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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


and without the addition of a separating agent, and
Distillation is by far the most important industrial hybrid processes (distillation, e.g., combined with crys-
separation process because it offers several advantages. tallization or membrane techniques), have been devel-
In distillation processes energy is used to create a oped. In azeotropic and extractive distillation a solvent
system of fluid phases (liquid, vapor) that can easily be (entrainer) is used besides energy to enable or facilitate
transported. Especially in continuous distillation, an the separation of systems with disadvantageous separa-
intensive contact between the liquid and vapor phases tion factors (0.9 < R12 < 1.1). The selection of suitable
as well as a simple separation of the phases due to their solvents has been the subject of numerous investigations
different densities can be realized in a countercurrent (e.g., Laroche et al., 1991, 1992; Simmrock et al., 1991;
process. These features facilitate the realization of a Stichlmair et al., 1989; Wahnschafft and Westerberg,
multistage process. Finally, distillation is based on 1993). The new conceptual design package (Figure 1)
vapor-liquid equilibrium (VLE) which can reliably be presented here specifically addresses the synthesis of
predicted by modern thermodynamic models, such as distillation processes for systems with disadvantageous
gE models (Wilson, NRTL, UNIQUAC (e.g., Prausnitz separation factors. This means that separation prob-
et al., 1986)), equations of state (e.g., Soave, 1972; Peng lems which arise from the VLE behavior of a system
and Robinson, 1976), and even by group contribution can be recognized, for example, by calculating all binary,
methods, for example, the UNIFAC methods (Freden- ternary, etc., azeotropic points of multicomponent sys-
slund et al., 1975, 1977; Hansen et al., 1991; Gmehling tems, and strategies to overcome these difficulties can
et al., 1993). The rank of distillation processes is be developed. As a part of the DDBSP program package
underlined by the fact that the worldwide throughput (Gmehling et al., 1996), the new process synthesis
of distillation columns (oil refineries, chemical and module provides information for the conceptual design
petrochemical industry, natural gas processing) is ap- of new processes as well as for the analysis of estab-
proximately 5.3 × 109 tons/year (Porter, 1995) and that, lished processes (retrofit problems) and makes extensive
e.g., in the United States nearly 3% of the total energy use of graphical tools for the synthesis and design of
consumption is needed for running about 40 000 distil- azeotropic and extractive distillation. The entire system
lation columns (Humphrey and Seibert, 1992). has been used successfully in test runs and for consult-
In distillation, only the difference R12 - 1 can be ing purposes.
exploited for separation purposes. For systems with
separation factors near unity the number of stages Calculation of Azeotropic Data
required for a separation into the pure components
increases enormously. In the case of azeotropic systems Process synthesis for distillation processes is based
(R12 ) 1) a separation by ordinary distillation becomes on the reliable knowledge on azeotropic data. Thus, the
impossible even with an infinite number of stages prediction of azeotropic points using thermodynamic
(Gmehling and Brehm, 1996). However, to maintain the models is a very important step within many proce-
advantages offered by distillation for azeotropic systems dures, such as the selection of suitable solvents, the
as well, several processes, for example, azeotropic and calculation of residue curve maps, etc. The calculation
of azeotropic data is actually performed by two separate
* Author to whom correspondence is addressed. E-mail: programs: one for the calculation of homogeneous
gmehling@tech.chem.uni-oldenburg.de. Phone: ++49-441- azeotropic points and the other for the calculation of
7983831. Fax: ++49-441-7983330. heterogeneous azeotropic points. The input for each of
† Present address: AspenTech Europe S.A./N.V., Rue Colo- the programs comprises the components, the system
nel Bourgstraat 127-129, B-1140 Brussels, Belgium. pressure for isobaric, and the system temperature for
S0888-5885(97)00782-3 CCC: $15.00 © 1998 American Chemical Society
Published on Web 05/23/1998
Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3113

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 for the calculation of both homogeneous and heteroge-
is the thermodynamic model and the estimation meth- neous azeotropic data is given by Gmehling et al. (1994).
ods for the pure-component vapor pressures and the An example for azeotropic behavior in multicompo-
fugacity coefficients that need to be specified. The nent mixtures is shown in Table 1. The modified
output covers data on pressure, temperature, and azeo- UNIFAC (Dortmund) method was applied to calculate
tropic composition (provided that an azeotrope has been the homogeneous quinary system acetone-chloroform-
detected) and a characterization of the type of azeotrope, methanol-ethanol-benzene and all its quaternary,
for example, homogeneous or heterogeneous, tempera- ternary, and binary subsystems. Note that this system
ture minimum or maximum, saddle point. exhibits six binary and four ternary homogeneous
Homogeneous Azeotropes. The program discussed azeotropes, some of which represent temperature maxima
here is capable of predicting homogeneous azeotropic or temperature minima while others represent saddle
data for multicomponent mixtures, whereby the real points. All other binary and higher systems show
behavior of the vapor phase can be taken into account zeotropic behavior. The experimental azeotropic data
by the chemical theory (e.g., for carboxylic acids) or the for each of the systems which are also given in Table 1
virial equation. The calculations are performed for all enable a direct comparison between experimental and
binary and higher systems. A binary system exhibits calculated data. The data indicate a good agreement
a homogeneous azeotrope, if for any composition the between the UNIFAC predictions and the experimental
separation factor becomes equal to unity: data from various authors (Gmehling et al., 1994). The
ability to directly compare experimental with calculated
K1 y1/x1 γ1P1s data is a unique and important tool not only to identify
R12 ) ) ) )1 (1) separation problems but also to distinguish correct from
K2 y2/x2 γ P s erroneous predictions and thus to test the reliability of
2 2
various thermodynamic models.
During the azeotropic search, the program actually
minimizes the difference between the equilibrium com- Residue Curves and Contour Lines
positions of the vapor and liquid phases. At the azeo-
tropic point, which represents one point of the vapor- Residue Curves. Processes such as azeotropic or
liquid equilibrium, not only the compositions but also extractive distillation are usually based on the addition
the chemical potentials of the two phases are equal, and of a separating agent to at least one binary system with
thus no further separation can be achieved by either a disadvantageous separation factor (0.9 < R12 < 1.1).
evaporation or condensation as part of an ordinary For this reason ternary diagrams, i.e., triangular dia-
distillation. grams, are frequently used to represent ternary com-
Heterogeneous Azeotropes. Binary and ternary position profiles or mass balances around unit opera-
heterogeneous azeotropic data are calculated by a tions. Thus, ternary diagrams are well suited for the
separate program. Once the vapor-liquid-liquid equi- graphical representation of feasible separations and
librium (VLLE) has been calculated for a given temper- product composition regions.
ature or pressure, the search for azeotropes begins. For For “simple” distillation column configurations with
example, the condition for binary heteroazeotropic one feed, two-outlet (for distillate and bottom product)
behavior is fulfilled if the calculated equilibrium com- residue curves can be used to describe internal concen-
position of the vapor phase is situated within the region tration profiles at infinite reflux ratio. The starting and
of liquid-liquid immiscibility, represented by the two end points of a residue curve then represent the
liquid compositions xi′ and xi′′. The search for ternary composition of the distillate and the bottom product,
azeotropes is a stepwise procedure in order to investi- respectively. At the same time both compositions
gate the ternary concentration region systematically and together with the feed composition have to fulfill the
usually starts from a binary heterogeneous subsystem. mass balance constraint as well, which means that all
The objective of this search is to find the pressure three compositions are located on the straight material
maximum on the vapor-pressure surface of the ternary balance line. Residue curves can be calculated by
system. A detailed description of the current procedure 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)

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
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
Figure 3. Contour lines for the ternary system acetone (1)schlo- and every system has. Universal properties that qualify
roform (2)-methanol (3): (a) isotherms (calculated at atmospheric
pressure); (b) F ) |R12 - 1| + |R13 - 1| + |R23 - 1| ) constant. b: or disqualify a solvent for the separation of a given
binary and ternary azeotropic points. binary mixture are the boiling points (vapor pressures)
of the pure components and the azeotropic points and
systems. Furthermore, the algorithm is capable of the activity coefficients (in particular γ∞) in the resulting
predicting cyclic lines and lines which consist of multiple ternary system. The first step in the design of azeo-
branches without any problems. In fact, ternary con- tropic or extractive distillation is then to find the
tour line diagrams can reveal a great variety of mixture appropriate solvent which fulfills the criteria based on
properties. Figure 3 shows two types of lines out of this those properties. With the help of either a large and
variety for the system acetone-chloroform-methanol. comprehensive factual database or reliable predictive
From the course of the isothermal lines the character methods used for the calculation of phase equilibrium
of the ternary azeotrope (saddle point) can be derived. data, it is possible to provide the necessary pure-
At the same time the plot of constant lines for the component and mixture information (γ∞, azeotropic
function data) and thus to find the suitable solvent for the
distillation process under consideration.
F) ∑i ∑
j*i
|Rij - 1|
Data Acquisition and Regression

not only helps to locate the ternary azeotropic composi- The separation task is provided interactively. The
tion but also allows to study its effect on the relative user only has to specify the binary system to be
volatilities over the entire concentration range. An separated and the conditions (system pressure, temper-
example of the contour line diagram of a ternary ature). All other required information (vapor pressures,
heterogeneous system is shown in Figure 4 which structural information, interaction parameters, ...) are
displays a selection of four isothermal curves at 66, 68, called from the Dortmund Data Bank (DDB) or will be
70, and 75 °C for the system ethanol-water-benzene calculated using a thermodynamic method. Before the
together with the liquid-liquid equilibrium tie-lines at solvent selection part actually starts, the program first
atmospheric pressure. of all examines the VLE behavior, and the user will be
noticed if a separation of the binary system can possibly
Entrainer Selection be achieved without a separating agent. This could be
done by either pressure-swing distillation, binary het-
The majority of processes for the separation of sys- eroazeotropic distillation, or vacuum (respectively under
tems with disadvantageous separation factors require elevated pressure) distillation. Note that the proposals
3116 Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998

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
Figure 5. Flowchart for the selection of solvents by access to the on azeotropic data and activity coefficients at infinite
Dortmund Data Bank (DDB). 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
Figure 6. Procedure for the selection of solvents using thermo- regression is used to estimate the values for Taz and
dynamic models (e.g., group contribution methods).
R∞12, respectively, from several experimental data sets
for each alternative are based on the data that has been for the given isobaric (isothermal) condition. Finally,
calculated or retrieved from the database. For pres- any solvent that fulfills the selection criteria is included
sure-swing distillation a criterion was derived from in a list with suitable solvents for the separation
systems that are actually separated this way, such as problem in hand.
water-tetrahydrofuran, etc. Thermodynamic Models. With modern and reli-
The selection of selective solvents is a good example able group contribution methods, for example, UNIFAC
for the importance of having a reliable knowledge of the (Fredenslund et al., 1977; Hansen et al., 1991) and
mixture data (azeotropic data and activity coefficients modified UNIFAC methods (Weidlich and Gmehling,
at infinite dilution) and information on the pure- 1987; Gmehling et al., 1993; Larsen et al., 1987) and
component boiling points (vapor pressures). The pure- the ASOG method (Kojima and Tochigi, 1979; Tochigi
component data are calculated using the Antoine equa- et al., 1990), the prediction of the required information
tion or estimated with the help of critical data and (γ∞i , azeotropic data) about a given mixture is possible
acentric factors (Gmehling and Kolbe, 1992). The from the information about the interaction between the
sources of the mixture data are given below. Note that concerned functional groups only. It is worth mention-
in the case of supercritical conditions and/or missing ing that the existing gE models such as the Wilson
parameters no calculation of data with thermodynamic (Wilson, 1964), the NRTL (Renon and Prausnitz, 1968),
models is performed, and thus no recommendation can or the UNIQUAC (Abrams and Prausnitz, 1975) model
be provided. Correspondingly, the method using the can be applied in a similar manner, but as the number
experimental database fails for systems for which no of functional groups is much smaller than the number
experimental data are available at all. The complete of possible compounds consisting of these groups, the
flowcharts of the two complementary methods for range of application increases and group contribution
solvent selection are shown in Figures 5 and 6. methods are to be recommended for a comprehensive
Experimental Database. For the selection of suit- and systematic search of solvents. Given a binary
able solvents by access to the Dortmund Data Bank system to be separated like 2-propanol-water or ben-
(DDB), two large databases provide the required mix- zene-cyclohexane for which group interaction param-
ture data. The information about the zeotropic/azeo- eters for most of the currently defined UNIFAC groups
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)

Figure 7. Condition for the occurrence of an azeotrope in a system N1 is the number of nodes among the pure components,
showing positive deviations (ln γ1 > 0) from Raoult’s law (ex- N2 is the number of nodes among the binary azeotropes,
ample: ethanol (1)-1,4-dioxane (2)). The temperature dependence S2 is the number of saddle points among the binary
(b) indicates the upper temperature limit for the existence of the
azeotropic point.
azeotropes, and N3 and S3 represent the number of
ternary nodes and saddles, respectively. This means
exist, a method such as modified UNIFAC is able to the singular points are embodied by the pure compo-
predict interactions for approximately 2500 ternary nents and the binary and ternary azeotropic points. As
systems and thus to provide a selection among up to an example Figure 8a shows the residue curve map of
2500 entrainer candidates. A review on thermodynamic the system benzene-cyclohexane-N-methyl-2-pyrroli-
models for the synthesis and design of separation done (NMP) at atmospheric pressure. In this system
processes is given by Gmehling (1994). NMP is the high-boiling entrainer for the separation of
The program using thermodynamic models is rather the binary benzene-cyclohexane temperature-minimum
similar to the procedure using experimental data sets. azeotrope. Thus, all residue curves start at the binary
In contrast to the latter, the program illustrated in azeotrope and approach the highest boiling point (NMP,
Figure 6 needs the specification on the solvents to be 202.0 °C). From the data in the residue curve map the
examined. With the help of data on activity coefficients following configuration in terms of singular points can
at infinite dilution (γ∞) and pure-component vapor be deduced: N1 ) 1, N2 ) 1, S2 ) 0. The azeotropic
pressures, it is possible to predict the occurrence of rule for such a system takes on the following form:
binary azeotropes, and thus it is possible to preselect
2(N3 - S3) + 1 - 0 + 1 ) 2 (5a)
potential solvents. The underlying principle of this
selection is shown in Figure 7. For binary systems
Equation 5a is fulfilled if the number of ternary nodes
showing positive deviation from Raoult’s law the natural
is equal to the number of ternary saddle points, a fact
logarithm of the ratio of the activity coefficients (ln γ2/
that implies multiple solutions (N3 ) S3 ) 0, 1, 2, ...).
γ1) as well as the ratio of the pure component vapor
However, up to now there is no experimental evidence
pressures ln(P1s/P2s) is plotted versus the mole fraction
for the existence of more than one ternary azeotropic
in the liquid phase for a given temperature. A binary
point in a ternary system (Gmehling et al., 1994), which
azeotrope with a pressure maximum (temperature
means that the practical solution to eq 5a is N3 ) S3 )
minimum) occurs when the following condition is ful-
0. Thus, for an extractive distillation entrainer it is not
filled:
necessary to check the existence of ternary azeotropes,
meaning that the rigorous calculation of azeotropic data
P1s is required for potential azeotropic distillation solvents
ln γ∞2 > ln > -ln γ∞1 (3)
P2s 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
In Figure 7a the azeotropic composition can be identi- for suitable solvents becomes much more effective by a
fied as the point of intersection of the two curves. Using significant reduction of the total time for the selection.
the above relation the occurrence and disappearance of However and as indicated earlier, azeotropic systems
azeotropes can be calculated provided that reliable can also exhibit residue curve boundaries. This is
information of the activity coefficients at infinite dilution demonstrated in Figure 8b,c, showing the residue curve
and vapor pressures as a function of temperature are maps of benzene-cyclohexane-acetone (one boundary)
available. In Figure 7b the courses of ln γ∞2 , -ln γ∞1 , and benzene-cyclohexane-2-butanone (two bound-
and ln(P1s/P2s) for the system ethanol (1)-1,4-dioxane aries). Each residue curve boundary is connecting two
(2) indicate that the azeotrope will disappear for tem- singular points, one of which is always a saddle point.
peratures above 80 °C because for higher temperatures For distillation processes these boundaries can limit the
ln γ∞2 is no longer larger than ln(P1s/P2s). This is product composition regions in such a way that they
approved by experimental data. The condition for a form compartments within the residue curve map with
binary pressure-minimum azeotrope, which assumes a curves starting and ending at different points. Note
system showing negative deviation from Raoult’s law, that for each of the three examples shown here the
can be derived in a way similar to that of eq 3: number of compartments is equal to the number of
stable nodes, which is, however, not a general rule. The
P1s behavior can become more complex in the case of
ln γ∞2 < ln < -ln γ∞1 (4) positive and negative deviations from Raoult’s law as
P2s shown in Figure 3. It has been demonstrated that
boundary distillation lines can be crossed (Stichlmair
Note that both conditions are simplified with respect 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 energy balance of the process negatively, those kinds
or the amount of one of the components from the original of processes will probably only be competitive when no
binary system that is supposed to be gained by decant- suitable high-boiling solvent is available.
ing will be too small. Note that for the selection of
selective solvents using thermodynamic models this Results and Discussion
ratio is part of the predicted output. For the selection Ester and ether compounds are promising entrainers
of solvents by access to DDB, the data can be retrieved for the separation of acetic acid and water. This can
directly from the liquid-liquid equilibrium (LLE) data be seen in Table 4 which gives an extract of the results
bank, which contains more than 10 500 data sets. that were obtained by searching the DDB for azeotropic
Extractive Distillation. In extractive distillation distillation entrainers. All the entrainers listed here
the entrainer is supposed to exhibit zeotropic behavior, form a binary heterogeneous azeotrope, with one of the
with all components of the system to be separated. components of the binary system to be separated, which
Moreover, its task is to alter the separation factor is water in this case. To decide which ester or ether is
the most suitable one for the process, graphical tools
K1 γ1P1s such as residue curve maps can be applied. With the
R12 ) ) (1) help of residue curves it is possible to decide whether a
K2 γ P s given solvent yields the desired products by determining
2 2
the product composition regions for a given feed com-
of the binary system in the desired way, so R12 or 1/R12 position (Stichlmair et al., 1989; Wahnschafft and
takes on values far from unity (Gmehling and Brehm, Westerberg, 1993). The residue curve map and column
1996). A criterion for the selection of selective solvents sequence for each of the solvents mentioned in Table 4
is the selectivity at infinite dilution S∞12: is, in principle, the same as that in Figure 9b, when
3-pentanone is exchanged, for example, by any ester or

γ∞1,SP1s ∞
P1s ether from Table 4. From the residue curve map in
R12,S ) ) S12,S s (6) Figure 9b it can be seen that the newly introduced
γ∞2,SP2s P2 binary heterogeneous azeotrope (A) is one product
(distillate) of the distillation of a ternary feed composi-
Thus, the entrainer should alter the activity coef- tion M, which results from mixing two streams with the
ficients of the components to be separated to a different compositions F (binary feed of acetic acid and water)
extent in order to achieve separation factors far from and S. The bottom product of this distillation is pure
unity. For a convenient recovery of the entrainer its acetic acid. The binary heterogeneous azeotrope (A)
boiling point must usually be sufficiently higher (e.g., splits into two liquid phases after condensation, one of
∆T ) 40 K) than for any component of the mixture to which is the entrainer-rich phase S to be recycled. The
be separated. Recent investigations have demonstrated other liquid phase contains mostly water that can be
the use of low-boiling solvents in so-called “reverse purified by stripping it in the second column of the
extractive distillation” processes (Láng et al., 1996), but separation sequence.
as the amount of solvent has to be increased enormously For the separation of vinyl acetate (1) and methanol
to ensure a sufficient liquid concentration of the en- (2) the selection method using thermodynamic models
trainer and the enthalpy of evaporation affects the 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- zeotropic behavior in all subsystems apart from the
tropic behavior) with a minimum boiling point difference binary that is to be separated, it should be rather easy
of 40 K. Furthermore, the entrainers are supposed to to achieve the separation of vinyl acetate and the
cause binary separation factors greater than 1.5 or entrainer. The temperature value in parentheses right
smaller than 1/1.5 by influencing the activity coefficients after the value for R12 is the temperature at which the
of the components to be separated to the desired extent. separation factor has been calculated. This is usually
Table 5 summarizes the results that were obtained an average value calculated from the boiling points of
using the modified UNIFAC (Dortmund) method to the three components (binary system to be separated
calculate the azeotropic data and separation factors for plus the entrainer) at the given pressure. For the
the selection. Obviously, there are some well-known selection based on data from the DDB this temperature
entrainers, such as aniline, dibutyl ether, xylenes, and corresponds to a temperature at which experimental
butyl acetate, included in the selection results. How- activity coefficients at infinite dilution are available in
ever, there are also some ketones and phenols in the the database. The vapor pressures for the separation
list. Taking phenol as an example, it is important to factor (see eq 1) are calculated with the help of the
mention that the melting point of an entrainer candi- temperature- and pressure-explicit Antoine equation. Of
date is also taken into account. Especially, some high- course, the Wagner equation shows an improved capa-
boiling solvents have high melting temperatures as well, bility when compared with the Antoine equation. How-
which could possibly lead to unwanted crystallization ever, the number of available Wagner parameters is
during the actual process. For this reason only entrain- much smaller, so that the number of potential solvents
ers with melting points lower than an upper limiting considered would be drastically reduced.
value defined by the user are selected. Note that the A third example presented in Table 6 is showing an
values for the melting points retrieved from the DDB extract of the results that were obtained using thermo-
are included in Table 5. From Table 5 it can be seen dynamic models once again. In contrast to the previous
that all the entrainers lead to separation factors lower example, this table actually comprises several selection
than unity. Thus, the volatility of component 1 (vinyl results, such as a list of solvents to be used for extractive
acetate) is smaller in relation to the value for methanol distillation, lists of solvents introducing one or two
(component 2), which means that using any of these binary azeotropes, a list of solvents introducing a
solvents will give methanol as the distillate of the ternary heterogeneous azeotrope, and finally a list of
extractive distillation column, whereas vinyl acetate and entrainers that can be used in reverse extractive distil-
the entrainer will leave as the bottom product. With lation and thus have a lower boiling point than the
the sufficiently high boiling point difference and 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 separation of a binary mixture of benzene and cyclo-
automatically, based on the azeotropic data and the hexane (as an example of the separation of aliphatics
activity coefficients at infinite dilution that have been from aromatics) by extractive distillation. Note that this
calculated for each component of the DDB for which list contains solvents that are, on one hand, of practical
interaction parameters with groups of the binary system importance for the industrial process but, on the other
for the modified UNIFAC method exist. Thus, the hand, cannot yet be described by any group contribution
selection using thermodynamic models is a very sys- method due to a lack of interaction parameters or group
tematic approach for the entrainer selection problem definitions. Thus, any procedure which searches sol-
with a fairly extended output, occasionally. It is par- vents using group contribution methods would fail to
ticularly useful for the investigation of certain compo- notice entrainers like sulfolane, N-formylmorpholine,
nent classes, such as alcohols, ethers, ..., etc. 6-caprolactam, or N-methyl-6-caprolactam, to name
Finally, Table 7 gives a list of selective solvents those of this example. (This discussion is based on the
(selection by DDB access) which can be applied to 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.

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
Figure 10. Experimental activity coefficients at infinite dilution solvent can be gained from the graphical representation
as a function of temperature for benzene (b) and cyclohexane (2) of the mixture properties. This information on, for
in N-formylmorpholine (NFM) from various authors (source: instance, the minimum entrainer supply, the product
DDB): s, linear regression.
composition regions, the feasibility, etc., can be used to
decide about the effectiveness and costs and thus to
its published group definitions and interaction param- compare solvents for a given separation problem in
eters. In the meantime within the company-supported order to find the “best” entrainer. Further criteria
UNIFAC consortium, the required parameters are concerning, for example, flash points, viscosity, certain
already available for the sponsors.) Afterall, the new functional groups (to be included or excluded), toxicity,
method of selecting solvents by DDB access gives and the extension to other separation processes (e.g.,
important additional information and is very innovative liquid-liquid extraction, absorption, ...), will be included
and practice-oriented in its results. As mentioned soon.
earlier, this method takes advantage of the large and
comprehensive factual database. Figure 10 gives as an Acknowledgment
example the graphical representation of the experimen- The authors thank Fonds der Chemischen Industrie
tal activity coefficients of benzene and cyclohexane at for financial support, DDBST GmbH, Oldenburg, Ger-
infinite dilution in N-formylmorpholine (NFM). These many, for providing the current version of the Dortmund
data were used to perform a linear regression to give Data Bank together with the accompanying software
coefficients for the temperature dependence of ln γ∞i . package, and Mr. Oliver Noll for his valuable contribu-
With the help of these coefficients it is then possible to tions to the present work.
calculate selectivities at infinite dilution at a given
temperature, and by using the pure-component vapor Nomenclature
pressures, it is finally possible to calculate the corre- Rij ) separation factor of components i and j
sponding separation factors listed in Table 7. γi ) activity coefficient of component i
Ind. Eng. Chem. Res., Vol. 37, No. 8, 1998 3123

ξ ) dimensionless measure of time Hansen, H. K.; Rasmussen, P.; Fredenslund, Aa.; Schiller, M.;
g ) molar Gibbs energy (J/mol) Gmehling, J. Vapor-Liquid Equilibria by UNIFAC Group
Ki ) K-factor of component i Contribution. 5. Revision and Extension. Ind. Eng. Chem. Res.
Pis ) saturation vapor pressure of component i (kPa) 1991, 30, 2352-2355.
Sij,k ) selectivity of the solvent k for the binary system of Humphrey, J. L.; Seibert, A. F. New Horizons in Distillation.
Chem. Eng. 1992, Dec, 86-98.
components i and j
t ) temperature (°C) Knapp, J. P.; Doherty, M. F. A New Pressure-Swing-Distillation
Process for Separating Homogeneous Azeotropic Mixtures. Ind.
T ) absolute temperature (K) Eng. Chem. Res. 1992, 31, 346-357.
Tb ) normal boiling point (K)
Kojima, K.; Tochigi, K. Prediction of Vapor-Liquid Equilibria by
xi ) liquid-phase mole fraction of component i the ASOG Method; Kodansha-Elsevier: Tokyo, 1979.
yi ) vapor-phase mole fraction of component i Láng, P.; Lelkes, Z.; Benadda, B.; Otterbein, M.; Moszkowicz, P.
Superscripts Extractive Distillation with Low Boiling Separating Agents.
12th International Congress of Chemical and Process Engineer-
′, ′′ ) liquid phases ing (CHISA ′96) 1996, C7.2: [1117].
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az ) at azeotropic composition Behaviour of Homogeneous Azeotropic DistillationsImplications
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Larsen, B. L.; Rasmussen, P.; Fredenslund, Aa. A Modified
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none ) zeotrope
Porter, K. E. Why Research is Needed in Distillation. Trans. Inst.
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Chem. Eng., Part A 1995, 73, 357-362.
Pmin ) pressure minimum
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