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 Fuel Processing Technology 106 (2013) 605–610

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Biodiesel production using supercritical methyl acetate in a tubular packed

bed reactor
G. Doná a, L. Cardozo-Filho b, C. Silva c, F. Castilhos a,⁎
a
Department of Chemical Engineering, Paraná Federal University, (UFPR), 81531–990, Curitiba-PR, Brazil
b
Department of Chemical Engineering, Maringá State University, (UEM). Maringá, PR, 87020–900, Brazil
c
Department of Technology, Maringá State University, (UEM). Umuarama, PR, 87506–370, Brazil

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

Article history: This work investigates the biodiesel production with supercritical methyl acetate in a tubular packed bed reactor.
Received 26 June 2012 The influence of temperature, oil to methyl acetate mass ratio and reaction time was evaluated throughout ex-
Received in revised form 24 September 2012 periments performed at pressure of 20 MPa. The temperature ranged between 300 and 400 °C, and the oil to
Accepted 25 September 2012
methyl acetate mass ratio varied between 1:2 and 1:5. Two different oils with very different composition and
Available online 24 October 2012
free fatty acid content were utilized: soybean oil and macauba oil. According to the results obtained, 44% was
Keywords:
the highest ester yield obtained for soybean oil at 350 °C, 45 min of reaction time and oil to methyl acetate
Supercritical biodiesel mass ratio of 1:5. In this condition a decomposition of 48% was also achieved. For the macauba oil, the highest
Soybean oil ester yield was 83% with a decomposition of 17%, achieved at 325 °C, oil to methyl acetate mass ratio of 1:5
Macauba oil and 45 min of reaction time. A comparison between the oils allows pointing out that macauba oil presented bet-
Continuous process ter performance, probably due to its high free fatty acid content.
Catalyst-free process © 2012 Elsevier B.V. All rights reserved.
Methyl acetate

1. Introduction Independently of the method used to produce biodiesel, the

Biodiesel use has a great potential in whole world, with a growing
market due to its great environmental benefits to the reduced levels
of environment pollution, mainly in the metropolitan areas. Also,
this combustive has been seen as a strategic source of renewable en-
ergy to substitute the diesel and other petroleum derivates.
The commonly chemical processes used in order to transform vege-
tal oils in biodiesel are esterification, cracking and transesterification re-
actions. Among them, the transesterification reaction is industrially the
most used process. The transesterification consists of the chemical reac-
tion between a triglyceride with an alcohol to produce esters and a by-
product, the glycerin. It can be conducted by catalytic and non-catalytic
routes. In the catalytic method, the transesterification process can use
different types of chemical catalysts, as acids and bases, and enzymatic
catalysts. Several researches can be found in the literature discussing
the advantages and drawbacks about the use of each catalyst [1–3].
Regarding the non-catalytic methods, the transesterification reac-
tions in supercritical conditions provide a higher solubility between
possible heterogeneous phases [4–6], reducing the transport limita-
tions between them and increasing the reaction rates. Besides, the
products separation steps are simplified [7,8].
⁎ Corresponding author. Tel.: +55 41 3361 3589; fax: +55 41 3361 3424.
E-mail address: fercastilhos@hotmail.com (F. Castilhos).
transesterification reaction with an alcohol will result in the glycerol
production. As the biodiesel production is increasing in the last years
in the whole world, the glycerin has been overproduced, causing its
devaluation in the market [9].
Some studies available in the literature have pointed out alterna-
tives to produce biodiesel and avoid the excessive glycerol produc-
tion. Some researches as Ilham and Saka [10] and Fabri et al. [11]
have reported the use of dimethyl carbonate in the biodiesel produc-
tion. Although this method does not produce glycerol, it utilizes the
alkaline catalyst, which is difficult to be adapted for some waste oils
and fats.
Another approach considers the biodiesel production from triglycer-
ides and methyl acetate. Xu et al. [12] proposed the use of methyl ace-
tate for the first time with a biocatalyst, but the process was not
considered be feasible due to the high reaction time, approximately
10 h. Orçaire et al. [13] produced biodiesel from sunflower oil and
methyl acetate but with a low ester yield and long reaction time,
about 200 h. More recently, others researches have reported the use
of supercritical methyl acetate [9,14,15]. In these studies, the authors
pointed out that the supercritical condition can reduce the reaction
times, increasing biodiesel yields and producing as a by-product the
triacetin, which can be used as a biodiesel additive. According to Saka
and Isayama [9], the global production of biodiesel can be considered
not only the fatty acids methyl esters, but also the triacetin content.
As it can be verified, just a few reports concern the use of methyl

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.047
606 G. Doná et al. / Fuel Processing Technology 106 (2013) 605–610
acetate, where the majority of them adopted the batch mode for biodie-
sel production.
In this context, the main goal of this work is to investigate the bio-
diesel production via transesterification with supercritical methyl ace-
tate in a tubular packed bed reactor. For this purpose, two different
vegetable oils were used in the experiments: soybean and macauba
oil. Soybean oil is well known raw material commonly used in the bio-
diesel production and the macauba oil, on the other hand, presents a
very high concentration of free fatty acids and higher water content.
Therefore, the first contribution of this work is about the production
of biodiesel with methyl acetate in a packed bed reactor, which to the
knowledge of these authors is not available in the literature. And the
second one refers to the influence of the vegetable oil utilized in the
ester yield.
2. Experimental section
2.1. Materials
Commercial refined soybean oil (Soya), macauba (Acrocomiaaculeata)
oil (CocalBrasil) and methyl acetate (Sigma-Aldrich 99.9%) were used as
substrates without further treatment. Other solvents, standards and re-
agents used in the derivatization step required for the analysis were sup-
plied by Sigma-Aldrich. Chemical composition of major fatty acids, acid
value (mg KOH/g) and water content (mass%, Karl Fischer titration meth-
od, DL 50, Mettler-Toledo) present in the vegetable oils used in this work
were shown in Table 1.
2.2. Apparatus and experimental procedure
The experimental reaction system used in this work, schematically
presented in Fig. 1, was constructed based on apparatus used previ-
ously by Silva et al. [16]. In order to improve mass transfer, reactions
were carried out in duplicate using a tubular reactor with packed bed
(TRPB). Reactor had a volume of 57.7 mL and it was made of stainless
steel tubing (316 L 1/4 in OD inner diameter 3.2 mm HIP) and stain-
less steel tubing (304 L 30.5 mm OD inner diameter 13 mm HIP)
packed with glass beads (diameter of 2.5 mm). Deviation obtained
between duplicates did not exceed 5%. The substrates, methyl acetate
and oil, were placed in a closed erlenmeyer and mixed by means of a
mechanical stirring device and then were fed into the reaction system
by a high-pressure liquid pump (Acuflow). The reactor was placed in
a furnace with controlled temperature and monitored by three ther-
mocouples directly connected at the inlet and outlet of the tubular re-
actor, and outlet of packed bed. With this arrangement, the reaction
temperature was controlled with accuracy better than 5 °C. The sys-
tem pressure was controlled by a back-pressure valve and monitored
by a pressure indicator. In this work the residence time was comput-
ed dividing the volume of the reactor (mL) by the flow rate of sub-
strates (mL/min) set in the liquid pump.
In this work, all the experiments were conducted at pressure of
20 MPa. The temperature ranged between 300 and 400 °C, the oil to
methyl acetate mass ratio varied between 1:2 and 1:5 and the reac-
tion times adopted were 18, 24, 36 and 45 min. In this work, oil to
Table 1
Chemical composition of soybean and macauba oils utilized.
Chemical composition Soybean oil Macauba oil
Palmitic acid (mass %) 10.80 14.87
Palmitoleic acid (mass %) – 3.96
Stearic acid (mass %) 3.80 1.09
Oleic acid (mass %) 27.70 67.38
Linoleic acid (mass %) 50.80 12.16
Linolenic acid (mass %) 4.40 0.55
Acid value (mg KOH/g) 0.20 79.24
Water content (mass %) 0.04 0.70
methyl acetate mass ratio adopted was between 1:2 and 1:5. For soy-
bean oil, the mass ratio of 1:2 corresponds to a 1:20 molar ratio, as the
1:4 mass ratio corresponds to a 1:40 molar ratio and finally, the 1:5
mass ratio refers to the 1:60 molar ratio.
Samples were collected periodically in a glass vial placed at the re-
actor outlet after reaching the steady state condition, i.e., after a reac-
tor space-time had been elapsed at least three times. The steadiness
of results and the low overall experimental error found for each
mean value (less than 5%) indicated excellent system stabilization.
The overall experimental error was determined by the execution of
experiments in triplicate.
2.3. Analytical methods
2.3.1. Gas chromatography (GC) analysis of fatty acid methyl esters
(FAME)
Samples were first submitted to methyl acetate evaporation to con-
stant weight (65 °C) and then diluted with 10 mL of n-heptane. After-
wards, a little amount was transferred to a 1 mL flask in order to obtain
a concentration of 4000 ppm and then it was added the internal standard
at a concentration of 1000 ppm using n-heptane as solvent. After that,
1μL of solution was injected in duplicate in the gas chromatograph
(Agilent GC 7890), equipped with FID and a capillary column (ZB-WAX,
30 m×0.25 mm×0.25 μm). Column temperature was programmed
from 100 °C, heating to 230 °C at 8 °C/min, holding 3 min. Helium was
used as carrier gas, and the injection and detector temperatures were
250 °C with split ratio: 1:50.
Compounds were quantified upon analysis following the standard
UNE-EN 14103 [17] and the percentage yield of fatty acid methyl es-
ters (YFAME) was defined according to the literature [14]:
measured amount of FAME in the sample
Y FAME ¼ 100  ð1Þ
theoretical amount f rom the initial oil content
2.3.2. Decomposition of fatty acids
Samples were treated with BF3/MeOH in order to derivatize all the
fatty acids (mono-, di- and triglycerides, free fatty acids) to the corre-
sponding 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
[18,19]. Degradation was thus calculated according to the following
equation, as described by Vieitez et al. [20,21] and Bertoldi et al. [22]:
     
∑P i P 16:0
decomposition ð% Þ ¼ 100  1−  ð2Þ
P 16:0 S ∑P i O
where ΣPi is the summation of all fatty acid methyl ester percentages,
P16:0 is the percentage of 16:0 ethyl ester, and subscripts s and o indi-
cate that the expressions between brackets were evaluated consider-
ing the composition of the sample product and the original oil,
respectively.
It is worthwhile to point out that, in this work, the use of the term
“decomposition” of fatty acids refers to the decrease in its percentage
(determined by gas chromatography analysis) due to the formation of
other compounds. It does not necessarily imply in the dissociation of
the fatty acids, may be involving some type of alteration.
3. Results and discussion
3.1. Soybean oil
Fig. 2 shows the effect of temperature and reaction time on YFAME
and on total decomposition of fatty acids for soybean oil. It can be
verified that up to 400 °C and short reaction times, the temperature
presents a positive influence on the ester yield. At longer reaction
 G. Doná et al. / Fuel Processing Technology 106 (2013) 605–610
Fig. 1. Schematic diagram of the experimental apparatus. RM, reactional mixture; MS, mechanical stirring device; LP, high-pressure liquid pump; CV, check-valve; F, furnace; TR, tubular
reactor; PB, packed bed; T1, temperature indicator at the tubular reactor inlet; T2, temperature indicator at the tubular reactor outlet; T3, temperature indicator at the packed bed outlet;
CS, cooling system; PI, pressure indicator; V, pressure control valve; S, glass collector.
times, as 45 min, the yield decreases for higher temperatures. Regard-
ing the degradation, Fig. 2b clearly presents the effect of temperature
and reaction time. It can be noted that even at lowest temperatures,
degradation is already relevant for soybean oil and at higher tempera-
tures; degradation phenomenon contributes to ester yield decreasing.
Based on these results, it can be concluded that the temperature of
350 °C is the most appropriate to perform the reaction, since it can
reach the highest ester yield and that the highest temperatures of 375
and 400 °C are very disadvantageous for this system.
These results are in accordance with the reported in the literature.
The biodiesel production by non-catalytic supercritical methyl acetate
Fig. 2. Effect of temperature on ester yield (a) and decomposition (b) with oil to meth-
yl acetate mass ratio of 1:2 for soybean oil.
607
using a batch reactor was reported by Niza et al. [23] and the results
shown at 1:30 (Jatropha oil to methyl acetate molar ratio), 30 min of re-
action and pressure above 4.7 MPa, 22.31% and 39.36% of ester yields at
360 and 400 °C, respectively. Campanelli et al. [14] present ester yield
about 100% in a batch reactor for the transesterification of soybean oil
and supercritical methyl acetate at 345 °C and 50 min of reaction. The
difference between the ester yields obtained in this work in continuous
reactor and the results available in the literature in batch mode can be
explained making an analysis of the reaction time in these two circum-
stances. According to the references available in the literature, in batch
mode the reaction time is computed not taking into account the time
spent in heating and cooling steps, which occur before and after the re-
action time. Nevertheless, in these previous and posterior periods, the
reaction still occurs since they are not instantaneous. On the other
hand, in continuous mode, the temperature and pressure are stabilized
before reaction time computing and samples obtaining. Another reason
that can also be considered is the vigorous stirring present in the reac-
tion carried out in batch mode that results in a more homogeneous re-
action medium compared to the continuous mode.
These authors also reported a yield decreasing with long reaction
times at 345 °C which was attributed to the degradation phenomenon.
Tan et al. [15] studied the transesterification of triglycerides with meth-
yl acetate and verified that the temperature has a great influence in the
ester yield. The study showed by Niza et al. [23] revealed that the ther-
mal stability of poly-unsaturated esters decreases dramatically as tem-
perature is increased from 330 to 420 °C. Degradation has been related
in literature for the transesterification of soybean oil with supercritical
ethanol and methanol [20,21,24–26]. Quesada-Medina and Olivares-
Carrillo [24] obtained about 30 wt.% of fatty acid decomposition for re-
actions of soybean oil at batch mode conducted at 623 K, 43 MPa, oil to
methanol molar ratio of 1:43 and 90 min of reaction.
To evaluate the effect of oil to methyl acetate mass ratio, experi-
ments were performed at 350 °C in the range of 1:2 to 1:5. The ester
yield and decomposition are presented in Fig. 3. As expected, the ester
yield increased with the oil to methyl acetate mass ratio, with a little dif-
ference between the 1:4 and 1:5 mass ratios. It is well known that an in-
crease in the oil to methyl acetate mass ratio is expected to shift the
reaction to methyl ester formation, but these results can be an evidence
of a limit for this phenomenon. With reference to decomposition shown
in Fig. 3b, it can be noticed an insignificant difference between the de-
composition values for the three oil to methyl acetate mass ratios,
608 G. Doná et al. / Fuel Processing Technology 106 (2013) 605–610
compared with the difference with the reaction time. From these re-
sults, it can be concluded that the oil to methyl acetate mass ratio of
1:4 is more advantageous for this process.
Similar results can be found in the literature. Campanelli et al. [14]
and Saka and Isayama [9] evaluated the oil to methyl acetate molar
ratio effect on the transesterification with supercritical methyl acetate
for the soybean oil and for the rapeseed oil in a batch reactor. Both the
researchers found that the best ester yield was 1:42 molar ratio. Tan
et al. [15] performed experiments in the range of 1:20 to 1:60 molar
ratio and noticed that the ester yield increased up to 1:30 oil to methyl
acetate molar ratio. Niza et al. [27] performed the transesterification of
the Jatropha curcas oil with supercritical methyl acetate in batch mode.
These authors investigated the influence of oil to methyl acetate molar
ratio and concluded that at long reaction times, it is more advantageous
to use low molar ratios.
3.2. Macauba oil
In order to assess the temperature effect on the transesterification
with macauba oil and supercritical methyl acetate, experiments were
conducted with oil to methyl acetate mass ratio of 1:2 and temperatures
of 300 and 325 °C. The ester yield and decomposition are presented in
Fig. 4. In this figure, it can be noted that the temperature has a positive
effect on the yield together the reaction time, as expected. The same be-
havior is demonstrated in relation to decomposition in Fig. 4b.
The effect of the oil to methyl acetate mass ratio was investigated at
300 and 325 °C, in the range of 1:2 to 1:5 mass ratios. Fig. 5 shows the
ester yield and decomposition for different oil to methyl acetate mass
ratio at 300 °C. It can be observed that the mass ratio has a positive ef-
fect on the ester yield and the highest yield is reached with mass ratio of
1:5. The decomposition values shown in Fig. 5 are very close for differ-
ent reaction times and mass ratios. Therefore, it can be pointed out that
the difference between the ester yields in Fig. 5a is due to the reaction
equilibrium displacement.
Fig. 3. Effect of oil to methyl acetate mass ratio on ester yield (a) and decomposition
(b) at 350 °C for soybean oil.
This positive effect of the oil to methyl acetate mass ratio becomes
more evident at the temperature of 325 °C, as shown in Fig. 6. The
strong effect can be seen, for 24 min, by means of the ester yield in-
crease from 54% to 72% with the raise of the mass ratio from 1:2 to
1:5. Besides, in comparison with the results presented in Fig. 5, it can
be noted that higher ester yields are achieved at 325 °C for the same
mass ratio and reaction times, as expected. Regarding the degradation
phenomenon, higher values were obtained at 325 °C, evidencing the
temperature effect on the decomposition reactions. Moreover, the de-
composition values with mass ratio of 1:2 were superior to the decom-
position values obtained with higher mass ratios, which is a similar
behavior already reported in the literature for soybean oil and supercrit-
ical ethanol [25].
3.3. Comparison between the oils
In order to compare the results obtained with both oils, ester yields
and decomposition values are shown in Fig. 7 at 325 °C and oil to meth-
yl acetate mass ratio of 1:2. It can be verified the great difference be-
tween the both oils, where the macauba oil reached a superior yield
for all reaction times. For the reaction time of 18 min, macauba oil
achieved about 50% of ester yield while soybean oil achieved only 8%.
In relation to decomposition shown in Fig. 7b, it can be verified that a
slight difference between the oils for all reaction times.
This significant difference in ester yield can be associated to the
different composition between the oil, mainly the major content of
free fatty acids of the macauba oil, as shown in Table 1. According
to the literature [9,28], free fatty acids react with methyl acetate in
the esterification reaction yielding methyl esters and acetic acid.
Saka and Isayama [9] investigated the hypothesis that acetic acid
would be a catalyst in the transesterification with supercritical meth-
yl acetate. The authors concluded that the ester yield increased with
the acetic acid content added to the reaction medium, in a short peri-
od of time. According to Campanelli et al. [14] a little amount of acetic
Fig. 4. Effect of temperature on ester yield (a) and decomposition (b) with oil to meth-
yl acetate mass ratio of 1:2 for macauba oil.
 G. Doná et al. / Fuel Processing Technology 106 (2013) 605–610
Fig. 5. Effect of oil to methyl acetate mass ratio on ester yield (a) and decomposition
(b) at 300 °C for macauba oil.
Fig. 6. Effect of oil to methyl acetate mass ratio on ester yield (a) and decomposition
(b) at 325 °C for macauba oil.
609
Fig. 7. Ester yield (a) and decomposition (b) for soybean and macauba oils at 325 °C
and an oil to methyl acetate mass ratio of 1:2.
acid added improve the global production of biodiesel due to its cat-
alyst effect and also due to reduce the thermal degradation of
triacetin. These results, available in the literature, can explain the re-
sults shown in Fig. 7. Therefore, these results can be seen as an indic-
ative that acetic acid is produced by esterification of FFA and is
catalyzing the transesterification reaction.
Further, from the results presented in Figs. 3 and 5, it can be conclud-
ed that macauba oil allows producing biodiesel via transesterification
with supercritical methyl acetate in milder conditions compared to soy-
bean oil. For instance, about 38% of ester yield were obtained for soy-
bean oil at 350 °C with an oil to methyl acetate mass ratio of 1:4 and
36 min of reaction time, while for the macauba oil a close yield (43%)
was obtained at 300 °C with an oil to methyl acetate mass ratio of 1:2
and in a shorter reaction time, 18 min. In relation to decomposition
values obtained in the conditions cited above, macauba oil also showed
to be advantageous, since soybean oil presented decomposition value
about 45% and macauba oil, about 17%. Campanelli et al. [14] present
some results for different raw materials, as Jatropha curcas oil, sunflow-
er oil and soybean oil in the transesterification with supercritical methyl
acetate and the results show a little difference in ester yield between
these raw materials. Despite the different compositions of these oils,
the free fatty acids content and the acid value are low, as reported by
the authors.
4. Conclusions
In this study, transesterification with supercritical methyl acetate
was investigated with soybean oil and macauba oil. Experiments were
conducted in a tubular packed bed reactor varying the reaction time,
temperature and oil to methyl acetate mass ratio. The highest ester
yield obtained for the soybean oil was 44% at 350 °C with oil to methyl
acetate mass ratio of 1:5 and 45 min of reaction time, but in this
610 G. Doná et al. / Fuel Processing Technology 106 (2013) 605–610
condition a decomposition of 48% was achieved. For the macauba oil, an
ester yield of 83% with a decomposition of 17% was obtained at 325 °C,
oil to methyl acetate mass ratio of 1:5 and 45 min of reaction time. A
comparison between the oils allows concluding that the macauba oil
presented a better performance, probably due to its high free fatty
acid content. The macauba oil seems to be a promising oil for the super-
critical transesterification with methyl acetate since it allows
conducting the reaction in milder conditions and is a non-expensive
raw material.
Acknowledgements
The authors would like to thank to CNPq and CAPES for the finan-
cial support and scholarships.
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