.
In the second and third cases, the columns are also
equipped with 120 stages, but they have two separate

Figure 19. Reactive distillation lines for a system A + B a C +


D (relative volatilities A/B/C/D, 4/1/8/2; equilibrium constant, K
) 10; pressure, P ) 1.013 bar).

Figure 20. Concentration profile of a reactive distillation with


120 stages for the properties given in Figure 19. The input data
for the simulation are molar ratio A/B ) 1:1; feed stage ) 50; reflux
ratio v ) 1.2; pressure, P ) 1.013 bar. The resulting conversion of
A is 83%.

Figure 21. Concentration profile of a reactive distillation with


120 stages for the properties given in Figure 19. The input data
for the simulation are molar ratio A/B ) 1:1; feed stages ) 50 and
36; reflux ratio v ) 1.2; pressure, P ) 1.013 bar. The resulting
conversion of A is 99%.

Figure 22. Concentration profile of a reactive distillation with


120 stages for the properties given in Figure 20. The input data
for the simulation are molar ratio A/B ) 1:1; feed stages ) 50 and
36; reflux ratio v ) 2:1; pressure, P ) 1.013 bar. The resulting
conversion of A is 90%.

feed stages. The second feed stage is one important


possibility to increase the conversion. The high boiler
is fed into the column above the low boiler to achieve
countercurrent flow of the educts. A conversion of 99%
can be achieved at a reflux ratio of 1.2:1, see Figure 21.

3038 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 23. Relation between reflux ratio and conversion. The


relative volatilities and the column data are given in Figures 19
and 22.

The figure also shows the concentration profiles for the


rectifying section, the section between the two feeds and
the stripping section. Using two feed stages, the
concentration profiles in the stripping and rectifying
section are shifted in the direction of the desired
products.
When the reflux ratio is increased (Figure 22), the
conversion decreases because the separation of the
unreacted educt B is improved. This example illustrates
the difficulties of reactive distillation if one of the
products is a saddle in the reactive distillation line
diagram.
In Figure 23, the results of the case study are
summarized. The low conversion on the left hand side
of the maximum is caused by the insufficient separation
of the educts. When the reflux ratio is increased up to
about 1.2:1, the product purities and the conversion are
improved. At reflux ratios higher than 1.2:1, the
conversion decreases because the separation of the
unreacted educt B is improved. In contrast to the
situation in Figure 23, it is known from Worz and Mayer
(1992) for examples similar to Figure 18 that by
increasing the reflux ratio the conversion increases also.
These relations between reflux ratio and conversion are
important for the optimization and control of reactive
distillation columns.
From the discussion of these different systems some
simple rules can be derived. Examples are as follows:
Reactive distillation is a feasible and probably an
economic operation if both products are connected by a
reactive distillation line, the products are nodes in a
reactive distillation line diagram, and the boiling point
difference between the products is large. If one or both
products are saddles, the concentration profile can be
shifted in the direction of the saddle by using a column
with two feed stages.
3.2. Highly Nonideal System. In this section the
considerations are extended to a highly nonideal system.
As an example the esterification of formic acid (FA) with
methanol (MeOH) to methyl formate (MF) and water
(H2O) is discussed:

FA + MeOH a MF +H2O

Kx ) 5

In the vapor phase formic acid dimerizes:

2FA a FADim
The dimerization equilibrium is described by the chemical theory (Gmehling et al., 1979). In the systems there
are five components and two equilibrium reactions.
Therefore the system has 2 degrees of freedom at a given
pressure or temperature.

Figure 24. Reaction: FA + MeOH a MF + H2O. Boiling point


surface as a function of transformed liquid composition coordinates
(P ) 3 bar).

Figure 25. Reactive distillation line diagram for the esterification


of formic acid and methanol (P ) 3 bar).

Figures 24 and 25 depict the boiling point surface and


the distillation line diagram for the system FA, MeOH,
MF, H2O. The azeotrope formic acid/water has the
highest boiling point and the azeotrope methyl formate/
methanol the lowest. All reactive distillation lines start
at the azeotrope FA/H2O and end at the azeotrope MF/
H2O. The azeotropes are nodes in this system, and the
pure components are saddles. The system has no
reactive distillation borders.
In Figure 26 the concentration profile of the reactive
distillation is depicted. The high-boiling component
(FA) is fed above the low-boiling component (MeOH) into
the reactive distillation column. Formic acid and methanol are nearly completely converted into methyl formate
and water. The products of this reactive distillation are
not the nodes but the saddles. There are three reasons
why this reactive distillation is easy: (a) the boiling
point differences between the azeotropes FA/H2O and
water on one side and the azeotrope MF/MeOH and
methanol on the other side are small, so that the
separation between the azeotropes (here the nodes) and
the pure components (here the saddles) is difficult; (b)
the boiling point difference between the desired products
is large; (c) the chemical equilibrium lies on the side of
the products (K ) 5).
The other way around, these are the reasons why no
economic design was found to produce formic acid and

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3039

Figure 27. Combined distillation line. Reaction A a B in the


presence of C as the inert component.
Figure 26. Concentration profile of a reactive distillation with
22 stages for the physical properties given in the Appendix. The
input data for the simulation are molar ratio FA/MeOH ) 1:1;
feed stages ) 17(FA) and 10(MeOH); reflux ratio, v ) 2.5; pressure,
P ) 3 bar. The resulting conversion of FA is 99.7%.

methanol from water and methyl formate in one reactive


distillation column.
From this and similar examples the following rule can
be derived: If one or both products are saddles, a high
conversion is required at a stoichiometric ratio of educts,
the separation between the saddles (desired top to bottom
product) and the nodes (undesired top to bottom product)
is difficult, the boiling point difference between the
products is large, no distillation border must be crossed,
and the chemical equilibrium is on the side of the desired
products, then the reactive distillation is a feasible and
probably an economic operation.
4. The Combination of Reactive and
Nonreactive Distillation
4.1. Combined Distillation Lines. The reactive
distillation line concept allows us to discuss the feasibility of a reactive distillation, if on all stages distillation
and the equilibrium reaction occur simultaneously. We
call this design simple reactive distillation. In a simple
reactive distillation the total concentration profile and
the products are located in the reaction space; see
Figures 3-10.
If it is necessary to separate a product that is not in
the reaction space, a section with nonreactive distillation
trays must be added.
Even for complex reacting systems, it is possible to
decide whether a product is located in the reaction
space. From the evaluation of the reaction spaces the
following rules can be deduced: (a) all components
which need a reactant for the forward or backward
reaction are located in the reaction space (e.g., for the
reaction A a B neither A nor B is located in the reaction
space, whereas for the reaction A + B a C only C is not
in the reaction space.); (b) all inert components are
located in the reaction space.
As an example, Table 2 shows the application of these
rules for the systems discussed in the present paper.
These rules can also be applied to other systems.
It should be noted that it is necessary to consider not
only the type of reaction but also the desired direction.
For example, if for the system A + B a C the component
C is the educt, a simple reactive distillation is feasible,
whereas if C is a desired product, a combination of

reactive and nonreactive distillation is necessary. This


consideration is independent of the stoichiometric coefficients if i * 0.
As an extension to the reactive distillation line
concept presented above, a combined distillation line
concept was developed to estimate the concentration
profiles at total reflux for a distillation column with a
reactive and a nonreactive distillation section. Consider
for example the reactive distillation problem in Figure
27 with the reaction A a B. The component B reacts
to the desired product A. The feed is a mixture of B
and the inert component C. A is the high-, B the
medium-, and C is the low-boiling component. According to the rules the product is not in the reaction space.
To produce A and to separate the inert component C,
the column is divided into two sections. Because the
product A is a high-boiling component, the nonreactive
section must be located in the stripping section. To
estimate the concentration profile, a nonreactive distillation line (Stichlmair, 1988) can be used.

yn-1 ) xn

(27)

yn ) f(xn,P)

(28)

As a starting point a concentration in the vicinity of


A is taken (stage 1, Figure 27). Stepwise the concentrations on higher stages in the nonreacting zone of the
stripping section are calculated (stages 2, 3, 4). The
vapor arising from stage 3 has the concentration 4.
However the concentration 4 is on the wrong side of
the chemical equilibrium line. Therefore the reactive
distillation line concept has to be applied. This switch
corresponds to the transition from 4 to 4. To estimate
the concentration profile in the reactive distillation
section, a reactive distillation line was calculated with
the concentration 4 as starting point.
This combined reactive distillation line concept is now
applied to the example in Figure 16, the reaction of A
+ B a C in the presence of D as an inert component. In
the column, A and B are converted to C in the presence
of D. Figure 28 shows the reaction space and the
concentration profile for this reactive distillation. It is
assumed that A and B are medium-boiling components,
C is a high-boiling component, and D is a low-boiling
component. The chemical equilibrium is on the side of
the products (K ) 10). Using a column with a reactive
distillation section above the feed stage and a section
with distillation only below the feed stage, it is possible
to separate the inert component D as the top and C as
the bottom product. Using a simple reactive distillation,

3040 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 28. Reaction space and concentration profile for the reactive distillation of A, B, and D with D as inert component. A and B are
converted to C. The equilibrium constant is K ) 10. The relative volatilities of the components A/B/C/D are 4/2/1/8. The pressure is P )
1.013 bar.
Table 2. Guideline for the Combination of Reactive and
Nonreactive Distillation in One Reactive Distillation
Column

reaction

inerts

AaB
AaB

AaB

C,D

A+BaC
A+BaC
A+BaC+D

desired products

section
only with
distillation
required

A or B
B/C
A/C
BC/D; BD/C; B/CD
AC/D; AD/C; A/CD
C
A/B
C/D
AD/B; A/BD
A/B
C/D

+
+
+
+
+
+
+
-

the product concentration is limited by the chemical


equilibrium. Because the desired product C is not
located in the reaction space, the column must be
divided into one reactive distillation and one nonreactive
distillation section. To separate the inert component
D, it is not necessary to interrupt the reactive distillation in the rectifying section because D is located in the
reaction space. The evaluation of the liquid concentration profile indicates that the upper part of the concentration profile in the rectifying section is on a nonreactive edge CD. Therefore it is not necessary to have a
reactive distillation zone in the whole rectifying section.
If the desired reaction is the decomposition of C to A
and B, it is not necessary to divide the column into a
reactive distillation and a distillation section (compare
Table 2). All products are located in the reaction space.
But the decomposition in one simple reactive distillation
only is possible, if the chemical equilibrium is on the
side of the decomposition product (compare Figures 15
and 16).
Concentration and temperature profile calculated
with a combined reactive distillation line can serve as
a starting point for rigorous simulation. Using this
approach, difficulties with convergence and multiplicity
analyzed for example by Jacobs and Krishna (1993) and
Nijhuis et al. (1993) for the methyl tert-butyl ether
(MTBE) system can be minimized.
4.2. Impact on the Process Design. A reactive
distillation column can be divided into sections with
reactive distillation and in sections with only distillation

Figure 29. Process for the design problem as in Figure 28. It is


supposed that a homogeneous high-boiling catalyst is applied.

to leave the reaction space by (a) using distillation trays


with a high-residence time in the reactive distillation
section and with a low-residence time in the distillation
section; (b) choosing the feed stage for the catalyst and
selecting a catalyst with a suitable boiling point; (c)
fixing a heterogeneous catalyst in the reactive distillation section of the column (see for example the patents
of Jones (1991), Ghelfi and Stringaro (1993), and Smith
(1990)). These methods can be applied separately or can
be combined.
Often the chemical reaction in the column must be
catalyzed. The type of catalyst has a large impact on
the process design. Assume, for example, that it is
possible to use two different types of catalyst for the
example in Figure 28: (a) a homogeneous catalyst,
which is the highest-boiling component in the system,
and (b) a heterogeneous catalyst, which can be fixed
inside the column.
If the reaction is fast in the presence of the catalyst,
the homogeneous catalyst must be separated to produce
C; see Figure 29. In the first reactive distillation column
the inert component D can be separated as the top
product. The mixture of the catalyst and C in chemical
equilibrium with A and B is the bottom product. In the
second distillation A, B, and C must be separated from
the catalyst. According to the rules of Schoenmakers
(1982) C will be partially decomposed into the educts A

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3041

and B in a undesired reaction in the stripping section


of this distillation column. Now it is possible in a third
distillation to separate C and to recycle the unconverted
educts A and B.
When a heterogeneous catalyst which can be fixed in
the reactive distillation column is applied, the whole
process can be performed in a reactive distillation
column; see Figure 28. An example of the impact of
catalyst selection on the process design is the synthesis
of MTBE. It is possible to catalyze the reaction with
sulfuric acid and with strong acid ion-exchange resins.
The process with the heterogeneous catalysis corresponds to the process in Figure 28, the process with the
homogeneous catalyst to the process in Figure 29. The
comparison of these to flow sheets (Figures 28 and 29)
indicates that it is very important that the catalyst is
really fixed in the reactive distillation section in the
process depicted in Figure 29. Otherwise, this process
is not feasible.
5. Summary and Future Development
In this paper the main elements of a design procedure
for reactive distillation processes with an equilibrium
reaction were identified. These elements are as follows: (a) Evaluation of the reaction space. When the
reaction space is analyzed, it can be decided whether a
reactive distillation must be combined with a nonreactive distillation. (b) Evaluation of the reactive distillation line diagrams. The interpretation of the reactive
distillation line diagrams supports the decision on the
feasibility of a reactive distillation process. The characteristics of the distillation line diagram give hints on
the basic column design. The necessity of two feed
stages can be predicted. (c) Application of combined
reactive/nonreactive distillation lines. The combined
reactive/nonreactive distillation line concept allows us
to check the proposed column design. (d) Rigorous
simulation and optimization. The information collected
above is the starting point for the rigorous simulation
and optimization.
This design procedure will be integrated in the
heuristic numeric system PROSYN for process synthesis; see the work of Schembecker et al. (1994) and
Schembecker and Simmrock (1996).
Notation
a, b, c ) parameters of the Antoine equation
B ) mole flow of bottom product
B
h ) transformed mole flow of bottom product
FG ) degrees of freedom
F ) mole flow of feed
F
h ) transformed mole flow of feed
D ) mole flow of distillate
D
h ) transformed mole flow of distillate
G ) mole flow of vapor
G
h ) transformed mole flow of vapor
K ) equilibrium constant (in this work defined as
nc i
K ) i)1
xi
L ) mole flow of liquid
L
h ) transformed mole flow of liquid
P ) pressure
nc ) number of components
N ) number of moles
N
h ) transformed number of moles
r ) number of independent chemical equilibrium reactions
R ) reaction
Xi ) transformed liquid phase composition of component i
vL ) liquid molar volume [cm3/mol]

Table 3
Antoine parameters
volatility

b[C]

c[C]

8
4
2
1

14.044
13.351
12.658
11.965

3984.923
3984.923
3984.923
3984.923

233.426
233.426
233.426
233.426

Table 4
Antoine parameters

liquid molar
volume

component

b [C]

c [C]

vL (cm3/mol)

water (H2O)
methyl formate (MF)
methanol (MeOH)
formic acid (FA)

11.9647
10.2965
11.9869
9.3703

3984.9228
2801.0487
3643.3136
2982.4463

233.426
240.37
239.726
218

18.07
61.54
40.73
37.91

xi ) mole fraction of component i in the liquid


Yi ) transformed vapor phase composition of component i
yi ) mole fraction of component i in the vapor
v ) reflux ratio
Greek Letters
I ) stoichiometric coefficient of component i
T ) the sum of the stoichiometric coefficients
nc
i
T ) i)1
) number of phases
Subscripts
) bottom product
D ) distillate
Dim ) dimer
i ) component i
I ) inert component
L ) liquid
P ) reference component (Barbosa and Doherty, 1988a;
Espinosa et al., 1995b)
m ) stage m (stripping section)
n ) stage n (rectifying section)
Abbreviations
Cat ) catalyst
FA ) formic acid
MeOH ) methanol
MF ) methyl formate

Appendix
Physical Properties. For the calculations of the
vapor-liquid equilibrium the parameters listed in
Tables 3 (Figures 15-23 and 28) and 4 (Figures 24 and
25) were used. The Antoine equation is defined as
follows:

ln(P) ) a -

b
; P [bar]
T+c

Parameters for the Wilson equation (Gmehling et al.,


1979) are as follows:
a12 ) 2001.7
a13 ) 515.9
a14 ) -194.6
24 ) 1
a23 ) 151.7973
34 ) 1

a21 ) 80.1
a31 ) 74.5
a41 ) 758.5
42 ) 1
a32 ) 907.572
43 ) 1

Chemical Theory. The dimerization of formic acid


in the vapor phase was taken into account by the

3042 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

chemical theory (Gmehling et al., 1979). The parameters are A ) -18.12 and B ) 7099 K.
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Received for review November 14, 1996


Revised manuscript received February 3, 1997
Accepted February 4, 1997X
IE960727P

X Abstract published in Advance ACS Abstracts, June 15,


1997.

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