RSCE-SOMCHE 2008 955

Edited by Daud et al.

MODELING AND SIMULATION OF CITRONELLYL
LAURATE ESTERIFICATION IN A BATCH REACTOR

S.A. Zulkeflee and N. Aziz*

School of Chemical Engineering, Engineering Campus, Universiti Sains
Malaysia, 14300 Nibong Tebal, Seberang Perai Selatan, Pulau Pinang, Malaysia
*Corresponding author. Phone: +604 5996457, Fax. +604 5941013,
Email: chnaziz@eng.usm.my

Keywords: batch reactor; Citronellyl laurate; esterification; modeling; simulation.

ABSTRACT

Operating batch esterification process at the required operating conditions is very

important to ensure the maximum conversion obtained. However, to control this
reactor is quite difficult due to its non-linear nature, time varying system and
unsteady state operating condition. Model based control strategies such as
internal model control (IMC) and model predictive control (MPC) have been
revealed as a better control system compared to the conventional method because
of its ability to satisfy strict performance required. To implement such model
based control, model representing the process is a must. In this work, a detailed
dynamic model is developed for Citronellyl Laurate esterification. The models
include all major aspects of the description of mass and energy balance, chemical
reactions and thermodynamics non-idealities. The kinetic data for the model is
obtained from experimental data. The effects of catalyst loading and temperature
are also be evaluated by simulating the model using MATLAB®. It is found that
the model predictions are in satisfactory agreement with the experimental data
with R2=0.982.

INTRODUCTION

Batch reactors are one of the most major equipment in the biochemical
industries. It is quite flexible, it can adopt to small volume production of various
products and provides the natural way to scale-up processes from laboratory to
industrial manufacturing. One of difficulties in analyzing the dynamic response
on biochemical processes is the fact that they are nonlinear (Hua et. al., 2004).
Due to these difficulties, linear controllers or control strategies based on a local
linearized model e.g. standard PID controller lead to a poor control performance
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(Liu & Macchietto, 1995). The common way of controlling process systems with
strong nonlinear character is to apply model-based controllers such as model
predictive controllers (MPC) or internal model controllers (IMC) where a
detailed dynamic process model is used (Seborg et. al., 2004; Dowd et. al., 2001;
Toivonen et. al., 2003). In this paper, the process of Citronellyl laurate
esterification is chosen as a case study (Yadav and Lathi, 2004). The set-ups of
the batch reactor are given together with the experimental procedures. The
analytical procedures performed to the samples are also explained. Finally, the
simulated models were then verified with the experimental data.

EXPERIMENTAL SETUPS

A schematic diagram of the experimental apparatus is provided in Fig. 1. The

reactor was a 1.5L pyrex glass cylindrical vessel. The temperature of the reactor,
inlet, and outlet water in jacket were measured by thermocouples. The reactor
mixture was agitated by a propeller of 8cm diameter. A variable speed driver
permitted the impeller speed to be varied from 100 to 500rpm. The flow rate of
the water in jacket was measured by a flowmeter. A computer with A/D and D/A
converters was employed to control the temperature of the reactor.

Digital
Computer A/D
T

T T
A/D
Triac
Module
Cooling

Heater

FIGURE 1: Schematic diagram of the esterification reactor system.

In the experiments, 0.03M of Citronellol, 0.02M lauric acid are used as

reactants, where 0.02M NaOH is used to stop the reaction and phenolphthalein is
used for titration indicator. The temperature and stirring rate are adjusted to 37oC
(optimal temperature) and 200rpm respectively. The system is operated to reach
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the steady state condition while samples are taken every five minutes. Then, the
flow rate of cooling water is increased and decreased from 40ml/min to 44ml/min
and 36ml/min respectively by giving ±10% step change, and the inlet
temperature of the cooling water is kept constant. For another test, the inlet
temperature of the cooling water is increased and decreased from 22oC to 37oC
and 17oC respectively by giving the ±10% step change, and the flow rate of
cooling water is kept constant.

RESULTS AND DISCUSSION

First Principle Model of the Esterification Batch Reactor

Obtaining a dynamical model for the considered process addresses objective

consists in simulating the process behavior. In practice, dynamical models for
chemical reactors are obtained by considering continuity equations. In the case of
stirred tank reactors, it is commonly assumed that the reactor is perfectly mixed.
The kinetic reaction sequence is (Garcia et. al., 2000);

dCA Al r
       1
dt KA KA Ac αK A
αK A 1 Al 1
Ac K βK Ac

The energy balance around the reactor is written as;

Reactor dT ∆H rA V Q (2)
dynamics: dt V CA CpA CA CpA CE CpE CW CpW

Jacket dT F Cp ρ T T Q (3)
dynamics: dt V Cp ρ

where Q UA  T T                                              4

Model of the reactor is solved using 4th/5th order Runge Kutta method
(MATLAB ODE45). Table 1 shows the operating and calculated data.

Model Validation: Fig. 2 depicts measurements and model predictions of percent

of ester conversion, reaction and jacket temperature profile that yields a least-
squares model fit. The figure shows that the predicted conversion of acid to ester
is initially higher than the measured conversion with R2=0.982. This result
indicates that the models developed are adequate to describe the esterification of
Citronellyl laurate in batch reactor.
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TABLE 1: Operating Conditions and Calculated Parameters

Parameters Units Values Parameters Units Values
AAc L mol/s 18.20871 Cpw J/mol K 75.40
AAl L mol/s 24.04675 V L 1.5
Ai L mol/s 0.319947 Vj L 0.8
3
EAc J mol/K -105.405 Q J/m 11.648
EAl J mol/K -66.093 ΔHrxn kJ 19.84
Ei J mol/K -249.944 α - 1
Tji K 294 β - 1
CpAc J/mol K 420.53 U J/s m2 K 2.857
CpAl J/mol K 235.27 A m2 0.077
CpEs\ J/mol K 617.79 R J/mol K 8.314

100

80

60
conversion (%)

40

20 ♦ Experimental
___ Simulation
0
0 10 20 30 40 50
time (min)
FIGURE 2: Measurements and model predictions profile that yielded a minimum
least-squares model fit (R2=0.982) for 3% catalyst loading and temperature 37oC

Effect of Reaction Conditions

a) Catalyst loading
The effect of enzyme concentration was studied in the range of 1-3% (w/v), at
37oC (optimal temperature). The results are illustrated in Fig. 3. It can be seen
that conversion of ester increased with increasing catalyst concentration. At the
concentration of 3% enzyme the highest initial rate was observed. All further
experiments were carried out with 3% (w/v) of lipase from Candida rugosa in
order to reach maximum initial rate and utilization of enzyme activity.
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100

80
conversion (%)

60

40 1%
2%
20 3%
0
0 10 20 30 40 50
time (min)
FIGURE 3: The effect of catalyst loading on the synthesis of Citronellyl laurate

b) Effect of temperature
The model predictions were also tested for responses to a temperature change.
The impact of temperature in the ester yield and velocity is difficult to predict
because it may affect reaction efficiency in opposite way. First, a temperature
raise would have a positive effect on the kinetic constant as defined by the
transition state theory. Conversely, the treatment at high temperatures may
disrupt enzyme tertiary structure, losing its catalytic activity. From previous
findings, (Aziah Serri et. al., 2006) heating was required for faster reaction and
the reaction time may vary from a few minutes to several hours for a temperature
range 30oC to 40oC for esterification process. The ester conversion was found to
increase with increasing temperature, as shown in Figure 4.

100

80
conversion (%)

60

40
30
20 35
40
0
0 10 20 30 40 50
time (min)
FIGURE 4: The effect of reaction temperature on the synthesis of Citronellyl
laurate
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CONCLUSION

A mathematical model for esterification process has been proposed by

developing the differential mass and energy balance equation for batch reactor.
The models have been solved and validated using 4th/5th order Runge Kutta
method (MATLAB ODE45) and the simulation showed good agreement with the
experimental results with R2=0.982. The amount catalyst loading and
temperature were found to have profound influence on the conversion of
Citronellyl laurate.

ACKNOWLEDGMENT

The authors wish to acknowledge the financial support by Ministry of Science,

Technology and Innovation (MOSTI), Malaysia through the NSF scholarship for
the first author and sciencefund project no 03-01-05-SF0090.

REFERENCES

Aziah Serri N., Kamaruddin A.H., and Long W.S. (2006). Studies of reaction
parameters on synthesis of Citronellyl laurate ester via immobilized Candida
rugosa lipase in organic media. Bioprocess and Biosystems Engineering 29,
253-260
Dowd, J. E., Kwok, K. E., and Piret, J. M. (2001). Predictive modeling and loose-
loop control for perfusion bioreactors), Biochemical Engineering Journal, 9, 1-
9
Garcia, T., Coteron, A., Martinez, M. and Aracil, J. (2000) “Kinetic model for
the esterification of oleic acid and cetyl alcohol using immobilized lipase as
catalyst” Chemical Engineering Science, 55, 1411-1423
Hua, X., Rohani S., Jutan A. (2004) Cascade closed-loop optimization and
control of batch reactor. Chemical Engineering Science 59, 5695-5708
Seborg, D. E., Edgar, T. F. and Mellichamp, D. A. (2004), On-line Controller
Tuning, Process Dynamics and Control, pp 317 – 321.
Toivonen H.T., Sandstrom K.V., and Nystrom R.H. (2003). Internal model
control of nonlinear systems described by velocity based linearizations. Journal
of Process Control 13, 215-224.
Yadav G.D., Lathi P.S. (2004) Synthesis of citronellol laurate in organic media
catalyzed by immobilizied lipases: kinetic studies, Journal of Molecular
Catalysis B:Enzymatic, 27, 113-119.