ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2016, Vol. 50, No. 4, pp. 404–413. © Pleiades Publishing, Ltd.

, 2016.

Simulation of Continuous Packed bed Reactive Distillation Column

for the Esterification Process using Activity Based Kinetic Model1
M. Mallaiah and G. Venkat Reddy
Department of Chemical Engineering, National Institute of Technology, Warangal 506004, India
e-mail: mmyadav2001@gmail.com
Received September 14, 2014

Abstract—A mathematical model for the continuous packed bed reactive distillation process of esterification
of acetic acid with methanol is developed. The kinetic rate equation, which plays a major role for the perfor-
mance of reactive distillation and it is the part of model, is required for the liquid phase reversible esterifica-
tion reaction. The mineral sulphuric acid is used as the catalyst. The kinetic experiments are carried out under dif-
ferent temperatures in the range of 305.15 to 333.15 K and catalyst concentrations in the range of 0.1267 mole
H+/lit to 0.6537 mole H+/lit. From that experimental data the kinetic model is developed and the same is
used for the simulation of reactive distillation process. Equilibrium stage model, in which the vapour and the
liquid leaving a stage are assumed to be in equilibrium with each other, has been used for the simulation of
reactive distillation process by incorporating our kinetic model. Conversion of acetic acid as function of reflux
ratio and reboiler ratio has been predicted. The liquid composition and temperature profiles versus stage
number have been also predicted. Finally, the optimum operating conditions obtained from the simulation
results for high pure methyl acetate by reactive distillation process.

Keywords: packed bed reactive distillation, esterification, rate equation, kinetic model, simulation
DOI: 10.1134/S0040579516040412

INTRODUCTION tic acid with methanol is essential. Agreda et al. [2],

Methyl acetate is a highly demandable chemical
due to its wide range of uses like as a solvent in glues,
nail polish removers, perfumes, cellulose adhesives
and dye manufacture. The major uses of this product
are in the paint, coatings, cosmetic, textiles and motor
industries.
The production of methyl acetate is one of the most
successful reactive distillation processes. Reactive dis-
tillation offers distinct advantage over conventional
approach of conducting reaction and separation in two
different units of equipment. The esterification of
methyl alcohol by acetic acid to produce methyl ace-
tate has been used as model reaction for reactive distil-
lation by numerous researchers and voluminous liter-
ature exists relating to various aspects of this reaction
[1–3]. The kinetically controlled reactive distillation
and kinetics of methyl acetate synthesis has attracted
considerable attention of researchers, in recent times
[4, 5]. Taylor and Krishna presented a comprehensive
review of reactive distillation modelling [3].
Experimental data relating to different device con-
figurations, for reactive distillation of methyl acetate
synthesis been reported [5–7]. For design and simula-
tion of reactive distillation process, a rate equation,
describing the kinetics of esterification process of ace-
1 The article is published in the original.
proposed a rate expression for esterification reaction
using sulphuric acid as a catalyst while carrying out the
reaction in a reactive distillation unit. The proposed
rate expression incorporates nonlinear dependence on
the catalyst concentration. Ganesh et al. [8], described
the reaction kinetics of reversible liquid-phase esteri-
fication of acetic acid with methanol by using sul-
phuric acid catalyst in the isothermal batch reactor.
They have studied the effect of catalyst concentration
and sensitivity to the presence of water on the rate
expression. They also observed that the rate constant is
influenced by the concentration of catalyst and the
reaction rate increased with an increase in the catalyst
concentration. One of the earliest works relating to
kinetics of esterification of acetic acid with methanol
was published by Rolfe and Hinsshel wood [9]. Ronn-
back et al. [10], investigated the kinetics of esterifica-
tion acetic acid with methanol reaction using a homo-
geneous hydrogen iodide catalyst, where the protona-
tion of carboxylic acid was considered as rate-
initiating step in the reaction mechanism. Elgue [11],
investigated the intensification of methyl acetate ester-
ification reaction in a continuous reactor.
Two approaches have been adopted by various
authors for modelling reactive distillation process [3].
In the first type the basic assumption made is that
streams leaving a stage are in equilibrium with each

404
 SIMULATION OF CONTINUOUS PACKED BED REACTIVE
other, the equilibrium between liquid and the vapour
on the stage play an important in the model develop-
ment, therefore the models are called equilibrium
models. The departure from the equilibrium is
accounted for by tray efficiency or height equivalent of
theoretical plate. In the second type the streams leav-
ing the stage are not in equilibrium with each other,
therefore the mass transfer rates play a crucial role,
and the models are known as non-equilibrium stage
models or rate-based models. One additional factor
which makes reactive distillation process more com-
plex than other separation processes is the super impo-
sition of chemical equilibrium over phase equilibrium.
A rate based model compared with an equilibrium
model [12] for production of ethyl acetate and con-
cluded that rate-based models are better, though no
experimental evidence provided to support their con-
clusion. Peng et al. [13] compared a steady-state equi-
librium model and rate-based model for packed reac-
tive distillation column for the production of tert-amyl
methyl ether and methyl acetate. They reported that
both the models are equally good for methyl acetate;
there is good agreement between experimental and
model predictions. There is overwhelming evidence
[7, 14] to show that two feeds, where acetic acid is fed
near the top of the column and methyl alcohol near
the bottom, in equimolar quantities, performs better
than any other feeding arrangement. A number of
research articles are available in the literature on equi-
librium stage models [15–18]. All the equilibrium
stage models assume that the vapour from stage below
and the liquid from the stage above are brought into
contact with each other on the stage along with any
fresh and recycle streams. The vapour and the liquid
leaving the stage are assumed to be in equilibrium with
each other. An impressive number of publications are
available in the literature on non-equilibrium stage
models [19–22]. Bessling et al. [7] presented a design
method based on the interpretation of reactive distilla-
tion line diagrams and used the same to identify the
main process parameters and provided a foundation
for experimental investigation. The influence of the
reflux ratio on the conversion with Raschig rings as a
heterogeneous catalyst was studied.
In the present study, the esterification of acetic acid
and methanol in presence of sulphuric acid catalyst is
investigated in the reactive distillation mode. The sim-
ulation of reactive distillation process is performed by
using our kinetic model [23]. The simulation of reac-
tive distillation is carried out by taking specifications
of our laboratory equipment. The effect of reflux ratio,
reboiler ratio and effect of feed location to reactive
zone for acetic acid conversion as well as the methyl
acetate formation is studied. The liquid composition
and temperature profiles with respect to stages are also
studied. Finally, the optimum operating conditions
obtained for the production of high purity of methyl
acetate by using reactive distillation in presence of
homogeneous catalyst.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
405
EXPERIMENTS
Chemicals
For the kinetic study the following chemicals were
used; methanol (purity = 99% w/w), acetic acid
(purity 99.95% w/w), and sulphuric acid (purity =
98% w/w). The chemicals were procured from SD
Fine Chemicals Limited, Mumbai, India.
Experimental Setup
The esterification reaction was carried out in a
500 mL three neck RB flask. The flask was placed in a
heating rota mantle which contains a heating knob and
stirrer speed control knob. The minimum stirring
speed was maintained 240 rpm for uniform mixing of
catalyst using the speed control knob. A spiral con-
denser was connected to the reaction flask vertically to
condense the vapours and mix them back with the
reacting mixture. The condensate acts as a direct cool-
ing medium for the reaction mixture. Simultaneously,
the heating is increased and controlled manually to
maintain a desired temperature in the reaction flask. A
mercury thermometer was inserted into the flask to
measure the reaction mixture temperature.
Experimental Procedure
In this experiment, equimolar quantities of metha-
nol (32 g) and acetic acid (60 g) are charged to the
reactor. The desired amount of sulphuric acid (as a
percentage with respect to the weight of acetic acid) is
added to initiate the reaction. When reaction mixture
reaches the desired reaction temperature, the reaction
time is noted from that time onwards. The samples are
withdrawn at regular intervals of time and analyzed for
the acetic acid concentration. The reaction is carried
out for sufficient time so that equilibrium conversion
is reached or when no further decrease of acetic acid
concentration takes place.
Analysis
Water used in the experiment to prepare the stan-
dard solution of NaOH was obtained from an ultra
pure water purifier system (Millipore-Synergy UV sys-
tem). The resistivity of water is recorded as 18.2 MΩ-
cm. The acetic acid concentration in the reaction mix-
ture is determined by titration with standard solution
of NaOH using phenolphthalein as the indicator.
MATHEMATICAL MODEL
Continuous reactive distillation operation is analo-
gous to that of continuous distillation operation. The
equilibrium model equations are essentially mass and
energy balances. In addition, it is assumed that the
interfacial compositions are in equilibrium with each
other, therefore they are related. HETPs of both reac-
Vol. 50 No. 4 2016
406 MALLAIAH, VENKAT REDDY

Lj–1 Vj
L V
T j–1
T j–1
H Lj–1 H Vj–1
Methyl
Acetic acid acetate xi, j–1 yi, j

Liquid Vapour
Methanol Reaction

Lj Vj+1
T jL T jV+1
Water H Lj H Vj+1
xi, j yi, j+1

Fig. 1. Schematic diagram of Reactive distillation and Equilibrium Stage.

tive and non-reactive packing are chosen empirically, For jth stageMolar component balances
and the same is used in our simulation studies, as the
number of theoretical stages. Figure 1 shows the sche- (L j −1 x i, j −1 − V j +1 yi, j +1
(9)
matic diagram of reactive distillation and equilibrium − L j x i, j − V j yi, j + ε j Ri, j ) = 0.
stage.
For Feed stage
The mathematic equations describing the steady state
equilibrium stage wise process are given below [13]. (L j −1 x i, j −1 + V j +1 yi, j +1 + F j Z iF, j
Total Condenser Molar component balance (10)
− L j x i, j − V j yi, j + ε j Ri, j ) = 0.
(V 2 yi,2 − (D + L1)x i,1) = 0. (1) Total energy balance
Total energy balance
(L j −1H Lj −1 + V jV+1 − L j H Lj − V j H Vj ) = 0. (11)
(V 2H 2V − (D + L1)H 1L − QC ) = 0. (2) For Feed stage
Summation
(L j −1H Lj −1 + V j +1H Vj +1
NC (12)
+ F j H Fj − L j H Lj − V j H Hj ) = 0.
∑x i,1 = 1. (3)
i =1 Summation
ReboilerMolar component balance NC

(LN −1 x i,N −1 − V N yi,N − LN x i,N ) = 0. (4) ∑x i, j = 1, (13)

i =1
Total energy balance NC

(LN −1H NL −1 − V N H NV − LN H NL + QR ) = 0. (5) ∑y i, j = 1. (14)

i =1
Summation
Vapour liquid equilibrium
NC
y i , j = K i , j x i, j .
∑x i,N = 1. (6) (15)
i =1 Equilibrium relations.The following form of vapour-
NC liquid equilibrium relationship can be employed for
∑y i ,N = 1. (7) multi- component mixture
i =1 y i , j = K i , j x i, j . (16)
Vapour- liquid equilibrium Where
y i ,N = K i ,N x i ,N . (8) Ki,, j = f(xi,j, Ti, Pi)

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

 SIMULATION OF CONTINUOUS PACKED BED REACTIVE 407

Conversion of acetic acid 0.8 0.8

Conversion of acetic acid

0.7 0.7
0.6 0.6
0.5 0.5 0.1267 mol H+/L
305.15 K
0.4 0.4 0.2576 mol H+/L
313.15 K
0.3 0.3 0.3846 mol H+/L
323.15 K
0.2 333.15 K 0.2 0.5153 mol H+/L
0.1 0.1 0.6537 mol H+/L

0 100 200 300 400 0 50 100 150 200 250 300 350
Time, min Time, min
Fig. 2. Effect of reaction time on conversion of acetic acid
(catalyst conc. 0.5153 moles H+/L). Fig. 3. Effect of catalyst concentration on conversion.

Ki, j is related to the pure component vapour pressure
by the relation
Ki,j = γPsi,j/P, (17)
where γ is the liquid activity coefficient and P is the
column pressure and Psi, j is the vapour pressure of
component j. Vapour-Liquid equilibrium equations
can be used to obtain Ki, j or Psi, j and also to compute
the bubble point temperature such that
NC
∑y i, j = 1.
i =1
The simulation using the Eqs. (1)–(18), with the
equipment parameters pertaining to our reactive dis-
tillation column, has been done by Radfrac of
ASPENPLUS version 7.2. The kinetic equation used
in the simulation has been developed from experimen-
tal data obtained in our laboratory.
RESULTS AND DISCUSSION
Experiments for Development of Kinetic Equation
Esterification reaction with sulphuric acid as cata-
lyst was investigated at temperatures 305.15–333.15 K,
for 1 : 1 mole ratio of acetic acid to methanol in our
earlier study [23]. The concentrated and activity based
models were developed and found that activity model
was the best one even with compared to other litera-
ture models. The reaction between acetic acid and
methanol without catalyst is very slow, therefore a cat-
alyst was used. The catalyst concentration was varied
from 0.1267 mole H+/lit-0.6537 mole H+/lit.
temperature and reaction is controlled by chemical
steps [23].
Effect of Catalyst Concentration on Acetic Acid
Conversion
The effect of catalyst concentration on the acetic
acid conversion was studied by varying the catalyst
concentration from 0.1267 mole H+/lit–0.6537 mole
(18) H+/lit and at a reaction temperature of 313.15. Figure 3
shows the effect of catalyst concentration at a tem-
perature of 313.15 K. From Fig. 3 it can be seen that as
the catalyst concentration increases the reaction rate
increases this is due to available of H+ ions. As the cat-
alyst concentration increases the reaction rate is more,
hence the system reaches equilibrium fast [23].
The Kinetic Equation for the Esterification of Acetic Acid
with Methanol
The following kinetic rate equation based on the
activity coefficients of reactants and the products has
been proposed
⎛ aa ⎞
ri = k1a1a2 − k −1a3a4 = k1 ⎜ a1a2 − 3 4 ⎟ , (19)
⎝ Ka ⎠
Table 1. UNIQUAC ri and qi values
ri qi
Component

Effect of Reaction Temperature on Acetic Acid Acetic acid 2.2024 2.0720

Conversion
The experimental results for conversion of acetic Methanol 1.4311 1.4320
acid with time, with fixed catalyst concentration
(0.5153 mole H+/lit of initial acetic acid by weight) are Methyl acetate 2.8042 2.5760
shown in Fig. 2. From the plot, it can be seen that the
Water 0.9200 1.4000
conversion of acetic acid increases with increase in

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

408 MALLAIAH, VENKAT REDDY

Table 2. UNIQUAC interaction parameters

i j aij bij cij
Acetic acid Methanol 390.26 0.97039 –3.0613 × 10–3
Methanol Acetic acid 65.245 –2.0346 3.1570 × 10–3
Acetic acid Methyl acetate –62.186 –0.43637 2.7235 × 10–4
Methyl acetate Acetic acid 81.848 1.1162 –1.3309 × 10–3
Acetic acid Water 422.38 –0.051007 –2.4019 × 10–4
Water Acetic acid –98.120 –0.29355 –7.6741 × 10–5
Methanol Methyl acetate 62.972 –0.71011 1.1670 × 10–3
Methyl acetate Methanol 326.20 0.72476 –2.3547 × 10–3
Methanol Water –575.68 3.1453 –6.0713 × 10–3
Water Methanol 219.04 –2.0585 7.0149 × 10–3
Methyl acetate Water 593.70 0.010143 –2.1609 × 10–3
Water Methyl acetate –265.83 0.96295 2.0113 × 10–4

where ai = xiγi. Further k1 and k–1 are related to the catalyst concen-
tration through the relation
Ka = ∏a vi
i = ∏x ∏γvi
i
vi
i , (20)
2
k10C t
⎛ϕ ⎞ ⎛θ ⎞ k10act = , (23)
ln(γ i ) = ln ⎜ i ⎟ + z qi ln ⎜ i ⎟ + l i γ A γB
eq eq

⎝ xi ⎠ 2 ⎝ ϕi ⎠
⎡ ⎤ k10 = 1.0 × 10 8 (WC ) + 8 × 10 7, (24)
nc ⎢ nc ⎥ (21)
ϕi θ1j τ ij ⎥
− ∑
x i j =1
1⎢
x j l j + qi ⎢1 − ln (∑
θ j τ ij −
1
) ∑
nc ⎥,
where WC is the concentration of catalyst (g moles
H+/L) in the initial reaction mixture.
⎢
⎢⎣
j =1
∑
θ k τ kj ⎥
1
⎥⎦ Figure 4 show the plots of lnk versus 1/T for both k1
k =1
and k–1 respectively. The activation energies E1 and E2
ri x i qi x i
ϕi = nc
, θi = nc
, for both forward and backward reactions are found
∑r x k k ∑q k xk
from the above graphs, to be 62.721 and 62.670 kJ/mol
respectively. The Eq. (19) has been incorporated into
k =1 k =1
our model for simulation of reactive distillation pro-
qi x i ⎛ b ⎞ cess in our laboratory column.
θi = τ ij = exp ⎜ aij + ij + cijT ⎟ ,
1
nc
,
⎝ T ⎠
∑q k xk
–4.0
k =1
–4.5 у = –7544.0x + 18.20
–5.0 R2 = 0.960
l i = z ( ri − qi ) − ( ri − 1) , –5.5
2 –6.0
ln (ki)

z = 10; nc = 4. –6.5
–7.0
The k1 and k–1 in Eq. (19) have been calculated –7.5 у = –7538.3x + 16.577
from the concentration model for the elementary –8.0
–8.5 R2 = 0.9603
reactions as given [24]. The ri and qi values are given
–9.0
Table 1. The parameters aij, bij and cij were given in 0.00295 0.00305 0.00315 0.00325
Table 2. 0.00300 0.00310 0.0032 0.00330
The temperature effect on the rate constants k1 and 1/T, K–1
k-1 is given by Arrhenius’ law
Fig. 4. Forward and backward reaction rate constants as a
k1 = k10actexp(–Ea/RT). (22) function of reciprocal of temperature.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

 SIMULATION OF CONTINUOUS PACKED BED REACTIVE 409

380 Acetic acid

1.0 Methanol
370 Methyl acetate
0.9
Temperature, K

Water

Liquid molefraction
360 0.8
0.7
350
0.6
340 0.5
330 0.4
0.3
320 0.2
1 6 11 16 21 26 31
0.1
Stage number
0
1 6 11 16 21 26 31
Fig. 5. Temperature profile with respect to stages. Stage number

Fig. 6. Liquid composition profiles with respect to stage.

Simulation of Reactive Distillation Processes
Simulation has been carried out by using equilib-
rium stage model. The equipment parameters used in
the simulation pertain to reactive distillation column
in our laboratory. Apart from steady-state mass and
energy balance equations presented in the model
development, the kinetic equation developed for
esterification of acetic acid with methanol has been
used in the simulation. The following assumptions
have been taken: (a) the reactive distillation operation
is steady-state; (b) vapour-liquid equilibrium is
reached on all the stages; (c) chemical equilibrium is
reached on all reactive stages; (d) no parallel reactions
are taking place except the esterification reaction; (e)
the column operated at atmospheric pressure; (f) feed
enters the column as saturated liquids.
The equipment parameters are given in Table 3.
HETP data supplied by Abhishek Scientific Company,
Mumbai, India has been used. The packing used in the
reactive section of our column is Equivalent Kat pack-
S. For non-reactive section, HYFLUX, a family of
structured tower packings, which are especially useful
Table 3. Reactive distillation column parameters
Column diameter
when a moderate to large number of theoretical stages
have to be accommodated in a limited height of the
tower, have been used. All the packing materials have
been supplied by Abhishek Scientific Company,
Mumbai. Two feed locations for Acetic acid have been
studied, i. e. stages 3 and 11. Methanol feed has been
located on stage 20. All our simulation results pertain
to acetic acid feed stage location at 11, unless men-
tioned otherwise. For simulation, Radfrac of Aspen
plus 7.2 has been used. The stages are counted starting
from condenser down to reboiler.
Temperature Variation Along the Height of the Column
Figure 5 shows the variation of temperature along
the column height. There are three distinct regions in
the column, i. e. rectifying section from stage 1–10;
reactive section from stage 11–20; and stripping sec-
tion stage 21–30. Temperature gradually falls from
reboiler to the reactive section. In the reactive section
the temperature remains constant. There is a drop in
the temperature from reactive section to rectifying sec-
tion. However within rectifying section, the tempera-
50 mm ture remains constant.

Column height 3000 mm

Concentration Profiles in the Liquid Phase
Number of reactive stages 10
Figure 6 shows the variation of liquid phase com-
Number nonreactive stages 18 position of all the components, along the column
HETP 100 mm height. The concentrations are shown in mole frac-
tions. From Fig. 6 it is clear that there is considerable
Interfacial area 750 m2/m3 amount of methyl alcohol present in the liquid phase
below the stage 20. However it almost disappears from
Column operating pressure 1 atm
the liquid phase close to the reboiler. This is due to
Feed flow rates: a)Methanol 32 mol/hr evaporation at higher temperatures prevailing near the
reboiler. Acetic acid is present only in the reactive sec-
b) Acetic acid 32 mol/hr tion, indicating reaction with methanol. Almost pure

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

410 MALLAIAH, VENKAT REDDY

0.0000015
Acetic acid
0.0000010 Methanol
Methyl acetate
Water

Reaction rate, Kmol/s

0.0000005

0
5 10 15 20 25 30
–5E-07

–0.000001 Stripping
Rectifying section
Reactive
–1.5E-06 section section
Stage number

Fig. 7. Rate of generation/disappearance of the components with respect to stage number.

methyl acetate and water report as distillates and bot- Figure 9 shows the effect of reflux ratio on the conver-
toms respectively. sion of acetic acid for the esterification process. The
conversion reaches maximum at a reflux ratio of about
1.9 and then it gradually decreases as the reflux ratio is
Rate of Generation/disappearance of the Components
from the Reaction
Figure 7 shows the rate of generation of the prod- 60
Acetic acid
ucts and disappearance reactants of the reactants 50 Methanol
during the reaction in the reactive zone or section. Methyl acetate
From this figure it is observed that maximum the pro- 40 Water
K Values

duction of the methyl acetate is taking place on the 30

17–20th stages because as the methanol in the vapour
state is contacting with condensed liquid from the 20
stages and reacts immediately to form the products. 10
From this one can conclude that the maximum extent
of reaction occurs between 17–20th stages. 0 5 10 15 20 25 30
Stage number
Effect of K Values
Fig. 8. Variation of the K values with respect to stage.
Figure 8 shows the variation of the equilibrium
constant values from the condenser stage (1) to 1.0
Conversion of acetic acid

reboiler stage (30). From this figure it is observed that

the desired product, methyl acetate has the highest K 0.8
value, hence maximum conversion and purity of
methyl acetate is possible. The other components 0.6
water and acetic has the K values of less than one,
hence these components always never found in the 0.4
distillate. Hence the high purity of the methyl acetate
0.2
is achieved by reactive distillation.

0 2 4 6 8 10 12 14
Effect of Reflux Ratio on Conversion of Acetic Acid Reflux ratio
In the reactive distillation process, reflux ratio has
very strong influence on the conversion of acetic acid. Fig. 9. Conversion of acetic acid with varying reflux ratio.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

 SIMULATION OF CONTINUOUS PACKED BED REACTIVE 411

1.0 1.00

Conversion of acetic acid

0.95
Liquid molefraction

0.8 0.90
0.85
0.6 0.80
0.75
0.70
0.4 Methyl acetate 0.65
Water 0.60
0.2 0.55
0.50
0 3 8 13 18 23
0 2 4 6 8 10 12 14 Feed stage
Reflux ratio
Fig. 10. Mole fractions of methyl acetate in distillate and Fig. 11. Conversion of acetic acid with varying the location
water in the bottoms with increasing reflux ratio. of feed stage.

Acetic acid Methanol

1.0
Methyl acetate Water 1.0
0.8

Conversion of acetic acid

Liquid molefraction

0.9
0.6
0.8
0.4
0.7
0.2
0.6
0
1 6 11 16 21 26 31 0.5
Stage number 0 2 4 6 8 10 12
Boilup ratio
Fig. 12. Liquid composition profiles with respect to stage.
(Feed position for acetic acid at 3rd stage). Fig. 13. Conversion of acetic acid with varying reboil ratio.

increased. From this, it is concluded that at a reflux
ratio of 1.9 the maximum conversion of acetic acid
occurs.
Product Purity as Function of Reflux Ratio
Figure 10 shows the mole fractions of methyl ace-
tate and water in distillate and bottoms respectively.
The purity of the products is highest at reflux ratio of
1.9 and then it decreases as the reflux ratio increases.
So the optimum reflux ratio found to be 1.9 to get the
high purity of the methyl acetate in the distillate as well
as other product water in the bottoms.
the conversion of acid gradually falls and becomes
negligible near stage 20. This signifies the importance
of two feeds for the reactive distillation of acetic acid
with methanol. Further as the feed stage moves
upwards of the column beyond stage 3, the conversion
of acetic acid again falls. Figures 6 and 12 show the
variation of liquid phase compositions against height
of the column, for acetic feed location on stage 11 and
3 respectively. Early introduction of acetic acid affects
the formation of methyl acetate. The liquid phase con-
centration of methyl acetate is very low between stages 3
and 11, when acetic acid is introduced on stage 3, when
compared to that when it is introduced in stage 11.

Feed Stage Position and Acetic Acid Conversion
Feed stage for acetic acid has considerable effect on
its conversion. Figure 11 shows the effect of feed stage
location on acetic acid conversion. The feed stage
location has been changed from 3 to 20 in our simula-
tion studies. As the feed stage location goes below 11,
Effect of Reboil Ratio on the Conversion of Acetic Acid
Figure 13 shows the effect of reboil ratio on the
conversion of acetic acid. The conversion is the high-
est when the reboil ratio about 2. As the reboil ratio
increases further the conversion falls drastically. At
reboil ratio 12, the conversion is only 70%.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 50 No. 4 2016

412 MALLAIAH, VENKAT REDDY
CONCLUSIONS
The simulation of reactive distillation is performed
by using activity based kinetic model in the equilib-
rium stage model. The performance of our laboratory
reactive distillation column has been simulated under
different operating conditions and found optimum
conditions for the high purity of methyl acetate. The
composition and temperature profiles versus stage
number have been predicted. Temperature gradually
falls from reboiler to condenser but the temperature
remains constant in reactive section. The methyl ace-
tate composition increased from reboiler position to
condenser while the water composition decreased.
The high purity of methyl acetate obtained in distillate
and water in the reboiler. As the acetic acid feed stage
position changed, the conversion of acetic acid
decreased which shows that, two feed locations for the
reactive distillation are giving better result. From the
simulation results, it is observed that the maximum
conversion of acetic acid is at a reflux ratio of
1.9.When the reboiler ratio increased to 12 the conver-
sion drops to 70% and the minimum reboiler ratio is 2.
NOTATION
a activity;
D distillate rate, mole/h;
Ea forward activation energy, J/mol;
F feed flow rate, mole/h;
H enthalpy, J/mole;
K vapor-liquid equilibrium constant;
Ka equilibrium constant;
k1 forward reaction rate constant, lit/mol-min;
k–1 backward reaction rate constant, lit/mol-min;
k10 forward frequency factor, lit/mol-min;
L liquid flow rate, mole/h;
N total number of segments;
QC condenser heat duty;
QR reboiler heat duty;
R gas constant, J/mol- K;
rA reaction rate of acetic acid, mol/lit-min;
T temperature, K;
t time, min;
V vapor flow rate, mole/h;
wc
catalyst loading, mol H+/L;
x liquid mole fraction;
y vapor mole fraction;
Z feed composition;
ε reaction volume, L.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
SUBSCRIPTS AND SUPERSCRIPTS
F feed;
i component index;
j segment(stage) index;
I interface;
L liquid phase;
t total;
V vapor phase.
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