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
Natural clay has been of interest to researchers
in recent times, its extensive use ranges from the pro-
duction of industrial absorbent [1] to its use as a het-
erogeneous catalyst in organic processes which has
yielded positive results, for instance - in the use of local
clay as a catalyst in the production of glycerol
monostearate and acetaldehyde as reported in [2, 3].
One of the major challenges of modern chemical
industries is the search for cleaner process routes for
manufacturing their products. The tightening environ-
mental legislation is forcing them to consider alterna-
tive processes that would not involve conventional min-
eral acids in catalyzing their reactions. The use of solid cata-
lysts will greatly simplify catalyst removal and recovery
thereby minimizing the amount of waste generated. The
advanced level of the green chemistry crusade has helped to
stimulate industrial interest, resulting in a growing number
of the use of environmental best practices [4, 5].
EXPERIMENTAL
Materials and method
Clay activation
The clay sample obtained from Udi in the Enugu
state of Nigeria, had been characterized to be montmo-
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
adsorption constant, as the case might be in the par-
ticular model [7-10].
RESULTS AND DISCUSSION
Effect of reaction variables
The results for the effects of the reaction tem-
perature, catalyst mass and reactants mole ratios are
shown on Figs. 1- 4. They were analysed by varying two
of the variables simultaneously while keeping the third
variable constant.
The empirical model equation obtained from the
Box-Behnkens design is given by eq. 7
Y = 63.478 + 3.674 X 1 + 15.611X 2 +
+9.895 X 3 0.87 X 1 X 2 2.275 X 1 X 3 (2)
2 2
0.326 X 2 X 3 + 0.506 X 1 3.539 X 2 3.877 X 3
2
Effect of the temperature on the esterification reac-
tion
Temperature has a very strong effect on the es-
terification reaction. Its effect is the strongest of those
of the three variables. From Figs.1 and 2, it can be seen
that an increase in temperature brought about a pro-
nounced increase in the conversion of the acetic acid.
High temperature caused the reaction to proceed faster
towards the equilibrium. The parameters of the empiri-
cal model given by eq. 2 also confirm that temperature
has the highest effect on the reaction. The temperature
coefficient is 15.611, while those of the catalyst mass
and reactants mole ratio are 3.674 and 9.895, respec-
tively. At temperature of 50oC, only about 50 % con-
version was attainable after six hours of reaction with 1:
4 mole ratio and 0.4 g catalyst against almost 82 %
obtained at 90oC for the same catalyst amount and mole
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
for the 1:1 mole ratio and 64.2 % conversion for the 1:4
mole ratio, after 120 hours (5days). Operating the es-
terification above the boiling of any of the reactants is
ineffective at atmospheric pressure due to phase sepa-
ration. Even though the vapourised components are re-
condensed with the use of a reflux condenser, phase
separation still cannot be eliminated within the reactor.
This leads to poor contact between the reactants and
hence - low conversion. This advised the use of stop-
pered bottles which acted as pressure vessels and al-
lowed the reaction to proceed only in liquid phase at
80 100oC well above the boiling point of ethanol. The
only disadvantage was that the effect of continuous stir-
ring was not utilized. However, this was not a major
factor because it was confirmed from literature that the
effects of internal and external diffusion limitations are
negligible [7].
Effect of the reactants mole ratio on the esterifica-
tion reaction
The reactants mole ratio also has a strong effect
on the rate of reaction hence the conversion obtainable
in Fig. 2. It can be seen that with mole ratio of 1:1, the
highest conversion is less than 63 % for all combinations
of catalyst masses and temperatures, while for the mole
ratio of 1:4, the final conversion is always above 75 %.
The empirical model was used to identify the effect of
the mole ratio as the second highest effect after tempera-
ture, because it has a coefficient of 9.895 against 15.611
for temperature and 3.674 for the catalyst mass. The
mole ratio also affects the equilibrium conversion of the
reaction. The equilibrium conversion for the 1:1 mole
ratio is 67 % while that of the 1:4 mole ratios is 85 %.
When the reactants mole ratio gets above 1:4, conversion
can no longer be improved significantly, thus operating
with much higher mole ratio becomes uneconomical.

392
 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-
tion
An esterification reaction is a very slow reaction
which can only give very small conversion in the absence
of catalyst even at high temperatures. The presence of a
catalyst is very crucial for the reaction to proceed to an
appreciable extent. When the reaction was run without
catalyst, the highest conversion after six hours was less
than 30 % even at high temperature and reactants mole
ratio. Also, from Figs. 1 - 3, it is obvious that the conver-
sion increased with the increase of the catalyst mass. The
response surface modeling results indicated that the ef-
fect of the catalyst mass on the reaction is less than those
of temperature and reactants mole ratio. This is, how-
ever, another way of saying that the presence of the cata-
lyst in the reaction is more important than the actual
amount of it presents. The coefficient of 3.674 obtained
for its effect from the response surface modeling was just
the effect between using 0.2 g and 0.4 g of the catalyst.
Analysis of the mechanistic models
The five mechanistic models were tested by com-
paring the goodness of fit of the experimentally obtained
rates of reaction to the calculated rates. It was seen that
the esterification reaction proceeded via a dual parallel
mechanism. The Acid- and Alcohol- complex models
fitted the calculated rates better than the other models
(Tables 2 and 3). From the values of the root mean
square errors (RMSE), there were strong indications,
however, that the alcohol-complex mechanism domi-
nated because of the presence of a reagent in excess.
CONCLUSIONS
The acid-activated montmorillonite clay has been
found to be a good catalyst for the esterification reac-
tion of acetic acid and ethanol. The result of the study
showed that the increase in the reaction temperature,
catalyst mass and reactant mole ratio have a positive
effect on the percentage conversion of the acetic acid.
The reaction followed a parallel dual mechanism with
the alcohol- and acid- complex kinetic models offering
the best fit. The knowledge of the magnitude of the ef-
fects of these key variables is useful in predicting con-
versions and enables the operation of the reaction with
a greater efficiency.
REFERENCES
1. T. Nakamura, N. Kawasaki, M. Hirata, Adsorption
of Hydrogen Sulphide by Zinc Containing Activated
Carbon, Journal of Toxicological and Environmen-
tal Chemistry, 82, 2001, 93-98.
2. P.K. Igbokwe, J.T. Nwabanne, Kinetics of Catalytic
Esterification of Stearic Acid with Glycerol using
Catalyst Obtained from local clay Resources, Journal
of Applied Science, 11, 2008, No.2, 7847 7852.
3. P.K. Igbokwe, F.L. Olebunne, S.O. Opebiyi, F.N.
Uzondu, Effect of Silica gel Support On Clay-
catalysed Vapour-phase Dehydrogenation of Ethanol,
International Journal of Engineering Science, Ghana,
1, 2, 2009, 132-137.
4. K. Wilson, J.H. Clark, Solid acids and their use as
393
 Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011
environmentally friendly Catalysts in Organic Synthe-
sis, Journal of Pure Applied Chemistry, 72, 7, 2000,
1313 1319.
5. K.S. Corra, A New Environmental Friendly Clay
Catalyst for One-pot Co-iodination and Epoxidation
of Alkenes, A Journal of Brazilian Chemical Soci-
ety, 18, 8, 2007, 1509-1514.
6. B. F. Okafor, C. O. Nwajagu, Characterization of Udi
clay Deposits, Journal of Nigerian Society of Chemi-
cal Engineers (NSChE), 2, 1, 1989, 32-35.
7. S.B. Nicol, R. Schwarzer, Esterification with Cation-
Exchange Resin Catalyst: Concept of an Active Sur-
face Layer, Journal of Catalysis, 2006, T2 T13P.
http:// www.ecce6.kt/cm/content/abstract2273.
394
8. S. Bouguerra-Neji, M. Trabelsi, M. H. Frikha, Prepa-
ration of Fatty Esters Catalysed by Tunisian Clay in
Semi-continuous Reactor, 98th AOCS Annual Meet-
ing and Expo., Quebec City Convention Centre,
Canada, 2007.
9. T. Prakoso, R. Khair, U. Khair, Kinetics of Free
Fatty Acid Esterification Contained in Crude Palm
Oil, Indonesian National Technical Seminar. v 17,
2009, 1-8.
10. B. Saha, A. Alrqahtani, H.T. Teo, Production of
Iso-amyl Acetate: Heterogeneous Kinetics and
Techno-feasibility Evaluation of Catalytic Distilla-
tion, International Journal of Chemical Reactor En-
gineering, 3, Article 30, 2005.