Chem. Eng. Technol. 2008, 31, No.

4, 597–603 597

Salvador Hernández1 Communication

1
Universidad de Guanajuato,
Facultad de Química,
Analysis of Energy-Efficient Complex
Guanajuato, México.
Distillation Options to Purify Bioethanol
Three complex extractive distillation options were studied for the purification of
a dilute mixture of ethanol and water. The first option uses an extractive distilla-
tion column and the other two options use thermally coupled extractive distilla-
tion sequences. The results indicate that the fully thermally coupled extractive op-
tion can reduce energy consumption by ca. 30 % compared to the scheme that
uses an extractive distillation column. This fully thermally coupled extractive dis-
tillation sequence can produce ethanol as distillate with a mass fraction of 0.995,
the entrainer as the bottoms product and a mixture of ethanol and water as the
sidestream.

Keywords: Bioethanol, Energy, Ethanol, Extractive distillation, Thermally coupled distillation

sequence
Received: December 4, 2007; revised: January 7, 2008; accepted: January 8, 2008
DOI: 10.1002/ceat.200700467

1 Introduction Fig. 1. It is important to highlight that in 1949, Wright [3] pa-

Due to significant increases in the price of oil and environ-
mental constraints, researchers in the area of process systems
engineering are interested in developing process systems capa-
ble of efficient energy use and alternatives in the form of bio-
fuels, including ethanol and biodiesel. In the case of bioetha-
nol, it has been reported that its use as a gasoline oxygenate
increases oxygen content, enabling improved oxidation of hy-
drocarbons, and consequently, a reduction in both hydrocar-
bon and carbon dioxide emissions [1].
Bioethanol can be produced by fermentation of sugarcane,
corn, sweet sorghum, etc. An important issue in the process of
bioethanol production is the purification of the ethanol from a
dilute solution, i.e., ca. 10 % ethanol in water. The key factor
in the purification process is the formation of the binary
homogeneous azeotrope of ethanol-water, and an additional
process is required to obtain high purity ethanol that can be
used in motor vehicles. Two methods can be used: the first is
dehydration using a salt, e.g., NaCl, KI, CaCl2, while the sec-
ond method involves the use of ethylene glycol as an entrainer
[2]. The main objective in these developments is to find a solu-
tion that can be useful in terms of both total annual cost and
operational control properties. One alternative currently em-
ployed in the chemical industry is the method using three ther-
mally coupled distillation sequences (TCDS), as depicted in
– distillation have led to industrial implementation of the divid-
Correspondence: Prof. S. Hernández (hernasa@quijote.ugto.mx), Uni-
versidad de Guanajuato, Facultad de Química, Noria Alta s/n,
Guanajuato, Gto., 36050 México.
tented the first thermally coupled distillation sequence using a
dividing wall. However, no practical implementations were re-
ported. This could be due to low oil prices (under US$ 5 per
barrel). In 1965, Petlyuk et al. [4] published a complete ther-
modynamic study of the Petlyuk column and showed that, in
fact, thermally coupled distillation sequences could have lower
energy requirements compared to conventional direct and in-
direct distillation sequences, see Fig. 2. However, once again,
no practical implementations were reported. Tedder and Rudd
[5] presented a complete comparison of the total annual costs
of eight distillation sequences, including conventional, side-
stream and thermally coupled configurations, and they found
that complex distillation sequences may offer significant ener-
gy savings over conventional distillation sequences for the sep-
aration of some ternary mixtures. Since their work [5], these
complex distillation sequences have been studied extensively in
terms of steady and dynamic behavior, and it has been found
that the complex distillation sequences can achieve energy sav-
ings of up to 40 % over conventional distillation sequences
[6–12]. Furthermore, studies on dynamic properties have
shown that the energy savings predicted can be achieved in in-
dustrial practice without introducing additional control prob-
lems [13–16]. With regard to controllability analysis, under
some operational conditions, thermally coupled distillation
schemes can exhibit better control properties than conven-
tional distillation sequences.
Important developments in the field of thermally coupled
ing wall distillation column [17, 18]. This practical implemen-
tation has led to savings in both energy and capital costs [18].
Moreover, no important control problems have been reported

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

598 S. Hernández Chem. Eng. Technol. 2008, 31, No. 4, 597–603

in the operation of the dividing wall

distillation columns. At present, the
number of thermally coupled distilla-
tion columns is increasing due to high-
er oil prices (around US$ 100 per bar-
rel). In the early part of the 21st
century, the reduction of energy con-
sumption has become a top priority,
and thermally coupled distillation se-
quences show great promise.
In the case of ternary mixtures, it is
possible to use two conventional distil-
lation sequences together, i.e., direct
and indirect distillation sequences, see
Fig. 2. Several nonconventional distil-
lation sequences can be used, including
the three TCDS sequences depicted in
Fig. 1, the thermally coupled distilla-
tion sequence using a side rectifier
(TCDS-SR), see Fig. 1a), the thermally
coupled distillation sequence with a
side stripper (TCDS-SS), see Fig. 1b),
and the fully thermally coupled distil-
lation sequence or Petlyuk column
(FTCDC), see Fig. 1c). It has been re-
ported that these complex distillation
sequences can have lower total annual
costs than conventional distillation
sequences for the separation of ternary
mixtures (A + B + C), where the mole
fraction of the intermediate compo-
nent B in the feed is lower than 10 %
(dictates use of the thermally coupled
distillation sequence with side rectifier
Figure 1. Thermally coupled distillation sequences for the separation of ternary mixtures: (a) or side stripper) or above 60 %
TCDS-SR, (b) TCDS-SS and (c) FTCDS. (dictates use of the Petlyuk column),

Figure 2. Conventional direct and indirect distillation sequences.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 4, 597–603
and the purity of product B is lower than that of products A
and C.
When the product of the fermentation process is subjected
to conventional distillation, a binary homogeneous azeotrope
is formed with 96 mass.-% of ethanol in water. When ethylene
glycol is added as an entrainer, a ternary mixture is formed.
Taking the foregoing mixture into account, differences in the
energy consumption of the three options for the separation of
an ethanol-water mixture are obtained and compared. The
first option includes an extractive distillation column and the
other two include thermally coupled extractive distillation col-
umns.
2 Description of the Purification Options
According to Fig. 3, a dilute feed of ethanol in water is intro-
duced to a conventional distillation column that removes the
binary homogeneous azeotrope as the distillate. The bottoms
product of the first distillation column is almost pure water.
Figure 3. Complex distillation sequences implemented in Aspen PlusTM.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Bioethanol 599
This conventional distillation column is required in the three
distillation options.
The first option uses an extractive distillation column with
ethylene glycol as the entrainer. The distillate of the column is
ethanol with a mass fraction of 0.995. The bottoms product of
the extractive distillation column is a ternary mixture of etha-
nol, water and ethylene glycol. This mixture is fed to a third
distillation column in order to recover the entrainer as the bot-
toms product, where the distillate is a mixture of ethanol and
water that can be returned to the first distillation column
where the azeotrope is formed.
The second distillation option uses an extractive TCDS-SR.
As indicated in Fig. 3, this complex distillation option has
three products. The distillate of the main column is ethanol
with the required purity and the bottoms product of this col-
umn is the entrainer. The side rectifier column removes a mix-
ture of ethanol and water that can be recycled to the first distil-
lation column.
The last option includes an extractive FTCDS. This option
recovers the ethanol in the distillate and the bottoms product
http://www.cet-journal.com
600 S. Hernández Chem. Eng. Technol. 2008, 31, No. 4, 597–603

is the entrainer. The sidestream removes a mixture of ethanol
and water that can be returned to the first conventional distil-
lation column. This option is particularly important because it
can be implemented in industrial practice using a single distil-
lation column divided by a wall [19].
3 Design and Optimization of the
Extractive Systems
The design and optimization methods for thermally coupled
distillation described in Hernández and Jiménez [7, 8] for tern-
ary mixtures can be extended to the study of extractive distilla-
tion. These methodologies require an initial tray structure that
can be obtained from the conventional distillation sequence,
and subsequently, the recycle stream (VF) is varied until mini-
mum energy consumption is achieved in the reboiler of the ex-
tractive TCDS-SR. In the case of fully thermally coupled ex-
tractive distillation, the two recycle streams (VF and LF) are
varied to detect the minimum energy required in the reboiler.
The optimization procedure requires three design specifica-
tions for the composition of the three products that are in-
cluded as constraints in the design and optimization proce-
dures implemented in Aspen PlusTM. The thermodynamic
properties for the liquid and vapor phases were calculated
through the use of the NRTL model and the Redlich-Kwong
equation, respectively. The proper modeling of the thermody-
namic properties is very important since in the first stage of
the separation procedure, a binary distillation column is re-
quired to obtain the binary ethanol-water azeotrope. In this as-
pect, the NRTL model can predict the formation of the binary
azeotrope. The addition of ethylene glycol as the entrainer in
the second stage of the separation sequence also causes interac-
tion with the other components.
The optimization procedure requires a rigorous model for
each equilibrium stage in the distillation columns that can be
obtained from a generic equilibrium stage [20]. Eqs. (1–5) de-
scribe the equilibrium stage model1).
– Total mass balance on stage j:
Lj–1 + Vj+1 + FjL + FjV – (Lj + Uj) – (Vj + Wj) = 0 (1)
– Component mass balances on stage j:
– Energy balance on stage j:
Lj–1h̄j–1 + Vj+1H̄j+1+FjLh̄jL + FjVH̄jV
– (Lj + Uj)h̄j – (Vj + Wj)H̄j + Qj = 0 (5)
TM
The flowsheet implemented in Aspen Plus is also depicted
in Fig. 3.
4 Results and Discussion
The results presented here correspond to the separation of a
dilute feed of ethanol in water (10 mol.-% ethanol in water) at
100 kg mol/h as a saturated liquid at 1 atm. The study focuses
on the stage of separation of ethanol with a high mass fraction
(0.995). The extractive columns have 20 stages and an entrai-
ner flow of 20 kg mol/h is introduced in stage 3 (numbered
from top to bottom). As indicated previously, the first option
uses an extractive distillation column with ethylene glycol as
the entrainer and a conventional distillation column to recover
the entrainer. This option has an energy consumption of
115.07 kW, see Tab. 1, and is considered as a basis for the anal-
ysis.
Table 1. Minimum energy consumption of the three complex dis-
tillation sequences.
Distillation Sequence Total Energy Percent of Energy
Consumption Savings with Respect
(kW) to the Extractive
Distillation Column
Extractive Distillation Column 115.07 0
Extractive TCDS-SR 124.13 –7.87
Extractive FTCDS 87.19 24.22
In the case of the extractive TCDS-SR option, Fig. 4 presents
the determination of the optimal interconnecting vapor flow
value. As can be seen from Fig. 4, a minimum energy con-
sumption of 124.13 kW is achieved at an interconnecting va-
por flow value of 3.5 kg mol/h. This energy consumption is

Lj–1Xi,j–1 + Vj+1Yi,j+1+FjLZLi,j + FjVZi,j

V

– (Lj + Uj)Xi,j – (Vj + Wj)Yi,j = 0 (2)

– Equilibrium relationship on stage j:

Yi,j = Ki,jYi,j (3)

– Summation constraint on stage j:

X
C
Ki;j Xi;j 1:0 ˆ 0 (4)
iˆ1

– Figure 4. Determination of the minimum energy consumption

1) List of symbols at the end of the paper. of the extractive TCDS-SR.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 4, 597–603
7.87 % above that which is required in the extractive distilla-
tion column.
For the extractive FTCDS, the determination of minimum
energy consumption was conducted by varying the intercon-
necting liquid flow and interconnecting vapor flow. Fig. 5 pre-
sents three interconnecting vapor flow values. In this case, de-
termination was made by varying the interconnecting liquid
Figure 5. Determination of the minimum energy consumption
of the extractive FTCD.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Bioethanol 601
flow for an assumed interconnecting vapor flow value. A mini-
mum energy consumption of 87.19 kW for this complex distil-
lation scheme was achieved for interconnecting vapor and liq-
uid flow values of 2 and 8.5 kg mol/h, respectively. This system
presents energy savings of 24.22 % over the scheme that in-
cludes an extractive distillation column. An important aspect
to highlight with regard to the extractive FTCDS is that multi-
ple solutions can be present for low interconnecting vapor flow
values. For instance, Figs. 5a) and 5b) show two solutions for
the same interconnecting liquid flow value. One solution pre-
sents higher energy consumption. If one analyzes Fig. 5a), it
can be seen that for an interconnecting liquid flow value of
5 kg mol/h, there are two solutions with energy consumptions
of 88.6 and 184.3 kW, respectively (points A and B). Moreover,
it was found in Fig. 5c, that when the interconnecting vapor
flow value is increased, only one solution is present for each
interconnecting liquid flow value. The presence of multiple so-
Figure 6. Mass composition profiles in the liquid phase in the
extractive distillation column.
Figure 7. Mass composition profiles in the liquid phase in the
extractive TCDS-SR.
http://www.cet-journal.com
602 S. Hernández Chem. Eng. Technol. 2008, 31, No. 4, 597–603

Acknowledgements
The financial support provided by Universidad de Guanajuato,
CONACyT and CONCyTEG (Mexico) is gratefully acknowl-
edged.

Symbols used
F [–] feed stream
H [kJ/mol] enthalpy of vapor
h [kJ/mol] enthalpy of liquid
K [–] vapor-liquid equilibrium
constant
L [kg mol/h] liquid flow rate
Q [kW] heat transferred
U [kg mol/h] liquid sidestream
Figure 8. Mass composition profiles in the liquid phase in the V [kg mol/h] vapor flow rate
extractive FTCDS. W [–] vapor sidestream
X [–] liquid mol fraction
Y [–] vapor mole fraction
lutions in thermally coupled distillation sequences for the sep- Z [–] composition of the feed stream
aration of ternary mixtures was reported by Chávez et al. [21],
in the case of separations using heat as the separating agent. Superscripts
Fig. 5 shows that multiple solutions can also be found for ther-
L liquid
mally coupled extractive distillation sequences.
V vapor
In addition, it is important to analyze the composition pro-
files in the extractive distillation systems. Figs. 6–8 present the
Subscripts
mass composition profiles of the extractive process. Fig. 6
shows that the extractive column can produce ethanol with a i component
high mass fraction (0.995) and the bottoms product is com- j stage
posed of ethylene glycol, water and ethanol. Figs. 7 and 8 show L liquid
that the thermally coupled extractive columns produce ethanol V vapor
with the same mass fraction, but it is important to highlight
that these complex columns separate the entrainer as the bot-
toms product and the side rectifier or side stream removes a References
mixture of ethanol and water.
According to the results, the extractive FTCDS is the most [1] J. A. Quintero et al., Energy 2008, 33, 285.
energy-efficient scheme to separate the binary homogeneous [2] R. T. P. Pinto, M. R. Wolf-Maciel, L. Lintomen, Comput.
azeotrope of ethanol and water. In addition, this complex dis- Chem. Eng. 2000, 24, 1689.
tillation sequence can reduce capital costs since it can be im- [3] R. O. Wright, US Patent 2 471 134, 1949.
plemented in a single distillation column using a dividing wall. [4] F. B. Petlyuk, V. M. Platonov, D. M. Slavinskii, Int. Chem.
Eng. 1965, 5, 555.
[5] D. Tedder, D. Rudd, AIChE J. 1978, 24, 303.
5 Conclusions [6] C. Triantafyllou, R. Smith, Trans. Inst. Chem. Eng., Part A
1992, 70, 118.
The separation of a typical mixture of ethanol and water from [7] S. Hernandez, A. Jiménez, Trans. Inst. Chem. Eng., Part A
a fermentation process was studied using an extractive distilla- 1996, 74, 357.
tion column and two thermally coupled extractive distillation [8] S. Hernández, A. Jiménez, Comput. Chem. Eng. 1999, 23,
sequences. The results show that the fully thermally coupled 1005.
extractive distillation sequence can produce energy savings of [9] B. G. Rong, I. Turunen, Trans. Inst. Chem. Eng., Part A 2006,
ca. 30 % in comparison to an extractive distillation column. 84, 1095.
Furthermore, it was found that multiple solutions can exist at [10] B. G. Rong, I. Turunen, Trans. Inst. Chem. Eng., Part A 2006,
some values for the interconnecting streams of the extractive 84, 1117.
FTCDS. Finally, savings in capital costs can be expected since [11] M. Mascia et al., Appl. Therm. Eng. 2007, 27, 1205.
the extractive FTCDS can be implemented in a dividing wall [12] I. Malinen, J. Tanskanen, Trans. Inst. Chem. Eng., Part A
distillation column. 2007, 85, 502.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 4, 597–603
[13] S. Hernández, A. Jiménez, Ind. Eng. Chem. Res. 1999, 38,
3957.
[14] J. C. Cárdenas et al., Ind. Eng. Chem. Res. 2005, 44, 391.
[15] K. Huang, M. Nakaiwa, A. Tsutsumi, Chem. Eng. Sci. 2006,
61, 5377.
[16] S. J. Wang, D. Wong, Chem. Eng. Sci. 2007, 62, 1010.
[17] B. Kaibel, H. Jansen, E. Zich, Z. Olujic, Distillation and Ab-
sorption ’06, IChemeE Symp. Series, No. 15, London 2006.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Bioethanol 603
[18] M. A. Schultz et al., in Proc. of 16th European Symp. on Com-
puter Aided Process Engineering (ESCAPE) and 9th Int. Symp.
on Process Systems Engineering (PSE) (Eds: C. Pantelides,
W. Marquardt), Elsevier, Amsterdam 2006.
[19] G. Kaibel, Chem. Eng. Technol. 1987, 10, 92.
[20] J. D. Seader, E. J. Henley, Separation Process Principles, 2nd
ed., John Wiley & Sons, New York 2006.
[21] C. R. Chávez, J. D. Seader, T. L. Wayburn, Ind. Eng. Chem.
Fundam. 1986, 25, 566.
http://www.cet-journal.com