20th European Symposium on Computer Aided Process Engineering – ESCAPE20

S. Pierucci and G. Buzzi Ferraris (Editors)

© 2010 Elsevier B.V. All rights reserved.

Comparison of the main ethanol dehydration

technologies through process simulation
Paola A. Bastidas,a Iván D. Gil,a Gerardo Rodrígueza
a
Grupo de Procesos Químicos y Bioquímicos – Departamento de Ingeniería Química y
Ambiental, Universidad Nacional de Colombia – Sede Bogotá, Carrera 30 45-03,
Bogotá, Colombia, idgilc@unal.edu.co

Abstract
Anhydrous ethanol production has become to be one of the most important issues for
many countries in the world due to the great efforts directed to use biofuels and
diminishment in pollution and environmental effects of fossil fuels. The process of
anhydrous alcohol production comprises three main important steps: fermentation,
distillation and dehydration. In the final dehydration step the quality of ethanol is
determined by the operating conditions, the technology used and its benefits related to
the quality and costs of ethanol. In Brazil and United States, the two largest producers
of ethanol in the world, azeotropic distillation with cyclohexane, extractive distillation
with ethyleneglycol and adsorption with molecular sieves are used.

In this work, an investigation and comparative analysis of the three main ethanol
dehydration technologies was made. Aspen Plus process simulator was used to simulate
azeotropic, extractive and adsorption processes and to determine the main operating
conditions taking a case base of 300 cubic meters per day of anhydrous ethanol.
Additionally, a preliminary costs analysis was implemented taking into account total
investment and operating costs of each technology. The results showed that extractive
distillation process is the most promising technology from operating and economical
points of view and that is necessary to investigate for new solvents that improve the
efficiency and sustainability of the alcohol production.

Keywords: ethanol dehydration, extractive distillation, azeotropic distillation,

adsorption

1. Introduction
Process simulation tools have become a very useful way in the design, analysis and
retrofit of processes of particular interest from energetic and economical point of view,
opening the possibility to make different sensitivity analyses and to combine
optimization studies, cost estimation, detailed design and controllability analysis.
Biofuels industry and in particular the bioethanol production process are demanding
from process engineering fast and easy answers about the technologies and optimal
conditions with they can be used. Ethanol is one of the most used biofuels that
contributes diminishing environmental effects of fossil fuels. Their properties and its
renewable origin ensure environmental sustainability and the process economy. In the
final dehydration step the quality of ethanol is determined by the operating conditions,
the technology used and its benefits related to the quality and costs of ethanol. In Brazil
and United States, the two largest producers of ethanol in the world, azeotropic
distillation with cyclohexane, extractive distillation with ethyleneglycol and adsorption
with molecular sieves are used.
 P. Bastidas et al.

Heterogeneous azeotropic distillation has been widely studied in many papers and
textbooks and widely applied in alcohol industry to dehydrate ethanol (e.g. 60% of
dehydration plants in Brazil are azeotropic distillation based). However, heterogeneous
azeotropic distillation reports some disadvantages associated with the high degree of
nonlinearity, multiple steady states, distillation boundaries, long transients, and
heterogeneous liquid-liquid equilibrium, limiting the operating range of the system
under different feed disturbances [1-5]. Extractive distillation is based on the
introduction of a selective solvent that interacts differently with each of the components
of the mixture and mainly shows affinity with one of the key components [3, 6]. The
principle driving extractive distillation is based on the introduction of a selective solvent
that interacts differently with each of the components of the original mixture and which
generally shows a strong affinity with one of the key components [4, 7, 8]. Adsorption
on molecular sieves takes advantage of the difference of molecular size of ethanol and
water molecules to adsorb in a selective way water molecules and allowing ethanol
separation. Molecular sieves are materials composed by microporous substances that are
characterized by their excellent ability to retain on its surface defined types of chemical
species. These materials packed into a vessel make possible to separate ethanol from
ethanol-water mixtures by adsorption mechanisms at high pressure.
In this work the three main ethanol dehydration technologies will be studied in order to
establish the main operating conditions required to obtain high purity ethanol. Rigorous
simulations in Aspen Plus for a plant producing 300 cubic meters per day of anhydrous
ethanol will be carried out and some economical considerations are included in the
comparison of the technologies available.

2. Process Simulation
Ethanol-water mixture at atmospheric pressure has a minimum-boiling homogeneous
azeotrope at 78.1°C of composition 89 mol% ethanol. The NRTL physical property
model is used to describe the nonideality of the liquid phase and the vapor is assumed to
be ideal. All NRTL model binary parameters are taken from Aspen Plus database. For
all of the three processes simulated azeotropic ethanol was the feed and anhydrous
ethanol with purity higher than 99.5 mole % was fixed as the main product. On the next
subsections are described briefly each one of the processes and the main operating
conditions established are reported.

2.1. Azeotropic distillation with cyclohexane

Azeotropic distillation uses a solvent with an intermediate boiling point to introduce
new azeotropes to the mixture and at the same time to generate two liquid phases that
allow, in a combined way, separating ethanol from water. This technique although is
widely used has lost acceptance due to its poor stability and high energy consumption.
The process flowsheet of azeotropic distillation is shown on Fig. 1. The process has two
columns and one decanter. The first heterogeneous azeotropic distillation column is
designed to obtain high-purity ethanol product at the column bottom while obtaining
minimum boiling ethanol-water-cyclohexane azeotrope at the top of the column. The
azeotrope obtained at the top is heterogeneous and the top vapor stream is then
condensed to form two liquid phases in the decanter [7, 9]. The organic phase
containing mainly cyclohexane is refluxed back to the heterogeneous azeotropic
distillation column. The aqueous phase is drawn out from the decanter to be sent to the
entrainer recovery column where at the bottoms stream is obtained water essentially
pure and at the top is removed cyclohexane to be recycled to the first column.
Comparison of the main ethanol dehydration technologies through process simulation

 
Makeup
Cyclohexane
0.855 kmol/h Recycle

65 ºC
Condenser Duty Condenser Duty
-6651.78 kW -4082.61 kW

P = 2 atm P = 1 atm

S1
1 2
R1-ORG D2
284.41 kmol/h 282.37 kmol/h
10 EtOH = 0.0765 EtOH = 0.7099
Water = 0.0029 RR = 0.3 Water = 0.2105
Cyclohex = 0.9205 11 NS = 22 Cyclohex = 0.0795
D1 ID = 1.74 m
15
F1 310.49 kmol/h
NS = 31
244.64 kmol/h EtOH = 0.6456
ID = 2.26 m
EtOH = 0.885 Water = 0.2819
Water = 0.115 30 Cyclohex = 0.0723 21

B2
B1 28.12 kmol/h
217.37 kmol/h EtOH = 0.0007
EtOH = 0.9959 Water = 0.9993
Reboiler Duty Reboiler Duty
Water = 0.0001 Cyclohex = 1.0 e-20
6580.15 kW 4335.95 kW
Cyclohex = 0.0039

Figure 1. Flowsheet for azeotropic distillation with cyclohexane

The results obtained show that is possible to produce anhydrous ethanol using
cyclohexane as entrainer with high mole recovery of ethanol. As the top vapor
concentration approaches to the ternary heterogeneous azeotrope, the separation is
achieved is improved in the dehydration column. As the organic reflux flow rate and the
recycle flow rate increase the ethanol concentration at the bottoms of the dehydration
column also increase improving the separation performance but also increasing the heat
duties. The operating conditions are used to calculate the hydraulic performance and to
estimate the column diameters, information useful to calculate the capital costs.

2.2. Extractive distillation with ethyleneglycol

Extractive distillation is a partial vaporization process in the presence of a non-volatile
and high boiling point entrainer which does not form any azeotropes with the original
components of the azeotropic mixture. The process flowsheet of extractive distillation
system is presented on Fig. 2. The process has two columns: the extractive distillation
column and the entrainer recovery column. The entrainer is continuously fed in one of
the top stages of the extractive column while the azeotropic feed is entered in a middle
stage lower down the column. At the top of the extractive distillation column is obtained
anhydrous ethanol and at the bottoms stream is removed a mixture of water-
ethyleneglycol which is send to the second entrainer recovery column. In the recovery
column at the top water is withdrawn with some traces of ethanol and at the bottom
high-purity ethyleneglycol is recycled back to the extractive distillation column [9].

Extractive distillation process with ethyleneglycol show some important advantages

respect to azeotropic ones. The makeup entrainer is much lower than azeotropic case
and additionally the quantity of entrainer is lower which affect the diameter of the
columns. It can be observed that the column diameters are smaller in the extractive
distillation systems and also the energy consumption in the columns. On the other hand,
 P. Bastidas et al.

the most important variables used to achieve the desired ethanol concentration are the
entrainer to feed molar ratio and the reflux ratio. The former has a little effect over the
energy consumption compared with the reflux ratio impact on the reboiler duty, for this
reason the reflux ratio in extractive distillation column is fixed at the best low value.
  Makeup
EthGlycol
0.180 kmol/h Ethylene-Glycol Recycle

80 ºC
Condenser Duty Condenser Duty
-3530.72 kW -650.40 kW

P = 1 atm P = 0.26 atm

D1 D2
217.13 kmol/h 27.693 kmol/h
2 EtOH = 0.9971 2 EtOH = 8.06 e-06
S1 Water = 0.0020 Water = 0.9999
3
EthGlyc = 8.3 e-04 EthGlyc = 1.0 e-06
RR = 0.5 RR = 1.0
NS = 22 6 NS = 12 Cooler Duty
ID = 1.48 m ID = 0.85 m -715 kW
14
F1
244.64 kmol/h
EtOH = 0.885
Water = 0.115 21 B1 12 B2
223.31 kmol/h 195.616 kmol/h
EtOH = 1.0 e-06 EtOH = 3.17 e-14
Water = 0.1243 Water = 4.32 e-04 157 ºC
EthGlyc = 0.8756 EthGlyc = 0.9996

Reboiler Duty Reboiler Duty

4316.82 kW 566.88 kW

Figure 2. Flowsheet for extractive distillation with ethyleneglycol

2.3. Adsorption with molecular sieves

 

Figure 3. Flowsheet for adsorption with molecular sieves

Comparison of the main ethanol dehydration technologies through process simulation

Dehydration by molecular sieves operates by dehydration/regeneration cycles; while

one bed is in a dehydrating cycle the other one is being regenerated. In the first bed is
passed azeotropic ethanol vapor from rectifying column that has been heated in a
vaporizer previously, in order to increase the pressure to 25 psig. Regeneration is made
by recirculating 15% of superheated anhydrous ethanol vapors to the second bed, in
order to remove accumulated moisture in the previous dehydration cycle. The process
flowsheet is shown on Fig. 3.

The net flowrate of the anhydrous ethanol produced is lower than the obtained in the
distillation based operations. This is due to the high ethanol recycle required to
regenerate the second bed. This affects in an important way the efficiency of the process
and increases the total energy consumption required to produce one kilogram of ethanol.
Also, it is important to take into account the energy involved in the vacuum pump used
in the regeneration cycle and the energy used to redistillate the dilute ethanol solution
obtained in the regeneration step.

3. Costs analysis
The capital costs of the columns and adsorption beds are affected seriously by reflux
ratios, recycle flow rates and entrainer usages in the distillation cases. Additionally
these parameters affect directly the heat duties of the process and the quality of the final
ethanol product. In order to evaluate the costs associated to each technology, empirical
correlations were used, and are briefly described below.

Table 1. Results of cost calculations for each technology

Azeotropic Extractive Adsorption
Equipment Cost (U$) Equipment Cost (U$) Equipment Cost (U$)
C1 1570510 C1 545501 T1 1040867
C2 619691 C2 151669 T2 379335
Decanter 308003 Cond-1 58755 Heater 825515
Cooler 72125 Reb-1 219090 Cooler 131098
Reb-1 115589 Cond-2 410391
Cond-2 63501 Reb-2 294533
Reb-2 276924 Cooler 321582
Total 3026342 Total 2001522 Total 2376816

For heat exchangers, condensers and reboilers of the distillation columns, the
correlations are based on the heat-exchange surface area; all heat exchangers were
simulated as shell and tube type, so this area is referred to the outside surface area of the
tubes. The correlations also have taken into account the corrections for the length tube,
the materials of the shell and tubes, the pressure drop in the shell side and the type of
equipment (kettle vaporizer, U-Tube, floating head, etc.) [10]. On the other hand,
correlations by Mulet, Corripio and Evans [11] were used to estimate distillation
columns and decanter costs. The vessels or towers could be horizontally (decanter) or
vertically (distillation columns) arranged; they also operate at pressure higher than
atmospheric pressure or at vacuum, and the correlations used differ according to these
parameters. The base cost is corrected by the weight of the empty shell including
nozzles, manholes and supports, and the cost of platforms and ladders. For the case of
 P. Bastidas et al.

adsorption with molecular sieves, the cost was estimated in two steps: the first,
estimating the cost of the vessel as described above, and the second, estimating the cost
of the molecular sieve by the volume required of this material. Table 1 summarizes the
results of costs estimation.

4. Conclusions
The process simulation allowed identifying extractive distillation with ethyleneglycol as
the best option to dehydrate ethanol and to be implemented to the fuel ethanol
production process. The current trend in process design demands energy efficiency in
all unit operations like one of the prerequisites to be considered. Naturally, ethanol
dehydration processes not escape to this trend and, hence, energy consumption in the
production of one kilogram of anhydrous ethanol is one of the main parameters in
choosing technology. Also, another important factor in selecting the best technological
alternative is the utilities consumption, as well as investment costs incurred during
initial deployment of technology. Then, taking into account these last two factors,
extractive distillation with ethyleneglycol represents the most interesting alternative
because the energy consumptions and capital investment costs are competitive and
represent important savings in final cost of ethanol produced.

5. Acknowledgements
This work is supported by the Departamento Administrativo de Ciencia, Tecnología e
Innovación - Colciencias under grant research project code 1101-452-21113.

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