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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
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2010 IUP. All Rights Reserved.
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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
(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)
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
...(3)
...(4)
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Popken et al.
(2001)
Present Study
Present Study
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
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
24
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
80
60
40
20
0
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
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
(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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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
0.9
0.8
2,000
0.7
1,000
0.6
1.0
0.5
0.4
0
0
10
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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.
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.
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
1.0
0.9
0.8
0.7
0.6
0.5
0.4
10
40
20
30
Distillate Rate (mol/h)
50
60
80
Temperature ( C)
90
70
60
50
RR=2.0
RR=2.1
RR=3.0
5
10
15
20
25
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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
1. Aspen Technologies Inc. (2006), Aspen Custom Modeller, Version 20.1, Aspen Plus,
Cambridge, MA.
2. Filipe R M, Turnberg S, Hauan S, Matos H A and Novais A Q (2008), Multi-Objective
Design of Reactive Distillation with Feasible Regions, Industrial Engineering and Chemistry
Research, Vol. 47, No. 19, pp. 7284-7293.
3. Kolah A K, Asthana N S, Dung T V, Carl T L and Miller D J (2008), Triethyl Citrate
Synthesis by Reactive Distillation, Industrial Engineering and Chemistry Research, Vol. 47,
No. 4, pp. 1017-1025.
4. Kumar R and Mahajani S M (2007), Esterification of Lactic Acid with n-Butanol by
Reactive Distillation, Industrial Engineering and Chemistry Research, Vol. 46, No. 21,
pp. 6873-6882.
5. Luo Z H, You X Z and Zhong J (2009), Design of a Reactive Distillation Column for
Direct Preparation of Dichloropropanol from Glycerol, Industrial Engineering and
Chemistry Research, Vol. 48, No. 24, pp. 10779-10787.
6. Mohl K D, Kienle A, Gilles E D et al. (1999), Steady-State Multiplicities in Reactive
Distillation Columns for the Production of Fuel Ethers MTBE and TAME: Theoretical
Analysis and Experimental Verification, Chemical Engineering Science, Vol. 54 No. 8,
pp. 1029-1043.
7. Popken T L, Gotze and Gmehling J (2000), Reaction Kinetics and Chemical Equilibrium
of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with
Methanol and Methyl Acetate Hydrolysis, Industrial Engineering and Chemistry Research,
Vol. 39, No. 7, pp. 2601-2611.
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