J . Chem. Tech. Biotechnol.

1992, 53, 181-188

Ethanol Dehydration by Extractive Distillation

Antonio Meirelles
Department of Food Engineering, State University of Campinas (UNICAMP), 13081, Campinas-SP,
Brazil

Siegfried Weiss & Herbert Herfurth

Sektion Verfahrenstechnik, Technische Hochschule ' Carl Schorlemmer ', Merseburg 4200, Germany
(Received 4 May 1991 ; accepted 29 August 1991)

Abstract : Experiments and process simulation enable favourable operating

conditions to be determined for the extractive distillation of ethanol-water, with
ethylene glycol as a solvent. The solvent molar rate to feed molar rate ratio
S / F = 0.6 and the reflux ratio R = 0.5 were determined in order to achieve at least
99.5 mole % purity of ethanol. Other parameters examined include feed
concentration, purity of solvent, and number of plates.
Extractive distillation can be used to achieve high purity of ethanol at low
energy consumption and under simple operating conditions.

Key words : ethanol, anhydrous ethanol, distillation, extractive distillation,

azeotropic distillation, ethylene glycol

NOTATION s Solvent
T TOP
ALPHA Non-randomness parameter in the NRTL 1 Water
equation ALPHA = A L P + A L T x t 2 Ethanol
ALP Parameter of the NRTL equation 3 Ethylene glycol
ALT Temperature-dependent parameter of the
NRTL equation ("C-')
A Interaction energies in the NRTL equation
1 INTRODUCTION
(kJ/kmol) A = A A + A T x t
AA Parameter of the NRTL equation (kJ/mol) The petroleum crisis in the 1970s was the starting point
AT Temperature-dependent parameter of the of an increasing interest in renewable sources of energy.
Since that time, ethanol produced by fermentation has
NRTL equation (kJ/kmol "C)
achieved enormous importance, particularly in Brazil, as
F Feed rate of ethanol/water (kmol/s)
Compound indexes an octane enhancer added to gasoline, or as its complete
I,J
n Number of theoretical plates substitute. As a mixture with gasoline, it can be used to
P Top product (anhydrous ethanol) rate operate conventional petrol engines without significantly
(kmol/s) reducing their efficiency.',' However, for this purpose,
R Reflux ratio the ethanol must be free of water.
S Solvent rate (kmol/s) Azeotropic distillation, one of the possible distillation
t Temperature ("C) procedures for producing absolute ethanol, has often
Mole fraction of component i been i n ~ e s t i g a t e d ~and
- ~ is considered to be energetically
x,
favourable.'j By contrast, extractive distillation with
Subscripts ethylene glycol was considered to be very expensive with
respect to energy cons~ mption. '.According ~ to Black,'
B Bottom extractive distillation with ethylene glycol consumes at
F Feed least 0.69 of the enthalpy of combustion of pure ethanol
181
J . Chem. Tech. Biorechnol. 0268-2575/92/$05.00 0 1992 SCI. Printed in Great Britain
182
for the purpose of separation, whereas azeotropic
distillation with pentane only requires 0,346. However,
Lynn and Hanson* demonstrated, by investigations with
the help of an ethanol-water pseudo-equilibrium curve
in the presence of ethylene glycol, that extractive dis-
tillation may be energetically more favourable. Thermal
integration studies by Knapp and Doherty' confirms
these results. Some industrial plants in the USA already
use ethylene glycol to produce anhydrous ethano1.l"
However, no experimental studies on the extractive
distillation of ethanol-water have been reported in the
literature.
The purpose of this paper is to relate the authors'
investigations on the extractive distillation of ethanol-
water with ethylene glycol. The reliable data obtained
may serve as a base for unequivocal comparison with
other procedures concerning energy consumption and in
the technological design of plants for producing pure
ethanol.
A laboratory column and a pilot-scale plant were used
to obtain concentration profiles at different solvent
molar rate to feed molar rate ratios and reflux ratios, and
the effects of these parameters on the purity of the
ethanol were examined. The results were extended by
process simulation with the help of the NRTL equation
for describing the phase equilibrium and the relaxation
method for calculating the column.
In these experimental and process simulation studies,
the required purity of ethanol was fixed at a value of
99.5 mole YO.The maximum permissible content of water
I I
I I
///////// ////// / / / / / / / / /// ///////;
c, MAlN EXTRACTIVE COLUMN
f ROTA METER
/? CONTAlNER
s SAMPLE
Fig. 1. Technological scheme of the pilot-scale plant.
A . Meirelles, S. Weiss, H . Herfurth
in the ethanol depends on the climatic conditions of the
country. For example, the average temperatures pre-
vailing in Brazil only require a purity of ethanol of 99.5
volume YO(at 20°C, 98.4 mole O h ) to prevent the mixture
with gasoline from separating.2
2 EXPERIMENTAL
The experiments were first carried out in a laboratory
column of 65 mm diameter, containing 24 plates with
one bubble cap each. The nearly azeotropic mixture of
ethanol and water is fed into the column on the 15th
plate, and the solvent on the 3rd plate (counted from the
top). Further experiments were then carried out on a
pilot-scale plant (Fig. I ) consisting of 2 columns of
80 mm diameter; the main extractive column containing
60 sieve plates with downcomer and the regeneration
column containing 40 sieve plates with downcomer. The
water-ethanol mixture was fed into the main extractive
column on plate 31 (counted from the top) and the
solvent on plate 3. The bottom product of this column
was fed into the regeneration column on plate 19 and
processed to give pure ethylene glycol.
Liquid samples required for representing the con-
centration profiles were taken every three plates in the
laboratory column and about every six plates in the
pilot-scale plant. Further samples were taken from the
top and bottom products and from the two feed products
in each plant. These samples were analysed by gas
8 m Platform
--
4m Platform
.-
77777777
C2 RECOVERY COLUMN
H CONDENSER
Re REBOILER
Ethanol dehydration by extractive distillation 183

TABLE 1
Experimental operating conditions S -m

Solvent to ,feed ratio Reflux ratio 06 -I

SIF R (L
W
a3
09-1
\WATER
p
\-ETHYLENE
GLYCOL iI-ETHANCL
Laboratory column 0.28 < S / F < 3.1 1 0.94 < R < 4.81 3z 12- I 0

Pilot plant 0.64 < S / F < 1.75 0.71 < R < 2.18 iI
chromatography, and the top product (pure ethanol) was
additionally checked with the help of a densimeter
i
during the experiments. 24
In the experimental studies, the solvent rate to feed
rate ratio S I F and the reflux ratio R were varied as
essential parameters. The ranges investigated are shown
in Table I . Fig. 2. Typical concentration profile from the laboratory
column: S / F = 0.82; R = 1.96.

3 RESULTS AND DISCUSSION greater part of the stripping column is approximately

3.1 Experimental results
Figure 2 represents a typical concentration profile from
the laboratory column. In most of the experiments, the
ethanol concentration at the top amounts to more than
99.5 mole %, and the ethanol does not contain any
ethylene glycol. Its concentration changes abruptly on
the two feed plates and reaches very small values at the
bottom. Starting from the top, the concentration of
water increases slowly, reaches a maximum near the
bottom, and then decreases again. The concentration of
ethylene glycol between the two feed plates and in the
constant.
The temperature profile (Fig. 3) shows somewhat
unusual behaviour as compared with normal distillation
processes, with a maximum temperature between the
two feed plates which is due to the greater solvent
concentration existing in this part of the column. The
absolute value of the temperature difference between the
two parts of the column (above and below the feed plate
for the water-ethanol mixture) depends on the SIF ratio
and reflux ratio and, as does the solvent concentration, it
decreases with an increased reflux ratio and increases
with an increased S I F ratio.
Table 2 summarizes the most important results of the

TABLE 2
Results of Experiments Conducted on Pilot-scale Plant

Run Feed Solvent to .feed Reflux TOP Bottom

composition ratio ratio composition composition
-‘IF SIF R x2 T
x2B X3B

1 0.1 32 1.75 1.44 0.999 0~0000 0.929

2 0.133 1.51 1.50 0.999 0.0005 0.912
3 0.139 1.35 1.57 0.999 0.002 1 0.862
4 0.156 1.32 1.59 0.999 0~0000 0.877
5 0.132 1.31 1.30 0.999 0.00 I 7 0,865
6 0138 1.12 1.04 0.996 0.0240 0.852
7 0.141 1.08 2.0 1 0.998 0~0000 0.842
8 0.287 1.08 0.7 1 0.998 0.0043 0.798
9 0.152 1.06 1.16 0.998 0.0006 0.864
10 0.124 0.92 0.87 0.997 0.0027 0.855
11 0.151 0.90 2.18 0.996 0~0000 0.823
12 0.141 0.90 1.81 0.996 0.0023 0.832
13 0.151 0.90 0.94 0.997 0.001 1 0.822
14 0.150 0.72 1.29 0.995 0.0430 0.807
15 0.115 068 1.07 0.995 0.006 1 0.836
16 0.151 0.64 1.50 0.996 0.0033 0.806
184 A . Meirelles, S. Weiss, H . Herfilrth

experimental determination of the equilibrium data as

24-1
B
70 90
L, ,
110
, *
130 150
I bar) according to Thorat and coworker^,'^ and they are
TEMPERATURE OC
Fig. 3. Temperature profile from the laboratory column :
S / F = 1.30; R = 1.45.
experiments conducted in the pilot-scale plant. At a S / F
ratio as small as 0.64, it is still possible to achieve the
required purity of ethanol. For a definite S j F ratio, the
purity is guaranteed within a wide range of the reflux
ratio, as is the case in experiments 7 to 9 within the range
R = 0.71-2.01, and in experiments 10 to 13 in the range
R = 0.87-2,18. As is evident from experiment 8, pure
ethanol can still be produced at considerably higher
concentrations of water in the feed mixture. At the
bottom, the ethanol concentration is very small, so that
almost no ethanol is lost.
3.2 Process simulation
Further investigations of extractive distillation were
carried out with the help of process simulation, using a
computer program according to the relaxation method."
The simulation is based upon rigorous solution of
material and enthalpy balances and equilibrium relation-
ships. The phase equilibrium of the water-ethanol-
ethylene glycol mixture was described using an NRTL
equation with temperature-dependent parameters (see
Table 3 ) .
Strongly polar systems, such as water-thanol-
cthylcnc glycol, arc known to present difficulties for the
well as for the representation of these data by one of the
known model equations of excess Gibbs energy." This
leads to the fact that the description of the phase
equilibrium is not always satisfactory. Using tempera-
ture-dependent parameters, it was possible to consider-
ably improve the description of each binary mixture,
which increases the accuracy of the prediction of the
phase equilibrium for the overall water-ethanol-ethylene
glycol system.
The parameters for the ethanol-ethylene glycol mix-
ture were obtained by regression of the isobar data (1.013
represented with a mean temperature deviation of 1.33"C
and a mean deviation of vapour composition of 0.0217
mole fraction. Using the NRTL parameters according to
Gmehling and Onken," these values amount to 5.02"C
and 0.0332 mole fraction.
The parameters for the water+thylene glycol mixture
were obtained by regression of different isobar and
isothermal data.12.15,1fi They represent the isobar data
(0-996bar) according to Trimble and Potts16 with a mean
temperature deviation of 1.22"C and a mean deviation of
vapour composition of 0.0200 mole fraction. Using the
NRTL parameters according to Gmehling and Onken,17
these values amount to 4.36"C and 0.0488 mole fraction.
The behaviour of the vapour phase was assumed to be
ideal. The vapour pressure was calculated by the Antoine
equation using the parameters according to Gmehling
and Onken.14.17
Process simulation was carried out for a main
extractive column with 24 theoretical plates, with the
solvent being fed into the column on the 2nd plate and
the feed mixture on the 12th plate. The column efficiency
of the pilot-scale plant was assumed to be 40 % (24: 60 =
0.4). This value was obtained on the basis of investi-
gations on the Murphree efficiency carried out using the
concentration profiles obtained from the laboratory
column.
The Murphree efficiency was determined for those
plates in the stripping column which exhibited appre-
ciable changes in the concentration of components
(cf. Fig. 2), and they were then averaged over the whole
range as a mean value. The results obtained for the

TABLE 3
Parameters of the NRTL Equation

Binury ALP" ALT A A (I,J) A T(I,J) MJ,O AT(J,O

mix turr ("C-I) (kJlkrnol) (kJfkmoPC) (kJlkmol) (kJ/kmoPC)

1-2 0.17 1 23 1 0.005 228 3 293.17 17.047 1 - 44 1.20 18.328 0

1-3 0.185894 - 1383.43 8.040 9 - 1445.97 -9.1 50 6
2-3 0.3704 - 13527.42 - 92.739 1 - 4 35 1.97 53.3769

'I
ALPHA = ALP+ A L T x t.
" A =AA+ATxt.
Ethanol dehydration by extractive distillation 185

a
U
m
5z 0.10 0:15 0.20
W
I- WATER CONCENTRATION IN FEED XIF
a
J
a Fig. 7. Purity of ethanol xPTversus water concentration in
feed x I F .

MOLE FRACTION x i
Fig. 4. Experimental points of experiment 14 compared with S/F=0.6 R = 0.5
the calculated concentration profile. u c I

( 9 9 . i
d 0
0.001 0.002 0.003 0.004
WATER CONCENTRATION IN SOLVENT XIS

Fig. 8. Purity of ethanol x Z T versus water concentration in

solvent xis.

to continue the investigations on the effects of various

I R = 0.5
process parameters by simulation with a high degree of
rr
2
a
II 0 R =?.O
accuracy. In these calculations the top rate was assumed
I I I I I to have the same value as the feed rate of ethanol in the
0.4 0.8 1.2 1.6 2.0
feed mixture.
SOLVENT - FEED RATIO S/F Figure 5 represents the purity of the ethanol over S / F
Fig. 5. Purity of ethanol x Z Tversus ratio SIF. at a constant reflux ratio. Ethanol of a purity of at least
99.5 mole YOcan still be prepared at a S / F ratio of 0.6.
This value agrees well with the experimental value of 0.64
(experiment no. 16).
J
Within a wide range of the reflux ratio (0.5 d R < 2.5)
the purity of ethanol shows small changes (cf. Fig. 6),
I S/F = 0 6 reaches a maximum near the value 1, and decreases
I- abruptly below 0.5. A further increase in reflux ratio
W

0.98
> been observed in experiments in the laboratory column.
k i
LL
efficiency, which range between 0.38 and 0.52, are clearly
below the values found in conventional distillation. They
show a decreasing tendency with increasing solvent
concentration. Similar results and the modelling of the
efficiency have been reported in the literature."
Figure 4 represents the experimental points of ex-
periment 14 in the pilot-scale plant and the concentration
profile obtained by simulation. They are in good
agreement with each other. This provided the possibility
15
results in decreased purity of ethanol, which has also
This is due to the dilution of the solvent in the column
and accordingly a smaller effect on the relative volatility
of ethanol-water. The smallest reflux ratio of 071
realised in the experiments can be further decreased to
0.50.
The above results of the simulation were all obtained
for water concentrations of 15 mole % in the feed
mixture. The effect of this value is represented in Fig. 7.
The purity of ethanol depends little on the concentration
of water. Thus, the required purity can still be achieved
at a water content of 20-0 mole YOwithout changing the
favourable process parameters SIP = 0.71 and R = 0.5
( S I P = 0.71 corresponds to S / F = 0.6 at xlv= 0.15).
In the experiments carried out in the laboratory
column, it was found that the purity of ethanol can be
considerably decreased when the solvent is contaminated
C T B 53
186 A . Meirelles, S . Weiss, H . Herfurth

2.5

2.0
(L

1.5
LL
X
3
14I8 22 26 1.0
w
NUMBER OF THEORETICAL LT
PLATES n
0.5
Fig. 9. Erect of the number of theorctical plates n and the
position of the feed platc n p on the purity of ethanol.
I
I

by water. The simulation showed that for the process I 2 3 4

parameters stated above, a water content as low as
0.3 mole % in the solvent does not ensure the required
purity (Fig. 8). Since the solvent is fed into the column
near the top, its content of water has a direct effect on the
purity of the ethanol. The requirement for anhydrous
ethanol necessarily results in the demand for a high pure
solvent of about 99.9 mole %. In the separation of
ethylene glycol-water, this degree of purity can be
achieved at relatively low expense.
The effect of the number of theoretical plates and the
position of the feed plate for ethanol-water is evident
from Fig. 9. Retaining the number of plates located
between the two feed positions, the overall number of
plates can be decreased to 16 plates without significantly
SPECIFIC ENERGY f 0 3 k J/kg ETHANOL
Fig. 10. Specific energy consumption at reboiler and energy
removed at condenser in dependence on SIF and R .
affecting the purity of the ethanol. The reduction of the
number of plates between the two feed positions will
make it impossible to achieve the required purity. Four
plates in the stripping column are sufficient for stripping
the ethanol from the bottom product, whereas the purity
of the top product can only be achieved by using more
than 10 theoretical plates.

TABLE 4
Typical Plants for Producing Absolute Ethanol
(a) Main Column

Plunt Solcent to Reflux Feed Bo t t omr TOP Speclfic

pro& I ratio XI F
~- XZT energy
ratio R XlB X3B consumption
Slp kJlkg ethanol

1 0.7 1 0.5 01500" 0.1968 0.7989 0.9963 1528

2 0.7 1 0.5 0.200 0" 0.257 5 0.737 8 0.9950 1562
3 0.94 0.5 0.1500' 0.1550 0.841 1 0.9955 634

(b) Recovery Column

Plant Reflux Bottom Top Specific

ratio XL< energy
R XI, XPT consumption
kJlkg ethanol

1 0.2 09998 09780 00211 232

2 0.1 0.9998 0.9812 0.0182 302
3 0.3 0.999 8 0.9736 0.025 0 252
~~ ~~~~ ~ ~

Saturated-liquid feed.
" Saturated-vapour feed.
' Feed composition to recovery column.
Ethanol dehydration by extractive distillation
3.3 Considerations with respect to energy saving
The specific energy consumption of the main extractive
column is represented in Fig. 10. As is well known, it is
strongly dependent on the reflux ratio, but very little on
the S I F ratio; this means that ethanol of almost any
degree of purity can be produced without significantly
changing the energy consumption, by increasing the S l F
ratio and maintaining the reflux ratio at the smallest
value.
On the basis of the experimental investigations and
process simulation, an SIP ratio = 071 and a reflux
ratio R = 0.5 can be fixed as favourable process para-
meters. Energy consumption in extractive distillation can
be further reduced by feeding a vaporous feed mixture
into the main column, since the vapor phase mainly
consists of ethanol. However, the vaporous feed reduces
the purity of the ethanol, so that an ethanol con-
centration of 99.55 mole YO is only achieved at
S I P = 0-94 and R = 0.5.
Table 4 summarizes the most important data obtained
for three typical plants for producing pure ethanol. The
column used for recovering the ethylene glycol contains
10 theoretical plates. Feed plate 5 (counted from the top)
is operated at a pressure of 20.25 KPa (bottom tem-
perature of about ISOOC) in order to avoid high
temperature. The reflux ratio of the recovery column is
the smallest value that can ensure a pure solvent and an
overhead product free of ethylene glycol. High recovery
of ethanol in the extractive column with values above
99.5 YOis reached. Small amounts of ethanol, entrained
together with water at the top of the recovery column
may be added to the mixture fed into the mash column,
which produces the feed mixture for the main extractive
column.
4 CONCLUSIONS
The favourable process parameters established in this
paper, particularly those for the reflux ratio, lead to
reduced energy consumption in extractive distillation, as
is evident from a comparison of the energy consumption
per kg ethanol with that of azeotropic distillation in
Table 5. When the mash column is included in the
TABLE 5
Comparison with Azeotropic Distillation from Energy Require-
ment Point of View
Main column Recovery column
(kJfkg ethanor) (kJ/kg ethanol)
Proposed process 1528 232
Azeotropic distillation
with Pentanefi 2615 696
187
considerations concerning the energy consumption, the
results are modified, taking account of energy-integrated
distillation plants. However, extractive distillation is also
of advantage in this case.
Extractive distillation is characterised by additional
favourable properties, such as flexibility and a simple
mode of operation, which are lacking in azeotropic
distillation. Here, the two columns, the azeotropic
distillation main column and the recovery column, as
well as the separator, are closely connected to each other,
so that every small disturbance in one of these parts will
directly affect the whole plant. The reflux ratio strongly
depends on the concentration of the feed stream, so that
a small increase in the water concentration, e.g. from 15
to 17 mole YO,requires a corresponding increase in the
reflux ratio in order to achieve the required degree of
ethanol purity. Further, the entrainer and water balances
have to be strictly checked in order to ensure both the
purity of the ethanol and the mechanical separability of
the overhead product. This complex character of the
operating conditions requires an accurate controlling
technique and sometimes leads to low recovery of alcohol
in the azeotropic column.
In extractive distillation, the main column and the
recovery column are largely independent of each other.
The concentration of the feed mixture has little effect on
the operating conditions. Disturbance or changes of
operating conditions, which may occur in the mash
column, e.g. increased water content in the overhead
product, can be largely compensated in the main
extractive column, with the process parameters remain-
ing the same, or with a small increase of the SIF ratio.
The characteristics of the temperature profile may be
used for an efficient control of the column. The
temperature difference at the feed plate for the water-
ethanol mixture increases when more water is removed
overhead, and decreases when more ethanol is removed
in the bottom. This fact can be used as a possibility of
controlling head product purity and ensuring a bottom
product free of ethanol.
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