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Energy Conversion and Management 49 (2008) 908912

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Biodiesel from soybean oil in supercritical methanol with co-solvent

Jian-Zhong Yin *, Min Xiao, Ji-Bin Song
School of Chemical Engineering, Dalian University of Technology, Dalian 116012, PR China
Received 14 March 2007; accepted 30 October 2007
Available online 20 February 2008

Abstract
Biodiesel synthesis from soybean oil using methanol was investigated at supercritical and subcritical conditions of methanol in a high
pressure vessel of 250 cm3 volume. Under the supercritical conditions, the maximum methyl ester yield exceeded 98% when the molar
ratio of methanol to oil was 42:1 and the reaction temperature ranged from 260 C to 350 C. In order to decrease the operational temperature and pressures and increase the conversion eciency of methanol, a novel idea was presented in which a co-solvent (hexane,
carbon dioxide, KOH) was added to the reactants. The results indicated that the yield of methyl ester was improved when hexane or
CO2 was added. With CO2 or hexane as co-solvent in the reaction system at 300 C, there was a signicant increase of the methyl esters
yield. With the optimal reaction temperature of 160 C and methanol to oil ratio of 24, a 98% yield of methyl esters was observed in
20 min at the subcritical condition with 0.1 wt% potassium hydroxide (KOH).
 2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Transesterication; Supercritical; Hexane; Carbon dioxide; Potassium hydroxide

1. Introduction
Biodiesel, dened as fatty acid methyl ester (FAME), is
derived from triglycerides by transesterication with alcohols. Biodiesel is made from renewable sources and has
become attractive because of its environmental benets
[1]. Biodiesel comes from vegetable or animal fat, making
it biodegradable and nontoxic. It has been proven that biodiesel fuels have viscosities close to those of diesel fuel and
have high cetane numbers and ash points [2]. It is an alternative for fossil fuels. So, biodiesel is becoming an area of
high concern [35].
There are dierent ways of producing biodiesel with different kinds of materials, and the popular methods focus on
catalyst or non-catalyst methods. As for the catalyst
method, traditional chemical reactions use dierent kinds
of catalysts, such as sodium or potassium hydroxides, sulfuric acid, ion exchange resins and lipases [6]. Synthesis of
*

Corresponding author. Tel.: +86 411 88993695; fax: +86 411

83633080.
E-mail address: jzyin@dlut.edu.cn (J.-Z. Yin).
0196-8904/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2007.10.018

biodiesel by an alkaline catalytic transesterication reaction

has several drawbacks: it is energy intensive, recovery of
glycerol is dicult, the alkaline wastewater retains fatty
acids and water interferes with the reaction. In addition,
alkaline transesterication is low in selectivity, leading to
undesirable side reactions [7,8]. Lipase has been used as a
biocatalyst for synthesis of biodiesel from vegetable oils or
animal fats and can overcome the problems of conventional
chemical processes. However, due to the high price of the
enzyme and the time consuming reaction process, this
method is not widely used in large scale production [9,10].
Saka has rstly proposed that biodiesel may be prepared
from vegetable oil via a non-catalytic method with supercritical alcohol [11]. Compared with the traditional chemistry
method, this novel method requires no catalyst, and nearly
complete conversions can be achieved in a very short time.
So, it can successfully resolve most problems in the conventional chemical processes.
However, the synthesis of biodiesel by supercritical methanol has a drawback with the high cost of apparatus due to
the high temperature and pressure, which are not viable in
the large scale practice in industry. So, many researches

J.-Z. Yin et al. / Energy Conversion and Management 49 (2008) 908912

2. Experimental
2.1. Materials
Rened edible soybean oil was used for the reactions.
Methanol was purchased from Tianjing Chem. Co. Ltd.
(analytical grade). Potassium hydroxide (KOH) was supplied by Shenyang Chem. Co. Ltd. (analytical grade). All
other chemicals were obtained commercially and were of
analytical grade.
2.2. Experimental procedure
A 250 ml cylindrical autoclave made of stainless steel,
equipped with a magnetic stirrer and internal cooling system was used. The pressure and temperature were monitored in real time up to maximum values of 32 MPa and
520 C, respectively. The reaction vessel was charged with
a given amount of soybean oil and liquid methanol with
dierent ratios. Then, the vessel was heated with an external heater, and the liquid solution was stirred at a constant
rate of 300 rpm at the same time. When the desired temperature was reached, the process remained for a set time. The
temperature of the reaction vessel was measured with a
thermocouple. Then, the vessel was transferred to an ice
water bath to quench the reaction. After that, the vessel
was opened, and the contents of the autoclave were poured
into a collecting vessel. The mixture product was decompression evaporated at 50 C for 30 min and then allowed
to settle for about 60 min in order to allow the two phases
to separate. The upper phase was the methyl ester, and the
lower phase was glycerin.
2.3. GC analysis for fatty acid methyl ester
The reaction samples were analyzed by gas chromatography (Agilent 6890, FID). The GC (gas chromatograph)
was equipped with a HP-5 column with dimensions
30 m 0.32 mm 0.25 lm. Sample volumes were 0.05 ll,
the carrier gas was nitrogen and the GC sample was separated in a constant ow mode with a ow rate of 9.0 ml/
min. A split injector was used with a split ratio of 40:1
and a temperature of 290 C. The FID (ame ionization

detector) was operated at 290 C. The oven was initially

held at 130 C and then elevated to 260 C at 5 C/min,
and remained for 4 min. Total run time for this method
was 30 min.
3. Results and discussion
3.1. Synthesis of biodiesel with supercritical methanol
For synthesis of biodiesel from soybean oil using supercritical methanol, the critical temperature and pressure of
methanol is 512.2 K and 8.1 MPa, respectively. So, all reactions were performed above this condition, As shown in
Fig. 1, the reaction was conducted at various temperatures
(260 C, 300 C, 350 C) with a constant molar ratio of
alcohol to oil of 42 at a xed rotation speed of 300 rpm.
The conversion increased with increase in temperature.
The system pressure also increased with increasing temperature, and the maximal pressures were up to 20 MPa. With
the reaction temperature of 350 C, a high conversion of
soybean oil to methyl esters is obtained with a yield of
95% in 10 min. The optimum molar ratio of methanol to
oil was obtained by conducting the reaction with dierent
ratios at 300 C (Fig. 2). In conclusion, the synthesis of biodiesel from soybean oil by supercritical methanol is promising. Because of sucient mixing among the reactants, a
high conversion can be obtained within a short time.
3.2. Synthesis of biodiesel with supercritical methanol and
hexane
Methanol and soybean oil do not dissolved in each other
at room temperature. To form a single phase of the reactants, hexane was added into the mixture. Fig. 3 shows
the conversion varied by the amount of hexane. It indicated

120

100

Methyl ester yield, %

have focused on how to decrease the severity of the reaction

conditions. Co-solvents, such as carbon dioxide, hexane and
calcium oxide [1214], added into the reaction mixture can
decrease the operating temperature, pressure and the
amount of alcohol. In this study, biodiesel production from
soybean oil in supercritical methanol was investigated.
Then, hexane and carbon dioxide, as co-solvent, were added
into the reactants, aiming to decrease the critical operational parameters. A little amount of potassium hydroxide
was also added to the reactants, and a high yield was
obtained with subcritical conditions. Potassium hydroxide
(KOH) can considerably improve the transesterication
reaction of soybean oil in supercritical methanol.

909

80
260 C
300 C
350 C

60

40

20

0
0

10

20

30

40

50

60

Time, min
Fig. 1. Synthesis of biodiesel at various temperatures in supercritical
methanol. Methanol and soybean oil were taken at a molar ratio of 42:1
with a constant shaking at 300 rpm.

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J.-Z. Yin et al. / Energy Conversion and Management 49 (2008) 908912

(239 C, 8.09 MPa). Fig. 4 shows the synthesis of biodiesel

from soybean oil under supercritical methanol with CO2 as
co-solvent. With a reaction temperature of 300 C, a CO2/
methanol ratio of 0.2 and a molar ratio of methanol to oil
of 42, a high yield of methyl ester is obtained with 90.6% in
30 min. Furthermore, CO2 is both easy to add to the system and remove from the system through depressurization.

Methyl ester yield (%)

100

80

60

40

3.4. Synthesis of biodiesel with subcritical methanol and

potassium hydroxide

20
0
20

30

40

50

60

The molar ratio of methanol to oil

Fig. 2. Synthesis of biodiesel with dierent molar ratio of methanol to oil.
Methanol and soybean oil were taken at 300 C with a constant shaking at
300 rpm for 20 min.

Fig. 5 presents the variations of methyl ester yield with

reaction temperature. The synthesis of biodiesel was conducted at various temperatures (120240 C) at the xed
molar ratio of alcohol to oil of 24:1. The mass ratio of
potassium hydroxide (KOH) to oil ranged from 0 to
100

Methyl ester yield (%)

Methyl ester yield (%)

100
80
60

40

80
60
40
20
0

20

0.2

0.4

0.6

0.8

The molar ratio of CO2 to methanol

0
0

10

12

The ratio of co-solvent

Fig. 3. Synthesis of biodiesel using supercritical methanol and hexane as
co-solvent. Methanol and soybean oil were taken at 300 C with a
constant shaking at 200 rpm for 30 min.

Fig. 4. Synthesis of biodiesel from soybean oil with supercritical methanol

and carbon dioxide. Methanol and soybean oil were taken at 300 C with a
constant shaking at 200 rpm for 30 min. the molar ratio of methanol to oil
was 42.

120

3.3. Synthesis of biodiesel with supercritical methanol and

carbon dioxide
Hexane is an excellent solvent for vegetable oil, which
shows the use of a co-solvent is feasible. Supercritical
CO2 is a good solvent for small and moderate organic molecules, and it is a low cost and facile material. CO2 has
critical parameters of 31 C and 7.38 MPa, which is easy
to achieve under the supercritical methanol condition

100

Methyl ester yield, %

that a little hexane could improve the conversion. For

example, the methyl ester yield was 67.7% without the hexane, while the yield was obtained as 85.5% with 2.5 wt% of
hexane. However, when the amount of hexane added was
any more, the yield decreased a little, but the maximum
yield was still above 67.7%. The main reason for this phenomenon is that the mutual solubility between methanol
and soybean oil was improved with the addition of hexane
so the reaction speed was increased.

80

60
0.05
0.1
0.25
0

40

20

0
100

150

200

250

Temperature,C
Fig. 5. Synthesis of biodiesel at various temperatures in subcritical
methanol. Methanol and soybean oil were taken at a molar ratio of 24:1
with a constant shaking at 300 rpm. The reaction time was 20 min.

J.-Z. Yin et al. / Energy Conversion and Management 49 (2008) 908912

100

Methyl ester yield (%)

100

80

60

40
160C
200C
240C

20

0
0

10

15

20

25

30

Reaction time (min)

Fig. 7. Eect of time for biodiesel synthesis with methanol. Methanol and
soybean oil were taken at a molar ratio of 24:1 with a constant shaking at
300 rpm. Quality ratio of potassium hydroxide (KOH) to oil was xed at
0.1 wt%.

yield. However, at a shorter reaction time (e.g. 5 min),

increasing the reaction temperature from 160 C to
240 C led to an increase of methyl ester yield from 60%
to 98%. This result indicates that under our condition,
the transesterication reaction is essentially complete after
the 10 min run. Therefore, comparing with the catalysis
method, the reaction time could be shortened from about
120 min to 10 min. This is in favor of decreasing the biodiesel production cost and enhancing the production eciency
for large scale industry practice.
4. Conclusions
Synthesis of biodiesel from soybean oil with supercritical methanol is superior to the conventional chemical
method. Compared with the conventional method, a less
puried process is required.
The supercritical methanol method with a co-solvent
can improve the product yield. Hexane and condensed
CO2 are excellent solvents for the vegetable oil. So, the
methyl ester yield is increased with the co-solvent. Furthermore, the CO2 is good for the environment, is easy to
obtain and has good properties in the supercritical conditions. The supercritical methanol method with potassium
hydroxide can largely decrease the reaction parameters,
such as decreasing temperature and pressure.

120

80
60
40
160C
200C
240C

20

120

Methyl ester yield (%)

0.25 wt%. It is noticed that very low yield (<5%) was

obtained in the subcritical conditions without any catalyst.
With the addition of the catalyst KOH into the reaction
mixture, even a very little amount, the methyl ester yield
remarkably increased. When the mass ratio of KOH to
oil was 0.1% and the reaction temperature was 160 C, a
98% methyl ester yield was obtained. It should be pointed
out that the system pressure was only 10 MPa at this temperature, which should be in the subcritical range. Comparing with the supercritical methanol method, the
reaction temperature was decreased from 350 C to
160 C to obtain the same yield. On the other hand, comparing with the alkali catalysis method (ACM), the catalyst
amount used in our subcritical methanol was only 10% of
that used in the ACM. Therefore, by coupling catalysis
with subcritical conditions, the catalyst amount can be largely decreased while the operation conditions became less
severe.
Fig. 6 shows the changes in percentage of methyl esters
formed with dierent molar ratios of methanol to oil. In
order to determine the optimal molar ratio of methanol
to oil, the reactions were conducted at a xed potassium
hydroxide (KOH) mass of 0.1 wt% and xed reaction time
of 30 min at the stirring speed of 300 rpm. It can be seen
that increasing the molar ratio of methanol to oil from
6:1 to 24:1 at a reaction temperature of 160 C increased
the methyl ester yield from 38% to 100%. Clearly, the methanol utilization can be signicantly improved when comparing with the case without any catalyst.
One of the advantages of operation in supercritical conditions is that the reaction time is very short. By coupling
catalysis with subcritical conditions, such an advantage
also exists. As shown in Fig. 7, after a reaction time of
10 min, the methyl ester yield almost attained its maximum
value. On the other hand, when the reaction time was
longer than 10 min, the variation in the reaction temperature did not result in a marked dierence in the methyl ester

911

References
0

10

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30

40

50

The mole ratio of methanol to oil

Fig. 6. Eect of molar ratio for biodiesel synthesis with methanol.
Potassium hydroxide (KOH) was xed with quality ratio to oil of 0.1 wt%
and a constant shaking at 300 rpm. The reaction time was 30 min.

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