Renewable Energy 35 (2010) 2581e2584

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Biodiesel production from waste coconut oil by esterication with ethanol:

The effect of water removal by adsorption
Joo Felipe G. Oliveira a, Izabelly Larissa Lucena a, Rosana M. Alves Saboya a, Marcelo L. Rodrigues a,
Antonio Eurico B. Torres a, Fabiano A. Narciso Fernandes a, Clio L. Cavalcante Jr. a, *,
Expedito Jos S. Parente Jr. b
a
Departamento de Engenharia Qumica, Universidade Federal do Cear, Campus do Pici, Bl. 709, 60455-760, Fortaleza, CE, Brazil
b
Tecnologias Bioenergticas (TECBIO), PARTEC, Rua Prof. Rmulo Proena, s/n, CEP 60455-700, Fortaleza, CE, Brazil

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

Article history: The production of biodiesel by esterication with ethanol using waste oil generated in the rening of
Received 10 December 2009 coconut oil was investigated in this study. The reaction was performed with and without adsorption of
Accepted 30 March 2010 water in order to verify the effect of removing water on the reaction conversion. Methanol was also
Available online 10 May 2010
evaluated as an esterication agent. For both ethanol and methanol, conversions over 99% mol were
observed. Simultaneous water adsorption allowed the use of lower alcohol/oil molar ratios thus enabling
Keywords:
better economics to a possible industrial process.
Biodiesel
2010 Elsevier Ltd. All rights reserved.
Esterication
Waste coconut oil
Ethanol
Adsorption

1. Introduction On esterication, the hydroxyl groups (-OH) of the carboxylic

The use of vegetable oils in diesel engines replacing petroleum
diesel has been studied since the last century [1e3]. However, some
physicochemical properties of vegetable oils (high density and
viscosity, low volatility, formation of carbon deposits, etc.) disable
their use in diesel engines due to the formation of substances that
may damage the engine [3,4]. Transesterication of vegetable oils
has been applied industrially to adjust their properties into more
adequate values for usage in diesel engines [3e5]. This product is
called biodiesel. Therefore, biodiesel is a mono-alkyl ester gener-
ated from vegetable oils or animal fats [2e5] and consequently
a renewable, non-toxic and biodegradable fuel [3,4].
Transesterication by basic catalysis, using vegetable oils and
animal fats that have appreciable amounts of free fatty acids, is
disadvantaged by soap formation, which prevents the separation of
biodiesel from the glycerin phase [2]. In order to reduce the amount
of free fatty acids, Canakci and Van Gerpen [2] proposed a method
for the production of biodiesel from oils and fats with high levels of
free acidity through a pre-treatment, based on an esterication
reaction using acid catalyst, followed by the usual transesterication.
* Corresponding author. Tel.: 55 (85) 3366 9611; fax: 55 (85) 3366 9610.
E-mail address: celio@ufc.br (C.L. Cavalcante Jr.).
acids are replaced by an alcoxy group (-OR) to form esters via
a condensation reaction catalyzed by strong acids. For biodiesel
production, a reversible reaction of a free fatty acid with an alcohol
can be performed [6]. This reaction is typically of second order [7]
and several factors can affect the speed of reaction such as temper-
ature and catalyst and reagents concentrations [8].
In the esterication reaction, the presence of water favors the
reverse hydrolysis reaction. It also helps to promote the deactivation
of the acid catalyst due to the formation of H3O by solvation within
the reaction system. The chemical stability of H3O makes the
protonation of the carbonyl group of the fatty acid more difcult thus
slowing the reaction rate [9]. Lucena et al. [10] proposed a procedure,
using adsorption on zeolite 3A, for the removal of the water formed
in the esterication between oleic acid and methanol. Conversion
values above 98% mol were obtained in this way, while the process
carried out without removing water presented values below 80%
mol, even for large molar ratios between alcohol and fatty acid, as
proposed by Liu et al. [9].
Short-chain alcohols (e.g. methanol, ethanol) can be used for
this reaction. Methanol has some advantages such as higher reac-
tivity and less possibility of decreasing the reaction rate by steric
hindrance when compared to other alcohols, since it has the lowest
carbon chain [6]. However, the main process for the production of
methanol currently uses natural gas, making it non-renewable and

0960-1481/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2010.03.035
2582 J.F.G. Oliveira et al. / Renewable Energy 35 (2010) 2581e2584
environmentally incorrect, besides being toxic. In Brazil, the use of
anhydrous ethanol has become more advantageous, since it is
produced on a large scale and is a product of biomass, thus
biodegradable and non-toxic to the environment [4].
In this study, we evaluate the esterication of waste coconut oil
(low cost raw material) with anhydrous methanol and, alternatively
with anhydrous ethanol, using sulfuric acid as catalyst. The reactions
were carried out with and without adsorption removal of the water
formed in the reaction. Zeolite 3A, known as a water selective
adsorbent [11,12], was employed.
2. Materials and methods
2.1. Reagents
Waste coconut oil was used as feedstock fat, kindly supplied by
Ducoco S.A (So-Paulo, Brazil). Sulfuric acid, ethanol and methanol
(99.8 purity % wt), were obtained from Vetec (Rio de Janeiro, Brazil).
2.2. Adsorbent
Zeolite 3A, in spherical shape (MS Sylobead ET 562), was kindly
supplied by Grace Davison (Porto Alegre, Brazil). The particles had
diameters ranging from 2.0 to 5.0 mm, solid density 3.295 g/m3,
bulk density 1.563 g/m3, and porosity 0.53. Pre-activation of the
adsorbent was performed at a temperature of 300  C, for at least 24
hours, following a slow temperature increase (1 /min) from room
temperature, using an Edgon 1P oven.
2.3. Experimental apparatus
The experimental reaction system has been presented in detail
by Lucena et al. [10]. The adsorption column has two parallel
sections: one of larger diameter, lled with zeolite 3A, and the other
one with a smaller diameter, without adsorbent. Above the
adsorption column, there is a condenser for condensation of
alcohol and water evaporated during the esterication reaction.
Details about the experimental method can also be found in Lucena
et al. [10]. In the case of reactions performed without adsorption,
the larger diameter section of the column was lled with inert solid
particles to simulate the adsorbent bed.
2.4. Esterication reaction
The esterication reaction was performed using the system above
described, using 207.5 g of waste coconut oil as feed. Alcohol:oil
molar ratios of 3:1 and 9:1 were evaluated in this study. At the
desired experimental temperature (between 90 and 110  C), 1% w/w
of catalyst (based on the mass of oil) was added. The reaction was
then monitored for 100 min, sampling (ca. 2 ml) every 10 min. The
acidity index value was used to follow the reaction performance.
2.5. Analysis of waste coconut oil and biodiesel
We used several analytical methods for the characterization of
the waste oil and of the biodiesel that was produced, following
methodologies suggested by the American Oil Chemists Society
(AOCS) and the American Society for Testing Materials (ASTM). The
acidity was determined by the methods Cd 3d-63 and Ca 5a-40.
This was an indication of the reaction performance, corresponding
to the decrease of fatty acids concentration in the oil, due to the
esterication.
The characterization of waste coconut oil was also done by gas
chromatography (SATURN 2000 MS/MS) for determination of the
fatty acids composition in the oil. The density and kinematic viscosity
Table 1
Properties of waste coconut oil.
Acidity index (mg KOH/mg) 195.80
Density @ 20  C (kg/m3) 917.36
Kinematic viscosity @ 40  C (mm2/s) 35.70
Iodine index (g/100 g) 7.21
were determined following ASTM D-4052 and ASTM D445, respec-
tively, using digital equipment Anton Paar SVM 3000-Stabinger
(Austria). The oil was also characterized by the iodine index,
following the standard Cd 1-25 of AOCS, which indicates the degree
of unsaturation of the carbon chains of the oil.
3. Results and discussions
3.1. Characterization of waste coconut oil
The physicalechemical characterization of the waste coconut oil
is presented in Table 1. It is observed that the waste oil that was used
had high acidity index (about 98% of free fatty acids), which suggests
that the esterication process would be recommended for the
production of biodiesel from this raw material. The oil also shows
a low value of iodine index, indicating low content of unsaturated
carbon compounds and therefore the biodiesel obtained from this
raw material should be more resistant to oxidation processes.
A chromatographic analysis allowed to quantify the oil content of
fatty acids in the waste coconut oil (see Table 2). It may also be
observed that oleic and linoleic acids are the predominant fatty acids.
3.2. Effect of adsorption on the esterication reaction with ethanol
Experimental conversions versus reaction time for the esteri-
cation of waste coconut oil with ethanol are shown in Fig. 1.
Experiments were performed with and without water removal by
adsorption for the following conditions: alcohol:oil molar ratio of
3:1, temperature 100  C and catalyst 1% wt. The reaction conver-
sions were calculated using the values of acidity as determined by
the AOCS method from Eq. (1), where IAf and IA0 are the nal and
initial acidity indexes, respectively.
IAf  IA0
Conversion %  100 (1)
IA0
It may be observed that after 100 min the reaction carried out using
zeolite 3A to remove the water produced allowed conversions
above 99% mol, while for the system without adsorption conver-
sion values below 80% mol were observed. In fact, the removal of
water formed in the esterication provides a signicant increase in
conversions, since water shifts the equilibrium of the reaction in
the opposite direction (hydrolysis) by reducing the amount of
mono-alkyl ester (biodiesel) formed, in addition to deactivating the
catalyst acid.
In both cases, with or without adsorption, we may observe that
the conversion values will increase steadily during the rst 40 min
Table 2
Composition of the waste coconut oil obtained by gas chromatography.
Organic acids % wt
Linoleic 47.4
Oleic 27.5
Palmitic 21.4
Stearic 3.0
Myristic 0.5
Palmitoleic 0.2
 J.F.G. Oliveira et al. / Renewable Energy 35 (2010) 2581e2584 2583

100 100

80 80
Conversion (%)

Conversion (%)
60 60

40 with water adsorpition

40
without water adsorpition Methanol
Ethanol
20 Ethanol; 100C; 3:1; 1% w/w 20 100C; 3:1; 1% w/w

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Time (min) Time (min)
Fig. 1. Effect of removing water formed in the esterication reaction. Experimental Fig. 3. Effect of alcohol type in the esterication reaction of waste coconut oil with
conditions: temperature 100  C, alcohol/oil molar ratio of 3/1 and 1% wt of catalyst. adsorption removal of water. Experimental conditions: temperature 100  C, 1% wt of
catalyst and alcohol:oil molar ratio of 3:1.
of reaction and, after that, the values of conversion become
approximately constant, showing that the reaction has practically renewable and biodegradable, whereas methanol is normally
reached equilibrium. obtained from fossil sources.

3.3. Effect of the alcohol/waste oil molar ratio

4. Conclusions

The inuence of different alcohol:oil molar ratios (3:1 and 9:1)

The adsorption removal of water in the esterication of waste
on the esterication of waste coconut oil with ethanol, using
coconut oil with alcohol was evaluated experimentally. The use of
adsorption removal of water, is illustrated in Fig. 2. The temperature
a raw material of high acidity in the esterication reaction enabled
was kept constant at 100  C and the concentration of catalyst in the
the processing of the waste generated in the rening of coconut oil.
reaction system was 1% wt. It can be seen that the conversion
As presented in this study, it is important to search procedures to
values are essentially the same, for both molar ratios, at any time
obtain higher conversion values when oil with high acidity is used,
during both experiments. Thus, we may conclude that the removal
since the usual method of biodiesel production (the trans-
of water by adsorption favors the esterication to the extent that
esterication reaction of vegetable oils) is not feasible with high
the amount of alcohol used in the process does not signicantly
acidity materials.
alter the reaction conversion. So we may use a lower excess of
The experimental results presented lower alcohol:oil molar
alcohol to obtain conversions higher than 99% mol. Therefore, for
ratios in the reaction medium when compared to systems without
this raw material with high residual acidity, the use of an apparatus
water removal by adsorption. In this study, an alcohol excess of 200%
that allows the adsorption removal of water produced during
using adsorption in zeolite 3A yielded higher conversion values than
esterication turned the process less expensive (since the waste of
when using 800% of alcohol excess in a system without water
alcohol can be avoided), and may provide more economic viability
adsorption. This can be very interesting for possible commercial
to the process.
usage of esterication of highly acidic waste oils in the biodiesel
industry.
3.4. Effect of alcohol used

The effect of the type of alcohol (methanol or ethanol) on the Acknowledgments

reaction conversion is shown in Fig. 3. It is possible to observe that
after 100 min, the conversion values showed practically the same The authors acknowledge nancial support from FINEP e Finan-
results (above 99% mol) for both alcohols, under similar experi- ciadora de Estudos e Projetos.
mental conditions. This may be interesting for industrial applica-
tions since ethanol may be obtained from biomass, which makes it References

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