Distillation

Troubleshooting
Distillation
Simulation
A tool called azeotrope pressure
Stanislaw K. Wasylkiewicz sensitivity analysis (APSA) can shed light
Aspen Technology, Inc. on the dependence of an azeotropes composition
and temperature on changes in pressure.

R
igorous, robust and reliable thermodynamic mod-
els are crucial for the synthesis and design of
separation systems for azeotropic mixtures.
Incorrect prediction of azeotropes often leads to infeasi-
ble separation sequences.
Although much progress in the modeling of physical
and chemical equilibrium has been made, there is no uni-
versal model that can be used for any mixture at any con-
ditions without adjusting various empirical parameters.
Furthermore, because we often neglect some terms that we
think are insignificant in rigorous thermodynamic models,
the adjustable empirical parameters must account for not
only what they were supposed to describe (e.g., interac-
tions between molecules in liquid phase), but also all
effects that have been neglected (1). This makes the mod-
els less predictable and their extrapolation to multicompo-
nent mixtures questionable. Even if model predictions for
all binary pairs are consistent with experimental vapor-
liquid equilibrium (VLE) data, we have to verify behavior
of the whole mixture before using a thermodynamic pack-
age for rigorous simulations.
Several excellent tools have recently been developed
for selecting, verifying and troubleshooting thermody-
namic models. Phase diagrams, residue curve maps
(RCMs) and distillation region diagrams (DRDs) are
invaluable for this purpose because of their visualization
capabilities. However, they are restricted to ternary and
quaternary mixtures.
There are no such restrictions for the azeotrope pres-
sure sensitivity analysis (APSA), where temperature and
composition bifurcation diagrams can be created for mix-
tures of any number of components. Since pressure
changes from stage to stage in distillation columns, APSA
is an excellent new tool for quick model verification and
troubleshooting of real, non-isobaric distillation columns.
It qualitatively reveals changes in the separation space that
are difficult to find using an RCM or a DRD.
This article describes, through several case studies, some
frequently encountered modeling problems during simula-
tion of non-isobaric azeotropic distillation columns, and
applies the new troubleshooting tools to these simulations.
An overview of the tools
The shape of the separation space, including distillation
boundaries, distillation regions and azeotropes (singular
points of the maps), can be easily examined on RCMs (2).
Visual analysis of an RCMs structure provides valuable
insight into the underlying thermodynamics, making
RCMs useful for screening binary VLE parameters based
on alternative databanks and regressions strategies (3).
Because RCMs depict VLE behavior in a ternary composi-
tion space, they can be more relevant than binary phase
diagrams in assessing the validity of various parameter
sets for distillation modeling.
Reference 3 shows examples of troubleshooting phase
equilibria that include using data outside their intended
range, employing VLE instead of vapor-liquid-liquid equi-
librium (VLLE) calculations, using parameter sets opti-

22 www.cepmagazine.org June 2006 CEP


mized for different regression objectives, and choosing the
appropriate model for the vapor phase. Reference 4 pres-
ents examples of utilizing RCMs and VLLE diagrams for
selection of the appropriate thermodynamic model and
verification of interaction parameters, and Refs. 5 and 6
explain how these methods can be applied in troubleshoot-
ing distillation columns. Conveniently, RCMs can now be
readily generated using commercial process simulation or
synthesis software. Moreover, the individual points of the
maps can be calculated for any number of components and
used to test phase equilibrium models.
Azeotropes determine distillation regions and distilla-
tion boundaries. Therefore, knowledge of temperatures
and compositions of all the azeotropes in a mixture at a
specified pressure is critical for both the design and opera-
tion of distillation systems. Calculating them is complicat-
ed by the strong non-linearities encountered in VLLE and
the presence of multiple solutions, both real and spurious.
One can attempt to find all of the solutions by using a
nonlinear solver with several starting points. However, even
with extreme calculation effort, this approach does not guar-
antee that all of the azeotropes will be found. Several tech-
niques have been proposed to solve this problem, e.g., the
Levenberg-Marquardt algorithm (7), the interval Newton
method (8), a global optimization method (9), etc.
The most reliable and robust method for calculating all
the azeotropes in a homogeneous mixture has been pro-
posed by Fidkowski, et al. (10) and later generalized to
include heterogeneous liquids (11). This method combined
with an arc length continuation and rigorous stability
analysis (12) is an efficient way to find all of the homoge-
neous and heterogeneous azeotropes predicted by a ther-
modynamic model at a specified pressure.
In the real world, plant operation is not static.
Changes in product quality and quantity often require
operation at different pressures. Even when operating
near steady state, many columns exhibit significant pres-
sure gradients between the distillate and the bottoms.
Thus, it is critical to understand the pressure sensitivity
of the azeotropes in a mixture.
When upper and lower pressure limits are specified, the
analysis can start from one pressure limit and then the
azeotrope composition can be calculated for gradually
increasing or decreasing pressures. This simple parameter-
continuation procedure can follow any known azeotrope.
However, it cannot find new azeotropes that appear as the
pressure changes.
An alternative is to apply rigorous azeotrope calcula-
tion procedures at each pressure interval. Such an
approach, though, would be extremely computationally
intensive and time consuming.
Table 1. Temperatures and compositions of binary
azeotrope WA at selected pressures.
Mole Mole
Pressure, Temperature, Fraction Fraction
kPa C of W of A
50 80.64 0.960958 0.039042
100 98.79 0.955925 0.044075
150 110.44 0.952532 0.047468
To overcome these difficulties, we have developed a new
method called azeotrope pressure sensitivity analysis
(APSA) that reveals how the compositions and temperatures
of azeotropes change with pressure. It applies bifurcation
theory together with an arc length continuation to perform
the calculations (13). This allows us to not only follow indi-
vidual azeotropes but also to find any new azeotrope that
appears in a specified pressure interval. Therefore, all bifur-
cation pressures, where azeotropes appear or disappear, can
be found. The computation time required for the entire pres-
sure sensitivity analysis is similar to the time necessary for
the homotopy-continuation method to find all azeotropes at a
single pressure.
The pressure-sensitivity of azeotropes provides new
opportunities in the design of azeotropic distillation
sequences. Increasing or decreasing operating pressures in
individual columns changes the composition of azeotropes
and positions of distillation boundaries, and can even
cause their appearance or disappearance. This can have
enormous effects on the topology of the RCM and the fea-
sibility of distillation sequences.
APSA shows opportunities for pressure-swing distilla-
tion and heat integration between columns in the
sequence. Pressure-swing distillation can often be an
attractive alternative for breaking homogeneous
azeotropes and sometimes can considerably simplify com-
plex separation systems.
Pressure-sensitivity information can also be important
in the design and troubleshooting of real distillation
columns, especially where there is a substantial pressure
drop in the column. In some cases, this can lead to a
switch in topology of distillation regions inside the col-
umn and cause serious problems in convergence of simu-
lators in steady-state and dynamic modes.
Troubleshooting non-isobaric
extractive distillation
Let us consider a typical separation problem. A mixture
containing mostly components A and W is to be separated.
There is a binary azeotrope between components A and W.
Since the azeotrope is not sensitive to pressure change
(Table 1), an entrainer, C, was selected to separate the bina-
CEP June 2006 www.cepmagazine.org 23
Distillation
Top Vapor Distillate
C+W
C pressure has been known
Upper
Feed Reflux
Lower
Feed Reboil
A+W
Bottoms A
Figure. Extractive distillation is used to break the binary azeotrope.
ry mixture in an extractive distillation sequence of two dis-
tillation columns (Figure 1). The first column was set up at
a constant pressure of 150 kPa and converged quickly to the
desired products: high-purity A and a binary mixture of W
and C. Then a pressure drop in the column was taken into
account. This time, the required high recovery of compo-
nent A in the bottom of the column was never achieved,
even with an extreme reflux and a large number of stages.
For the three key components (W, A and C), distilla-
tion region diagrams were created for three selected
pressures to examine the three-component space for
azeotropes and distillation boundaries, as shown in
Figure 2. By examining the DRDs, one can easily con-
clude that it is impossible to achieve complete recovery
of component A in the bottom product of the first col-
umn at 50 kPa because of the presence of a distillation
boundary at this pressure. But in our simulation case,
pressure at the top of the column does not drop as low
it always stays above 100 kPa. To troubleshoot this
case further, we will use APSA.
A A
50 kPa 100 kPa
C W C
Figure 2. Distillation region diagrams for ternary mixture W-A-C at 50, 100 and150 kPa,
based on the NRTL-Ideal model.
24 www.cepmagazine.org June 2006 CEP
Azeotrope pressure
Top Vapor sensitivity analysis
Distillate
The sensitivity of
W azeotropes to changes in
and studied for years. The
Reflux
magnitude of pressure
effects depends on the mix-
ture. Sometimes, composi-
Reboil tions of azeotropes change
very little (e.g., the ethanol-
water azeotrope (13)).
However, there are mixtures
C
where compositions of some
Bottoms
azeotropes change rapidly
with pressure and even
azeotropes that appear or
disappear as pressure varies.
Knapp (14) introduced the concept of a bifurcation
pressure, where an azeotrope appears or disappears, and
showed the necessary conditions for a homogeneous bina-
ry azeotrope to bifurcate. An azeotrope exists on one side
of a bifurcation pressure and a tangent pinch on the other
side. As the pressure increases or decreases away from the
bifurcation pressure, the severity of the tangent pinch
decreases. Therefore, a distillation column should not
operate near a bifurcation pressure.
In real distillation columns, pressure changes from
stage to stage. This can lead to a switch in topology of dis-
tillation regions and cause serious problems in both real
operation and in convergence of calculations for simula-
tors in steady-state or dynamic modes. In such cases,
information about the bifurcation pressures could be
extremely useful in troubleshooting both for simulators
and real operations.
The APSA method (15) is based on bifurcation theory
together with an arc length continuation. The method finds
all bifurcation pressures within specified pressure limits
and allows one not only to follow indi-
A vidual azeotropes, but also to efficient-
ly find any azeotrope that appears with-
in the pressure range. (More details are
150 kPa
available in Ref. 13.) This article
applies the APSA tool to create various
bifurcation diagrams, which are
extremely useful in troubleshooting of
azeotropic distillation columns.
The pressure sensitivity analysis of
W C W
azeotropes starts with a branch for each
pure component and each azeotrope
found at 50 kPa. Each branch is fol-
 A 1.0
1.0
Branch WAC,
0.8 Component W
0.9

Mole Fraction
NRTL

Branch WC
0.8 50150 kPa 0.6 Branch WAC,
Component C
0.7
Branch WA 0.4
0.6 Branch WC
Branch WAC 0.2
0.5
Branch WAC,
Component A
0.4
0.0
0.3
85 90 95 100 105 110 115 120 125 130
Pressure, kPa
0.2
Figure 5. Composition branches WC and WAC for pressure
0.1 analysis of azeotropes for ternary mixture W-A-C between 85 and
130 kPa, based on the NRTL-Ideal model.
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
C W
is also a turning point on branch WAC at 89 kPa.
Figure 3. Homotopy continuation branches WA, WC and WAC Notice how much more information the APSA pro-
for pressure analysis of azeotropes for ternary mixture W-A-C vides compared to DRD diagrams created for a few
between 50 and 150 kPa, based on the NRTL-Ideal model. selected pressures (Figure 2). The DRDs confirm the
existence of only one azeotrope, WA. The binary
azeotrope WC exists only in a very narrow range of pres-
106
sures (see Figure 4 and Figure 5) and is practically visible
104 as a homotopy continuation branch WC only in Figure 3.
The ternary azeotrope WAC was not found by the
Temperature, C

102 azeotrope searching algorithm (the 100-kPa DRD in

100
98
96
94
85 90 95 100 105 110 115 120 125 130
Pressure, kPa
Figure 4. Temperature branches WA, WC and WAC for pressure
analysis of azeotropes for ternary mixture W-A-C between 85 and
130 kPa, based on the NRTL-Ideal model.
lowed and continually checked for new bifurcations
between 50 and 150 kPa or until the branch disappears. The
corresponding homotopy continuation branches are shown
in Figure 3, temperature branches in Figure 4, and composi-
tion branches in Figure 5.
The binary azeotrope WA is not sensitive to pressure
change (see also Table 1). On the other hand, the WC and
WAC azeotropes are very pressure sensitive and exist only in
a narrow pressure range (WAC between 89 and 127 kPa, WC
only in the proximity of 127 kPa). There are two bifurcation
points where the WAC branches collapses: one on branch
WA (at 112 kPa), the other on branch WC (at 127 kPa). There
Figure 2) because the homotopy method used in the algo-
Branch WA
rithm cannot find isolas i.e., continuation paths not
connected to any homotopy branch that starts from a pure
Branch WC
Branch WAC component (10). The model actually predicts two WAC
azeotropes at 100 kPa (Figure 5) one that is a saddle,
and another that is an unstable node. Because two
azeotropes have been missed and their contributions can-
cel each other, the consistency test is fulfilled and there is
no warning during creation of DRD at 100 kPa.
Troubleshooting the distillation of
cyclohexanone-cyclohexanol-phenol
Another problem in the simulation of distillation
columns has been reported for the mixture of cyclohexa-
none (CC6one), cyclohexanol (CC6ol) and phenol.
APSA has been applied to the mixture to verify the
accuracy of predictions of two VLE models throughout
a pressure range of industrial interest. The NRTL (non-
random two-liquid) model predicts the existence of the
ternary maximum-boiling azeotrope in a wide pressure
range (only slightly pressure-sensitive), whereas the
Wilson model predicts the existence of the ternary sad-
dle azeotrope only in a very narrow range of pressures
(extremely pressure sensitive).

CEP June 2006 www.cepmagazine.org 25

Distillation

CC6ol CC6ol CC6ol tures of all azeotropes are so

85.19 99.25 108.19
close that any small change
Wilson Wilson Wilson in pressure can change their
5 kPa 10 kPa 15 kPa type and the structure of the
DRD. At 5 kPa, the CC6ol-
102.44 118.16 128.22 phenol azeotrope is a stable
118.15 node and the CC6one-phenol
97.82 101.88 113.53 118.22 123.55 128.65
azeotrope is a saddle, where-
71.40 87.24 97.34
Phenol CC6one Phenol CC6one Phenol CC6one as at 15 kPa the CC6ol-phe-
nol azeotrope is a saddle and
the CC6one-phenol azeotrope
Figure 6. Distillation region diagrams for the mixture of cyclohexanone (CC6one), cyclohexanol
(CC6ol) and phenol at 5, 10 and 15 kPa, based on the Wilson model. is a stable node.
The homotopy continua-
0.8 tion method (11) was used to find all azeotropes at par-
ticular pressures. The topological consistency was
0.7 checked using a topological constraint (10, 18) and all
Phenol diagrams presented are topologically consistent. If the
0.6
topological constraint is not fulfilled, one or more
Mole Fraction

0.5 azeotropes are missing or their properties have been

0.4
estimated incorrectly. However, fulfillment of the topo-
CC6ol logical constraint does not guarantee that all azeotropes
0.3 have been found or that the system properties have been
determined correctly. The topological constraint is a
0.2
necessary, but not a sufficient, condition for consistency
0.1 in azeotrope calculations (11).
CC6one
APSA was performed for the mixture between 5 kPa
0.0
and 15 kPa. Branches of solutions are shown in a compo-
5 6 7 8 9 10 11 12 13 14 15 sition bifurcation diagram (Figure 7). In this pressure
Pressure, kPa range, two bifurcation points have been found, as shown
in Table 2:
Figure 7. Composition changes of azeotropes with pressure for the B1 at 8.26 kPa, where the ternary CC6one-CC6ol-
mixture of cyclohexanone (squares), cyclohexanol (diamonds) and
phenol (triangles) between 5 and 15 kPa, based on the Wilson model.
phenol branch bifurcates from the CC6one-phenol branch,
and the CC6one-phenol azeotrope changes type from sad-
For this ternary system, it is known from measure- dle to stable node
ments (16) that: B2 at 10.94 kPa, where the ternary CC6one-CC6ol-
there is a maximum-boiling azeotrope in the binary phenol branch collapses on the CC6ol-phenol branch, and
system CC6one-phenol between 8.00 and 101.32 kPa the CC6ol-phenol azeotrope changes type from stable
there is a maximum-boiling azeotrope in the binary node to saddle.
system CC6ol-phenol between 9.33 and 101.32 kPa Both binary azeotropes are only slightly sensitive to
the three-component system does not form a ternary pressure changes. On the other hand, the ternary azeotrope
azeotrope at 12.00 kPa. (saddle) is extremely pressure-sensitive and exists only in
Distillation region diagrams for the mixture are present- the very narrow pressure range, between the two bifurca-
ed in Figure 6 for a few selected pres-
sures. VLE calculations were based on
Table 2. Results of bifurcation pressure search for the mixture of
the Wilson model. Binary interaction
cyclohexanol (CC6ol), cyclohexanone (CC6one) and phenol
parameters were taken from Ref 17. between 5 and 15 kPa, based on the Wilson model.
The Wilson model does not predict
the existence of the ternary azeotrope at Bifurcation Pressure, Bifurcation Composition, Temperature,
5 kPa and 15 kPa. There is, however, a Point kPa mole fraction C
very narrow range of pressures where the B1 8.26 0.0 0.262584 0.737416 113.54
ternary azeotrope exists. The tempera- B2 10.94 0.323241 0.0 0.676759 120.34

26 www.cepmagazine.org June 2006 CEP

 CC6ol CC6ol CC6ol in the wider pressure range
85.19 99.25 108.19
of 1100 kPa, all three
NRTL NRTL, NRTL azeotropes (two binary sad-
5 kPa 10 kPa 15 kPa dles and one ternary maxi-
mum-boiling) exist and do
105.57
129.55
119.57
145.12
128.53
155.05
not change their types.
APSA was performed for
97.82 101.75 113.53 118.08 123.55 128.51
the mixture in the pressure
71.40 87.24 97.34
Phenol CC6one Phenol CC6one Phenol CC6one range 1100 kPa. Branches
of solutions predicted by the
Figure 8. Distillation region diagram for the mixture of cyclohexanone (CC6one), cyclohexanol NRTL model are shown in a
(CC6ol) and phenol at 5, 10 and 15 kPa, based on the NRTL model. composition triangle in
Figure 9. No bifurcation
CC6ol
pressures were found. In this case, the binary CC6ol-phe-
1.0
nol azeotrope is the most pressure-sensitive, whereas the
0.9
ternary maximum-boiling CC6one-CC6ol-phenol
NRTL azeotrope is the least sensitive. This contradicts the predic-
0.8 1100 kPa tions of the Wilson model (Figure 7).
0.7
Performing both equilibrium and azeotrope calcula-
tions for this ternary system is challenging. The two
0.6 models give qualitatively different predictions for the
0.5 ternary CC6one-CC6ol-phenol azeotrope: an extremely
pressure-sensitive saddle azeotrope in a very narrow
0.4
range of pressures for the Wilson model, and a moder-
0.3 ately pressure-sensitive maximum-boiling azeotrope in
a wide pressure range for the NRTL model. At the
0.2
same time, the binary azeotropes are predicted equally
0.1 well by both models and are consistent with binary
experimental data.
0.0 More experiments for the ternary system are neces-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Phenol CC6one sary, especially in the pressure range between the
bifurcation pressures (8.26 and 10.94 kPa), to allow us
Figure 9. Branches of pressure sensitivity analysis of to accept or reject the Wilson model predictions. Based
azeotroopes for the mixture of cyclohexanone (CC6one), cyclo- on the only one available experimental data point for
hexanol (CC6ol) and phenol between 1 and 100 kPa, based on the ternary mixture at 12.00 kPa (16), we can conclude
the NRTL model.
that the NRTL model should be corrected (better inter-
tion pressures 8.26 and 10.94 kPa. Experiments have action parameters should be regressed). Generally, if a
shown that the three-component system does not form the model is expected to reflect reality, interaction parame-
ternary azeotrope at 12.00 kPa (16). This agrees well with ters should be regressed for the model using experi-
the Wilson model predictions. New experiments are need- mental data covering the particular pressure range of
ed in the pressure range between the two bifurcation pres- interest. In this case, special attention is required for
sures to check the model predictions. It must be empha- the saturated pressure correlation for pure components
sized here that, unlike stable and unstable azeotropes, it is (e.g., the Antoine equation). Since CC6ol and CC6one
much more difficult to confirm experimentally the exis- are close-boiling components, small inaccuracies in
tence of a saddle azeotrope. prediction of saturated pressure can cause significant
Distillation region diagrams for the mixture calculat- changes in the DRD structure.
ed based on the NRTL model are presented in Figure 8
for the same pressures as for the Wilson model. Binary Closing thoughts
interaction parameters were taken from Ref. 17. The It is extremely important to select the proper ther-
NRTL model predicts the existence of the ternary maxi- modynamic model and carefully verify the behavior of
mum-boiling azeotrope for all of these pressures. Even the mixture for a particular set of components before

CEP June 2006 www.cepmagazine.org 27

Distillation
any attempt is made to simulate a distillation column.
DRDs are extremely useful for this verification
because of their visualization capabilities. They are,
however, restricted to ternary and quaternary mixtures.
There are no such restrictions for APSA, which
involves calculating bifurcation pressures and creating
temperature and composition bifurcation diagrams for
any numbers of components. This provides an excellent
tool for both design and troubleshooting of real distil-
lation columns.
The extreme sensitivity of azeotropes to pressure
change in the examples discussed here has been detect-
ed in several distillation systems, especially when
close-boiling components were present. If detected,
this extreme sensitivity should trigger more careful
examination of the thermodynamic model (applicabili-
ty, parameters) and perhaps some additional VLE
measurements. At a minimum, it should draw attention
to the situation so the particular pressure range can be
avoided both in the design and operation of the distilla-
tion column.
Changes in product quality and quantity often require
operation of distillation columns at different pressures.
Even when operating at a near-steady-state condition,
many columns exhibit significant pressure gradients
between the distillate and bottoms. In some cases, this can
lead to a switch in the topology of the distillation regions
and cause serious problems in convergence of calculations
for steady-state or dynamic simulators.
APSA provides an understanding of the dependence
of an azeotropes compositions and temperatures on
changes in pressure. This information can be of critical
importance in the design and troubleshooting of distilla-
STANISLAW K. WASYLKIEWICZ, PhD, P.Eng., is a senior advisor at Aspen
Technology, Inc. (900, 125 9th Ave. SE, Calgary, Alberta T2G 0P6, Canada;
Phone: (403) 303-1047; E-mail: stan.wasylkiewicz@aspentech.com), where
his primary emphasis is conceptual design and simulation of distillation
processes. He is currently working on new tools for petroleum distillation
in the computer program RefSYS, a new product that enables companies
to optimize refinery-wide performance using an integrated model of their
facilities. He is a graduate in chemical engineering from the Technical Univ.
of Wroclaw (Poland), where he received his MSc and PhD and taught for
several years. Prior to joining the Conceptual Design Team of Hyprotech
(Calgary, Canada), he worked as a researcher at the Univ. of
Massachusetts (Amherst), where he was developing Mayflower, software
for the conceptual design of distillation systems. Throughout his
engineering career, he has become involved in several areas of expertise,
including thermodynamics, phase equilibrium, process synthesis,
simulation and optimization, and the design of non-azeotropic, azeotropic,
heterogeneous and reactive distillation columns. He has published over
100 scientific papers and contributed to technical books. He is a member
of AIChE and a registered professional engineer in Alberta, Canada.
28 www.cepmagazine.org June 2006 CEP
tion systems. APSA can also be used to verify the suit-
ability and accuracy of the VLE models throughout a
pressure range if the system is known to have particular
azeotropes at particular pressures. CEP
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