Reactions and Separations

Navigate Phase
Equilibria via Residue
Curve Maps
These maps provide a rapid, graphical means
to visualize the separation possibilities and
constraints of azeotropic ternary systems.
They also help check the soundness of
models used to predict equilibrium data.

Waldo E. de Villiers,
Raymond N. French and
George J. Koplos,
Shell Global Solutions
(US) Inc.

esidue curve maps (RCMs) have attracted interest from the academic and conceptual engineering design communities. Despite their usefulness, RCMs have received little attention from
practicing process engineers. In addition to being useful as
a separation synthesis tool, RCMs can also be used by the
practicing engineer to visualize and investigate vapor/liquid/liquid equilibrium (VL(L)E) issues affecting modeling
of distillation and liquid/liquid extraction columns.
[VL(L)E denotes systems that contain two liquid phases
and a vapor phase in equilibrium]. Other areas of application are column troubleshooting and control analysis.
This article reviews the physical significance and termiExperimentally:

Low-boiling
Component

Vapor at y()

Residue
at x()

Heat

Feed
Composition
High-boiling
Component

Intermediate-boiling
Component

Figure 1. RCMs, using experimental or generated data, show the

composition of the residue of a simple batch distillation over time.

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nology of RCMs, and illustrates their use to evaluate the

underlying thermodynamics of ternary systems. Four examples cover: using data outside their intended range; employing VLE calculations instead of VL(L)E; using parameter sets optimized to different regression objectives; and
choosing the appropriate model for the vapor phase. Wasylkiewicz and Shethna (1) present additional examples of
using RCMs for data evaluation.
RCMs are readily generated using commercial process
simulation software, such as Aspen Plus or DISTIL. A
residue curve represents the composition of the residue of a
simple batch distillation involving three components over
time (Figure 1). Mathematically:
di/dx = xi yi

(1)

where is a nonlinear time scale that spans the duration

of the experiment, x and y are the familiar mole fractions in the liquid and vapor, respectively, and i is the ith
component.
By integrating forward and backward in time from different starting positions, a family of curves the residue curve
map, is obtained. The usefulness of RCMs lies in the fact
that the composition profiles of continuous distillation
columns approximate the composition trajectories of the
residue curves (RCs). Fien and Liu (2) provide a more-detailed discussion of this relationship. Figure 2 presents the
RCM terminology. Nodes represent the starting and end
points of RCs and can be pure components, or binary or
ternary azeotropes. The nodes and saddle points are used to

Stable Node
(Pure Component)

Saddle Point

(Binary Azeotrope)
define distillation boundaries and associated
regions. Residue curves point toward increasDistillation Boundary
ing temperature and decreasing volatility.
or Separatrix
In Figure 2, each region has a different
heavy boiler or stable node. The feed and
Residue Curve
product compositions of a distillation column
can be overlaid in a geometrically simple
Saddle Point
manner as a mass balance line. The product
Unstable Node
(Binary Azeotrope)
(Light-Boiling
flows can be determined using the inverseTernary Azeotrope)
lever-arm rule. RCMs do not explicitly show
Distillation
relative volatility. A related construction using
Boundary
distillation lines is useful in this regard.
Compared to using sets of individual binary diagrams (Figure 3), RCMs display the behavior of the entire ternary system in one
Saddle
Stable Node
Stable Node
composition space. Both binary VL(L)E and
Point (Binary
Distillation
(Pure Component)
(Pure Component)
Azeotrope)
Boundary
ternary LLE data can be represented on
RCMs (Figure 3). As summarized by Doherty
and Malone (3): The structure of the residue Figure 2. Curves point toward increasing temperature and decreasing volatility, and reveal the
curve map is the underlying thermodynamic presence of azeotropes and distillation boundaries.
principle that governs the shape of composition profiles and consequently the products
that can be obtained from a distillation. This
Ethanol
structure, in turn, is determined by the underlying VL(L)E data.

x,

Using data outside their intended

range
Figure 4 shows a series of RCMs for the
ternary system methyl ethyl ketone, acetone
(which is dimethyl ketone), and water
(MEK/DMK/water) calculated at 1 atm and 6
atm. This was carried out using a commercial
process-simulation program. For the first
three RCMs, the VLE data were predicted
using the NRTL method with binary parameCyclohexane
Water
ters taken from one of two of the simulator
databanks, noted here as either databank A or
databank B.
At 1 atm, the two data sets generated
equivalent VLE predictions (only the RCM
from databank A is shown). At 6 atm, the parameters from databank B predicted a shift in
the VLE, but no change in the general features of the RCM. However, using the parameters from databank A predicted a change Figure 3. Mapping VL(L)E data to the sides of an RCM.
into a highly unusual, albeit permissible,
topology. For comparison, the RCM predicted by the Dortmund-modified UNIFAC method (4) (an esbinary azeotrope for MEK/DMK, as well as a ternary sadtimation method based on group contributions) is shown
dle azeotrope, which are highly suspicious.
to agree qualitatively with that generated using the dataTo solve this quandary and test the parameters used
bank B parameters.
in the two databanks, predictions were made for the
Without validation of the underlying binary VLE data, it
three sets of binary pairs (Figures 510). These comparis not possible to select one set of parameters over the other.
isons were generated using the binary-analysis feature
However, the RCM predicted by the databank A includes a
of the process simulator.
T

x,

x, y

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67

Reactions and Separations

Acetone

Water

Acetone

MEK

Water

MEK

Databank A @ 1 atm

Databank B @ 6 atm

Acetone

Acetone
Similar

is considerable disagreement between the

two. The A set predicts that the activity
coefficient of water increases indefinitely
with increasing temperature. In contrast,
the B set predicts the opposite behavior, a
decrease in the activity coefficient. Although, databank B appears to predict
high-temperature behavior more reliably
than the other set, a more in-depth comparison involving actual VLE data is warranted before validating the set for generating RCMs as a function of pressure.

DMK/MEK
As a mixture of two ketones differing
by only one carbon atom, this system
Topology
should behave nearly ideally. Figures 8 and
Suspect
9 demonstrate that databank A predicts unrealistic behavior at a higher pressure of 6
Water
MEK
Water
MEK
atm that is, DMK becomes less volatile
Mod. UNIFAC @ 6 atm
Databank A @ 6 atm
than MEK in MEK-rich mixtures. The activity coefficient plot, Figure 10, provides
Figure 4. RCMs for MEK/DMK/water differ at 6 atm for two prediction methods.
more information. The A parameters are
MEK/water
based on overfitting data for a single isobar, a pressure of
MEK and water would be expected to form a highly non1 atm. By generating temperature-dependent parameters
ideal binary mixture. For this pair, databases A and B both
for an ideal system from such a narrow range of data, the
gave nearly identical predictions of a heterogeneous azeotrope
resulting fit extrapolates poorly. The resulting model pre(Table 1). A sensitive way of evaluating VLE models is to
dicts activity coefficients well below 1, meaning large
look at the predictions of activity coefficients at infinite dilunegative deviations from ideality. The B parameter set
tion, o, as a function of temperature. Both sets of parameters
was fit to data over a much wider temperature range and,
generated similar values (Table 2). These parameters were reas expected, predicts nearly ideal behavior, with activity
gressed over a relatively narrow temperature range, correcoefficients close to 1.
sponding to 1-atm isobaric data, and the activity coefficients
at infinite dilution, o, show the typical monotonic function
Using VLE calculations instead of VL(L)E
that is inversely proportional to temperature.
In modeling distillation columns for systems capable of
highly non-ideal behavior, one must address whether to
DMK/water
Figure 5 shows that the two-parameTable 1. Comparison of azeotrope predictions for the
ter sets predict qualitatively similar
binary mixture MEK/water.
VLE at 1 atm, with databank A predictParameter
Temperature,
Pressure,
No. of
Azeotropic
ing a somewhat more difficult separaSet
F (~C)
atm
Liquid
Composition,
tion. In Figure 6, the B set predicts that
xMEK
Phases
the increase in pressure makes the sepaA
164.4 (74)
1
2
0.6500
ration more difficult, while the general
B
164.6 (74)
1
2
0.6488
shape of the binary diagram is the same.
A
269.7 (132)
6
2
0.5451
B
269.9 (132)
6
2
0.5438
However, set A predicts the occurrence
of a heterogeneous azeotrope at the
higher pressure. It is unusual for such
Table 2. Comparison of activity coefficients at infinite dilution
for the binary mixture MEK/water.
non-ideal behavior to appear as pressure
and temperature increase. Figure 7 indiTemperature, C
Parameter Set A
Parameter Set B
oDMK
oWater
oDMK
oWater
cates the basis for this suspect prediction. Set B is based on data over a much
30
62
6.6
63
6.5
wider temperature range than databank
70
39
6.1
39
6.0
100
29
5.8
29
5.7
A. Interestingly, in the range where
130
22
5.5
23
5.4
both data sets overlap (2095C), there

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P = 6 atm

P = 1 atm
1

1
Databank A

y, DMK

y, DMK

Databank B

0.6

0.4

0.6

Databank B

0.4

0.2

0.2

Databank A

0.8

0.8

0
0

0.2

0.4

0.6

0.8

0.2

0.4

0.6

0.8

x DMK

x, DMK

Figure 5. Vapor vs. liquid predictions for DMK/water at 1 atm are almost

Figure 6. DMK/water at 6 atm databank A parameters incorrectly

the same for databanks A and B.

predict a more-difficult separation at the higher pressure.

ternary and all three binary azeotropes reasonably, but sigconsider two liquid phases in the calculations. The tradinificantly overpredicted the solubility of water in SBE-rich
tional reluctance to enable more-complicated thermodymixtures. RCMs offer a convenient way to visualize the
namic calculations has largely been overcome by the comtrade-offs implicit in using such restricted sets in a ternary
puting power of modern process simulation programs, at
composition space.
least for steady-state simulations. However, VL(L)E calcuUsing the appropriate model for the vapor
lations can be problematic in dynamic modeling and in
some particularly difficult steady-state models. The situaBecause distillations for most chemical processes take
tion is exacerbated by the limitations of the state-of-the-art
place at low pressures, selecting the model to represent
thermodynamic models to simultaneously represent multithe vapor phase fugacities usually has a minimal impact on
component VLE and VL(L)E.
VLE calculations. It is not uncommon for NRTL parameRCM analysis can be a useful screening tool to see the
ters regressed using one model for the vapor phase (e.g.,
impact of VLE vs. VL(L)E calculations. In Figure 11, the
the Redlich-Kwong equation of state) to be used in simulacomposition profiles for two simulations are plotted on an
tions in which another model for the vapor phase (e.g.,
RCM. In one case, the thermodynamic calculations considideal) is specified. Such mixing and matching of parameered only VLE in the column, with VL(L)E allowed only in
ters will generate incorrect VLE predictions for systems
the condenser. In the second case, VL(L)E was enabled on all
that are significantly non-ideal in the vapor phase.
stages and resulted in a significantly different result. (Note:
Figures 12 and 13 show RCMs for an aqueous mixture
RR is the reflux ratio, and F, B and D are
100
the feed, bottom and distillate flowrates,
"Suspect Extrapolation"
respectively.)
H2O Databank A
DMK Databank B
o

Parameter sets optimized to

different regression objectives
As discussed above, it is often not
possible to simultaneously represent
vapor/liquid and vapor/liquid/liquid
equilibria to a desired precision. Thus, it
is not uncommon to have separate parameter sets optimized for either VLE or
LLE, or some compromise between the
two. An example of this was found with
the system sec-butyl alcohol, di-secbutyl ether, and water (SBA/SBE/water).
Using binary and ternary VL(L)E data
from Kovach and Seider (5), an LLE-optimized parameter set represented the
LLE behavior well, but failed to predict
the SBA-SBE azeotrope. At the same
time, a VLE-optimized set predicted the

10

DMK Databank A
230C

95C

20C

H2O Databank B
1
0.0019

0.0027

0.0035

1/T, K-1

Figure 7. DMK/water databank B is based on a wider temperature range and gives truer predictions.

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69

Reactions and Separations

P = 6 atm

P = 1 atm
1

1
Ideal

Databank A

0.8

0.8

Ideal

y, DMK

y, DMK

Databank B
0.6
Databank A

0.4

Databank B
0.4

0.2

0.2

0.6

0
0

0.2

0.4

0.6

0.8

0.2

0.4

0.6

0.8

x, DMK

x, DMK

Figure 8. DMK/MEK at 1 atm Interaction parameters from databanks

Figure 9. DMK/MEK at 6 atm databank A incorrectly predicts that

A and B are a reasonably close match.

DMK becomes less volatile at high MEK concentrations.

of formic and acetic acids, calculated using the same set of

NRTL parameters but different models for the vapor phase.
The NRTL parameters were regressed from binary data,
using an association model to represent the complexation
involving the carboxylic acids in the vapor phase. The
RCM in Figure 12 was generated using the same association model for the vapor phase, and it correctly predicts the
ternary maximum boiling azeotrope, as well as the one binary azeotrope (formic-acid/water) (6).
Figure 13 was generated, assuming an ideal vapor
phase, and it yields incorrect predictions. The ternary

Literature Cited

azeotrope is missing, and two binary azeotropes are shown

(formic-acid/water and acetic-acid/water). Thus, inconsistent handling of the vapor phase produced an RCM missing a key feature for the separation design, the distillation
boundary involving the ternary azeotrope.
An RCM predicted using the Dortmund-modified
UNIFAC model for the liquid phase with an ideal
vapor phase will result in a very similar RCM to that
shown in Figure 13. This suggests that the UNIFAC
method can reasonably predict the liquid phase nonideality in carboxylic-acid/water mixtures, but it can-

10

MEK Databank B
o

1. Wasylkiewicz., S., and H. Shethna, VLE

Data Estimation for Synthesis of Separation
Systems for Azeotropic Mixtures, Paper 4e
presented at AIChE Spring National Meeting,
New Orleans, LA (Mar. 2002).
2. Fien, G. A. F., and Y. A. Liu, Heuristic Synthesis and Shortcut Design of Separation Processes Using Residue Curve Maps, Ind. Eng.
Chem. Res., 33, pp. 25052522 (1994).
3. Doherty, M. F., and M. F. Malone, Conceptual Design of Distillation Systems, McGrawHill, New York (2001).
4. Gmehling J., The UNIFAC Consortium,
http://www.uni-oldenburg.de/tchemie/Consortium/ (2001).
5. Kovach, J. W., III, and W. D. Seider, VaporLiquid and Liquid-Liquid-Equilibria for the
System sec-Butyl Alcohol Di-sec-Butyl
Ether Water, J. Chem. Eng. Data, 32, 16
(1988).
6. Gmehling, J., et al., Azeotropic Data Part
II, VCH Publishers, New York, pp. 81, 92, 93,
291, 292, 1607 (1994).

1
DMK Databank B
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56C

MEK Databank A
DMK Databank A
0.1
0.0019

0.0027

0.0035

1/T, K-1

Figure 10. DMK/MEK binary databank A overfits data from 1 atm and yields incorrect
predictions when temperature varies.

70

79C

Ethanol

not compensate for the selection of the

incorrect vapor phase model.

Conclusions
Visual analysis of the structure or
topology of an RCM can provide valuable insight into issues affecting the underlying VL(L)E data. RCMs are useful
to screen binary parameters based on alternative databanks and regressions
strategies. Because RCMs depict
VL(L)E behavior in a ternary composition space, they can be more relevant
than standard binary phase diagrams in
assessing the utility of various parameter sets for distillation modeling. Not
only are RCMs a useful (qualitative)
tool for the practicing engineer involved
with distillation analysis, but they also
are a convenient bridge between practicing engineers and the thermodynamics

Column Profiles
VLLE Condenser Only
VLLE All Stages

Column Specs
Same Feed
RR = 10
F = 100
B = 71.6
D = 28.4

Cyclohexane

Water

Figure 11. Cyclohexane/water/ethanol considering two liquid phases yields a column

composition profile that differs significantly if only one phase is used.
Acetic Acid

Acetic Acid

106.59 C

Formic Acid

106.90 C

Water

101.16 C

Formic Acid

Water

Figure 12. Formic-acid/acetic-acid/water using NRTL plus an

Figure 13. Formic-acid/acetic-acid/water here, NRTL plus an ideal

association model for the vapor phase yields correct predictions.

vapor-phase model do not predict what will actually happen.

WALDO E. DE VILLIERS is a distillation specialist

in the Distillation Business Group of Shell
Global Solutions (US) Inc. (Westhollow
Technology Center, 3333 Highway 6 South,
Houston, TX 77082-3101; Phone (281)
544-6074; Fax: (281) 544-8123; E-mail:
waldo.devilliers@shell.com). He has 14 years
of experience in process simulation,
conceptual process development and process
design at Shell and before that was with
Sasol Technology. He has a BS and
MS in chemical engineering from
the Univ. of Stellenbosch, South Africa.

RAYMOND N. FRENCH is team leader for the

engineering data and physical properties
team in the Fluid Flow Business Group of
Shell Global Solutions (US) Inc. (Phone:
(281) 544-8382; Fax: (281) 544-7705;
E-mail: raymond.french@shell.com). He
has 21 years of experience in applied
thermodynamics and phase equilibria,
particularly for process simulation. French
has a BS in chemistry from Rensselaer
Polytechnic Institute and a PhD in physical
chemistry from the Univ. of Miami, Coral
Gables, FL. He is a member of AIChE and ACS.

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GEORGE J. KOPLOS is a senior technical

associate for the engineering data and
physical properties team in the Fluid
Flow Business Group of Shell Global
Solutions (US) Inc. (Phone: (281)
544-7580; Fax: (281) 544-7705;
E-mail: george.koplos@shell.com). He
has been with Shell for 24 years, the
greater part of which he was involved with
phase-equilibria experimentation. His current
focus is on physical-property validation for
process simulation. He has a BS Ed in
biology from Southwest Texas State Univ.

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