3112 Ind. Eng. Chem. Res.

1998, 37, 3112-3123

Synthesis of Distillation Processes Using Thermodynamic Models

and the Dortmund Data Bank
1 rgen Gmehling* and Christian Mo1 llmann†
Ju
Carl von Ossietzky Universität Oldenburg, Technische Chemie (FB 9), Postfach 2503,
D-26111 Oldenburg, Germany

A new and comprehensive procedure for process synthesis for binary and ternary distillation
processes with an emphasis on entrainer selection is presented. This procedure consists of two
complementary methods for entrainer selection and a variety of graphical tools for the
representation of various mixture properties of the given system. The methods for entrainer
selection are based on (a) the concept of thermodynamic models, such as group contribution
methods (e.g., modified UNIFAC), and (b) the access to a large computerized factual data bank
with experimental data on activity coefficients at infinite dilution and azeotropes. Explicit criteria
for the selection of solvents for azeotropic and extractive distillation are reported. With the
help of residue curves and contour lines it is shown how further information for a comparison
and advanced selection of entrainers can be obtained.

Introduction extractive distillation, pressure-swing distillation with

Distillation is by far the most important industrial
separation process because it offers several advantages.
In distillation processes energy is used to create a
system of fluid phases (liquid, vapor) that can easily be
transported. Especially in continuous distillation, an
intensive contact between the liquid and vapor phases
as well as a simple separation of the phases due to their
different densities can be realized in a countercurrent
process. These features facilitate the realization of a
multistage process. Finally, distillation is based on
vapor-liquid equilibrium (VLE) which can reliably be
predicted by modern thermodynamic models, such as
gE models (Wilson, NRTL, UNIQUAC (e.g., Prausnitz
et al., 1986)), equations of state (e.g., Soave, 1972; Peng
and Robinson, 1976), and even by group contribution
methods, for example, the UNIFAC methods (Freden-
slund et al., 1975, 1977; Hansen et al., 1991; Gmehling
et al., 1993). The rank of distillation processes is
underlined by the fact that the worldwide throughput
of distillation columns (oil refineries, chemical and
petrochemical industry, natural gas processing) is ap-
proximately 5.3 × 109 tons/year (Porter, 1995) and that,
e.g., in the United States nearly 3% of the total energy
consumption is needed for running about 40 000 distil-
lation columns (Humphrey and Seibert, 1992).
In distillation, only the difference R12 - 1 can be
exploited for separation purposes. For systems with
separation factors near unity the number of stages
required for a separation into the pure components
increases enormously. In the case of azeotropic systems
(R12 ) 1) a separation by ordinary distillation becomes
impossible even with an infinite number of stages
(Gmehling and Brehm, 1996). However, to maintain the
advantages offered by distillation for azeotropic systems
as well, several processes, for example, azeotropic and
* Author to whom correspondence is addressed. E-mail:
gmehling@tech.chem.uni-oldenburg.de. Phone: ++49-441-
7983831. Fax: ++49-441-7983330.
† Present address: AspenTech Europe S.A./N.V., Rue Colo-
nel Bourgstraat 127-129, B-1140 Brussels, Belgium.
S0888-5885(97)00782-3 CCC: $15.00 © 1998 American Chemical Society
Published on Web 05/23/1998
and without the addition of a separating agent, and
hybrid processes (distillation, e.g., combined with crys-
tallization or membrane techniques), have been devel-
oped. In azeotropic and extractive distillation a solvent
(entrainer) is used besides energy to enable or facilitate
the separation of systems with disadvantageous separa-
tion factors (0.9 < R12 < 1.1). The selection of suitable
solvents has been the subject of numerous investigations
(e.g., Laroche et al., 1991, 1992; Simmrock et al., 1991;
Stichlmair et al., 1989; Wahnschafft and Westerberg,
1993). The new conceptual design package (Figure 1)
presented here specifically addresses the synthesis of
distillation processes for systems with disadvantageous
separation factors. This means that separation prob-
lems which arise from the VLE behavior of a system
can be recognized, for example, by calculating all binary,
ternary, etc., azeotropic points of multicomponent sys-
tems, and strategies to overcome these difficulties can
be developed. As a part of the DDBSP program package
(Gmehling et al., 1996), the new process synthesis
module provides information for the conceptual design
of new processes as well as for the analysis of estab-
lished processes (retrofit problems) and makes extensive
use of graphical tools for the synthesis and design of
azeotropic and extractive distillation. The entire system
has been used successfully in test runs and for consult-
ing purposes.
Calculation of Azeotropic Data
Process synthesis for distillation processes is based
on the reliable knowledge on azeotropic data. Thus, the
prediction of azeotropic points using thermodynamic
models is a very important step within many proce-
dures, such as the selection of suitable solvents, the
calculation of residue curve maps, etc. The calculation
of azeotropic data is actually performed by two separate
programs: one for the calculation of homogeneous
azeotropic points and the other for the calculation of
heterogeneous azeotropic points. The input for each of
the programs comprises the components, the system
pressure for isobaric, and the system temperature for

Figure 1. Menu for the conceptual design package for the synthesis of distillation processes as a part of DDBSP (Gmehling et al., 1996).
isothermal calculations, respectively. Furthermore, it
is the thermodynamic model and the estimation meth-
ods for the pure-component vapor pressures and the
fugacity coefficients that need to be specified. The
output covers data on pressure, temperature, and azeo-
tropic composition (provided that an azeotrope has been
detected) and a characterization of the type of azeotrope,
for example, homogeneous or heterogeneous, tempera-
ture minimum or maximum, saddle point.
Homogeneous Azeotropes. The program discussed
here is capable of predicting homogeneous azeotropic
data for multicomponent mixtures, whereby the real
behavior of the vapor phase can be taken into account
by the chemical theory (e.g., for carboxylic acids) or the
virial equation. The calculations are performed for all
binary and higher systems. A binary system exhibits
a homogeneous azeotrope, if for any composition the
separation factor becomes equal to unity:
K1 y1/x1 γ1P1s
R12 ) ) ) )1
K2 y2/x2 γ P s
2 2
During the azeotropic search, the program actually
minimizes the difference between the equilibrium com-
positions of the vapor and liquid phases. At the azeo-
tropic point, which represents one point of the vapor-
liquid equilibrium, not only the compositions but also
the chemical potentials of the two phases are equal, and
thus no further separation can be achieved by either
evaporation or condensation as part of an ordinary
distillation.
Heterogeneous Azeotropes. Binary and ternary
heterogeneous azeotropic data are calculated by a
separate program. Once the vapor-liquid-liquid equi-
librium (VLLE) has been calculated for a given temper-
ature or pressure, the search for azeotropes begins. For
example, the condition for binary heteroazeotropic
behavior is fulfilled if the calculated equilibrium com-
position of the vapor phase is situated within the region
of liquid-liquid immiscibility, represented by the two
liquid compositions xi′ and xi′′. The search for ternary
azeotropes is a stepwise procedure in order to investi-
gate the ternary concentration region systematically and
usually starts from a binary heterogeneous subsystem.
The objective of this search is to find the pressure
maximum on the vapor-pressure surface of the ternary
system. A detailed description of the current procedure
Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3113
for the calculation of both homogeneous and heteroge-
neous azeotropic data is given by Gmehling et al. (1994).
An example for azeotropic behavior in multicompo-
nent mixtures is shown in Table 1. The modified
UNIFAC (Dortmund) method was applied to calculate
the homogeneous quinary system acetone-chloroform-
methanol-ethanol-benzene and all its quaternary,
ternary, and binary subsystems. Note that this system
exhibits six binary and four ternary homogeneous
azeotropes, some of which represent temperature maxima
or temperature minima while others represent saddle
points. All other binary and higher systems show
zeotropic behavior. The experimental azeotropic data
for each of the systems which are also given in Table 1
enable a direct comparison between experimental and
calculated data. The data indicate a good agreement
between the UNIFAC predictions and the experimental
data from various authors (Gmehling et al., 1994). The
ability to directly compare experimental with calculated
data is a unique and important tool not only to identify
(1) separation problems but also to distinguish correct from
erroneous predictions and thus to test the reliability of
various thermodynamic models.
Residue Curves and Contour Lines
Residue Curves. Processes such as azeotropic or
extractive distillation are usually based on the addition
of a separating agent to at least one binary system with
a disadvantageous separation factor (0.9 < R12 < 1.1).
For this reason ternary diagrams, i.e., triangular dia-
grams, are frequently used to represent ternary com-
position profiles or mass balances around unit opera-
tions. Thus, ternary diagrams are well suited for the
graphical representation of feasible separations and
product composition regions.
For “simple” distillation column configurations with
one feed, two-outlet (for distillate and bottom product)
residue curves can be used to describe internal concen-
tration profiles at infinite reflux ratio. The starting and
end points of a residue curve then represent the
composition of the distillate and the bottom product,
respectively. At the same time both compositions
together with the feed composition have to fulfill the
mass balance constraint as well, which means that all
three compositions are located on the straight material
balance line. Residue curves can be calculated by
numerical integration of
3114 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998

Table 1. Predicted (Modified UNIFAC) and Experimental Azeotropic Data (DDB) for the Quinary System Acetone
(1)-Chloroform (2)-Methanol (3)-Ethanol (4)-Benzene (5) and All Its Subsystems at Atmospheric Pressure
predicted experimentala
type of type of
system azeotrope t, °C y1,az y2,az y3,az y4,az y5,az azeotrope t, °C y1,az y2,az y3,az y4,az y5,az
1-2 homPmin 64.24 0.3562 0.6438 homPmin 64.42 0.352 0.648
1-3 homPmax 55.31 0.7867 0.2133 homPmax 55.56 0.790 0.210
1-4 none none
1-5 none none
2-3 homPmax 53.72 0.6496 0.3504 homPmax 53.49 0.651 0.349
2-4 homPmax 59.89 0.8636 0.1364 homPmax 59.36 0.842 0.158
2-5 none none
3-4 none none
3-5 homPmax 58.10 0.6150 0.3850 homPmax 58.00 0.610 0.390
4-5 homPmax 67.96 0.4637 0.5363 homPmax 67.93 0.448 0.552
1-2-3 homPsad 57.50 0.3359 0.2240 0.4401 homPsad 57.68 0.319 0.237 0.444
1-2-4 homPsad 63.14 0.3448 0.4820 0.1732 homPsad 63.30 0.345 0.465 0.190
1-2-5 none none
1-3-4 none none
1-3-5 none none
1-4-5 none none
2-3-4 none none
2-3-5 homPsad 58.66 0.1024 0.6034 0.2942 homPsad 59.30
2-4-5 homPsad 68.66 0.1244 0.4383 0.4373 n.a.b
3-4-5 none none
1-2-3-4 none n.a.
1-2-3-5 none n.a.
1-2-4-5 none n.a.
1-3-4-5 none n.a.
2-3-4-5 none n.a.
1-2-3-4-5 none none
a Mean values of the data stored in the Dortmund Data Bank. b n.a. ) not available.

dxi(ξ)
) xi(ξ) - yi(x
b(ξ)) i ) 1, ..., n - 1 (2)
dξ

where ξ is a dimensionless measure of time. A so-called

residue curve map comprises a collection of residue
curves within a ternary diagram. As an example,
Figure 2 shows the residue curve diagram of the system
benzene-2-propanol-water at atmospheric pressure. It
can be seen that due to the presence of azeotropes these
curves can have different starting points and end points,
and the resulting distillation regions are bordered by
residue curve boundaries. At infinite reflux ratio a
column with a given number of stages is usually
expected to have its maximum performance in terms of
separation. At the same time, the infinite reflux limit- Figure 2. Residue curve diagram for the system benzene (1)-2-
ing case can be used to approximate very high but finite propanol (2)-water (3) at atmospheric pressure: thick line, residue
curve boundaries; thin line, residual lines; - -, binodal curve;
reflux ratios. For these reasons residue curves are used - - -, liquid-liquid equilibrium tie-lines; b, binary and ternary
within this context to represent column profiles at azeotropic points.
infinite reflux ratio in distillation processes and to locate
product composition regions for a separation. Table 2. Objective Functions (Constant Properties) To
Be Used for the Calculation of Contour Lines
Contour Lines. Within this program system we
define contour lines as a series of liquid-phase composi- P ) constant (isobars)
tions (xi) that common constant properties can be T ) constant (isotherms)
assigned to. Again, triangular diagrams are useful to yi γiPoyiφisPis
display the course of these lines for any ternary system. Ki ) ) ) constant i ) 1, ..., n
For the synthesis of distillation processes, contour lines xi φ VP
i
with constant vapor-liquid equilibrium related proper-
Ki
ties are of particular interest. Table 2 shows the Rij ) ) constant
Kj i ) 1, ..., n
thermodynamic properties that have been defined as j ) 1, ..., n
objective functions in the algorithm so far. j*i
The algorithm itself is based on a spline interpolation F ) |R12 - 1| + |R13 - 1| +
among equally distanced points of the VLE for a given |R23 - 1| ) constant
ternary mixture. Note that these VLE data points have
been calculated rigorously, i.e., by means of gE models to calculate the liquid mole fractions (provided one xi is
or group contribution methods, before. Using the fixed in a ternary system) that belong to a given bubble
parameters of the spline equation, it is then possible to point temperature (objective function). This procedure
invert the phase equilibrium calculation, for example, applies to homogeneous as well as to heterogeneous

Figure 3. Contour lines for the ternary system acetone (1)schlo-
roform (2)-methanol (3): (a) isotherms (calculated at atmospheric
pressure); (b) F ) |R12 - 1| + |R13 - 1| + |R23 - 1| ) constant. b:
binary and ternary azeotropic points.
systems. Furthermore, the algorithm is capable of
predicting cyclic lines and lines which consist of multiple
branches without any problems. In fact, ternary con-
tour line diagrams can reveal a great variety of mixture
properties. Figure 3 shows two types of lines out of this
variety for the system acetone-chloroform-methanol.
From the course of the isothermal lines the character
of the ternary azeotrope (saddle point) can be derived.
At the same time the plot of constant lines for the
function
F) ∑i ∑
j*i
|Rij - 1|
not only helps to locate the ternary azeotropic composi-
tion but also allows to study its effect on the relative
volatilities over the entire concentration range. An
example of the contour line diagram of a ternary
heterogeneous system is shown in Figure 4 which
displays a selection of four isothermal curves at 66, 68,
70, and 75 °C for the system ethanol-water-benzene
together with the liquid-liquid equilibrium tie-lines at
atmospheric pressure.
Entrainer Selection
The majority of processes for the separation of sys-
tems with disadvantageous separation factors require
Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3115
Figure 4. Isothermal curves (t ) 65, 68, 70, and 75 °C) for the
system ethanol (1)-water (2)-benzene (3) at atmospheric pres-
sure: b, binary and ternary azeotropic points.
separating agents, i.e., solvents or entrainer, e.g., for
azeotropic and extractive distillation or extraction. The
solvent is added either to influence the activity coef-
ficients of the components to be separated to a different
extent (extractive distillation) or to introduce a new
lower boiling azeotrope which for its part can easily be
separated (e.g., heterogeneous azeotropes). The question
behind the problem of entrainer selection is, how does
one find out which solvents enable the separation of a
given binary system? The knowledge of simple and at
the same time sufficient conditions that have to be
fulfilled by entrainer candidates should enable a quick
and easy comparison among a high number of solvents.
Entrainers that do not meet the requirements could be
recognized and discarded immediately. For the devel-
opment of simple criteria which permit a solvent
screening, it takes properties that almost every solvent
and every system has. Universal properties that qualify
or disqualify a solvent for the separation of a given
binary mixture are the boiling points (vapor pressures)
of the pure components and the azeotropic points and
the activity coefficients (in particular γ∞) in the resulting
ternary system. The first step in the design of azeo-
tropic or extractive distillation is then to find the
appropriate solvent which fulfills the criteria based on
those properties. With the help of either a large and
comprehensive factual database or reliable predictive
methods used for the calculation of phase equilibrium
data, it is possible to provide the necessary pure-
component and mixture information (γ∞, azeotropic
data) and thus to find the suitable solvent for the
distillation process under consideration.
Data Acquisition and Regression
The separation task is provided interactively. The
user only has to specify the binary system to be
separated and the conditions (system pressure, temper-
ature). All other required information (vapor pressures,
structural information, interaction parameters, ...) are
called from the Dortmund Data Bank (DDB) or will be
calculated using a thermodynamic method. Before the
solvent selection part actually starts, the program first
of all examines the VLE behavior, and the user will be
noticed if a separation of the binary system can possibly
be achieved without a separating agent. This could be
done by either pressure-swing distillation, binary het-
eroazeotropic distillation, or vacuum (respectively under
elevated pressure) distillation. Note that the proposals
3116 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998
Figure 5. Flowchart for the selection of solvents by access to the
Dortmund Data Bank (DDB).
Figure 6. Procedure for the selection of solvents using thermo-
dynamic models (e.g., group contribution methods).
for each alternative are based on the data that has been
calculated or retrieved from the database. For pres-
sure-swing distillation a criterion was derived from
systems that are actually separated this way, such as
water-tetrahydrofuran, etc.
The selection of selective solvents is a good example
for the importance of having a reliable knowledge of the
mixture data (azeotropic data and activity coefficients
at infinite dilution) and information on the pure-
component boiling points (vapor pressures). The pure-
component data are calculated using the Antoine equa-
tion or estimated with the help of critical data and
acentric factors (Gmehling and Kolbe, 1992). The
sources of the mixture data are given below. Note that
in the case of supercritical conditions and/or missing
parameters no calculation of data with thermodynamic
models is performed, and thus no recommendation can
be provided. Correspondingly, the method using the
experimental database fails for systems for which no
experimental data are available at all. The complete
flowcharts of the two complementary methods for
solvent selection are shown in Figures 5 and 6.
Experimental Database. For the selection of suit-
able solvents by access to the Dortmund Data Bank
(DDB), two large databases provide the required mix-
ture data. The information about the zeotropic/azeo-
Table 3. Current Status of the DDB Database for
Azeotropic Data on Nonelectrolyte Systems (Oct 1997)
number of data points
components 2 3 4 ∑
zeotropic data 20 650 804 51 21 505
azeotropic data 17 727 1390 81 19 198
total 38 372 2194 132 40 703
number of systems 18 606 1338 97 20 041
tropic behavior is taken from the database for azeotropic
data (Gmehling et al., 1994). The approximately 40 700
data points represent a critically evaluated collection
of binary, ternary, and a few quaternary systems. The
current status of these databases is shown in Table 3.
The database on activity coefficients at infinite dilution
(Gmehling et al., 1986/1994) which contains approxi-
mately 33 200 data points is used to account for
information on selectivity and separability according to
eq 6. The program starts searching all binary data sets
on azeotropic data and activity coefficients at infinite
dilution for component 1 and later on for component 2
in the Dortmund Data Bank. Note that at this stage
the second component in the binary search has an
indefinite status (“wildcard character”) and is deter-
mined by the available binary data. A search for
ternary data sets is performed for systems with com-
ponents 1 and 2 and one of the components found during
the search for binary data. Since the number of data
sets for ternary systems is much lower than the number
of binary data sets (see Table 3), the absence of
information about the ternary system is interpreted as
zeotropic behavior, in order not to discard a solvent
because of missing ternary information only. With the
selected data it is possible to determine the number of
solvents with the required information on selectivity and
VLE. For the identified solvents the separation factors
at infinite dilution (R∞12) and temperatures at azeotro-
pic composition (Taz, yaz) for a given system pressure
will be estimated in the data regression step. Linear
regression is used to estimate the values for Taz and
R∞12, respectively, from several experimental data sets
for the given isobaric (isothermal) condition. Finally,
any solvent that fulfills the selection criteria is included
in a list with suitable solvents for the separation
problem in hand.
Thermodynamic Models. With modern and reli-
able group contribution methods, for example, UNIFAC
(Fredenslund et al., 1977; Hansen et al., 1991) and
modified UNIFAC methods (Weidlich and Gmehling,
1987; Gmehling et al., 1993; Larsen et al., 1987) and
the ASOG method (Kojima and Tochigi, 1979; Tochigi
et al., 1990), the prediction of the required information
(γ∞i , azeotropic data) about a given mixture is possible
from the information about the interaction between the
concerned functional groups only. It is worth mention-
ing that the existing gE models such as the Wilson
(Wilson, 1964), the NRTL (Renon and Prausnitz, 1968),
or the UNIQUAC (Abrams and Prausnitz, 1975) model
can be applied in a similar manner, but as the number
of functional groups is much smaller than the number
of possible compounds consisting of these groups, the
range of application increases and group contribution
methods are to be recommended for a comprehensive
and systematic search of solvents. Given a binary
system to be separated like 2-propanol-water or ben-
zene-cyclohexane for which group interaction param-
eters for most of the currently defined UNIFAC groups

Figure 7. Condition for the occurrence of an azeotrope in a system
showing positive deviations (ln γ1 > 0) from Raoult’s law (ex-
ample: ethanol (1)-1,4-dioxane (2)). The temperature dependence
(b) indicates the upper temperature limit for the existence of the
azeotropic point.
exist, a method such as modified UNIFAC is able to
predict interactions for approximately 2500 ternary
systems and thus to provide a selection among up to
2500 entrainer candidates. A review on thermodynamic
models for the synthesis and design of separation
processes is given by Gmehling (1994).
The program using thermodynamic models is rather
similar to the procedure using experimental data sets.
In contrast to the latter, the program illustrated in
Figure 6 needs the specification on the solvents to be
examined. With the help of data on activity coefficients
at infinite dilution (γ∞) and pure-component vapor
pressures, it is possible to predict the occurrence of
binary azeotropes, and thus it is possible to preselect
potential solvents. The underlying principle of this
selection is shown in Figure 7. For binary systems
showing positive deviation from Raoult’s law the natural
logarithm of the ratio of the activity coefficients (ln γ2/
γ1) as well as the ratio of the pure component vapor
pressures ln(P1s/P2s) is plotted versus the mole fraction
in the liquid phase for a given temperature. A binary
azeotrope with a pressure maximum (temperature
minimum) occurs when the following condition is ful-
filled:
P1s
ln γ∞2 > ln > -ln γ∞1 (3)
P2s
In Figure 7a the azeotropic composition can be identi-
fied as the point of intersection of the two curves. Using
the above relation the occurrence and disappearance of
azeotropes can be calculated provided that reliable
information of the activity coefficients at infinite dilution
and vapor pressures as a function of temperature are
available. In Figure 7b the courses of ln γ∞2 , -ln γ∞1 ,
and ln(P1s/P2s) for the system ethanol (1)-1,4-dioxane
(2) indicate that the azeotrope will disappear for tem-
peratures above 80 °C because for higher temperatures
ln γ∞2 is no longer larger than ln(P1s/P2s). This is
approved by experimental data. The condition for a
binary pressure-minimum azeotrope, which assumes a
system showing negative deviation from Raoult’s law,
can be derived in a way similar to that of eq 3:
P1s
ln γ∞2 < ln < -ln γ∞1 (4)
P2s
Note that both conditions are simplified with respect
Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3117
to fugacity coefficients and Poynting corrections. For a
ternary system all three binary subsystems can be
checked this way. In the case of either a high- or low-
boiling entrainer which does not introduce any further
binary azeotropes, the absence of a ternary azeotrope
can be confirmed by the azeotropic rule for ternary
systems (Doherty and Perkins, 1979), which reflects the
connections between the so-called singular points of a
system:
2(N3 - S3) + N2 - S2 + N1 ) 2 (5)
N1 is the number of nodes among the pure components,
N2 is the number of nodes among the binary azeotropes,
S2 is the number of saddle points among the binary
azeotropes, and N3 and S3 represent the number of
ternary nodes and saddles, respectively. This means
the singular points are embodied by the pure compo-
nents and the binary and ternary azeotropic points. As
an example Figure 8a shows the residue curve map of
the system benzene-cyclohexane-N-methyl-2-pyrroli-
done (NMP) at atmospheric pressure. In this system
NMP is the high-boiling entrainer for the separation of
the binary benzene-cyclohexane temperature-minimum
azeotrope. Thus, all residue curves start at the binary
azeotrope and approach the highest boiling point (NMP,
202.0 °C). From the data in the residue curve map the
following configuration in terms of singular points can
be deduced: N1 ) 1, N2 ) 1, S2 ) 0. The azeotropic
rule for such a system takes on the following form:
2(N3 - S3) + 1 - 0 + 1 ) 2 (5a)
Equation 5a is fulfilled if the number of ternary nodes
is equal to the number of ternary saddle points, a fact
that implies multiple solutions (N3 ) S3 ) 0, 1, 2, ...).
However, up to now there is no experimental evidence
for the existence of more than one ternary azeotropic
point in a ternary system (Gmehling et al., 1994), which
means that the practical solution to eq 5a is N3 ) S3 )
0. Thus, for an extractive distillation entrainer it is not
necessary to check the existence of ternary azeotropes,
meaning that the rigorous calculation of azeotropic data
is required for potential azeotropic distillation solvents
only. Solvents for extractive distillation can be distin-
guished from those suitable for azeotropic distillation
processes with the help of these insights, and the search
for suitable solvents becomes much more effective by a
significant reduction of the total time for the selection.
However and as indicated earlier, azeotropic systems
can also exhibit residue curve boundaries. This is
demonstrated in Figure 8b,c, showing the residue curve
maps of benzene-cyclohexane-acetone (one boundary)
and benzene-cyclohexane-2-butanone (two bound-
aries). Each residue curve boundary is connecting two
singular points, one of which is always a saddle point.
For distillation processes these boundaries can limit the
product composition regions in such a way that they
form compartments within the residue curve map with
curves starting and ending at different points. Note
that for each of the three examples shown here the
number of compartments is equal to the number of
stable nodes, which is, however, not a general rule. The
behavior can become more complex in the case of
positive and negative deviations from Raoult’s law as
shown in Figure 3. It has been demonstrated that
boundary distillation lines can be crossed (Stichlmair
et al., 1989) or moved when the conditions (e.g., pres-
3118 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998

Figure 8. Singular points in the ternary residue curve map for (a) benzene-cyclohexane-NMP (N1 ) 1, N2 ) 1, S2 ) 0 ), (b) benzene-
cyclohexane-acetone (N1 ) 2, N2 ) 1, S2 ) 1), and (c) benzene-cyclohexane-2-butanone (N1 ) 3, N2 ) 1, S2 ) 2): b, binary azeotropic
point.

sure) are changed (Knapp and Doherty, 1992). Finally,

it is once again important to mention that the reliability
of the predicted data on the selected solvents can be
checked with the help of the large and unique experi-
mental database.

Selection Criteria

After their retrieval and evaluation, the required data

are used to perform a selection procedure. Different
distillation processes have different demands. The
following paragraphs indicate the most important cri-
teria for the selection of solvents suitable for azeotropic
and extractive distillation. Apart from criteria that are
related to thermodynamic properties and phase equi-
librium behavior, there are other properties that will
practically influence the solvent selection. Therefore,
it is planned to extend the entrainer selection procedure,
taking into account flash points and transport proper-
ties, such as viscosity, etc. Experimental data on these
properties are already available in a large pure-
component data bank (Rarey et al., 1995). However,
despite all the differences the appropriate entrainer for
distillation processes should also be thermally stable,
nontoxic, and available at a low price.
Azeotropic Distillation. The task of a suitable
solvent for azeotropic distillation is the formation of one
(or more) lower boiling azeotrope(s), which on their part
can easily be separated (Gmehling and Brehm, 1996;
Stichlmair et al., 1989). This is especially true for
heterogeneous azeotropes, and thus the newly intro-
duced azeotrope should favorably be a heteroazeotrope.
Suitable solvents can introduce (a) a ternary azeotrope,
(b) a binary azeotrope, and (c) two binary azeotropes.
The resulting ternary residue curve maps for exem-
plary systems with one or more azeotropes introduced
to a binary mixture together with their corresponding
separation sequences are shown in Figure 9a-d. In all
cases one azeotropic constituent is separated by the
removal of the newly introduced azeotrope. Separation
of this component from the entrainer and solvent
recovery can be achieved, for example, by extraction
(Figure 9a: cyclohexane + acetone with water), exploi-
tation of a liquid-liquid equilibrium (Figure 9b: recycle
of entrainer-rich phase S), stripping (Figure 9c: toluene-
water separation), and a combination of stripping and Figure 9. Residue curve maps and column sequences for four
a water trap in the separation of ethanol-water using typical azeotropic distillation processes.
benzene (Figure 9d). mine the ratio of the amounts of the two liquid phases.
For the suitability of an entrainer which introduces If this ratio takes on a value far from unity, the
a heterogeneous azeotrope, it is also decisive to deter- entrainer is probably not useful for the process because
 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3119

Table 4. Results (Extract) of the Entrainer Selection for Azeotropic Distillation for the System Acetic Acid (1)-Water
(2) by DDB Access
components to be separated
(1) acetic acid C2H4O2 64-19-7
(2) water H2O 7732-18-5
system pressure ) 101.32 [kPa]
Tb(1) ) 391.01 [K]
Tb(2) ) 373.15 [K]
DDB access
List of Solvents Introducing One Further Binary Azeotrope (with Pressure Maximum)
types of azeotropes introduced
selective solvent (3) 1-3 2-3 1-2-3 Tb(az,bin.) [K] Tm(3) [K]
cyclopentanone none hetPmaxMisgap n.a. 367.75 222.50
3-pentanone none hetPmaxMisgap n.a. 355.98 234.15
ethyl propionate none hetPmaxMisgap n.a. 353.15 199.25
butyl acetate none hetPmaxMisgap noneMisgap 363.81 199.70
propyl acetate none hetPmaxMisgap noneMisgap 355.52 178.00
dipropyl ether none hetPmaxMisgap n.a. 348.55 147.05
diethyl ether none hetPmaxMisgap n.a. 307.34 156.85
dibutyl ether none hetPmaxMisgap n.a. 366.65 175.30
2-pentanone none hetPmaxMisgap n.a. 356.15 196.25
diisopropyl ether none hetPmaxMisgap none 336.15 186.35
ethyl butyl ether none hetPmaxMisgap n.a. 349.15 149.15
1,2-dichloroethane none hetPmaxMisgap noneMisgap 344.80 237.65
dichloromethane none hetPmaxMisgap none 311.25 178.01
isopentyl acetate none hetPmaxMisgap n.a. 366.95 195.15
diisobutyl ketone none hetPmaxMisgap n.a. 370.15 227.17
2,3-butanedione none hetPmaxMisgap n.a. 351.60 270.75
methyl propionate none hetPmaxMisgap n.a. 344.75 185.70
butyl propionate none hetPmaxMisgap n.a. 367.95 183.65

either the amount of entrainer which can be recycled
or the amount of one of the components from the original
binary system that is supposed to be gained by decant-
ing will be too small. Note that for the selection of
selective solvents using thermodynamic models this
ratio is part of the predicted output. For the selection
of solvents by access to DDB, the data can be retrieved
directly from the liquid-liquid equilibrium (LLE) data
bank, which contains more than 10 500 data sets.
Extractive Distillation. In extractive distillation
the entrainer is supposed to exhibit zeotropic behavior,
with all components of the system to be separated.
Moreover, its task is to alter the separation factor
K1 γ1P1s
R12 ) ) (1)
K2 γ P s
2 2
of the binary system in the desired way, so R12 or 1/R12
takes on values far from unity (Gmehling and Brehm,
1996). A criterion for the selection of selective solvents
is the selectivity at infinite dilution S∞12:
∞
γ∞1,SP1s ∞
P1s
R12,S ) ) S12,S s (6)
γ∞2,SP2s P2
Thus, the entrainer should alter the activity coef-
ficients of the components to be separated to a different
extent in order to achieve separation factors far from
unity. For a convenient recovery of the entrainer its
boiling point must usually be sufficiently higher (e.g.,
∆T ) 40 K) than for any component of the mixture to
be separated. Recent investigations have demonstrated
the use of low-boiling solvents in so-called “reverse
extractive distillation” processes (Láng et al., 1996), but
as the amount of solvent has to be increased enormously
to ensure a sufficient liquid concentration of the en-
trainer and the enthalpy of evaporation affects the
energy balance of the process negatively, those kinds
of processes will probably only be competitive when no
suitable high-boiling solvent is available.
Results and Discussion
Ester and ether compounds are promising entrainers
for the separation of acetic acid and water. This can
be seen in Table 4 which gives an extract of the results
that were obtained by searching the DDB for azeotropic
distillation entrainers. All the entrainers listed here
form a binary heterogeneous azeotrope, with one of the
components of the binary system to be separated, which
is water in this case. To decide which ester or ether is
the most suitable one for the process, graphical tools
such as residue curve maps can be applied. With the
help of residue curves it is possible to decide whether a
given solvent yields the desired products by determining
the product composition regions for a given feed com-
position (Stichlmair et al., 1989; Wahnschafft and
Westerberg, 1993). The residue curve map and column
sequence for each of the solvents mentioned in Table 4
is, in principle, the same as that in Figure 9b, when
3-pentanone is exchanged, for example, by any ester or
ether from Table 4. From the residue curve map in
Figure 9b it can be seen that the newly introduced
binary heterogeneous azeotrope (A) is one product
(distillate) of the distillation of a ternary feed composi-
tion M, which results from mixing two streams with the
compositions F (binary feed of acetic acid and water)
and S. The bottom product of this distillation is pure
acetic acid. The binary heterogeneous azeotrope (A)
splits into two liquid phases after condensation, one of
which is the entrainer-rich phase S to be recycled. The
other liquid phase contains mostly water that can be
purified by stripping it in the second column of the
separation sequence.
For the separation of vinyl acetate (1) and methanol
(2) the selection method using thermodynamic models
was applied. The intention in this particular case was
3120 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998

Table 5. Results (Extract) of the Entrainer Selection for Extractive Distillation for the System Vinyl Acetate
(1)-Methanol (2) Using Modified UNIFACa
components to be separated
(1) vinyl acetate C4H6O2 108-05-4
(2) methanol CH4O 67-56-1
system pressure ) 101.325 [kPa]
Tb(1) ) 345.88 [K]
Tb(2) ) 337.70 [K]
azeotropic data for system 1-2
type of azeotrope: homPmax
Tb ) 334.51 [K]
model: modified UNIFAC (Dortmund)
List of Solvents Introducing No Further Azeotrope (Extractive Distillation Entrainer)
types of azeotropes introduced
selective solvent (3) Tb [K] R∞1,2 1-3 2-3 1-2-3 Tm(3) [K]
aniline 457.83 0.360 (380.47 [K]) none none none 266.85
dibutyl ether 415.10 0.194 (366.23 [K]) none none none 175.30
decane 447.27 0.146 (376.95 [K]) none none none 243.45
dodecane 489.43 0.171 (391.00 [K]) none none none 263.59
butyl acetate 399.10 0.270 (360.89 [K]) none none none 199.70
1-hexadecene 558.02 0.208 (413.87 [K]) none none none 277.55
2-heptanone 424.20 0.386 (369.26 [K]) none none none 237.65
butylbenzene 456.45 0.142 (380.01 [K]) none none none 185.25
4-methyl-2-pentanone 389.34 0.392 (357.64 [K]) none none none 189.15
2-methylphenol 463.97 0.218 (382.52 [K]) none none none 304.09
1-octadecene 587.25 0.230 (423.61 [K]) none none none 291.15
4-methylphenol 474.91 0.225 (386.16 [K]) none none none 308.95
phenol 455.08 0.184 (379.55 [K]) none none none 314.05
tetradecane 525.85 0.196 (403.14 [K]) none none none 279.02
m-xylene 412.25 0.144 (365.28 [K]) none none none 225.35
p-xylene 411.50 0.144 (365.03 [K]) none none none 286.35
isopentyl acetate 410.21 0.266 (380.47 [K]) none none none 195.15
cyclopentanone 403.80 0.452 (362.46 [K]) none none none 222.50
cyclohexanone 428.15 0.426 (370.58 [K]) none none none 242.00
3-hexanone 396.65 0.350 (360.08 [K]) none none none 217.65
4-heptanone 419.47 0.348 (367.68 [K]) none none none 240.15
butyl butyrate 438.15 0.243 (373.91 [K]) none none none 181.15
a Minimum boiling point difference (entrainer - binary mixture) ) 40.00 K. Minimum required value for R (1,2 or inverse) at infinite

dilution ) 1.500.

to find high-boiling extractive distillation solvents (zeo-
tropic behavior) with a minimum boiling point difference
of 40 K. Furthermore, the entrainers are supposed to
cause binary separation factors greater than 1.5 or
smaller than 1/1.5 by influencing the activity coefficients
of the components to be separated to the desired extent.
Table 5 summarizes the results that were obtained
using the modified UNIFAC (Dortmund) method to
calculate the azeotropic data and separation factors for
the selection. Obviously, there are some well-known
entrainers, such as aniline, dibutyl ether, xylenes, and
butyl acetate, included in the selection results. How-
ever, there are also some ketones and phenols in the
list. Taking phenol as an example, it is important to
mention that the melting point of an entrainer candi-
date is also taken into account. Especially, some high-
boiling solvents have high melting temperatures as well,
which could possibly lead to unwanted crystallization
during the actual process. For this reason only entrain-
ers with melting points lower than an upper limiting
value defined by the user are selected. Note that the
values for the melting points retrieved from the DDB
are included in Table 5. From Table 5 it can be seen
that all the entrainers lead to separation factors lower
than unity. Thus, the volatility of component 1 (vinyl
acetate) is smaller in relation to the value for methanol
(component 2), which means that using any of these
solvents will give methanol as the distillate of the
extractive distillation column, whereas vinyl acetate and
the entrainer will leave as the bottom product. With
the sufficiently high boiling point difference and
zeotropic behavior in all subsystems apart from the
binary that is to be separated, it should be rather easy
to achieve the separation of vinyl acetate and the
entrainer. The temperature value in parentheses right
after the value for R12 is the temperature at which the
separation factor has been calculated. This is usually
an average value calculated from the boiling points of
the three components (binary system to be separated
plus the entrainer) at the given pressure. For the
selection based on data from the DDB this temperature
corresponds to a temperature at which experimental
activity coefficients at infinite dilution are available in
the database. The vapor pressures for the separation
factor (see eq 1) are calculated with the help of the
temperature- and pressure-explicit Antoine equation. Of
course, the Wagner equation shows an improved capa-
bility when compared with the Antoine equation. How-
ever, the number of available Wagner parameters is
much smaller, so that the number of potential solvents
considered would be drastically reduced.
A third example presented in Table 6 is showing an
extract of the results that were obtained using thermo-
dynamic models once again. In contrast to the previous
example, this table actually comprises several selection
results, such as a list of solvents to be used for extractive
distillation, lists of solvents introducing one or two
binary azeotropes, a list of solvents introducing a
ternary heterogeneous azeotrope, and finally a list of
entrainers that can be used in reverse extractive distil-
lation and thus have a lower boiling point than the
binary azeotrope to be separated. Note that the assign-
 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3121

Table 6. Results (Extract) of the Entrainer Selection for Azeotropic and Extractive Distillation for the System
2-Propanol (1)-Water (2) Using Modified UNIFACa
(1) 2-propanol C3H8O system pressure ) 101.325 kPa Tb(1) ) 355.47 K
(2) water H2O Tb(2) ) 373.15 K
azeotropic data for system 1-2
type of azeotrope: homPmax
Tb ) 353.64 K
model: modified UNIFAC (Dortmund)
List of Solvents Introducing No Further Azeotrope (Extractive Distillation Entrainer)
types of azeotropes introduced
selective solvent (3) Tb [K] R∞1,2 1-3 2-3 1-2-3 Tm(3) [K]
1,2-ethanediol 470.69 4.234 (399.77 [K]) none none none 261.65
dimethyl sulfoxide 466.74 5.108 (398.45 [K]) none none none 291.69
N-methyl-2-pyrrolidone (NMP) 475.13 0.443 (401.25 [K]) none none none 248.75
N-methyl-2-piperidone 483.42 0.401 (404.01 [K]) none none none n.a.
N-methyl-6-caprolactam 510.21 0.343 (412.94 [K]) none none none n.a.
List of Solvents Introducing One Further Binary Azeotrope (with Pressure Maximum)
types of azeotropes introduced
selective solvent (3) 1-3 2-3 1-2 Tb(az,bin.) [K] Tm(3) [K]
butane none hetPmaxMisgap none 272.58 134.85
dichloromethane none hetPmaxMisgap none 311.34 178.01
2-methylpropane none hetPmaxMisgap none 261.21 113.73
List of Solvents Introducing Two Further Binary Azeotropes (with Pressure Maximum)
types of azeotropes introduced
selective solvent (3) 1-3 2-3 1-2-3 Tb(1,3) [K] Tb(2,3) [K]
ethyl acetate homPmax hetPmaxMisgap none 349.18 344.62
methyl butyl ether homPmax hetPmaxMisgap none 342.62 339.36
isopropyl chloride homPmax hetPmaxMisgap none 309.59 308.43
1-chloropropane homPmax hetPmaxMisgap none 319.47 317.59
ethyl propyl ether homPmax hetPmaxMisgap none 336.07 333.02
List of Solvents Introducing a Ternary Heterogeneous Azeotrope
solvent (3) Tb(az) [K] yaz(1) yaz(2) yaz(3) Tm(3) [K]
benzene 339.71 0.2031 0.2527 0.5442 278.68
methylcyclopentane 333.48 0.1605 0.1891 0.6504 130.73
heptane 345.04 0.3271 0.3127 0.3602 182.55
diisopropyl ether 335.29 0.0886 0.2122 0.6992 186.35
toluene 349.16 0.3692 0.3738 0.2571 178.16
dipropyl ether 347.62 0.2197 0.3600 0.4204 147.05
isopropyl acetate 349.74 0.1733 0.3958 0.4309 199.75
methyl propionate 345.12 0.0870 0.3268 0.5862 185.70
methyl tert-amyl ether 347.67 0.1731 0.3628 0.4641 n.a.
1-chloropentane 349.74 0.3608 0.3847 0.2545 174.15
ethyl tert-butyl ether 339.18 0.0848 0.2536 0.6616 179.15
ethyl tert-amyl ether 350.21 0.3397 0.3948 0.2655 n.a.
List of Solvents Introducing No Further Azeotrope (Reverse Extractive Distillation Entrainer)
types of azeotropes introduced
selective solvent (3) Tb [K] R∞1,2 1-3 2-3 1-2-3 Tm(3) [K]
1-butene 266.89 0.231 (331.83 [K]) none none none 87.85
isobutylene 266.25 0.295 (331.62 [K]) none none none 132.75
a Minimum boiling point difference (entrainer - binary mixture) ) 40.00 K. Minimum required value for R (1,2 or inverse) at infinite

dilution ) 1.500.

ment to each class of solvents has been performed
automatically, based on the azeotropic data and the
activity coefficients at infinite dilution that have been
calculated for each component of the DDB for which
interaction parameters with groups of the binary system
for the modified UNIFAC method exist. Thus, the
selection using thermodynamic models is a very sys-
tematic approach for the entrainer selection problem
with a fairly extended output, occasionally. It is par-
ticularly useful for the investigation of certain compo-
nent classes, such as alcohols, ethers, ..., etc.
Finally, Table 7 gives a list of selective solvents
(selection by DDB access) which can be applied to the
separation of a binary mixture of benzene and cyclo-
hexane (as an example of the separation of aliphatics
from aromatics) by extractive distillation. Note that this
list contains solvents that are, on one hand, of practical
importance for the industrial process but, on the other
hand, cannot yet be described by any group contribution
method due to a lack of interaction parameters or group
definitions. Thus, any procedure which searches sol-
vents using group contribution methods would fail to
notice entrainers like sulfolane, N-formylmorpholine,
6-caprolactam, or N-methyl-6-caprolactam, to name
those of this example. (This discussion is based on the
capabilities of the modified UNIFAC method with
3122 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998

Table 7. Extractive Distillation Entrainers (Extract) for the Separation of the Binary System Benzene (1)-Cyclohexane
(2) Method: Selection by DDB Accessa
components to be separated
(1) benzene C6H6 Tb ) 353.25 [K]
(2) cyclohexane C6H12 Tb ) 353.86 [K]
system pressure ) 101.32 [kPa]
azeotropic data for system 1-2
type of azetrope: homPmax
Tb ) 351.52 [K]
types of azeotropes introduced
selective solvent (3) Tb [K] R∞1,2 1-3 2-3 1-2-3 Tm(3) [K]
N-methyl-6-caprolactam 510.21 0.586 (405.77 [K]) none none n.a. n.a.
4-methyl-2-pentanone 389.34 0.420 (293.15 [K]) none none none 189.15
aniline 457.83 0.323 (388.31 [K]) none none none 266.85
1,2-ethanediol 470.69 0.256 (392.60 [K]) none none n.a. 261.65
N-methyl-2-pyrrolidone (NMP) 476.15 0.299 (394.42 [K]) none none n.a. 248.75
triethylene glycol 551.49 0.367 (419.53 [K]) none none n.a. 268.85
sulfolane 559.96 0.275 (422.36 [K]) none none n.a. 301.65
6-caprolactam 546.32 0.267 (348.15 [K]) none none n.a. 342.45
furfural 434.67 0.306 (380.59 [K]) none none n.a. 234.45
3-methylphenol 475.82 0.379 (298.15 [K]) none none n.a. 284.95
cyclohexylamine 407.14 0.646 (303.15 [K]) none none n.a. 255.15
tetrahydrofurfuryl alcohol 450.20 0.247 (300.15 [K]) none none n.a. n.a.
nitrobenzene 483.94 0.289 (397.02 [K]) none none n.a. 278.85
cyclohexanone 428.15 0.293 (293.15 [K]) none none n.a. 242.00
anisole 428.79 0.328 (293.15 [K]) none none n.a. 235.65
N-formylmorpholine 519.05 0.269 (408.72 [K]) none none n.a. n.a.
butyronitrile 390.77 0.195 (298.15 [K]) none none n.a. 161.00
a Minimum boiling point difference (entrainer - binary mixture) ) 35 K. Minimum required value for R (1,2 or inverse) at infinite

dilution ) 1.500.

Figure 10. Experimental activity coefficients at infinite dilution
as a function of temperature for benzene (b) and cyclohexane (2)
in N-formylmorpholine (NFM) from various authors (source:
DDB): s, linear regression.
its published group definitions and interaction param-
eters. In the meantime within the company-supported
UNIFAC consortium, the required parameters are
already available for the sponsors.) Afterall, the new
method of selecting solvents by DDB access gives
important additional information and is very innovative
and practice-oriented in its results. As mentioned
earlier, this method takes advantage of the large and
comprehensive factual database. Figure 10 gives as an
example the graphical representation of the experimen-
tal activity coefficients of benzene and cyclohexane at
infinite dilution in N-formylmorpholine (NFM). These
data were used to perform a linear regression to give
coefficients for the temperature dependence of ln γ∞i .
With the help of these coefficients it is then possible to
calculate selectivities at infinite dilution at a given
temperature, and by using the pure-component vapor
pressures, it is finally possible to calculate the corre-
sponding separation factors listed in Table 7.
Conclusion
Group contribution methods and large factual data
banks are ideal tools for the synthesis and design of
thermal separation processes. New methods for the
selection of solvents for azeotropic and extractive distil-
lation have been presented. One method makes exten-
sive use of thermodynamic models, whereas the other
one allows a selection of solvents by access to a
comprehensive database with experimental data (γ∞i ,
azeotropic data). The methods work complementarily;
i.e., in the limits of thermodynamic models data re-
trieved from experimental data banks can provide
important additional information. Information about
the performance of a separation process with a given
solvent can be gained from the graphical representation
of the mixture properties. This information on, for
instance, the minimum entrainer supply, the product
composition regions, the feasibility, etc., can be used to
decide about the effectiveness and costs and thus to
compare solvents for a given separation problem in
order to find the “best” entrainer. Further criteria
concerning, for example, flash points, viscosity, certain
functional groups (to be included or excluded), toxicity,
and the extension to other separation processes (e.g.,
liquid-liquid extraction, absorption, ...), will be included
soon.
Acknowledgment
The authors thank Fonds der Chemischen Industrie
for financial support, DDBST GmbH, Oldenburg, Ger-
many, for providing the current version of the Dortmund
Data Bank together with the accompanying software
package, and Mr. Oliver Noll for his valuable contribu-
tions to the present work.
Nomenclature
Rij ) separation factor of components i and j
γi ) activity coefficient of component i

ξ ) dimensionless measure of time
g ) molar Gibbs energy (J/mol)
Ki ) K-factor of component i
Pis ) saturation vapor pressure of component i (kPa)
Sij,k ) selectivity of the solvent k for the binary system of
components i and j
t ) temperature (°C)
T ) absolute temperature (K)
Tb ) normal boiling point (K)
xi ) liquid-phase mole fraction of component i
yi ) vapor-phase mole fraction of component i
Superscripts
′, ′′ ) liquid phases
E ) excess property
∞ ) at infinite dilution
Subscripts
az ) at azeotropic composition
S ) solvent
Abbreviations for Azeotrope Types
n.a. ) not available
hom ) homogeneous
het ) heterogeneous
none ) zeotrope
Pmax ) pressure maximum
Pmin ) pressure minimum
Psad ) saddle point
Misgap ) miscibility gap (liquid-liquid equilibrium)
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Received for review November 5, 1997
Revised manuscript received March 30, 1998
Accepted April 3, 1998
IE970782D