Computers and Chemical Engineering 39 (2012) 129–142

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Computers and Chemical Engineering

journal homepage: www.elsevier.com/locate/compchemeng

Control of an extractive distillation process to dehydrate ethanol using glycerol

as entrainer
Iván D. Gil a,∗ , Jorge M. Gómez b , Gerardo Rodríguez a
a
Grupo de Procesos Químicos y Bioquímicos, Departamento de Ingeniería Química y Ambiental, Universidad Nacional de Colombia – Sede Bogotá, Ciudad Universitaria – Carrera 30
45-03, Bogotá, Colombia
b
Grupo de Diseño de Productos y Procesos, Departamento de Ingeniería Química, Universidad de los Andes, Carrera 1 Este 19A-40, Bogotá, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, an investigation of the design and control of an extractive distillation process to produce
Received 23 April 2011 anhydrous ethanol using glycerol as entrainer is reported. The extractive distillation process receives the
Received in revised form azeotropic mixture ethanol–water that is fed into a dehydration column in one of the intermediate stages
27 December 2011
while at the same time glycerol is fed into one of the top stages. As overhead product high purity ethanol
Accepted 12 January 2012
is withdrawn and in the bottom stream a mixture of water/glycerol is sent to a recovery column. The
Available online 21 January 2012
effects of the entrainer to feed molar ratio, reflux ratio, feed stage, feed entrainer stage and entrainer feed
temperature were studied to obtain the best design with minimal energy requirements. A control scheme
Keywords:
Ethanol dehydration
is developed in order to maintain stable operation for large feed disturbances. Dynamic simulations show
Extractive distillation that is possible to use only one temperature control to hold the purity specifications.
Glycerol © 2012 Elsevier Ltd. All rights reserved.
Entrainer
Distillation control

1. Introduction
Distillation processes represent a high percentage of the sep-
aration operations used in the refining and chemical industries.
Distillation, in addition to being a very common operation, has
a strong impact on energy consumption of the processes and it
is used in the purification steps, where the products will have a
higher added value and specifications are more rigorous, which is
the case of dehydration step in the anhydrous ethanol production.
Anhydrous ethanol is widely used in the chemical industry as a
raw material in chemical synthesis of esters and ethers, and as sol-
vent in production of paint, cosmetics, sprays, perfumery, medicine
and food, among others. Furthermore, mixtures of anhydrous
ethanol and gasoline may be used as fuels, reducing environmen-
tal contamination and improving gasoline octane index, mainly
due to the addition of ethanol (Barba, Brandani, & Di Giacomo,
1985; Black, 1980; Chianese & Zinnamosca, 1990; Meirelles, Weiss,
& Herfurth, 1992). Among the most popular processes used in
ethanol dehydration, heterogeneous azeotropic distillation uses
solvents such as benzene, pentane, iso-octane and cyclohexane;
extractive distillation with solvents and salts as entrainers; adsorp-
tion with molecular sieves; and, processes that use pervaporation
∗ Corresponding author. Tel.: +57 1 3165672; fax: +57 1 3165617.
E-mail address: idgilc@unal.edu.co (I.D. Gil).
membranes (Black, 1980; Gomis, Pedrasa, Francés, Font, & Asensi,
2007; Hanson, Lynn, & Scott, 1988; Pinto, Wolf-Maciel, & Lintomen,
2000; Ulrich & Pavel, 1988).
Heterogeneous azeotropic distillation has been widely stud-
ied 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, distilla-
tion boundaries, long transients, and heterogeneous liquid–liquid
equilibrium, limiting the operating range of the system under dif-
ferent feed disturbances (Chien, Wang, & Wong, 1999; Widagdo &
Seider, 1996). Extractive distillation is a partial vaporization pro-
cess in the presence of a non-volatile separating agent with a
high boiling point, which is generally called solvent or entrainer,
and which is added to the azeotropic mixture to alter the rela-
tive volatility of the key component with no additional formation
of azeotropes (Black & Distler, 1972; Perry, 1992). The princi-
ple 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 (Doherty &
Malone, 2001; Lee & Gendry, 1997). In the case of extractive
distillation many of the disadvantages found in azeotropic ones
are not present, because there is no heterogeneous liquid–liquid
equilibrium, no additional azeotropes are formed with the

0098-1354/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2012.01.006
130 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142

1,0 105
EtOH-Water T-x Exp.
100 EtOH-Water T-y Exp.
0,8
EtOH-Water T-x Est. NRTL
EtOH-Water T-y Est. NRTL
95

Temperature (°C)
y Ethanol

0,6

90
0,4
85

0,2
x-y Exp. 80
x-y Est. NRTL
0,0 75
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
x Ethanol x-y Ethanol
1,0
290

0,8 250

210
Temperature (°C)
0,6
y Water

170
0,4
130
Water-Gly T-x Exp.
0,2
x-y Exp. 90 Water-Gly T-y Exp.
Water-Gly T-x Est. NRTL
x-y Est. NRTL Water-Gly T-y Est. NRTL
0,0 50
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
x Water x-y Water
1,0
290 EtOH-Gly T-x Exp.
EtOH-Gly T-x Est. NRTL
0,8 EtOH-Gly T-y Est. NRTL
250
Temperature (°C)

0,6 210
y Ethanol

170
0,4
130

0,2
x-y Exp. 90
x-y Est. NRTL
0,0 50
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
x Ethanol x Ethanol

Fig. 1. T-xy and x–y experimental and predicted diagrams at 1 atm for the ethanol–water, water–glycerol and ethanol–glycerol systems (Carey & Lewis, 1932; Chen &
Thompson, 1970; Coelho, dos Santos, Mafra, Cardozo-Filho, & Coraza, 2011).

addition of the entrainer and therefore there are no distillation
boundaries.
Distillation control is a very important topic and it has been
subject of study during several decades by control engineers in aca-
demic and industrial contexts (Hurowitz, Anderson, Duvall, & Riggs,
2003; Ross, Perkins, Pistikopoulos, Koot, & van Schijndel, 2001;
Shinskey, 1996; Wolf-Maciel & Brito, 1995). The selection of control
configuration appropriated for the distillation involves an initial
step where regulatory controls are implemented in a good way and
then the control problem is reduced to identify the best pairing
of the controlled and manipulated variables that allow obtaining
composition control in the column (Hurowitz et al., 2003; Luyben,
2006a; Skogestad, 1992). The available methodologies in the task
of select the configuration of composition control are multiple
and they use criteria based on steady state and dynamic mod-
els (Fruehauf & Mahoney, 1993; Luyben, 2006a, 2006b; Shinskey,
1977). Control of azeotropic and extractive distillation has been
subject of different studies. Luyben (2006b) studied a control struc-
ture for a multiunit heterogeneous azeotropic distillation process
that uses benzene as entrainer to dehydrate ethanol. Also the dehy-
dration of isopropyl alcohol by extractive distillation using ethylene
glycol (Luyben, 2006c) and dimethyl sulfoxide (Arifin & Chien,
 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142 131

Fig. 2. T–xy and x–y experimental and predicted diagrams at 1 atm for the ethanol–water and water–glycerol systems (Carey & Lewis, 1932; Chen & Thompson, 1970). (a)
Residue curve map, (b) pseudo-binary vapor–liquid equilibrium for ethanol–water–glycerol system (Lee & Pahl, 1985).

2008) as entrainers has been reported. However, there are no stud-
ies that report ethanol dehydration using glycerol as entrainer and
considering at the same time the control strategy required to pro-
duce high purity ethanol and recover totally the glycerol stream.
The purpose of this work is to design and control an extractive
distillation process to produce anhydrous ethanol using glycerol
as entrainer. This is a new alternative for dehydrate ethanol taking
into account that glycerol is available at low costs as consequence of
the high production of this substance in the biodiesel process. Addi-
tionally, it has been demonstrated the potential effect of glycerol in
modifying the vapor–liquid equilibrium of the ethanol–water mix-
ture eliminating the azeotrope. The steady state design involves the
selection of the appropriate thermodynamic model and the study
of the effect of the main design variables. The control strategy con-
siders the control of only one temperature on each column in order
to be used for wider industrial applications and to provide good
product quality control.
2. Thermodynamic model
Ethanol–water mixture at atmospheric pressure has a
minimum-boiling homogeneous azeotrope at 78.1 ◦ C of com-
position 89 mol% ethanol. Thus, this mixture cannot be separated
in a single distillation column and if it is fed to a column operating
at atmospheric pressure, the ethanol purity in the distillate cannot
exceed 89 mol% while high purity water can be produced out from
the bottom. The NRTL physical property model (Renon & Prausnitz,
1968) is used to describe the nonideality of the liquid phase and
the vapor phase is assumed to be ideal. The complete NRTL model
binary parameters are taken from Aspen Plus database.
The thermodynamic model prediction is validated with experi-
mental data from Carey and Lewis (1932), and Chen and Thompson
(1970) for ethanol–water and water–glycerol mixtures, respec-
tively. The y–x and T–xy vapor–liquid equilibrium plots are shown
in Fig. 1, where it can be seen that the model fits the experimental

Fig. 3. Flowsheet for extractive distillation system.

132 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142

Fig. 4. Effect of RR and EFS on ethanol purity and reboiler energy consumption of extractive distillation column.

data very well for the case of ethanol–water mixture and with some
difficulties for the case of water–glycerol mixture in the zone of
lower water composition.
Ternary-phase diagrams with residue curves, distillation
boundaries and tie lines, provide very useful tool into the con-
straints encountered in the highly nonideal systems and they can
be used as simple method for identifying and designing feasible
extractive distillation sequences. Fig. 2a gives the residue curve
map for the ethanol–water–glycerol system calculated using Aspen
Split at 1 atm and Fig. 2b shows the pseudo-binary vapor–liquid
equilibrium diagram for the same system with the experimen-
tal data reported by Lee and Pahl (1985). In Fig. 2b it is evident
that glycerol modifies the vapor–liquid equilibrium curve, elimi-
nating the azeotrope and allowing obtaining high purity ethanol.
Lee and Pahl (1985) report that the glycols used as solvents elim-
inate the ethanol–water azeotrope and change the VLE curve.
Ethylene glycol is well known as solvent in extractive distilla-
tion of ethanol–water mixtures with a good performance results.
However, glycerol shows a better performance in modifying the
VLE curve favorably for distillation as consequence of its longer car-
bon chain length and the existence of oxygen in the carbon chain,
according to the results reported by Lee and Pahl (1985).
3. Steady state design
Extractive distillation includes an entrainer to increase the rel-
ative volatility of the key components of the feed. This process
is used to separate low relative volatility systems, or those that
have an azeotrope (Treybal, 1955). The process flowsheet of the
extractive distillation process is presented in Fig. 3. The process
has two columns, one for extractive separation and another for sol-
vent recuperation. The azeotropic mixture (F1) and the entrainer
(S1) streams are fed to the extractive distillation column, where
the dehydration of the desired compound (ethanol) takes place.
The bottom product of the extractive distillation column feeds the
entrainer recovery column, where the entrainer (leaving from the

Fig. 5. Effect of RR and E/F on ethanol purity and reboiler energy consumption of extractive distillation column.
 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142
Fig. 6. Effect of EFT and RR on ethanol purity and reboiler energy consumption of extractive distillation column.
reboiler) is separated from water and is recycled to the extractive
distillation column.
Glycerol alters the liquid activity coefficients and in conse-
quence the relative volatility of ethanol–water mixture causing
water to move toward the bottoms and pure ethanol is withdrawn
at the top. The mixture water–glycerol (B1) from the bottoms of
extractive column is fed into the entrainer recovery column to
produce almost pure water in the distillate (D2) and high purity
glycerol in the column bottoms (B2). Glycerol will be recirculated
back to the extractive column. Notice that a small makeup glycerol
stream is required to balance small entrainer losses in both D1 and
D2 streams.
The minimal product specifications in the two columns are set
to be the following: 99.5 mol% min. of ethanol in D1 and 99.95 mol%
min. of glycerol in B2 in order to be recycled to the extractive
distillation column. To establish the operating conditions for the
extractive distillation process, a sensitivity analysis was done to
determine the main design variables such as number of stages (NS),
reflux molar ratio (RR), binary feed stage (BFS), entrainer feed stage
(EFS), entrainer feed temperature (EFT) and entrainer to feed molar
ratio (E/F). The binary mixture was fed in the extractive distillation
column at azeotropic composition. The operating pressure in the
200
180
Liquid Composion Profile
160
Temperature (°C)
140
120
100
80
60
0 5 10 15 20
Stage
Fig. 7. Temperature and composition profiles of the extractive distillation column.
133
extractive distillation column is fixed a 1 atm and for the case of
entrainer recovery column is fixed at 0.02 atm in order to avoid the
thermal degradation of glycerol because of high temperatures.
The effect of changing the reflux molar ratio (RR), entrainer feed
stage (EFS) and entrainer to feed molar ratio (E/F) on the distil-
late composition and reboiler energy consumption of extractive
distillation column are shown in Figs. 4 and 5. It can be seen that
for a given entrainer feed stage (EFS) and entrainer to feed molar
ratio (E/F) there is an optimum reflux molar ratio (RR) that gives
maximum ethanol purity. However, the value of RR ratio must be
low to avoid energy wastes during operation. Reflux molar ratios
in a range of 0.3–0.5 reach composition requirements with lower
energy consumption in the reboiler as can be noted in Figs. 5 and
6. Entrainer feed stage should be located close to the condenser to
improve ethanol purity and its effect on energy consumption is no
significant (see Fig. 4). Entrainer to feed molar ratio (E/F) causes
a direct effect on the distillate purity. Sensitivity analyses, shown
in Fig. 5, show that increasing E/F ratio it is possible to have an
important improvement in the ethanol quality, without consider-
ably affecting energy consumption. At a constant reflux ratio, for
different values of E/F ratio within the interval 0.3–0.4, the energy
consumption increased in 4%. In the same way, maintaining the
1
0,9 Ethanol
Water
0,8
Glycerol
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0
0 5 10 15 20
Stage
134 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142

1
210
0,9

0,8

Liquid Composion Profile

160
0,7
Temperature (°C)
Ethanol
0,6 Water
0,5 Glycerol
110
0,4

0,3
60
0,2

0,1

10 0
0 2 4 6 0 2 4 6
Stage Stage

Fig. 8. Temperature and composition profiles of the entrainer recovery column.

E/F ratio at 0.3, and increasing values of the reflux ratio until a
distillate composition equivalent to the one obtained in the previ-
ous variation is reached; the increase in energy consumption was
30%. Consequently, the reflux ratio must be operated in the lowest
possible value, so the ratio E/F ratio can be manipulated to reach
the distillate composition without high energy consumption, and
reminding that high E/F ratios increase the energy consumption in
reboiler of the recovery column. Also, Figs. 4 and 5 show that the
change in reflux molar ratio (RR) has a greater effect on the reboiler
energy consumption than that of the entrainer feed stage (EFS) and
entrainer to feed molar ratio (E/F). To achieve the desired 99.5 mol%
of ethanol in D1, the entrainer to feed molar ratio must be about
0.45 at a low reflux molar ratio of about 0.35.
Entrainer feed temperature (EFT) has an important effect on
the distillate composition and the reboiler energy consumption.
Several authors recommend considering EFT as design variable
and operating 5–15 ◦ C below the top temperature of the extractive
distillation column (Doherty & Malone, 2001; Knight & Doherty,
1989). As it can be observed in Fig. 6, using high entrainer feed
temperatures demands high reflux molar ratios to reach a spec-
ified separation. This occurs because, as EFT is increased, part of
the water found in the stage vaporizes, increasing the content of
water in the distillate and decreasing its purity. Then increasing RR
is necessary to compensate this effect. In conclusion, low reflux
operations need entrainer fed at temperatures between 70 and
80 ◦ C to keep the distillate purity which is in accordance with the
value recommended by other authors taking into account that the
overhead temperature in the extractive column is 78 ◦ C approxi-
mately. The least energy demand corresponds to low entrainer feed
temperatures and low reflux molar ratios.
Temperature and composition profiles in the two columns are
given in Figs. 7 and 8. It is noticed that the goal of extractive

Fig. 9. Final flowsheet design for the ethanol dehydration system.

 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142 135

3 15

+5%
2 +5%
10 -5%
-5%

Temperature Difference (°C)

Temperature Difference (°C) 1
5
0
0
-1

-5
-2

-3 -10

-4 -15
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 2 3 4 5 6
Stage Stage

Fig. 10. Sensitivity analysis for ±5% changes in extractive and recovery reboiler duties.

distillation is fulfilled in eliminating water going into the rectify-
ing section. Entrainer is fed on stage 3 and the azeotropic feed is
introduced on stage 10. Fig. 9 shows the final flowsheet for this sys-
tem. It is important to observe that the overhead temperature in the
entrainer recovery column corresponds to 16 ◦ C. Therefore, cool-
ing water cannot be used as cooling medium and a more expensive
cooling medium must be used instead.
4. Control strategy design
The development of the control strategy requires the conversion
of the steady state model in a dynamic one in order to evaluate the
effect of the main disturbances to the extractive distillation system.
The model developed in Aspen Plus is exported to a pressure-driven
simulation in Aspen Dynamics. Before converting the Aspen Plus
model to Aspen Dynamics, the sizing of equipment is necessary.
The Pack-Sizing utility of the RadFrac distillation column block in
Aspen Plus is used to calculate the column diameters to be 0.85 m
and 0.57 m for the extractive and recovery column, respectively.
Reflux drums and base levels are calculated to provide 5 min of
holdup when at the 50% liquid level. Pumps and valves are sized
to provide adequate pressure drops over valves to handle changes
in flow rates appropriately (good rangeability). The Aspen Plus file
is pressure checked and exported into Aspen Dynamics. The top
pressures of the extractive and recovery column are set at 1 atm
and 0.02 atm, respectively.

Fig. 11. Configuration of control strategy 1.

136 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142

108,00 195,00

107,50 194,00

T in 17th stage of C-1 (°C)

T in 5th stage of C-2 (°C)

107,00 193,00

106,50 192,00

106,00 191,00

105,50 87 mol % Ethanol 190,00

87 mol % Ethanol
85 mol % Ethanol
105,00 189,00 85 mol % Ethanol

104,50 188,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
0,99700 0,99300

0,99680
0,99200
0,99660
0,99100
XD1 (ethanol)

XD2 (water)
0,99640

0,99620 0,99000

0,99600
0,98900
0,99580 87 mol % Ethanol
87 mol % Ethanol
0,98800 85 mol % Ethanol
0,99560 85 mol % Ethanol

0,99540 0,98700
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
90,00 61,00

89,00 60,00

59,00
88,00
58,00
D1 (kmol/h)

B1 (kmol/h)

87,00
57,00
86,00
56,00
85,00
55,00
84,00
87 mol % Ethanol 54,00 87 mol % Ethanol
83,00 85 mol % Ethanol 53,00 85 mol % Ethanol

82,00 52,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
15,00 45,30

45,25
14,00
45,20
13,00
D2 (kmol/h)

B2 (kmol/h)

45,15
87 mol % Ethanol
12,00 45,10
85 mol % Ethanol
45,05
11,00
45,00
87 mol % Ethanol
10,00
85 mol % Ethanol 44,95

9,00 44,90
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)

Fig. 12. Dynamic responses for feed composition disturbances in the control strategy 1.
 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142 137

114,00 200,00

112,00 198,00

T in 17th stage of C-1 (°C)

T in 5th stage of C-2 (°C)

110,00
196,00
108,00
194,00
106,00
192,00
104,00
190,00
102,00
Azeotropic Feed = +20% 188,00 Azeotropic Feed = +20%
100,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
98,00 186,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
0,99710 0,99000

0,99700
0,98800
0,99690
0,98600
0,99680
XD1 (ethanol)

XD2 (water)
0,99670 0,98400

0,99660 0,98200
0,99650
0,98000
0,99640
Azeotropic Feed = +20% Azeotropic Feed = +20%
0,97800
0,99630 Azeotropic Feed = -20% Azeotropic Feed = -20%
0,99620 0,97600
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
110,00 70,00
105,00 65,00
100,00
60,00
95,00
B1 (kmol/h)

55,00
D1 (kmol/h)

90,00
85,00 50,00
80,00 45,00
75,00
40,00
70,00
Azeotropic Feed = +20% 35,00 Azeotropic Feed = +20%
65,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
60,00 30,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
14,00 66,00

13,00
56,00
12,00
46,00
B2 (kmol/h)
D2 (kmol/h)

11,00

10,00 36,00

9,00
26,00
8,00
Azeotropic Feed = +20% 16,00 Azeotropic Feed = +20%
7,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
6,00 6,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)

Fig. 13. Dynamic responses for feed flow disturbances in the control strategy 1.
138 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142
Fig. 14. Configuration of control strategy 2.
Initially, a basic regulatory control scheme is determined
through the various control loops as follows:
(1) Reflux drum levels for both columns are controlled by manip-
ulating the distillate valves located in the streams D1 and D2.
(2) The fresh feed to the extractive column is flow control in order
to guarantee the constant flowrate.
(3) The top pressures of both columns are controlled by manipu-
lating the corresponding condenser duties.
(4) The base level for extractive column is controlled by manipu-
lating the bottoms flow rate.
(5) The base level for recovery column is controlled by manipulat-
ing the makeup flow rate, according to the suggested by Grassi
(1992) and Luyben (2008) for other extractive distillation sys-
tems.
(6) The entrainer feed temperature is controlled at 80 ◦ C by manip-
ulating cooler duty.
(7) The entrainer flow rate is ratioted to the azeotropic feed and
the ratio is controlled by manipulating the bottoms flow rate of
the recovery column.
(8) Reflux ratios are held constant in each column at their nominal
values during disturbances. It was also worked in other previous
works (Arifin & Chien, 2008; Luyben, 2008).
(9) The reboiler duties of both columns are used to control the
temperature in a particular stage of each column.
Temperature control stage location is selected applying two
criteria: (a) stage with a high slope in the temperature profile, and
(b) stage with high sensitivity to changes in reboiler duty. Temper-
ature profiles of both columns are shown in Figs. 7 and 8. Also, Fig.
10 shows the results of an open loop sensitivity analysis with ±5%
changes in reboiler duty of the extractive distillation column and
recovery column. For the extractive distillation column, the tem-
perature at the 17th stage has the higher slope in temperature and
additionally, as can be seen in Fig. 10, it is a sensitive point; for these
reasons the 17th stage is chosen as the control point. In the case of
recovery column the 2nd stage has the highest slope in the temper-
ature profile and the most noticeable stage to changes in reboiler
duty is the 5th stage. Taking into account the importance of consid-
ering the dynamic response, the temperature control points in the
rectifying sections of the columns (e.g. the 8th stage in extractive
column and the 2nd stage in the recovery column) are not chosen
because of the larger deadtime and to prevent a poor control perfor-
mance. The 5th stage is chosen as the control point in the recovery
column.
The most control loops described above correspond to a typi-
cal distillation control configuration. Only two particular loops are
defined in a special manner: (1) the entrainer flow rate is ratioted
to the feed flow rate through the “ratio” multiplier which sends
the remote setpoint to the entrainer flow control which operates
on cascade and, (2) the base level in the recovery column is con-
trolled by manipulating the makeup entrainer flow rate. Because
the makeup entrainer flow rate is much smaller than the total
entrainer feed to the extractive column, the 5-min holdup time in
the base of the recovery column is not able to handle changes in the
entrainer flow rate and the bottom level oscillates continuously. For
+20% changes of the feed flowrate the bottom level is continuously
dropping until it is empty and the valve is fully opened. To over-
come this situation a 10-min holdup time is fixed in the base of the
two columns. The overall control configuration initially proposed
is summarized in Fig. 11 as control strategy 1.
All level loops are Proportional only controllers with Kc = 2
for reflux drum levels according to the recommended by Luyben
(2002) and Kc = 10 for both base bottoms levels for faster
dynamics in the internal flow of the process. The pressure con-
trollers are Proportional-Integral with Kc = 20 and  I = 12 min, the
default values used by Aspen Dynamics. All flow controllers
are Proportional-Integral with the settings recommended by
 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142 139

107,50 196,00

195,00
107,00

T in 17th stage of C-1 (°C)

T in 5th stage of C-2 (°C)

194,00

106,50 193,00

192,00
106,00
191,00

105,50 87 mol % Ethanol 190,00

87 mol % Ethanol
85 mol % Ethanol 189,00
105,00 85 mol % Ethanol
188,00

104,50 187,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
0,99690 0,99300
0,99680
0,99200
0,99670
0,99660 0,99100
XD1 (ethanol)

XD2 (water)
0,99650
0,99000
0,99640
0,98900
0,99630
0,99620 0,98800
87 mol % Ethanol 87 mol % Ethanol
0,99610
85 mol % Ethanol 0,98700 85 mol % Ethanol
0,99600
0,99590 0,98600
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
90,00 64,00

89,00
62,00
88,00
60,00
D1 (kmol/h)

B1 (kmol/h)

87,00

86,00 58,00

85,00
56,00
84,00
87 mol % Ethanol 87 mol % Ethanol
54,00
83,00 85 mol % Ethanol 85 mol % Ethanol

82,00 52,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
15,00 48,00

14,00 47,50

47,00
13,00
B2 (kmol/h)
D2 (kmol/h)

46,50
12,00
46,00
11,00
45,50
87 mol % Ethanol 87 mol % Ethanol
10,00 45,00
85 mol % Ethanol 85 mol % Ethanol

9,00 44,50
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)

Fig. 15. Dynamic responses for feed composition disturbances in the control strategy 2.
140 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142

114,00 198,00

112,00 197,00

T in 17th stage of C-1 (°C)

T in 5th stage of C-2 (°C)

110,00 196,00

108,00 195,00

106,00 194,00

104,00 193,00

102,00 192,00
Azeotropic Feed = +20% Azeotropic Feed = +20%
100,00 191,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
98,00 190,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
0,99900 0,99000

0,99850 0,98000

0,99800
0,97000
XD1 (ethanol)

XD2 (water)
0,99750
0,96000
0,99700
0,95000
0,99650

Azeotropic Feed = +20% 0,94000 Azeotropic Feed = +20%

0,99600
Azeotropic Feed = -20% Azeotropic Feed = -20%
0,99550 0,93000
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
110,00 70,00
105,00 65,00
100,00
60,00
95,00
B1 (kmol/h)

55,00
D1 (kmol/h)

90,00
85,00 50,00
80,00 45,00
75,00
40,00
70,00
Azeotropic Feed = +20% 35,00 Azeotropic Feed = +20%
65,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
60,00 30,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)
14,00 66,00

13,00
56,00
12,00
46,00
D2 (kmol/h)

B2 (kmol/h)

11,00

10,00 36,00

9,00
26,00
8,00
Azeotropic Feed = +20% 16,00 Azeotropic Feed = +20%
7,00
Azeotropic Feed = -20% Azeotropic Feed = -20%
6,00 6,00
0 2 4 6 8 10 0 2 4 6 8 10
Time (h) Time (h)

Fig. 16. Dynamic responses for feed flow disturbances in the control strategy 2.
 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142
Table 1
Temperature controllers tuning parameters.
Parameter
TC – Column C-1
Ultimate gain 1.568
Ultimate period 4.2 min
Kc 0.4902
I 9.24 min
TC – Column C-2
Ultimate gain 2.727
Ultimate period 4.8 min
Kc 0.8523
I 10.56 min
TC – Cooler
Open loop gain 6.77
Time constant 0.59 min
Dead time 0.6 min
Kc 0.13
I 0.899 min
Luyben (2002) Kc = 0.5 and  I = 0.3 min and a filter time constant
 F = 0.1 min. The two temperature control loops for the columns are
closed loop tested for determining the ultimate gains and periods,
and Tyreus–Luyben tuning rule (Tyreus & Luyben, 1992) is used. For
the cooler temperature control loop, open loop tests are performed
for determining the PI tuning constants following the IMC-PI tun-
ing rule (Chien & Fruehauf, 1990). The results of those calculations
and the final controller tuning parameters are shown in Table 1.
Extractive distillation process is the final step in the ethanol pro-
duction. The dehydration column is fed with azeotropic ethanol
coming from a rectification column. Changes in the operating
conditions of this column could originate disturbances in the
feed composition to the extractive distillation system, particularly
diminishing the concentration of stream to lower values of ethanol
mole fraction. Here have been considered two ethanol composi-
tion disturbances to test the control strategy from 89 to 87 mol%
ethanol and from 89 to 85 mol% ethanol at time = 2 h. Additionally,
feed flow disturbances of ±20% also have been considered. Figs. 12
and 13 show the closed-loop results for these disturbances applied
to the control strategy 1.
Analyzing the results for the feed composition disturbances pre-
sented in Fig. 12, in the two top plots the temperature control point
on each column works well in rejecting disturbances and the tem-
peratures back to their setpoints. The variation in temperature is
not higher than 3 ◦ C in extractive column and 5 ◦ C in the recov-
ery column, but the system rapidly achieves the steady state. In
parallel, the results for the feed flow rate disturbances presented
in Fig. 13 show that temperature control points vary 10 and 12 ◦ C
for extractive and recovery column, respectively. This is due to the
most important effect that has the feed flow rate on the energy
required for the separation. Product purities are held quite close
to their specifications and they are mainly affected by changes in
the feed composition, however the quality of ethanol stream never
is negatively affected and the control strategy ensures the quality
product. Inventory control loops are stabilized rapidly. In particular,
when the feed flow rate increases, the cascade controller increases
the entrainer flow rate fed to the extractive column making the base
level of the recovery column begins to drop. Because the flow rates
of entrainer and feed to the extractive column have increased the
material balance is adjusted increasing the feed to the recovery col-
umn, which brings the base level back up. However, good results
only are obtained augmenting the holdup time in the base level
which implies increase the size of the sump level of the recovery
column to achieve good controllability and compensate the loop
poor dynamics.
In order to improve the dynamic performance an alterna-
tive control strategy 2 is proposed modifying slightly the control
141
structure. Now the base levels of both columns are controlled by
manipulating the bottom flow rates and the entrainer flow rate is
ratioted to the azeotropic feed and the ratio is controlled by manip-
ulating the makeup flowrate. Again the entrainer flow rate control
is on cascade with the feed flow rate. The base levels are calculated
to provide 5 min of holdup when at the 50% liquid level. The rest
of the control loops are maintained as specified above. The overall
control configuration proposed is summarized in Fig. 14 as control
strategy 2.
In the case of feed composition disturbances, the two top plots of
Fig. 15 show the temperature control point on each column. As can
be seen the good tuning of the loop makes that the change in tem-
perature to be very small and therefore the system is not affected by
the disturbances bringing the temperatures back to their setpoints.
The variation in temperature for both columns is not higher than
3 ◦ C which is very desirable because the energy consumption of the
system is not strongly affected in the transient periods and there-
fore the operation is more energy efficient. In the next two plots for
the composition of ethanol in the extractive column and water in
the recovery column, it can be observed the corresponding perfor-
mance verifying that the composition or quality of the top products
of both columns is affected only positively, i.e. ensuring the product
purities are held quite close or higher to their specifications. Spe-
cially can be noticed that the ethanol composition always is higher
than 99.5 mol% ethanol.
Finally, in the case of the inventory loops, the mole flows of
distillate and bottoms are stabilized rapidly and in general all the
system takes about 2 h approximately to come to a new steady
state. This favorable performance could be explained taking into
account the more direct effect of the bottoms flow rate valve of the
recovery column on the base level and at the same time the makeup
flow rate effect over entrainer feed rate to the extractive column.
Fig. 16 shows the results for the feed flow disturbances applied over
the control strategy at time = 2 h. Once again, the temperature loop
responses relatively fast and the main products composition are
maintained at the specifications required. The time used to come
back to the steady state is about 3 h. In this way, with the control
strategy 2 is easier to compensate the effects of feed composition
and feed flow rate disturbances because there is more direct effect
over the variables of interest, mainly in the case of base level of
the recovery column and in the control of entrainer flow rate. From
the practice point of view is possible that the significant increase
in feed flow rate have influence on the transient response because
of small control valve installed in the make-up stream. In practice
it could be possible to select a good characteristic valve that allows
working with a good response when sporadically changes as high
as +20% are presented. However, this should be clearly verified for
the particular application.
5. Conclusions
This article presents the design and control of an ethanol
dehydration process via extractive distillation using glycerol as
entrainer. The design flowsheet is simulated using the NRTL ther-
modynamic model which describes appropriately the experimental
vapor–liquid equilibrium data and supports on a solid thermody-
namic basis the simulation results. From the sensitivity analysis
is possible to establish the main operating conditions of the sys-
tem and to determine the effect of the design variables. Reflux
ratio on the extractive distillation column has the greatest effect
on the energy consumption and it must be operated at low values.
Entrainer to feed molar ratio is useful in compensating changes
in some operating conditions without affecting the energy con-
sumption in an important manner compared with the effect of
the reflux ratio. Glycerol is an interesting candidate entrainer in
142 I.D. Gil et al. / Computers and Chemical Engineering 39 (2012) 129–142
extractive distillation taking advantage of its low cost, high avail-
ability and great effect on azeotropic mixtures to improve the
relative volatility. The only possible drawback for ethanol dehydra-
tion via extractive distillation is that the two columns need to be
operated at higher temperatures demanding high pressure steam
to be used in the two reboilers.
Two control structures are developed and tested, providing
effective quality and production rate control. Control strategy 1
which uses the entrainer makeup flow rate to control the base level
in the recovery column has good control performance rejecting for
the disturbances in feed flow rate and feed composition, however,
it is necessary to adjust the size of sump level in order to obtain
good controllability and additionally the perturbations in temper-
ature of the control point of each column are important. On the
contrary, control strategy 2 which uses the entrainer makeup flow
rate to control the entrainer feed flow rate to the extractive col-
umn allows to achieve a soft-regulating control with a minimal
changes in the temperature profile for both columns and main-
taining the high purity of the products. Therefore, control strategy
2 is recommended for the extractive distillation of ethanol.
Acknowledgment
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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