Ind. Eng. Chem. Res.

2006, 45, 4429-4432 4429

RESEARCH NOTES

A Fast Method To Calculate Residue Curve Maps

Claudia Gutiérrez-Antonio,† Miguel Vaca,†,‡ and Arturo Jiménez*,†
Departamento de Ingenierı́a Quı́mica, Instituto Tecnológico de Celaya, AV. Tecnológico y Garcı́a Cubas s/n,
38010, Celaya, Guanajuato, and DiVisión de Ingenierı́a Quı́mica y Bioquı́mica, Tecnológico de Estudios
Superiores de Ecatepec, AV. Tecnológico s/n, Valle de Anáhuac, 55210, Ecatepec, México
Residue curve maps are used in the preliminary stages of azeotropic distillation problems to establish feasible
separation targets. Their calculations involve an iterative procedure, because of bubble point determinations.
In this work, a simplified method for the generation of residue curve maps is presented. The method is based
on the use of a mean relative volatility, independent of temperature, that avoids iterative calculations. Several
case studies are used to show the effectiveness of the proposed method.

1. Introduction the liquid and vapor phase, respectively, and ξ is a dimensionless

Residue curves represent the change in composition of the
residue of a simple distillation process with time.1 A distinction
between residue curves and distillation lines should be made.
Distillation lines represent the liquid compositions whose vapor
compositions at equilibrium also lie on the same line. Unlike
the residue curve, the distillation line is the operating line at
total reflux.1 However, frequently, the assumption that residue
curves approximate the profiles in staged columns at total or
finite reflux is made, because that provides a convenient tool
in the preliminary steps of the design of distillation columns
(azeotropic and reactive), either packed or staged.2 For instance,
for azeotropic separations, a residue curve map (RCM) helps
the designer to visualize feasible splits, and to discard infeasible
specifications; once this is accomplished, one can determine
the feasible product region, which requires the calculation of
the distillation line passing through the feed point.3
It is well-known that relative volatilities are less dependent
on temperature than composition for almost-ideal mixtures. Also,
temperature effects on relative volatilities are not as significant
for nonideal mixtures at low pressures. In this work, we take
advantage of this behavior and calculate RCMs, neglecting the
effect of temperature on the relative volatilities, but preserving
the composition effect. Although this assumption has been
widely used for ideal mixtures, it has seldom been applied for
nonideal mixtures, regardless of whether they are zeotropic or
azeotropic. A comparison of the resulting RCMs with those
evaluated rigorously is also presented.
2. Residue Curve Calculation
time. If eq 1 is integrated forward and backward in time from
a given initial composition, a residue curve is obtained. A small
integration step is usually recommended to generate the RCM.
Each residue curve requires a great number of points to be
constructed, each one involving the calculation of the vapor-
phase composition in equilibrium with the liquid phase. Bubble
point calculations are needed to obtain the vapor-phase com-
position. Because such calculations are iterative, the generation
of RCM requires considerable numerical effort.4 In this work,
we propose the use of relative volatilities for RCM calculations.
Because relative volatilities show a rather weak dependence on
temperature, such an effect on the calculation of residue curves
can be neglected. The calculation of vapor-phase compositions
is as follows.
At low to moderate pressures, the modified Raoult’s law
properly represents the vapor-liquid equilibrium of nonideal
mixtures:4
γiPsat
i xi
yi ) (2)
P
where γi is the liquid-phase activity coefficient of component
i, Psat
i is the saturated pressure of pure component i, and P is
the total pressure of the system. After substituting the total
pressure and rearranging the equation, one obtains the following
equation for the vapor-phase composition:
Ri,Rxi
yi ) (3)
C

∑Rk,RxK
The equation to determine the residue curves is a modification
of the Rayleigh equation:2
k)1
dxi
) xi - yi (1) where C is the number of components, and Ri,R is the relative
dξ volatility of component i, with respect to a reference component
where xi and yi are the molar compositions of component i in R, which is given by

* To whom correspondence should be addressed. Tel. (+52-461) Psat

i γi
611-7575, Ext. 130. Fax: (+52-461) 611-7744. E-mail: arturo@
Ri,R ) sat γ
(4)
P R R
iqcelaya.itc.mx.
†
Departamento de Ingenierı́a Quı́mica, Instituto Tecnológico de
Celaya. Because of the small temperature effect on the relative
‡
División de Ingenierı́a Quı́mica y Bioquı́mica, Tecnológico de volatilities,4 eq 3 has been widely applied to ideal mixtures (γi
Estudios Superiores de Ecatepec. ) 1.0). For nonideal mixtures (zeotropic or azeotropic), eq 3
10.1021/ie051132+ CCC: $33.50 © 2006 American Chemical Society
Published on Web 05/04/2006
4430 Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006
Figure 1. Vapor-liquid equilibrium for two binary mixtures using rigorous
bubble-point estimations and the constant relative volatility method.
has not had the same degree of use, because of the effect of the
liquid composition.
When the temperature effect over Ri,R is neglected, a good
estimation of the bubble temperature (TB) is sufficient to obtain
a good description of the vapor-phase equilibrium composition.
In this work, a weighted sum of the pure-component boiling
temperatures (Tbi) is used:
N
TB ) ∑
i)1
Tb xi
i
(5)
After eq 5 is used, the vapor-phase composition is calculated
with eqs 4 and 3. Because of the fact that the bubble point
temperature is not determined with an iterative procedure, a
significant reduction in computer time should be observed.
To show the use of eq 4 on vapor-liquid equilibrium
calculations, two binary systemssthe acetone-benzene and
2-propanol-water systemssare analyzed. Figure 1 shows the
equilibrium curves (vapor mole fraction versus liquid mole
fraction) for each mixture at 101.3 kPa. The curve labeled
“rigorous” was calculated using eq 2, with rigorous bubble
temperature calculations, whereas the curve labeled “short” was
determined with eq 3, where relative volatilities were calculated
at the bubble temperature given by eq 4. An excellent agreement
between the rigorous and short curves for both mixtures can be
observed. The differences in boiling temperatures of the pure
components may affect the agreement between both approaches.
As a reference, such differences are 24 K for the acetone-
benzene system (a zeotropic mixture), and 18 K for the
2-propanol-water system (an azeotropic mixture). Under these
conditions, the agreement proved to be very good.
Figure 2. Residue curve map (RCM) for the acetone-2-propanol-water
mixture.
3. Results and Discussion
In this section, the results obtained from the application of
the proposed short method for the calculation of RCMs (here-
after referenced as “short curves”) are shown, and they are
compared to those obtained with the traditional method based
on iterative bubble-point calculations (labeled as “rigorous
curves”). RCMs were calculated for five ternary azeotropic
mixtures at atmospheric pressure (101.3 kPa). Three mixtures
have only one distillation boundary: the acetone-2-propanol-
water (M1), acetone-chloroform-benzene (M2), and methanol-
2-propanol-water (M3) systems. The other two ternary mixtures
have four separatrices: the methanol-chloroform-methyl
acetate (M4) system and the acetone-chloroform-methanol
(M5) system. The NRTL solution model was used to describe
the liquid-phase nonideality, whereas the vapor phase was
considered as an ideal gas, which is an implicit assumption in
eq 2. Binary interaction parameters, which are required by the
NRTL model, were taken from the Dechema Collection.5 The
results for ternary mixtures that have one boundary are discussed
first.
Figure 2 shows the RCMs for the acetone-2-propanol-water
(M1) mixture. An excellent agreement between both residue
curves is observed; for practical uses, both residue curves can
be considered as overlaid.
In Figure 3, the RCMs for the acetone-chloroform-benzene
(M2) mixture are presented. In this case, the distillation
boundary has a pronounced curvature. Nevertheless, an excellent
agreement is again observed between the rigorous curve and
the short residue curve.
The RCMs for the methanol-2-propanol-water (M3) mix-
ture are shown in Figure 4. Although the short curve does not
match the rigorous curve as well as it does for mixtures M1
and M2, it may provide a proper use for preliminary applica-
tions, because a good description of the space composition is
observed.
One aspect worth of mention is the reduction in computer
time achieved by the proposed method. Table 1 presents the
computer times involved with both types of residue curves for
mixtures M1-M3. For each mixture, 17 residue curves were
calculated (although not all of them are included in Figures 2-4,
for the sake of clarity). Table 1 shows that the computer time
required for the calculation of the RCM with the proposed
method is 10%-14% of the time with the rigorous method.
Such a reduction is obtained without a practical loss of the
quality of each RCM.
 Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006 4431

Figure 3. RCM for the acetone-chloroform-benzene mixture.

Figure 5. RCM for the acetone-chloroform-methanol mixture.

Figure 4. RCM for the methanol-2-propanol-water mixture.

Figure 6. RCM for the methanol-chloroform-methyl acetate mixture.
Table 1. Computer Times Required for Residue Curve Map (RCM)
Calculations located in a neighbor distillation region (an inconsistent estima-
Computer Time (CPU s) short RCM/rigorous RCM tion). This happened because the boundary prediction differed
mixture rigorous RCM short RCM ratio from each method. Nonetheless, one can still observe an overall
M1 353.6 49.1 0.14 good agreement between the short and rigorous curves.
M2 180.5 18.4 0.10 One last observation is in place. RCMs are calculated using
M3 208.5 26.9 0.13 an approximate TB value that is bounded by the pure-component
boiling temperatures (eq 5). For mixtures M1-M3, the azeo-
Mixtures M4 and M5 are more complex, because they involve trope for each mixture has a TB value within the interval of the
a higher number and different types of nodes. Figure 5 shows boiling temperatures for the pure components. The proposed
the RCM for mixture M4. Four separatrices arise, because of method provides good results in those cases. However, in cases
the existence of three binary azeotropes and one ternary M4 and M5, there are azeotropes with temperatures outside the
azeotrope. The binary azeotropes consist of two unstable nodes range given by the bubble points of the pure components. Even
and one stable node, whereas the ternary azeotrope is a saddle under those conditions, the method provides residue curves that
node.2 There is a good agreement between the short curves and satisfactorily match those provided by rigorous calculations. This
that based on iterative calculations. observation seems to indicate that the proposed method offers
The residue curves for mixture M5 are shown in Figure 6. good robustness properties.
This mixture shows four azeotropic nodes: two unstable nodes,
one saddle node, and one stable node. In addition, pure methanol 4. Concluding Remarks
provides a stable node, and chloroform and methyl acetate are
saddle nodes. The complex nature of these mixtures is reflected Residue curve maps (RCMs) are important tools to analyze
in the shapes of their RCMs. Four regions are identified. Note the feasibility of a proposed split for nonideal azeotropic
that (i) the residue curves end in the methanol node and (ii) separations in an easy, fast, and qualitative format. In this paper,
they just pass through the chloroform and methyl acetate nodes. the use of a temperature-independent (but liquid-phase-composi-
Also, there is a short residue curve that seemingly is not calcu- tion-dependent) relative volatility has been proposed to calculate
lated with the rigorous model; such a rigorous curve is actually residue curves. The results indicate that a good representation
4432 Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006
of the residue curve maps is obtained with the simplified
method, even for azeotropic mixtures with more than one
separatrix. The region in which some differences are sometimes
observed is located in the neighborhood of the distillation
boundaries. This does not seem to be a major problem, because
the use of RCM is quite restricted to assessing the preliminary
characteristics of azeotropic separation problems, as opposed
to their use within a formal numerical method; a quick approach
to obtain residue curves such as that presented in this work can
be particularly helpful during those preliminary design stages
for azeotropic distillation problems. However, if a better
representation in the neighborhood of the distillation boundaries
is important, a hybrid approach can be used: the boundary and
two additional neighbor curves, for instance, can be determined
with the rigorous model, whereas the rest of the space
composition can be described with the proposed method. For
example, if we take a typical calculation of 17 curves (as we
did for some of the case studies), then three of those curves
would be calculated rigorously and the other 14 would be
calculated with the short method. In this form, both a reduction
in computer time and a good description of the RCMs would
be preserved.
Acknowledgment
Financial support from CONACYT, Mexico (project number
SEP-2003-C02-43898) is gratefully acknowledged. Also, C.G.-
A. and M.V. were supported with scholarships from CONA-
CYT. M.V. is also grateful to the Instituto Mexicano del Petróleo
for financial support.
Nomenclature
C ) number of components
Pisat ) saturated pressure of the pure component i
P ) total pressure
TB ) bubble-point temperature
Tbi ) boiling temperature of component i
xi ) liquid-phase mole fraction of component i
yi ) vapor-phase mole fraction of component i
Ri,R ) relative volatility of component i, with respect to
component R
γi ) liquid-phase activity coefficient of component i
ξ ) dimensionless time
Literature Cited
(1) Seider, W.; Widagdo, S. Azeotropic Distillation. AIChE J. 1996, 42
(1), 96-130.
(2) Doherty, M. F.; Malone, M. F. Conceptual Design of Distillation
Systems; McGraw-Hill: New York, 2001.
(3) Fair, J. R.; Stichlmair, J. G. Distillation: Principles and Practice;
Wiley: New York, 1998.
(4) Henley, E. J.; Seader, J. D. Equilibrium Stage Separation Operations
in Chemical Engineering; Wiley: New York, 1981.
(5) Gmehling, J.; Onken, U. Vapor-Liquid Equilibrium Data Collection,
Dechema; Chemistry Data Series; DECHEMA: Frankfurt/Main, Germany,
1977.
ReceiVed for reView October 10, 2005
ReVised manuscript receiVed February 22, 2006
Accepted April 20, 2006
IE051132+