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Article history: In this work, esterication of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is
Received 17 April 2013 studied in the temperature range of 305.15333.15 K. Sulfuric acid is used as the homogeneous catalyst with
Received in revised form 2 July 2013 concentrations ranging from 0.0633 molL1 to 0.3268 molL1. The feed molar ratio of acetic acid to methanol
Accepted 5 August 2013
is varied from 1:1 to 1:4. The inuences of temperature, catalyst concentration and reactant concentration on the
Available online 13 November 2014
reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The
Keywords:
forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot.
Esterication The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful
Homogeneous catalyst for the simulation of reactive distillation column for the synthesis of methyl acetate.
Kinetic rate-equation 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
Simulation
1. Introduction using heterogeneous sulfonic ion exchange resin as the catalyst. Liu et al.
[8] developed a rate expression for the esterication reaction of metha-
Carboxylic acid esters constitute major components of numerous nol with acetic acid using homogeneous sulfuric acid catalyst, present-
natural products and synthetic compounds. They are widely used as ing a linear kinetics on catalyst concentration. Elgue et al. [9] also
softeners, emulsiers, dispersants, detergents, surfactants, solvents proposed a linear kinetics on catalyst concentration and applied it for
and biodiesel fuels. Several synthetic routes are available to obtain intensication of methyl acetate production in a continuous reactor.
carboxylic acid esters. A comprehensive review of ester synthesis The catalytic esterication reaction between methanol and acetic acid
route is available [1]. for the synthesis of methyl acetate with Amberlyst-15 (dry) as hetero-
The kinetics of esterication reaction between acetic acid and geneous catalyst was studied by Ismail et al. [10] in the temperature
methanol in alcoholic and non-hydroxylic media was investigated ear- range of 318338 K. The similarities and differences between heteroge-
lier by Rolfe and Hinsshelwood [2]. They proposed a kinetic model neous and homogeneous catalyzed esterication reactions of acetic acid
based on the theory of molecular statistics of esterication reaction by with methanol were described by Liu et al. [11]. They presented the
using hydrochloric acid as the catalyst. The kinetics of esterication of kinetics using a commercial naon/silica nano composite catalyst
acetic acid with methanol using a homogeneous hydrogen iodide (SAC-13) and H2SO4 separately, reported that heterogeneous and
catalyst was investigated by Ronnback et al. [3], where the protonation homogeneous catalysts show similar reaction inhibition by water
of carboxylic acid was considered as the rate-initiating step in the reac- formation, and suggested a common reaction mode based on Bronsted
tion mechanism. They observed that hydrogen iodide was esteried acid sites.
by methanol and produced methyl iodide as a by-product. Hilton The kinetics of reversible liquid-phase esterication of acetic acid
and Smith [4] found that the kinetics of acid catalyzed esterication of with methanol using sulfuric acid catalyst in an isothermal batch reactor
n-aliphatic acid with methanol is inuenced by the length of carbon was investigated by Ganesh et al. [12]. They observed that the rate con-
chains with different buffer solutions. stant is inuenced by the concentration of catalyst and the reaction rate
Agreda et al. [5] proposed a rate expression for esterication reaction increases with the catalyst concentration. They also observed that the
using homogeneous sulfuric acid as a catalyst while carrying out the re- catalyst activity is slightly inhibited by the formation of water in the
action in a reactive distillation unit. The kinetic model shows nonlinear reaction mixture. The reaction kinetics and chemical equilibrium of
dependence on the catalyst concentration without the kinetic parame- the reversible catalytic esterication of acetic acid with methanol
ters reported. Engell and Fernholz [6] and Kruel et al. [7] modied the were investigated by Popken et al. [13]. The reaction was catalyzed
kinetic model proposed by Agreda et al. [5] for the esterication reaction homogeneously by acetic acid itself and heterogeneously by an acidic
ion-exchange resin.
Corresponding author. Without catalyst it requires very long time to reach equilibrium [13].
E-mail address: mmyadav2001@gmail.com (M. Mekala). Although acetic acid itself may act as a catalyst, its activity for reaction is
http://dx.doi.org/10.1016/j.cjche.2013.08.002
1004-9541/ 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105 101
very low due to its weak acidic nature. The addition of catalyst improves 3.1. Effect of different factors on the reaction
the acidic nature of the reaction mixture by providing more H+ ions for
the reaction. Homogeneous catalysts such as hydrochloric acid, hydro- 3.1.1. Effect of temperature
gen iodide, hydrogen bromide and sulfuric acid have been used for the The experimental results for conversion of acetic acid at different
esterication reaction between acetic acid and methanol. It is reported temperatures with xed catalyst concentration (0.1288 molL1) are
that sulfuric acid is a better catalyst due to its greater density of acid shown in Fig. 1. The rate of conversion of acetic acid increases with tem-
sites per gram and it can prevent the side reactions [11]. It is more effec- perature. At the lowest temperature (305.15 K), the reaction reaches
tive than the heterogeneous catalyst for the esterication reaction, so it equilibrium after 400 min and at higher temperature, and the time re-
is selected for the present study. quired for the reaction to reach equilibrium reduces drastically. At
Although a large number of studies are available in literature, some 333.15 K the time needed is only 100 min. The higher the reaction tem-
uncertainties remain in the reported kinetic models. In the present perature, the shorter the time required to reach equilibrium. At equilib-
paper, the esterication reaction of acetic acid with methanol to pro- rium, the acetic conversion is 0.69 or 69%.
duce methyl acetate using homogeneous sulfuric acid catalyst is studied
at different temperatures, catalyst concentrations and feed molar ratios.
The kinetic models based on concentration as well as activity are devel-
oped and the model predictions are compared with experimental data.
The model predictions are also compared with the models in literature.
2. Experimental
2.1. Chemicals
The esterication reaction was carried out in a 500 ml three neck Fig. 1. Effect of temperature on reaction kinetics at 0.1288 molL1 catalyst concentration.
round-bottom ask placed in a heating rota mantle, which contains a 305.15 K; 313.15 K; 323.15 K; 333.15 K.
heating knob and a speed control knob. The rota-mantle was main-
tained at constant temperature by adjusting the heating knob. The 3.1.2. Effect of catalyst concentration
minimum stirring speed was maintained at 240rpm for uniform mixing Fig. 2 shows the effect of catalyst concentration on the conversion of
of catalyst in the reaction mixture using the speed control knob. A glass acetic acid at a xed temperature of 323.15 K. As the catalyst
thermometer inserted into the reactor was used to measure the reaction concentration increases the reaction reaches equilibrium faster. At
mixture temperature inside the ask. A spiral condenser was connected 0.3268 molL1 catalyst concentration the reaction takes about
vertically to the reaction ask to reduce the vapor losses from the 70 min to reach equilibrium whereas at 0.0633 molL1 it only takes
reactor. about 150 min. The effect of catalyst concentration on the acetic acid
conversion is similar to that of the effect of temperature.
2.3. Experimental procedure
2.4. Analysis
The present esterication reaction with homogeneous catalyst is in- 3.1.3. Effect of initial reactant mole ratio
vestigated at 1:1 mole ratio of acetic acid to methanol, with the temper- Fig. 3 shows the effect of initial molar ratio of acetic acid to methanol
ature varied from 305.15 to 333.15 K and the catalyst concentration on the acetic acid conversion at xed catalyst concentration of 0.1288
varied from 0.0633 molL1 to 0.3268 molL1. molL1 and reaction temperature of 333.15 K. The equilibrium
102 M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105
conversion of acetic acid increases with mole ratio due to the availability Eb
kb kb0 exp 4b
of excess methanol. With an increase in mole ratio of acetic acid to RT
methanol from 1:1 to 1:4, the equilibrium conversion of acetic acid
increases from 69% to 91.7%. where kf0 and kb0 are the pre-exponential factors, Ef and Eb are the acti-
vation energies for forward and backward reactions, respectively, R is
the gas constant, and T is the temperature.
The inuence of temperature on the reaction rate constant is deter-
mined by tting kf and kb to the Arrhenius Eqs. (4a) and (4b). Fig. 4
shows the Arrhenius plot of lnkf vs. 1/T and lnkb vs. 1/T. The forward and
backward activation energies are found to be 62,721 and 62,670
Jmol1, respectively. Because the two activation energies are nearly
equal, it can be concluded that the equilibrium constant (Keq) for this re-
action is nearly independent of temperature [5], and is approximately
equal to 5.07. The equilibrium constant can be determined experimental-
ly from the equilibrium conversion XAe of acetic acid as follows
Fig. 3. Effect of reactant initial mole ratio on the acetic acid conversion at 0.1288 molL1
catalyst concentration and reaction temperature 333.15 K. 1:1; 1:2; 1:3; 1:4.
2 m2 2m1 X A 2m2
ln m2 k f C A0 t 3
2m2 2m1 X A 2 m2
p
where m1 1 K1 and m2 2 1m1 .
eq
From Eq. (3), the forward reaction rate constants at different tem-
peratures and at 0.1288 molL1 catalyst concentration are calculated.
The temperature dependency of the reaction rate constants is expressed
by the Arrhenius equation.
E f
k f k f0 exp 4a
RT Fig. 5. Relation between pre-exponential factor and catalyst concentration.
M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105 103
where WC is the concentration of catalyst (molL 1) in the initial The UNIQUAC ri and qi values and the interaction parameters are given
reaction mixture. in Tables 1 and 2, respectively [12].
Fig. 6 shows the comparison of acetic acid conversion from experi-
mental results with that from the concentration based model for differ-
ent catalyst concentrations at 323.15 K. As the catalyst concentration Table 1
increases, the conversion of acetic acid increases. At lower catalyst UNIQUAC ri and qi values
concentrations, the model predictions are in close agreement with ex- Component ri qi
perimental results. The predictions are a little lower than experimental Acetic acid 2.2024 2.0720
values at the early stages but as the time proceeds they are in good Methanol 1.4311 1.4320
agreement. At higher catalyst concentration the predictions are lower Methyl acetate 2.8042 2.5760
in magnitude in the initial stage then they tend to approach the exper- Water 0.9200 1.4000
imental results closely. One of the reasons for the mismatch is the
formation of water, which may inhibit the rate of reaction until reaching
the equilibrium.
Table 2
UNIQUAC interaction parameters
Fig. 7 shows the comparison for the conversion of acetic acid from
Fig. 6. Comparison of experimental results with concentration based model results for the experimental results with that predicted from the activity based
conversion of acetic acid at different catalyst concentrations at 323.15 K. 0.0635 model at different catalyst concentrations at 323.15 K. The deviation is
molL1; 0. 1288 molL1; 0.3268 molL1; 0.0635 molL1; 0.1288 little between the experimental and predicted results, except at lower
molL1; 0.3268 molL1 (symbols represent experimental data and lines
represents concentration based model results).
catalyst concentrations.
ai i xi i C i =C t : 7
with
eq xeq eq eq eq
C xD C D
K act eq eq eq eq : 9
xA xB A B Fig. 7. Comparison of experimental results with activity-based model results for the con-
version of acetic acid at different catalyst concentrations at 323.15 K. 0.0635 molL1;
0.1288 molL1; 0.3268 molL1; 0.0635 molL1; 0.1288 molL1;
Based on the equilibrium conversion, the activities and mole frac-
0.3268 molL1 (symbols represent experimental data and lines represents activity
tions are computed and substituted into Eq. (9) to nd the equilibrium based model results).
constant based on activity. kfact is related to the temperature through an
Arrhenius relation
The experimental results and the activity-based model predicted
values are plotted for acetic acid conversion with constant catalyst con-
E
kfact kfact0 exp f 10 centration of 0.1288 molL 1 and different reaction temperatures as
RT
shown Fig. 8. The predicted and experimental values match well except
with at lower temperature. As the temperature increases the reaction rate
also increases, which may be due to the increase in the kinetic energies
2
k f0 C t resulting in more inter-molecular collisions.
kfact0 11
eq
A B
eq
Fig. 9 compares the experimental conversion of acetic acid with that
predicted by the concentration based model and activity based model at
where kf0 is calculated from the concentration-based model. The non- a xed catalyst concentration of 0.1288 molL1 and different temper-
ideality of the reaction mixture is calculated by the UNIQUAC equation. atures. Both models are in good agreement with the experimental data.
104 M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105
Fig. 8. Comparison of experimental results with activity- based model results for the
conversion of acetic acid at different reaction temperatures at 0.1288 molL 1
catalyst concentration. 305.15 K; 313.15 K; 323.15 K; 333.15 K; Fig. 10. Comparison of different kinetic models at 313.15 K and 0.3268 molL1 catalyst
305.15 K; 313.15 K; 323.15 K; 333.15 K (symbols represent exper- concentration. experimental; concentration based; activity based; Liu
imental data lines represents activity based model results). et al. [8]; Elugu et al. [9]; Bonnaillie et al. [15]; Agreda et al. [5].
Table 3
Kinetic models and parameters in literature
kb = 0.322
Ef = 53,800
Eb = 52,580
h i
4 r A W C kf exp E Eb kf = 0.0055 [15]
RT C A C B kb exp RT C C C D
f
kb = 0.011
Ef = 41,800
Eb = 41,800
the concentration-based model. Comparing Fig. 11 with Fig. 10, we can CD water concentration, molL1
conclude that even at higher temperatures, while maintaining the cata- CAe, CBe,
lyst concentration constant, activity-based and concentration-based CCe and CDe equilibrium concentration of acetic acid, methanol,
models predict the results with reasonable accuracy. methyl acetate and water, molL1
Fig. 12 compares the available kinetic models [5,8,9,15], our models Eb backward activation energy, Jmol1
and the experimental data at temperature of 323.15 K and catalyst con- Ef forward activation energy, Jmol1
centration of 0.1288 molL 1. The models proposed in the present Keq equilibrium constant
study, concentration-based and activity-based models, are better than kb backward reaction rate constant, Lmol1min1
the models available in the literature. Our models provide better t to kb0 backward frequency factor, L mol1 min1
the experimental data. kf forward reaction rate constant, Lmol1min1
kf0 forward frequency factor, Lmol1min1
rA reaction rate of acetic acid, molL1min1
R gas constant, Jmol1K1
T absolute temperature, K
t time, min
WC catalyst concentration, molL1
XA acetic acid conversion
XAe acetic acid equilibrium conversion
i activity coefcient of component i
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Nomenclature
homogeneously and heterogeneously catalyzed acetic acid esterication with
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