Professional Documents
Culture Documents
BUTANOL/ETHANOL/WATER SEPARATION
C. L. da SILVEIRA1, N. P. G. SALAU1
1
Universidade Federal de Santa Maria, Departamento de Engenharia Química
E-mail para contato: christiansilveira86@gmail.com
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.
1. INTRODUCTION
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).
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.
(1)
(2)
(3)
(4)
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.
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.
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
ethanol.
4. CONCLUSIONS
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.
6. REFERENCES
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.