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Sensitivity Analysis of Steady-State Methyl

Acetate Synthesis Reactive Distillation


Column Using Aspen Plus
Dipaloy Datta* and Dipesh S Patle**

In chemical processing, simultaneous reaction and separation of the product help to


increase conversion rate and productivity, and saves material handling and processing
costs. In this study, a sensitivity analysis of heterogeneous Reactive Distillation (RD)
using Aspen Plus was carried out to understand the complex behavior of a reactive
distillation column. The esterification reaction of methanol by acetic acid to form
methyl acetate was considered for the sensitivity analysis. The steady state results
were validated with the experimental results reported by Popken et al. (2001).
Considering these steady state results as reference, sensitivity analysis was done.
In the simulation, RADFRAC model was chosen to take care of the complexities
arising due to simultaneous reaction and separation in a single unit. UNIQUAC
property method was selected in the simulator for equilibrium calculations.
Keywords: Reactive distillation (RD), RADFRAC, UNIQUAC, Sensitivity analysis, Aspen Plus

Introduction
Reactive Distillation (RD) is a combination of reaction and distillation in a single unit having
a number of specific advantages over conventional sequential approach of reaction followed by
distillation or any other separation techniques. The combined effect of reaction and separation
increases the selectivity of the product and enhances the conversion of the reactant. The RD
unit provides better control and proper utilization of reaction heat. Moreover, easier separation
of the components can be achieved and formation of azeotropes can be avoided in the RD
column. The complex behavior of the RD column arises because of the complicated vaporliquid interactions, mass transfer between solid, liquid and vapor phases, intra-particle (catalyst)
diffusion in the case of catalyzed reactions, and reaction kinetics involved with separation.
Therefore, such kinds of multi directional interactions in the RD system lead to multiple
steady-states and complex dynamics (Taylor and Krishna, 2000).
Therefore, to understand the complete behavior of the simultaneous reaction and
separation process, research on various fields, like modeling and simulation, process synthesis,
*

Lecturer, Chemical Engineering Group, Birla Institute of Technology and Science (BITS) Pilani, Pilani 333031,
Rajasthan, India; and is the corresponding author. E-mail: dipaloy@bits-pilani.ac.in

* * Lecturer, Chemical Engineering Group, Birla Institute of Technology and Science (BITS) Pilani, Pilani 333031,
Rajasthan, India. E-mail: dipeshp@bits-pilani.ac.in
24
2010 IUP. All Rights Reserved.

The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

column design, nonlinear Vapor-Liquid Equilibrium (VLE) behavior, and development of


control strategy, has been on. But the feasibility of the RD process for a particular reaction
may depend upon some of the important factors like relative volatilities of the components
involved in the reaction, column and reaction temperature, pressure, optimum reflux ratio,
etc. Hence, RD may not always be the choice for every chemical reaction. Hence, substantial
consideration to enlarge the domain of research on RD processes is required.
RD is a useful method to recover the product from reactant in the case of equilibriumlimited reactions like esterification and ester hydrolysis. RD can also be used with a wide
variety of reactions, including acetylation, aldol condensation, alkylation, amination,
dehydration, etherification, isomerization, oligomerization and trans-esterification. By this
method, because of the continuous separation of reaction products from the reactive section,
conversion rates can be increased far beyond the levels achieved in equilibrium-limited
reactions. As both the unit process and unit operation are carried out in a single column,
there is a reduction of capital and investment costs and may lead to sustainable improvement
in utilization of the resources.
RD experiments were performed for the synthesis and hydrolysis for methyl acetate using
the structured catalytic packing Katapak-S with an acidic ion-exchange resin (Amberlyst
15) as the heterogeneous catalyst. The reaction kinetics and chemical equilibrium were also
investigated. This system is of major importance as a model reaction for RD (Popken et al.,
2000 and 2001).
A nonlinear dynamic behavior of RD columns for the production of MTBE (Methyl
Tertiary Butyl Ether) and TAME (Tert-Amyl Methyl Ether) was studied. The focus was on
steady-state multiplicity. A rigorous bifurcation analysis of pilot plant RD columns for both
processes was presented (Mohl et al., 1999).
Yang et al. (2006) modeled RD processes for synthesis of ethylene glycol and ethyl tertbutyl ether with the simulation package, Aspen Plus. For both the synthesis processes, using
the method of sensitivity analysis, the input and output multiplicity was discussed. The
steady-state multiplicities were explained in terms of effective liquid hold-up volume and
boil-up ratio for the synthesis of ethylene glycol process. In the case of ethyl tert-butyl ether
production process, the composition, temperature and reaction-rate profiles within the RD
column were studied with the help of the user kinetic subroutine in the Aspen Plus and the
input multiplicities observed for a range of reboiler duty at several values of reflux ratio. They
also suggested that the study helped to arrive at the optimum design of the RD column and to
reduce the energy consumption in the process.
A comparison of computer simulation results of RD obtained by Aspen Plus and Hysys
software was carried out by Smejkal and Soos (2002) for the esterification of acetic acid, and
1-butanol was chosen as the model reaction, proceeding in a reactor and RD column system.
The simulated results were comparable with the experimental data generated by the pilot plant.
Kumar and Mahajani (2007) reported the study of esterification of lactic acid with
n-butanol in continuous RD. They used Aspen Plus steady-state simulator with the
Sensitivity Analysis of Steady-State Methyl Acetate Synthesis
Reactive Distillation Column Using Aspen Plus

25

RADFRAC module, which has a rigorous model for carrying out equilibrium-stage modeling,
for the simulation. Further, the effects of operating parameters like feed mole ratio, catalyst
loading, and boil-up rate were evaluated on the conversion of lactic acid in batch RD.
Experimental results of the continuous RD were also compared with the simulation results
observed using the Aspen Plus process simulator.
Filipe et al. (2008) addressed, in their work, the multi-objective design of complex RD
columns through the use of feasible regions. A cost indicator reflecting energy usage and
column size was introduced and used to build the Pareto surface describing the optimal
combinations of cost and performance. They included the use of superheated and subcooled
feed streams and found out the optimal distribution of feeds and catalyst inside the column.
The best tradeoff solutions for each system were identified, the operating conditions analyzed,
and a selected number of cases were further investigated using rigorous simulation in Aspen
Plus.
Kolah et al. (2008) proposed a continuous RD process for the synthesis of tri-ethyl citrate
from citric acid and ethanol in the presence of macroporous Amberlyst 15 ion-exchange
resin catalyst. From the laboratory kinetic and thermodynamic studies and pilot scale RD
experiments, the process design was developed and the catalyst effectiveness was determined
using Aspen Plus simulation software. Further, the effect of ethanol feed position and values
of reflux and boil-up ratios were also examined.
Luo et al. (2009) proposed a reactor design for the direct preparation of di-chloropropanol
from glycerol. To study the optimum design considerations, the chlorination reaction of
glycerol was carried out in an RD column. For the optimization study in the RD column,
Aspen Plus simulator was used. The group also studied the effect of reflux ratio, material mole
ratio, feed stage position, distillation rate and residence time on the yield and mole fraction
of the di-chloropropanol produced in the distillate. On the basis of the pilot plant data and
simulated results from Aspen Plus, a new technology of di-chloro-propanol production was
proposed.

2. Simulation Study
The present work deals with simulation and sensitivity analysis of RD column. Esterification
of methanol by acetic acid is taken up to perform the study. The data was taken from the
experimental results performed by Popken et al. (2001) for run number S-1 of the methyl
acetate synthesis using the two-feed setup. The RADFRAC model from the steady-state
simulator, Aspen Plus, version 20.1 was considered to simulate the process. The RADFRAC
model is based on a rigorous equilibrium-stage model for solving the MESH (material balance,
vapor-liquid equilibrium, mole fraction summations and heat balance) equations. The model
is both rigorous enough to represent the process complexity and simple enough to ensure
feasibility of the process simulation.
The Aspen Plus, sequential modular simulator, contains an extensive model library that
allows most unit operations to be simulated easily and accurately. The vapor-liquid equilibrium
calculations are taken care of by selecting the UNIQUAC property method from the simulator
26

The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

(Aspen Tech Inc., 2006). The feed conditions and column specification are shown in
Figure 1. The stages are numbered from top of the RD column (condenser, stage 1) to the
bottom (reboiler, stage 25).
Figure 1: Reactive Distillation Column for the Production of Methyl Acetate (MeOAc)

Acetic Acid (99.5%) Feed


T = 21.1 C , P = 1017 mbar
Flow Rate = 30.80 mol/h
Feed Stage = 6

L/D = 2.1
Methyl Acetate (99.05%)
D = 30.10 mol/h

Rectifying Section
(Stage 2-10, BX Packing)
10
11
Reactive Section
(Stage 11-19, KERAPAK Packing)
Methanol (99.5 %) Feed
T = 20.1 C, P = 1017 mbar
Flow Rate = 32.20 mol/h
Feed Stage = 19

19
20
Stripping Section
(Stage 20-24, BX Packing)
24
25
Water (90.78%)
B = 32.90 mol/h

The reaction for the production of methyl acetate from acetic acid and methanol
esterification is given by Equation (1).
CH3COOH + CH3OH CH3COOCH3 + H2O
(Ac)

(MeOH)

(MeOAc)

(H2O)

...(1)

The rate of formation of methyl acetate is described by Equation (2), and the corresponding
forward and backward rate constants are given by Equations (3) and (4).

r k f Ac MeOH k b MeOAc H 2O

1 1
k f 29610 mol g cat
s * exp 49190 Jmol 1 / RT

...(2)

1 1
k b 134800 mol g cat
s * exp 69230 Jmol 1 / RT

Sensitivity Analysis of Steady-State Methyl Acetate Synthesis


Reactive Distillation Column Using Aspen Plus

...(3)

...(4)
27

3. Results and Discussion


The steady-state simulated results are shown in Table 1 and compared with the experimental
results obtained by Popken et al. (2001). The results from simulation are in good agreement
with the experimental results. The mole fraction of MeOAc in the distillate is found to be
0.991 (experimental 0.877). This difference may be due to some kind of wastage/leakage in
the experimental setup of the distillation column. Again, the reboiler duty is found to be
592.1 W from the simulation, compared with 1105 W obtained experimentally. The
discrepancy may be attributed to the heat loss from the reboiler in the actual experiment.
Table 1: Comparison of Simulated Results with Experimental Results
(Run Number S-1 of the Two Feed Setup of Methyl Acetate Synthesis)
Popken et al.
(2001)

Popken et al.
(2001)

Present Study

Distillate Mole Fraction

Present Study

Bottoms Mole Fraction

MeOAc

0.877

0.991

0.002

0.000

Ac

0.000

0.000

0.104

0.025

MeOH

0.107

0.000

0.070

0.067

H2O

0.016

0.009

0.824

0.908

54.900

54.180

91.700

91.130

1105.000

592.100

87.600

93.060

Temperature (C)
Reboiler Duty (W)
Conversion (%X)

Figures 2, 3 and 4 show the steady-state liquid phase composition, temperature and liquidvapor flow rate profiles along the length of the column.
Figure 2: Steady-State Liquid Phase Composition Profiles for the Synthesis of Methyl Acetate

Liquid Phase Mole Fraction

1.0
0.8
0.6
0.4

0.2
0.1

28

MeOH
CH3COOH
MeOAc
H2 O

18
9
12
15
Theoretical Stage Numbers

21

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The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

Figure 3: Steady-State Temperature Profile for the Synthesis of Methyl Acetate


95
90

Temperature (C)

85
80
75
70
65
60
55
50

10
20
15
Theoretical Stage Numbers

25

Figure 4: Steady-State Liquid and Vapor Flow Rate Profiles for the
Synthesis of Methyl Acetate
100

Flow Rate (mol/h)

80
60
40
20
0

Liquid Flow Rate


Vapor Flow Rate
3

20
10
15
Theoretical Stage Numbers

25

In Figure 5, Txy diagrams for MeOAc/Ac, MeOAc/MeOH and MeOAc/H2O are shown at
1 atm pressure. Methyl acetate (b.p. = 56.3 C) and methanol (b.p.= 64.5 C) form a binary
azeotrope boiling at 54 C with 81.3 wt% methyl acetate and 18.7 wt% methanol. Methyl
acetate also forms a binary azeotrope with water which boils at 56.1 C with 95 wt% methyl
acetate.
Generally, methyl acetate, methanol and water do not constitute a ternary azeotropic
mixture. But in the rectification zone, methyl acetate, water, acetic acid and methanol mixture
form lowest boiling constituent, the methyl acetate-methanol azeotrope. Hence, it is a tedious
Sensitivity Analysis of Steady-State Methyl Acetate Synthesis
Reactive Distillation Column Using Aspen Plus

29

Figure 5: Txy Plots for (a) MeOAc/Ac


120

T-x 1 atm
T-y 1 atm

110

Temperature (C)

100
90
80
70
60
50
0.0

0.2

0.4

0.6

0.8

1.0

Liquid/Vapor Mole Fraction of MeOAc

(b) MeOAc/MeOH
66

T-x 1 atm
T-y 1 atm

64

Temperature (C)

62
60
58
56
54
0.0

0.2
0.4
0.6
0.8
Liquid/Vapor Mole Fraction of MeOAc

1.0

task to separate out methyl acetate from methanol mixture by rectification, as the lowest
boiling azeotrope will always come off the overhead as the initial product. Any mixture of
methyl acetate and methanol subjected to rectification at one atmosphere pressure will produce
an overhead product boiling at 54 C. But the steady-state temperature profile in Figure 3
shows that the reactive zone temperature varied in the range of 64 to 71 C, which confirms
that there will not be any formation of methyl acetate and methanol azeotrope as soon as the
product methyl acetate is formed. Hence, the simultaneous reaction and separation of the
product in an RD column help overcome this problem.
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The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

Figure 5 (Cont.)
(c) MeOAc/H2O at 1017 mbar
100

T-x 1 atm
T-y 1 atm

Temperature (C)

90
80
70

60

50

0.0

0.2

0.4

0.6

0.8

1.0

Liquid/Vapor Mole Fraction of MeOAc

3.1 Effect of the Molar Reflux Ratio


The effect of molar reflux ratio is illustrated in Figure 6. Initially, increase in reflux ratio
increases the mole fraction of MeOAc in the product and then decreases. The maximum
mole fraction of MeOAc was found to be 0.991 at reflux ratio of 2.1. However, the low value
of the reflux ratio leads to insufficient product separation and builds up the amount of
Figure 6: Effect of Molar Reflux Ratio on the MeOAc Mole Fraction in the Distillate
and on Reboiler Duty
3,000

0.9
0.8

2,000

0.7
1,000

0.6

Reboiler Duty (W)

Mole Fraction of MeOAc in the Distillate

1.0

0.5
0.4
0

0
10

Molar Reflux Ratio

Sensitivity Analysis of Steady-State Methyl Acetate Synthesis


Reactive Distillation Column Using Aspen Plus

31

reactants or by-products in the distillate, which limits the conversion of acetic acid and
methanol into methyl acetate. In addition, at a high reflux ratio, the reactants are separated,
which effectively limits the conversion of reactants. Again, the increase in the reflux ratio
increases the heat load on the reboiler, but at the cost of product purity in the distillate.
Hence, there is a tradeoff between the desired purity of the product and reboiler duty. Reflux
ratio has to be selected in such a way that higher mole fraction is achieved at a low consumption
of heat duty in the reboiler.

3.2 Effect of the Feed Stage Position


The product quality depends on the performance of the reaction zone in the RD column as
well as the position of the feed stage. Again, the feed stage position affects the performance of
the reaction section, as the reactants should come in proper contact with each other to form
the product. The effect of feed stage position on the mole fraction of MeOAc in the distillate
is shown in Figure 7.
Figure 7: Effect of Feed Stage Position on MeOAc Mole Fraction in the Distillate

MeOAc Mole Fraction Distillate

1.0

0.9

0.8

0.7

Ac Feed Stage
MeOH Feed Stage

0.6
6

10

12

14

16

18

20

Feed Stage

It is observed from the figure that when the reactants were introduced into the reactive
region of the RD column, a relatively low mole fraction of the MeOAc was obtained in the
distillate. The product purity would increase when the feed location was above or below the
reaction section of the RD column. Also, when the lower boiling reactant (MeOH) was
introduced from the top of the column, it produced a low amount of MeOAc in the distillate.
The figure shows that the optimal feed position is 6th for acetic acid and 19th for methanol,
which is also validating the experimental setup.

3.3 Effect of the Distillation Rate


The relationship of the distillation rate with the mole fraction of MeOAc is illustrated in
Figure 8. It is observed from the figure that with the increase of the distillation rate, the mole
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The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

fraction of MeOAc in the distillate increases initially and after that decreases. The mole
fraction of MeOAc in the distillate was 0.99523 at a distillate rate of 19 mol/h.
Figure 8: Effect of Distillate Rate on MeOAc Mole Fraction in the Distillate

MeOAc Mole Fraction in Distillate

1.0
0.9
0.8
0.7
0.6
0.5
0.4

10

40
20
30
Distillate Rate (mol/h)

50

60

3.4 Effect of Molar Reflux Ratio on Stage Temperature


The effect of reflux ratio on the stage temperature is shown in Figure 9. It is observed that at
relatively low reflux ratio, the reactive zone temperature rises and at high reflux ratio the
reaction zone temperature drops. At moderately low and high reflux ratio, the mole fraction
of MeOAc in the distillate decreases. This is because the increase in temperature in the
reaction zone enhances the backward reaction rate, and fall of temperature decreases the
forward reaction rate.
Figure 9: Effect of Molar Reflux Ratio on Stage Temperature

80

Temperature ( C)

90

70

60

50

RR=2.0
RR=2.1
RR=3.0
5

10

15

20

25

Theoretical Stage Numbers


Sensitivity Analysis of Steady-State Methyl Acetate Synthesis
Reactive Distillation Column Using Aspen Plus

33

Conclusion
Sensitivity analysis of esterification reaction of acetic acid and methanol to form methyl
acetate in an RD column was carried out. The effect of operating parameters on the
performance of the column was also analyzed using Aspen Plus simulator. In the simulator,
RADFRAC model was considered to handle the complexities arising from the simultaneous
reaction and separation in a single unit. The UNIQUAC property method was selected to
take care of the equilibrium calculations. It was observed that to get total conversion of the
reactants into product and better separation of the product, optimized design variables
have to be considered. A higher reflux ratio may give higher purity of the product but at
the cost of total reboiler duty and low mole fraction of MeOAc in the distillate. The reflux
ratio may also affect the stage temperature abruptly, which would limit the reactant
conversion into product. A proper selection of the feed stage position is also a key parameter
in the design of RD column, as it would decide appropriate distribution of the reactants
into the column and confirm better interaction of acetic acid and methanol to form methyl
acetate.

References
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The IUP Journal of Science & Technology, Vol. 6, No. 3, 2010

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Sensitivity Analysis of Steady-State Methyl Acetate Synthesis


Reactive Distillation Column Using Aspen Plus

35

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