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Design and simulation of a reactive distillation


process to produce high-purity ethyl acetate
Article in Journal of the Taiwan Institute of Chemical Engineers July 2013
Impact Factor: 3 DOI: 10.1016/j.jtice.2012.12.023

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Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585

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Journal of the Taiwan Institute of Chemical Engineers


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

Design and simulation of a reactive distillation process to produce high-purity


ethyl acetate
Yadollah Tavan a,*, Seyyed Hossein Hosseini b
a
b

Gas Engineering Department, Petroleum University of Technology, 63431 Ahwaz, Iran


Chemical Engineering Department, Faculty of Engineering, University of Ilam, 69315-516 Ilam, Iran

A R T I C L E I N F O

A B S T R A C T

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).

of unused reactants [69]. This simultaneous reaction and


separation allows crossing of azeotropic concentrations and
distillation boundaries, hence facilitating product purication.
The equilibrium yield can be signicantly increased far beyond
equilibrium limitations by continuous product removal from the
reaction mixture [5,10]. This process also provides some important
advantages including considerable reduction in energy, solvent
consumption, the number of equipment unit and avoidance of hot
spots by simultaneous liquid evaporation [7]. These advantages
result in capital investment and operating costs reductions.
However, the application of RD is somewhat limited by constraints,
like, e.g. common operation range (temperature and pressure) for
distillation and reaction and difculties in providing proper
residence time characteristics [6]. On the other words, applications
of RD are limited to systems in which the reaction rates are fairly
high and there is no mismatch of temperatures favorable for
reaction and separation [11]. Due to strong interactions of
chemical reaction and heat and mass transfer, the RD behavior
tends to be quite complex and high sensitive to operating variables.
Hence special consideration should be given to the design of the RD
columns.
Ethyl acetate has been reported in some recent studies as an
important organic solvent widely used in the production of
varnishes, ink, synthetic resins, and adhesive agents [12,13].
Moreover, the mixtures containing ethyl acetate are commonly
used in chromatography columns and extractions in the

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

Normal boiling point (8C)

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

laboratory. Ethyl acetate (EtAc) is normally produced via reversible


reaction of acetic acid (HAc) with ethanol (EtOH) as
CH3 CH2 OH CH3 COOH CH3 COOCH2 CH3 H2 O

(1)

This mixture converts to the ester in about 65% yield at room


temperature. One major drawback of this reversible reaction is the
relatively low conversion to the desired products. On the other
hand, the reaction can be accelerated by acid catalysis and the
equilibrium shifts to the right by removal of water. Therefore, to
surpass equilibrium conversion, RD process can be utilized to
improve the reaction yield.
Only a few works have been published in the literature on the
subject of EtAc production by RD technique [8,12,14]. On the other
hand, various owsheet alternatives have been investigated,
previously. Some researchers have designed RD process using
one or two columns and some other have developed a combination
of pre-esterication reactor and RD and the other authors have
used catalyzed and uncatalyzed processes. However, in the
addressed researches the control process of RD column has been
mainly focused and the relevant process intensication has not
been investigated.
It has been also found that a single RD column is not capable to
produce the adequate purity of EtAc, and therefore, subsidiary
units are needed [14]. Accordingly, two serial columns of RD and
rectier are used in the present study to produce highly pure EtAc.
The rst column is based on reaction, whereas the second is
employed for separation. It is shown that such an arrangement
provides more exibility compared to a single RD column to
produce EtAc. Furthermore, the steady state design of the RD
process is evaluated using HYSYS 3.1 and the sensitivity analysis is
also conducted. The temperature and concentration distributions
and duty for the proposed design are investigated.
2. The base simulation
2.1. Thermodynamics study and residue curves
The process of EtAc production includes ve components and
four azeotropes which the azeotropes are listed in Table 1. It is
evident that the reactants HAc and EtOH have highest and
intermediate boiling points, respectively. The lowest temperature
in the system is related to azeotrope no. 4 (ternary azeotrope) with
the value of 70.33 8C and then azeotrope nos. 1 and 2 with the
values of 71.38 and 71.78 8C, respectively. It is noteworthy that
the azeotrope products, EtAc, and water are neither the lightest nor
the heaviest components in the system and this matter causes the
further complexity to the system. Fig. 1 shows the residue curve

maps for the components at atmospheric pressure. It is clear that


the singular points in Fig. 1a show the location (composition and
temperature) of the four azeotropes and maps the distillation
boundary for the system. Fig. 1b shows a signicant liquidliquid
envelope where the azeotrope no. 4 lies closely to the boundary of
this envelope. In addition, the tie lines slope toward pure water
node and, consequently, relatively pure water can be recovered
from this process. Fig. 1c and d also shows the residue curves of the
other components.
The exothermic and reversible reaction (DH8 = 1.5  104 kJ/
kg mol) in liquid phase, catalyzed by sulfuric acid homogeneously.
The reaction kinetic of EtAc formation based on the reactant (HAc)
is as follows


E1
 C HAc C EtOH  7:1
r HAc 2:8  107 exp
RT


E1
 106 exp
 C EtAc C Water
RT

(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

579

Fig. 1. Residue curves of components.

Fig. 2. Typical static analysis of EtAc production process.

top product from the RD column, because, after phase splitting in


the decanter, the organic phase EtAc composition becomes much
purer. Thus, this azeotrope is assumed as the top product stream.
Actually, the overhead vapor composition is a combination of two
azeotropes, and rather stays inside the heterogeneous phase
splitting region.

Due to the phase and chemical equilibriums, the maximum


obtainable mol fraction of EtAc in the RD process is about 0.67. By
connecting X* to the assumed top product of RD, the operating
condition of RD column is dened. Therefore, to produce high
purity of EtAc, a combination of reactive and some ordinary
distillation columns is mandatory and more columns are required.

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Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585

Fig. 3. Conguration of the complete EtAc production process.

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

In addition, a part of distillation lines lies inside the forward


reaction region, which implies the reaction at the mentioned
conditions is feasible and can be evaluated.
2.3. Process simulation using HYSYS 3.1
The process is simulated using HYSYS 3.1 under license of
Hyprotech at National Iranian South Oil Company (NISOC). The
nonrandom two-liquid (NRTL) activity coefcient model is used for
the vaporliquidliquid equilibrium of the system. The owchart
for the system is shown in Fig. 3. In this system, most of the
esterication reaction is allowed to occur in the CSTR with about
65% conversion and the products are heated until the temperature
reach to 93 8C and then ow is fed to the RD. The lowest
temperature of azeotrope (No. 4) is drawn out from the top of the
RD column and bottom product is mainly water. The top products
are also fed to the rectier column for more purication. Now, the
heterogeneous azeotrope (No. 1) is formed in the top and
withdrawn from the rectier and enters to the decanter at
27 8C. In order to guarantee liquidsplitting, an additional fresh
water stream is injected into the decanter to achieve high-purity of
EtAc in the bottom of the decanter. After splitting phenomenon in
the decanter, the organic phase contains EtAc with composition of
85 mol% is fed into the stripper for further purication. The
aqueous phase contains water is returned to the rectier. The
bottom stream of rectier has a composition of azeotrope No. 3
that is recycled to the RD (rst column). Fig. 1c also shows the
behavior of bottom rectier stream.
The towers operate at atmospheric pressure and include 28, 22
and 15 stages with 50% efciency, respectively. It is worth
mentioning that the specications for run of the RD and rectier
columns are overhead rate and reboiler temperature with the
values of 3624 kg/h, 100 8C and 758 kg/h, 78 8C, respectively. The

0.71480
0.05680

0.99000
0.00912

main product of this conguration is highly pure EtAc with


conversion of 99.2 mol% from bottom of the stripper. The top
product of the stripper column is also returned to the decanter.
Note that sulfuric acid circulates in the RD due to its low
concentration. Unfortunately, NRTL model could not well predict
the liquidliquid equilibrium in the decanter and for this reason;
the thermodynamics model is changed to PengRobinson. Due to
such problems, HYSYS software was not used to simulate EtAc
process in the previous studies. The cutters shown in Fig. 3 indicate
the changing in liquidliquid equilibrium model. The input
information and simulation results as well as the experimental
results of Lai et al. [18] are listed in Table 2. From the table, it
reveals that the simulation results are in a good agreement with Lai
et al. [18] ndings.
3. Results and discussions
3.1. The known methods for RD simulation
To perform RD in the process simulators, there are seven well
known techniques, namely uh, NewtonRaphson, Simultaneous
correction by linearization, Insideoutside, Homotopy-continuation, Powells DoglegHomotopy and Newton Insideoutside. The
method of Insideoutside is imbedded in the Aspen Plus process
software. The process simulation software of HYSYS uses the
simultaneous correction by linearization and NewtonRaphson
techniques for RD, although the simultaneous correction method is
more favorable, wherein the equilibrium stage is assumed.
However, K-values, vapor and liquid enthalpies as well as the
rate equation are a function of temperature, pressure, and
compositions of the phases. For linearization it is assumed that
these parameters are only depend on the temperature, pressure,
and compositions of the liquid phase. Meanwhile, the existence of

Y. Tavan, S.H. Hosseini / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 577585

581

Fig. 4. The effect of EtOH ow rate on (a) reactor (b) reux ratio and (c) heat of columns.

reaction terms does not signicantly change the shape of MESH


(mass balance, equilibrium, summation and heat balance)
equations, but have a great effect on the equilibrium parameters.
3.2. Sensitivity analysis
Before performing sensitivity analysis, the consideration
is needed to keep the nal product stream (stream number
13 from Fig. 3) at industrial requirement (EtAc > 99.5 wt.%;
HAc < 0.01 wt.%; EtOH < 0.2 wt.%) [14]. The complete process
conguration is highly complex due to exhibiting multiple steady
states phenomenon and many factors (design and operation
variables) which inuence purity of EtAc. In this work, the effects of
RD trays, reactants rates and feed location on the RD column are
examined. Accordingly, the parameters are changed with variation
of 510% around their steady state point and the obtained results
are compared with the base simulation.
3.3. The effect of reactants (EtOH ow rate)
Fig. 4 shows the inuence of EtOH ow rate on conversion of
CSTR, reux ratio and heat of the columns. It is observed that a
change in the ow rate of EtOH stream from 7.47 to 9.13 kg mol/h
inuences on the process signicantly. Therefore, EtOH ow rate is
an important parameter in RD design. As shown in Fig. 4a, an
increase in EtOH ow rate leads to an increase in CSTR conversion.
Excess EtOH in the feed plays a key role in consumption of all the
acid and to meet the stringent acid specication for product. This
effect also causes producing more EtOH in stream nos. 6, 9 and
consequently alters in liquidliquid separation of the decanter. In
the decanter more water can be separated and recycled to the
rectier and RD columns, which changes mol fraction of the
components. However, from Fig. 5ad, which shows proles of
the components and temperature distributions in the columns, it is
observed that only water and EtOH components mostly are
affected by any change in EtOH ow rate and the other mol fraction
of the components almost remain constant.

As shown in Fig. 4b and c, the EtOH ow rate in steady state


point (EtOH ow rate of 8.30 kg mol/h, minimum point) leads to a
signicant reduction in energy consumption. However, by
increasing ow rate of EtOH more than the minimum point,
energy consumption increases due to presence of more products
such as water in the RD column, which conducts the reduction in
esterication reaction rate. Furthermore, the reux ratio increases
by increasing the ow rate of EtOH, resulting in rising RD column
duty.
It is noteworthy that RD reux ratio and total required heat of
the process (summation of all duties of reboilers and condensers in
the process) exhibit the same trend with increase of EtOH ow
rate. Therefore, RD reux ratio has a signicant impact on the
energy requirement; consequently in economical standpoint in
using the ow rate of EtOH, RD reux ratio should be evaluated.
Moreover, in SA, the operating line is approached to the azeotrope
that leads to the increase of required duty substantially for the RD
column more than the other columns duties.
With an exclusive attention to the RD reux ratio, it is found
that a minimum reux ratio is appeared in the economic EtOH ow
rate. Note that the main objective of using RD is crossing of
distillation boundaries such as equilibrium controlled reactions by
continuous product removal from the reaction mixture. Thus,
energy requirement in RD is a higher priority than conversion in
CSTR for choosing the optimum amount of EtOH ow rate. Hence,
the optimum amount of EtOH ow rate for a minimum total energy
demand (3.05  106 kcal/h) is 8.30 kg mol/h where the inlet ratio
of HAc/EtOH is nearly equal to stoichiometric ratio.
In addition, the temperature proles for the RD and rectier is
shown in Fig. 5e and f. It reveals that by increasing the EtOH ow
rate, the temperature of upper trays in the RD column decreases
which mostly is attributed to RD reux ratio. In the rectier
column, the temperature difference between trays is lower than
the corresponding term in RD column due to absence of reaction.
However, it is evident that temperature of inlet streams to the
rectier is nearly constant, but with increasing the EtOH ow rate,
the amount of returned water increases and to maintain

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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.

temperatures in the bottom and top of the rectier, the duties of


condenser and reboiler is altered (Fig. 4b and f). While,
temperature prole of the rectier column exhibits low sensitivity
to EtOH ow rate, the most sensitivity to change of EtOH ow rate
in the rectier is observed for the 5th stage. The temperatures of
stages 4, 5, and 6 in the RD column show more sensitivity to EtOH
ow rate among the others. In addition, the response of
temperature for stage 6 is faster than that of stages 4 and 5.
Besides, Lee et al. [14] choose the 4th tray of the RD column as the
most sensitive to temperature.
3.4. The effect of RD trays
It is worth mentioning that the effect of reux ratio in a RD is too
complex. Luo et al. [19] mentioned that reux ratio exhibits some
advantages and disadvantages. They observed that reux ratio not
only enhances the separation of the components, but also the
reaction by recycling the unconverted reactants to the reaction
zone. However, several negative effects can be endowed by
increasing the reux ratio [20].
The inuence of the stage number of the RD column is
investigated by xing the stage number of the rectier and stripper
columns. Figs. 6 and 7 show this matter. It is found that the number
of trays in the RD column is an important design parameter that
needs to be optimized. As can be seen in Fig. 6a, when the stage
number of the RD column rises from 27 to 31, RD reux ratio
diminishes signicantly from 2.81 to the minimum value of 1.03.
With further increase in the RD stage number, RD reux ratio
increases to 1.35 due to the increase of residence time. It should be
noted that with enhancement of the RD stage number, residence

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.

time and reaction conversion increase and more water produces


through esterication reaction which causes more energy consumption.
Fig. 7a and b shows the effects of RD tray number on water and
EtOH mol fractions in RD column. It is seen, an increase in the
RD stage number causes a decrease in amount of water in the RD
column due to the low reux ratio. As mentioned previously, RD
reux ratio has a direct inuence on the energy requirement,
which is also seen in Fig. 6b. Therefore, the optimum number of
stages for the RD column is 29.
Fig. 7c and d shows the temperature proles of the RD and
rectier columns respect to the base simulation (RD stages equal to
28). It reveals that the number of trays in the RD column has a small
effect on the rectier composition and temperature prole.
Although the rise of RD stage number decreases the temperature
prole and increases the residence time, it raises the cost of RD
process. It is noteworthy that the most sensitive to change of the
stage number of the RD column is mostly observed for stages 3, 4
and 5 in the RD column. Therefore, the temperature of stage 4
should be used for temperature control loop, which is in good
agreement with Lee et al. [14] ndings.

close to reboiler (high temperature in the RD column) and ejected


water stream from the RD column. In addition, lower position of RD
feed inlet increases outlet water ow rate from the RD column,
which causes reduction in the overhead vapor stream. In the RD

3.5. The effect of feed inlet stage to rd column


Another dominant parameter for design of highly pure EtAc is
the feed inlet stage of the RD column. As shown in Fig. 8, the
location of the feed inlet strongly affects on the required energy,
the RD reux ratio, and duties. In the present study, the steady
state RD feed inlet stage is 4th stage from top and sensitivity
analysis is conducted to change RD feed inlet location from steady
sate feed stage to 2, 3 and 6 stages. As can be seen, when the RD
feed inlet stage is changed, the reux ratio alters. From the
previous discussion, by changing RD reux ratio the amount of
required energy changes, signicantly. When RD feed inlet location
is shifted to lower section of the column, simulation results show
that RD reux ratio diminishes due to the feed inlet location more

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.

column the specications are reboiler temperature and overhead


rate. Therefore, the RD feed inlet located in the lower portions
causes a decrease in overhead vapor stream and consequently a
decrease in RD reux ratio.
As mentioned earlier, the RD reux ratio has a direct effect on
the required amount of energy in the system. Therefore, more
ejected water from bottom of the RD column and low reux ratio
lead to decrease in energy demand for the process. The minimum
values for the RD reux ratio (0.62) and energy demand
(2.72  106 kcal/h) are found when the RD feed inlet is located
at stage number of 6 from the top of RD column.
Fig. 9a and b indicates water and EtOH compositions along the
RD column. It is evident that by shifting the RD feed inlet location
to the lower portions, the water mol fraction decreases which
attributes to further ejection of the water from bottom of the RD
column.
The temperature prole in the RD and the rectier columns for
studying location of feed inlet stage are shown in Fig. 9c and d.
Though, changing in location of the RD feed inlet has a small effect
on the rectier column performance, it has a remarkable inuence
on the upper trays of the RD column. A rise in the RD feed inlet
location leads to a decrease in the temperature of upper trays
because of decreasing the vapor phase in the RD column. It can also
be seen the peak of maximum difference in the temperature of
trays relevant to steady state point is shifted to the bottom of the
RD column. The results of changing the RD feed inlet location show
that appropriate feed inlet stage is related to 6th stage from top of
the RD column. Also, the most sensitive to change of the location of
RD feed inlet is found at 4th stage from top of the RD column which
is shown in Fig. 9.

increase of the RD stage number led to the increase of residence


time and reaction conversion wherein more water produced
through esterication reaction which caused more energy
consumption. It was also found that the feed inlet location has
an important effect on the required energy, the RD reux ratio, and
the columns duties.
It was revealed that water and ethanol components in the
system are strongly affected by any change in the system. In
addition, the proles of compositions and temperature in the
rectier column almost remained constant with change in the
operating and design parameters. Furthermore, the model showed
that the reux ratio in the reaction zone (RD column) has a critical
impact on the required energy in the process and to optimize
operating condition, this parameter should be evaluated because
reux ratio plays a multifunctional role in the reaction zone (RD
column). It was shown that the reux ratio inuences on the
column specication and produces water from the RD column.
Furthermore, the feasibility of using the HYSYS 3.1 process
software for reactive distillation process was revealed. The HYSYS
3.1 suffers from appropriate thermodynamic model to predict the
liquidliquid separations. For overcoming this problem, a combination of two thermodynamic models namely, NRTL and Peng
Robinson was used in the present study.
Acknowledgement
The author would like to thank Dr. Masoud Beheshti for
providing data.
References

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

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