Energy 35 (2010) 4142e4148

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Energy
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Castor oil transesterification reaction: A kinetic study

and optimization of parameters
K. Ramezani a, S. Rowshanzamir a, b, *, M.H. Eikani c
a
Fuel Cell Research Laboratory, Green Research Center, Iran University of Science and Technology, Tehran, Iran
b
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
c
Department of Chemical Industries, Iranian Research Organization for Science and Technology (IROST), Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, parameters affecting castor oil transesterification reaction were investigated. Applying four
Received 6 December 2009 basic catalysts including NaOCH3, NaOH, KOCH3 and KOH the best one with maximum biodiesel yield
Received in revised form was identified. Using Taguchi method consisting four parameters and three levels, the best experimental
21 May 2010
conditions were determined. Reaction temperature (25, 65 and 80
C), mixing intensity (250, 400 and
Accepted 27 June 2010
Available online 4 August 2010
600 rpm), alcohol/oil ratio (4:1, 6:1 and 8:1) and catalyst concentration (0.25, 0.35 and 0.5%) were
selected as experimental parameters. It was concluded that reaction temperature and mixing intensity
can be optimized. Using the optimum results, we proposed a kinetic model which resulted in estab-
Keywords:
Castor oil
lishing an equation for the beginning rate of transesterification reaction. Furthermore, applying ASTM D
Kinetic 976 correlation, minimum cetane number of produced biodiesel was determined as 37.1.
Biodiesel Ó 2010 Elsevier Ltd. All rights reserved.
Transesterification

1. Introduction ethanol to cottonseed oil and reaction temperature for percentage

Biodiesel (fatty acid alkyl esters) is an alternative diesel fuel
derived from the reaction of vegetable oils or lipids and alcohol
with or without the presence of a catalyst. Despite the invention of
the vegetable oil fuelled engine by Rudolf Diesel dated back in the
1900s, full exploration of vegetable oil based fuel such as biodiesel
only came into light in the 1980s as a result of renewed interest in
renewable energy sources for reducing greenhouse gas (GHG)
emissions, and alleviating the depletion of fossil fuel reserves [1].
Biodiesel is environmentally safe, nontoxic and biodegradable.
The raw material exploited commercially includes edible fatty oils
derived from rapeseed, soybean, palm, sunflower, coconut, linseed,
etc. Biodiesel can be used as the basis for a clean substitute for fossil
fuel without any modification in diesel engines, boilers or other
combustion equipments [2].
Transesterification of cottonseed oil was carried out using
ethanol and potassium hydroxide (KOH) by Chandra Joshi et al. A
central composite design with six center and six axial points was
used to study the effect of catalyst concentration, molar ratio of
* Corresponding author. Iran University of Science and Technology, Green
Research Centre, Postal code 16846-13114, Resalat Square, Hengum Street,
Elmosanat Avenue, Tehran, Iran. Tel.: þ98 2177491223; fax: þ98 2177491242.
E-mail address: rowshanzamir@iust.ac.ir (S. Rowshanzamir).
yield and percentage initial absorbance of the biodiesel [3].
Park et al. investigated the feasibility of biodiesel production
from tung oil. Optimal condition of methanol and catalyst for the
esterification was established by response surface methodology [4].
Wild mustard (Brassica juncea L.) oil is evaluated as a feedstock
for biodiesel production by Jham. Biodiesel was obtained in 94 wt.%
yield by a standard transesterification procedure with methanol
and sodium methoxide catalyst [5].
Sinha et al. studied base-catalyzed transesterification with KOH
and NaOH as catalyst for biodiesel production from rice bran oil.
The effects of the parameters, namely process temperature, reac-
tion time, molar ratio of alcohol to oil and catalyst concentration on
the ester (biodiesel) yield and the viscosity were investigated [6].
Coriander (Coriandrum sativum L.) seed oil methyl esters were
evaluated as an alternative biodiesel fuel and were prepared in
94 wt% yield by a standard transesterification procedure with
methanol and sodium methoxide catalyst by Moser and Vaughn.
Using standard methods, the following fuel properties were
determined: low temperature properties, oxidative stability, cetane
number, sulfur content, free and total glycerol content, kinematic
viscosity, acid value (AV), phosphorous content, lubricity, heat of
combustion, Gardner color, iodine value (IV), fatty acids (FA) profile,
and tocopherol content [7].
Sabudak and Yildiz established the most appropriate method for
use in the purification and characterization of biodiesel from waste

0360-5442/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.06.034
 K. Ramezani et al. / Energy 35 (2010) 4142e4148 4143

Table 1 Table 2
Working conditions for the TLC/FID Shimadzu GC 2010 analyzer. Obtained result for identification of the highest yield from basic catalysts. Reaction
conditions: temperature: 65
C, catalyst concentration: 0.35% of oil, reaction time:
Injection port Split 2 h, rpm: 250.
Temperature 280
C
Carrier gas He Catalyst NaOCH3 NaOH KOCH3 KOH
Flow control mode Velocity Yield (%) 67.1 75 76.2 58.7
Pressure 120.0 kPa
Total flow 57.7 ml/min
Column flow 1.03 ml/min European specifications for biodiesel (DIN e 14214) using those
Liner velocity 30 cm/s sources of biomass is presented and discussed. It was observed that
Purge flow 5.0 ml/min the biodiesel obtained from castor oil presents problems for specific
Split ratio 50
gravity and viscosity specification within the European limits.
Column oven Blends of castor biodiesel oil with the other biodiesel oils can
Initial temperature 150
C
improve these properties in order to comply with the European
Equilibration time 0.2 min specification [9].
Total program time 21.0 min A continuous biodiesel plant was designed and simulated in
Column oven temperature programY HYSYS simulator using castor oil as feedstock by Santana. The
Rate (
C/min) Temperature (
C) Hold time (min) developed process was capable of producing biodiesel at high
e 150.0 2.00 purity using an alkali catalyst. Material and energy flows, as well as
10 270.0 7.0 sized unit operations were used to conduct an economic assess-
Column name OMEGA WAX 250
ment of the process. Total capital investment, total manufacturing
cost and after annual equivalent cost were also calculated. A study
Film thickness 0.25 mm
Column length 30.0 m of production costs was performed considering the fluctuations of
Inner diameter 0.25 mm ID the raw material prices and the glycerin purification step [10].
Column max temperature 280
C Castor oil biodiesel has lower cost compared to the one obtained
from other vegetable oils due to its solubility in alcohol and thus
Detector FID
the transesterification reaction can occur under the ambient
Temperature 300.0
C
temperature. Moreover, it does not contain sulfur, it has greater
Make up gas N2/Air
Make up flow 30.0 ml/min cetane number, which indicates a better quality of ignition, and it
H2 flow 40 ml/min has more oxygen, making its combustion more complete. Con-
Air flow 300 ml/min ceicao et al. studied the thermoanalytical and physical-chemistry
Sampling rate 40 ms
characterization of castor oil and biodiesel using some techniques
Stop time 21.0 min
such as thermal analysis and gas chromatography (GC) [11].
Sousa et al. have studied the neutralization of castor oil with
frying oils WFO. Waste frying oils, collected from several McDo- glycerol, a by-product of biodiesel production, and its effect on the
nald’s restaurants by the Alternative Energy and Biodiesel transesterification reaction of castor oil and methanol. The yield of
Producers Association (ALBIYOBIR) in Istanbul, were used in the methyl esters obtained from neutralized castor oil was higher than
production of biodiesel using a one-step basic, two-step basic and the yield obtained from raw oil under the same operating condi-
two-step acid-basic transesterification. Each transesterification tion. A flowchart was proposed to include the neutralization stage
reaction took place with and without tetrahydrofuran (THF) as a co- into the industrial flowchart [12].
solvent. However, three different purification procedures were The oxidation stability of castor oil fatty methyl ester (FAME),
applied in the production of biodiesel. Seven parameters were doped with four different phenolic antioxidants, was evaluated
assessed in the biodiesel produced to test for compliance with using a rapid method of thermal and air-contact degradation by
European Standard 14214 [8]. Araújo et al. The addition of antioxidants increased from 6 to 15
Albuquerque evaluated the properties of biodiesel oils obtained times the stability of castor oil FAME., with BHA (butylated
from different biomass sources (castor, soybean, cotton, and canola) hydroxyanisol) showing the best results for improving anti-
and their binary blends prepared in concentration ranges between oxidation in castor oil biodiesel [13].
20 and 80 %vol. Each sample was analyzed for viscosity, specific Previous studies have shown that castor has improved lubricity
gravity and iodine index. The proper formulation to meet the over other oils with similar carbon chain-length fatty acids. The
hypothesis was that the hydroxylated fatty acids of ricinoleic acid in
castor oil impart it better performance as lubricity enhancer than
other common vegetable oil esters. Goodrum and Geller have
tested this theory by including Lesquerella oil methyl ester in the

Table 3
Taguchi design method (3 level and 4 variables).

Variable

Run 1 2 3 4
1 1 1 1 1
2 1 2 2 2
3 1 3 3 3
4 2 1 2 3
5 2 2 3 1
6 2 3 1 2
7 3 1 3 2
Fig. 1. The GC chromatogram with KOH catalyst, the temperature was 65
C, methanol/
8 3 2 1 3
oil molar ratio was 6:1, catalyst concentration was 0.35 wt% of oil, reaction time was
9 3 3 2 1
120 min and mixing intensity was 250 rpm.
4144 K. Ramezani et al. / Energy 35 (2010) 4142e4148
Table 4
Parameters and levels used for Taguchi design method.
Parameters Level 1 Level 2
Temperature (
C) 25 65
Mixing intensity (rpm) 250 400
Methanol/oil molar ratio 4:1 6:1
Catalyst Concentration (wt% of oil) 0.25 0.35
study. It is believed that the uniquely high level of hydroxylated
fatty acids in Lesquerella oil methyl ester would also increase its
relative effectiveness as a lubricity enhancer [14].
De Oliveira et al. have studied the production of fatty acid ethyl
esters from castor oil using n-hexane as solvent and two
commercial lipases, Novozym 435 and Lipozyme IM, as catalysts.
For this purpose, a Taguchi experimental design was adopted
considering the following variables: temperature (35e65
C), water
(0e10 wt/wt%), and enzyme (5e20 wt/wt%) concentrations and oil-
to-ethanol molar ratio (1:3 to 1:10) [15].
De Lima Da Silva et al. have presented the transesterification of
castor oil (CO) using sodium ethoxide. The transesterification vari-
ables studied in this work were reaction temperature, catalyst
concentration and alcohol oil molar ratio. Response surface meth-
odology (RSM) or response surface analysis was used, because it
allows the simultaneous consideration of many variables at different
levels and the interactions between those variables, using a smaller
number of observations than conventional procedures. Further-
more, statistical-interference technique can be used to assess the
importance of individual factors, the appropriateness of their func-
tional form and the sensitivity of the response of each factor [16].
Panwar et al. carried the transesterfication process of castor oil
with alkaline catalyst, and it produces 95.8% yield. Also, their
properties for use in the engine have been evaluated [17].
Jeong and Park conducted experiments using response surface
methodology (RSM) to identify the optimal reaction factors for
a biodiesel synthesis process that utilized castor oil as a feedstock.
Among the three factors, reaction temperature affected the reaction
slightly, owing primarily to certain characteristics of castor oil, most
notably alcohol solubility and high viscosity. Their statistical
experiments yielded the following optimal reaction factor values:
reaction temperature, 35.5
C; oil-to-methanol molar ratio, 1:8.24;
and 1.45 wt.% catalyst (KOH), with a reaction time of 40 min. Under
these predicted optimum conditions, they obtained castor oil bio-
diesel with a fatty acid ester content of approximately 92 wt% [18].
De Oliveira et al. have reported experimental data on the
production of fatty acid ethyl esters (FAEEs) from refined and
degummed soybean oil and castor oil using NaOH as catalyst. For
this purpose, a Taguchi experimental design was adopted consid-
ering the variables temperature (30e70
C), reaction time (1e3 h),
catalyst concentration (0.5e1.5 w/wt%, by weight of oil), and oil-to-
ethanol molar ratio (1:3e1:9). The effects of main and cross vari-
ables on the reaction conversion are presented as well as the
optimum experimental conditions for all systems studied [19].
Cavalcante et al. have optimized the synthesis of fatty acid esters
from castor oil using an alkaline catalyst. The variables reaction time,
catalyst amount and oil:ethanol molar ratio were studied using
a central composite rotatable design. The effects and significance of
the models on the response variable and on ethyl biodiesel yield
derived from pure castor oil were evaluated using a response surface
curve and analysis of variance. All the variables significantly affected
Table 5
Yields of methyl ester obtained from Taguchi design method experiments.
Run T1 T2 T3 T4 T5 T6 T7
Yield (%) 68.3 83.6 87.3 80.5 85.5 75.3 82.3
the reaction yield, the amount of catalyst being the most effective.
The highest yield was obtained using an oil:ethanol molar ratio of
Level 3 1:11, 1.75% KOH and a reaction time of 90 min [20].
80 Conventionally, transesterification can be performed using
600 alkaline, acid, or enzyme catalysts. Transesterification using acid
8:1 catalysts is much slower than that obtained from alkali catalysis,
0.5
typically 4000 times slower. Sulfuric acid, which is commonly used,
leads to the formation of undesirable by-products with a difficult
separation step and requires careful removal of catalyst from the
biodiesel fuel, because acid catalyst residues can damage engine
parts. Although considerable progress has been made in recent years
toward developing cost-effective systems using enzyme catalysts for
biodiesel production, at present, the high cost of enzyme production
remains as the major obstacle to commercialization of enzyme-
catalyzed processes. Alkali-catalyzed systems are extremely sensi-
tive to both water and free fatty acid contents, but they do provide
high conversion levels of triglycerides to their corresponding methyl
or ethyl esters in short reaction times. Among several base catalysts,
NaOH is widely used in industrial biodiesel production owing to its
effectiveness and cheapness. Methanol has been the most commonly
used alcohol to perform transesterification in alkali-, acid-, and
enzyme-catalyzed reactions [19]. However, ethanol is superior to
methanol because that ethanol comes from a renewable resource. If
methanol is the reagent used in esterification there is loss of some of
the carbon neutrality if, as is highly probable, the methanol has been
made from natural gas or from coal via synthesis gas. The acids in
biodiesel are typically C18. Such an acid esterified with methanol
becomes C19 and the loss of carbon neutrality is (1/19) z5%. Ethanol
on the other hand is almost certain to have been made by fermen-
tation and is carbon neutral. A C18 acid becomes, if esterified with
ethanol, a totally carbon neutral C20 molecule. [19,21].
At first, in this study the four experiments were conducted to
select a suitable basic catalyst. The catalysts used include NaOCH3,
NaOH, KOCH3 and KOH. All experiments were at the same reaction
conditions, but the types of catalysts were different. The results
obtained by GC analysis of methyl ester showed that maximum
yield was obtained with KOCH3 catalyst. Then, we have studied the
production of methyl esters from castor oil using methanol as
solvent and KOCH3 as catalyst. For this purpose, a Taguchi experi-
mental design was adopted considering the following variables:
reaction temperature, mixing intensity, alcohol/oil ratio and cata-
lyst concentration. Therefore, three levels for four parameters were
selected and 9 runs were performed. The Win Robust Software
(Version 1.0) was used to determine the optimum conditions. Only
optimum values were determined for optimal reaction temperature
(65
C) and mixing intensity (400 rpm). Also, the reaction kinetic
was studied experimentally at optimum conditions, and a kinetic
correlation was presented to predict the production of methyl
esters. Finally, refractive index, viscosity and density of produced
biodiesel in optimum conditions were measured by ASTM
methods. Furthermore, a simple ASTM standard (ASTM D 976-91)
correlation was validated to predict cetane number of the produced
biodiesel. The predicted cetane number at optimum conditions was
compared to the other published experimental results.
Therefore, innovation of this research is as follows: selection of
a suitable alkaline catalyst, determination of optimum operating
conditions using the Taguchi design method, investigation of
reaction kinetic at optimum operating conditions, providing
a kinetic correlation and biodiesel characterization.
2. Materials
T8 T9 Refined castor oil (FFA w negligible, MW: 932 g per gmol,
80.7 72
Merck) and methanol (99.5%, Merck) were used as reactants. 30%
sodium methylate/methanol solution (Merck), 30e35% potassium
 K. Ramezani et al. / Energy 35 (2010) 4142e4148
Fig. 2. Response of results, maximizing of methyl ester yield from castor oil. Parameters are 1 e temperature, 2 e mixing intensity (rpm), 3 e molar ratio, 4 e catalyst concentration.
methylate/methanol solution (Merck), sodium hydroxide (99.9%,
Merck), potassium hydroxide pellets (99.9%, Merck) were applied
as the reaction catalysts. Sulfuric acid (95e98%, Merck) as
neutralizing agent and NaSO4 (Merck) as drying agent were used.
Standard for ricinoleic acid methyl ester was purchased from Fluka.
3. Analytical method
Methyl ester analysis was performed by thin layer gas chro-
matography/flame ionization detector by Shimadzu GC 2010
analyzer equipped with a capillary injection system. Working
conditions for TLC/FID are given in Table 1.
4. Apparatus and experimental procedure
The experimental set up consists of a 250 mL three necked batch
reactor which equipped with a reflux condenser, a magnetic stirrer
and digital thermometer (accuracy within 0.1
C). The reactor was
immersed to constant temperature paraffin bath in the designed
constant temperature. At first, the measured amount of castor oil
was preheated in a constant temperature water bath, separately.
Mixture of methanol and catalyst was stirred and heated in the
batch reactor. The amounts of methanol and oil were calculated
from the designed methanol/oil molar ratio. Hot oil was added to
bath reactor instantly and reaction was timed. After appropriate
time, the mixture was transferred to a decanter. With respect to the
catalyst type and its basic strength, phase separation occurred in
various time periods. For example, in case of potassium methoxide
as a catalyst, separation time was nearly 30 min. After phase
separation, lower phase rich in glycerol, was removed and the
upper phase rich in methyl ester, was neutralized by sulfuric acid,
and was washed three times by deionized water. Then, the mixture
was distilled recovering the surplus methanol, and dried using
NaSO4 powder to eliminate water drops. The ester phase was kept
in 5
C until for GC analysis. Yield was defined as the ratio of the
mass of ME in the reaction product to the mass of initial oil (% w/w).
To achieve the optimum condition using Taguchi method, the
Win Robust Software (Version 1.0) was used.
5. Results and discussion
5.1. Catalyst selection
In order to obtain maximum yield using four basic catalysts
including NaOCH3, NaOH, KOCH3 and KOH, four runs were carried
out. All runs were at the same reaction conditions, but the types of
catalysts were different. The GC chromatogram for KOH catalyst has
been shown in Fig. 1. The results obtained by GC analysis of methyl
ester are illustrated in Table 2.
Table 6
Reaction conditions in kinetic investigation.
Catalyst Methanol/oil Temperature Mixing Time Catalyst
type molar ratio (
C) intensity (h) concentration
(rpm) (wt% of oil)
CH3OK 8:1 65 400 2 0.5
4145
Referring to Table 2, maximum yield of methyl ester was
obtained using KOCH3 catalyst. Because of non-formation of water
in transesterification reactions, methoxide catalysts usually make
the highest methyl ester yields. Mixing of methanol and sodium
hydroxide produces water according to the equation
NaOH þ MeOH / H2O þ Naþ þ MeO. There is an equilibrium
between MeO and OH: MeO þ H2O 4 MeOH þ OH. For alkali-
catalyzed transesterification, glycerides and alcohol must be
substantially anhydrous because water causes a partial reaction
change to saponification, which produces soap [22].
5.2. Optimization of the other parameters
Parameters such as temperature, catalyst concentration, alcohol/
oil molar ratio and mixing intensity directly affect methyl ester yield.
Transesterification can occur at different temperatures, depending
on oil used. In methanolysis of Castor oil to methyl ricinoleate, the
reaction proceeded most satisfactorily at 20e30
C with molar ratio
of 6:1e12:1 and 0.005e0.35% (by weight of oil) NaOH catalyst [23].
Free fatty acid or moisture can interfere in transesterification reac-
tion [22]. It may be avoided by selecting of refined oil and anhydrous
methanol. Taguchi design method is used to optimize the measur-
able parameters. This method reduces the number of reactions with
saving of time and materials and also investigates all parameters
varying in an experiment. The wide of selected parameters must be
taken from prior researches, so this is a weakness of Taguchi Design
Method. In this work, three levels for four parameters were selected
and according to Taguchi design method nine runs must be carried
out. Information about four parameters, three levels and selected
levels are shown in Tables 3 and 4.
The obtained yields for each of nine experiments are presented
in Table 5. Data was transferred to the Win Robust Software, and
response shows that two parameters can be optimized. As shown in
Fig. 2, at the two points there is the highest efficiency; temperature
and mixing intensity at 65
C and 400 rpm, respectively. It’s
noticeable that applying higher temperature and more mixing
intensity reduces the yield. It may be the result of reversibility of
reaction and interference of non-desirable components in reaction
such as free fatty acid. Optimization of the other two parameters
could not be reached, but considering other aspects such as product
0,9
0,8
0,7
0,6
Methyl Ester
0,5
Yield
0,4
0,3
0,2
0,1
0
0 20 40 60 80 100 120 140
Time(min)
Fig. 3. Progress of transesterification reaction versus time. Reaction condition;
methanol/oil molar ratio, 8:1, temperature, 65
C, mixing intensity, 400 rpm, reaction
time, 1.5 h, catalyst, CH3OK, catalyst concentration 0.5%.
4146 K. Ramezani et al. / Energy 35 (2010) 4142e4148

Table 7 Table 8
Initial condition, parameters and reaction rate constant. Refractive index, viscosity and density: methods and values.

[ML]0 (mol) k0 k (min1) Intercept Property Refractive Viscosity Density

0.57 0.0028 4.91  103 1.0029 index (mm2/s @ 40
C) (g/ml @ 15
C)
Method ASTM D 1747-99 ASTM D 445-03 ASTM D 1298-99
Value 1.46 20.02 0.922
cost and biodiesel quality may be helpful to select the best oper-
ating conditions.
 
½ TG
5.3. Kinetic investigation ln ¼ k0 t (3)
½ TG0
Overall equation of transesterification reaction can be presented where [TG] and [ML] refer to the concentrations of triglyceride (TG)
as follows: and methanol (ML). [TG]0 and [ML]0 are initial concentrations (at
time t ¼ 0).
Triglycerides ½TG þ 3 methanol ½ML/3 methyl ester ½ME Using conversion instead of time:
þ Glycerol (1)  
TG ¼ ½TG0 ð1  XTG Þ (4)
Although there are a number of kinetics studies in literature on
transesterification of esters with alcohol, only a few researches are 1
concerned with transesterification of vegetable oils. Freedman et al. XTG ¼ X (5)
3 ME
studied the kinetics of the acid- and base-catalyzed trans-
esterification of soybean oil with 1-butanol and methanol at 30: 1 where XTG and XME refer to the triglyceride conversion and methyl
and 6:1 molar ratio of alcohol to oil [24]. Noureddini and Zhu ester yield in the reaction system, respectively.
studied the kinetics of base-catalyzed transesterification of soybean
oil with methanol at 6:1 molar ratio of alcohol to oil. Significantly, lnð3  XME Þ ¼ k0 t þ ln 3 (6)
they found that pseudo-first-order kinetics provided a satisfactory By plotting lnð3  XME Þ versus time, k0 and then k will be obtained
mechanism with experimental results at large molar excess of from the slope of the curve.
alcohol and second-order kinetics provided a satisfactory mecha-
5.4. Experimental procedure
nism with experimental results at 6:1 molar ratio of alcohol to oil.
For the latter case, an inclusion of shunt mechanism was not
According to optimized parameters listed in Table 6, hot oil and
necessary [25]. Darnoko and Cheryan studied the kinetics of base-
dissolved catalyst in methanol were mixed in the reactor. During
catalyzed transesterification of palm oil with methanol at 6:1 molar
reaction, 2 mL samples were withdrawn from reactor at different
ratio of alcohol to oil. They reported that the best kinetics mecha-
times, and were quenched suddenly. Approximately 11 samples
nism appeared to be a pseudo second-order [26].
were collected during the reaction (120 min). At the beginning of
In this research, the kinetic study has been done in the optimum
the reaction, more frequent sampling was required. The procedure
conditions obtained from Taguchi design (Table 6).
of quenching is Komers technique [29]. Samples led to 5 ml of cold
However, there are few studies about kinetic of Castor oil trans-
acidic water. The amount of acid was calculated by considering
esterification. Agra et al. [27] and Cotes and Wenzel [28], reported
amount of basic catalyst in the mixture. It was assumed that no
a kinetic mechanism for Castor oil in presence of acid catalyst.
saponification reaction occurs. After quenching and naturalization,
Transesterification reaction is not elementary, and it is a reversible
the samples were separated to two phases. Upper phase as methyl
reaction, but some simplifications can be assumed to predict
ester phase was transferred to clean vial, dried in vacuum oven, and
a simple kinetic equation only for the beginning time of the reaction.
kept in 5
C for GC analysis. The kinetic results are shown in Fig. 3.
By irreversible reaction assumption and constant molar concentra-
Using experimental data, a liner equation was fitted (Table 7).
tion of methanol during reaction, a pseudo-first-order reaction is
According to Fig. 4, the correlation coefficient (R2) is 0.9191 and the
suggested. The governing equation of reaction will be as following:
intercept of equation is 1.0029 that approximately is equal to “ln 3”;
1 d½TG the predicted constant in Equation (6). Hence the correlation to
rTG ¼ r ¼  ¼ k0 ½ TG (2) predict ME yield will be
3 ME dt
where XME ¼ 3  expð1:0029  0:0028tÞ (7)
k0 ¼ k[ML]0 and k ¼ rate constant.After integration, the result
will be as following:
5.5. Characterization of produced biodiesel
1, 4
y = -0, 0028x + 1, 0029 Refractive index, viscosity and density of produced biodiesel in
1, 2
R2 = 0,9191 optimum conditions were measured by ASTM methods. In Table 8,
1
the obtained values and ASTM methods have been shown. The
Ln(3-X ME)

0, 8
0, 6
Table 9
0, 4 Viscosity comparisons for biodiesel from castor oil
0, 2
Reference Kinematic viscosity (mm2/s @ 40
C)
0
[36] 13.75
0 5 10 15 20 25
[32] 17.02
Ti m e (m i n)
[33] 13.34
In this study 20.02
Fig. 4. Plot of methyl ester yield versus reaction time.
 K. Ramezani et al. / Energy 35 (2010) 4142e4148
Table 10
Density and boiling point of rapeseed and soybean oil [32e34].
Min. Boiling Max. Boiling
Point (K) Point (K)
Methylate of rapeseed oil 640.5 650
Methylate of soybean oil 625.8 630.3
range of kinematic viscosity of biodiesel according to ASTM D6751-
02 is 1.6e9 mm2 per s @ 40
C. Because of the presence of ricinoleic
acid in castor oil with hydroxyl group, biodiesel of castor oil has
higher kinematic viscosity, 20.02, comparing other vegetable oils.
This value of kinematic viscosity was compared to the other data
presented in literatures, Table 9. Density in standards is not
mentioned as biodiesel character directly but usually it has the
values between 0.85 and 0.9 g per ml [30]. This value is used in
a correlation for prediction of cetane number.
5.6. Cetane number of castor oil biodiesel
ASTM D 613 is a method to measure the cetane number of
biodiesel. Minimum value is 47. ASTM D 976-91 is another corre-
lation that is used to predict the cetane number of petroleum diesel.
In this study we validated this correlation for biodiesel by experi-
mental data from different literatures, and then the cetane number
of produced biodiesel at optimum conditions was predicted.
The correlation is
Calucated cetane index ¼ 420:34 þ 0:016G2 þ 0:192G log M
þ 65:01ðlog MÞ2 0:0001809M 2
G ¼ API gravity is obtained from ASTM D 287 or ASTM D 1298;
M ¼ mid boiling point (
F).
Biodiesel of rapeseed oil and soybean oil has been used for this
validation. The density and boiling point for these two oils are listed
in Table 10. Using these values, the cetane numbers of two types of
oil were calculated, and compared to real cetane number from
different literatures. The results are considered in Table 11. Errors
were calculated based on minimum cetane number.
48  44:3
error ¼  100 ¼ 7:07% for rapeseed oil
48
4147
Density
(g/ml)
0.87e0.89
0.885
Fig. 5. Variation of boiling point and cetane numbers calculation at the constant
density (0.885 g per ml).
There are two parameters affecting cetane number calculation:
boiling point and density. Vegetable oils contain different kinds of
triglyceride, and it causes different boiling points of oil but in
narrow range. In constant density of soybean oil boiling points have
been changed and its effect on cetane number has been shown in
Fig. 5. A hypothetical range of density we assumed in Fig. 6 at
a constant boiling point, and effect of density on correlation was
illustrated. According to Fig. 5, boiling point has poor effect on
cetane number value. Considering Fig. 6, the sharp curve shows the
high effect of density on cetane number calculation. It means that
sensitivity of correlation with density is much higher than boiling
point.
Using Equation (8), calculated cetane number of biodiesel
ð8Þ produced in optimum conditions was 37.1. For comparison to the
other published results, the cetane numbers have been calculated
by their densities, Table 12.
As can be seen in Table 12, biodiesel produced in this work has
higher cetane number. However, it is not in the range defined in
ASTM D6751-02 because the minimum value should be 47. But,
while biodiesel is blended to diesel (10% or 20% by volume), the
predicted cetane number gives better value, and can be acceptable
to use in diesel engine. Also, the density was improved. Other
advantages of biodiesel from castor oil such as lubricity property,
higher pour and flash point make it suitable for safe transportation
and using in cold weather [31]. In Table 13, some flow properties of
diesel and three types of biodiesel have been compared. Conse-
 
45  45:7 quently, this product can be the best additive for petrodiesel and
error ¼    100 ¼ 1:55%
 for soybean oil may be make a clean fuel.
45
These errors are acceptable especially for soybean oil and it shows
that this correlation can be used for prediction of minimum cetane
number and even it might be expected that cetane number be
higher in the real diesel engine.

Table 11
Cetane numbers for two type of oil: real [35] and predicted.

Methyl ester of rapeseed oil Methyl ester of soybean oil

51.9 45
48.0 46.2
54.4 54.7
49.9 67
54.5 45.0
54-65 54.8
61.2 60.0
61.8 51.9
e 48.6
44.3 (predicted) 45.7 (predicted) Fig. 6. Variation of density and cetane numbers calculation at constant boiling point
(625.8 K).
4148 K. Ramezani et al. / Energy 35 (2010) 4142e4148

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