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Comparative Analysis of Sharp Separation Regimes in the Distillation of Ternary

Zeotropic Mixtures

Article  in  Theoretical Foundations of Chemical Engineering · September 2014

DOI: 10.1134/S0040579514050200

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ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2014, Vol. 48, No. 5, pp. 622–628. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © P.O. Mavletkulova, L.A. Serafimov, R.Yu. Danilov, 2014, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2014, Vol. 48, No. 5, pp. 565–571.

Comparative Analysis of Sharp Separation Regimes

in the Distillation of Ternary Zeotropic Mixtures
P. O. Mavletkulovaa, L. A. Serafimova, and R. Yu. Danilovb
a
Moscow State University of Fine Chemical Technologies, pr. Vernadskogo 86, Moscow, 119571 Russia
b
IKT Servis, Protopopovskii per. 25B, Moscow, 129090 Russia
email: eleventhirteen@mail.ru
Received January 27, 2014

Abstract—A comparative analysis of the direct and indirect splits and class1 fractionation of ternary zeotro
pic mixtures has been carried out in terms of total vapor flow rate by means of a mathematical experiment.
Composition regions in which a certain separation flowsheet minimizes the total vapor flow rate have been
found.

Keywords: distillation, direct and indirect splits, class1 fractionation, minimum reflux ratio, optimization
DOI: 10.1134/S0040579514050200

INTRODUCTION A general algorithm was suggested [3] for calculat

Because of the irreversibility of distillation, there is
a certain set of process flowsheets allowing a mixture
to be separated into its pure components. The number
of these flowsheets is a function of the number of com
ponents in the initial mixture and the structure of its
phase diagram. In the case of a zeotropic ncompo
nent mixture, the number of flowsheets for sharp sep
aration, in which all components are distributed
between the final products, can be calculated via an
equation suggested by L’vov [1]:
[ 2 ( n – 1 ) ]!
Z =  .
n! ( n – 1 )!
This equation was obtained empirically and was
rigorously proved in a later work [2]. The number of
possible process flowsheets increases dramatically
with an increasing number of components in the
initial mixture. If distillation is conducted revers
ibly, the whole set of flowsheets will reduce to the
single flowsheet in which n – 1 components are
present in the distillate and bottoms in each col
umn.
Distillation at a minimum reflux ratio is revers
ible only in constantcomposition zones, i.e., at
singular points associated with internal material
balance or with the variation of the number of
components in the mixture along the distillation
trajectory.
Combining the sharpseparation and minimum
reflux regimes makes it possible to determine the min
imum energy requirement for the limiting possible
separation variants.
ing the minimum reflux ratio in simple distillation col
umns for multicomponent, ideal and nonideal, homo
geneous mixtures. This algorithm was implemented in
the DistillDesigner program. The algorithm involves
the concept of trajectory bundles and regularities of
reversible distillation [4, 5].
There has been a general analysis of the isocriterial
manifolds demarcating optimum feed composition
regions in concentration simplexes [6–9]. However,
only an approximate analysis of flowsheet variants in
terms of energy requirements has been carried out
(1)
because of the absence of a precise method for calcu
lating the minimum reflux ratio for mixtures of arbi
trary chemical nature. At the same time, those works
deal not only with ternary mixtures separated in two
section columns, but also with fourcomponent mix
tures separated in two and threesection columns.
The algorithm comparing the total vapor flow rates
in two separation variants for a ternary zeotropic
mixture [3] was used for the first time in a previous
work [10]. With this algorithm, the run and
arrangement of isocriterial manifolds differ from
those reported earlier [6] even for ideal mixtures.
This fact is quite understandable, since the relative
volatilities of components depend on the composi
tion and boiling point of the mixture being sepa
rated.
Here, we report a comparison of three separa
tion variants, namely, direct and indirect splits and
class1 fractionation. The analysis was carried out

622
 COMPARATIVE ANALYSIS OF SHARP SEPARATION REGIMES 623

for ternary zeotropic mixtures, both ideal and non (а)

ideal. (1) D1 1 2
For a ternary zeotropic mixture, Eq. (1) implies
only two process flowsheets differing in product
stream arrangement, each consisting of two adiabatic F
columns (Figs. 1a, 1b).
F
Among the intermediate separation variants, of
particular interest is class1 fractionation, whose defi
nition was introduced by Shiras et al. [11]. In this 23
D2 (2) W1 (3) W2 3
regime, the composition on the feed tray is equal to the
feed composition, which is one of the distillation
reversibility conditions [4]. The liquid–vapor equilib (b)
rium tie line in this regime is the material balance D2 (1) 1
directrix. Thus, the distillate and bottoms composi 12
tions are predetermined by the direction of the equi
librium tieline vector. Class1 fractionation in the D1
minimumreflux regime can be regarded as being F
F
intermediate between the direct and indirect splits
under the same conditions. Three columns are neces
sary for the class1 fractionation of a ternary zeotropic
mixture (Fig. 1c). In the first column, both the distil W2 (2) (3) W1 3 2
late and the bottoms will contain the intermediate
volatility component. (c)
1
The purpose of this work is to compare the energy
requirements of the direct and indirect splits and class D2 (1)
1 fractionation. It will also be elucidated whether there 12
are conditions under which separation in three col
D1
umns is energetically preferable to separation in two
columns. F 2
F
QUALITATIVE CHARACTERISTICS
OF THE DISTILLATION W2,D3 (2) W1 (3) W3 23
REGIMES COMPARED
The concept of sharp distillation was considered in
detail in an earlier publication [5]. Figure 2 demon 3
strates how the concepts of sharp distillation and sharp
separation can be related to the concepts of direct and Fig. 1. Distillation flowsheets in which the first column
indirect splits and class1 fractionation. Here, each carries out (a) direct split, (b) indirect split, and (c) class1
fractionation. F = feed, D = distillate, and W = bottoms.
oval represents the set of variants of some regime. For
example, the direct split can be viewed as sharp distil
lation with respect to the most volatile component if component of the feed in the distillate and there is no
this component is separated out in the pure state at the most volatile component in the bottoms.
column top. In this case, the overhead product point is
a stable node of the dynamic system and some con Figure 3 maps distillation trajectories for the
stantcomposition zone corresponds to it. Because the regimes considered and the corresponding constant
other product point is not a singular point of the composition zones in the case of minimumreflux dis
dynamic system, but the most volatile component is tillation.
entirely boiled off there, sharp separation takes place We will use the concept of oneway infinity in
in the column. the case of the distillation trajectory discontinuing
Likewise, when the indirect split is carried out, at a singular point, and the concept of twoway
sharp distillation with respect to the least volatile com infinity will be used when a singular point divides
ponent takes place. the distillation trajectory into two portions (pinch
In class1 fractionation, there will be sharp separa regime [13]) or, the number of components
tion on fractions only when there is no least volatile changes along the distillation trajectory.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 48 No. 5 2014

624 MAVLETKULOVA et al.

Direct
split

Sharp
separation
Sharp
distillation

Class1
fractionation
Indirect
split

Fig. 2. Scheme of obtaining hybrid regimes.

The key section, in which the second constant When the feed is introduced as a boiling liquid, the
composition zone with an infinite number of sepa minimum reflux ratio and the maximum reboil ratio
ration stages is observed, changes on passing from are correlated as
the direct split to the indirect split. This passage
D F
can be mediated by class1 fractionation, since the x – y .
R min = θ max  (3)
distillate and bottoms compositions vary continu F
x –x
W
ously.
In the direct split, the constantcomposition zones For a flowsheet involving n – 1 columns or more,
are observed in the following cases: (1) in the distillate the energy requirement equation is
region (oneway infinity); (2) on passing from a binary k
mixture to the ternary mixture (twoway infinity);
∑ λ D (R
Σ
Q = i i mini + 1 ), (4)
(3) on mixing of the downward liquid flow with the
i=1
feed on the feed tray, which is the first tray of the rec
tifying section (oneway infinity); (4) on passing where i is the sequence number of the column in the
from the ternary mixture to a binary mixture (twoway flowsheet, which varies between 1 and k.
infinity).
Since heat of evaporation data for individual com
The corresponding constantcomposition zones in pounds and mixtures are lacking and their theoretical
the indirect split are (1) twoway infinity), (2) one or experimental determination is a complicated prob
wayinfinity, (3) twoway infinity, and (4) oneway lem, the total vapor flow rate in the columns of the
infinity (sharp distillation). flowsheet was chosen to be the optimization criterion
In class1 fractionation, all of the three constant in this study. Verification in terms of additive heats of
composition zones are twoway infinities. evaporation, whose values are sometimes used in engi
neering practice, led to qualitatively identical relation
ships.
SEPARATION VARIANT
OPTIMALITY CRITERION The equation for the optimization criterion con
sidered in this study is
Energy consumption in irreversible processes
depends on the process pathway. Therefore, a certain k

∑ D (R
Σ
total energy requirement corresponds to each particu V = i mini + 1 ). (5)
lar process flowsheet. i=1
The energy requirement for a distillation column
can be determined via the formula For a ternary mixture, the minimum reflux ratio is
D given by
Q = λD ( R min + 1 ), (2)
D FT D FT D FT
where λ is the specific heat of the total condensation of R min
x1 – y1
= 
x2 – y2
= 
x3 – y3
= . (6)
the vapor flow, D is the amount of distillate, and Rmin is FT
y1 – x1
FT FT
y2 – x2
FT FT
y3 – x3
FT

the minimum reflux ratio.

JOURNAL OF THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 48 No. 5 2014

 COMPARATIVE ANALYSIS OF SHARP SEPARATION REGIMES 625

The fact that, in class1 fractionation, the com (а)

position on the feed tray is equal to the feed com CCZ 1 XD
position allows expression (5) to be rewritten as XD CCZ 1
D F D F D F CCZ 2
x1 – y1 x2 – y2 x3 – y3
R min = 
 = 
 = 
. (7) CCZ 2 XF
F F F F F F
y1 – x1 y2 – x2 y3 – x3 XF CCZ 3
The product stream compositions in this case are CCZ 3
determined using expressions that can easily be CCZ 4
obtained relying on the results presented by Rozen
fel’d [14]: XW
2 CCZ 4 XW 3
D F D F D F
x1 – x1 x2 – x2 x3 – x3
F
 = 

F F
 = 
F F
,
F
(8) (b)
y1 – x1 y2 – x2 y3 – x3 1
XD
W F W F W F
x1 – x1 x2 – x2 x3 – x3 CCZ 1

F

F
= 
F

F
= 
F

F
. (9)
y1 – x1 y2 – x2 y3 – x3 XF CCZ 2
XD
Thus, the vapor flow rate in a column operating in XF
the class1 fractionation regime can be calculated CCZ 1 CCZ 3
without employing specialpurpose software provided
CCZ 2 CCZ 4
that vapor–liquid equilibrium data for the feed are XW
available.
2 CCZ 3 CCZ 4 XW
In the direct and indirect splits, as distinct from
class1 fractionation, the liquid composition on the (c)
feed tray (xFT) and the composition of the vapor that is 1
in equilibrium with the liquid (yFT) are unknown. For XD
this reason, the minimum reflux ratio in this case was CCZ 1
determined using data calculated using the DistillDe XD XF
signer program. CCZ 2
The minimum reflux ratio for binary distillation is CCZ 1 XF
given by CCZ 2
CCZ 3
D F
x1 – y1
R min = 
F

F
. (10) XW
y1 – x1 2 CCZ 3 XW 3
Fig. 3. Distillation trajectories for (a) direct split, (b) indi
rect split, and (c) class1 fractionation. CCZ = constant
RESULTS AND DISCUSSION composition zone.

The objects of our study were the following ternary

zeotropic mixtures: methanol–ethanol–isobutanol,
benzene–toluene–ethylbenzene, hexane–toluene–
chlorobenzene, chloroform–toluene–chloroben
zene, tetrachloromethane–toluene–aniline, and ace
tone–isopropanol–isobutanol.
The feed compositions were determined by the
secant method. The input data for calculating the sat
uration vapor pressures of components were the coef
ficients of the Antoine equation [15]. The activity
coefficients of components were calculated using the
NRTL equation. The vapor–liquid equilibria in ter
nary and binary mixtures were simulated under the
assumption that the vapor phase is ideal and the liquid
phase is nonideal.
Based on computational experiments, we con
structed, in the concentration simplex, Rmin isomani
folds for each of the separation flowsheets considered.
By way of example, we present the Rmin isomanifolds
for the direct and indirect splits and class1 fraction
ation (Fig. 4).
In this way, we determined the regions in which the
minimum reflux ratio and the maximum reboil ratio
for class1 fractionation are smaller than for the other
regimes considered (Fig. 5). Below the upper shaded
area, the minimum reflux ratio in the case of class1
fractionation is smaller than those in the case of the
direct and indirect splits. For the feed compositions
above the shaded area adjoining the triangle edge 23,
the maximum possible reboil ratio in class1 fraction
ation is smaller than in the direct and indirect splits.
Thus, the unshaded area indicates the composition
range in which both the minimum reflux ratio and the
maximum reboil ratio in class1 fractionation are the
smallest.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 48 No. 5 2014

626 MAVLETKULOVA et al.

(а) (b)
Methanol (1) Methanol (1)

3
0.5
4 0.6
0.8
6 1.0
7 1.2
2
3
4
6
7 0.5 0.6 0.8 1.0 1.2
Ethanol (2) Isobutanol (3) Ethanol (2) Isobutanol (3)
(c)
Methanol (1)

0.5
0.6
0.7
0.8
0.9
1.1
1.3
1.7

0.5 0.6 0.8 1.0 1.3 1.7

0.7 0.9 1.1
Ethanol (2) Isobutanol (3)
Fig. 4. Minimum reflux ratio isomanifolds for the distillation of the methanol–ethanol–isobutanol mixture: (a) direct split, (b)
indirect split, and (c) class1 fractionation.

(а) (b)
Benzene (1) Hexane (1)

Rmin
Rmin

Θmax
Θmax

Toluene (2) Ethylbenzene (3) Toluene (2) Chlorobenzene (3)

(c)
Acetone (1)

Rmin
Θmax

Isopropanol (2) Isobutanol (3)

Fig. 5. Minimum reflux ratio and maximum reboil ratio boundaries for class1 fractionation: (a) benzene–toluene–ethylben
zene, (b) hexane–toluene–chlorobenzene, and (c) acetone–isopropanol–isobutanol systems.

JOURNAL OF THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 48 No. 5 2014

 COMPARATIVE ANALYSIS OF SHARP SEPARATION REGIMES 627

Total vapor flow rate values in the direct and indirect splits and class1 fractionation at the optimality boundary for the hex
ane–toluene–chlorobenzene mixture

Feed composition in mole fractions Minimum corre

V cll fr,
Secant no. Point no. Vav, kmol/h sponding to class1
kmol/h
x1 x2 x3 fractionation

I 1 0.09 0.82 0.09 2.20 2.16 Exists

II 2 0.08 0.74 0.18 2.11 1.20 Exists

III 3 0.07 0.65 0.28 2.00 0.83 Exists

IV 4 0.07 0.56 0.37 1.90 0.71 Exists

V 5 0.08 0.46 0.46 1.81 0.68 Exists

VI 6 0.09 0.35 0.55 1.70 0.65 Exists

VII 7 0.09 0.28 0.63 1.64 0.61 Exists

VIII 8 0.09 0.18 0.73 1.53 0.56 Exists

IX 9 0.1 0.09 0.81 1.43 0.55 Exists

av—the averaged value of criterion for direct and indirect splits; cl1 fr—lass1 fractionation.

In an earlier work [10], based on the total vapor
flow rate criterion, we mapped the process opti
mality boundaries in the concentration simplex for
the direct and indirect splits. Figure 6 plots this
boundary for the benzene–toluene–ethylbenzene
mixture.
Further studies in this field demonstrated that,
when the feed composition point belongs to this
boundary, the energyoptimal distillation regime is
Benzene (1)
I regions are twodimensional. Thus, in the case of
II
Toluene (2) Ethylbenzene (3)
class1 fractionation; that is, the threecolumn linear
flowsheet is the least energyintensive in this case. The
data calculated for the hexane–toluene–chloroben
zene mixture (table) corroborate this inference. Above
the optimality boundary, the direct split is the least
energyintensive regime among the three regimes con
sidered; below this boundary, the indirect split is ener
getically preferable.
CONCLUSIONS
The results of this study provide evidence that
class1 fractionation is intermediate between the
direct and indirect splits.
Note that the energy requirements for class1 frac
tionation are represented by the onedimensional
region in which the total vapor flow rate is lower than
in the direct and indirect splits, whose optimality
equal energy requirements for the direct and indirect
splits, class1 fractionation will be the least energy
intensive regime. This result is quite understandable,
because class1 fractionation retains an element of
reversible distillation, namely, the identity between
the composition at the feed level and the feed com
position.

Fig. 6. Optimality boundary. Optimality region for the dis

Reversible distillation is known to be the least
tillation of the benzene–toluene–ethylbenzene mixture: energyintensive regime. However, it is impossible to
(I) direct split; (II) indirect split. retain all features of this regime in practice, while

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 48 No. 5 2014

628 MAVLETKULOVA et al.

class1 fractionation can be carried out as an interme
diate regime between the direct and indirect splits.
ACKNOWLEDGMENTS
This study was supported by the Russian Founda
tion for Basic Research, project no. 130300222a.
NOTATION
D—distillate flow rate, mol/s;
n—number of components in the mixture;
QD—energy requirement of separation, J/s;
R—reflux ratio;
V—vapor flow rate, mol/s;
x—mole fraction of a component in the liquid
phase;
y—mole fraction of a component in the vapor
phase;
Z—number of distillation flowsheets;
Θ–reboil ratio;
λ—specific heat of the total condensation of vapor
flow, J/mol.
SUBSCRIPTS AND SUPERSCRIPTS
D—distillate;
F—feed;
FT—pertaining to the feed tray;
max—maximum;
min—minimum;
W—bottoms;
Σ —total.
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Translated by D. Zvukov

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