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Modeling and simulation for reactive distillation


process using Aspen Plus

Conference Paper · January 2010

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National Symposium on Reaction Engineering, (NSRE), 22-23 Jan, 2010

Modeling and simulation for reactive distillation process


using aspen plus
Kiran D.Patil a*and Bhaskar D. Kulkarni b
a
Department of Petrochemical and Petroleum Engineering, MAEER’S, Maharashtra
Institute of Technology, Paud Road, Pune-411 038
b
Chemical and Process Engineering Division, National Chemical Laboratory,
Pune-411 008
* Corresponding author: kiranpatil@mitpune.com

Abstract
Reactive Distillation (RD) is a combination of reaction and distillation in a single vessel
owing to which it enjoys a number of specific advantages over conventional sequential
approach of reaction followed by distillation. Improved selectivity, increased conversion,
better heat control, effective utilization of reaction heat, scope for difficult separations
and the avoidance of azeotropes are the few of the advantages offered by RD. This paper
describes an investigation into modelling and simulation work of the heterogeneous
esterification of acetic acid with Isoamyl alcohol, catalyzed by an acidic cation –
exchange resin. The simulations are based on the equilibrium-stage (EQ model)
approach and, for comparison; a Non-equilibrium model (NEQ model) is also used. This
paper addresses the development of a satisfactory steady state model for RD, which
requires attention considering the fundamental behavior of the system, including the
reaction and phase behavior, together with the principles behind the equilibrium stage
model for distillation operations. The full RD column model is presented and then
applied to simulation of Isoamyl acetate column where experimental data is available.
Once the model is developed and validated, it was used to study the behavior of RD. The
simulation studies were performed in Aspen Plus® and MATLAB. The reaction kinetics
developed by us in laboratory batch reactor and the published experimental data on phase
equilibrium are used to verify the model predictions and were found to be close to those
available in the literature. The effects of the variables such as the reflux ratio, boil up
ratio, feed flow rate and feed plate locations etc are important in RD process. Therefore
the results of sensitivity studies for these variables are discussed using Aspen Plus® to
see the optimum performance of RD column.
Keywords: Reactive distillation, esterification, EQ and NEQ model, Aspen Plus
simulation, reaction kinetics, model prediction, sensitivity studies

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1. Introduction
Reactive distillation (RD) is a combination of reaction and distillation in a single vessel
owing to which it enjoys a number of specific advantages over conventional sequential
approach of reaction followed by distillation or other separation techniques. Improved
selectivity, increased conversion, better heat control, effective utilization of reaction heat,
scope for difficult separations and the avoidance of azeotropes are a few of the
advantages that are offered by RD [1].

The introduction of an in situ separation process in the reaction zone or vice versa
leads to complex interactions between vapor–liquid equilibrium, mass transfer rates,
diffusion and chemical kinetics, which poses a great challenge for design and synthesis
of these systems [2]. RD being a relatively new field, research on various aspects such as
modeling and simulation, process synthesis, column hardware design, non-linear
dynamics and control is in progress. The suitability of RD for a particular reaction
depends on various factors such as volatilities of reactants and products along with the
feasible reaction and distillation temperature [3]. Hence, the use of RD for every reaction
may not be feasible. Exploring the candidate reactions for RD, itself is an area that needs
considerable attention to expand the domain of RD processes.
Esterification (e.g. synthesis of iso- amyl acetate/ n-hexyl acetate) has been the
model reaction for the research studies in reactive distillation. Reaction of acetic acid
with higher alcohols falls in a category of typical class of reacting systems. The alcohol
is sparingly soluble in water and esters and water are almost immiscible. An additional
feature is that the ester-water-alcohol forms a ternary heterogeneous azeotrope, which is
minimum boiling. Hence, the vapors at the top condense to form two liquid phases of
which aqueous phase is almost pure water. One can conveniently separate water and
enhance the conversion [4] The esterification of acetic acid with alcohols like n-butanol,
ethanol, isobutyl alcohol, amyl alcohol and hexyl alcohol fall in a typical class of
reacting systems. Iso amyl acetate has been used in the industry as a solvent, and
extractants, and polishing agent. It is used as artificial flavoring in banana-flavored
bubble gums, as preservative in sodas and soft drinks as well as artificial scent for
covering unpleasant odors [5].

In this paper, simulation studies for esterification reaction of acetic acid with
Isoamyl alcohol using MATLAB and Aspen Plus® were presented.

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2. Synthesis of Iso Amyl Acetate via Reactive Distillation


It can be synthesized from acetic acid and amyl alcohol via esterification reaction as
follows
k
CH 3 - COOH + C5 H11 - OH ←→ C5H11 - COO - CH 3 + H 2O (1)
(Acetic acid) (Iso amyl alcohol) (Iso amyl acetate) (Water)

H 2O CH 3COOH C5 H11 - OH C5 H11 − COO - CH 3 (2)


(100oC) (118oC) (137.8oC) ( 148.8oC)

Since the self-catalyzed reaction is rather slow, reaction (1) is commonly


catalyzed using strong inorganic acid, like sulfuric acid, or strongly acidic ion exchange
resins. Most of previous researcher used acidic cation exchange resin, for example
Amberlyst 15 [1], Purolite CT- 175 [6].

2.1 Why RD?


The two reactants, acetic acid and amyl alcohol, are intermediate boilers, whereas the
products, water and Isoamyl acetate, are low and high boilers respectively. As Isoamyl
acetate and water are the heaviest and lightest boiling substances respectively in the
quaternary system, they can be continuously removed from the reaction zone in a RD
column so that high conversions can be achieved, thus RD an attractive process for
producing iso-amyl acetate. That’s why reactions (1) are well suited for reactive
distillation. However, the large boiling temperature difference between the reactants can
be unfavorable from the reactions point of view.

3. Mathematical Modeling
The esterification of acetic acid (with Isoamyl alcohol) is considered inside a RD
column. The column has a total condenser and a reboiler. The theoretical stages are
numbered from top to bottom. The condenser is represented by stage 1 and reboiler is
represented by stage 27. The equilibrium reaction is given by equation(1) as above.
3.1 Model assumptions

The various assumptions made during the development of model were as follows:
1. The vapor and liquid on each plate and leaving on each plate are perfectly mixed.
Moreover, the liquid on the plate has the same compositions as the liquid leaving
the plate.
2. Constant molar liquid holdup is assumed for each stage.
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3. Molar vapor holdup is negligible in comparison with the molar liquid holdup.
4. Simple or complex reaction(s) proceed only in the liquid phase and their rate can
be described by an appropriate kinetic expression(s). (Preferably second order
reaction kinetics)
5. The liquid phase is in equilibrium with the vapor phase leaving the plate.
6. Phase splitting is considered only in the decanter; liquid-liquid splitting inside the
column is neglected.
7. The reactive zone is considered to be a multistage column with six theoretical
stages per meter for KATAMAX catalyst packing (Saha et.al, 2005)
8. The nonreactive zone is considered to be multistage column with 22 stages per
meter for PRO-PAK packing
9. The pressure decrease along the column height is assumed to be negligible.
The third assumption about the vapor holdup is reasonable since the column
works under atmospheric pressure. In such conditions, liquid density is much higher than
vapor density. The first assumption is reasonable for small and medium diameter
columns in which the liquid on the plates is well mixed by the flowing vapor phase.
However, this assumption is not valid, in case of large diameter columns and a more
rigorous model of mixing on plates has to be applied.

The assumptions above lead to a model that consists of a set of ordinary


differential and algebraic equations (DAE’s). From the mass and energy dynamic
balances on the jth plate according to Figure 1 and Figure 2, the model is derived as
follows:

The Mass balance of component i around plate j is given by:


d(x i, jM j )
= Vj + 1yi, j + 1 − L jx i, j + L j − 1x i, j − 1 − Vjyi, j + ∆R i, j (3)
dt
dx i, j dM j
+ Mj + x i, j = Vj + 1yi, j + 1 − L jx i, j + L j − 1x i, j − 1 − Vjyi, j + ∆R i, j (4)
dt dt
This is combined with overall mass balance around plate J:
dM j
= Vj+1 − L j + L j−1 − Vj + ∆R j (5)
dt
The subscripts “ i ” range in value from 1 to the number of components in the mixture.
The subscripts j ranges in value from 1 to the number of plates, N.
The Equilibrium equation:
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yi, j = K i, jx i, j (6)

Where K= equilibrium constant


d(x i, j )
M j = Vj + 1K i, j + 1x i, j + 1 − L jx i, j + L j − 1x i, j − 1 − V jK i, jx i, j + ∆R i, j −
dt (7)
(Vj + 1 − L j + L j − 1 − V j + ∆R j )x i, j

The Energy balance equation around the plate j is given by:


d(Hi, jM j )
= Vj + 1h i, j + 1 − L jHi, j + L j − 1Hi, j − 1 − Vjh i, j (8)
dt
dHi, j dM j
Mj + Hi, j = Vj + 1h i, j + 1 − L jHi, j + L j − 1Hi, j − 1 − Vjh i, j (9)
dt dt
This is combined with overall energy balance around plate J:
dHi, j
M j = V j + 1h i, j + 1 − L jHi, j + L j − 1H i, j − 1 − V jh i, j −
dt (10)
(Vj + 1 − L j + L j − 1 − V j + ∆R j ) + Hi, j

These equations are coupled with algebraic equations for reaction kinetics and vapor-
liquid equilibrium.

4. Phase Equilibria and Reaction Kinetics Data


The two reactants, acetic acid and 1-pentanol, are intermediate boilers, whereas the
products, water and amyl acetate, are the low and high boilers, respectively. The
nonrandom two-liquid (NRTL) activity coefficient model was used for the vapor-liquid-
liquid equilibrium. (VLLE) for the quaternary system containing acetic acid, Isoamyl
alcohol, amyl acetate, and water [1]. Vapor liquid equilibrium (VLE) data are available
for all of the binary pairs, and liquid-liquid equilibrium (LLE) data for two ternary
systems (acetic acid- Isoamyl alcohol, water and acetic acid-Isoamyl acetate-water) [7]
Reaction kinetics is developed and VLE data available in literature is used to predict the
RD column performance and verify the model predictions.
The kinetic expressions and other data is used for simulation work is given below:
r = ( k f C CH 3COOH .C C5 H11OH − k b C C 5H11COOCH 3 .C H 2 0 ) (11)

The reaction kinetics results are presented in Table 1.

5. Solutions of Model Equations

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The model equations form a mixed set of set of ordinary differential equations (ODE’s)
and algebraic equations. The equations for 27 stages for the system and four-component
system can be solved in MATLAB by ODE 15 S solver (which is an ordinary differential
and algebraic equation (DAE) solver for stiff equations, variable order method) and
using Aspen plus simulation. In Figure 3 process flow sheet for Isoamyl acetate synthesis
in Aspen Environment is presented.
Base specification in Aspen Plus Simulation taken was:
Molar flow rates:
Feed 1 1096 mol/sec
Feed 2 1985 mol/sec
(HOAC 35.6%, ISAMOH 64.4%)
Pressure 1 atm
Number of stages 27
Reactive zone 13-18
Feed stage location
Feed 1 13
Feed 2 28

6. Results and Discussion


The Figure 4 and 5 shows comparison of typical composition profiles obtained by
MATLAB and Aspen plus.

The Figure 6 (a) and (b) shows the comparison of temperature and composition
profiles obtained by simulation using Aspen plus and our own experimental results
conducted in Laboratory cum pilot scale RD column. (Run No. 5). (a) Steady State
Temperature Profile (b) Steady State Composition Profile
As can be seen from the simulation results as shown in Figure 4 and 5,
conversion of 99.5% of isoamyl acetate, with iso amyl acetate purities of 88.4 %was
achieved. The extremely low concentration of water in the reactive zone helps reaction to
proceed near completion. The composition at position 7 comprises of two phases viz.
organic and aqueous phase. In all the runs, the temperature in reactive zone is in the
range of 120-130oC. Sufficiently high temperature ensure reaction to be at the chemical
equilibrium and driven by distillation. The temperature is below the limit set by the
thermal stability of the catalyst (1350C) (TULSION MP T-63, Thermax Ltd., India).

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7. Sensitivity Studies
Figure 7 shows effect of boil up rate on purity of top product. It was observed that as boil
up increases, the purity of top product also increases. From Figure 8 it is clear that as we
increase the reflux ratio, the top product purity also increases, following linear relation.
Figure 9 and 10 depict effect of feed plate location on top product purity. It was observed
that feed stage 13 for acetic acid and feed stage 18 from Isoamyl alcohol is the best-feed
locations for optimum RD column performance.

8. Conclusions
The equilibrium model for synthesis of Isoamyl acetate was developed. The simulation
studies were performed in Aspen Plus® and MATLAB. The reaction kinetics developed
by us in laboratory batch reactor and the published experimental data on phase
equilibrium are used to verify the model predictions. The experimental results from RD
experiment in our laboratory were compared with model predictions and were found to
be close to those available in literature. The effects of the variables such as the reflux
ratio, boil up ratio, feed flow rate and feed plate locations etc are presented for RD
column performance using sensitivity studies.

Acknowledgements

KP is grateful to BCUD, University of Pune and AICTE, New Delhi for financial
support under RPS scheme grant No. RPS 18/2007.

References
1. Hiwale R. S., Bhate N. V., Mahajani Y, S., Mahajani S. M. “Industrial applications
of reactive distillation: Recent trends”, International. Journal of Chemical Reactor
Engineering (Review), 2004, 2, 1-17.
2. Chiang S. F., Chien Lin Kuo, Cheng Ching Yu, Wong D. S. H. “Design alternative
for the amyl acetate process: coupled reactor/ column and reactive distillation”,
Industrial and Engineering Chemistry Research, 2002, 41, 3233-3246.
3. Taylor R., Krishna R. “Modeling reactive distillation”, Chemical Engineering
Science, 2000, 55, 5183-5229.

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National Symposium on Reaction Engineering, (NSRE), 22-23 Jan, 2010

4. Sharma M. M., Mahajani S. M., "Industrial applications of reactive distillation" (A


review), in "Reactive Distillation: Status and future directions" by Sundmacher K.
and Kienle A. (Eds), Wiley VCH, Germany 2003.
5. Sundmacher K., Kienle A. (Eds.). “Reactive distillation-Status and future trends”,
Wiley-VCH: New York, 2003.
6. Teo H. T. R., Saha B., Alqahtani A., “iso-Amyl acetate synthesis by catalytic
distillation”, International Journal of Chemical Reactor Engineering, 2005, 3, 1-14.
7. Lee M. J., Wu H.T., Lin H-M, “Kinetics of catalytic esterification of acetic acid and
amyl alcohol over Dowex”, Industrial and Engineering Chemistry Research, 2000,
39, 4094-4099.
8. Teo H. T. R., Saha B. “Heterogeneously catalyzed esterification of acetic acid with
iso-amyl alcohol: kinetic studies”, Journal of Catalysis, 2004, 228, 174-182.

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Table 1. Reaction kinetics results


Model Pre- Activation
exponential energy (KJ/mol)
factor
(mols/g.min)

LHHW 2.4 x 105 47

E-R 3.65 x 105 46.7

QH 3.39 x 103 40.3

Figure 1. RD column for esterification Figure 2. Single stage (j) in the column
showing the corresponding streams

1.0

WATER 0.8
Mole Fraction (X)

ISAMOH
HOAC
0.6
ISAMOH
RDCOLUMN
H2O
0.4 ISAMAC

HOAC
0.2

0.0
5 10 15 20 25
ISAMAC
Stage No.

Figure 3. Process flow sheet for Isoamyl acetate Figure 4. Steady State composition
Synthesis in Aspen Environment profiles(Aspen plus)

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1.0

0.8

Mole Fraction
0.6 HOAC
ISAMOH
H2O
0.4
ISAMAC

0.2

0.0
2 4 6 8 10 12 14 16 18 20 22 24 26

Stage Number

Figure 5. Steady State Compositions


Profiles (MATLAB)

160
1.0

0.9
Steady state temperature ( 0 C )

140
0.8
120 0.7
HOAC-Experiment
Mole fraction (x)

HOAC-Aspen Plus
0.6 ISAMOH-Experiment
100 ISAMOH-Aspen Plus
0.5 H2O-Experiment
H2O-Aspen plus
0.4 H ISAMC-Experiment
80 IISAMC-Aspen plus
0.3

60 0.2
Aspen Plus
Experiment 0.1
40 0.0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Stage number Stage Number

(a) Steady State Temperature Profile (b) Steady State Composition Profile
Figure 6. Comparisons of Simulation and Experimental. Results (# Run 5) for
Temperature and Composition Profiles

1.00
0.9998

0.9996 0.95
Purity of Product (Mole Fractions)
Purity of Product (Mole Fractions)

0.9994 0.90

0.9992 0.85
0.9990 0.80
0.9988
0.75
0.9986
0.70
0.9984
0.65
0.9982
0.60
0.9980

0.9978 0.55

0.9976 0.50
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 0.5 1.0 1.5 2.0 2.5
Boil up Ratio Reflux Ratio

Figure 7. Effect of Boil up Ratio on Purity Figure 8. Effect of Reflux Ratio on Purity

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1.00 1.0

0.95

Purity of Product ( Mole Fractions)


0.90 0.8

0.85

Purity of Product
0.80 0.6

0.75

0.70
0.4
0.65

0.60
0.2
0.55

0.50 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Feed Stage Location ( Acetic Acid)
Feed Stage Location ( Iso Amyl Alcohol)

Figure 9. Effect of Feed Stage Location Figure 10. Effect of Feed Stage
Location (Iso Amyl Alcohol) on Purity (Acetic Acid) on Purity

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