International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 24

104403-5656 IJET-IJENS June 2010 IJENS

I J E N S
Preliminary Study of the Heat Release From
Esterification Process

Syed Azhar Syed AB. Rahman
1*
, Mohd Zailani Abu Bakar
2
, Zainal Ahmad
2
*
E-mail: syedazhar@micet.unikl.edu.my
1
Section of Chemical Engineering Technology, Universiti Kuala Lumpur, Malaysian Institute of Chemical & Bioengineering
Technology, Lot 1988, Vendor City Industrial Area, Taboh Naning, 78000 Alor Gajah, Malacca, Malaysia
2
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
14300 Nibong Tebal, Seberang Prai Selatan, Pulau Pinang, Malaysia.


Abstract-- Esterification is one of the popular processes in
chemical engineering. Various important products are
produceD from this reaction and their applications are varies.
Esterification process can be classified as exothermic reaction
where in every reaction; a few amount of heat will be released
to the surrounding. Hence it is a quite simple reaction; the
study on heat releases should not be exceptional. In this study,
two different parameters (effect of different catalyst
concentration and different operating temperature) are
applied to determine the amount of heat release and the
possibility of the reaction in creating runaway reaction. The
study has selected an esterification reaction between acetic acid
and methanol because of their well known reaction and it is a
moderated exothermic process.

I ndex Term-- esterification reaction, exothermic reaction,
runaway reaction

I. INTRODUCTION
Esterification of carboxylic acids with alcohol in the
presence of acid catalyst has been the subject of
investigation by many research workers. Both homogeneous
and heterogeneous catalyst had been used for this purpose.
Mineral acids can be given as the example of homogeneous
catalyst and a cation-exchange resin in the acid form can
serve as heterogeneous catalyst [1]
Esterification process involved the reaction of ethanol and
acetic acid catalyzed by sulfuric acid were chosen in this
work. The stoichiometry reaction of the process is as below;
CH
3
CH
2
OH + CH
3
COOH CH
3
COOCH
2
CH
3
+ H
2
O
(1)

Ethanol reacts with acetic acid in producing ethyl acetate.
This reaction is called a homogeneous liquid phas e.
Normally, in the absence of a catalyst, the reactions are very
slow and require typically several days to attain the
equilibrium [7]. Therefore, a catalyst was added to enhance
the reaction. The catalyst could be heterogeneous or
homogenous. In this reaction, sulfuric acid acted as a
homogeneous catalyst. This catalyst is already known as an
efficient mineral acid catalyst [7].

The reaction was selected because it is a well known
reaction, simple and moderately exothermic [Heat or
reaction, H= -0.0114kJ/mol] with no danger of
decomposition reaction. Furthermore, this type of reaction
also got the attention of other researchers in studying the
possible runaway reaction on different chemical types [3]
[4] [6].

The commercial production of ethyl acetate is mainly by
two processes: the Tischenko reaction produces ethyl
acetate by direct conversion of ethanol via acetaldehyde
using an aluminum alkoxide catalyst and the production of
ethyl acetate by direct esterification of ethanol with acetic
acid and sulfuric acid catalyst. In this experiment, the direct
synthesis of ethyl acetate was chosen. For a normal
operation, the reactant concentration and catalyst
concentration were set respectively to be 6M and 3M [2].
The reaction was carried out at room temperature with 5%
catalyst volume and without cooling water.

Furthermore, the product from this reaction (i.e., ethyl
acetate) is a very important solvent and is used in many
products and industries [5]. It is used extensively as a
solvent for high-resolution printing inks and laminating
adhesives. It is also an important solvent in paints, resin
coatings and varnishes and also used in the pharmaceutical
industry as a process and purification solvent.

To the best of our knowledge, no researcher has reported the
study on the heat release from esterification of acetic acid
with ethanol in the presence of sulfuric acid. The
information of heat release from esterification process can
be used to detect the possibility of runaway reaction [3] [4]
[6]. The function of temperature and concentration can be
applied to investigate runaway phenomena [6].

This work was undertaken to study on the heat release from
esterification of acetic acid with ethanol in the presence of
sulfuric acid as a catalyst. The reaction was selected because
it is a well-known reaction and is moderately exothermic
reaction with no danger of decomposition reactions and for
which accurate kinetic exist; the reaction exhibits second-
order kinetics when no strong acid is present and a kind of
autocatalytic behaviour when the acid is introduced.

II. EXPERIMENTAL SECTION
A Pilots-Plant Installation
The experiment was carried out in a pilot-plant batch
reactor. The schematic diagram for the pilot-plant batch
reactor is shown in Figure 1.

International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 25

104403-5656 IJET-IJENS June 2010 IJENS
I J E N S
The pilot-plant batch reactor consists of reaction vessel,
electric heating via heating mantle, variable speed stirrer,
temperature indicator, cooling coil, feed vessel, gas feed
pipe and solid discharge pipe. The maximum capacity of the
reaction vessel is 20 liters.

9.5L of ethanol and 9.5L of ethyl acetate were charged to
the reaction vessel via the feed vessel and charge port. The
reaction vessel was fitted with a manually adjusted variable
speed (0-800 rpm) stirrer enabling the degree of mixing to
be varied. Heating was supplied by a heating mantle with
manually adjusted power setting; the reaction temperature
was indicated by a dial thermometer in the reaction vessel.
The reaction vessel was also fitted with an internal cooling
coil allowing the reaction mixture to be cooled. By varying
the heating and cooling, exothermic reaction could be
studied.

During the reaction process, any vapors produced passed up
through the fractionating packed column to the condenser
where they were condensed. Any non-condensable gases
passed through the condenser to vent or to the vacuum
system. Condensate from the condenser flowed back down
to the reflux divider where it could be directed either to the
top of the packed column or removed as product by
adjusting the reflux valve.

During all the experiments, the process temperature and
conductivity were recorded using a temperature indicator
and conductivity meter. On the other hand, the concentration
of product (ethyl acetate) was measured from the titration
process.

B. Experiment Design
A set of three experiments were carried out in the pilot -scale
chemical plant. The selected reaction was the catalyzed
esterification between acetic acid and ethanol. In this
experiment sulphuric acid is acted as a catalyst for the
reaction. It is our interest to analyze the reaction because it
is moderately exothermic reaction with no danger of side or
decomposition reactions. In addition, this reaction has been
extensively studied in the past.

Water out
Water in
Condenser
Condenser
Cooling coil
Drain
Drain
Dosing vessel
M
Heater
Product Vessel
TI
Fig. 1. Pilot -plant bat ch react or

The reactor was operated with three different catalyst
concentrations and with three different temperatures. The
parameters and operating conditions are listed in Table I.

TABLE I
OPERATIONG CONDITION FOR THE ESTERIFICATION
EXPERIMENT
Experiment 1:
Different catalyst concentration

Temperature: room temp
Acetic acid concentration: 6M
Ethanol concentration: 6M
Sulfuric acid concentration: 3M, 4M & 5M
Stirrer speed: 50 rpm

Experiment 2:
Different operating temperature

Temperature: room temp, 40C & 50C
Acetic acid concentration: 6M
Ethanol concentration: 6M
Sulfuric acid concentration: 3M
Stirrer speed: 50 rpm

C. Experimental Procedure
The esterification experiments have been carried out
following the procedure summarized below:

Experiment 1:
(i) Ethanol (reactant B) was weighted and loaded
into the reactor vessel using feed vessel.
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104403-5656 IJET-IJENS June 2010 IJENS
I J E N S
(ii) Acetic acid (reactant A) was weighted and
loaded into reactor vessel.
(iii) Sulfuric acid (catalyst) is added to the reactor
vessel.
(iv) When the reaction had finished, the reactor
contents were discharged.
(v) The experiment is repeated with different
catalyst concentration.

Experiment 2:
(i) Ethanol (reactant B) was weighted and loaded
into the reactor vessel using feed vessel.
(ii) Acetic acid (reactant A) was weighted and
loaded into other reactor vessel.
(iii) Reactor vessel and other reactor vessel
temperatures were set at the desired
temperature.
(iv) Once both reactor vessel and other reactor
vessel had reached the set-point temperature,
acetic acid was added to the reactor from the
feed vessel.
(v) Sulfuric acid (catalyst) is added to the reactor
vessel.
(vi) The experiment is repeated with different
temperature set-up.

III. RESULTS
Figure 2 and 3 represent the experimental results for both
two experiments. In the first experiment, the differential
temperature will increase gradually with time by increasing
the catalyst concentration for the 3, 4 and 5 M until they
reach the equilibrium at 70, 60 and 30 min respectively. The
differential temperature then reaches other equilibrium stage
at 130, 120 and 110 min. At this stage, the differential
pressure constant at 57.14%, 64.29% and 75% respectively.
The differential pressure were constant because of the
reaction already reached the equilibrium. The running of the
experiment after 200 min is believed will not change the
differential temperature.

Compared to Figure 3, the differential pressure at this
experiment is quite longer to reach the equilibrium stage. By
increasing the operating temperature, the equilibrium st age
is difficult to achieve. It shown at ambient, 40C and 50C,
the equilibrium stage only reach after 70, 80 and 120 min
respectively. It also shows that at every 10C temperature
increase, the differential pressure will increase between 43-
50%. From this experiment, the temperature will increase
1.4-1.5 times from their operating temperature.

Graph Differential Temperature (%) vs time for
esterification process with different catalyst
concentration
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
80.00
90.00
100.00
0 50 100 150 200 250
Time (min)
D
T

(
%
)
3M 4M 5M

Fig. 2. Graph different ial t emperat ure (%) versus t ime wit h different
cat alyst concent rat ion

Graph Differential Temperature (%) vs time for
esterification process with different operating
temperature
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
160.00
180.00
200.00
0 50 100 150 200 250
Time (min)
D
T

(
%
)
ambient temperature 40oC 50oC

Fig. 3. Graph different ial t emperat ure (%) versus t ime wit h different
operat ing t emperat ure

IV. CONCLUSION
The results show that the possibility more heat will be
released from this reaction with higher catalyst
concentration and higher operating temperature. It also
shows that the possibility runaway reaction will occur.
Dangerous process conditions which cannot be carried out
in experimental set-ups were simulated by special developed
simulators. The information from this experiment was
applied to develop a fault detection system.

ACKNOWLEDGEMENT
The authors acknowledge Ministry of Science, Technology
and Innovation Malaysia for the Science Fund Grant (03-01-
05-SF0220) to support the present research work.


VI. REFERENCES
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[3] Bosch, J., Kerr, D. C., Snee, T. J., St rozzi, F., & Zaldivar, J. M.
(2004a). Runaway det ection in a pilot-plant facilit y. Industrial
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104403-5656 IJET-IJENS June 2010 IJENS
I J E N S
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ht t p://www.chemicalweekly.com/Profile/Et hyl-Acet at e.PDF
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