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Conventional and In Situ Transesterification of Sunflower Seed Oil for the

Production of Biodiesel

Article  in  Fuel Processing Technology · May 2008

DOI: 10.1016/j.fuproc.2007.10.004

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 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 5 0 3–5 0 9

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Conventional and in situ transesterification of sunflower seed

oil for the production of biodiesel

K.G. Georgogianni a , M.G. Kontominas a,⁎, P.J. Pomonis a , D. Avlonitis b , V. Gergis c

a
Section of Industrial and Food Chemistry, Department of Chemistry, University of Ioannina 45110-Ioannina, Greece
b
Department of Petroleum Technology, TEI of Chalkida, 34600-Kavala, Greece
c
Department of Food Technology, TEI of Athens, 12210-Egaleo, Greece

AR TIC LE I N FO ABS TR ACT

Article history: In the present work the alkaline transesterification of sunflower seed oil with methanol and
Received 24 April 2007 ethanol, for the production of biodiesel fuel was studied. Both conventional and in situ
Received in revised form transesterification were investigated using low frequency ultrasonication (24 kHz) and
10 October 2007 mechanical stirring (600 rpm). Use of ultrasonication in conventional transesterification
Accepted 16 October 2007 with methanol gave high yields of methyl esters (95%) after a short reaction time (20 min)
similar to those using mechanical stirring. Use of ultrasonication in conventional
Keywords: transesterification with ethanol gave similar yields to those using mechanical stirring but
Sunflower seed oil significantly lower than respective yields using methanol. In the in situ transesterification
Transesterification the use of ultrasonication and mechanical stirring led to similar high yields (95%) of methyl
In situ esters after approximately 20 min of reaction time. In the presence of ethanol use of
Biodiesel ultrasonication led to high ester yields (98%) in only 40 min of reaction time while use of
Ultrasonication mechanical stirring gave lower yields (88%) even after 4 h of reaction time.
Kinetics In situ transesterification gave similar ester yields to those obtained by conventional
transesterification being an alternative, efficient and economical process. In all cases a
concentration of 2.0% NaOH gave higher ester yields.
Reaction rate constants were calculated, using first order reaction kinetics, to be equal
to 3.1 × 10− 3 s− 1 for conventional transesterification using methanol and 2.0% NaOH, and
9.5 × 10− 4 s− 1 using ethanol.
© 2007 Elsevier B.V. All rights reserved.

1. Introduction production. Alcoholysis of these oils has been studied

Alternative fuels for diesel engines are becoming increasingly
important due to diminishing petroleum reserves and the
environmental consequences of exhaust gases from petro-
leum-fuelled engines. Biodiesel is a promising renewable fuel
comprised of mono-alkyl esters of long chain fatty acids,
which are derived from vegetable oils [1]. Seeds of high oil
content, such as sunflower, rapeseed and soybean seeds, have
gained much attention lately as renewable energy sources
both because of their relatively high yield and widespread
intensively by numerous investigators [2–4].
Transesterification of vegetable seed oils is conventionally
carried out by subjecting the pre-extracted oil to treatment
with the appropriate alcohol, in the presence of an acid or an
alkaline catalyst [4].
The amount of catalyst used depends on the pH (acidity) of
the oil. To complete the reaction stoichiometrically a 3:1 molar
ratio of alcohol to triglyceride is necessary. Due to the fact that
transesterification is an equilibrium reaction, an excess of
alcohol is used to displace the reaction towards ester formation.

⁎ Corresponding author. Tel.: +30 2651098342; fax: +30 2651098795.

E-mail address: mkontomi@cc.uoi.gr (M.G. Kontominas).

0378-3820/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.10.004
504 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 5 03 –5 0 9
One of the main advantages of biodiesel is that the
transesterification reaction used for its production can be
carried out at almost any scale from laboratory scale using a
few liters of oil on up to a large industrial scale capable of
producing millions of liters of biodiesel per year.
However, in spite of the favourable impact that its
commercialization may provide, the direct use of vegetable
oils and oil blends is generally considered to be impractical.
The high viscosity, fatty acid composition and free fatty acid
content of such oils, as well as gum formation due to oxidation
and polymerization during storage and combustion, carbon
deposits and lubricating oil thickening are some of its more
obvious drawbacks [1,6].
In the last two decades, sonochemistry, the chemical
reaction during ultrasound irradiation, has developed into
an expanding research area. Ultrasound energy is known to
produce chemical and physical effects that arise from the
collapse of cavitation bubbles. The collapse of cavitation
bubbles disrupts the phase boundary in a two-phase liquid
system and causes emulsification by ultrasonic jets that
impinge one liquid in to the other [11]. This effect can be
employed for biodiesel production [10,12–14].
In situ transesterification differs from the conventional
reaction in that the oil-bearing material contacts with
acidified or alkalized alcohol directly instead of reacting with
pre-extracted oil and alcohol. That is, extraction and transes-
terification proceed in one step, the alcohol acting both as an
extraction solvent and an esterification reagent. In situ
transesterification of sunflower oil with acidified methanol
produces fatty acid methyl esters in yields significantly
greater than those obtained from the conventional reaction
with pre-extracted seed oils [10].
The main objective of the present work was to apply the
biodiesel production technology using an alkaline catalyst to the
transesterification of sunflower seed oil/sunflower seeds and
particularly to study the effect of (a) ultrasonication versus me-
chanical stirring, (b) in situ versus conventional transesterifica-
tion and (c) nature of alcohol (methanol versus ethanol) on yield
and time of completion of the transesterification reaction. A
second objective was to determine respective reaction rate con-
stants by applying basic reaction kinetics to experimental data.
2. Experimental part
2.1. Reagents and materials
Sodium hydroxide (N96%) was purchased from Merck (Darm-
stadt-Germany) and used after milling, to facilitate the
dilution in methanol. Methanol of purity N95%, ethanol of
purity 95% and petroleum ether (pro analysis) employed were
purchased from Fluka (Sigma-Aldrich, Germany). The sun-
flower seeds (5.6% moisture content) were provided by the
Agricultural Cooperative of Kavala in Greece.
2.2. Procedures
2.2.1. Solvent extraction
Whole sunflower seeds (20 g) were conditioned by heating in
an oven at 85 °C for 1 h, macerated in the extracting solvent,
petroleum ether (50–100 ml) in a home type blender, to give a
product with a particle size of coarse sand. The solid material
was transferred quantitatively to a Soxhlet thimble and
extracted for various periods of time. Solvent was removed
from both the extracted oil and the solid residue using a
vacuum rotary evaporator at 40 °C.
2.2.2. Conventional oil transesterification
Sunflower seed oil (80 g, 0.102 mol) produced as described
above, methanol (30 ml/0.75 mol) or ethanol (32.9 ml/0.75 mol)
corresponding to a 7:1 molar ratio of alcohol to oil and NaOH in
various concentrations (1.0%, 1.5%, 2.0% w/w) were refluxed
together in a 500 ml glass reactor equipped with a glass
anchor-shaped mechanical stirrer, a water condenser and
funnel. Heating was achieved by means of a heating mantle
controlled by a proportional integral derivative (PID) tempera-
ture controller. The temperature was raised to 60 °C for
methanol or 80 °C for ethanol and the mixture was stirred
either using a mechanical stirrer (600 rpm) or a low frequency
ultrasonicator (24 kHz, 200 W, UP 200 S, IKA, England). Ten ml
samples were taken from the reaction mixture at predeter-
mined time intervals, neutralized and analyzed, for the
qualitative conversion of the oil to methyl or ethyl esters, by
thin layer chromatography (TLC) [8,9].
TLC analysis was performed on glass plates coated with
Silica Cel G (Merch), and developed in a solvent system of
petroleum ether/diethyl ether/hydrochloric acid (8:2:0.1).
Spots were developed by iodine vapor stain [9].
After the complete conversion of the vegetable oil, the
reaction was stopped and the mixture was allowed to stand
for phase separation: the ester mixture formed the upper layer
and glycerin formed the lower layer [10]. The residual catalyst
and non-reacted alcohol were distributed between the two
phases. After phase separation, using a separatory funnel, the
ester mixture was purified further by dissolving in petroleum
ether adding water and phosphoric acid to adjust pH to ca.7
and washing three times with water. Esters were then dried
over anhydrous sodium sulfate and analyzed by Gas
Chromatography.
2.2.3. In situ oil transesterification
Whole sunflower seeds (20 g) were macerated in methanol
or ethanol (50 ml) as above and transferred to the previously
described reaction flask. Methanol (150 ml) or ethanol
(216 ml) and 2.0% NaOH diluted in the corresponding
alcohol (10 ml) were added and the mixture was refluxed
at 60 °C (for methanol) or 80 °C (for ethanol) and stirred
either using the mechanical stirrer (600 rpm) or the low
frequency ultrasonicator. After the complete conversion of
the vegetable oil, the reaction was stopped. The reaction
mixture was filtered, washed as described above, dried over
anhydrous sodium sulfate and analyzed by Gas Chromato-
graphy [15].
2.3. Sampling and analysis
The fatty acid composition of sunflower seed oil was
determined by a well-established Gas Chromatographic
procedure, [15,16] and is shown in Table 1. In brief, 0.1 ml of
the transesterified oil sample was dissolved in 5 ml of
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 5 0 3–5 0 9 505

Table 1 – Principal fatty acid composition and molecular

weight (MW) for sunflower seed oil
Fatty acid MW Content, %
Palmitic (16:0) 256
Stearic (18:0) 284
Oleic (18:1) 282
Linoleic (18:2) 280
petroleum ether, and 3 μl of this solution were injected into
a Varian 3700 GC for identification and quantification
purposes. The standard mixture of the fatty acid methyl/
ethyl esters used was purchased from Sigma (stock No. 189-3).
The analysis of biodiesel by GC was carried out by
dissolving 0.050 g of the methyl or ethyl ester mixture sample
in 5 ml of petroleum ether, and injecting 3 μl of this solution
into the GC, under the same conditions as above.
The content of biodiesel for each sample was quantified by
comparing the FID response for each methyl ester of the
biodiesel sample to the FID response of each methyl ester in
the standard mixture of fatty acid methyl esters.
The conversion of oil in each experiment was calculated
from the content in methyl/ethyl esters of biodiesel as
analysed by GC, and the material balance of the reaction:
weightbiodiesel
ConversionðkÞ ¼ MWbiodiesel
biodiesel concentrationðkÞ
weightoil3
MWoil
Where:
MW is the mean molecular weight of biodiesel/oil. The
mean molecular weight of biodiesel was calculated averaging
the individual molecular weights (MWi) of each constituent
methyl/ethyl ester, according to the biodiesel fatty acid alkyl
ester analysis (χi). That is MW = ΣMWi×χi. The mean molecular
weight of the oil was calculated averaging the individual
molecular weights (MWi) of each constituent triglyceride
according to the fatty acid oil analysis (χi). The factor 3
appears in the formula since each triglyceride molecule yields
three alkyl ester molecules.
3. Results and discussion
3.1. Fatty acid composition of sunflower seed oil
6.6
5.1 Fatty acid composition of sunflower seed oil is shown in
19.6
Table 1. Given that its acid value was determined to be 0.50%
68.7
that is less than 1.0% alkaline transesterification was chosen
for experimental biodiesel production. High free fatty acid and
water content are known to produce large amounts of soap
which in turn lower the yield of esters while making the
separation of ester and glycerol difficult [17].
Free fatty acid content of sunflower seed oil in the present
work correlates rather well with that reported by Bikou et al.
[18] for refined sunflower seed oil (0.09%), given the fact that
the latter had undergone refining.
3.2. Conventional versus ultrasound assisted
transesterification reaction: effect of stirring method, catalyst
concentration and type of alcohol
A set of experiments was carried out to determine the effect of
ultrasonication versus mechanical stirring on the transester-
ification reaction. Yields of methyl esters isolated by conven-
tional transesterification using mechanical stirring and
ultrasonication as a function of time and NaOH concentration
are given in Table 2.
Results in Table 2 showed that the highest yields were
obtained when the catalyst was used at higher concentrations.
To be more specific, by using 2.0% NaOH wt/wt of oil and
mechanical stirring the transesterification reaction was close
to being completed after 20 min. On the other hand, by using
lower concentrations of NaOH (1.0 or 1.5% wt/wt) the reaction
was not completed even after 60 min. In conclusion, by
increasing the amount of catalyst the yields of methyl esters
also increased. As stated previously, high concentrations of
alkaline catalyst form soaps in the presence of large residues
of fatty acids resulting in emulsion formation between soaps
and water molecules. Thus, the yields of isolated esters are
very low. In the present study, this phenomenon did not occur
and the increase of catalyst's concentration caused an

Table 2 – The yields of isolated methyl esters with mechanical stirring (600 rpm) and ultrasonication (24 kHz)
Time 1.0% w/w NaOH 1.5% w/w NaOH 2.0% w/w NaOH
(min)
Yield (%) Constant rate (s− 1) Yield (%) Constant rate (s− 1) Yield (%) Constant rate (s− 1)

Mechanical stirring (600 rpm) 5 42 5.0 × 10− 3 53 1.1 × 10− 3 58 3.1 × 10− 3
10 51 61 88
15 57 68 93
20 64 72 95
30 82 85 94
40 86 87 96
60 90 92 96
Ultrasonication (24 kHz) 5 32 0.8 × 10− 3 48 2.1 × 10− 3 69 3.0 × 10− 3
10 43 75 82
15 55 86 93
20 61 91 94
30 74 96 94
40 88 96 95
60 92 96 95
506 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 5 03 –5 0 9

Table 3 – Yields and rate constants of isolated ethyl esters with mechanical stirring and ultrasonication
Time 1.0% w/w NaOH 1.5% w/w NaOH 2.0% w/w NaOH
(min)
Yield (%) Rate constant (s ) Yield (%) Rate constant (s ) Yield (%) Rate constant (s− 1)
−1 −1

Mechanical Stirring (600 rpm) 5 22 5.0 × 10− 4 29 6.0 × 10− 4 35 9.0 × 10− 4
10 31 38 46
15 37 45 58
20 43 54 65
30 56 67 78
40 68 76 83
60 72 81 88
Ultrasonication (24 kHz) 5 25 6.0 × 10− 4 32 7.0 × 10− 4 39 1.0 × 10− 3
10 36 43 51
15 41 49 62
20 53 58 70
30 62 69 79
40 73 78 85
60 80 85 90

increase in the yield of the isolated fatty acid methyl esters.
Part of the explanation for such a finding is the fact that the
sunflower seed oil used in the present study was crude rather
than refined thus the transesterification reaction requires
larger quantities of alcohol [7]. However, a further increase in
catalyst concentration (i.e 2.5% NaOH) led to extensive soap
formation and thus to a decrease in yields of fatty acid methyl
esters. This finding supports the above postulation. With
regard to NaOH concentration used, Ataya et al. [5] similarly
reported an increased triglyceride conversion with increasing
NaOH concentration between 1.0 and 3.0% w/w for canola oil
in a two-phase agitated system.
As mentioned previously the molar ratio of methanol to oil
was chosen to be 7:1 based on literature reports according to
which sunflower seed, peanut, sunflower seed and soybean
oils behaved similarly and that the highest conversion to ester
(93–98%) was observed at a ratio of 6:1 [6]. Yields of methyl
esters under present experimental conditions (i.e 95%) are
higher than those reported by Freedman et al. [6] for sunflower
seed oil (i.e 90%) after 50 min of reaction time using a molar
ratio of 6:1 and 0.5% of sodium methoxide as catalyst.
Similar results were obtained by using ultrasonication
instead of mechanical stirring. To be more specific, by using
2.0% NaOH wt/wt of oil the transesterification reaction was
close to being completed in approximately 20 minutes. On the
other hand, by using lower concentrations of NaOH (1.5% wt/
wt) the reaction was completed in 30 min and by using 1.0%
NaOH the reaction was not completed even after 60 min. In
conclusion, by increasing the amount of catalyst the yields of
methyl esters also increase. For a given time the yields of
isolated products with ultrasonication are generally higher
than those with mechanical stirring, probably due to less soap
formation through the use of ultrasonication. Indeed, after
less than one minute of mixing with sonication the mixture
became homogeneous. Despite this general observation a 95%
conversion to esters was achieved in the same amount of time
(i.e 20 min) using both mechanical stirring and ultrasonica-
tion. Present conversion to esters' values are comparable to
those of Colucci et al. [14] who reported a 95% conversion of
refined soybean oil to methyl esters using a molar ratio of
methanol to oil 6:1 after 10 min at 60 °C, using KOH catalyst at
a concentration of 2.2% w/w.
Present results differ however than those of Stavarache
et al. [10] who reported that conversion of vegetable oil (no
further information on the nature of the oil was provided) to
methyl esters was the highest for a 1.0% (w/w) NaOH
concentration (i.e 95% after 10 min at room temperature
using ultrasonication (28 kHz) versus 91% after 10 min using
mechanical stirring (1800 rpm). In this case ultrasonication
increased conversion of oil to methyl esters. Lifka and
Ondruscka [13] studied the effect of ultrasonication versus
mechanical stirring on the alkaline transesterification of
rapeseed oil using NaOH at a concentration of 0.5% w/w at
45 °C. A conversion of 80–85% was obtained for both
ultrasonicated and mechanically stirred reactions after
30 min. Finally, Siatis et al. [19] reported a 95% conversion of
Cynara seed oil to fatty acid methyl esters using an alkali-
catalyzed ultrasonically assisted transesterification reaction
in approximately 30 min.
Yields of ethyl esters isolated by conventional transester-
ification using mechanical stirring and ultrasonication as a
function of time and NaOH concentration are given in Table 3.
Results in Table 3 show that the highest yields were obtained
when the catalyst was used at higher concentrations. That is the
triglycerides conversion to ethyl esters reached 72%, 81% and
88% after 60 min with mechanical stirring, when using 2.0%,
1.5% and 1.0% NaOH. (w/w) respectively. Respective conversion
values using ultrasonication were 80%, 85% and 90%.
Comparing data in Tables 2 and 3 it is observed that the
yield of ethyl esters is lower as compared to yield of methyl
esters. Due to increased miscibility between ethanol, glycerine
and esters the separation and purification of esters' mixture is
Table 4 – Yields of isolated methyl esters with in situ
transesterification using 2.0% NaOH as catalyst
Time Mechanical stirring Ultrasonication
(min) (600 rpm) Yield (%) (24 kHz) Yield (%)
10 85 88
15 89 90
20 93 95
40 94 97
60 95 96
120 97 95
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 5 0 3–5 0 9
Table 5 – Yields (%) of isolated ethyl esters with in situ
transesterification using 2.0% NaOH as catalyst
Time Mechanical stirring Ultrasonication
(min) (600 rpm) Yield (%) (24 kHz) Yield (%)
20 58 78
40 64 98
60 80 97
120 82 95
180 88 98
240 90 95
difficult. This causes low yields of ester product. These
findings are in agreement with those of Stavarache et al. [10]
who studied the alkaline transesterification of vegetable oil at
room temperature using methanol and ethanol and reported
similar results.
In general, the physical and chemical properties and the
performance of ethyl esters are comparable to those of methyl
esters. Ethanol is produced as a more environmentally
friendly fuel and in contrast to methanol is more biodegrad-
able and less toxic. Moreover ethanol is derived from
agricultural products and is renewable [17,20]. On the other
hand, methanol is not miscible in hydrocarbons, and separa-
tion occurs readily in the presence of small quantities of
water, particularly with decreasing temperature [20]. Based on
the above, methanol is generally more suitable for transester-
ification because it accelerates the reaction substantially and
gives high yields of fatty acid methyl esters.
3.3. In situ transesterification reaction
Based on the above results, NaOH at a concentration of 2.0% w/
w was used in all subsequent experiments. Yields of methyl
esters isolated by alkali-catalyzed (NaOH) in situ transester-
ification using both mechanical stirring and ultrasonication
are given in Table 4.
Results in Table 4 show that the alkali-catalyzed in situ
transesterification reaction was extremely fast, requiring only
20 min to reach complete conversion using both mechanical
stirring and ultrasonication.
Harrington and Catherine [8] studied in situ transesterifi-
cation of a series of sunflower seeds under acid catalysis using
methanol and compared data to conventional transesterifica-
tion. Results showed that in all cases the yields of crude
methyl esters (seed basis) obtained from in situ reaction were
greater than those from conventional treatments (i.e. 38.9%
versus 33.2%). Respective values for purified ethyl esters were
36.8% versus 30.2%. Kildiran et al. [9] studied the in situ
Fig. 1 – Transesterification reaction of sunflower seed oil.
507
transesterification of soybean oil using a series of alcohols
(methanol, ethanol, n-propanol and n-butanol) and sulphuric
acid as the catalyst. Methanol proved to be a poor solvent for
soybean oil while ethanol and the higher alcohols gave high
yields of alkyl esters. Conversions in the range of 80–85% were
obtained after 3 h at 78 °C. Finally Siatis et al. [19] reported that
for sunflower seeds, 40% of the total triglyceride, originally
contained in the seed, was transesterified with the use of
alkali-catalyzed ultrasonically assisted in situ extraction
transesterification (USAET). If the standard method of extrac-
tion of triglyceride from the seed with sufficient conversion to
fatty acid methyl esters was applied, 48% of the total
triglyceride would be extracted and then converted at best
by 96%. Hence the total fatty acid methyl esters derived by the
standard method from sunflower would be 46% which is
comparable to the 40% direct conversion by USAET.
Yields of ethyl esters isolated by alkali-catalyzed (NaOH) in
situ transesterification using both mechanical stirring and
ultrasonication are given in Table 5.
Results in Table 5 show that the alkali-catalyzed in situ
transesterification reaction with ethanol was not completed
even after 4 h using mechanical stirring. However, using
ultrasonication the reaction was completed in 40 min. Also,
for a given reaction time, the yields of the isolated ethyl esters
were higher for the ultrasonicated as compared to the
mechanically stirred system. This can be explained assuming
that ultrasounds produce less soap thus increasing ester
yields. Comparing data in Tables 4 and 5 it is observed that the
yield of ethyl esters is lower as compared to yield of methyl
esters. Explanation on this finding is analogous to that given
previously.
3.4. Kinetics of sunflower seed oil to methyl- and
ethyl- esters
The transesterification kinetics of vegetable oil have been
reported in a limited number of studies. Freedman et al. [21]
investigated both acid- and alkaline-catalyzed transesterifica-
tion of soybean oil with butanol and methanol. They
determined the reaction rate constants as reaction para-
meters such as temperature, molar ratio of alcohol to soybean
oil and catalyst type and concentration were varied. Generally,
a second order reaction for all three reversible reactions
(TG⇄DG, DG⇄MG, MG⇄GL) provided a satisfactory mechan-
ism at a molar ratio of methanol to oil of 6:1.
Noureddini and Zhu [22] studied the same reaction
focusing on the effect of mixing intensity and temperature
on the rate of reaction. A reaction mechanism consisting of an
508 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 5 03 –5 0 9
Fig. 2 – ln (1-XTG) versus time with 1.0% NaOH w/w, 1.5%
NaOH w/w and 2.0% NaOH w/w, using methanol and
mechanical stirring.
initial mass transfer-controlled region followed by a kineti-
cally controlled region was proposed. The experimental data
for the latter region appear to be a good fit into a second order
kinetic mechanism. Reaction rate constants and activation
energies were determined for all forward and reserve
reactions.
Darnoko and Cheryon [23] studied the kinetics of palm oil
transesterification using KOH as the catalyst at temperatures
up to 60 °C. Second order reaction kinetics were assigned to all
three stepwise reactions (TG⇄DG, DG⇄MG, MG⇄GL). Diasakou
et al. [24] studied the thermal non-catalytic transesterification
reaction of soybean oil with methanol at 200 and 235 °C. Each
of the three stepwise reactions was assumed to be of first
order with respect to each reacting component and irrever-
sible. Rate constants were determined for all stepwise
reactions. Kusdiana and Saka [25] studied the kinetics of
rapeseed oil transesterification using supercritical methanol.
The reaction was assumed to follow a first order mechanism
as a function of the concentration of triglycerides and reaction
temperature. Rate constants for the overall transesterification
reaction were determined. Finally, Ataya et al. [5] studied the
Fig. 3 – ln (1-XTG) versus time with 1.0% NaOH w/w, 1.5%
NaOH w/w and 2.0% NaOH w/w, using methanol and
ultrasonication.
Fig. 4 – 1/(1-XTG) versus time with 1.0% NaOH w/w,
1.5% NaOH w/w and 2.0% NaOH w/w, using methanol and
mechanical stirring.
kinetics of canola oil transesterification reaction in both a two-
phase as well as single phase system by the addition of a
common solvent (tetrahydrofuran) and reported a first order
reaction mechanism.
Ignoring intermediate reactions namely: TG⇄DG, DG⇄MG,
MG⇄GL the 3 step reaction can be simplified to the one overall
reaction shown in Fig. 1.
 1 
For a first order reaction a plot of ln 1XTG (where XTG is the
conversion of triglycerides at time t), as a function of time will
be linear with a slope equal to the reaction rate constant k [5].
XTG
For a second order reaction a plot of 1XTG as a function of time
will be a straight line [23].
Fitting data of the conventional transesterification reaction
of sunflower seed oil to above two models, showed a better fit
(for a straight line) for a first order reaction than for a second
order reaction. R2 values for first order reaction ranged between
0.961 and 0.996 for varying NaOH concentration, between 1.0%
and 2.0% (conventional transesterification reaction with
mechanical stirring), (Fig. 2) and between 0.930 and 0.981 for
the same reaction with ultrasonication (Fig. 3). R2 values for a
second order reaction ranged between 0.919 and 0.965 for
varying NaOH concentration, between 1.0% and 2.0% (conven-
tional transesterification reaction with mechanical stirring)
(Fig. 4) and between 0.802 and 0.853 for the same reaction with
ultrasonication (Fig. 5).
Fig. 5 – 1/(1-XTG) versus time with 1.0% NaOH w/w,
1.5% NaOH w/w and 2.0% NaOH w/w, using methanol and
ultrasonication.
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 5 0 3–5 0 9
Based on above data, it can be stated that the reaction in
our experiment is rather of pseudo-first order than true first
order.
Based on the first order reaction kinetics, overall reaction
rate constants are shown in Tables 2 and 3.
Data in Tables 2 and 3 show that reaction rates are
substantially affected by method of stirring, catalyst concentra-
tion as well as by type of alcohol. Rate constant values for the
production of ethyl esters were lower by factor of approximately
3 (3.1 × 10− 3 s− 1 versus 9.5 × 10− 4 s− 1) than respective values for
the production of methyl esters (Table 2 versus 3).
4. Conclusions
In the present study both conventional and in situ transester-
ification of sunflower seed oil with both methanol and ethanol
using mechanical stirring and ultrasonication was investi-
gated. It was shown that ultrasonication in most cases led to
similar yields of alkyl esters as compared to mechanical
stirring. Regarding in situ transesterification, ultrasonication
and mechanical stirring are both equally efficient in the case
of production of methyl esters. However, in the case of
production of ethyl esters, ultrasonication was substantially
more efficient in triglycerides' conversion. Furthermore, a
considerable increase in yield of esters is obtained in a
remarkably short time span (the ultrasonication assisted
reaction is completed in 20 min with methanol and in
40 min with ethanol) achieved by the use of alkali-catalyzed
in situ transesterification. Methanol gave shorter reaction
times and higher yields of alkyl esters than ethanol.
Finally, the rate constants in the conventional transester-
ification using ethanol were lower than the respective ones
using methanol.
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