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(C) Biodiesel Production by Esterification of Oleic Acid With Methanol Using A Water PDF
(C) Biodiesel Production by Esterification of Oleic Acid With Methanol Using A Water PDF
The production of biodiesel was investigated using a new reaction system consisting of a reactor coupled to
an adsorption column. The esterification 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 esterification 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.
Figure 1. Experimental apparatus. (a) Overall view; (b) adsorption column; (c) schematic diagram.
The esterification reaction is an equilibrium reaction and, operating conditions affecting the reaction: temperature, alcohol
therefore, is subject to a maximum yield of methyl ester that to free fatty acid molar ratio, and catalyst amount.
depends mainly on the process temperature and on the initial
alcohol to FFA ratio. As the reaction proceeds, water and methyl Materials and Methods
ester are formed until the equilibrium is reached. Methyl ester
yield can be increased if water is removed from the reaction Reagents. Oleic acid was obtained from Vetec (Rio de
mixture during the esterification reaction. Removal of water can Janeiro, Brazil) and presented 94.4% oleic acid and 5.6%
be achieved using adsorbents selective for water adsorption, such mixture of palmitoleic acid, palmitic acid, and myristic acid.
as zeolite 3A. 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
Adsorbents have been employed in biodiesel production by based on the AOCS methods for biodiesel feedstock quality,
some researchers. Yori et al.16 have used silica gel to remove Cd3d-63 and Cd1-25.19,20 Methanol (>99%) and sulfuric acid
glycerol from biodiesel streams. Lopes et al.17 have employed were obtained from Synth (São Paulo, Brazil).
clay-polymer to remove residual sodium from biodiesel. The Zeolite. Zeolite 3A (Sylobead MS 562 ET) was obtained from
use of Magnesol has been applied to remove water from the Grace Davison (Porto Alegre, Brazil) in spherical shape and
reaction mixture by Kucek et al.18 In this work the transesteri- was used to adsorb the water formed during the esterification
fication reaction of soybean oil with ethanol was carried out in reaction. The zeolite 3A presented a particle size ranging from
2.0 to 5.0 mm in diameter. Zeolite spheres were separated into
two steps. In the first step the reaction was carried out without
four grades ranging from 2.60 to 4.38 mm (from 4 to 8 mesh
adsorbent, achieving conversions of 90%, and in the second
Tyler). Based on prior tests, zeolites with an average particle
step Magnesol 2% w/w was added to the system to adsorb water size of 3.68 mm diameter were used to adsorb the water formed
and contaminants, resulting in a final conversion of 98%. Other during the esterification reaction. The particles with this average
applications of zeolites in biodiesel production are restricted to particle size showed a slightly higher yield of FAME (fatty acid
the use of zeolites as supports for heterogeneous catalysts. methyl ester).21 The particles presented a density of 3295 g/m3,
In the present work, the esterification reaction of oleic acid an apparent density of 1563 g/m3, and 0.53 porosity.
with methanol was investigated using a new reaction system Prior to use, the zeolite was activated in a drying oven
(Edgcon Model 1P) during 24 h at 300 °C.22 This procedure
consisting of a reactor coupled to an adsorption column filled
was done to allow total desorption of any water molecule present
with zeolite 3A. The esterification reaction was carried out above in the zeolite. This procedure does not damage the crystalline
the boiling points of methanol and water to evaporate the water structure of the zeolite.22
produced during the reaction. A condenser placed above the Experimental Apparatus. The experimental apparatus con-
adsorption column was responsible for condensing the water sisted of a 1000 mL round-bottom flask with three parallel necks.
and methanol vapor, returning water-free methanol to the reactor A thermocouple connected to a temperature controller was
after passing through the adsorption column. Surface response inserted in the first neck. The agitator was inserted in the second
methodology was used to evaluate the effects of the main neck, and an adsorption column was connected to the third neck.
Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008 6887
A heating jacket was used to control the temperature of the Table 1. Yield of Biodiesel, After 80 min of Reaction, at Different
reaction mixture (Figure 1). Operating Conditions
The adsorption column consisted of a riser section and a alcohol to yield of biodiesel yield of biodiesel
temperature catalyst
downer section. The downer section was filled with zeolite 3A oleic acid without adsorption with adsorption
[°C] [% w/w]
ratio column [%] column [%]
and was primarily used to adsorb the water produced during
the esterification reaction. The downer was 21 cm in height and 90 0.50 3:1 61.2 ( 0.2 91.3 ( 0.4
2.5 cm in diameter and presented a bed porosity of 0.60. The 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
riser was not filled with zeolite, so methanol and water vapor
110 1.00 3:1 76.6 ( 0.6 98.8 ( 0.3
could flow through the riser because of the low pressure drop 90 0.50 9:1 82.7 ( 0.2 94.1 ( 0.4
in this section. The dimensions of the riser were 23 cm height 110 0.50 9:1 85.6 ( 0.3 96.9 ( 0.3
and 1.0 cm diameter (Figure 1). 90 1.00 9:1 87.0 ( 0.3 97.6 ( 0.3
A bulb condenser was placed at the top of the adsorption 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
column to condense the methanol and the water vapor. The 100 0.75 6:1 74.6 ( 0.6 97.4 ( 0.3
condensate returned to the round-bottom flask passing through 100 0.75 6:1 75.5 ( 0.6 97.7 ( 0.3
the downer section filled with zeolite 3A. In the downer section,
water was adsorbed by the zeolite. Methanol flowed back to Table 2. Analysis of Perturbation of Factors on Yield of Biodiesel
the round-bottom flask. variable effect standard error p
The amount of zeolite added to the column was calculated mean a
96.488 0.331 0.000
based on the sorption capacity of water by zeolite 3A (4.9 mol Ta 3.624 0.775 0.018
of water/kg of zeolite at 98-107.6 °C) reported by Lalik et Ca 2.933 0.775 0.032
al.23 Approximately 160 g of zeolite was added to the column, A 1.799 0.775 0.103
T×C -0.415 0.775 0.629
which is enough to adsorb all water produced by total conversion
T×A -1.181 0.775 0.225
of 220 g of oleic acid into FAME. C×A 0.237 0.775 0.779
Esterification Reaction. The esterification reaction was T×C×A 0.058 0.775 0.944
carried out in the experimental apparatus described previously a
Variables significant at a 95% level of confidence. T is the
(Figure 1). Oleic acid (200 g) was added to the round-bottom temperature, C is the catalyst content, and A is the alcohol to free fatty
flask. Methanol and catalyst (sulfuric acid) were added according acid ratio.
to a 23 experimental design where temperature, catalyst con-
centration, and methanol to oleic acid molar ratio were studied. to 99.7% when the water adsorption column filled with zeolite
The reaction was carried out for 80 min, and samples of 3 mL 3A was employed.
were collected for analysis every 10 min. The yield of biodiesel increased, for all experimental condi-
tions, when the water adsorption column was employed,
Temperatures ranging from 90 to 110 °C were studied. These
showing that the adsorption system was effective in shifting
temperatures were higher than the normal boiling point of
the equilibrium toward the products. The adsorption column
methanol (78 °C) and near the boiling point of water (100 °C).
was able to remove the water from the condensate, decreasing
Catalyst concentrations ranging from 0.5 to 1.0% w/w were
the amount of water in the reaction mixture and consequently
studied. Alcohol to oleic acid ratios ranging from 3:1 to 9:1
shifting the equilibrium to produce more FAME.
were studied. The ranges studied for catalyst concentration and
Studies carried out by Lalik et al.23 showed that the sorption
for the alcohol to oleic acid ratio are within the industrial ranges
capacity of water by zeolite 3A was 4.9 mol of water/kg of
used in free fatty acids esterification.24
zeolite (88.2 g of water/kg of zeolite) at 98-107.6 °C. The
Response surface methodology was used to analyze the results sorption capacity of ethanol by zeolite 3A was 0.044 mol of
from the experiments. The software Statistica v7.0 (Statsoft, ethanol/kg of zeolite (2.0 g of ethanol/kg of zeolite). Given the
Tulsa, OK) was used to handle the data. Analyses were carried size and polarity of methanol, the sorption capacity of methanol
out at a 90% level of confidence. The reactions were carried by zeolite 3A will be lower than the sorption capacity of water
out with and without the adsorption column to analyze the and higher than the sorption capacity of ethanol. This observa-
efficiency of the adsorption system. tion shows that the adsorption column used in this work adsorbs
Biodiesel Analyses. Conversion of oleic acid into fatty acids water preferentially over methanol, which has returned to the
methyl esters (FAME) was calculated based on the AOCS reactor and did not affect the FFA to methanol molar ratio in
(American Oil Chemist’s Society) official methods for acid value the reaction mixture.
(Cd 3d-63) and FFA amount (Ca 5a-40).19,25 An analysis of perturbation of factors on yield of biodiesel
Samples were also analyzed by a Shimadzu (Model QP5050) was carried out for the process using the adsorption system
gas chromatograph with mass spectrometry (GC-MS), using (Table 2). The “effect” column shown in Table 2 is a statistical
a packed OV-5 column (30 m × 0.25 mm i.d. × 0.25 µm film). parameter that measures how an independent variable affects
The temperature of the injector was set at 280 °C, and helium the dependent variable. A high absolute value of the effect
was used as carrier gas. The oven temperature was initially set column means that a small change in the independent variable
at 50 °C, increasing to 180 °C, and after a 5 min steady period produces a significant change in the dependent variable. A
the temperature was increased to 300 °C. The temperature positive value of the effect means that an increase in the
increase for both ramps was set at 20 °C/min. independent variable will increase the value of the dependent
variables, whereas a negative value of the effect means that an
Results and Discussion increase in the independent variable will decrease the value of
the dependent variable. From a process point of view, variables
The yields of oleic acid into biodiesel, obtained after 80 min with high effect values produce significant changes in the
of reaction, are presented in Table 1. The results show that the process and can be considered the most important variables for
highest yield of oleic acid into biodiesel was 88.2% when the a given process. The p column denotes the probability that an
water adsorption column was not used. Conversion increased independent variable has to do not produce any effect on the
6888 Ind. Eng. Chem. Res., Vol. 47, No. 18, 2008