Antonio Espuña, Moisès Graells and Luis Puigjaner (Editors), Proceedings of the 27th European

Symposium on Computer Aided Process Engineering – ESCAPE 27

October 1st - 5th, 2017, Barcelona, Spain © 2017 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/B978-0-444-63965-3.50181-1

Design and Control of a Separation Process for

Bioethanol Purification by Reactive Distillation
Devrim B. Kaymaka*
a
Istanbul Technical University,Ayazaga Campus, Department of Chemical Engineering,
Maslak, Istanbul, 34469, Turkey
devrim.kaymak@itu.edu.tr

Abstract
Bioethanol is one of the most promising alternatives among sustainable biofuels. Methods
such as extractive distillation columns are used for the production of bioethanol, because
the binary azeotrope of ethanol-water mixture limits the ethanol purity achievable with
conventional separation techniques. Since these methods comprise several disadvantages
in terms of solvents usage, capital and energy costs, alternative methods are investigated
in the industry. This study focuses on the steady-state design and dynamic controllability
of a new configuration including a pre-concentrator column and a reactive distillation
column to overcome these problems. Steady-state process is simulated using Aspen Plus
and Aspen Dynamics is used for dynamic simulations. This configuration is capable to
produce ethylene glycol with 99.4 mole% purity as a second product besides bioethanol
with 99.7 mole% purity. Dynamic results show that a stable base-level regulatory control
is possible for this configuration. Both product purities are held at their design
specification against disturbances such as change in production rate handle and feed
composition.
Keywords: Bioethanol purification, reactive distillation column, process control

1. Introduction
Economic and environmental concerns force the industry to focus on alternative
renewable energy sources, and bioethanol is considered as one of the most promising
alternatives for sustainable biofuels. According to the current international standards,
there is a maximum allowed water content for bioethanol. However, a binary azeotrope
of ethanol-water mixture limits the maximum ethanol purity achievable with the
traditional separation techniques.
There are several methods in the literature to break the azeotrope and purify the
bioethanol such as distillation and pervaporation, pressure swing distillation, dividing-
wall distillation, reverse osmosis membrane pretreatment and extractive distillation
(Hoch and Espinosa, 2008; Mulia-Soto and Flores-Tlacuahuac, 2011; Kiss and Ignat,
2012, Kanchanalai et al., 2013, Errico et al., 2013a).
To overcome the disadvantages of energy intensive distillation methods, industry looks
for alternative methods based on process intensification, and reactive distillation columns
combining the reaction and separation units into a single equipment is a well-known
example of process intensification. The aim of this study is designing and controlling a
process including a reactive distillation column to achieve bioethanol with international
standards starting from fermentation broth.
1076 D.B. Kaymak

Figure 1. Flow diagram for the four-column configuration (Errico et al., 2013a)

2. Problem statement
Processes including extractive distillation columns are the most widely used methods in
case of large scale production of bioethanol. Different configurations of this process have
been studied in the literature (Errico et al., 2013a, Errico et al., 2013b). Figure 1 illustrates
the well-known four-column extractive distillation configuration. The problem is that this
configuration presents relatively high energy cost, since it consists of two energy
intensive separation steps to reach the purity target; the pre-concentration step and ethanol
dehydration step. In addition, a separation agent must be used to break the azeotrope, and
this component should be recovered during the process, which results in a higher capital
cost. On the other hand, there have been papers published in the literature on the design
and control of the ethylene glycol reactive distillation columns where ethylene oxide and
water reacts to produce high purity ethylene glycol (Al-Arfaj and Luyben, 2002; Zhu et
al., 2009). Recently, a modified configuration of the ethylene glycol reactive distillation
column has been proposed in the literature where ethanol-water azeotrope is fed into the
system instead of pure water (Tavan and Hosseini, 2013; An et al., 2014).

Based on these reactive distillation column studies in the literature, design and control of
a two-column process including a pre-concentrator and a reactive distillation column is
investigated in order to solve the above-mentioned problems of extractive distillation
configurations. The main advantage of this process is that there is no need for a separation
agent to break the ethanol-water azeotrope. In addition, high purity ethylene glycol is
produced as a co-product besides the dehydrated ethanol.

3. Process studied
3.1. Process Design
A fermentation broth with a flowrate of 1700 kmol/h including 5 mole % ethanol and 95
mole % water is fed to the pre-concentrator column. The excess of water leaves the
column from the bottoms stream, while a mixture close to azeotropic composition, i.e.
containing 85 mole % ethanol and 15 mole % water, is removed from the distillate stream
and fed to the reactive distillation column. The second feed stream of the reactive
distillation column is ethylene oxide. An ethylene oxide and water molar feed ratio of 1.0
is employed. Bioethanol with a mole purity of 0.997 is obtained from the distillate stream,
while ethylene glycol with a mole purity of 0.994 is removed from the bottoms stream.
Design and Control of a Separation Process for Bioethanol Purification 1077
by Reactive Distillation

Table 1. Design parameters of the configuration

C1 C2
Number of stages 44 17
Feed stage locations 30 12Mix / 15EG
Pressure (atm) 1 4.5
Reflux ratio (molar) 2.42 2.29
Diameter (m) 1.36 0.92
Condenser duty (kW) 3754.37 2756.56
Reboiler duty (kW) 4912.10 2674.72

The reaction kinetics of ethylene glycol formation is taken from Tavan and Hosseini
(2013), and given by

Ethylene Oxide + Water → Ethylene Glycol (1)

r(kmol m-3 s-1) = 3.15 x 1012 exp[-9547/T] XEO XWater (2)

The steady-state simulations have been performed by the process simulator Aspen Plus.
The NRTL method has been applied to evaluate the activity coefficients. In the pre-
concentrator column, the reflux ratio is varied to achieve the desired design specification
which is the ethanol mole purity of 0.85 in the distillate stream. In the reactive column,
an ethanol mole recovery of 0.999 and an ethanol mole purity of 0.997 in distillate stream
are used as design specifications, and the distillate rate and reflux ratio are varied to
achieve these specifications, respectively. The sensitivity analysis is used to choose the
operating parameters minimizing the reboiler heat duty such as pressure, number of trays,
feed tray locations of azeotropic mixture and ethylene oxide. The design parameters for
both columns are reported in Table 1.

3.2. Process Control

In this study, decentralized multi-loop control systems employing several single-input,
single-output (SISO) feedback controllers are considered. Control structure of the
configuration is given in Figure 2. The fresh feed to the pre-concentrator column is flow
controlled and used as the production rate handle. The reflux drum levels of both columns
are controlled by manipulating distillate flowrates. The base levels of both columns are
controlled by manipulating bottoms flowrates. The reflux ratios are held constant in each
column at their nominal values using a ratio control. The operating pressures of all
columns are controlled by manipulating the corresponding condenser duties. Reboiler
heat duty of the pre-concentrator column is manipulated to control the temperature of tray
37. The temperature of tray 16 in reactive distillation column is controlled by
manipulating the corresponding reboiler duty. Tray locations for temperature control are
selected based on the steady-state temperature profiles of columns given in Figure 3.
Since there is only a small section in the reactive column with a sufficient temperature
change and the rest of the column exhibits a flat temperature profile, it is not possible to
use a second temperature controller in this column. Thus, the composition of ethylene
oxide in its feed tray (x15,EO) is controlled by manipulating the feed flowrate of ethylene
oxide to satisfy the stoichiometric balance between reactants of the reaction.
1078 D.B. Kaymak

'7

X
X

'7
'7

Figure 2. Control structure of the configuration

All level control loops are proportional-only controllers with a controller gain of 2. PI
controllers are used for temperature and composition control loops. These control loops
are tuned by using the closed loop ATV method and the tuning parameters are calculated
using Tyreus-Luyben settings. A 3 minute dead-time is used in the composition analyzer,
while the temperature control loops include a 1 minute dead-time. It should be noticed
that all the valves are half open at steady state conditions. The robustness of the control
structures is demonstrated by subjecting the processes to disturbances in production rate
handle and feed composition.

4. Results and discussion

The variables in Figure 4 and Figure 5 are given as deviation variables. The top row
figures are for ethanol and ethylene glycol mole fractions at the top and bottoms of the
reactive column, respectively. The second row figures illustrate the change in the
controlled variables of the reactive column, while the bottom row figures give the results
of the corresponding manipulated variables. Figure 4 illustrates the performance of the
control structure to ±20% step changes in the production rate handle F. It is seen that all
controlled variables settle down into their setpoints in ~5 hours. Results demonstrate that
both ethanol and ethylene glycol purities in the product streams of reactive distillation
column are also recovered, and settle down into their steady-state values. However, it is
observed that the maximum transient deviation of the ethanol purity increases up to 2
mol% in the case of negative 20% step change.

Figure 3. Steady-state temperature profiles: (A): C1, (B): C2

Design and Control of a Separation Process for Bioethanol Purification 1079
by Reactive Distillation

Figure 4. Closed-loop results to ±20% step changes in the production rate handle
The response of the control structure to the changes in the feed composition is given in
Figure 5. The results illustrate that the product purities return back to their desired values
in less than 6 h. Similar to the results of step changes in the production rate handle,
relatively large transient deviations are observed in the ethanol product purity compared
to those of ethylene glycol product purity.

Figure 5. Closed-loop results to the changes in the feed composition

1080 D.B. Kaymak

5. Conclusions
In this study, the steady-state design and dynamic controllability of an alternative process
configuration for the purification of bioethanol is presented. The configuration studied is
a two-column process including a pre-concentrator column and a reactive distillation
column. Thus, the number of columns in the separation sequence is reduced compared to
the well-known four-column process, which results in a significant decrease in the capital
cost. In addition, a second product, ethylene glycol, is obtained besides the main product,
bioethanol, as the result of reaction between water and ethylene oxide. Dynamic results
indicate that stable base-level regulatory control is possible for the studied design
configuration. Both bioethanol and ethylene glycol purities could be held at their design
specification against disturbances studied, although some deviations are observed during
the transient behavior. Besides, it is found that a composition controller is necessary in
the reactive distillation column because of the flat temperature profile.

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