Professional Documents
Culture Documents
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
The evaluation of various kinetic models for base-catalyzed ethanolysis of palm oil
Sanaz Shahla, Gek Cheng Ngoh , Rozita Yusoff
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
a r t i c l e
i n f o
Article history:
Received 25 July 2011
Received in revised form 2 November 2011
Accepted 3 November 2011
Available online 11 November 2011
Keywords:
Transesterication
Palm oil
Ethanolysis
Kinetic models
Activation energy
a b s t r a c t
In this paper, the kinetics of palm oil ethanolysis with various models have been investigated in a temperature range of 2555 C. The highest yield was achieved when the conversion to ethyl ester was
97.5 0.5% in the stated temperature range, using ethanol:oil molar ratio of 12:1, and 1.0 wt.% sodium
ethoxide. The level of conformity of the reaction with reversible second order, irreversible second order
and rst order kinetic models were evaluated by means of the R2 values of the linear curves. The ethanolysis showed the best conformity with irreversible second order kinetic model with 9298% level of condence. The reaction rate constants were within 0.0180.088 dm3/mol min and the activation energy of
the reaction was 42.36 kJ/mol.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Partially degrading chemical products have been proven to be
harmful to the environment and living creatures. Thus, biodegradability and renewability of the products are important features for
study (Graziani and Fornasiero, 2007). Application of vegetable oil
alkyl esters is extended to include the production of biodegradable
materials particularly bio-fuels, bio-surfactants and bio-lubricants
(Dossat et al., 2002). Conversion of the vegetable oils to alkyl esters
through transesterication using mono-alcohols qualies their
required specications of the fuel such as viscosity, boiling point
and ash point (Tiwari and Ghosal, 2007). Methanol is widely used
in the formulation of bio-fuels due to its low cost and availability
(Fukuda et al., 2001; Shahla et al., 2010). However, it has been
documented that ethanol can replace methanol to improve the
renewability of the produced bio-fuel. Moreover, ethanol offers
enhanced solubility for vegetable oils and is less toxic than
methanol (Cheirsilp et al., 2008; Marjanovic et al., 2010).
In spite of the widespread of published research on the production of bio-fuel from vegetable oils based methyl esters, most of
the recent studies on bio-fuel production are focused on the ethanolysis of vegetable oils (Alamu et al., 2008; Anastopoulos et al., 2009;
Cavalcante et al., 2009; Encinar et al., 2010; Gutirrez et al., 2009;
Hamad et al., 2008; Kumari et al., 2007; Moreira et al., 2007). It is
known that transesterication of vegetable oils with methanol involved a mass controlled regime followed by a chemically controlled
regime. However, researchers have reported that ethanol has higher
Corresponding author. Tel.: +603 7967 6879; fax: +603 7967 5319.
E-mail address: ngoh@um.edu.my (G.C. Ngoh).
0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.11.010
In general, a molar ratio of alcohol to oil higher than the stoichiometric amount is required for the initiation and acceleration of
the transesterication. Due to the presence of excessive alcohol
Table 1
Kinetic studies on transesterication of vegetable oils with ethanol.
Vegetable oil
Reaction order
Activation energy(kJ/
mol)
References
Cottonseed
2 wt.% NaOH
First order
Canola
Castor
Jatrophacurcas
2 wt.% Mg2CoAl
1 wt.% NaOH
0.8 wt.% NaOCH3
First order
First order
n = 1.266a
60.5
70.6
Sunower
3.443.9
Sunower
Palm
1 wt.% NaOC2H5
1 wt.% NaOC2H5
Georgogianni et al.
(2008)
Li et al. (2009)
Silva et al. (2009)
Om Tapanes et al.
(2008)
Marjanovic et al.
(2010)
Richard et al. (2011)
This work
51.0
42.36
A
n, order of triglyceride concentration in reaction equation: r A dC
kC A .
dt
in the reaction media, researchers often assumed that transformation of intermediates i.e. diglyceride and monoglyceride to alkyl
ester occurs rapidly. Therefore, most of the kinetic studies on the
methanolysis and ethanolysis of vegetable oils were based on the
overall reaction (Georgogianni et al., 2008; Li et al., 2009; Marjanovic et al., 2010; Om Tapanes et al., 2008; Richard et al., 2011; Silva et al., 2009). The overall equation of transesterication of palm
oil with ethanol is rewritten in the form of Eq. (3).
k1
A 3B 3C D
k2
dC A
k1 C A C B k2 C C C D
dt
h
i
dxA
k1 C AO 1 xA M 3xA 3Kx2A
dt
xA
C AO C A
C AO
p
D
p ln
p K t t C
2C AO D 61 KxA M 3 D
1
61 KxA M 3
1 xAe M 3xAe
3x2Ae
The conformity of the reaction with reversible second order kinetic model was tested by plotting Y(t) versus t. Y(t) was calculated
based on the terms on the left side of Eq. (7), whereas the integration constant of C was equal to the intercept of the achieved trend
line.
2.2. Irreversible second order kinetic model
r A
D M 32 12M1 K
r A
dC A
K 1CACB
dt
10
dxA
k1 C AO 1 xA M xA
dt
11
1
M 3xA
ln
k1 t C
C AO M 3
1 xA
12
dC A
dt
r A
dxA
k1 1 xA
dt
14
ln1 xA k1 t C
15
The conformity of the reaction with the rst order kinetic model
can be tested by plotting Yt ln1 xA versus t.
Meanwhile, the activation energy of the reaction can be calculated using Arrhenius equation as shown in Eq. (16):
Ea
k A exp
RT
13
16
Table 2
Palm oil conversion (%) at different times and temperatures.
Time (min)
1
2
3
4
5
6
10
15
20
25
30
40
50
60
Temperature (C)
25
35
45
55
6.59
12.40
63.92
66.72
70.82
77.88
89.87
92.54
94.16
96.58
97.30a
97.07
96.09
96.66
13.04
58.80
68.55
70.93
79.00
80.96
91.61
97.06a
96.01
96.70
96.38
63.23
74.55
85.58
87.41
93.76
95.99
97.95a
97.34
96.82
68.52
83.71
87.36
91.51
96.50
97.54a
97.52
96.01
97.19
a
Equilibrium conversion of palm oil = highest conversion at each reaction
temperature.
These ndings suggest that by increasing the reaction temperature, using an optimum molar ratio of the reactants and a suitable
amount of catalyst, the reaction can be accelerated and the required reaction duration to achieve the maximum triglyceride conversion is reduced without affecting the ethyl ester yield. On the
other hand, in a previous study by the authors, it was found that
99.68% ethyl ester was achievable at 25 C with optimum catalyst
concentration of 1.2 wt.% in 2 h (Shahla et al., 2011).
4.2. Kinetic model
A number of models implementing different kinetic orders for
ethanolysis of vegetable oils have been reported in the literature.
However, there are no studies reporting whether using simplifying
assumptions for the development of the kinetic model affects on
the conformity of the model. This work evaluates the conformity
of the alkaline catalyzed ethanolysis of palm oil with different kinetic models from the most detailed equations to the simplest version. Kinetics of the reaction was tested with reversible second
order, irreversible second order and rst order kinetic models
according to Eqs. (7), (12), and (15), respectively. The results obtained are presented in Figs. 24. As can be seen in these gures,
the slope and the intercept of the trend lines give the forward
Fig. 2. Conversion of palm oil to ethyl esters at different times and temperatures
achieved from the reversible second-order kinetic model (Eq. (7)).
Fig. 3. Conversion of palm oil to ethyl esters at different times and temperatures
achieved from the irreversible second-order kinetic model (Eq. (12)).
Reaction
temperature
(C)
Reversible second
order kinetic
model (Eq. (7))
25
35
45
55
0.901
0.968
0.942
0.976
0.918
0.978
0.946
0.975
0.906
0.901
0.934
0.797
Fig. 4. Conversion of palm oil to ethyl esters at different times and temperatures
achieved from the pseudo rst-order kinetic model (Eq. (15)).
Table 4
Rate constants for the irreversible second order ethanolysis of palm oil.
Reaction temperature (C)
25
35
45
55
0.018
0.037
0.055
0.088
Fig. 5. Arrhenius plot for irreversible second-order kinetic model for ethanolysis of
palm oil.