Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

Research Article 110

Separation of Azeotropes by Shifting the Azeotropic Composition

Billal, S.F *1, Elamin, I.H.M 2, Mustafa, H.M 3, and Gasmalseed , G.A4 ,
(1- 4)

University Of Science and Technology, Sudan, Department of Chemical Engineering.

1*
Corresponding author Email: Samah.faisal@hotmail.com
2
Email: Ibrahimelamin@hotmail.com
3
Email: hamidmustafa5@gmail.com
4
Email:gurashigar@hotmail.com
(Received: March 15, 2014; Accepted: June 12, 2014)

Abstract Distillation is a process of separation of binary and

multicomponent systems in fractionation column .The efficiency
of the separation depends on the difference in volatility, the more
the driving force, the better is the separation. When the relative
volatility approaches unity separation will be difficult and unity
there will be no separation, this is referred to as azeotropic
systems. The aim of this study is to determine the azeotropic point
of a chemical system by running the column using Aspen Hysys
simulator, the top product has then been introduced to a second
column in series after the addition of a pure component that
would raise the composition above the azeotropic point. The
azeotropic point was determined using Aspen Hysys simulator
version 3.2, when the composition reach the azeotropic point, no
separation would occur. The result shows, the composition of the
azeotropic point is almost constant with the average of 0.8966
ethanol, the number of stages in the first column being 10. The
number of stages in the second column is 25 for a concentration of
0.9515 of ethanol.
Index Terms Hysys, Azeotropic separation; Breaking of
azeotropism, Number of theoretical stages, Makeup.

I.

INTRODUCTION

nhydrous ethanol is widely used in chemical industry as a

powerful solvent and as a raw material or intermediate in
chemical synthesis of esters, organic and cyclic compound
chains, detergents, paints, Cosmetics, aerosols, perfumes and
medicine, among others. Besides, ethanol and gasoline
mixtures can be used as fuels reducing environmental
contamination and anhydrous ethanol addition improves octane
index [1, 2, 3]. Several processes for ethanol dehydration are
used such as heterogeneous azeotropic distillation, which uses
different solvents such as benzene, pentane and cyclohexane
[4], adsorption with molecular sieves and processes that include
the use of pervaporation membranes [5]. All these processes
have had industrial application but some are no longer in use
due to the high operating costs, operative problems and high
energy consumption [3].
Ethanol is produced by fermentation which is biologically
process by which sugar are converted into ethanol and carbon
dioxide with the aid of yeast. Thus ethanol-water mixture
produced should be subjected to further process treatment for
purification [1] .Distillation is the most widely used separation
technique in the chemical and petroleum industry. However not

all liquid mixtures are amenable to ordinary fractional

distillation .When the components of the system have low
relative volatilities, separation becomes difficult and expensive
because a large number of trays are required. Usually a high
reflux ratio as well as both equipment and utilities costs
increased markedly and the operation can become
uneconomical. In other cases the formation of a binary
azeotrope may make it impossible to produce nearly pure
products by ordinary fractionation [6].
Distillation, where a liquid mixture is separated by successive
evaporation and condensation. The basis for the separation is
that the vapor phase is richer in the more volatile components
than the liquid. This enrichment is determined by the
vapor-liquid phase equilibrium. As a result, feasible separations
in distillation columns and the operating parameters required
for these separations depend on the vapor-liquid equilibrium of
the mixture to be separated. For ideal and nearly ideal mixtures
the components can be ranked in order of their volatility, or,
equivalently, in order of the pure components boiling points
and one can easily list all feasible separation sequences. In
practice, we often have to deal with non-ideal mixtures where
the composition space is split into regions with different
volatility order of the components, and the identification of
feasible sequences is much more difficult. Azeotropic behavior
is often encountered where at some points in the composition
space the equilibrium vapor and liquid phases are of equal
composition for a given pressure and temperature. These points
are called azeotropes and mixtures with these phenomena are
called azeotropic mixtures. The highly nonlinear vapor-liquid
equilibrium behavior of azeotropic mixtures complicates the
prediction of feasible separation sequences further. An
azeotrope itself cannot be separated by ordinary distillation and
usually, special methods are required. Generally, there are two
cases of azeotropic distillation:
1.

Where the original mixture to be separated is an

azeotropic mixture

2.

Where an azeotropic mixture is formed deliberately by

adding one or more azeotrope forming components to
the original mixture.

In the first case we a way should have been found to separate

the azeotropic mixture and obtain the desired product

Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

111

specifications and recovery. In the second case, in addition,

component have to be selected (called entrainer) that is

effective for the desired separation and easily recovered

afterwards [6].

separation of ethanol-water of a chemical system by running

the column using Aspen Hysys simulator.

The aim of this study is to determine the azeotropic point and

development of an appropriate technique for azeotropic

The equilibrium data for the system ethanol -water was cited
from the literature [7].and the equilibrium diagram was drawn
as shown in the following diagram:

Figure 1. Vapor liquid equilibrium ethanol -water [7]

II. MATERIALS AND METHODS
Separation of ethanol and water by Azeotropic distillation
Process Simulation Methodology
All the work was developed using Aspen plus Simulator,
version 3.2 Activity coefficient calculations for the mixture
were determined Appling with the UNIQUAC thermodynamic
model, using Aspen Hysys Simulator. Fig. 2 Shows the
flow-sheet of the system on which the simulation was run. The
arrangement has a first azeotropic distillation column to which

an alcoholic solution which is near to the azeotropic

composition, is fed at plate three 3 then the number of stage is
changed using Hysys program until a constant composition at
the top is reached this product is the azeotrope. The distillate
from column 1 is mixed with a pure ethanol in a mixer to
change the composition of the feed; it is fed to the plate 3 in the
distillation column 2. Alcohol with a high molar concentration
is obtained as distillate overhead product, and water is
withdrawn as a bottom product.

Figure 2. Flow-sheet for the azeotropic distillation using pure ethanol as a makeup of the feed

Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

112

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Research
Article 110
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process in Column 2 is azeotropic ethanol-water out from

a) Thermodynamic Model
The thermodynamic model was used to calculate the
vapor-liquid-binary equilibrium in the Aspen Split simulator by
Aspen Hysys Tech. the simulator was run with the UNIQUAC
thermodynamic model.
b) Configuration
In this work the reflux ratio, number of theoretical stages,
azeotropic mixture and ethanol makeup flow rate, feed
temperature of makeup agent are required for the separation.
Operating pressure was set at pressure less than atmospheric.
The thermal condition for the azeotropic feed 1 was saturated
liquid, as in other works [8]; a flow sheet for the simulation of
azeotropic distillation system is shown in Fig 2.The azeotropic
distillation column 1,2 are modeled. The efficient operating
criteria considered were: number of stages and the distillate
composition in the azeotropic columns, which should reach a
higher molar concentration of ethanol. The inlet streams for the

distillation column1 and pure ethanol mixed together in a mixer,

feed out from the mixer with purity higher than the
concentration of the azeotropic point. Other initial informations
required are:
Theoretical number of stage for distillation column 1
and 2.
Feed stage
Reflux Ratio
III. RESULTS AND DISCUSSION
Determination of the azeotropic point in column 1 using Hysys
software:

The flow diagram is shown in Fig. 3 below.

Figure 3. The flow diagram for the distillation column 1

Feed of composition 0.4 is introduced to the column 1. The number of theoretical plates is changed and the azeotropic point ware
determined using Hysys software, these are found to be 10 plate, as shown in Table 1.

Table 1. Determination of the azeotropic point in column 1

Feed composition,
Number
of Ethanol composition as a Ethanol composition in a
Mass fraction
plate
top
product,
mass bottom,
fraction
mass fraction
0.4
6
0.8849
0.1167

2
3
4

0.4
0.4
0.4

7
8
9

0.8994
0.8995
0.8996

0.1081
0.1080
0.1077

0.4

10

0.8996

0.10 77

Run
number

Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE) 113
At plate number 6 through the plate number 10, the composition is almost constant with average of 89.66 % 0f ethanol which in
agreement with published value. This is the azeotropic point of ethanol water.
Operating the two distillation columns in series, where the product from the first column is at a composition less than the azeotropic
point, is introduced as a feed to the second column, then its concentration is raised by an addition of a makeup of pure ethanol, the
result is shown in Table 2.

Operating variable

Table 2. Operating conditions for the two distillation columns

Distillation column 1
Distillation column 2

Feed flow (k g/h)

100

42

Feed temperature (C)

80

33.1

Feed pressure (k pa)

12.6

12.6

Feed Ethanol composition , (mass fraction)

0.4

0.9116

Distillate flow rate (kg/h)

36.9

40

Molar reflux ratio

Number of theoretical stages

3
10

5
25

The flow diagram for the distillation column 2 is shown in Fig. 4 below:

Figure 4. Flow diagram for the distillation column 2

Manual Calculation and material balance on a mixer

Execution the Hysys softwar

Feed to column 2 was estimated (F) = 41.9 kg/h (Table 3)

Distillate to column 2 (D) = 36.9 kg/h
Makeup of the feed2 (M)
F2=D+M
(1)
42=36.9+M
M=5 kg/h
A balance on the ethanol gives
F2 (xf2) =D (x d) +M (x M)
(2)
41.9*(xf2) =36.9*0.8996+5.1(1)
(3)

The flow rate of the makeup stream was estimated M=5 kg/h
(Table 4)

x f2=0.9116

The liquid rate in the distillate was estimated=40 kg/h

The liquid rate in the bottom was estimated=1.9 kg/h
On the Parameters tab, Solver page, check the Azeotropic box
And supply a Fixed Damping Factor of 0.5 and the column was
run

Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE) 114
Table 3.The result on column 2 when the feed1composition equal 0.4 mass fraction
Feeds
Flow rate k g/h

41.9008

Ethanol composition, mass fraction

0.9116

Water composition, mass fraction

0.0884

Products
Distillate

Bottom

Flow rate k g/h

40.0034

1.8973

Ethanol composition, mass fraction

0.9515

0.0690

Water composition, mass fraction

0.0458

0.9310

Minimum reflux ratio leads to a smaller diameter and less operating cost, thereby the value of a reflux ratio of 5 was taken for this
work.
During execution of the program when the feed composition to column 1 is 0.4 and that to column 2 is 0.9116 , as shown in Table
5 it is observed that there is small effect of the reflux ratio on the ethanol product composition also it is found the concentration of
the ethanol increases with the increase of the number of stages as in Table 6.
Table 4. Effect of the makeup flow rate on the azeotropic distillation column 2
Run number

Makeup flow rate

kg/h

Feed to column 2

Ethanol

Ethanol composition

Ethanol% recovery as a

composition,

composition as a top

in a bottom,

top product

Mass fraction

product , mass

mass fraction

fraction
1

0.9116

0.9515

0.0690

99.657

10

0.9210

0.9522

0.1808

99.206

13.1

0.9259

0.9531

0.6295

98.839

23.1

0.9382

0.9558

0.4239

98.505

33.1

0.9471

0.9563

0.6306

98.1076

Ethanol % rcovery top product =

amount of ethanol in a distillate product

amount of ethanol in the bottm product

(4)

Table 5. Effect of the Reflux Ratio on the Azeotropic distillation column 2 with the makeup flow rate 5 kg/h
Run

Reflux ratio

number

Feed

to

column

Ethanol

composition,

composition

Mass fraction

product

top
mass

Ethanol

Ethanol%

composition in a

recovery

bottom,

product

fraction

mass fraction

0.9116

0.9279

0.5742

97.0906

0.9116

0.9415

0.2789

98.6178

0.9116

0.9466

0.1717

99.1481

0.9116

0.9495

0.1089

99.4604

0.9116

0.9515

0.0686

99.65

0.9116

0.9542

0.0145

99.9279

0.9116

0.9544

0.0096

99.9522

0.9116

0.9548

0.0006

99.9973

top

Journal of Applied and Industrial Sciences, 2014, 2 (3): 110-115, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE) 115

Table 6. Effect of the number of plates on the ethanol product composition

Number of

Reflux

Ethanol composition top product

Ethanol composition in a bottom

Ethanol % recovery as a

plate

ratio

,mass fraction

,mass fraction

top distillate

12

0.9451

0.2050

98.98

14

0.9466

0.1736

99.1359

16

0.9481

0.1398

99.3058

18

0.9496

0.1114

99.4447

20

0.9513

0.0757

99.6228

25

0.9515

0.0686

99.65

Nomenclature:
F
D
M
W
Qc
Qb
xf
xd
xw
xm
V

flow rate of the feed kg/h

flow rate of the Distillate kg/h
flow rate of the makeup kg/h
flow rate of the bottom kg/h
condenser energy kJ/h
reboiller energy kJ/h
mass fraction of the feed
mass fraction of the distillate
mass fraction of the bottom
mass fraction of the makeup
vapor flow rate kg/h

IV. CONCLUSIONS
The thermodynamic model chosen fits properly the
experimental vapor-liquid equilibrium data for the mixture
ethanol-water. Thereby, the simulation results were supported
on a thermodynamic basis, and can describe the mixture
behavior in a very accurate way. From table 3 to table 6 as
shown, it has been found that proper separation of
ethanol-water is achieved with least cost by Appling the value
of reflux ratio is 5, and makeup flow rate is 5 kg/h of pure
ethanol. The ethanol composition achieved (0.9515) is a
suitable feed to molecular sieve to produce pure ethanol. This
work made it possible to establish operating conditions for an
azeotropic distillation process when using pure ethanol as a
makeup to the feed. In the same way, it is concluded that
ethanol makeup flow rate is a useful variable for compensating
the changes in operating conditions of the column, and that can
be used to obtain high ethanol concentrations in the overhead
product. Therefore, Azeotropic distillation is the most cheap,
fast, and effective of ethanol distillation.
ACKNOWLEDGMENTS
The authors wish to thank the Collage of Graduate studies and
scientific research, of karary University, for their support and
provision of funds. This research is made in partial fulfillment
of the requirements for the degree of Ph.D. In chemical
engineering at Karary University.

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