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P. K.

Igbokwe,
Journal of the University of Chemical F. L. Olebunne
Technology and Metallurgy, 46, 4, 2011, 389-394

ON THE CATALYTIC ESTERIFICATION OF ACETIC ACID WITH ETHANOL USING


NIGERIAN MONTOMOROLLONITE CLAY: EFFECT OF REACTION VARIABLES
ON CATALYST EFFICIENCY
P.K. Igbokwe1, F.L. Olebunne2

1
Department of Chemical Engineering, Received 08 June 2011
Nnamdi Azikiwe University, Awka, Accepted 28 October 2011
P.M.B. 5025, Anambra State, Nigeria.
E-mail: philoigbokwe@yahoo.com.
2
Department of Chemical Engineering,
Federal University of Technology,
Owerri,Imo State, Nigeria

ABSTRACT

Montmorillonite clay from Udi in Nigeria was acid-activated and used as a catalyst in liquid-phase esterification of
acetic acid with ethanol. The effects of the catalyst mass, reaction temperature and reactants mole ratios were studied. The
results showed that an increase in each of the three variables produced a corresponding increase in the percentage
conversion of the acetic acid. The magnitude of the effects of the variables was obtained by modeling the reaction
empirically using the Box-Behnken design of experiments. The results showed that the reaction temperature had the
highest effect with a coefficient of 15.611, followed by the reactants mole ratio with a coefficient of 9.895 and then the
catalyst mass with a coefficient of 3.674. Mechanistic modeling of the reaction was performed using five models: Pseudo-
homogeneous, Eley-Rideal (E-R), Langmuir-Hinshlewood-Hougen-Watson (LHHW), Acid-complex and Alcohol-com-
plex models. From the analysis of the Root Mean Square Errors (RMSE) of the models, the Alcohol-complex model gave
the best fit. There were indications that the reaction also proceeded with the Acid-complex mechanism as a parallel
reaction.
Keywords: clay catalysts, esterification, empirical modeling, mechanistic modelling.

INTRODUCTION eral acids in catalyzing their reactions. The use of solid cata-
lysts will greatly simplify catalyst removal and recovery
Natural clay has been of interest to researchers thereby minimizing the amount of waste generated. The
in recent times, its extensive use ranges from the pro- advanced level of the green chemistry crusade has helped to
duction of industrial absorbent [1] to its use as a het- stimulate industrial interest, resulting in a growing number
erogeneous catalyst in organic processes which has of the use of environmental best practices [4, 5].
yielded positive results, for instance - in the use of local
clay as a catalyst in the production of glycerol EXPERIMENTAL
monostearate and acetaldehyde as reported in [2, 3].
One of the major challenges of modern chemical Materials and method
industries is the search for cleaner process routes for Clay activation
manufacturing their products. The tightening environ- The clay sample obtained from Udi in the Enugu
mental legislation is forcing them to consider alterna- state of Nigeria, had been characterized to be montmo-
tive processes that would not involve conventional min- rillonite [6], was crushed and screened with a microme-

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Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011

ter sieve. It was then activated by treating with 1M H2SO4 ii) Acid-complex model:
to form a slurry which was heated in an oven at 373K
E
for 4 hours. The dried acidified clay was pulverized and RT a b
(2)
stored in an air-tight container. Ae C A CB
rA = a
H

The reaction k o e RT CW + C A

The activated clay sample was used to catalyse
the liquid-phase esterification reaction. The summary iii) Alcohol-complex model:
E
of the reaction is given by eq. 1. a b
Ae RT C A C B
CH3COOH + C2H5OH P CH3COOC2H5 + H2O (1) rA =
H b
2.5 ml of acetic acid was pipetted into a 10 ml
k o e RT CW + C B (3)
stoppered bottle; 0.15 g of the clay catalyst was added

to it firstly, and then 2.5 ml of ethanol was pipetted into
it to ensure that the active sites of the catalyst were not
blocked by the alcohol. The container was tightly closed, iv) Eley-Rideal model:
the contents shaken vigorously and immersed in a wa-
E
(C A C B CC C D )
k oWe RT
ter bath maintained at 323K for 6 hours after which the K eq
content was titrated with 1M NaOH. The experiments rA = (4)
were conducted at temperatures of 80oC and 90oC using
1 + K A C A + K B C B + K C CC + K D C D
catalyst masses of 0.15 g and 0.3 g, acid to alcohol
reactant mole ratios 1:1 and 1:4. The Box-Behnken de- v) Langmuir-Hinshelwood-Hougen-Watson
model:
sign of experiment was used to run the set of experi-
ments, to obtain an empirical model of the reaction
k oWe
E
RT
(C AC B CC C D )
and to evaluate the magnitude of the effects of the three K eq
rA = (5)
variables.
(1 + K AC A + K B C B + K C CC + K D C D )2
Mechanistic Modeling of the Reaction
where CA, CB, CC, and CD are the concentrations
Based on the recommendations from the litera-
ture [7 - 10], five models were selected for testing: of acid, alcohol, ester and water, respectively and W is
the catalyst mass. KO, KA, KB, KC, KD are the frequency
i)Pseudo-homogeneous model:
E factor, the activation energy, the acid adsorption, the
rA = k oWe RT CACB CCCD alcohol adsorption, the ester adsorption, and the water
(1)
K eq adsorption constants, respectively, or the power of the

Table 1. Natural and coded values of the independent variables.

Variables Natural values Coded values


Low Mid High Low Mid point High
level point level level level
Catalyst , 0.2 0.3 0.4 -1 0 +1
mass,(g), x1
Reaction 50 70 90 -1 0 +1
temp.,(oC),
x2
Alcohol/Acid 1 3 5 -1 0 +1
mole ratio, x3

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P. K. Igbokwe, F. L. Olebunne

acid, power of the alcohol, and the acid-water complex Effect of the temperature on the esterification reac-
adsorption constant, as the case might be in the par- tion
ticular model [7-10]. Temperature has a very strong effect on the es-
terification reaction. Its effect is the strongest of those
RESULTS AND DISCUSSION of the three variables. From Figs.1 and 2, it can be seen
that an increase in temperature brought about a pro-
Effect of reaction variables nounced increase in the conversion of the acetic acid.
The results for the effects of the reaction tem- High temperature caused the reaction to proceed faster
perature, catalyst mass and reactants mole ratios are towards the equilibrium. The parameters of the empiri-
shown on Figs. 1- 4. They were analysed by varying two cal model given by eq. 2 also confirm that temperature
of the variables simultaneously while keeping the third has the highest effect on the reaction. The temperature
variable constant. coefficient is 15.611, while those of the catalyst mass
The empirical model equation obtained from the and reactants mole ratio are 3.674 and 9.895, respec-
Box-Behnkens design is given by eq. 7 tively. At temperature of 50oC, only about 50 % con-
version was attainable after six hours of reaction with 1:
Y = 63.478 + 3.674 X 1 + 15.611X 2 + 4 mole ratio and 0.4 g catalyst against almost 82 %
+9.895 X 3 0.87 X 1 X 2 2.275 X 1 X 3 (2) obtained at 90oC for the same catalyst amount and mole
2 2
0.326 X 2 X 3 + 0.506 X 1 3.539 X 2 3.877 X 3
2
ratio. The same reaction conducted at room tempera-

Fig. 1. Effects of catalyst mass and temperature for 1:1 mole ratio.

Fig. 2. Effects of catalyst mass and temperature for 1:4 mole ratio.

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Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011

Table 2. Summary table for the goodness of fit of all the models*.

Model Plan 1 Plan 2 Plan 3 Plan 4


RMSE RMSE RMSE RMSE

Eley-Rideal 3.2310-6 7.3210-6 1.8010-6 1.4710-6

Pseudo- Homogeneous 1.5110-6 3.4510-6 2.0010-6 7.7310-7

LHHW 3.2210-6 7.2210-6 1.7110-6 1.4610-6

Acid- Complex 6.6910-7 3.4410-7 5.1310-7 1.0410-6

Alcohol- Complex 6.6910-7 3.4410-7 4.7310-7 2.3810-7

* calculated for experimental plans using acid: alcohol ratio of 1:1 in the Box
Benken Design.

Table 3. Summary table for the goodness of fit of all the models*
Model Plan 5 Plan 6 Plan 7 Plan 8
RMSE RMSE RMSE RMSE

Eley-Rideal 1.0410-5 1.9310-6 1.5810-6 8.3710-7

Pseudo- Homogeneous 4.7110-6 8.6910-6 8.8510-7 6.7010-7

LHHW 1.0410-5 1.9310-6 1.5710-6 8.6410-7

Acid- Complex 6.6110-7 5.3910-7 1.0610-6 5.8810-7

Alcohol- Complex 6.6110-7 5.1710-7 2.7810-7 5.8810-7

* calculated for experimental plans using acid:alcohol ratio of 1:4 in the Box
Benken Design.

ture (30oC) with 0.4 g catalyst gave 40.2 % conversion Effect of the reactants mole ratio on the esterifica-
for the 1:1 mole ratio and 64.2 % conversion for the 1:4 tion reaction
mole ratio, after 120 hours (5days). Operating the es- The reactants mole ratio also has a strong effect
terification above the boiling of any of the reactants is on the rate of reaction hence the conversion obtainable
ineffective at atmospheric pressure due to phase sepa- in Fig. 2. It can be seen that with mole ratio of 1:1, the
ration. Even though the vapourised components are re- highest conversion is less than 63 % for all combinations
condensed with the use of a reflux condenser, phase of catalyst masses and temperatures, while for the mole
separation still cannot be eliminated within the reactor. ratio of 1:4, the final conversion is always above 75 %.
This leads to poor contact between the reactants and The empirical model was used to identify the effect of
hence - low conversion. This advised the use of stop- the mole ratio as the second highest effect after tempera-
pered bottles which acted as pressure vessels and al- ture, because it has a coefficient of 9.895 against 15.611
lowed the reaction to proceed only in liquid phase at for temperature and 3.674 for the catalyst mass. The
80 100oC well above the boiling point of ethanol. The mole ratio also affects the equilibrium conversion of the
only disadvantage was that the effect of continuous stir- reaction. The equilibrium conversion for the 1:1 mole
ring was not utilized. However, this was not a major ratio is 67 % while that of the 1:4 mole ratios is 85 %.
factor because it was confirmed from literature that the When the reactants mole ratio gets above 1:4, conversion
effects of internal and external diffusion limitations are can no longer be improved significantly, thus operating
negligible [7]. with much higher mole ratio becomes uneconomical.

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P. K. Igbokwe, F. L. Olebunne

Fig. 3. Effects of reactants mole ratios and catalyst mass at 80 oC.

Effect of the catalyst mass on the esterification reac- CONCLUSIONS


tion
An esterification reaction is a very slow reaction The acid-activated montmorillonite clay has been
which can only give very small conversion in the absence found to be a good catalyst for the esterification reac-
of catalyst even at high temperatures. The presence of a tion of acetic acid and ethanol. The result of the study
catalyst is very crucial for the reaction to proceed to an showed that the increase in the reaction temperature,
appreciable extent. When the reaction was run without catalyst mass and reactant mole ratio have a positive
catalyst, the highest conversion after six hours was less effect on the percentage conversion of the acetic acid.
than 30 % even at high temperature and reactants mole The reaction followed a parallel dual mechanism with
ratio. Also, from Figs. 1 - 3, it is obvious that the conver- the alcohol- and acid- complex kinetic models offering
sion increased with the increase of the catalyst mass. The the best fit. The knowledge of the magnitude of the ef-
response surface modeling results indicated that the ef- fects of these key variables is useful in predicting con-
fect of the catalyst mass on the reaction is less than those versions and enables the operation of the reaction with
of temperature and reactants mole ratio. This is, how- a greater efficiency.
ever, another way of saying that the presence of the cata-
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