558

Energy & Fuels 2009, 23, 558563

Effect of Temperature on the Continuous Synthesis of Soybean

Esters under Supercritical Ethanol
Ignacio Vieitez, Camila da Silva, Isabella Alckmin, Gustavo R. Borges,
Fernanda C. Corazza, J. Vladimir Oliveira, Maria A. Grompone, and Ivan Jachmanian*,
Laboratorio de Grasas y Aceites, Departamento de Alimentos, Facultad de Qumica, UniVersidad de la
Republica, MonteVideo 1157-11800, Uruguay, and Department of Food Engineering, URI-Campus de
Erechim, Erechim 99700-000, Brazil
ReceiVed August 4, 2008. ReVised Manuscript ReceiVed October 1, 2008

This work investigated the effect of temperature on the reaction efficiency of soybean oil transesterification
in supercritical ethanol in a continuous catalyst-free process under different water concentrations and at varying
substrate flow rates. Experiments were performed in the temperature range from 250 to 325 C, at 20 MPa,
with an oil to ethanol molar ratio of 1:40. Results showed that temperature and substrate flow rates strongly
affected the reaction conversion to fatty acid ethyl esters, decomposition, and trans-isomerization of unsaturated
fatty acids, mainly for C18:2 and C18:3. It is shown that the synthesis of esters was favored by the addition
of water to the reaction medium and the degradation phenomenon decreased as water concentration increased
from 0 to 10 wt %.

Introduction
The use of vegetable oils to produce biodiesel and its merits
as an alternative, renewable energy source to mineral diesel is
well documented in the literature.1-4 Because of the well-known
environmental benefits arising from its use and also due to the
relief reliance on import needs, biodiesel fuel is a good
alternative to petroleum-based fuel.5,6
Transesterification, among other processes used for biodiesel
production, has been the most common way to produce
biodiesel.1,2 The method, also called alcoholysis, refers to a
reaction involving the displacement of alcohol from an ester
by another alcohol to yield fatty acid alkyl esters (i.e., biodiesel)
and glycerol as a byproduct.
Conventionally, transesterification can be performed using
alkaline, acid, or enzyme catalysts.1,2,5 Although chemical
transesterification through alkali-catalyzed processes provides
high conversion levels of triglycerides to their corresponding
fatty acid alkyl esters in short reaction times, it suffers from
several drawbacks.1
Transesterification using acid catalysts is known to be
much slower than that obtained from alkali catalysis, may
lead to the formation of undesirable byproduct with a difficult
separation step, and requires careful removal of catalyst from
the biodiesel fuel because acid catalyst residues can damage
* To whom correspondence should be addressed. Telephone:
+59829290707. Fax: +59829241906. E-mail: ijachman@fq.edu.uy.
Universidad de la Repu
blica.
URI-Campus de Erechim.
(1) Fukuda, H.; Kondo, A.; Noda, H. J. Biosci. Bioeng. 2001, 92, 405
416.
(2) Ma, F.; Hanna, M. A. Bioresour. Technol. 1999, 70, 115.
(3) Srivastava, A. E.; Prasad, R. Renewable Sustainable Energy ReV.
2000, 4, 111113.
(4) Altin, R.; Cetinkaya, S.; Yucesu, H. S. Energy ConVers. Manage.
2001, 42, 529538.
(5) Zhang, Y.; Dube, M. A.; Mclean, D. D.; Kates, M. Bioresour.
Technol. 2003, 89, 116.
(6) McCormick, R. L.; Graboski, M. S.; Alleman, T. L.; Herring, A. M.
EnViron. Sci. Technol. 2001, 35, 17421747.

engine parts.7 The use of enzyme-catalyzed transesterification

methods, however, can overcome these problems, but at
present, the high cost of enzyme production still remains the
major obstacle to commercialization of enzyme-catalyzed
processes.8
Currently, industrial-scale synthesis of biodiesel generally
is performed by transesterification of vegetable oils with a
short chain alcohol, mainly methanol, using chemical catalysts.9 As ethanol is readily available from fermentative
processes using biomass from a varied source, ethanol
biodiesel appears as a 100%-renewable alternative additionally enabling the replacement of traditionally used methanol
by an innocuous reagent. Besides, in the regional context,
ethanol has been the natural choice because Brazil is one of
the worlds biggest ethanol producers, with a well-established
technology of production and a large industrial plant capacity
installed throughout the country. The cost of ethanol,
however, is still higher than that of methanol, in particular
where absolute (dry) ethanol is used in processes based on
conventional catalytic methods.1,2
To overcome the drawbacks of chemical and enzymecatalyzed processes, a free-catalyst technique for the transesterification of vegetable oils using an alcohol at supercritical
conditions has been proposed.10-15 Some advantages have been
attributed to the use of the so-called supercritical method such
as improved phase solubility, reduction of mass-transfer limitations, higher reaction rates, and easier separation and purification
(7) Al Saadi, A. N.; Jeffreys, G. V. AIChE J. 1981, 27, 754761.
(8) Iso, M.; Chen, B.; Eguchi, M.; Kudo, T.; Shrestha, S. J. Mol. Catal.
B 2001, 16, 5358.
(9) Knothe, G.; Gerpen, J. V.; Krahl, J. The Biodiesel Handbook; AOCS
Press: Champaign, IL, 2005.
(10) Kusdiana, D.; Saka, S. Fuel 2001, 80, 225231.
(11) Kusdiana, D.; Saka, S. Fuel 2001, 80, 693698.
(12) Kusdiana, D.; Saka, S. J. Chem. Eng. Jpn. 2001, 34, 383387.
(13) Demirbas, A. Energy ConVers. Manage. 2002, 43, 23492356.
(14) Madras, G.; Kolluru, C.; Kumar, R. Fuel 2004, 83, 20292033.
(15) Warabi, Y.; Kusdiana, D.; Saka, S. Bioresour. Technol. 2004, 91,
283287.

10.1021/ef800640t CCC: $40.75 2009 American Chemical Society

Published on Web 11/24/2008

Effect of Temperature on Synthesis of Soybean Esters

steps; it is more tolerant to the presence of water and free fatty

acids than the conventional alkali-catalyzed technique and,
hence, more versatile regarding the use of various types of
vegetable oils.16
Nevertheless, the majority of reports using the supercritical
method adopted the batch-mode for biodiesel production and
methanol as substrate. The disadvantages of this process are
well-known: long batch time, low quality of the products,
and high cost of the process.17 Thus, feasibility of a
continuous transesterification process is of primary importance to ensure a competitive cost to biodiesel fuel, because
it can be operated at high temperatures and pressures with
higher reaction performance than batch reactors, with more
consistent and reproducible product quality.17-21 Regrettably,
isomerization from cis- to trans-type, even degradation and
polymerization of unsaturated fatty acids at temperatures above
300 C, has been reported in the supercritical method.22
Although the use of supercritical methanol (SC-MeOH) has
resulted in full ester yields for substantially high water contents
(up to 50 wt % on the alcohol basis) in the reaction medium16
and high yields have been reported for supercritical ethanol (SCEtOH),23 no relevant data were found in the literature concerning
the use of rectified ethanol. Our previous studies were directed
to investigating the effect of water content on the efficiency of
soybean oil transesterification with SC-EtOH and the effect of
reaction conditions on the composition profile of fatty acid ethyl
esters (FAEE), performed in a continuous process at constant,
350 C temperature, and 20 MPa pressure, with an oil:ethanol
ratio of 1:40.24
Results obtained in that work showed that although high
conversions of oil to biodiesel were achieved, even with a 10
wt % of water in the water-ethanol mixture, the ester content
in the product was not higher than 77.5 wt %. This relatively
low ester content was shown not to be the result of the partial
conversion of the oil, which was almost complete, as confirmed
by the absence of glycerides (mono-, di-, and triglycerides) in
the product, but rather to a certain extent the consequence of
the degradation of the fatty acids to byproduct. These previous
results suggested that the effect of temperature should be more
studied in greater detail, in an attempt to prevent fatty acid
degradation while keeping, at the same time, the reaction
conversion levels.
On the basis of these aspects, the main goal of this work
was to investigate the effect of temperature on the yield of the
continuous transesterification of soybean oil under supercritical
ethanol conditions. Assessment of the effect of temperature on
oil conversion to FAEE and degradation is obviously of great
importance to determine whether this parameter can be conveniently managed to afford satisfactory results. Moreover,
investigation of technical viability of using hydrated alcohol
(ethanol-water mixtures), a much cheaper substrate in a regional
context than anhydrous ethanol, may be of relevance for scaleup purposes.
Experimental Section
Materials. Refined soybean oil (Cocamar, Brazil) and absolute
ethanol (Merck, 99.9%) were used for the synthesis of biodiesel.
(16) Kusdiana, D.; Saka, S. Bioresour. Technol. 2004, 91, 289295.
(17) He, H.; Tao, W.; Zhu, S. Fuel 2007, 86, 442447.
(18) Kusdiana, D.; Saka, S. Appl. Biochem. Biotechnol. 2004, 113, 781
792.
(19) Minami, E.; Saka, S. Fuel 2006, 85, 24792483.
(20) Goto, F.; Sasaki, T.; Takagi, K. U.S. Patent 6,812,359, 2004.
(21) van Kasteren, J. M. N.; Nisworo, A. P. Resour., ConserV. Recycl.
2007, 50, 442458.

Energy & Fuels, Vol. 23, 2009 559

Other solvents, standards, and reagents used in the derivatization
step required for the analysis were supplied by Sigma-Aldrich.
Apparatus and Experimental Procedure. The experimental
reaction system used was that reported in a previous work.24 Ethanol
was first added into the mixer, followed by the addition of water
in the desired proportion (0, 5.0, and 10.0 wt %). Finally, soybean
oil was finally added in an amount such that a 40:1 ethanol:oil
molar ratio was kept in all cases. The mixture was agitated until
homogeneous dispersion of phases, and, keeping the stirring device
in operation, the pump was set to the desired flow rate (0.8, 1.0,
1.5, 2.0, or 2.5 mL/min). Finally, temperature was adjusted and
pressure increased to 20 MPa by means of a high-pressure liquid
pump, and once the system was stabilized at the desired operating
conditions, samples were collected in quadruplicate and conditioned
prior to analysis.
Gas Chromatography (GC) Analysis. Samples were subjected
to a gentle nitrogen flow until a constant weight at 40 C, ensuring
elimination of remnant ethanol. The residue was dissolved in 1 mL
of n-hexane, and the resulting solution was washed twice with 2
mL of water and later centrifuged (10 min, 3000 rpm) to guarantee
the elimination of glycerol generated during reaction. The organic
phase was dried using anhydrous Na2SO4, prior to the analysis
described below. To determine the fatty acid ester composition,
1.5 mL of the sample was transferred to a 25 mL flask and the
solvent was removed under nitrogen flow and the mass of residue
was computed; the residue was then dissolved in n-hexane, keeping
the level of the calibration mark. The ethyl ester samples were
analyzed directly by capillary gas chromatography, using a GC
Shimadzu GC-2014, equipped with FID and a capillary column
SGE BPX70 (25 m 0.5 mm 0.25 m). The temperature
program started at 160 C, followed by a heating step (4 C/min),
and was held for 10 min at 230 C. Nitrogen was used as carrier
gas, at 40 kPa at column head with a split ratio of 1:80.
For the identification of all cis/trans ethyl ester isomers, samples
were analyzed by capillary gas chromatography, using the GC
described before, equipped with a capillary column SP 2560 (100
m 0.25 mm 0.2 m). The temperature program started at 50
C, followed by a heating step (8 C/min) to 180 C, then a second
heating step (4 C/min), and was held for 45 min at 220 C.
Nitrogen was used as the carrier gas, at 250 kPa at column head,
with a split ratio of 1:80.
The identification and quantification of the compounds were
accomplished through the injection of authentic standards (ethyl
palmitate, stearate, oleate, linoleate, and linolenate) (Sigma) and
methyl heptadecanoate (Sigma), as internal standard, comparing
the mass spectra and GC retention times.
FAEE Decomposition. Samples were treated with BF3/MeOH25
to derivatize all of the fatty acids (mono-, di-, and triglycerides,
free fatty acids, and also ethyl esters) to the corresponding methyl
esters, and then analyzed by GC as described above. For the
evaluation of the degradation percentage, palmitic acid was assumed
not liable to degradation, considering its high stability.17,22 Thus,
degradation was calculated as:

decomposition (%) ) 100 1 -

( ) ( ) ]
Pi

P16:0

P16:0

Pi

(1)

where Pi was the summation of all fatty acid methyl ester

percentages, P16:0 was the percentage of 16:0 ethyl ester, and
subscripts s and o indicate that the expressions between brackets
were evaluated considering the composition of the sample product
and the original oil, respectively.
(22) Imahara, H.; Minami, E.; Hari, S.; Saka, S. Fuel 2008, 87, 16.
(23) Silva, C.; Weschenfelder, T. A.; Rovani, S.; Corazza, F. C.;
Corazza, M. L.; Dariva, C.; Oliveira, J. V. Ind. Eng. Chem. Res. 2007,
46, 530409.
(24) Vieitez, I.; Silva, C.; Borges, G. R.; Corazza, F. C.; Oliveira, J. V.;
Grompone, M. A.; Jachmanian, I. Energy Fuels 2008, 22, 28052809.

560 Energy & Fuels, Vol. 23, 2009

Vieitez et al.

Table 1. Ethyl Ester Content and Composition of the FAEE Fraction in the Product from Continuous Transesterification of Soybean
Oil at 20 MPa and Different Reaction Conditions (c, cis; t, trans)
FAEE (wt %)
T (C)

250

flow rate
(mL/min)

0.8
1.0
1.5
2.0
2.5

275

0.8
1.0
1.5
2.0
2.5

300

0.8
1.0
1.5
2.0
2.5

325

0.8
1.0
1.5
2.0
2.5

water
(wt %)

0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0
0.0
5.0
10.0

FAEE content
(wt %)

8.6
16.5
16.7
6.8
14.1
14.5
3.9
5.0
6.2
2.3
2.4
2.3
1.3
1.1
0.9
20.9
50.2
50.9
14.7
40.0
39.9
8.2
20.4
21.4
5.0
12.6
10.3
3.3
5.3
5.0
29.7
70.0
67.9
22.7
58.0
68.8
13.8
42.6
57.1
8.7
27.3
38.2
6.2
18.7
14.3
51.8
70.8
65.4
45.9
70.6
69.0
28.2
66.2
60.5
20.2
56.8
58.2
15.3
44.1
44.0

C16:0

C18:0

c-C18:1 plus t-C18:1

10.9

3.5

Original Oil
26.0

11.9
13.1
13.5
11.8
12.8
12.3
11.7
13.0
14.0
11.2
12.2
12.4
10.9
12.1
12.6
11.6
11.4
11.4
11.9
12.1
12.5
12.1
12.0
12.1
11.5
12.3
12.3
11.4
12.4
12.3
12.7
11.2
11.7
11.6
12.1
11.2
11.5
12.1
11.4
11.6
11.9
11.8
11.3
12.0
12.0
12.9
12.4
12.7
11.8
11.7
12.1
11.7
11.5
13.1
12.1
11.3
11.3
11.6
11.5
11.8

4.0
4.0
4.0
3.9
4.2
4.1
3.6
3.9
4.0
3.9
4.1
4.2
3.4
4.0
4.2
3.8
3.8
3.8
3.7
3.8
3.8
4.0
4.0
4.0
4.1
4.1
4.2
3.9
4.3
4.3
3.8
3.8
3.7
3.9
3.8
3.8
3.9
3.8
3.8
3.9
3.9
3.9
3.8
4.1
4.1
4.7
4.4
4.4
4.2
4.7
4.2
4.0
3.9
3.8
4.0
4.3
3.9
4.0
3.9
3.9

Processed Oil
27.3
26.3
26.5
26.7
27.1
26.6
26.8
27.1
26.0
25.7
25.7
26.1
25.0
25.5
22.4
26.8
26.6
26.6
26.3
26.5
26.3
27.4
26.5
26.6
27.0
26.5
26.7
26.5
27.1
26.9
27.0
27.3
26.7
27.2
26.7
27.2
26.8
26.6
26.8
26.5
26.7
26.8
26.5
26.6
26.7
31.1
29.8
30.0
29.5
28.4
29.0
27.9
27.7
27.4
27.4
27.0
27.4
27.4
27.0
26.9

c,c-C18:2 plus t,c-C18:2

c,t-C18:2

t,t-C18:2

C18:3

52.7

0.0

0.0

5.0

50.8
51.3
50.1
50.9
50.4
51.6
50.0
49.1
49.2
49.1
48.2
48.1
47.8
46.6
46.0
48.4
52.6
52.7
49.6
52.4
52.4
50.3
51.8
52.0
50.8
51.7
51.6
50.5
49.7
49.6
43.3
42.6
42.6
46.3
46.2
44.9
48.5
48.6
48.5
50.0
50.2
49.5
50.5
50.2
50.2
28.1
29.8
29.6
32.5
33.4
32.9
38.9
39.1
39.2
43.2
42.5
43.3
46.4
46.2
46.5

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
4.7
0.0
0.0
2.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
9.4
9.4
9.8
6.6
6.4
7.4
4.0
4.1
4.2
2.3
2.2
3.0
2.0
1.9
1.8
16.3
17.2
16.5
15.5
14.5
15.4
11.7
11.7
12.6
9.2
8.7
8.6
6.4
6.3
6.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.5
0.8
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.3
1.9
2.1
1.7
2.6
1.7
0.9
0.9
0.8
0.0
1.5
0.6
0.0
0.0
0.0

1.2
1.1
1.3
0.9
1.1
1.1
0.8
0.9
0.8
0.7
1.5
0.8
1.3
1.3
1.2
2.4
2.4
2.4
2.0
2.1
1.9
1.6
1.5
1.5
1.2
1.2
1.0
1.0
0.7
0.8
2.2
2.7
2.7
2.6
2.8
2.8
2.1
2.2
2.6
1.7
1.9
2.0
1.5
1.6
1.4
1.1
1.1
1.1
1.8
1.8
1.9
2.2
2.3
2.0
2.3
2.6
2.6
2.4
2.6
2.6

Analysis of Mono-, Di-, and Triglycerides. Compounds were

quantified upon analysis following the normative UNE-EN 14105.26
Samples, conditioned as described above, were treated with
MSTFA/pyridine to ensure derivatization of free alcohols to their

corresponding trimethylsilyl esters. GC analyses were conducted

on the above-described equipment, with a column OPTIMA-1TG
(Machery-Naguel, 10 m 0.32 mm 0.1 m). Nitrogen was the

(25) Official Methods and Recommended Practices of the American Oil

Chemists Society (Method AOCS Ce 2-66), 4th ed.; Walker, R. E., Ed.;
American Oil Chemists Society: Champaign, IL, 1990.

(26) Standard UNE-EN 14105: Determinacion de los contenidos de

glicerol libre y total y de mono-, di- y trigliceridos; Asociacion Espanola
de Normalizacion y Certificacion: Madrid, Spain, 2003.

Effect of Temperature on Synthesis of Soybean Esters

Figure 1. Effect of temperature and flow rate on the ethyl esters content
in the products obtained by the continuous transesterification of soybean
oil in supercritical ethanol at 20 MPa with different water content: (a)
0 wt % water, (b) 5 wt % water, and (c) 10 wt % water.

carrier gas, at 70 kPa at column head, and the oven temperature

was programmed following the steps recommended in the standard.

Results and Discussion

Table 1 presents the FAEE compositions obtained from the
transesterification reactions for all conditions studied. One can
observe that, in general, the FAEE contents were very similar
to that of the original (nonreacted) vegetable oil for the

Energy & Fuels, Vol. 23, 2009 561

Figure 2. Effect of temperature and flow rate on the degradation of

fatty acids of soybean oil transesterification in supercritical ethanol at
20 MPa with different water content: (a) 0 wt % water, (b) 5 wt %
water, and (c) 10 wt % water.

temperatures of 250 and 275 C, while significantly different

results were obtained for 300 and 325 C. It can be noted that
an increase in temperature led to a reduction in the content of
unsaturated fatty acids, mainly for C18:2 and C18:3, and also
the appearance of their corresponding trans isomers, which were
absent in the original oil. Note that this effect became progressively important as the substrates flow rates were decreased,
hence corroborating the expected feature that longer residence
times favor product degradation.

562 Energy & Fuels, Vol. 23, 2009

Vieitez et al.

Figure 4. Effect of temperature and flow rate on the content of

monoacylglycerols and diacylglycerols in the products obtained by
continuous transesterification of soybean oil in supercritical ethanol at
20 MPa with 5 wt % of water: (a) monoacylglycerols content and (b)
diacylglycerols content.

Figure 3. Effect of temperature and flow rate on the content of

triacylglycerols in the products obtained by the continuous transesterification of soybean oil in supercritical ethanol at 20 MPa with different
water contents: (a) 0 wt % water, (b) 5 wt % water, and (c) 10 wt %
water.

Figure 1a shows the effects of temperature and flow rate on

the ester contents when soybean oil was subjected to transesterification in anhydrous supercritical ethanol. For each individual flow rate, an increase in the ester content with increasing
reaction temperature was observed. For all temperatures, except
for 350 C,24 the ester content also increased as flow rate was
reduced, which is in agreement with an increase in the
conversion as residence time is increased.
However, for the reaction carried out at 350 C, a maximum
value in ester content was observed at 1.5 mL/min with a clear
reduction in the ester content for lower flow rates. This result

suggested that for higher residence times, another side phenomenon was taking place, which should involve ethyl esters
consumption. As we noted previously,24 the degradation of fatty
acids was favored by higher residence times and reaction
temperatures. Thus, the occurrence of a maximum in esters
content within the flow rate range studied at 350 C (Figure
1a) seems to be a result of two competing phenomena: while
low flow rates increase the FAEE production, higher residence
times lead to greater losses of unsaturated FAEE due to
degradation reactions.
Figure 1b and c shows the effect of water addition on ester
contents at two different levels, 5 and 10 wt % of water in the
alcohol, respectively. A significant increase in the ester content
was observed for 325, 300, and 275 C for all flow rates studied,
suggesting that reaction conversions should be improved by the
presence of water in the reaction medium. No relevant changes
were observed corresponding to 350 C,24 probably due to the
persistence of side degradation reactions. A moderate increase
in the ester content also was found for the reaction performed
at 250 C, which seemed to be the minimum temperature value
that should be considered for conducting catalyst-free transesterification reactions under supercritical conditions. These results
are in agreement with those reported by Imahara and coworkers,22 who established that the reaction temperature should
be kept lower than 300 C (preferably 270 C), in terms of
thermal stabilization for high-quality biodiesel production.
Figure 2 shows the percentages of total degradation of the
fatty acids determined by derivatization with BF3/MeOH, as

Effect of Temperature on Synthesis of Soybean Esters

described above. It can be observed that, for all water contents

tested, the fatty acid degradations were higher for lower flow
rates, as one should expect because the reagents were exposed
to drastic reaction conditions for larger times. Temperature
strongly affected the degree of degradation, where the highest
degradation values were observed for the reaction performed
at 350 C and 0.8 mL/min (26% and 28% for 0 and 5 wt % of
water, respectively).24 Degradation degree decreased as the
temperature was decreased and flow rate was increased. From
these results, one can conclude that the temperature should be
maintained below 300 C to avoid degradation greater than 5%.
With respect to the effect of water concentration in the
reaction medium on the degradation degree, it was observed
that the degradation phenomenon decreased as water concentration increased from 0 to 10 wt %, according to Figure 2. This
reduction is in agreement with results depicted in Figure 1,
showing that the addition of water provided lower degradation
levels and, accordingly, higher reaction conversions.
Although no previous studies under similar conditions were
found, these results are in agreement with some available
references concerning the well-known favorable effect of the
relatively low water activity on the oxidative stability of methyl
linoleate27 or of vegetable oils.28 This phenomenon was attributed to different mechanisms, like the bonding of hydroperoxides, which decreases their reactivity, and an antioxidant
effect due to hydration of traces of metals, which reduces their
catalytic action.
To define which phenomenon, transesterification or degradation, limited the ester content in the product, the concentration
of triglycerides was determined, as shown in Figure 3. Figure
3a shows that a gradual rise in TAG concentration occurred
with increasing flow rate (shorter residence times) and also that
TAG consumption was favored by higher temperature. It can
be clearly seen from this figure that water had a remarkable
effect on TAG concentration, even at its lowest concentration
of 5 wt %, which led to almost complete disappearance of TAG
for all flow rates tested.
(27) Heidelbaugh, N. D.; Karel, M. J. Am. Chem. Soc. 1970, 47, 539
544.
(28) Ambrosone, L.; Angelico, R.; Cinelli, G.; Di Lorenzo, V.; Ceglie,
A. J. Am. Chem. Soc. 2002, 79, 577582.

Energy & Fuels, Vol. 23, 2009 563

Figure 4 shows MAG and DAG concentration for 5 wt % of

water addition, where it can be observed that at 300 C MAG
concentration exhibited a maximum value at the flow rate of
1.5 mL/min. For flow rates smaller than 1.5 mL/min, the
residence time was increased, thus favoring the final steps of
the reaction, leading to higher ester contents (Figure 1 b) and
lower MAG contents, an intermediate compound of the reaction.
Howerver, at higher temperatures (325 and 350 C24), the esters
formation benefited from an increased residence time possibly
due to the availability of energy for the reaction. DAG
concentrations are shown in Figure 4b, where it can be observed
that an increase in flow rate (smaller residence times) and a
decrease in temperature led to higher DAG concentrations and,
hence, lower ester contents, which is consistent with the results
presented in Figure 1b.
Figures 3 and 4 show that at the highest temperature (350
C)24 and the lowest flow rates (0.8 and 1.0 mL/min), the product
presented low concentrations of MAG, DAG, and TAG, which
confirms that the relatively low ester contents shown in Figure
1 were probably a consequence of the fatty acids degradation
and not a result of low conversions of the transesterification
reaction.
Conclusions
Our results demonstrated that temperature strongly affected
both oil transesterification and fatty acid degradation processes.
The presence of water in the reaction medium showed a
favorable effect on the ester synthesis, due to its possible
catalytic role for the transesterification process and reduction
of the degradation of the fatty acids. Further work should be
focused on kinetic aspects of the process, which involves several
reaction and degradation steps of different classes of compounds,
so as to allow a better control of the reaction process and
maximize the ester content of the product.
Acknowledgment. We thank CNPq, Petrobras S.A., and Intecnial S.A. (Brazil) and Uruguays PDT program for financial support
and scholarships.
EF800640T