You are on page 1of 6



Universidade Federal de Santa Maria, Departamento de Engenharia Química
E-mail para contato:

ABSTRACT – The main goal of this work is to reproduce the behavior of a ternary
mixture of ethanol/1-butanol/water in a batch distilation process. The modeling is based
on a simple approach of material balances and the vapor-liquid equilibrium
thermodynamic model used was the NRTL. The distillation column model, together with
the NRTL, has presented results with good agreement to what was expected as a behavior
of the components along the distillation process. Although with some inherent limitations
in predictions for ternary mixtures, the use of the NRTL model seems to be reliable for the
studied system.

The modeling in phase equilibrium process has been used as a manner to obtain the optimal
design and control, and best operation conditions, reducing energetic costs of process operation
and equipment maintenance. Even though there is wide data and many works available for binary
mixtures predictions of vapor-liquid equilibrium (VLE) with well-established models - such as
NRTL (Non-Random Two-Liquids), UNIFAC (UNIQUAC Functional-group Activity
Coefficients) and UNIQUAC (Universal Quasi Chemical) – the predictions in ternary mixtures
are more restrict and, frequently, less accurate using the referred methods (Marcilla et al. 2015,
Marcilla et al. 2016).

Luyben (2015) has performed simulations of a ternary mixture composed of benzene,

toluene, and o-xylene with the software Aspen ® using the NRTL model. Also, Luyben has tested
different control structures available in the software library to evaluate their efficiency.

Faúndez et al. (2006) compared the accuracy of four different models – PSRK, UNIFAC,
UNIQUAC, and NRTL) in describing the VLE of a mixture composed of water/ethanol/congener
for wine distillation. The authors concluded that the non-empirical models (PSRK and UNIFAC)
are not reliable for the vapor phase concentrations prediction, and that the semi-empirical models
(NRTL and UNIQUAC) predicted more accurately the temperature behavior.

Marcilla et al. (2015, 2016) report, however, that the NRTL model has some inherent
limitations in predictions for ternary mixtures, mainly for azeotropes. Kosuge and Iwakabe
(2005) presented a parameter estimation for VLLE of ethanol/water/(1 and 2)-butanol, which is a
partially miscible mixture, using NRTL and UNIQUAC, claiming that both models can be used
for this mixture. Li et al. (2016) also reported that both NRTL and UNIQUAC models were
sucessfully used to predict a LLE for the ternary system isopropyl acetate/2-propanol/glycerol.

The main goal of this work is to present a ternary (ethanol/1-butanol/water) distillation

column simulation based on the NRTL model. The parameters used for the model were the ones
presented on Kosuge and Iwakabe (2005) work.


In this work a phenomenological model is used, it comes from the mass balance in a batch
distillation column where all the components are fed to the bottom of the column before the
process starts. In this manner, the mass balances for each component results in Equation 1 for the
condenser, Equation 2 for the stages, Equation 3 for the boiler, and Equation 4 for the global
material balance.





Where x i and y i are the molar fraction of the component in the theoretical stage i in the
liquid and vapor phase, respectively; M D , M P , and M B are the molar hold-up in the
condenser, in the stages, and in the boiler, respectively; L , V , and D are the liquid, vapor and
distillate flow-rates; N T is the total number of mols fed to the column; and NS is the total
number of stages of the column.

The parameters used in this work are listed on Table 1. The vapor flow-rate is calculated
using the boiler potency and an experimental value of mols vaporized in the boiler per second.
The initial conditions are also provided by a realized experiment.

Table 1 – Parameters and initial conditions used for simulation

Parameter Value Units Description

x ethanol,NS ( t= 0 ) 0.3773 Dimensionless Initial ethanol molar


x butanol,NS ( t= 0 ) 0.1006 Dimensionless Initial butanol molar


x water,NS ( t= 0 ) 0.5220 Dimensionless Initial water molar fraction

NT ( t= 0 ) 239.84 Mols Initial number of mols

NS 11 Dimensionless Number of stages

R 6 Dimensionless Reflux ratio

q 488.6 J/s Heat

c 4 .1772×10−6 Mol/J Mols vaporized in boiler

0.3 Dimensionless Condenser molar hold-up

0.1 Dimensionless Stages molar hold-up

2.0 Dimensionless Boiler molar hold-up

P 760 mmHg Pressure

R 8.314472 J/mol.K Universal gas constant

Also, for the thermodynamics calculations, it was used the Antoine coefficients and the
NRTL parameters, as can be seen in Table 2.

Table 2 – Antoine coefficients and NRTL parameters

A ethanol 7.6811 α 1,1 0 b1,1 0

B ethanol 1332.0400 α 1,2 0.3038 b1,2 38 .0723×R

C ethanol 199.2000 α 1,3 0.2 b1,3 −223 . 2760×R

A butanol 7.9306 α 2,1 0.3038 b2,1 −32 . 9414×R

B butanol 1738.4000 α 2,2 0 b2,2 0

Cbutanol 226.6060 α 2,3 0.2 b2,3 −211 . 9310×R

A water 8.1402 α 3,1 0.2 b3,1 888 .3400×R

B water 1810.9400 α 3,2 0.2 b3,2 1699. 5870×R

C water 244.4850 α 3,3 0 b3,3 0

The NRTL model equations can be seen in Kosuge and Iwakabe (2005) work.

The model was programmed in Matlab and all the simulations were performed in a Intel®
Core™ i7-2670QM with 2.20 GHz processor with 8 Gb of RAM memory, running in a Ubuntu
14.04 LTS 64 bits Operating System.


The pure boiling point of the components, at normal pressure and temperature conditions, is
78.03, 117.34, and 100.9 for ethanol, 1-butanol, and water, respectively. The ternary mixture
boiling point, at its initial condition, calculated using a COSMO-SAC model (Lin and Sandler,
2002), is 104.70 ºC. In this manner, it is expected that ethanol and a little fraction of water comes
out in the condenser as distillate, enriching the mixture in 1-butanol, which is supposed to leave
the column later.

Figures 1 and 2 depicts this behavior inside the distillation column.

Figure 1 – Ethanol profile in the distillation column through time.

Figure 2 – Butanol profile in the distillation column through time.

As it can be seen in Figures 1 and 2, firstly the ethanol rises to the condenser, leaving the
column and diminishing its content inside of it. As the ethanol leaves, the 1-butanol relative
content rises, and the equilibrium changes, allowing the component to leave the column after the

Modeling and simulation is a well-known procedure to obtain previous results to visualize
the process behavior. Also, it could be used as a manner to optimize design and operation
conditions in processes, and develop control strategies, leading to several advantages such as
energy economy or more pure products.

Although the NRTL inherent limitations in predictions for ternary mixtures, as referred in
literature, the model could depict the expected behavior of the distillation process of the ternary
mixture of ethanol/1-butanol/water. Better results could be obtained by using UNIFAC,
UNIQUAC, or even COSMO-SAC methods. All of these thermodynamic models will be
compared for the studied system in a further work.

FAÚNDEZ, A. C., ALVAREZ, V. H., VALDERRAMA, J. O. Predictive models to describe VLE in
ternary mixtures water + ethanol + congener for wine distillation. Thermochimica Acta, v. 450, p.
110-117, 2006.
KOSUGE, H., IWAKABE, K. Estimation of isobaric vapor-liquid-liquid equilibria for partially
miscible mixture of ternary system. Fluid Phase Equilibria, v. 233, p. 47-55, 2005.
LI, Y., XU, Q., LIU, S., LI, H., ZHANG, F., ZHANG, G., XIA, Q. Liquid-liquid equilibrium for the
ternary system of isopropyl acetate + 2-propanol + glycerol at different temperatures under
atmospheric pressure. Fluid Phase Equilibria, v. 412, p. 199-204, 2016.
LIN, S., SANDLER, S. I. A priori phase equilibrium pediction from a segment contribution solvation
model. Industrial & Engineering Chemistry Research, v. 41, p. 899-913, 2002.
LUYBEN, W. L., Aspen Dynamics simulation of a middle-vessel batch distillation process. Journal
of Process Control, v. 33, p. 49-59, 2015.
MARCILLA, A., OLAYA, M. M., REYES-LABARTA, J. A. Simultaneous VLLE data correlation for
ternary systems: Modification of the NRTL equation for improved calculations. Fluid Phase
Equilibria, p. 1-9, 2015.
MARCILLA, A., OLAYA, M. M., REYES-LABARTA, J. A. Comments on the correlation of vapor-
liquid equilibrium (VLE) data in azeotropic ternary sytems. Fluid Phase Equilibria, p. 1-9, 2016.