Bioresource Technology 91 (2004) 289–295

Effects of water on biodiesel fuel production

by supercritical methanol treatment
Dadan Kusdiana, Shiro Saka *

Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University, Yoshida-Honmachi,
Sakyo-ku, Kyoto 606-8501, Japan
Received 3 March 2003; received in revised form 2 May 2003; accepted 30 June 2003

Abstract
In the conventional transesterification of fats/vegetable oils for biodiesel production, free fatty acids and water always produce
negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst
effectiveness, all of which result in a low conversion. The objective of this study was, therefore, to investigate the effect of water on
the yield of methyl esters in transesterification of triglycerides and methyl esterification of fatty acids as treated by catalyst-free
supercritical methanol. The presence of water did not have a significant effect on the yield, as complete conversions were always
achieved regardless of the content of water. In fact, the present of water at a certain amount could enhance the methyl esters
formation. For the vegetable oil containing water, three types of reaction took place; transesterification and hydrolysis of trigly-
cerides and methyl esterification of fatty acids proceeded simultaneously during the treatment to produce a high yield. These results
were compared with those of methyl esters prepared by acid- and alkaline-catalyzed methods. The finding demonstrated that, by
a supercritical methanol approach, crude vegetable oil as well as its wastes could be readily used for biodiesel fuel production in
a simple preparation.
Ó 2003 Elsevier Ltd. All rights reserved.

Keywords: Supercritical methanol; Biodiesel; Methyl esters; Transesterification; Methyl esterification

1. Introduction products from free fatty acids. In addition to that, more

Because of having similar properties to petroleum-
based diesel fuel, biodiesel fuel, a transesterified product
of vegetable oil, is considered as the most promising
diesel fuel substitute. Biodiesel development can be
found in 28 countries among which Germany and France
are so far the largest producers of biodiesel fuel in the
world (Ranses et al., 1999). Since 1997, Japan has started
a project in Kyoto city intended to put biodiesel at the
commercial level. As many as 220 municipal-city-owned
garbage trucks are running by 100% biodiesel fuel and
this trial has been extended into 81 municipal busses with
a blend of 20% biodiesel and 80% petroleum diesel fuel.
This corresponds to an annual consumption of 1500 ton
biodiesel produced from used frying oil (Saka, 2001).
Most of the methods for biodiesel production use an
alkaline catalyst in a batch-type process, followed by
additional effort to remove the catalyst and saponified
*
Corresponding author. Tel./fax: +81-75-753-4738.
E-mail address: saka@energy.kyoto-u.ac.jp (S. Saka).
catalyst is required to neutralize free fatty acids of an oil
with higher free fatty acids content. This not only causes
the production process to be longer, but also reduces the
yield because no methyl esters are produced from free
fatty acids. Therefore, Freedman et al. (1984) have
earlier stated that refined vegetable oils with free fatty
acids content of less than 0.5% (acid value less than 1)
should be used to maximize methyl esters formation.
In the biodiesel production, it is well known that the
vegetable oils/fats used as a raw material for the
transesterification should be water-free since the pres-
ence of water has negative effects on the reaction (Ko-
mers et al., 2001). Water can consume the catalyst and
reduce catalyst efficiency. The presence of water has a
greater negative effect than that of the free fatty acids.
So, the water content should be kept below 0.06% (Ma
et al., 1998), much lower than the allowable free fatty
acids content. These problems may hinder the most ef-
ficient utilization of waste vegetable oils and crude oils
since they generally contain water and free fatty acids
(Tomasevic and Marinkovic, 2003).

0960-8524/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0960-8524(03)00201-3
290 D. Kusdiana, S. Saka / Bioresource Technology 91 (2004) 289–295
Recently, we have developed a catalyst-free method
for biodiesel fuel production by employing supercritical
methanol (Saka and Kusdiana, 2001). The supercritical
treatment at 350 °C, 43 MPa and 240 s with a molar
ratio of 42 in methanol is the optimum condition for
transesterification of rapeseed oil to biodiesel fuel
(Kusdiana and Saka, 2001a). The great advantage of
this method was that free fatty acids present in the oil
could be simultaneously esterified in supercritical meth-
anol (Kusdiana and Saka, 2001b).
Because of the important effect of water and fatty
acids on the transesterification reaction, their effect on
the yield of methyl esters by supercritical methanol
treatment was studied in the present work, and the
yields were compared with those from alkaline- and
acid-catalyzed methods. In addition, the effect of water
on the methyl esterification of fatty acids was also
investigated.
2. Methods
A refined rapeseed oil was chosen as a sample for this
study. Fatty acid methyl esters as well as various fatty
acids; palmitic, stearic, oleic, linoleic and linolenic, were
purchased from Nacalai Tesque Inc., Japan and used as
standards. These fatty acids are generally contained in
rapeseed oil in small quantities. All those samples were
used without any purification. Anhydrous methanol and
distilled water were also purchased from the same
company. In addition, used frying oil, crude palm oil
and its waste whose contents of free fatty acids and
water are known were used in this study for comparison.
The experiment was carried out in the batch-type
supercritical biomass conversion system. A reaction
vessel was constructed of Inconel-625 with a volume of 5
ml, allowing reaction pressure as high as 200 MPa. As a
heating medium, molten tin, which has a capability to
provide the heat from 250 to 550 °C, was used. To start
the reaction a given amount of rapeseed oil and liquid
methanol was charged into the reaction vessel to give a
molar ratio of 42 in methanol. The reaction vessel was
then quickly immersed into the tin bath preheated at the
desired temperature, and kept for a set time interval for
supercritical treatments of methanol, from 60 to 240 s. It
was, subsequently, moved into the water bath to stop
the reaction.
The treated rapeseed oil was then allowed to settle for
about 30 min to separate into three phases. The top
phase, consisting of methanol, was then removed, and
for the remaining phases, the upper and the lower por-
tions were separately evaporated to remove water and
the remaining methanol.
The products were then analyzed by using the high
performance liquid chromatography (HPLC) (Shim-
adzu, LC-10AT) which consisted of the column (STR
ODS-II, 25 cm in length  4.6 mm in inner diameter,
Shinwa Chem. Ind. Co.) and refractive index detector
(Shimadzu, RID-10A) operated at 40 °C with 1.0 ml/
min flow rate of methanol as a carrier solvent. The
sample injection volume was 20 ml and a peak identifi-
cation was made by comparing the retention time be-
tween the sample and the standard compound. Fatty
acids were treated and analyzed in the same manner.
The effect of water on the yield of methyl esters in
transesterification of triglycerides and methyl esterifica-
tion of fatty acids was investigated under set reaction
conditions of a molar ratio of 42 in methanol and su-
percritical treatment at 350 °C and 43 MPa reaction
temperature and pressure, respectively.
In the alkaline-catalyzed method, experiments were
carried out at a temperature of 65 °C with a molar ratio
of 6 in methanol. Sodium hydroxide (1.5 wt%) was
dissolved in methanol and the mixture was then heated
to its reaction temperature to start the reaction with
continuous stirring. The reaction was stopped after 1 h
by adding acetic acid to neutralize the catalyst (Ma et al.,
1998). In the acid-catalyzed method, 3 wt% sulfuric acid
in methanol was prepared at room temperature, and the
solution added to vegetable oil at 65 °C. The mixture
was gently stirred for 48 h at atmospheric pressure
(Canakci and Gerven, 1999). In both alkaline- and acid-
catalyzed methods, methyl esters were washed four
times with distilled water after the mixture had been
separated.
3. Results and discussion
3.1. Effect of water on the yield of methyl esters in
transesterification of triglycerides
Water content is an important factor in the acid- and
alkaline-catalyzed transesterification of vegetable oil.
Fig. 1 shows a direct comparison of the yield of methyl
esters from various preparation methods as triglycerides
with various water contents were treated. The alkaline-
catalyzed method used 1.5% sodium hydroxide as a
catalyst in methanol (Ma et al., 1998), while in the acid-
catalyzed method, 3% sulfuric acid in methanol was
added to the reaction system (Canakci and Gerven,
1999). For the alkaline-catalyzed method, the conver-
sion was slightly reduced when more water was added.
In the acid-catalyzed method, however, only as little as
0.1% of water added led to some reduction of the yield
of methyl esters and the conversion was significantly
reduced to 6% when only 5% of water was added. On
the other hand, in the supercritical methanol method the
amount of water added into the reaction system did not
have any significant effect on the conversion, as a com-
plete conversion was observed from any level of water
content.
 D. Kusdiana, S. Saka / Bioresource Technology 91 (2004) 289–295
100
80
Methyl esters, %
60
40
20
0 esters.
0 2 4 6
Water content, %
Fig. 1. Yields of methyl esters as a function of water content in

transesterification of triglycerides. Legend: ( ) supercritical methanol;
(j) alkaline-catalyzed; (N) acid-catalyzed.
Several experiments at higher water contents were
also carried out to study the effect of water on the yield
of methyl esters, although the results are not shown in
Fig. 1. Rapeseed oil was mixed with methanol contain-
ing 10%, 18%, 25% and 36% of water and subjected to
supercritical treatment. Interestingly, at the end of the
reaction of the 4 min treatment, the products obtained
were all completely converted to methyl esters from
rapeseed oil as observed in the previous work (Saka and
Kusdiana, 2001). In the supercritical methanol method,
water presumably acts as an acid catalyst more strongly
than methanol itself.
3.2. Effect of water on the yield of methyl esters in methyl
esterification of fatty acids
We have shown that in the presence of water, trigly-
cerides can be successfully transesterified to methyl es-
ters by the supercritical methanol method. Previously,
we found that fatty acids are effectively converted to
their methyl esters in supercritical methanol (Kusdiana
and Saka, 2001a,b). It is known that triglycerides are
non-polar compounds, while fatty acids are a kind of
carboxylic acid with slightly polar and acidic compo-
nents. Because of their difference in nature, we expanded
our work to study the effect of water on the methyl
esterification reaction of fatty acids. Oleic acid was,
therefore, chosen as a model of fatty acids; other reac-
tion conditions were kept similar to those in the
transesterification (350 °C, 43 MPa for 4 min treatment
with a molar ratio of 42 in methanol).
We confirmed that in the alkaline-catalyzed method,
there was no methyl esters formation observed when
oleic acid was treated with methanol at any level of
water content. In a water-free reaction system, a part of
the oleic acid reacted with the catalyst to form a sapo-
nified product, while in the reaction system with higher
water content, oleic acid remained intact at the end of
291
the reaction, indicating that no reaction occurred since
water consumed the catalyst. Conversely, oleic acid
could be highly converted to methyl oleate when it was
treated by the acid-catalyzed method without water in
the reaction system. Interestingly, the conversion was
only slightly affected by the water content, as an almost
constant yield of methyl oleate could be achieved from
any level of water addition. On the other hand, by the
same method, in the transesterification of triglycerides,
the presence of water resulted in a low yield of methyl
Fig. 2 shows the result of oleic acid as treated by
supercritical methanol in various water contents. The
conversion of oleic acid to methyl oleate was somewhat
reduced when the water content was increased. The
reasons for this decrease of methyl oleate have not yet
been fully elucidated. However, one of the possible
reasons is that the methyl oleate formed may be hydro-
lyzed further to oleic acid over a prolonged treatment
and high temperature. Although fatty acids reaction was
affected by the presence of water, the results, as dis-
cussed in connection with Fig. 1, demonstrated that the
supercritical methanol method is more water-tolerant
than the conventional one with the use of an alkaline
catalyst. This was probably the reason why the con-
version of methyl esters could not reach 100%.
Water in the reaction system during methyl esterifi-
cation of fatty acids gave a similar effect for both the
acid-catalyzed and supercritical methanol methods. This
finding supported the assumption that in the supercrit-
ical state, methanol acts as acid catalyst in enhancing the
transesterification and methyl esterification reactions, as
reported in our previous work (Saka and Kusdiana,
2001; Kusdiana and Saka, 2001a).
3.3. Effect of free fatty acids on the yield of methyl esters
in biodiesel fuel production
To study the effect of free fatty acids on the yield of
methyl esters in the supercritical methanol method, oleic
100
80
Methyl ester, %
60
40
20
0
0 10 20 30 40
Water content, %
Fig. 2. Yields of methyl esters as a function of water content in methyl
esterification of oleic acid. Results of alkaline-catalyzed method are in
the text. For legends, see Fig. 1.
292 D. Kusdiana, S. Saka / Bioresource Technology 91 (2004) 289–295
acid was chosen as a model of free fatty acids because
oleic acid is most abundant in rapeseed oil. Rapeseed oil
with a number of oleic acid contents was treated by
supercritical methanol. The results obtained as well as
those by catalyzed methods are presented in Fig. 3. A
highly constant conversion is apparent in the supercrit-
ical methanol method for any level of oleic acid content.
Actually, the conversion tended to slightly increase lin-
early as oleic acid content was increased in rapeseed oil.
On the other hand, both acid- and alkaline-catalyzed
methods resulted in a lower conversion when fatty acids
content increased in the reaction system. In the acid-
catalyzed method, a reaction system with 20% of fatty
acids resulted in a reduction of the conversion to about a
half, while in the alkaline-catalyzed method only 35%
methyl esters were obtained.
Furthermore, in a study by Ma et al. (1998) of
transesterification of beef tallow with alkaline catalyst,
the apparent yield of methyl esters reached the lowest
value, less than 5%, when 0.9% of fatty acids was present
in the reaction mixture. Thus, they stated that the fatty
acids content needs to be kept below 0.5%. It means that
the fats/vegetable oils, particularly crude, waste and
used frying oils, must be refined to remove fatty acids.
As an attempt to increase the yield of methyl esters,
Frohlich et al. (2001) proposed alkaline-catalyzed
transesterification followed by an acid-catalyzed process
to esterify further the saponified products of fatty acids.
Another approach, developed by Boocock (2002), was
that fatty acids were first methyl esterified with the help
of an acid catalyst, followed by transesterification of
triglycerides under alkaline-catalyzed conditions.
The presence of free fatty acids in vegetable oils
makes the oil more acidic. In the alkaline-catalyzed
method, the amount of catalyst used depends very much
on the acidity of the vegetable oil. Therefore, the success
of the biodiesel fuel production will depend on the ac-
curacy in measuring the pH or the acidity of vegetable
oil to determine the amount of catalyst used. More
catalyst is necessary to eliminate fatty acids in crude and
100
80
Methyl esters, %
60
40
20
0 0
0 10 20 30 40
Free fatty acids content, %
Fig. 3. Yields of methyl esters as a function of fatty acids content in
biodiesel fuel production. For legends, see Fig. 1.
used frying/waste vegetable oils since they usually con-
tain more fatty acids than do the refined ones. The
presence of fatty acids in high content in vegetable oil
deactivates alkaline catalysts, and the addition of an
excessive amount of alkali as compensation gives rise to
the formation of emulsions, which increase viscosity,
thus leading to the formation of gels and the problems
associated with glycerol separation and the loss in the
yield of methyl esters (Crabble et al., 2001). They further
result in a more complicated production process, par-
ticularly in the purification step, which may in turn in-
crease the production cost. Even if methyl esterification
of fatty acids could proceed in the presence of water,
formation of water from methyl esterification of fatty
acids would reduce the catalyst activity in the trans-
esterification in the acid-catalyzed method. On the other
hand, our supercritical methanol method offers a sim-
pler process which is more tolerant to various types of
vegetable oils from virgin to crude and their wastes.
3.4. Water-added supercritical methanol method
The above results demonstrated that in the catalyzed
method, vegetable oils/fats should be water free, while
our supercritical methanol method was a relatively more
tolerant of the presence of water. To study further the
effect of water on the reaction system, we carried out
experiments with a greater amount of water in the re-
action mixture. The results, shown in Fig. 4, revealed
that as high as 50% of water addition did not greatly
affect the yield of methyl esters. It was observed that
treatment time was a critical parameter of the reaction.
When treatment was more prolonged than the critical
time, methyl esters were hydrolyzed further to fatty
acids.
In the previous work (Kusdiana and Saka, 2001b), we
found that in the supercritical methanol treatment,
transesterification of triglycerides and methyl esterifica-
Volumetric ratio of water to rapeseed oil
0 0.2 0.4 0.6 0.8 1.0
100
80
Methyl esters, %
60
40
20
0
20 40 60 80 100 120
Water content, %
Fig. 4. Yields of methyl esters as rapeseed oil was treated in super-
critical methanol at 350 °C for 4 min in the presence of various water
contents. Molar ratio of methanol to rapeseed oil was kept at 42.
 D. Kusdiana, S. Saka / Bioresource Technology 91 (2004) 289–295
Vegetable oil
Triglycerides Fatty acids
Transesterification Hydrolysis
Fatty acids
Methyl esterification
Methyl esters
Fig. 5. Reaction involved in the treatment of rapeseed oil by super-
critical methanol in the presence of water.
tion of fatty acids took place simultaneously for methyl
esters formation. In addition to these reactions, we be-
lieved that in the presence of water, triglycerides in
vegetable oil were hydrolyzed to fatty acids during su-
percritical treatment at 350 °C for 4 min. Theoretically,
an addition of 50% of water would give a molar ratio of
26 in water to triglycerides. In terms of the amount of
water present in the reaction mixture, this is more than
enough for the hydrolysis reaction itself. Since the hy-
drolysis reaction is much faster than transesterification
(Kusdiana and Saka, 2002), free fatty acids produced
can be further methyl esterified during supercritical
treatment of methanol. Therefore, three types of reac-
tions are involved during the treatment of vegetable oil,
as shown in Fig. 5.
Table 1 shows the yields of methyl esters from various
types of raw materials treated with supercritical meth-
anol, acid- and alkaline-catalyzed methods. Used frying
oil and waste palm oil have a high content of free fatty
acids. Therefore, the alkaline-catalyzed method resulted
in a lower yield, while the acid-catalyzed method gave a
high yield. However, waste palm oil, which contains a
high amount of water, gave a failure in reaction for both
acid and alkaline methods. On the contrary, all the re-
sults obtained by the supercritical methanol method
were similar to that of rapeseed oil as a complete con-
Table 1
Comparison of the yields of methyl esters in supercritical methanol, alkaline-catalyzed and acid-catalyzed methods
Vegetable oil FFA contenta (wt%)
Rapeseed oil 2.0
Palm oil 5.3
Used frying oilb 5.6
Waste palm oil >20.0
a
In weight percentage of free fatty acids to vegetable oil.
b
Obtained from households in Kyoto city.
293
version was achieved. These results proved that crude
vegetable oils as well as their wastes could be readily
used for biodiesel production by the supercritical
methanol method.
Separation of methyl esters from the reaction mixture
is an important step during biodiesel production. In
several conventional processes, separation is usually
performed together with a purification process. It will
include centrifugation, standing separation and repeated
water washing to obtain methyl esters and glycerol.
With water added supercritical methanol method, sep-
aration of methyl esters and glycerol from the reaction
mixture becomes much easier since in the presence of
Hydrolysis
water, glycerol will be in the water portion (lower por-
tion), while methyl esters are in the upper portion. In the
one-step supercritical methanol method (without addi-
tion of water), glycerol is present in the methanol-solu-
ble portion because a large excess of methanol is used
and some part may be soluble with methyl esters. In this
case, removal of methanol should be performed first to
produce a mixture separated into methyl esters and
glycerol.
Water has the capability of dissolving both non-polar
and polar solutes since its dielectric constant can be
adjusted from a room temperature value of 80 to a value
of 5 at its critical point (Holliday et al., 1997). Therefore,
water can solubilize most non-polar organic compounds
including most hydrocarbons at temperature above 250
°C. In addition, water at temperature between 280 and
350 °C is rich with ionic products. When it is mixed with
polar methanol, the mixture will have both strong hy-
drophilic and hydrophobic properties. It is probably one
reason why the reaction rate is higher in the water-added
supercritical methanol treatment.
The basic idea of supercritical fluid treatment is in the
effect of the relationship between pressure and temper-
ature upon the thermophysical properties of the solvent
(methanol), such as dielectric constant, viscosity, specific
gravity, and polarity. For example, ionic product, which
is an important parameter for chemical reactions, can be
improved by increasing the pressure (Broll et al., 1999).
Therefore, in the supercritical methanol treatment of
vegetable oil, in addition to acting as a reactant, meth-
anol is expected to be an acid catalyst. In addition, its
Water content (wt%) Yield of methyl esters, wt%
Alkaline-catalyzed Acid-catalyzed Supercritical methanol
0.02 97.0 98.4 98.5
2.1 94.4 97.8 98.9
0.2 94.1 97.8 96.9
>61.0 No reaction No reaction 95.8
294 D. Kusdiana, S. Saka / Bioresource Technology 91 (2004) 289–295

Table 2 transfer, whereby the fatty acid methyl ester and digly-
Physicochemical properties of methanol in ordinary and supercritical ceride are formed. In a similar way, diglyceride is
conditionsa
transesterified to form methyl ester and monoglyceride
Properties Ordinary condition Supercritical which is converted further to methyl ester and glycerol
(25 °C, atmospheric condition (250 °C,
pressure) 20 MPa)
in the last step.
Specific gravity, kg/l 0.7915 0.2720
Ionic product, log Kw )0.77 Not available
Dielectric constant 32.6 7.2
4. Conclusion
4
Viscosity, Pa s 5.4  10 0.58  10 4
Hydrogen bonding, 1.93 <0.7 The effect of water on the yield of methyl esters in
number transesterification of triglycerides and methyl esterifica-
Solubility parameter, 7.1 4.1 tion of fatty acids under supercritical methanol has
(MPa)1=2
been investigated. In catalyzed methods, the presence of
a
From Franck and Deul (1978), Panayiotou (1997) and Yamaguchi water has negative effects on the yields of methyl esters.
et al. (2000).
However, the presence of water affected positively the
formation of methyl esters in our supercritical methanol
method. In addition, compared with alkaline-catalyzed
δ-
δ- O method, a higher yield could be obtained from free fatty
O acids.
+

ROOCR1
δ
C R1 δ +C
R1 OR
O
''R H product of transesterification, is more soluble in water
δ-
O
R1 δ +
C
OR
R1COOR'
R O H
ROH : diglyceride
R1 : long chain hydrocarbon
R' : alkyl group
Fig. 6. A proposed reaction mechanism of transesterification of
vegetable oil/triglycerides in supercritical methanol.
dielectric constant dramatically changes to a number
closer to that of vegetable oil allowing a homogenous
mixture in supercritical condition (Franck and Deul,
1978; Panayiotou, 1997). Table 2 presents a comparison
of some physicochemical properties of methanol in an
ordinary condition and supercritical state.
A reaction mechanism of vegetable oil in supercritical
methanol was proposed based on the mechanism
developed by Krammer and Vogel (2000) for the hydro-
lysis of esters in sub/supercritical water. In a catalyst-
free transesterification with supercritical methanol, as
presented in Fig. 6, it is assumed that an alcohol mole-
cule directly attacks the carbonyl atom of the trigly-
ceride because of the high pressure. In the supercritical
state, depending on pressure and temperature, hydrogen
bonding would be significantly decreased, which would
allow methanol to be a free monomer. As shown in
Table 2, the hydrogen bonding is weakened to 0.7 in the
supercritical state from 1.9 in an ordinary condition.
The transesterification is completed via a methoxide
OR The water-added supercritical methanol method has a
R O H feature of easier product separation, since glycerol, a co-
than in methanol. The finding demonstrated that, by
supercritical methanol approach, crude vegetable oil as
well as its wastes could be readily used for biodiesel fuel
production in a simple preparation.
+ HOR
Acknowledgements
This work was done in the COE program in the
21st century of ‘‘Establishment of COE on Sustainable-
Energy System’’, and Grant-in-Aid for Scientific Re-
search (B) (2) (13556058, 2001. 4-2003.3) from the
Ministry of Education, Science, Sports and Culture,
Japan.
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