Вы находитесь на странице: 1из 5

Bioresource Technology 104 (2012) 15

Contents lists available at SciVerse ScienceDirect

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
Palm oil
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.

solubility for vegetable oils and by applying minimum agitation

speed of 600 rpm the mass controlled regime in ethanolysis reactions can be eliminated (Encinar et al., 2002; Marjanovic et al., 2010).
Previous studies on kinetics of vegetable oils alcoholysis are
summarized in Table 1. It can be seen from this table that ethanolysis processes of vegetable oils are described with models considering different kinetic orders. In the ndings reported so far, there
is lack of information on the kinetics of ethanolysis of palm oil. In
this work, three different kinetic models for palm oil ethanolysis
were evaluated to determine the best conforming kinetic model
for the reaction involved.
2. Kinetic model development
Transesterication of vegetable oils with mono-alcohols such as
methanol and ethanol to produce alkyl esters are as shown in Eq.

Triglyceride Mono-alcohol Diglyceride Alkyl ester

Diglyceride Mono-alcohol Monoglyceride Alkyl ester
Monoglyceride Mono-alcohol Glycerol Alkyl ester

The three stepwise reactions can be simplied into an overall

reaction as shown in Eq. (2).

Triglyceride 3Mono-alcohol 3Alkyl ester Glycerol

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

S. Shahla et al. / Bioresource Technology 104 (2012) 15

Table 1
Kinetic studies on transesterication of vegetable oils with ethanol.

Vegetable oil

Catalyst type and concentration


Reaction order

Activation energy(kJ/



2 wt.% NaOH

First order


2 wt.% Mg2CoAl
1 wt.% NaOH
0.8 wt.% NaOCH3

First order
First order
n = 1.266a



0.751.25 wt.% NaOH



1 wt.% NaOC2H5
1 wt.% NaOC2H5

Reversible second order after an irreversible second order

Irreversible pseudo second order
Irreversible second order

Georgogianni et al.
Li et al. (2009)
Silva et al. (2009)
Om Tapanes et al.
Marjanovic et al.
Richard et al. (2011)
This work


n, order of triglyceride concentration in reaction equation: r A  dC
kC A .

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).

A 3B 3C D

2.1. Reversible second order kinetic model

The kinetic model of chemical transesterication of vegetable
oils (Eq. (3)) is a reversible second order model as shown in Eq.
(4). During the reaction, one mole of palm oil has been transesteried into three moles of ethyl ester and one mole of glycerol. Substitution of these equivalents into Eq. (4) results in Eq. (5).
Furthermore, conversion of palm oil (xA) can be obtained using
Eq. (6). The integration of this equation yields Eq. (7) in which,
, CAO and CBO are the initial molar concentrations of palm
oil and ethanol, respectively. The equilibrium constant, K kk21
and D can be calculated from the integrated Eqs. (8) and (9). The
equations are the modied forms of the equations developed by
Stamenkovic et al. (2008).

dC A
k1 C A C B  k2 C C C D

k1 C AO 1  xA M  3xA  3Kx2A


p ln
p K t t C
2C AO D 61  KxA  M 3 D

61  KxA  M 3 

1  xAe M  3xAe

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
2.2. Irreversible second order kinetic model

where A, B, C and D represent palm oil, ethanol, ethyl ester, glycerol

and k1 and k2 refer to the rate constants for the forward reaction
and the reverse reaction, respectively.
The reversible second order kinetic model is comprehensive and
can be used for the investigation of chemical transesterication. A
few assumptions have been made by researchers to simplify the
kinetic model of vegetable oil ethanolysis such as irreversible second order model to rst order kinetic model. In this work the conformity of alkaline ethanolysis of palm oil was tested via different
kinetic models including the reversible second order, irreversible
second order and rst order kinetic models.

r A 

D M 32  12M1  K

By assuming the fast disappearance of the reaction intermediates

being transformed into alkyl esters, the kinetic model of the reaction
can be simplied to Eq. (10). This equation can be further expressed
in the form of Eq. (11) which is integrated to Eq. (12). Conformity of
the reaction kinetics with irreversible second order kinetic model is
tested through plotting Yt C AO M3
ln M3x
versus t.

r A 

dC A


k1 C AO 1  xA M  xA


M  3xA
k1 t C
C AO M  3
1  xA


2.3. First order kinetic model

Some researchers assumed that, by minimizing the alcohol loss
during the reaction, the concentration of vegetable oil can be
considered as the sole determining factor of the reaction kinetics
(Joelianingsih et al., 2008). Hence, the reaction kinetic model can
be simplied into a pseudo rst order kinetic model as shown in
Eq. (13). This equation was rearranged in terms of palm oil conversion as shown in Eq. (14). Subsequent integration of this rst order
equation yields Eq. (15).

dC A

r A 

k1 1  xA


 ln1  xA k1 t C


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):

k A exp 



S. Shahla et al. / Bioresource Technology 104 (2012) 15

where Ea is the activation energy and A is the frequency factor.

By plotting ln k versus 1/T, the slope and intercept of the trend
line gives the value of Ea/R and A, respectively.
3. Methods
HCl 0.1 N Titrisol and n-hexane analytical grade were purchased
from Merck. Palm oil (rened, bleached and deodorized) was obtained from local market. Ethanol and sodium ethoxide were purchased from R&M Chemicals and Fluka, respectively.
Palm oil, ethanol and sodium ethoxide that was previously dissolved in ethanol were charged into a glass reactor. The desired
reaction temperatures were monitored by a circulating water bath.
Ethanol loss from the reactor was minimized using a Graham coil
condenser. Ethanol to oil molar ratio of 12:1 and sodium ethoxide
concentration of 1.0 wt.% were used for the kinetic studies of palm
oil ethanolysis where the temperature was in the range of 2555 C
and the agitation speed was xed at 600 rpm.
Samples of the reaction blend were taken at certain time intervals using a Pasteur pipette and added to the 1.5 ml centrifuge
tubes which already contained 0.1 ml of 0.1 N HCl for neutralization of the catalyst and termination of the reaction. Samples were
centrifuged for 15 min and then allowed to rest for a few hours to
ensure the separation of the reaction phases. The ethyl ester phase
was withdrawn by Pasteur pipette and puried by passing through
a 0.2 lm PTFE syringe lter. Samples of the ethyl ester were analyzed by Agilent GC-MSD equipped with 30 m  0.25 mm
id  0.25 lm DB-Wax column, using hydrogen as the carrier gas.

Table 2
Palm oil conversion (%) at different times and temperatures.
Time (min)


Temperature (C)








Equilibrium conversion of palm oil = highest conversion at each reaction

4. Results and discussion

Throughout the experiments, agitation was applied to initiate
the reaction, causing the formation of white slurry which turned
into a clear yellow blend within a few seconds. This induction period of the catalyst is assumed to be the time required for catalyst
activation. It continued for 50 s, 20 s, 12 s and 7 s at increased reaction temperatures of 25 C, 35 C, 45 C and 55 C, respectively. The
induction period is thought to be the mass transfer controlling
stage of the reaction. It can be seen that this interval is shorter than
1 min at 25 C and it decreases signicantly at higher reaction
temperatures. Therefore, with respect to the short induction period
and by applying agitation speed of 600 rpm, the mass transfer
effect could be ignored in the transesterication with ethanol
(Encinar et al., 2002; Marjanovic et al., 2010) and the kinetic
models were developed solely based on the chemical reactions.
4.1. Conversion of palm oil to ethyl ester
Kinetic study on transesterication of palm oil with ethanol was
conducted at a temperature range of 2555 C using ethanol:oil
molar ratio of 12:1 and 1.0 wt.% catalyst. Conversion results of
the reaction blends to ethyl esters at different time intervals and
temperatures are summarized in Table 2 and plotted in Fig. 1. It
can be observed from these results that the ethyl ester yield from
ethanolysis of palm oil reached a maximum of 97.5 0.5% at the
equilibrium point for all reaction temperatures. As the reaction
temperature was increased, the same conversion was achieved
but at shorter times. It was observed that ethanolysis at 25 C,
35 C, 45 C, and 55 C reached to the equilibrium point with reaction times of 30 min, 15 min, 10 min, and 6 min, respectively. This
observation concurs with the results obtained for the ethanolysis
of castor oil at 30 C, which resulted in 99% ethyl ester in 30 min
(Silva et al., 2009) and also the ethanolysis of sunower oil which
completed within 2030 min (Marjanovic et al., 2010).

Fig. 1. Conversion of palm oil to ethyl esters achieved experimentally at different

times and temperatures.

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

S. Shahla et al. / Bioresource Technology 104 (2012) 15

Table 3
R2 values for conformity of palm oil ethanolysis with various kinetic models.

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)).


R2 values of the trend lines

Pseudo rstorder kinetic
model (Eq. (15))

Irreversible secondorder kinetic model

(Eq. (12))

Reversible second
order kinetic
model (Eq. (7))





pseudo rst order kinetic model while the lowest condence of

90.1% applies to the reaction at 25 C and the highest condence
of 97.6% corresponds to the reaction at 55 C.
When comparing the R2 values of the irreversible second order
with the pseudo rst order kinetic models, Table 3 illustrates that
the reactions at temperature range of 2545 C showed better conformity with the irreversible second order kinetic model than the
pseudo rst order kinetic model. Meanwhile, the reaction at
55 C follows both pseudo rst order and irreversible second order
kinetic models with a close level of conformity. On the other hand,
when comparing the reversible second order with the pseudo rst
order kinetic models at 25 C, the former gave better conformity.
However, reactions at other temperatures indicated less conformity with reversible second order kinetic model than both irreversible second order and rst order kinetic models.
It is apparent that taking all the temperature range into consideration, chemical ethanolysis of palm oil in this study tted well
with an irreversible second order kinetic model. Since the reaction
at 25 C showed minimum condence level of conformity, the
inclusion of the effect of mass transfer controlling regime in the
kinetics study might gave a better conformity with all the kinetic
models studied. This agrees with the ndings reported on the ethanolysis of sunower oil (Richard et al., 2011).

4.3. Rate constants and activation energy

Fig. 4. Conversion of palm oil to ethyl esters at different times and temperatures
achieved from the pseudo rst-order kinetic model (Eq. (15)).

reaction constant and the model integration constant, respectively.

Furthermore, it is important to note that the values of R2 of the
trend lines presented in Table 3 give the condence levels of the
reaction conformity with the corresponding kinetic model.
Here, the conformity of the experimental results with all the kinetic models from the simplest form to the most specied one is
discussed. Table 3 shows that the alkaline catalyzed ethanolysis
of palm oil gave 90.197.6% condence level in conformity with

The best conforming kinetic model for the transesterication of

palm oil with ethanol was the irreversible second order. Table 4
presents the rate constants for this model, which were calculated
from the slope of the trend lines in Fig. 3. The rate constant at
25 C was found to be 0.018 dm3/mol min and it increased to
0.088 dm3/mol min at 55 C which clearly indicates that elevated
temperatures accelerate ethanolysis and reduce reaction duration
to achieve maximum product. This observation is in agreement
with the equilibrium times of the reaction at different temperatures as previously shown in Table 2. The rate constants of the forward and reverse reactions of alkaline ethanolysis of C12C18 fatty
acids based on a reversible second order kinetic model were in the
range of 0.00210.0174 dm3/mol min and 0.00161.1673 dm3/
mol min, respectively (Camara and Aranda, 2011). The rate constants obtained in this work were obviously within the range reported by other researchers (Pisarello et al., 2010).
Based on Eq. (16) and Fig. 5., the calculated activation energy of
the ethanolysis of palm oil was 42.36 KJ/mol which also agreed

Table 4
Rate constants for the irreversible second order ethanolysis of palm oil.
Reaction temperature (C)

Rate constant (dm3/mol min)



S. Shahla et al. / Bioresource Technology 104 (2012) 15

Fig. 5. Arrhenius plot for irreversible second-order kinetic model for ethanolysis of
palm oil.

well with the activation energies of alkaline transesterication of

vegetable oils reported in Table 1.
5. Conclusions
Ethanolysis of palm oil yielded 97.5 0.5% ethyl ester at a
temperature range from 25 C to 55 C. The catalyst activation time
and the reaction duration were inversely proportional to the
temperature. Palm oil ethanolysis conformed well to an irreversible
second order kinetic model at temperatures up to 45 C whereas the
reaction conformed to both pseudo rst order and irreversible second order kinetic models at 55 C. The rate constants and activation
energy obtained were within the range of ndings of other
researches. The present investigation has veried that modication
of the kinetic models into simpler forms affect its level of conformity.
Financial support by University Malaya PPP grant PS129/2009C
and UMRG grant RG006/09AET is gratefully acknowledged.
Alamu, O.J., Waheed, M.A., Jekayinfa, S.O., 2008. Effect of ethanol-palm kernel oil
ratio on alkali-catalyzed biodiesel yield. Fuel 87, 15291533.
Anastopoulos, G., Zannikou, Y., Stournas, S., Kalligeros, S., 2009. Transesterication
of vegetable oils with ethanol and characterization of the key fuel properties of
ethyl esters. Energies 2, 362376.
Camara, L.D.T., Aranda, D.A.G., 2011. Reaction kinetic study of biodiesel production
from fatty acids esterication with ethanol. Ind. Eng. Chem. Res. 50, 25442547.
Cheirsilp, B., H-Kittikun, A., Limkatanyu, S., 2008. Impact of transesterication
mechanisms on the kinetic modeling of biodiesel production by immobilized
lipase. Biochem. Eng. J. 42, 261269.

Cavalcante, K.S.B., Penha, M.N.C., Mendona, K.K.M., Louzeiro, H.C., Vasconcelos,

A.C.S., Maciel, A.P., de Souza, A.G., Silva, F.C., 2009. Optimization of
transesterication of castor oil with ethanol using a central composite
rotatable design (CCRD). Fuel 89, 11721176.
Dossat, V., Combes, D., Marty, A., 2002. Efcient lipase catalyzed production of a
lubricant and surfactant formulation using a continuous solvent-free process. J.
Biotechnol. 97, 117124.
Encinar, J.M., Gonzlez, J.F., Martnez, G., Romn, S., 2010. Biodiesel by enzymatic
transesterication of sunower oil with ethanol. J. Biobased Mater. Bioenerg. 4,
Encinar, J.M., Gonzlez, J.F., Rodrguez, J.J., Tejedor, A., 2002. Biodiesel fuels from
vegetable oils: transesterication of cynaracardunculus L. Oils with ethanol.
Energ. Fuel 16, 443450.
Fukuda, H., Kondo, A., Noda, H., 2001. Biodiesel fuel production by
transesterication of oils. J. Biosci. Bioeng. 92, 405416.
Graziani, M., Fornasiero, P., 2007. Renewable Resources and Renewable Energy: A
Global Challenge, CRC press.
Gutirrez, L.F., Snchez, .J., Cardona, C.A., 2009. Process integration possibilities for
biodiesel production from palm oil using ethanol obtained from lignocellulosic
residues of oil palm industry. Bioresour. Technol. 100, 12271237.
Georgogianni, K.G., Kontominas, M.G., Pomonis, P.J., Avlonitis, D., Gergis, V., 2008.
Alkaline conventional and in situ transesterication of cottonseed oil for the
production of biodiesel. Energy Fuel 22, 21102115.
Hamad, B., Lopes de Souza, R.O., Sapaly, G., Carneiro Rocha, M.G., Pries de Oliveira,
P.G., Gonzalez, W.A., Andrade Sales, E., Essayem, N., 2008. Transesterication of
rapeseed oil with ethanol over heterogeneous heteropoly acids. Catal. Commun.
10, 9297.
Joelianingsih, Maeda, H., Hagiwara, S., Nabetani, H., Sagara, Y., Soerawidjaya, T.H.,
Tambunan, A.H., Abdullah, K., 2008. Biodiesel fuels from palm oil via the noncatalytic transesterication in a bubble column reactor at atmospheric
pressure: a kinetic study. Renew. Energy 33, 16291636.
Kumari, V., Shah, S., Gupta, M.N., 2007. Preparation of biodiesel by lipase-catalyzed
transesterication of high free fatty acid containing oil from madhucaindica.
Energy Fuel 21, 368372.
Li, E., Xu, Z.P., Rudolph, V., 2009. MgCoAl-LDH derived heterogeneous catalysts for
the ethanol transesterication of canola oil to biodiesel. Appl. Catal., B-Environ.
88, 4249.
Marjanovic, A.V., Stamenkovic, O.S., Todorovic, Z.B., Lazic, M.L., Veljkovic, V.B., 2010.
Kinetics of the base-catalyzed sunower oil ethanolysis. Fuel 89, 665671.
Moreira, A.B.R., Perez, V.H., Zanin, G.M., de, C.H.F., 2007. Biodiesel synthesis by
enzymatic transesterication of palm oil with ethanol using lipases from
several sources immobilized on silica PVA composite. Energy Fuel 21, 3689
Om Tapanes, N.C., Gomes Aranda, D.A., de Mesquita Carneiro, J.W., Ceva Antunes,
O.A., 2008. Transesterication of jatrophacurcas oil glycerides: theoretical and
experimental studies of biodiesel reaction. Fuel 87, 22862295.
Pisarello, M.L., Dalla Costa, B., Mendow, G., Querini, C.A., 2010. Esterication with
ethanol to produce biodiesel from high acidity raw materials: kinetic studies
and analysis of secondary reactions. Fuel Process. Technol. 91, 10051014.
Richard, R., Li, Y., Dubreuil, B., Thiebaud-Roux, S., Prat, L., 2011. On-line monitoring
of the transesterication reaction between triglycerides and ethanol using near
infrared spectroscopy combined with gas chromatography. Bioresour. Technol.
Shahla, S., Ngoh, G.C., Yusoff, R., 2010. An overview on the transesterication of
natural oils and fats. Biotechnol. Bioprocess Eng. 15, 891904.
Shahla, S., Ngoh, G.C.,Yusoff, R., 2011.Optimization of base-catalyzed ethyl ester
production from palm oil. Asia-Pac. J. Chem. Eng. doi:10.1002/apj.622.
Silva, N.d.L.d., Batistella, C.B., Filho, R.M., f Maciel, M.R.W., 2009. Biodiesel
production from castor oil: optimization of alkaline ethanolysis. Energy Fuel
23, 56365642.
Stamenkovic, O.S., Todorovic, Z.B., Lazic, M.L., Veljkovic, V.B., Skala, D.U., 2008.
Kinetics of sunower oil methanolysis at low temperatures. Bioresour. Technol.
99, 11311140.
Tiwari, G.N., Ghosal, M.K., 2007. Fundamentals of Renewable Energy Resources,
Alpha Science International Ltd.