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May, 2016
Key words:
Heat Duty

The following report is delivered with the intention of presenting a review of the
process simulation of anhydrous ethanol production
plant of azeotropic
distillation, using the software package ASPEN PLUS 8.6 V, which it is
reported in Chapter 9 of the book Anlisis y simulacin de procesos en
Ingeniera Qumica. For ensure convergence of the system a set of changes to the
aconfiguration of the simulation referred in the book are made. In the results
shown the concentration profiles of dehydration and recovery columns involved in
the process, and the heat duty used to obtain anhydrous ethanol. .

Currently, Colombia produces about 35 million liters of ethanol per day, which is produced by chemical
transformation of the sugars contained in sugarcane, essential part of the agrochemical industry in the country.
Large part of product is supply of biofuels, which should be produced anhydrous ethanol than can be blended
with petroleum naphthas in use in internal combustion engines. In the sugar mills from Valle del Cauca, as byproducts in the process for the production of refined sugar is taken large parts of treacle and honey B used as
raw material to produce of fuel alcohol. Due to the exhaustive studies being made to understanding and
implementing processes for obtaining anhydrous ethanol, it has been managed to identify the variables that
affect this series of operations.
The separation and purification of ethanol contained in wine fermentative follows a general scheme: initially
has a fermented a breeding ground with an initial ethanol concentration between 2.5 and 10% w / w, which
should be concentrated the ethanol until a top fraction 99% w / w, so that it meets the technical characteristics
to be used as anhydrous alcohol used as additive to gasolines oil. The first step for obtaining a fuel alcohol is to
make a pre concentration from the broth to 45-50% w/w in ethanol by conventional distillation. Then, the
obtained concentrate stream is sent to a rectification column where a distillate is obtained with a concentration
of 90-92% w/w in etanol. Owing to physical and chemical properties of mixture of ethanol water, it is infeasible
in practice to obtain ethanol to a concentration higher than 95.6% w/w (89.4 %mol) due to the formation of an
azeotrope (Bastidas A, Parra , Gil , & Rodriguez, 2012)
One of the alternatives implemented in the industry for the production of anhydrous ethanol is azeotropic
distillation, wherein the addition of a third component to the water-ethanol enriched mixture is done, which
modifies the phase equilibria between the components, new form azeotropes in the system and enables an
operationally a viable separation that involves two or more distillation columns. The additional component is
termed "entrainer", and as a azeotropic distillation agent is used usually benzene, toluene, n-pentane and
mixtures of benzene and n-octane that reduce the energy costs of the column. The most influential parameters
on the cost of the operation is the reflux ratio and flow entraining recycle that comes from the reclaimer
column. Some of the difficulties that arise with the azeotropic distillation are linked to operation sensitivity to
small pressure changes, and the nature of the entrainer, because benzene and toluene have contraindications for
its carcinogenic and teratogenic character, therefore it has developed a comprehensive study to use agents who
meet the standards of industrial and environmental safety, mainly cyclohexane. In this paper the simulation of
ethanol dehydration process by azeotropic distilling is presented, for the production of 300,000 L / day of
anhydrous ethanol. The flow chart is presented in Appendix 1.

The ternary diagram is used as a tool to determine the compositions of recycle streams of entrainer
(cyclohexane) in the process, and the magnitude of the reflux stream in dehydration column. The diagram of
ethanol-water-cyclohexane system was generated by Aspen Plus V8.6, to thermodynamic conditions of 2 atm
and 40 C, and residual curves was plotted for observing three distillation zones that converge in three saddle
points (binary azeotropes) and a node in the equilibrium zone, the ternary azeotrope (Appendix 2). Ethanol and
water are obtained as bottoms flows if mixtures with compositions that feed in Zones I and II of ternary the
diagram are distilled (Gil Chaves, Guevara Lopez, Garca Zapata, Leguizamn Robayo, & Rodriguez Nio,
In the ternary diagram with lines curve residual are determined the equilibrium lines for the operation of each
separation column with an azeotropic fed mixed with pure cyclohexane, obtaining a mixture of concentrations
located in zone I of the thermodynamic map. This mixture is distilled in the dehydration column, where the

anhydrous ethanol is obtained by bottoms stream, and in the distillate stream is obtained a mixture near the
ternary azeotrope at the partial miscibility zone, which is sent to a decanter. In this equipment are obtained a
reflux stream (organic) and aqueous stream that is sent to a recovery column.
For achieve a convergence of the simulated process should be considered at the moment when that the cycles of
recycle streams of cyclohexane and reflux of the first column are closed should change the system
specifications: First the open loops that specified the reflux and recycle streams compositions should be very
close, before to closing the process loops. For dehydration column it should be considered that the bottoms flow
of ethanol should be smaller than the preset quantity (217 kmol / hr), because this value decompensates the
composition of the other process streams, especially effluent from the decanter, and the composition of the
streams obtained in the recovery column. In the recovery column the conditions initially set for operation are
modified, iterating on several occasions the reflux ratio, which allows the highest possible recovery
cyclohexane (0.01 molar% cyclohexane in the bottoms), but drastically cuts down the flow water in bottoms.
These conditions are associated with increased composition of ethanol in the aqueous fed.
In the simulation shows that the azeotropic distillation allows the lowest spending of entrainer possible during
ethanol dehydration: In the process a cyclohexane fed stream is input smaller than 0.1 kmol / hr, which is mixed
with a distillate stream of 21 kmol/hr in cyclohexane from the recovery column. Column of dehydration has a
molar ratio of 1/25 (mol of anhydrous ethanol produced / mol of cyclohexane fed).
The energy consumption of the columns is very high: 6300 kW for dehydration column and 4150 kW for
recuperating column. This occurs because over 70% of the moles fed to the system are continually recirculated
to the system, increasing the heat duty of the operation.
The concentration profile of the dehydration column allows observation of the change in concentration of each
component of the system when the streams are fed as described below (Appendix 3.a): Between yhe units 1 and
9, has a high composition of cyclohexane because on the plate 1 reflux is fed with a composition of entrainer
superior to 90%. Between the units 10 and 14, increases the composition of ethanol because on the plate 10 the
recycle stream is fed, with a composition of ethanol above 70%. From the plate 15 the composition of ethanol
increases gradually because there is the fed of azeotropic alcohol, and in the plate 22 begins to operate in the
distillation zone of the ternary diagram which is desired, obtaining on the plate 31 an anhydrous ethanol stream
Much of the water in the dehydration column is extracted by the distilled. In the temperature profile of the first
column low temperature zone is observed, where the distillation of ternary azeotrope is located.
The concentration profile of the rectifying column allows observing the lowest concentration of cyclohexane in
the process, because large part of entrainer is recovered and recirculated into the decanter (Appendix 3.b). After
plate 16 the column rectifies the mixture, increasing the concentration of water until a flow of bottoms with a
composition rich in water. The convergence of this unit is conflictive because the recycle flow that is obtained
by distilled in this unit affects the operation of the process. As is observed in the profile, is possible that the
columns is overdimensioned, since between the plate 4 and 11 there are no significant changes in the
composition of the units

Azeotropic distillation allows to obtain anhydrous ethanol with a high energy cost because a large amount of
moles which are fed in the dehydration column is recirculated to it. Despite this the rectification step reduces
the operating cost of using cyclohexane in separation. The azeotropic distillation is highly sensitive to pressure
changes and changes in the composition of fed streams, reason for which convergence system is tied to
correctly establish of operating conditions of the columns.

Bastidas A, P., Parra , J., Gil , I., & Rodriguez, G. (2012). Alcohol distillation plant simulation: thermal and hydraulic
studies. ELSEVIER, 80-89.
Gil Chaves, I. D., Guevara Lopez, J., Garca Zapata, J., Leguizamn Robayo, A., & Rodriguez Nio, G. (2011). Anlisis y
simulacin de procesos de Ingeniera Qumica. Bogot: Universidad Nacional de Colombia.


Guevara Lopez, Garca Zapata & Leguizamn Robayo,2011)


Figure 1. (Left) Ternary diagram of water-ethanol-cyclohexane system using NRTL model (2 atm); (Right) Main process
streams located un Ternary Diagram (Gil Chaves, Guevara Lopez, Garca Zapata, Leguizamn Robayo, & Rodriguez
Nio, 2011)


Appendix 3.a. (Up) Concentration profile of the dehydration column (Down) temperature profile of the dehydration

Appendix 3.b. (Up) Concentration profile of the rectification column (Down) temperature profile of the rectification