Fuel Processing Technology 91 (2010) 194–196

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Transesterification of castor oil: Effect of the acid value and neutralization of the oil
with glycerol
Louise L. Sousa, Izabelly L. Lucena, Fabiano A.N. Fernandes ⁎
Universidade Federal do Ceara, Departamento de Engenharia Quimica, Campus do Pici, Bloco 709, 60455-760 Fortaleza - CE, Brazil

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

Article history: This paper evaluates the production of methyl esters from castor oil and methanol after neutralization of
Received 23 April 2009 castor oil with glycerol. The reaction was carried out under atmospheric pressure and ambient temperature
Received in revised form 23 August 2009 in a batch reactor, employing potassium hydroxide as catalyst. Results showed high yield of castor oil into
Accepted 28 September 2009
methyl esters after neutralization of castor oil with glycerol. The highest yield observed was of 92.5% after
15 min of reaction. The best operating condition was obtained applying an alcohol to oil molar ratio of 6.0
Keywords:
and 0.5% w/w of catalyst.
Biodiesel
Methyl esters
© 2009 Elsevier B.V. All rights reserved.
Castor oil
Transesterification
Methanolysis

1. Introduction
Methyl and ethyl esters derived from vegetable oil or animal fat,
known as biodiesel, have good potential as alternative diesel fuel. Cetane
number, energy content, viscosity and phase changes of biodiesel are
similar to those of petroleum-based diesel fuel [1,2]. Biodiesel fuels have
some advantages over petroleum based diesel fuels. Biodiesel fuels are
biodegradable, non-toxic and produce less particles, smoke and carbon
monoxide.
At present, fatty acid alkyl esters (FAAE) are obtained by reacting
triglycerides with lower alcohols, such as methanol or ethanol, in the
presence of a strong base used as catalyst. The reaction yields glycerin
as a by-product. The triglycerides that are used in the reaction come
from a variety of oils, including soybean, castor, sunflower, corn, palm
and other oils [3,4,5]. Oils used in alkaline transesterification reactions
should contain no more than 1% free fatty acids (FFA) [6,7]. If the FFA
level exceeds this threshold, saponification hinders separation of the
ester from glycerin and reduces the yield and formation rate of FAE.
Water and FFA rapidly react with the catalyst, consuming it and
giving way to long chain soaps for which the tensile properties do not
allow an efficient separation of the pure glycerol in the final step of the
process. A pre-treatment step must be considered as mandatory for oils
with high content of FFA, like in waste oils, to eliminate the free acidity,
which should be reduced to levels below 1% w/w [8]. The pre-treatment
may consist of an esterification step [9] or a neutralization step. Thus, the
improvement of a pre-treatment to reduce free acidity represents a key
point that need to be studied.
⁎ Corresponding author. Tel.: +55 85 33669611.
E-mail address: fabiano@ufc.br (F.A.N. Fernandes).
In this work we have studied the neutralization of castor oil with
glycerol, a by-product of biodiesel production, and its effect on the
transesterification reaction of castor oil and methanol.
2. Materials and methods
2.1. Materials
Commercial castor oil was obtained from Campestre (São Paulo,
Brazil) with chemical composition consisting of 94.2% ricinoleic acid, 2.8%
linoleic acid, 2.0% oleic acid and 1.0% other acid (weight percentages).
Based on the chemical composition of the oil, its molecular weight was
assumed to be 891.1 g/mol. The castor oil presented an acid value of
4.7mgKOH/g, an iodine value of 83.5 g iodine/100 g oil, a saponification
value of 169.4 mg KOH/g oil and 8.1% w/w as di and monoglycerides.
Castor oil properties were calculated based on the AOCS methods for
biodiesel feedstock quality Cd3d-63 and Cd1-25 [10,11]. Analytical grade
methanol (99%) and potassium hydroxide (>96%) were obtained from
Vetec (Rio de Janeiro, Brazil). Glycerol produced as by-product from
transesterification of castor oil was provided by Tecbio (Fortaleza, Brazil).
2.2. Neutralization of castor oil with glycerol
Castor oil and glycerol were fed into a glass vessel with nominal
volume of 500 mL. The reaction mixture was prepared by mixing 100 mL
of castor oil and 200 mL of glycerol. The reaction was carried out at
120 °C, atmospheric pressure and vigorous stirring for 30 min. A heating
jacket was used to control the temperature of the reaction mixture.
After 30 min, the mixture was transferred to a separation funnel
and allowed to stand for phase separation (for at least 24 h). The oil

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.09.016
 L.L. Sousa et al. / Fuel Processing Technology 91 (2010) 194–196
phase collect to be used in the production of methyl esters. A sample
was collected to analyze its acid value.
2.3. Transesterification reaction
Potassium hydroxide was dissolved into the alcohol before its
addition into the reactor. Methanol, castor oil and potassium hydroxide
were fed into a glass vessel with nominal volume of 250 mL. The
reaction mixture was prepared by mixing the amounts of methanol;
castor oil and potassium hydroxide required to prepare 200 mL of the
reaction mixture. The reaction mixture was prepared at a methanol to
castor oil molar ratio of 6.0. The amount of catalyst used in each run is
reported in Tables 1 and 2. The reaction was carried out under ambient
temperature (28 °C), atmospheric pressure and vigorous stirring in a
closed vessel. A closed reactor was used to reduce the vaporization of
alcohol to the atmosphere. A heating jacket was used to control the
temperature of the reaction mixture.
After sampling, the reaction was stopped by acidifying the mixture
with sulfuric acid, to neutralize the remaining catalyst, and was allowed to
stand for phase separation (for at least 24 h). After phase separation the
traces of catalyst and alcohol were washed out with water from the esters
mixture until the water layer remain completely translucent. Finally, the
ester layer was dried on anhydrous calcium chloride and analyzed. All
experiments were done in triplicate, and the average data are presented.
2.4. Analysis
The methyl ester content was assayed by gas chromatography in an
Thermos Ultra chromatograph provided with a flame ionization detector,
employing a silica capillary column of 30 m length and 0.25 mm inner
diameter, packed with poly (ethylene glycol) (0.25 μm film thickness).
Solution of methyl esters (1 μL) in hexane containing approximately 1%
esters was injected under the following conditions: the carrier gas was
helium at a flow rate of 2 mL/min. The injector and detector temperatures
were 250 °C. Oven temperature started at 50 °C for 1 min, increased up to
250 °C at a rate of 5 °C/min and held for 10 min.
3. Results and discussions
Castor oil with an acid value of 4.7 mg KOH/g was neutralized with
glycerin. The method described previously was applied for a period of
1 and 2 h, reducing the acid value of the oil to 2.7 and 0.44,
respectively. The results confirmed that glycerol (produced during the
transesterification reaction) can be used to neutralize the oil before its
use in the production of biodiesel.
The glycerol-rich process stream often comprises methanol (a
volatile component), water, residual catalyst and a small amount of
fatty acid salts or soaps that were present in the starting material or
unintentionally produced in the transesterification reaction. The
neutralization effect of glycerol is mostly caused by saponification of
free fatty acids with residues of base catalyst that remain with the
glycerol after its separation from the methyl esters. These free fatty
acids are converted into salts and soaps, which are miscible to the
glycerol-rich phase and leave the oil-rich phase. This proposed
neutralization step helps to reduce the acid value of the oil and also
helps to remove traces of catalyst from glycerol.
Table 1
Yield of castor oil into methyl esters for oils with different acid value (reaction
time = 15 min; catalyst content = 0.5% w/w).
Sample Acid Value (mg KOH/g) Yield (%)
A 0.44 92.0
B 2.71 87.6
C 4.69 19.9
195
Table 2
Yield into methyl esters after transesterification of castor oil and methanol (reaction
time = 15 min).
Run Catalyst (w/w %) Yield into methyl esters (%)
Raw castor oil (acid value = 4.6 mgKOH/g)
1 0.1 13.4
2 0.5 19.9
3 1.0 89.1
Neutralized castor oil (acid value = 0.4 mgKOH/g)
1 0.1 80.9
2 0.5 92.0
3 1.0 92.5
A basic scheme of an industrial process employing the neutralization of
the oil is shown in Fig. 1. Transesterification of oil and methanol produce
methyl esters and glycerol, which are transferred to a separation vessel
where methyl esters are separated from glycerol and methanol. The
mixture of methanol and glycerol is distilled yielding methanol, which is
recycled to the transesterification reactor. The glycerol stream leaving the
distillation column is heated and sent to a neutralization reactor where it
will neutralize the raw oil. The mixture of glycerin and oil is separated in a
settling vessel. The neutralized oil is sent to the transesterification
reaction, while glycerin is sent to further purification.
Further experiments were carried out to evaluate the effect of the
acid value on the yield of methyl esters, and thus, to evaluate the
neutralization step (Table 1). The yield into methyl esters showed a
yield of 92.0% with neutralized castor oil and 19.9% with raw castor oil.
The results confirmed that the acidity of the raw material affects the
yield into methyl esters. High acid value oils have a considerable
concentration of free fatty acids that react very fast with base
catalysts, reducing the amount of catalyst available for the transester-
ification reaction, acting as a poison for the alkaline catalyst.
For example, Sample C reported in Table 1 will consume 93.8% of
the catalyst to neutralize the free fatty acids of the oil, leaving only
6.2% of the catalyst (or 0.03% w/w) for the transesterification reaction.
The neutralized oil (Sample A) however, will consume only 8.8% of the
catalyst to neutralize the free fatty acids of the oil, leaving most of the
potassium hydroxide to available to catalyze the transesterification
reaction.
The influence of the concentration of catalyst on the yield of castor oil
into methyl esters was carried out to evaluate the optimal concentration of
catalyst that should be used in the transesterification of neutralized castor
oil (Table 2). The results suggest that 0.5% w/w of potassium hydroxide
should be employed, because higher amounts of catalyst do not increase
the conversion of oil into methyl ester and would increase the cost of
neutralization of glycerin and methyl esters at the end of the process.
Table 2 also shows the effect of the concentration of catalyst on the yield of
raw castor oil into methyl esters. The amount of catalyst that should be
employed in this case was much higher than for the neutralized castor oil.
The dynamics of the transesterification reaction was studied for the
best operation condition for the neutralized and raw oils (conditions
that presented the highest yields into methyl esters). For the neutralized
castor oil the reaction was carried out with 0.5% w/w of catalyst, while
for the raw castor oil the reaction was carried out with 1.0% w/w of
catalyst. The study showed that the reaction time to reach equilibrium
was reduced from 30 min to 15 min when the neutralized castor oil was
employed (Fig. 2).
The conversion of castor oil into fatty acids methyl esters (FAME)
obtained using the neutralized castor oil was higher than several studies
reported in the literature. Jeong and Park [12] have studied the
transesterification of castor oil using methanol and potassium hydrox-
ide. In their study, castor oil with high acid value (18 mgKOH/g) was
employed and the highest yield into methyl esters was 89.5% after
40min of reaction, employing 1.5% w/w of potassium hydroxide and a
methanol to oil molar ratio of 10.5. Under the same optimum conditions
196 L.L. Sousa et al. / Fuel Processing Technology 91 (2010) 194–196
Fig. 1. Proposed industrial flowchart to produce methyl esters with neutralized castor oil.
found in our study, the process carried out by Jeong and Park would have
yielded approximately 70% of the oil into biodiesel after 40 min of
reaction (based on the regression presented for the surface response
methodology), which is much lower than the optimum yield found in
our research. The low conversion into biodiesel found by Jeong and Park
[12] may have been related to the high acid value of the castor oil that
was used. As such the use of a neutralization step may be useful to
increase the yield of castor oil into methyl esters.
Albuquerque et al. [13] have studied the use of CaO-based catalyst
and have obtained yields of 67.5% of castor oil into methyl esters after
1 h of reaction (60 °C). The study has not reported the acid value of
castor oil, so it was not possible to compare the effect of acid value on
the yield into methyl esters. It is important to notice that the lower
yield observed for CaO-based catalyst is also caused by the blockage of
solid catalysts by partial glycerides/glycerol, which is high under the
condition applied by Albuquerque et al. [13]. Peña et al. [14] have
studied the addition of hexane as co-solvent in castor oil transester-
ification. The results obtained by Peña et al. [14] showed that the use of
mixture of methanol (85% v/v) and hexane (15% v/v) and sodium
methoxide (1% w/w) as catalyst yielded 95.5% of methyl esters after
2 h of reaction. The yield into methyl esters after 1 h was approx-
imately 81.5%. The yield obtained by Peña et al. [14] was higher than
the obtained by this study.
The neutralization of castor oil with glycerin proved to yield higher
amount of methyl esters than non-neutralized castor oil. Meneghetti
et al. [15] have studied the transesterification of castor oil using four
homogeneous catalysts (KOH, NaOH, CH3OK and CH3ONa). The castor
Fig. 2. Yield of castor oil into methyl esters as a function of time, using raw and neutralized
castor oil.
oil that was used in the reactions presented 1.2% of free fatty acids and
the highest yields were obtained at 1 h of reaction and the process
yielded 58%, 77%, 81% and 84% respectively for NaOH, KOH, CH3ONa
and CH3OK.
4. Conclusions
In this work the transesterification of castor oil with methanol was
carried out in a batch reactor, employing raw castor oil and neutralized
castor oil. The yield of methyl esters obtained from neutralized castor oil
was higher than the yield obtained from raw oil under the same
operating condition. A flowchart was proposed to include the neutral-
ization stage into the industrial flowchart.
Acknowledgments
The authors thank the Brazilian funding institute CAPES for the award
of a scholarship and CNPq and Tecbio (Fortaleza, CE) for the financial
support.
References
[1] D. Darnoko, M. Cheryan, Kinetics of palm oil transesterification in a batch reactor,
JAOCS 77 (2000) 1263–1267.
[2] P.R. Muniyappa, S.C. Brammer, H. Noureddini, Improved conversion of plant oils
and animal fats into biodiesel and co-product, Bioresour. Technol. 56 (1996) 19–24.
[3] G. Antolin, F.V. Tinant, Y. Briceño, V. Castaño, C. Pérez, A.I. Ramirez, Optimization of
biodiesel production by sunflower oil transesterification, Bioresour. Technol. 83
(2002) 111–114.
[4] M.I. Al-Widyan, A.O. Al-Shyoukh, Experimental evaluation of the transesterifica-
tion of waste palm oil into biodiesel, Bioresour. Technol. 85 (2002) 253–256.
[5] F. Ma, L.D. Clements, H.A. Hanna, The effect of mixing on transesterification of beef
tallow, Bioresour. Technol. 69 (1999) 289–293.
[6] B. Freedman, E.H. Pryde, T.L. Mounts, Variables affecting the yields of fatty esters
from transesterified vegetable oils, JAOCS 61 (1984) 1638–1643.
[7] K. Liu, Preparation of fatty acid methyl esters for gas-chromatographic analysis of
lipids in biological materials, JAOCS 71 (1994) 1179–1187.
[8] R. Tesser, M. Di Serio, M. Guida, M. Nastasi, E. Santacesaria, Kinetics of oleic acid
esterification with methanol in the presence of triglycerides, Ind. Eng. Chem. Res.
44 (2005) 7978–7982.
[9] I.L. Lucena, G.F. Silva, F.A.N. Fernandes, Biodiesel production of oleic acid with methanol
using a water adsorption apparatus, Ind. Eng. Chem. Res. 47 (2008) 6885–6889.
[10] American Oil Chemist′s Society, Cd 3d-63 acid value, Official Methods and
Recommended Practices of the AOCS5th Ed., 2007, 2 pp.
[11] American Oil Chemist′s Society, Cd 1-25 iodine value (Wijs), Official Methods and
Recommended Practices of the AOCS5th Ed., 2007, 2 pp.
[12] G.T. Jeong, D.H. Park, Optimization of biodiesel production from castor oil using
response surface methodology, Appl. Biochem. Biotechnol. 156 (2009) 431–441.
[13] M.C.G. Albuquerque, I. Jiménez-Urbistondo, J. Santamaría-González, J.M. Mérida-
Robles, R. Moreno-Tost, E. Rodríguez-Castellón, A. Jiménez-López, D.C.S. Azevedo, C.L.
Cavalcante Jr., P. Maireles-Torres, CaO supported on mesoporous silicas as basic
catalysts for transesterification reactions, Appl. Catal. A Gen. 334 (2008) 35–43.
[14] R. Peña, R. Romero, S.L. Martinez, M.J. Ramos, A. Martinez, R. Natividad,
Transesterification of castor oil: effect of catalyst and co-solvent, Ind. Eng. Chem.
Res. 48 (2009) 1186–1189.
[15] S.M.P. Meneghetti, M.R. Meneguetti, C.R. Wolf, E.C. Silva, G.E.S. Lima, L.L. Silva, T.M.
Serra, F. Cauduro, L.G. Oliveira, Biodiesel from castor oil: a comparison of
ethanolysis versus methanolysis, Energy Fuels 20 (2005) 2262–2265.