Chemical Engineering and Processing 42 (2003) 543 /552

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Dehydration of ethanol with salt extractive distillation* a

comparative analysis between processes with salt recovery
/

E.L. Ligero, T.M.K. Ravagnani *

Departamento de Engenharia de Sistemas Qumicos, Faculdade de Engenharia Qumica, Universidade Estadual de Campinas, CP 6066, CEP 13083-970
Campinas, Sao Paulo, Brazil
Received 9 January 2002; received in revised form 21 June 2002; accepted 21 June 2002

Abstract
Anhydrous ethanol can be obtained from a dilute aqueous solution of ethanol via extractive distillation with potassium acetate.
Two process flowsheets with salt recovery were proposed. In the first, dilute ethanol is directly fed to a salt extractive distillation
column and, after that, the salt is recovered in a multiple effect evaporator followed by a spray dryer. In the second, the concentrated
ethanol from conventional distillation is fed to a salt extractive distillation column. In this case, salt is recovered in a single spray
dryer. In both processes the recovered salt is recycled to be used in the extractive distillation column. Every component of each
process was rigorously modeled and its behavior was simulated for a wide range of operating conditions. A global simulation was
then carried out. The results show that the second process is more interesting in terms of energy consumption than the first.
Furthermore, it would be easier to implement changes on existing benzene extractive anhydrous ethanol plants to convert them to
more ecologically attractive concentrated ethanol feed processes.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Anhydrous ethanol; Salt extractive distillation; Spray dryer; Multiple effect evaporators

1. Introduction
A highly used technique in industry to separate
azeotropic mixtures such as ethanol /water is extractive
distillation with liquid separation agents. There are
several liquid separation agents that can be used in
ethanol dehydration such as benzene, pentane, furfural,
ethylene glycol, diethyl ether and toluene. The most
utilized is benzene, which, due to its carcinogenic effect,
has been progressively eliminated.
One alternative process to produce anhydrous ethanol
is the extractive distillation that uses soluble salts as
separation agents. One comprehensive review of the
literature related to the vapor/liquid equilibrium of salt
systems and the salt extractive distillation was presented
by Furter and Cook [1] and complemented by Furter [2].
The salt extractive distillation is basically similar to
extractive distillation with liquid entrainers. The salt, a
non-volatile component, is introduced at the top or near
* Corresponding author
E-mail address: kakuta@desq.feq.unicamp.br (T.M.K. Ravagnani).

the top tray of the distillation column, flows downward

along the column, and is completely removed with the
bottom product [2].
Besides the lower toxicity level of certain salts
comparing with previously cited liquids used in the
anhydrous ethanol production, one of the advantages of
the salt extractive distillation is the production of a
distillate completely free from the separation agent.
Another favorable aspect related to salt distillation is
the high level of energy savings due to the absence of the
evaporation /condensation cycle of the volatile separation agent inside the column.
These superior properties of salt extractive distillation
against the liquid extractive distillation process encourage the study of soluble salts in ethanol dehydration.
Theoretical and experimental studies on salt extractive distillation of ethanol /water mixtures available in
the literature reinforce the likelihood of replacing liquid
separation agents by salt in the production of anhydrous
ethanol.
Several authors [3 /9] have demonstrated that it is
possible to obtain ethanol with high purity level by using
the proper salts. However, most of the studies consider

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E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

only the ethanol production step, without taking into

account the salt recovery step. Likewise, the number of
available process flowsheets with salt recovery procedures is limited in the literature. The studies that take
global simulations into account are even scarcer. There
are only qualitative discussions. There is indeed, a great
interest in alternative processes to produce anhydrous
ethanol with addition of salt. Although the knowledge
of the major characteristics of salt extractive column is
of utmost importance to obtain anhydrous ethanol, the
study of the salt recovery step is also very important.
This step accounts for the economic feasibility of the
process, allowing the salt to remain in a closed circuit
with no need to be continuously introduced in the
system. The global simulation process of anhydrous
ethanol production enables the two steps to be well
known.
Two distinct processes were proposed and analyzed in
this study. Their basic difference is in the way to
produce ethanol: with or without utilization of a preconcentrating distillation column. The proposed way to
recover salt consists of using an evaporation system to
concentrate the salt solution and a spray dryer to
complete the purification of the salt.

2. Proposed processes
The success of salt extractive distillation to produce
anhydrous ethanol is directly related to the salt chosen.
The choice of the correct salt for extractive distillation is
not exclusively limited to its ability to break the
azeotrope, but other factors including toxicity, easy
handling properties resulting from the system and
availability in the marketplace should also be taken
into account. The salt used in both processes was
potassium acetate. It is able to completely eliminate
ethanol /water azeotrope under atmospheric pressure
even if it is present in small concentrations in the liquid
phase of the extractive column [8,10].
In the anhydrous ethanol production by the salt
extractive distillation technique, the following two
distinct steps were taken into account: the production
step and the salt recovery step. In the first step, the
dilute ethanol aqueous solution was fed to a salt
distillation column in order to produce 98.9 mol%
anhydrous ethanol. Next, the dilute salt solution produced at the bottom of this column was fed to the
recovery step, where it was completely dried. Finally, the
recovered salt was reintroduced in the distillation
column within the reflux stream.
The proposed processes for anhydrous ethanol production were named according to the aqueous solution
concentration of ethanol fed in the salt distillation
column as follows: process with dilute ethanol feed
and process with concentrated ethanol feed.

2.1. Process with dilute ethanol feed

In this process, the production of anhydrous ethanol
is carried out in a single distillation column, which
operates in the presence of potassium acetate. The
recovery step of the salt consists of a multiple effect
evaporation system and of spray drying. The flowsheet
of this process is presented in Fig. 1.
The dilute aqueous ethanol feed is directly introduced
into the salt distillation column. The distillate is
anhydrous ethanol free from the separation agent, while
all the water and all the salt introduced in the column
are removed as bottom product.
The dilute aqueous potassium acetate solution coming
from the salt distillation column is sent to the salt
recovery step. The purpose of the multiple effect
evaporation system is to remove part of the water in
the solution before it is introduced in the spray dryer
where the complete drying of the salt takes place. Thus,
dried salt is completely recycled in the solid state to the
top of the salt distillation column in a way that will not
affect the purity level of the distillate.
2.2. Process with concentrated ethanol feed
The second alternative proposed for the production of
anhydrous ethanol by salt extractive distillation consists
of the use of two distillation columns in the anhydrous
ethanol production step: the first column is the preconcentrator column and the second one is the salt
extractive distillation, as shown by the flowsheet in Fig.
2.
In the pre-concentrator column, which operates in the
absence of salt, a large amount of water is removed as
the bottom product and an ethanol/water mixture is
obtained as the distillate with a composition close to the
azeotrope. This concentrated aqueous ethanol solution
is then sent to the salt distillation column, which
produces a concentrated aqueous solution of potassium
acetate as the bottom stream which is sent to the salt
recovery step.
In the salt recovery step, contrary to the flowsheet
presented in Fig. 1, there is no need to use the

Fig. 1. Process with dilute ethanol feed.

E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

545

by Fredenslund et al. [12]. The required changes due to

the presence of salt were taken into account in the
equilibrium relationships [4]:
Ee;i K e;f V e
Le 

l e;i
N
salt
X

(1Ee;i )ve1;i
hs vse;s

Ve
V e1

ve;i

s1

0

Fig. 2. Process with concentrated ethanol feed.

evaporation system since the aqueous salt solution from

the ethanol production step is already concentrated.
Therefore, the final drying of the salt is performed
exclusively in the spray dryer. Similar to the former
process, the potassium acetate is recycled in the solid
state to the salt distillation column and added to the
reflux stream.

3. Simulation of the processes

In the study of alternative processes for ethanol
dehydration, each piece of equipment used in the
ethanol production and salt recovery steps is individually modeled. Subsequently, these devices are connected
between themselves for global simulation. In Figs. 1 and
2 the presence of a recycle stream, generated in the salt
recovery step, would make one consider the need to use
an iterative sequential method to simulate the global
process. However, the fact that the salt used in the
extractive distillation is totally recovered in pure state at
the dryer, makes the recycle properties known and
eliminates the need for iterative calculation.
The modelings of the plant components are described
below.
3.1. Salt distillation column
The steady state salt distillation column is designed
with the rigorous method proposed by Naphtali and
Sandholm [11] with proper modifications in order to
take into account the presence of salts in the liquid
phase.
In the original Naphtali and Sandholm model [11],
the mass and energy balance equations and the equilibrium relationships were written for each component in
each stage. Since the salt is totally dissolved in the
distillation column and is not part of the mass transfer
process, the balance equations of the phases are written
only for the volatile components. The mass and energy
balance equations in the salt system remain unaffected
in relation to the system of equations describing the
conventional distillation column without salt, presented

(1)

In the calculation of the pre-concentrating distillation

column that operates in the absence of salt, Fig. 2, the
expressions for the equilibrium relationships are identical to those presented by Fredenslund et al. [12].
The Murphree efficiency, Ee,i on Eq. (1), for ethanol /
water system, was considered as 70%. For the ethanol /
water/potassium acetate system the value adopted was
60% [7].
The Sander et al. [13] model was used to predict the
liquid /vapor equilibrium of the ethanol /water /potassium acetate. According to this model, the activity
coefficient of volatile components results in a sum of
two contributions: one of Debye /Huckel type and the
other of the Uniquac modified model.
The mass and energy balance equations and the
equilibrium relationships make a total of N (2Nsolv/l)
non-linear algebraic equations, whose resolution by
generalized Newton Raphson method determines the
volatile components flow rates in the liquid and vapor
phase, the temperature in each stage and the heat
exchange rates involved in the reboiler and condenser.

3.2. The evaporation system

For the process with dilute ethanol feed stream (see
Fig. 1) the salt recovery starts in a multiple effect
evaporation system. Each step of this evaporator is
operated with forced circulation that is proper for
evaporation of salt solutions.
The method used to design the steady state feed
forward multiple effect evaporation system is the one
proposed by Holland [14]. This method takes into
account the boiling point rise effect.
The equations for each effect of the evaporator
consist of the energy balance, convection heat transfer
flow rate, phase equilibrium and material balance. The
only exception relates to the last effect, which has only
the two first equations since the pressure and composition of this effect are specified values. These equations
make a total of 4n/2 non-linear algebraic equations
whose resolution by Broyden method determines the
heat transfer area of each effect and the mass flow of
steam. The variables such as pressure, boiling temperatures of pure solvent and of solution, flow, and mass
fraction of concentrated salt solution of each effect also
become known.

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E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

For the water/potassium acetate system, the equilibrium relationships follow the Duhring rule, i.e. the
boiling temperature of the solution is a linear function
of the boiling temperature of pure water, which is
calculated according to the Sander et al. [13] method.
3.3. Spray drying chamber
The design of the spray dryer used in the final drying
process of potassium acetate follows the Gauvin and
Katta model [15]. This model joins the fundamental
principles of the transport phenomena with experimental evidences. Its major considerations are the assumption of a saturated condition of the drop surface and
neglect the falling-rate drying period, resulting in a
constant temperature on the surface of the particles. As
a quasi-one-dimensional condition, this model does not
take into account the temperature and the humidity
gradients of the drying air in the radial direction, in a
way that these variables remain uniform in a given
cross-section of the chamber. One major criterion of the
spray dryer design is that the largest particle formed at
the atomizer should be dried before it reaches the drying
chamber wall. The drying chamber is made up of an
upper cylindrical section in which the height and the
radius have the same length, and a lower conical section
in which the height is the same value of the cylindrical
part diameter. Another important aspect of the chamber
is the fact that the drying air is tangentially introduced
by a single flow into the top of the cylindrical section,
resulting in a co-current flow.
The chosen atomizer was a centrifugal pressure
nozzle, especially adequate for viscous solutions. The
atomizer characteristics and the droplet particle size
distribution are those presented by Gauvin and Katta
[15], except that the range of droplet diameter was 80/
350 mm.
In the model for the spray dryer, the equations of the
three-dimensional movement of the droplets in the
centrifugal and gravitational fields were solved simultaneously with the equat ions of mass and heat transfer
with a three-dimensional model of the airflow and with
the instantaneous properties of the drying air. The
following considerations were made:

characteristics. In the studied chamber, the air velocity

depends on the place the particle is located, i.e. the
tangential, radial and axial components of the air
velocity change with the zone and region in the
chamber. In the nozzle zone, the particles are highly
affected by the atomizing nozzle. The nozzle zone
finishes, according to [19], when the drying air flow
and entrainment flow become equal. The best relation to
express entrainment flow is given by Bennat and
Eisenklam [20]. The free entrainment zone represents
the area in which the particles are freely dragged by the
drying air. In the cylindrical section, this zone is divided
into two distinct regions that depend on the radial
position: central and annular.
The droplets movement equation together with the
mass and heat transfer and air flow equations form a set
of ordinary differential equations whose solution defines
the dimension of the chamber, the required air flow in
the drying operation and the total quantity of energy
involved in the process. These equations can be solved
using the Euler explicit integration method.

4. Results
The following results correspond to process simulations of an anhydrous ethanol unit producing 13.5 mol/
s.
4.1. Dilute ethanol feed process
4.1.1. Salt distillation column
In this process, the dilute aqueous ethanol solution is
directly introduced into the column of salt distillation in
which the anhydrous ethanol is obtained as a distillate
[21]. The operating conditions of the atmospheric
pressure column are presented in Table 1. The table
also presents the operating conditions of the salt
distillation column used in the concentrated ethanol
feed process.
The potassium acetate, introduced in the salt distillation column, has its maximum flow determined as a
function of the molar fraction of the salt inside the
column. It should meet three requirements: salt solubi-

/ the drag coefficient, CD, and the lift force, FL,

required in the droplets movement equations were
determined using equations proposed, respectively,
by Beard and Pruppaeher [16] and Saffman [17];
/ the instantaneous particle diameter is obtained considering the particles as a dense material;
/ Ranz and Marshall [18] correlations were applied in
mass and heat transfer equations.

Table 1
Operating conditions of salt distillation column

The three-dimensional model of the airflow in the

inner part of the chamber depends on the chamber

Feed component, ethanol /water; distillate composition, 98.9 mol%

ethanol; distillate flow, 13.5 mol/s.

Process type

Dilute ethanol feed

Feed flow (mol/s)

555.5
Feed composition
2.4
(mol% ethanol)
Feed temperature (K) 303.15

Concentrated ethanol
feed
22.22
60
353.45

E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

lity in pure boiling ethanol (10 mol%) [10]; salt solubility

in the pure water (50 mol%) [10] and finally the limits
suggested by the Sander et al. model [13] to predict the
liquid/vapor equilibrium. In the case of the dilute
ethanol aqueous feed, the determinant factor to set the
maximum salt flow is the potassium acetate solubility in
anhydrous ethanol at the reflux stream, assumed as 10
mol%.
This column is designed to operate at optimum reflux
ratio. The minimum reflux obtained for the column
studied is equal to 2.1 as shown in Fig. 3. Assuming a
20% increase in the minimum reflux, the optimum reflux
ratio is equal to 2.5. The figure also shows the effect of
the reflux ratio on the number of column stages for
concentrated ethanol feed process, which will be discussed later.
The design data for the salt distillation column
operating at optimum reflux are presented in Table 2.
One of the important aspects for the operation of a
salt distillation column is the effect of potassium
acetated composition at the reflux on the distillate
composition. Fig. 4 shows that the molar fraction of
the resulting salt in the reflux should not be smaller than
10% molar, once the ethanol produced is out of the
desired specification, which is 98.9% M. The salt
concentration in the reflux can be reduced by increasing
the number of stages. The simulation results show that
for each 4% reduction in the molar composition of
potassium acetate in the reflux one more stage in the
column is required to produce the desired ethanol
specification.
Although the feed pre-heating diminishes the reboiler
heat requirements, the increase of the feed temperature
above 330 K does not lead to good results due to the
increase in the minimum reflux ratio and salt flow.
4.1.2. Evaporation system
The bottom product of the salt distillation column,
which is basically formed by an aqueous solution with
3.6 wt.% of potassium acetate, is sent to the evaporation
system as shown in the flowsheet of Fig. 1. The salt
concentration in the last effect outlet stream is limited by

547

Table 2
Design of salt distillation column
Process type

Dilute ethanol feed Concentrated ethanol feed

Number of stages
37
Optimum reflux ratio 2.5
Feed stage number
18
Salt flow (mol/s)
3.74
Reboiler duty (W)
4.85 106

35
1.2
5
1.80
3.07 105

Fig. 4. Effect of salt composition at reflux stream on distillate purity.

the solubility of the salt in water, and the accepted value

for this KAc concentration is 60 wt.%.
The heat transfer rate obtained in the multiple-effect
evaporator depends on the operating pressure difference
between consecutive effects, which is a function of the
steam fed to the first effect and of the vacuum in the last
effect. All specified variables needed to design the
evaporation system are shown in Table 3.
The relative flexibility of the evaporation system
design regarding the number of effects leads to several
possible configurations. Fig. 5 presents the relation
between the number of effects and its individual heat
transfer area.
The heat transfer area, according to Fig. 5, is high
when the operation is achieved in a single effect. In a
double effect system, however, there is an abrupt fall in
the heat transfer area. The use of a number of effects
higher than two reduces even more the heat transfer
area, but this area reduction becomes increasingly
smaller. Thus, in the simulation of the evaporators
Table 3
Operating conditions of the evaporation system
Feed

Final solution

Fig. 3. Effect of reflux ratio on the distillation columns.

Components: water/KAc
Flow: 10.13 kg/s
Composition: 3.6 wt.% of salt
Temperature: 373.45 K
Components: water/KAc
Composition: 60 wt.% of salt

Steam pressure, 10.1 105 Pa; last effect pressure, 0.11 105 Pa.

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E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

Fig. 5. Influence of number of effects of evaporator on the heat

transfer area.

with six or more effects, the heat transfer area practically remains constant.
The relation between steam consumption and the
number of effects of the evaporation system follow the
pattern shown in Fig. 5. The increase from one to two
effects causes a strong reduction in the vapor consumption, and the use of an evaporator with five or more
effects causes the required amount of vapor to reach a
constant value.
Considering the relation between the heat transfer
area and the steam consumption with number of effects,
the simulation results show that the evaporation of
potassium acetate solution in a system with four effects
is the best option. The major variable values obtained in
the design of the evaporation system are presented in
Table 4.
One of the determining factors in the design of the
evaporation system is the final concentration of the
KAc. The results of the different final values of the
required solution concentration in the design of the
evaporation system are listed in Figs. 6 and 7. In the
analyzed concentration range, the heat exchange area is
more strongly affected by the final concentration of the
salt than by the total steam required to achieve
evaporation or by the pressure of the last effect.

4.1.3. Spray dryer

The aqueous potassium acetate solution in the outlet
of the evaporation system constitutes the feed to the
spray dryer as illustrated in the flowsheet in Fig. 1. The
feed of the dryer has its flow and concentration set by
the level of pre-concentration assumed in the evaporation system. The feed temperature depends exclusively
Table 4
Design of evaporation system
Number of effect
Heat surface of each effect
Steam flow
Total heat requirement

4
76 m2
3.36 kg/s
2.16  107 W

Fig. 6. Effect of final salt concentration on heat transfer area.

Fig. 7. Effect of last effect pressure on vapor requirement.

on the operating pressure of the last effect of the

evaporator.
The drying of the salt solution, in the form of a spray
in the chamber, occurs by contact with a significant
amount of hot air. Typically, the value of the air outlet
temperature is limited with the purpose to prevent
problems such as combustion, explosion, and thermal
instability of the salt. In the case of the potassium
acetate, it is limited by the salt melting point.
The operating conditions of the spray dryer are shown
in Table 5 for both proposed processes.
The criterion used in the design of the dryer is highly
conservative, which leads to a chamber with larger
dimensions than those actually required. The basic
variable values defined in the design of the spray dryer
are listed in Table 6 for both proposed processes.
One essentially important aspect in the spray dryer
design is the influence of the feed concentration that in
this design is equal to the pre-concentration level
specified in the outlet stream of the evaporation system.
The immediate consequence of the increase in the preconcentration level of the aqueous potassium acetate
solution in the evaporation system is the reduction of
the feed stream to the spray dryer. Thus, an increase in
salt composition in the outlet of the evaporation system
corresponds to a decrease in the feed flow to the

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549

Table 5
Operating conditions of spray dryer

Feed

Process type

Dilute ethanol feed

Concentrated ethanol feed

Flow (kg/s)
Salt composition (wt.%)
Temperature (K)

0.608
60
335.6
0.36

0.33
52.8
388.6
0.18

Product flow (kg/s)

Feed solutions, water/potassium acetate; product, potassium acetate. Drying air: inlet moisture: 0.005 kg water/kg dry air; inlet temperature,
650.15 K; outlet temperature, 420.15 K.

chamber. The effect of different salt concentrations in

the outlet of the evaporation system is shown in Fig. 8.
This figure shows that an increase in the pre-concentration level of the feed salt solution results in chambers
with smaller dimensions. Once the feed flow is lower, the
amount of moisture to be evaporated will decrease.
The height of the column increases for feed solutions
with a concentration level below 40%, although in
higher concentrations the chamber becomes lower. For
the evaporation system, the increase in the demand for
highly concentrated salt solutions will result in larger
heat exchange areas and more steam consumption, once
the saturated state of the solution is approximated. For
this reason, both the designs of evaporation system and
spray dryer have shown that a concentration of 60% of
potassium acetate in the outlet of the evaporation
system would result in devices with acceptable dimensions. Fig. 8 also shows the behavior of the drying
airflow with the increase of the pre-concentration level
of the solution in the outlet of the evaporation system.
Likewise the preceding discussion, a pre-concentration
level of 60 wt.% of potassium acetate in the evaporation
system will result in an acceptable value for the drying
air.

4.2. Process with concentrated ethanol feed

4.2.1. Pre-concentrating distillation column

The other possibility analyzed in the production of
anhydrous ethanol is the use of a pre-concentrating
atmospheric pressure distillation column operating
without salt with the purpose to remove most of the
water in the dilute ethanol feed, as shown in the
flowsheet in Fig. 2.

Fig. 8. Effect of feed salt concentrations on dryer height and air flow
rate.

The feed for this column has the same flow, composition and temperature specifications shown in Table 1.
The purity level of the distillate concentration, however,
is limited by the composition of the ethanol /water
azeotrope. In order to prevent the use of a large number
of stages in the following salt distillation column, the
ethanol content in the distillate was set to 60 mol% and
its flow was kept at 22.22 mol/s.
The minimum reflux ratio and some combinations of
reflux ratio and number of stages that lead to the
production of a distillate with the desired specifications
are shown in Fig. 3. The results of the pre-concentrating
column operating in the optimum reflux of 1.1 are
presented in Table 7.

4.2.2. Salt distillation column

The feed to the salt distillation column was the
distillate produced in the pre-concentrating column
that was in the saturated vapor state because it was
operating with a partial condenser. The operating

Table 6
Design of spray dryer

Dimension
Drying air flow (kg/s)
Total heat involved (W)

Process type

Dilute ethanol feed

Concentrated ethanol feed

Radius (m)
Total height (m)

2.2
6.6
1.81
4.53  105

2.6
7.8
0.0156
5.55  105

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E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

precipitation of salt in the trays of the column that is

rich in water. The applicability limit to predict the
vapor/liquid equilibrium, however, was exceeded in the
bottom of the column in all cases, once the molar
fraction of the potassium acetate in pure water is slightly
above 0.15. In spite of that, the temperatures found at
the bottom of the column are in agreement with the
boiling temperature of the aqueous solution with 15
mol% of potassium acetate that was obtained experimentally.
The minimum reflux ratio for the salt distillation
column is equal to 1.1 as shown in Table 8. The
operation of the column at the optimum reflux ratio
of 1.3 with a potassium acetate flow of 1.56 mol/s (that
satisfy the model limit in trays rich in water) requires 50
separation stages to produce anhydrous ethanol at the
required specification. This high number of stages does
not justify column operation at optimum reflux ratio.
The effect of the salt feed flow on the distillation column
design was already shown in Table 2.
As the composition of the bottom product of this
column is 52.8 wt.% in potassium acetate, the multiple
effect evaporation system is not required to recover the
salt.

Table 7
Design of pre-concentrating distillation column
Number of stages
Reflux ratio
Feed stage number
Reboiler duty

22
1.1
17
4.84  106 W

conditions of the salt distillation column are summarized in Table 1.

Since the feed to the salt distillation column was
concentrated in ethanol, this resulted in a lower quantity
of water inside the column, and therefore, the quantity
of salt introduced in the system is not limited by its
solubility in anhydrous ethanol as in the case of dilute
feed process, but now it is limited by its solubility in the
outlet water solution at the bottom of the column. In
addition to these solubility limits, it is important to
observe the ion concentration limitation imposed by
Sander et al. model [13] to predict the liquid /vapor
equilibrium of the salt system. For this reason, the
distillate composition of the pre-concentrating column
was fixed with lower purity than azcotrope. Besides, as
the water flow inside the salt distillation column is very
low, the salt flow is also low. This low salt quantity
produces low salt concentration at the top of the column
requiring a large number of stages to accomplish the
separation. The salt distillation column feed with 60
mol% of ethanol results in a column with acceptable
dimensions as can be seen on Table 2 and also avoids
any possibility of salt precipitation inside the column.
Table 8 presents some of the reflux ratios and number
of stages combinations in the salt distillation column to
produce a specified ethanol. The salt flow, which is
calculated assuming reflux potassium acetate of 10
mol%, is also presented in this table with the molar
fractions of potassium acetate resulting at the bottom of
the column.
In all cases presented in Table 8, the use of potassium
acetate flows that result in a 10 mol% content of the salt
in the top of the column eliminates the likelihood of salt
precipitation in a region that is rich in ethanol. Analyzing the potassium acetate composition in the bottom of
the distillation column, it can be observed that in all
situations its value was kept below the maximum
solubility of this salt in pure water, which is 50 mol%.
These conditions also ensure that there will be no

4.2.3. Spray dryer

The spray dryer feed is the bottom of the salt
distillation column that consists of a concentrated
aqueous solution of potassium acetate. The drying air
admitted to the chamber presents the same initial and
final conditions considered in the design of the spray
dryer of the dilute ethanol feed process (see Table 5).
The operating conditions of the spray dryer, as well as
the design results are also included in Tables 5 and 6,
respectively.
4.3. Comparison between processes
The basic difference between the two alternative
processes for the anhydrous ethanol production by salt
extractive distillation is related to the fact that the
aqueous dilute ethanol feed is or is not subjected to a
pre-concentration.
In spite of the process of concentrated ethanol feed
demands two distinct distillation columns to produce
98.9 mol% ethanol, as shown in Table 2, this option
requires lower reflux ratio and lower salt quantities than

Table 8
Optimum reflux ratio of salt distillation column
Number of stages

Reflux ratio

Salt flow (mol/s)

Salt concentration at bottom (mol%)

T (bottom) (K)

35
40
45

1.2
1.1
1.1

1.80
1.65
1.65

0.170
0.158
0.158

388.5
387.3
388.0

E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

the dilute ethanol feed process. It also results in a

column with lower diameter. In regards to energy
consumption, in the ethanol production step, the salt
distillation column employs only 6% of the total energy.
The major part of the supplied energy (94%) was used to
remove the water in the pre-concentrating column. For
this reason, regardless of the presence of the two
distillation columns in the process of concentrated
ethanol feed, it does not require multiple-effect evaporators and the increase in energy consumption in
relation to the dilute ethanol feed process is only 6%.
The presence or not of a pre-concentrating distillation
column in the ethanol production step affects directly
the way of performing salt recovery, i.e. the presence or
not of multiple effect evaporators. Considering the
energy consumption in the potassium acetate recovery
step, Tables 4 and 6 show that in the process with dilute
ethanol feed the consumption was 2.21 /107 W, in
which only 2% is required in the spray dryer. Otherwise,
in the process of concentrated ethanol feed, the energy
consumption in the salt recovery step is related only to
the spray dryer and, as shown in Table 6, is equal to
5.55 /105 W.
For this reason, the high level of energy consumption
in the evaporation system of the dilute ethanol feed
process becomes unacceptable. Indeed, the energy consumption to recover salt in the dilute ethanol feed
process accounted for 82% of the total energy consumption in the process, and in the concentrated ethanol feed
process only 9.7% of the total energy was used to
recover the salt.
Besides the previously mentioned energy advantages,
due to the lower equipment size, in this process there is
less demand for utilities like hot air (to spray dryer) and
cool water (to condenser). Steam to evaporator is not
required. But the major advantage of the concentrated
ethanol feed process is that it can be installed easily in
units that are in operation.
Independently of the technique employed to separate
the ethanol/water mixture, such as azeotropic distillation or extractive distillation with liquid separation
agents, high energy consumption is required. One of
the various advantages of the extractive distillation with
salt is the reduction of this energy requirement. The
energy consumption obtained in the proposed process is
compared with the ones presented by Black [22]. This
comparison reveals the advantage of the extractive
distillation with potassium acetate to other conventional
processes as indicate in Table 9. This result is in
agreement with the experimental observation of Schmitt
[23] who obtained lesser energy consumption using
extractive distillation with potassium acetate when
compared with the azeotropic distillation with benzene.

551

Table 9
Comparative energy consumption of processes
Distillation process (extractive/azeotropic)
Potassium acetate (concentrated
ethanol feed)
Ethylene glycol
Pentane
Benzene
Diethyl ether

Energy consumption (MJ/kg

ethanol)
9.27
34.06
10.87
12.15
13.59

5. Conclusion
The use of potassium acetate as an extractive agent in
the production of anhydrous ethanol has proven to be
an effective alternative in replacing highly toxic separation liquid agents, such as benzene.
Regarding the two possibilities of anhydrous ethanol
production studied, the simulation results showed that
the concentrated ethanol feed process is the most
advantageous alternative. Although this process needs
two distillation columns, it eliminates the need for a
multiple effect evaporator in the salt recovery step.
Compared with dilute ethanol feed process, it requires
lower reflux ratio, which means lower column diameter
and lower salt consumption. Furthermore, it would be
easier to implement changes on existing benzene extractive anhydrous ethanol plants to convert them to
more ecologically attractive concentrated ethanol feed
processes.

Appendix A: Nomenclature
CD
E
FL
/
/K
l
/
/L
N
Nsalt
Nsolv
N
V/
v
vs
T
hs

/ /

drag coefficient (/)

Murphree tray efficiency (/)
lift force (N)
equilibrium ratio (/)
component molar liquid flow (mol/s)
liquid phase total molar flow of volatiles components (mol/s)
total numbers of stage of distillation column
total number of the salt (/)
total number of the volatile component (/)
total numbers of stage of multiple effect evaporator system
total molar vapor phase flow (mol/s)
component molar vapor phase flow (mol/s)
salt molar flow (mol/s)
temperature (K)
summation of the stoichiometric coefficients of
the salt ions

Subscript and superscript

e
generic stage of distillation column (/)

E.L. Ligero, T.M.K. Ravagnani / Chemical Engineering and Processing 42 (2003) 543 /552

552

i
s

generic volatile component (/)

generic salt

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