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Article history:
Received 25 June 2012
Received in revised form 20 December 2012
Accepted 22 December 2012
Available online 13 February 2013
In this work, production of high-purity ethyl acetate (EtAc) is studied using reactive distillation (RD)
embedded in HYSYS process simulation software. A new conguration of a RD process is proposed by
dividing a single RD column into two separate columns namely, RD and rectier. Impacts of three
parameters, including reactant ow rate, reaction trays, and feed-inlet location on the temperature
prole and component compositions in the columns are investigated to achieve an optimum condition of
the process in terms of energy demand. The simulation results show that ratio of reactants near the
stoichiometric values with a small amount of ethanol lead to the industrial specication output results.
Additionally, it is found that with increasing the reaction stage number, the residence time and the
reaction conversion increase. Meanwhile extra water is produced through esterication reaction,
resulting in more energy consumption. The optimum number of trays for the RD column is determined to
be 29 by HYSYS simulator. Moreover, it is shown by simulation that a lower RD reux ratio and low
required duty can be demonstrated when the feed-inlet of the reaction column is located in lower
portion of the column.
2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords:
Simulation
Reactive distillation
Process design
Ethyl acetate
1. Introduction
Throughout the chemical industry, the demand for purer
products, coupled with relentless pursuit for greater efciency, has
necessitated continued research into the techniques of distillations
[1]. Distillation is one of the oldest and most important separation
processes used in the chemical and petrochemical industries.
Distillation is therefore the process most popular when the issue of
energy consumption is addressed [2,3]. This process is mainly
based on the difference in volatility of the components which
should be separated. Noted that the distillation processes design in
industrial practice is still conducted by heuristic simulations that
require a detailed specication of design parameters [4].
Although several distillation techniques have been investigated
including simple distillation, partial distillation, ash distillation
(equilibrium distillation), rectication, azeotropic distillation,
solvent-extraction distillation, and reactive distillation (RD), RD
has become an interesting alternative for some conventional
processes, especially the equilibrium-limited reactions as esterications and etherications [5]. The RD combines reaction and
distillation in a single column, in which reactants are converted to
products with simultaneous separation of the products and recycle
* Corresponding author. Tel.: +98 611 5550868; fax: +98 611 5550868.
E-mail address: yadollahtavan@gmail.com (Y. Tavan).
1876-1070/$ see front matter 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2012.12.023
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Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
Table 1
Investigations to nd azeotropes at atmospheric pressure.
Component ID
Component name
ETHYL-01 or EtAc
WATER
ETHAN-01 or EtOH
ACETI-01or HAc
Ethyl-acetate
Water
Ethanol
Acetic-acid
77.20
100.02
78.31
118.01
Number of azeotrope
Components
Mol fraction
Temperature (8C)
Type
EtAc
Water
EtAc
EtOH
Water
EtOH
EtAc
Water
EtOH
0.6734
0.3266
0.5533
0.4467
0.1048
0.8952
0.5370
0.2819
0.1811
71.39
Heterogeneous
71.78
Homogeneous
78.15
Homogeneous
70.33
Homogeneous
2
3
4
(1)
(2)
E1 = 41,868 kJ/kg mol, R (kg mol/m3 K), T (K), C (kg mol/m3),
Liquid phase.
2.2. Static analysis
Static analysis (SA) is an essential method to analyze the
feasibility of a certain extent of reaction in the RD processes. In this
method and based on the information of the distillation diagrams,
some hints in design of the process are determined. One of its
advantages is that it does not depend on the particular column
structure. The basic assumptions used in this method are: (1) the
vapor and liquid ow rates in the column are innite and the
number of trays is also innite, (2) only one reversible equilibrium
reaction is treated, (3) the liquid hold-up on each stage is large
enough to realize a given conversion rate, and (4) the column is
operated at steady state, and theoretical stages are chosen [1517].
When the boiling points of the azeotropes are very close
together, the SA application is encountered to the problems. In this
method, the feed material (0% conversion, near stoichiometric
reagents, XF) is converted to the pseudo initial mixture, X*, by
assuming a specied conversion rate of reaction (65% conversion in
the CSTR) as typically shown in Fig. 2. In addition, the constraints
stable states of the system are shown in Fig. 2 by the azeotropes
temperature and dash lines. It is worth mentioning that the EtOH
EtAcH2O azeotrope has the lowest temperature and appears in
the top section of the RD column. However, this azeotrope is not
appropriate for separation of the components with a high-purity.
The second azeotrope is the binary mixture of EtAcH2O, which has
a heterogeneous phase split. The EtAcH2O azeotrope is a suitable
Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
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Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
Table 2
Essential data and simulation results.
Parameter/stream Number
Simulation results
Temperature (8C)
Flow rate (kg mol/h)
Composition (mol%)
EtAc
Water
EtOH
HAc
Sulfuric acid
Lai et al. [18] results
Composition (mol%)
EtAc
EtOH
Sulfuric acid
EtOH
HAc
11
1200
13
25
0.2008
25
8.3018
25
7.3337
71
11.5615
26.7
11.1872
76.7
19.5013
76.8
7.9437
0.0000
0.0000
0.0000
0.0000
1.0000
0
0.1183
0.8817
0.0000
0.0000
0.0000
0.0000
0.0000
1.0000
0.0000
0.6580
0.2910
0.0510
0.0000
0.0000
0.7615
0.0723
0.1662
0.0000
0.0000
0.8525
0.0428
0.1047
0.0000
0.0000
0.9920
0.0000
0.0080
0.0000
0.0000
0.71480
0.05680
0.99000
0.00912
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Fig. 4. The effect of EtOH ow rate on (a) reactor (b) reux ratio and (c) heat of columns.
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Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
Fig. 5. The effect of EtOH ow rate on (a) water mol fraction in RD (b) EtOH mol fraction in RD (c) water mol fraction in rectier (d) EtOH mol fraction in rectier (e)
temperature prole in RD and (f) temperature prole in rectier.
Fig. 6. The effect of RD tray number on (a) reux ratio and (c) heat of columns.
Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
583
Fig. 7. The effect of RD tray number on (a) WATER mol fraction in RD (b) EtOH mol fraction in RD (c) temperature prole in the RD and (d) temperature prole in the rectier
respect to steady state point.
Fig. 8. The effect of the RD feed inlet stage on (a) reux ratio and (c) heat of columns.
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Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
Fig. 9. The effect of RD feed inlet stage on (a) water mol fraction in RD (b) EtOH mol fraction in RD (c) temperature prole in the RD and (d) temperature prole in the rectier
respect to steady state point.
4. Conclusions
This paper demonstrates the effect of three main parameters on
the reactive distillation process to produce EtAc using dehydration
of ethanol and acetic acid in three distillation columns. It was
found that keeping the reactants rates near the stoichiometric ratio
leads to signicant energy saving for various EtOH ow rates. The
Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585
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