Biodiesel Production by Esterication of Oleic Acid with Methanol Using a Water

Adsorption Apparatus
Izabelly L. Lucena,

Giovanilton F. Silva,

and Fabiano A. N. Fernandes*

,
Departamento de Engenharia Qu mica, UniVersidade Federal do Ceara, Campus UniVersitario do Pici, Bloco
709, 60455-760 Fortaleza, CE, Brazil, and Tecnologias Bioenergeticas Ltda., AVenida Santos Dumont,
2088/701, 60150-160 Fortaleza, CE, Brazil
The production of biodiesel was investigated using a new reaction system consisting of a reactor coupled to
an adsorption column. The esterication reaction was carried out above the boiling points of methanol and
water to evaporate the water produced during the reaction. A condenser placed above the adsorption column
was responsible for condensing the water and methanol vapor, returning water-free methanol to the reactor
after passing through the adsorption column. The adsorption system was employed to remove the water
produced during the reaction to shift the equilibrium toward fatty acid methyl ester production. Biodiesel
was produced by the esterication reaction of oleic acid and methanol, using sulfuric acid as catalyst. The
results showed that the new reaction system yielded up to 99.7% biodiesel, while the highest yield obtained
using the traditional agitated batch reactor was 88.2%. The best operating condition was found when the
reactor was operated at 100 C, 1% catalyst (w/w), and with an oleic acid to methanol ratio of 3:1.
Introduction
Biodiesel, which consists of long-chain fatty acid alkyl esters
(FAAE) obtained from renewable lipids such as those in
vegetable oils or animal fat, can be used both as an alternative
fuel and as an additive for petroleum diesel. Cetane number,
energy content, viscosity, and phase changes of biodiesel are
similar to those of petroleum-based diesel fuel.
13
Biodiesel fuels have some advantages over petroleum-based
diesel fuels. Biodiesel fuels are derived from renewable
resources, are biodegradable, are nontoxic, and produce less
particles, smoke, and carbon monoxide. The carbon dioxide
produced when biodiesel is burnt in motors is mostly recycled
by the CO
2
cycle since the oil has vegetable origin, and the
alcohol can also be of vegetal origin if ethanol is used.
4
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 byproduct. The triglycerides that
are used in the reaction come from a variety of oils, including
soybean, sunower, corn, palm, and other oils.
57
Oils used in
alkaline transesterication reactions should contain no more than
1% free fatty acids (FFA).
8,9
If the FFA level exceeds this
threshold, saponication hinders separation of the ester from
glycerin and reduces the yield and formation rate of FAE.
The presence of moisture and free acidity strongly inuences
the process performance and economics of biodiesel production.
Both 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 efcient separation of the pure
glycerol in the nal step of the process. A pretreatment
esterication step must be considered as mandatory for oils with
high content of FFA, such as in waste oils, to eliminate the
free acidity, which should be reduced to levels below 1% w/w.
10
Thus, the improvement of the esterication step could represent
one of the key points that need to be studied.
The feasibility of transesterifying vegetable oils is dictated
by the FFA and moisture content. Low-cost feedstocks generally
present high amounts of FFA, which should be removed before
transesterication. Several studies have reported a decrease in
the yield of fatty acid methyl esters (FAME) when high amounts
of FFA are present. Van Gerpen
11
found that in the presence
of 6.7% FFA the yield of FAME decreased by 7-11%. Ma et
al.
12
found that the yield of FAME in beef tallow was higher
when no FFA and water were present in the reaction medium,
while the addition of 0.6% FFA decreased the yield of FAME
to less than 5%.
Some low-cost feedstocks, such as palm fatty acid distillate
(PFAD), present a FFA content higher than 90% w/w and could
be used as feedstock for biodiesel production. With FFA
feedstock the production of water during the reaction limits the
yield of FAME because of the equilibrium reaction. Chongkhong
et al.
13
found that the highest yield of FAME for PFAD was
96% even using a high methanol to FFA ratio (12:1).
The esterication reaction is generally carried out using
sulfuric acid as catalyst, and several researchers have studied
this catalyst in biodiesel production. Sulfuric acid is used
because its acid strength is responsible for releasing more H
+
species to protonate the carboxylic moiety of the fatty acid (rate-
determining step).
14
A small amount of catalyst (0.01% w/w)
is enough to promote the reaction, with the conversion increasing
with higher amounts of catalyst. Yields above 90% can obtained
using a minimal 0.1% w/w, but at high temperatures (130 C).
14
At lower temperatures (55 C) higher amounts of catalyst should
be employed (>2.0% w/w) to achieve yields of 90%.
15
Chongkhong et al.
13
reported that conversions up to 96% could
be obtained when the reaction is carried out at 100 C using
1.8% w/w sulfuric acid and a methanol to FFA molar ratio of
5.3:1, after 2 h of reaction. Other strong acids, such as
methanesulfonic acid, can be used, but the yield is slightly lower
than 90% even using 1% w/w catalyst and 130 C.
14
The esterication reaction between FFA and methanol,
producing FAME (fatty acid methyl ester), can be represented
by the following:
FFA+methanol TFAME+water (1)
* To whom correspondence should be addressed. Tel.: 55-85-
33669611, ext. 27. Fax: 55-85-33669610. E-mail: fabiano@ufc.br.

Universidade Federal do Ceara.

Tecnologias Bioenergeticas Ltda.

Ind. Eng. Chem. Res. 2008, 47, 68856889 6885
10.1021/ie800547h CCC: $40.75 2008 American Chemical Society
Published on Web 07/30/2008
The esterication reaction is an equilibrium reaction and,
therefore, is subject to a maximum yield of methyl ester that
depends mainly on the process temperature and on the initial
alcohol to FFA ratio. As the reaction proceeds, water and methyl
ester are formed until the equilibrium is reached. Methyl ester
yield can be increased if water is removed from the reaction
mixture during the esterication reaction. Removal of water can
be achieved using adsorbents selective for water adsorption, such
as zeolite 3A.
Adsorbents have been employed in biodiesel production by
some researchers. Yori et al.
16
have used silica gel to remove
glycerol from biodiesel streams. Lopes et al.
17
have employed
clay-polymer to remove residual sodium from biodiesel. The
use of Magnesol has been applied to remove water from the
reaction mixture by Kucek et al.
18
In this work the transesteri-
cation reaction of soybean oil with ethanol was carried out in
two steps. In the rst step the reaction was carried out without
adsorbent, achieving conversions of 90%, and in the second
step Magnesol 2% w/w was added to the system to adsorb water
and contaminants, resulting in a nal conversion of 98%. Other
applications of zeolites in biodiesel production are restricted to
the use of zeolites as supports for heterogeneous catalysts.
In the present work, the esterication reaction of oleic acid
with methanol was investigated using a new reaction system
consisting of a reactor coupled to an adsorption column lled
with zeolite 3A. The esterication reaction was carried out above
the boiling points of methanol and water to evaporate the water
produced during the reaction. A condenser placed above the
adsorption column was responsible for condensing the water
and methanol vapor, returning water-free methanol to the reactor
after passing through the adsorption column. Surface response
methodology was used to evaluate the effects of the main
operating conditions affecting the reaction: temperature, alcohol
to free fatty acid molar ratio, and catalyst amount.
Materials and Methods
Reagents. Oleic acid was obtained from Vetec (Rio de
Janeiro, Brazil) and presented 94.4% oleic acid and 5.6%
mixture of palmitoleic acid, palmitic acid, and myristic acid.
The oleic acid presented an acid value of 196.6 mg of KOH/g
and an iodine value of 92.5 g/100 g, which were calculated
based on the AOCS methods for biodiesel feedstock quality,
Cd3d-63 and Cd1-25.
19,20
Methanol (>99%) and sulfuric acid
were obtained from Synth (Sao Paulo, Brazil).
Zeolite. Zeolite 3A (Sylobead MS 562 ET) was obtained from
Grace Davison (Porto Alegre, Brazil) in spherical shape and
was used to adsorb the water formed during the esterication
reaction. The zeolite 3A presented a particle size ranging from
2.0 to 5.0 mm in diameter. Zeolite spheres were separated into
four grades ranging from 2.60 to 4.38 mm (from 4 to 8 mesh
Tyler). Based on prior tests, zeolites with an average particle
size of 3.68 mm diameter were used to adsorb the water formed
during the esterication reaction. The particles with this average
particle size showed a slightly higher yield of FAME (fatty acid
methyl ester).
21
The particles presented a density of 3295 g/m
3
,
an apparent density of 1563 g/m
3
, and 0.53 porosity.
Prior to use, the zeolite was activated in a drying oven
(Edgcon Model 1P) during 24 h at 300 C.
22
This procedure
was done to allow total desorption of any water molecule present
in the zeolite. This procedure does not damage the crystalline
structure of the zeolite.
22
Experimental Apparatus. The experimental apparatus con-
sisted of a 1000 mL round-bottom ask with three parallel necks.
A thermocouple connected to a temperature controller was
inserted in the rst neck. The agitator was inserted in the second
neck, and an adsorption column was connected to the third neck.
Figure 1. Experimental apparatus. (a) Overall view; (b) adsorption column; (c) schematic diagram.
6886 Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008
A heating jacket was used to control the temperature of the
reaction mixture (Figure 1).
The adsorption column consisted of a riser section and a
downer section. The downer section was lled with zeolite 3A
and was primarily used to adsorb the water produced during
the esterication reaction. The downer was 21 cm in height and
2.5 cm in diameter and presented a bed porosity of 0.60. The
riser was not lled with zeolite, so methanol and water vapor
could ow through the riser because of the low pressure drop
in this section. The dimensions of the riser were 23 cm height
and 1.0 cm diameter (Figure 1).
A bulb condenser was placed at the top of the adsorption
column to condense the methanol and the water vapor. The
condensate returned to the round-bottom ask passing through
the downer section lled with zeolite 3A. In the downer section,
water was adsorbed by the zeolite. Methanol owed back to
the round-bottom ask.
The amount of zeolite added to the column was calculated
based on the sorption capacity of water by zeolite 3A (4.9 mol
of water/kg of zeolite at 98-107.6 C) reported by Lalik et
al.
23
Approximately 160 g of zeolite was added to the column,
which is enough to adsorb all water produced by total conversion
of 220 g of oleic acid into FAME.
Esterication Reaction. The esterication reaction was
carried out in the experimental apparatus described previously
(Figure 1). Oleic acid (200 g) was added to the round-bottom
ask. Methanol and catalyst (sulfuric acid) were added according
to a 2
3
experimental design where temperature, catalyst con-
centration, and methanol to oleic acid molar ratio were studied.
The reaction was carried out for 80 min, and samples of 3 mL
were collected for analysis every 10 min.
Temperatures ranging from 90 to 110 C were studied. These
temperatures were higher than the normal boiling point of
methanol (78 C) and near the boiling point of water (100 C).
Catalyst concentrations ranging from 0.5 to 1.0% w/w were
studied. Alcohol to oleic acid ratios ranging from 3:1 to 9:1
were studied. The ranges studied for catalyst concentration and
for the alcohol to oleic acid ratio are within the industrial ranges
used in free fatty acids esterication.
24
Response surface methodology was used to analyze the results
from the experiments. The software Statistica v7.0 (Statsoft,
Tulsa, OK) was used to handle the data. Analyses were carried
out at a 90% level of condence. The reactions were carried
out with and without the adsorption column to analyze the
efciency of the adsorption system.
Biodiesel Analyses. Conversion of oleic acid into fatty acids
methyl esters (FAME) was calculated based on the AOCS
(American Oil Chemists Society) ofcial methods for acid value
(Cd 3d-63) and FFA amount (Ca 5a-40).
19,25
Samples were also analyzed by a Shimadzu (Model QP5050)
gas chromatograph with mass spectrometry (GC-MS), using
a packed OV-5 column (30 m 0.25 mm i.d. 0.25 m lm).
The temperature of the injector was set at 280 C, and helium
was used as carrier gas. The oven temperature was initially set
at 50 C, increasing to 180 C, and after a 5 min steady period
the temperature was increased to 300 C. The temperature
increase for both ramps was set at 20 C/min.
Results and Discussion
The yields of oleic acid into biodiesel, obtained after 80 min
of reaction, are presented in Table 1. The results show that the
highest yield of oleic acid into biodiesel was 88.2% when the
water adsorption column was not used. Conversion increased
to 99.7% when the water adsorption column lled with zeolite
3A was employed.
The yield of biodiesel increased, for all experimental condi-
tions, when the water adsorption column was employed,
showing that the adsorption system was effective in shifting
the equilibrium toward the products. The adsorption column
was able to remove the water from the condensate, decreasing
the amount of water in the reaction mixture and consequently
shifting the equilibrium to produce more FAME.
Studies carried out by Lalik et al.
23
showed that the sorption
capacity of water by zeolite 3A was 4.9 mol of water/kg of
zeolite (88.2 g of water/kg of zeolite) at 98-107.6 C. The
sorption capacity of ethanol by zeolite 3A was 0.044 mol of
ethanol/kg of zeolite (2.0 g of ethanol/kg of zeolite). Given the
size and polarity of methanol, the sorption capacity of methanol
by zeolite 3A will be lower than the sorption capacity of water
and higher than the sorption capacity of ethanol. This observa-
tion shows that the adsorption column used in this work adsorbs
water preferentially over methanol, which has returned to the
reactor and did not affect the FFA to methanol molar ratio in
the reaction mixture.
An analysis of perturbation of factors on yield of biodiesel
was carried out for the process using the adsorption system
(Table 2). The effect column shown in Table 2 is a statistical
parameter that measures how an independent variable affects
the dependent variable. A high absolute value of the effect
column means that a small change in the independent variable
produces a signicant change in the dependent variable. A
positive value of the effect means that an increase in the
independent variable will increase the value of the dependent
variables, whereas a negative value of the effect means that an
increase in the independent variable will decrease the value of
the dependent variable. From a process point of view, variables
with high effect values produce signicant changes in the
process and can be considered the most important variables for
a given process. The p column denotes the probability that an
independent variable has to do not produce any effect on the
Table 1. Yield of Biodiesel, After 80 min of Reaction, at Different
Operating Conditions
temperature
[C]
catalyst
[% w/w]
alcohol to
oleic acid
ratio
yield of biodiesel
without adsorption
column [%]
yield of biodiesel
with adsorption
column [%]
90 0.50 3:1 61.2 ( 0.2 91.3 ( 0.4
110 0.50 3:1 65.5 ( 0.3 96.5 ( 0.3
90 1.00 3:1 71.4 ( 0.5 94.4 ( 0.4
110 1.00 3:1 76.6 ( 0.6 98.8 ( 0.3
90 0.50 9:1 82.7 ( 0.2 94.1 ( 0.4
110 0.50 9:1 85.6 ( 0.3 96.9 ( 0.3
90 1.00 9:1 87.0 ( 0.3 97.6 ( 0.3
110 1.00 9:1 88.2 ( 0.3 99.7 ( 0.3
100 0.75 6:1 74.3 ( 0.6 97.1 ( 0.3
100 0.75 6:1 74.6 ( 0.6 97.4 ( 0.3
100 0.75 6:1 75.5 ( 0.6 97.7 ( 0.3
Table 2. Analysis of Perturbation of Factors on Yield of Biodiesel
variable effect standard error p
mean
a
96.488 0.331 0.000
T
a
3.624 0.775 0.018
C
a
2.933 0.775 0.032
A 1.799 0.775 0.103
T C -0.415 0.775 0.629
T A -1.181 0.775 0.225
C A 0.237 0.775 0.779
T C A 0.058 0.775 0.944
a
Variables signicant at a 95% level of condence. T is the
temperature, C is the catalyst content, and A is the alcohol to free fatty
acid ratio.
Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008 6887
dependent variable. In other words, low values of p mean that
there is high probability that a change in the independent
variable will produce a signicant change in the dependent
variable.
The analysis of perturbation carried out on the yield of
biodiesel showed that the operating conditions that most affected
the yield of oleic acid into biodiesel were the temperature and
the amount of catalyst (Table 2). These two variables showed
to be statistically signicant at a 95% level of condence (p <
0.05).
Temperature was the variable with the greatest effect on yield,
with high temperatures (100 and 110 C) resulting in conver-
sions ranging from 96.5 to 99.7%. Figure 2 shows the effect of
temperature on biodiesel production using the adsorption system.
Temperatures above 100 C showed dynamics and nal yield
of biodiesel similar to the process carried out at 110 C. Lower
yields were obtained at temperatures below the normal boiling
point of water.
As expected, increasing the process temperature increased
the yield of biodiesel because of the increase in the equilibrium
constant. The reaction rate also showed an increase, observed
by the higher yield after 10 min. The reaction shows the typical
behavior of reactions with high activation energy that are favored
by higher temperatures.
The amount of water in the reaction medium had great
inuence on the reaction and nal yield. Below the boiling point
of water, the yield was higher than the yield for the process
carried out without the adsorption column, demonstrating that
the boiling methanol was capable of dragging part of the water
toward the adsorption column, but only part of the water formed
during the reaction has evaporated, causing a lower conversion.
Statistically, the highest temperature should be chosen as the
optimum operating condition since the analysis of perturbation
has shown that the temperature is the most important variable
in the process. The yield increase observed from 90 to 100 C
supports this choice, but the increase observed from 100 to 110
C is within the experimental error and is thus not signicant.
Therefore, the optimum temperature for the process can be
dened as 100 C because it demands less energy than at 110
C.
The amount of catalyst also had a positive effect on yield,
increasing the yield of biodiesel with the increase in catalyst
concentration. An increase by 100% in the catalyst amount
resulted in an increase of between 3 and 4% in the yield of
biodiesel (Figure 3).
According to Tesser et al.
10
the reaction rate of the esteri-
cation reaction is directly proportional to the amount of catalyst.
The amount of sulfuric acid employed as catalyst is related to
the formation of H
+
that catalyzes the reaction. Increasing the
amount of catalyst increases the reaction rate and consequently
reduces the time to achieve high yields.
In the conventional process (without using an adsorption
column) a higher methanol to FFA molar ratio resulted in a
signicant increase in yield of biodiesel (Table 1). Increasing
the methanol to FFA molar ratio from 3:1 to 9:1 increased the
yield of biodiesel by up to 35.1% (at 90 C and 0.5% w/w
catalyst). The increase is explained by the shift in the equilibrium
caused by the excess of methanol.
Using the adsorption column, a higher methanol to FFA molar
ratio resulted in slightly higher yields (up to 3.1% at 90 C and
0.5% w/w catalyst). The equilibrium condition was more
effectively shifted when the water formed during the reaction
was removed.
The effect of the methanol to FFA molar ratio was observed
mainly on the reaction rate. A higher methanol to FFA molar
ratio increased the reaction rate and consequently decreased the
processing time. The use of a higher methanol to FFA molar
ratio reduced the process time in about 20 min when the process
was carried out at 110 C (Figure 4). Higher concentrations of
alcohol increased the reaction rate, because the reaction is a
second-order reaction, and also displaced the equilibrium toward
the products. The combination of these factors with the removal
of water by the adsorption column contributed to accelerate the
reaction.
The use of the adsorption column for water removal may
allow the use of lower alcohol to FFA molar ratios in biodiesel
processing. The use of a lower alcohol to FFA molar ratio has
several economic and ecological advantages. Smaller process
equipment needs to be designed, reducing capital costs. Less
mass needs to be heated, reducing energy costs. Less volume
of alcohol needs to be processed, reducing the operating cost.
Less methanol needs to be washed to remove catalyst, reducing
the impact of wastewater on the environment.
Conclusions
The production of biodiesel by esterication of oleic acid
and methanol resulted in yields ranging from 61.0 to 88.0%.
Figure 2. Effect of temperature on the process dynamics for biodiesel
production with a methanol to FFA molar ratio of 3:1 and 1% sulfuric acid
(w/w).
Figure 3. Effect of catalyst amount on the process dynamics for biodiesel
production with a methanol to FFA molar ratio of 3:1 and temperature of
90 C.
6888 Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008
The reaction system with the adsorption column attached to the
reactor increased the conversion into biodiesel to yields ranging
from 91.2 to 97.2%.
The adsorption system was effective in adsorbing the water
produced during the reaction and in increasing conversion by
displacing the equilibrium toward the products. Temperature
and catalyst concentration were the operating conditions that
most affected the conversion. The alcohol to oleic acid ratio
was also important, especially at lower processing temperatures.
The best operating condition found was at 100 C, 1.0% w/w
catalyst, and with a methanol to oleic acid molar ratio of 3:1.
The use of the adsorption column for water removal allows
the use of lower alcohol to FFA molar ratios in biodiesel
processing with several economic and ecological advantages.
Acknowledgment
The authors gratefully acknowledge the Brazilian research
funding institution CAPES for the award of a scholarship and
TECBIO for nancial support.
Nomenclature
A ) alcohol to oil ratio
C ) catalyst amount [% w/w]
T ) temperature [C]
Literature Cited
(1) Darnoko, D.; Cheryan, M. Kinetics of palm oil transesterication in
a batch reactor. J. Am. Oil Chem. Soc. 2000, 77, 1263.
(2) Muniyappa, P. R.; Brammer, S. C.; Noureddini, H. Improved
conversion of plant oils and animal fats into biodiesel and co-product.
Bioresour. Technol. 1996, 56, 19.
(3) Chongkhong, S.; Tongurai, C.; Chetpattananondh, P.; Bunyakan, C.
Biodiesel production by esterication of palm fatty acid distillate. Biomass
Bioenergy 2007, 31, 563.
(4) Noureddini, H.; Harkey, D.; Medikonduru, V. A continuous process
for the conversion of vegetable oils into methyl esters of fatty acids. J. Am.
Oil Chem. Soc. 1998, 75, 1775.
(5) Antolin, G.; Tinant, F. V.; Briceno, Y.; Castano, V.; Perez, C.;
Ramirez, A. I. Optimization of biodiesel production by sunower oil
transesterication. Bioresour. Technol. 2002, 83, 111.
(6) Al-Widyan, M. I.; Al-Shyoukh, A. O. Experimental evaluation of
the transesterication of waste palm oil into biodiesel. Bioresour. Technol.
2002, 85, 253.
(7) Ma, F.; Clements, L. D.; Hanna, H. A. The effect of mixing on
transesterication of beef tallow. Bioresour. Technol. 1999, 69, 289.
(8) Freedman, B.; Pryde, E. H.; Mounts, T. L. Variables affecting the
yields of fatty esters from transesteried vegetable oils. J. Am. Oil Chem.
Soc. 1984, 61, 1638.
(9) Liu, K. Preparation of fatty acid methyl esters for gas-chromato-
graphic analysis of lipids in biological materials. J. Am. Oil Chem. Soc.
1994, 71, 1179.
(10) Tesser, R.; Di Serio, M.; Guida, M.; Nastasi, M.; Santacesaria, E.
Kinetics of oleic acid esterication with methanol in the presence of
triglycerides. Ind. Eng. Chem. Res. 2005, 44, 7978.
(11) Van Gerpen, J. Biodiesel processing and production. Fuel Process.
Technol. 2005, 86, 1097.
(12) Ma, F.; Clements, L. D.; Hanna, M. A. The effect of catalyst, free
fatty acid and water on transesterication of beef tallow. Trans. ASAE 1998,
41, 1261.
(13) Chongkhong, S.; Tongurai, C.; Chatpattananondh, P.; Bunyahan,
C. Biodiesel production by esterication of palm fatty acid distillate. Biomass
Bioenergy 2007, 31, 563.
(14) Aranda, D. A. G.; Santos, R. T. P.; Tapanes, N. C. O.; Ramos,
A. L. D.; Antunes, O. A. C. Acid-catalyzed homogeneous esterication
reaction for biodiesel production from palm fatty acids. Catal. Lett. 2008,
122, 20.
(15) Marchetti, J. M.; Errazu, A. F. Esterication of free fatty acids
using sulfuric acid as catalyst in the presence of triglycerides Biomass
Bioenergy 2008, in press; http://dx.doi.org/10.1016/j.biombioe.2008.01.001.
(16) Yori, J. C.; DIppolito, S. A.; Pieck, C. L.; Vera, C. R. Deglycer-
olization of biodiesel streams by adsorption over silica beds. Energy Fuels
2007, 21, 347.
(17) Lopes, T. J.; Goncalves, O. H.; Quadri, M. G. N.; Machado,
R. A. F.; Quadri, M. B. Production of a clay-polymer composite aiming
the removal of residual sodium from biodiesel. Macromol. Symp. 2006,
245-246, 191.
(18) Kucek, K. T.; Oliveira, M. A. F. C.; Wilhelm, H. M.; Ramos, L. P.
Ethanolysis of rened soybean oil assisted by sodium and potassium
hydroxides. J. Am. Oil Chem. Soc. 2007, 84, 385.
(19) American Oil Chemists Society. Cd 3d-63 Acid value. In Ofcial
Methods and Recommended Practices of the AOCS, 5th ed.; 2007; 2 pp.
(20) American Oil Chemists Society. Cd 1-25 Iodine value (Wijs). In
Ofcial Methods and Recommended Practices of the AOCS, 5th ed.; 2007;
2 pp.
(21) Lucena, I. L. Otimizacao do processo de obtencao de biodiesel
atraves da adsorcao de agua formadadurante areacao de estericacao. Master
Degree Thesis, Universidade Federal do Ceara, Fortaleza, Brazil, 2008; 90
pp.
(22) Teo, W. K.; Ruthven, D. Adsorption of water from aqueous ethanol
using 3-A molecular sieves. Ind. Eng. Chem. Process Des. DeV. 1986, 25,
17.
(23) Lalik, E.; Mirek, R.; Rakoczy, J.; Groszek, A. Microcalorimetric
study of sorption of water and ethanol in zeolites 3A and 5A. Catal. Today
2006, 114, 242.
(24) Unnithan, U. R.; Tiwari, K. K. Kinetics of esterication of oleic
acid and mixtures of fatty acids with methanol using sulfuric acid and
p-Toluenesulfonic acid as catalysts. Indian J. Technol. 1987, 25, 477.
(25) American Oil Chemists Society. Ca 5a-40 Free fatty acids. In
Ofcial Methods and Recommended Practices of the AOCS, 5th ed.; 2007;
2 pp.
ReceiVed for reView April 05, 2008
ReVised manuscript receiVed June 2, 2008
Accepted June 20, 2008
IE800547H
Figure 4. Effect of methanol to FFA molar ratio on the process dynamics
for biodiesel production carried out at 110 C and with 1% sulfuric acid
(w/w).
Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008 6889