Continental J.

Engineering Sciences 7 (3): 40 - 48, 2012 ISSN: 2141 – 4068

© Wilolud Journals, 2012 http://www.wiloludjournal.com
Printed in Nigeria doi:10.5707/cjengsci.2012.7.3.40.48

MODELLING THE CHEMICAL KINETICS OF MILK BUSH (Thevetia peruviana) OIL

TRANSESTERIFICATION PROCESS FOR BIODIESEL PRODUCTION.

O. M. Olatunji1, A. J. Akor1 and M.F.N Abowei2

1
Department of Agricultural and Environmental Engineering
2
Department of Petrochemical Engineering, Rivers State University of Science and Technology, PMB 5080,
Port
Harcourt, Nigeria.

ABSTRACT
In this research work, mass balance equation was used to develop a mathematical model describing
chemical kinetics of transesterification process of milk bush (Thevetia peruviana) oil for biodiesel
production. The model is based on the reverse mechanism of transesterification reactions and describes
dynamic concentration changes of triglycerides, diglycerides and monoglycerides, biodiesel (ester) and
glycerol production. The alcohol to oil molar ratios used were (6.1, 9:1 and 12: 1), the reaction
temperatures (30oC, 40oC and 50oC) and the catalyst loading percentages were 0.5%, 1.0% and 1.5%
for the kinetic model. From the results obtained, the ester concentration was found to rise with increase
in the catalyst loading and the reaction temperature, with a decrease in the alcohol to oil molar ratio.
The kinetic model developed was analysed using MATLAB. The correlation coefficient obtained
between the experimental and calculated values are 0.9980 for Triglyceride, O.9994 for Diglyceride,
0.9997 for Monoglycerides, 0.9999 for Ester and 0.9993 for glycerol. There is a good correlation
between the model developed and the experimental result.

KEYWORDS: Chemical kinetics, Milk bush, Transesterification, Biodiesel, Production.

INTRODUCTION
Growth in the world’s population has resulted in a surge of energy demand. Conventional petroleum-based
diesel fuel is non-renewable, and generates a significant amount of pollutants. Therefore it is important to look
for an alternative energy source that is renewable, non-toxic, biodegradable and environmentally friendly and
produced without undesired consequences of the burning of fossil fuels such as high carbon dioxide emissions
considered to be the major contributing factor to the global warning.

The major feed stock for biodiesel production is vegetable oils and animal fats. Most of these oils are edible
except Jathropha (Ma and Hanna, 1999).

In Nigeria, the ever increasing demand of edible oils for food which prevents their use in biodiesel production
makes us look for alternative oil that is not edible, readily available with better fuel properties which can be
used as fuel. Therefore a cheaper feed stock such as milk bush (Thevetia peruviana) oil can be used as an
alternative or substitute (Olatunji et al., 2011).

Milk bush (Thevetia peruviana) oil is readily available, popular and non-edible. However, like other vegetable
oils there are limitations in the use of this non-edible oil as fuel. Its high viscosity and poor combustion
characteristics can cause poor atomization, fuel injector blockage, excessive engine deposit and engine oil
contamination. With the transesterification of oil we can get better fuel properties (Akor et al, 1983, Boocock,
1986 and Olatunji et al., 2011) rather than using straight vegetable oil as fuel.

Biodiesel is synthesized from oils and fats by either an acid or a base. The transesterification reaction of
triglycerides, is known to be a three step process. The kinetic studies of transesterification of soyabean,
sunflower palm and rape seed oils have been reported (Darnoko and Cheryan, 2000). More recently, research on
alchololysis

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

of oil has focus on the use of heterogeneous catalysts. Zeolites and metal catalysts have also been used for the
transesterification of soyabean oil (Supper, 2004).

Although, base catalyzed transesterification of oils is widely accepted method for biodiesel production.
Chemical properties and purity of oil warrants complete optimization of the reaction conditions (Canakei and
Gerpen, 1999). Therefore, the objectives of this study is to develop a flexible kinetic model of transesterification
process of milk bush (Thevetia peruviana) oil including a reverse mechanism of the three consecutive chemical
reactions and check the validity of the model by comparing experimental results with the calculated results. An
accurate kinetic model is a necessary tool for the optimization of Biodiesel production

MATERIALS AND METHODS

Fresh milk bush (Thevetia Peruviana) fruits were obtained from Federal Government College, Port Harcourt,
Nigeria on 15th January, 2012. The fruits were transported to the process centre and manually separated to
remove all foreign matter and immature seeds. The clean seed were then held at room temperature for three days
to soften the mesocap for easy removal of the kernel. The kernels from the fruits were crushed to obtain a paste
which was exhaustively extracted by soxhlet method with n – Hexane (100% pure) to obtain the oil.

After the oil extraction, the oil was allowed to cool at room temperature. The seed of the plant contains about
60% oil, which hydrolyses to give about 48.9% Oleic acid, 20.39% palmitic acid, 19.27% linoleic acid, 7.56%
stearic
acid, 1.66% arachidic acid, 0.19% palmitoleic acid and 0.08% myristic acid. The defatted seed cake is about
37%
protein but rich in toxins .

In order to avoid saponification problem, a two-step acid/alkali-catalyzed method was used for the production of
biodiesel. In the first step esterification of the Free Fatty Acid (FFA) present in the oil was carried out using
sulfuric acid (H2SO4) as catalyst and in the second step, transesterification of the neutral milk bush oil was
carried out using potassium Hydroxide as a catalyst.

Analysis of the Products.

The High Performance Liquid Chromatography (HPLC) – Hewlett – Packard 1100 series was used for the
analysis of concentration of triglyceride, diglycerides, monoglycerides, Ester (biodiesel) and Glycerol.

Mathematical Model
When vegetable oil or animal fat is transesterified that is mixture of alcohol and oil in the presence of a base as a
catalyst. The following reactions are formed.

K1
TG + ROH DG + E ………………………… (1)
K11

DG + ROH K2 MG + E …………………….. (2)

K22
MG + ROH K3 GL + E ……………………..... (3)

K33
The overall reaction is
TG + 3ROH GL + 3E ……….(4)

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

Where,
TG = Triglyceride
DG = Diglyceride
MG = Monoglycerides
E = Ester or Biodiesel
ROH = Alcohol
GL = Glycerol

The proposed mechanism assumed homogeneous catalytic reactions that each reaction step is reversible and
kinetics is first order with respect to the reacting components’ concentration. Higher order forward and
backward chemical reactions can also be assumed to take place, but for simplicity and clarity the first
assumption is good enough. The mass-transfer and transport phenomena limitations are out of consideration.
The kinetic constants can be written as a function of reaction temperature using the well-known Arrhenius
model.

The three consecutive transesterification reactions can be either equilibrium reactions or forward reactions
depending on working conditions and the chosen catalyst and molar ratio of Alcohol to the oil, milk bush. Based
on the above mechanism and model assumptions, the kinetics of transesterification process can be described by
using component mass balances by differentiating the concentration of each step with respect to time.


=  =   + 


= −   +    … . (5)
Where,
CTG = Concentration of Triglyceride
CA = Concentration of Alcohol
CDG = Concentration of Diglyceride
K = Rate Constant.
But,
K1CA = Kˊ1


=   =  = − ˊ  +  +    …..…..


Where,
Kˊ1 = effective rate constant
CE = concentration of Ester
In order to find a solution to equation (6) there is need to express CD and CE as a function of time. At the initial
period when the reaction start to the final period (ie. time ti to tf, ti = 0 and tf = tDG1). The diglyceride
concentration was increased and then decreased.

Applying the equation proposed by Fogler (Fogler, 1999).

The suggested formula for this type of change in concentration is composed of two exponential terms.

    !"
 = ! 
… … (7)

Where,
β1 , β2 and β3 are constants
t= time

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

     !  "

 = $ + ! 
… … … … … … … … … … … . .. (8)
Where,
CDGO = Initial concentration of Diglyceride

After the final period, ie. tf = tdg1, diglyceride concentration went below its initial value, hence, equation (8)
cannot be used to predict the final concentration of Diglyceride at this period. Therefore equation 8 may be
written as equation 9.

     !  " &  '   (  "

 = $ + ! 
− ( '
… … … … … .. (9)
Also,
*  +   +!  "
 = $ + *! *
… … … … … … … … … … … . . … (10)
Substituting equation (9) and (10) into equation 6, taking the Laplace of the new equation developed; also by
applying the partial fraction technique, and taking the inverse Laplace of the final equation.
CTG, CDG, and CMG final equations were developed.

. /21  . /21 
. /01 /21 3 4 3 4
 = + ! 
5  6
− ! 
5 ! 6
.ˊ .ˊ  .ˊ !

7 8 & 7 8 & 7 8 ; <

3 4 3 4 =
( ' ( ' <! <
− 5 ' 6
+ 5 ( 6
+ 5 < 6
7 ˊ − 9: 7 ˊ − 9: 7 ˊ − >

7 8 ; 9 >
< 7 3 4; =
<! <
= 9? − 9 >? − >
− 5 <! 6
+ 5 ( @< )6́
7 ˊ − >? 7 ˊ − (9 + > )

9 > 9 >
7 3 4; = 7 3 4 ;> − > =
9? − 9 >? − > 9 − 9
+ 5 (! @<! )6́
− ?  ? 
5 ( @<! )6́
7 ˊ − (9? + >? ) 7 − (9 + >? )
ˊ

9 > 9B >
7 3 4 ;> − > = 7 3 4 ;> − > =
9? − 9 9 − 9:
− ? 
5 (! @< )6́
− ? 
5 (' @< )6́
7 − (9? + >? )
ˊ
7 − (9: + > )
ˊ

9B > 9B >
7 3 4; = 7 3 4 ;> − > =
9 − 9: >? − > 9 − 9
− 5 (( @<! )6́
+  : ? 
5 (' @<! )6́
7 ˊ − (9 + >? ) 7 ˊ − (9: + >? )

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

9B >
7 3 4; =
9 − 9: >? − >
+ 5 (( @< )6́
7 ˊ − (9 + > )

(7 C0 D0 ) 9 9
− − E7 D0 3 4F + E7 D0 3 4F
7 ˊ 9? − 9 9? − 9
9 9B
G−7 D0 3 4H G−7 D0 3 4H
9? − 9 9 − 9:
− +
7 ˊ − 9: 7 ˊ − 9
> >
G7 C0 ;> − > =H G7 C0 ;> − > =H
?  ? 
− +
7 ˊ − > 7 ˊ − >?
9 > 9 >
G7 3 4; =H G7 3 4; =H
9? − 9 >? − > 9? − 9 >? − >
+ − − 5 . 6́
7 ˊ − (9 + > ) 7 ˊ − (9? + >? )
9 > 9 >
G7 3 4 ;> − > =H G7 3 4 ;> − > =H
9? − 9 ?  9? − 9 ? 
+ +
7 ˊ − (9 + > ) 7 ˊ − (9? + > )
9B > 9B >
G−7 3 4; =H G−7 3 4; =H
9 − 9: >? − > 9 − 9: >? − >
− −
7 ˊ − (9: + > ) 7 ˊ − (9 + >? )
9B > 9B >
G−7 3 4; =H G−7 3 4; =H
9 − 9: >? − > 9 − 9: >? − >
+ + 8
7 ˊ − (9: + >? ) 7 ˊ − (9 + > )
…………………………11

Where,

K= rate constants

The final concentration of Diglyceride, Monoglyceride, Ester (Biodiesel) and Glycerol were derived in the same
manner.

Where,αi , βi, ωi, are constants derived from Fogler’s equation to calculate the change in concentration of Tri, Di,
Mono glycerides, Ester and glycerol.

These constants are determined using initial guess values. From Linear Regression method using MATLAB
programming which was written to validate the model.

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

RESULTS AND DISCUSSIONS

Process optimization
The effects of catalyst concentration, reaction temperature, and alcohol-to-oil molar ratio were studied in the
optimization of milk bush (Thevetia peruviana) oil transesterification process. Table 1 summarized the effects
of catalyst concentration, reaction temperature, and alcohol-to-oil molar ratio in terms of conversion.

Effect of catalyst loading

The catalyst loading (KOH) was varied from 0.5 to 1.5 wt.% in this study. Figure 1 (a), (b) show ester
concentration distribution using 6:1 alcohol to oil molar ratio at 30, 40, and 50 oC, respectively. To avoid the
escape of methanol into gas phase during the reaction, the reaction temperature was maintained at 10oC below
boiling point of methanol. Hence, the reaction temperatures of 300C, 400C, and 500C were chosen for this study.

The results show that ester concentrations increase with catalyst loading. This is a typical observation which
agrees with the findings of Zhous et al., (2003). However, the rate of the increase in ester concentration
dropped when catalyst concentration was increased beyond 1 wt. %. In addition, the conversion increased as
catalyst concentration increased. Potassium Hydroxide ions react with the methanol molecule to produce
methoxide ions, and the rate of reaction increased when hydroxide concentration was increased.

Table 1: The Percentage Conversion of Alkali-Catalyzed Transesterification of Milk bush Oil at Various
Temperatures and Alcohol to Oil Molar ratio.

Catalyst Temperature Alcohol to Conversion, mol %

Replication concentration oil molar
(wt. %) (oC) ratio 1 min
5 min 10 min

1 0.5 30 6:1 16.5 44.5 53.6

2 0.5 40 6:1 27.5 61.8 66.0

3 0.5 50 6:1 34.6 66.6 71.6

4 1.0 30 6:1 61.5 76.8 84.3

5 1.0 40 6:1 72.5 81.9 83.6

6 1.0 50 6:1 75.4 82.2 84.1

7 1.5 30 6:1 81.7 86.8 90.1

8 1.5 40 6:1 78.9 87.3 90.1

9 1.5 50 6:1 81.5 90.4 99.9

10 1.0 30 9:1 35.8 65.4 78.0

11 1.0 40 9:1 42.4 78.0 86.1

12 1.0 50 9:1 55.3 83.7 89.5

13 1.0 30 12:1 21.0 48.2 70.2

14 1.0 40 12:1 45.2 73.6 83.7

15 1.0 50 12:1 52.5 52.5 92.7

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

From Figures 1, the rate of ester formation increased significantly when catalyst concentration was increased
from 0.5 to 1.0 wt.%. However, further increases in catalyst concentration from 1.0 to 1.5 wt.% did not show
any significant improvement in the rate of ester formation. Therefore the optimum catalyst concentration for
transesterification of Milk bush (Thevetia peruviana) oil was determined to be 1.0 wt.% KOH.

Fig 1. Effect of catalyst loading on ester concentration with 6:1 methanol to oil molar ratio at 30Oc and 40oC

Effect of reaction temperature

The effect of reaction temperature on ester concentration was studied at 6:1, 9:1 and 12:1 methanol to oil molar
ratios using 0.5, 1.0, and 1.5 wt.% KOH The temperature range was between 30OC to 50OC. Figures 2.0 show an
ester concentration profile of transesterification of milk bush oil with 6:1 alcohol to oil molar ratio using
0.5%KOH and with 9:1 alcohol to oil molar ratio using 1.0% KOH, respectively.

Fig 2: Effect of reaction temperature on ester concentration with 6:1, 9.1 methanol to oil molar ratio using
1.0wt%
KOH.

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

It is evident from these figures that the higher ester formation rate is favoured by higher reaction temperatures.
Also, Table 1 illustrates higher conversion at higher reaction temperature. Many research groups have also
observed similar results (Freedman et al., 1986, Darnoko and Cheryan, 2000). The reason for this behavior is
due to the endothermic nature of the reaction. The higher reaction temperature would favour endothermic
reaction, thus increasing the rate of reaction as well as the ester concentration. However, reaction temperature
did not show any significant impact on conversation when using the higher catalyst loading (1.5 wt. %) (Table
1). This is because the reaction was driven close to completion at high catalyst loading.

Results from this part of the study shows that the higher ester concentration is obtained at higher reaction
temperature. The optimum temperature was observed to be 50oC. This study also shows that transesterification
of Milk bush oil using solely ethanol may be operated at higher temperatures for higher yield since ethanol has a
higher boiling point (78.4oC).

Effect of alcohol-to-oil molar ratio

The effect of alcohol to oil molar ratio (6:1, 9:1, and 12:1) on ester concentration was studied at 30, 40, and
50oC. These results are given in Figure 2 (a), (b). As shown in Figures 2 and Table 1, ester concentration as
well as the % conversion decreased as the alcohol-to-oil molar ratio was increased. This can be explained on
the basis of the reactant (oil) concentration in the reaction mixture. By increasing alcohol to oil molar ratio, the
amount of alcohol was increased, therefore the Milk bush and catalyst concentrations were diminished, which
reduced the rate of reaction. Results published by Boocock et al., (1998) showed a similar trend in which the
methyl ester percentage decreased as the alcohol-to-oil molar ratio was increase. In the case of a higher reaction
temperature, although the similar trend of ester concentration (ester concentration decreased with an increase in
alcohol-to-oil molar ratio) was observed as shown in Figure 2 (b) the % conversion increased with alcohol-to-oil
molar ratio (Table 1). As alcohol molar ratio was increased, the polarity of the system was also increased thus
improving ionization of KOH. As a result, the rate of the reaction as well as the % conversion was increased.

Results from this part of the study suggest that the optimum in alcohol-to-oil molar ratio operating at low
temperature (30oC and 40oC) was 6:1. However, the higher in alcohol-to-oil molar ratio (12:1) is recommended
at higher operating temperature (50oC).

Fig 3: Effect of alcohol to oil molar ratio on ester concentration using 1.0wt% KOH at 300c and 40oC.

CONCLUSION
The rate of formation reaction temperature, catalyst concentration, or decreasing alcohol to oil molar ratio was
observed. The optimum conditions for milk bush oil methanolysis are a reaction temperature of 50oC and 1.0 wt
% KOH. The 6:1 alcohol-to-oil molar ratio was found to be optimum at low reaction temperature (30oC and
40oC). At high reaction temperature (50oC), 12:1 alcohol-to-oil molar ratio is recommended.

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 O. M. Olatunji et al.,: Continental J. Engineering Sciences 7 (3): 40 - 48, 2012

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Canakei M. and J.V. Gerpen. (2001). “Biodiesel Production from Oils and Fats with High Free Fatty
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Darnoko, D. and M. Cheryan. (2000). Kinetics of palm oil transesterification in a Batch reactor. J. Am. Oil
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Freedman B., R.O. Butterfield and E. H. Pryde. (1986).“Transesterification Kinetics of Soybean Oil”, JAOCS
63(10), 1375-1380.

Ma, F. and M.A. Hanna. (1999). “Biodiesel Production: A Review”, Bioresource Technology 70, 1-15.

Olatunji, O.M., Akor, A.J., Abowei, J.F.N. and Akintayo, C.O. (2011). Transesterification for the preparation of
Biodiesel from crude oil of Milk bush. Research Journal of Environmental and Earth Science, 3(4): 358 – 363,
2011.

Suppes, G.J., Dasari, E.J., Doskosil, E.J., Mankidy, P.J. and Goff, M.J, (2004). Transesterification of Soyabean
oil with zeolite and metal catalysis. Appl. Catal. A: Gen., 257(2): 213-223.

Received for Publication: 16/10/12

Accepted for Publication: 12/12/12

Corresponding author
O. M. Olatunji
Department of Agricultural and Environmental Engineering, Rivers State University of Science and
Technology, PMB 5080, Port Harcourt, Nigeria.
Email: ololade_moses1@yahoo.com

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