Energy xxx (2014) 1e8

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Catalyst free esterication of fatty acids with methanol under

subcritical condition
Alchris Woo Go a, Phuong Lan Tran Nguyen a, Lien Huong Huynh b, Ying-Tsung Liu a,
Sylviana Sutanto a, Yi-Hsu Ju a, *
a
b

Department of Chemical Engineering, National Taiwan University of Science and Technology, 43, Keelung Rd., Sec. 4, Taipei 106-07, Taiwan
Department of Chemical Engineering, Can Tho University, 3-2 Street, Can Tho City, Viet Nam

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 27 March 2013
Received in revised form
7 March 2014
Accepted 5 April 2014
Available online xxx

This study provides an alternative way to produce biodiesel from low quality feedstock oil. Feedstock oil
with high water and free fatty acid contents can be hydrolyzed into fatty acids using conventional
methods or subcritical water processes. Fatty acids produced can be reacted with methanol to produce
fatty acid methyl esters under conditions developed in this work, which is much milder than the supercritical methanol condition and without the use of catalyst. Using palmitic acid and oleic acid as the
model free fatty acid, at 175e205
C, 2.0e2.8 MPa and with a fatty acid:methanol:water ratio of 1:2:0.05
(w/w/w), a conversion of 96.5% can be achieved in 3e4 h. The method can be applied to feedstock with
water content up to 15%.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Biodiesel
Catalyst free
Esterication
Subcritical water
Subcritical methanol

1. Introduction
Biodiesel is a biodegradable and non-toxic alternative for petrodiesel, derived from animal fats, plant oils or lipids from various
microorganisms. It has received much attention in recent years due
to reasons such as, it is capable of replacing petro-diesel in boilers
and internal combustion engines without the need of major
modication [1], it provides a near-zero sulfur and aromatic content fuel, and it produces lower exhaust emissions in terms of unburnt hydrocarbon, carbon monoxide and particulate matter
hereby reducing harmful emissions [2,3]. Blending of biodiesel
from different oil sources helps improve its physical and chemical
properties and resolves cold ow properties and oxidative stability
[4,5]. Recent research also shows that biodiesel blended in lowsulfur diesel fuel greatly improved its lubrication properties
without negative effects to the diesel fuel properties [6].
Despite of several advantages of biodiesel over petro-diesel,
economical considerations have posed certain limitations to its
industrialization. Many studies have suggested that oil feedstock

Abbreviations: AOCS, American Oil Chemists Society; FA, fatty acids; FFA, free
fatty acids; FAME, fatty acid methyl esters.
* Corresponding author. Tel.: 886 2 27376612.
E-mail address: yhju@mail.ntust.edu.tw (Y.-H. Ju).

covers the biggest portion of biodiesel production cost. Globally

there are more than 350 oil-bearing crops identied as potential
sources for biodiesel production and selecting the cheapest, industrial scale feedstock is vital to lower down the cost of biodiesel
production [1,4]. The use of non-edible oils may signicantly reduce
the cost of biodiesel production [4]. Cheap feedstock such as waste
cooking oil, activated sludge and low quality rice bran oil may lower
down the cost of biodiesel feedstock but poses additional problems
during biodiesel production due to its high moisture and high free
fatty acid contents as well as content of impurities, which later
requires more purication steps, thus still resulting in high production cost.
Many attempts to overcome such problems have been explored.
Enzyme-catalyzed reaction has been employed to overcome
problems associated with feedstock impurities and provides easy
product recovery and separation, but the cost of enzyme is still too
expensive to justify its commercialization [7]. Heterogenous
catalysis including ion exchange technologies and catalyst immobilization have also been investigated to simplify post-reaction
separation but still fail to lower down production cost, mainly
due to requirement of feedstock purication. Biodiesel production
under supercritical methanol condition has been explored, which
can tolerate high content of free fatty acid and moisture in feedstock oil and has no need of conventional acid/base catalyst [8,9].
However, operating at severe temperature and pressure conditions

http://dx.doi.org/10.1016/j.energy.2014.04.013
0360-5442/ 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

requires a well-engineered process that can efciently recover the

spent energy [10], which probably needs very high capital cost and
for the moment is not feasible to commercialize. An alternative
route to produce biodiesel is the esterication of fatty acids.
Through hydrolysis, low quality feedstock oil such as waste cooking
oil, beef tallow and palm distillate waste can be turned into mixtures of free fatty acids, from which biodiesel can then be produced
following the solid acid-catalyzed esterication route, thus avoiding the use of a neutralization step in biodiesel production [11].
Kusdiana and Saka [9] on the other hand employed this procedure
by rstly turning the feedstock oil into fatty acids (FAs) and then
turned the FAs into fatty acid methyl esters under supercritical
conditions in the hope of lowering down the process cost and
avoiding the use of catalyst. The drawback of this approach was the
need to use supercritical conditions during the esterication step,
which could probably lead to degradation of the products.
Many efforts have been put into nding alternative ways to
efciently produce biodiesel. Each alternative offers a different set
of advantages and disadvantages. A recent development by Ju et al.
[12] opens the possibility of producing biodiesel under subcritical
condition without the need of conventional acid/base catalyst.
Their initial study used soybean oil as the model feedstock oil. The
method was later employed for the in in-situ production of biodiesel from wet activated sludge [13] and wet microalgae Chlorella
vulgaris [14] where in both cases the feedstock lipid had high free
fatty acid content. A challenge still needed to be addressed in the
previous works is to lower down the amount of methanol used
under subcritical conditions.
It is still a challenge to develop an efcient process that is able to
use low quality feedstock such as activated sludge, waste cooking
oil, low quality rice bran oil, yeast cells (Yarrowia lipolytica) and
microalgae for biodiesel production. Most of these feedstocks have
high free fatty acid and water contents. Currently, most published
works on non-catalytic esterication of fatty acids were carried out
under supercritical methanol condition [8e10]. Since the presence
of water and free fatty acids in low quality feedstock is inevitable, it
is preferable to hydrolyze acylglycerides in feedstock oil fatty acids,
which then can be esteried into FAME. The objective of this study
was to investigate the effects of amount of water and methanol on
the esterication of free fatty acids with methanol under subcritical
condition, with goals to effectively utilize the presence of water in
the reaction mixture and lower down the amount of methanol
required. The successful development of such a process greatly
increases the likelihood of using low quality feedstock for
economical biodiesel production.
2. Materials and methods
2.1. Materials
Palmitic acid (98%) and oleic acid (98%) was purchased from
Acros Organics (NJ, USA) and Showa Chemical Corporation Ltd.
(Tokyo, Japan), respectively. Standards of fatty acid (FA) and fatty
acid methyl esters (FAMEs) were obtained from Supelco (Bellefonte, PA, USA) and used as received. All solvents and reagents used
were either high performance liquid chromatography (HPLC) or
analytical reagent grade, obtained from commercial sources.
2.2. Subcritical wateremethanol esterication of fatty acids
Fatty acid (4 g, palmitic or oleic) was mixed with predetermined
amounts of deionized water and methanol in a glass chamber
(190 ml capacity) and placed in a high-pressure reactor (290 ml)
provided by HC Scientic and Instrument Co. (Taipei, Taiwan)

Fig. 1. Subcritical Water Reactor (1. Nitrogen gas cylinder, 2. Safety valve, 3. Check
valve, 4. Inlet valve 5. Pressure gauge, 6. Filter, 7. Outlet valve, 8. Reactor, 9. Glass
chamber).

(Fig. 1). The reactor is capable of withstanding a pressure up to

30 MPa. The reactor is equipped with an external electric heater.
Temperature in the reactor was measured using a thermocouple
and controlled using a PID (proportional-integral-differential)
controller to within 2
C. A pressure of at least 2.0 MPa, which is
higher than the saturated vapor pressure of water (0.89 MPa) at
175
C, can be applied to the reaction mixture using high purity
nitrogen gas (4N5). This was to ensure all experiments were carried
out under subcritical condition of water and methanol and to avoid
any oxidation reactions.
After a predetermined time, pressure inside the reactor was
released to rapidly stop the reaction in the reactor. The released
vapor was collected and condensed in an ice-water bath. Products
in the reactor were collected as soon as the reactor is cooled down
to room temperature. Hexane (50 ml) and sodium chloride solution
(5 wt.%, 20 ml) were added and the mixture was shaken vigorously
inside a separation funnel and allowed to settle and separate into
two phases. The upper hexane phase, which contained fatty acid
methyl ester (FAME), was withdrawn and the remaining liquid
phase was re-extracted with hexane to recover the products.
Hexane from the combined extracts was evaporated under vacuum
using a rotary evaporator. The recovered product was weighed and
analyzed for its FAME and FA contents. Experiments were carried
out in triplicates.
2.3. Conventional acid catalyzed esterication (H2SO4)
Acid catalyzed esterication at various water and methanol
loadings were also investigated with sulfuric acid as the catalyst.
Fatty acids (4 g), methanol and water at different ratios were premixed at room temperature. A specied amount of catalyst was
then added to the mixture. The mixture was placed in a Teon lined
screw cap bottle and the bottle was then immersed in a 70
C water

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

bath for a predetermined time. After the reaction, the bottle was
quenched in an ice-water bath and water and hexane were
immediately added to stop the reaction. Separation of the product
was done following the same procedure above, except that the
wash water obtained was measured of its pH using a pH meter
(model UB-10 by Denver Instruments, USA). The organic phase was
washed at least 5 times with 20 ml of deionized water until the pH
was close to neutral in order to remove sulfuric acid before analysis
of the products to avoid damaging the capillary column.
2.4. Gas chromatography analysis
Analysis of unreacted FA together with the FAME produced was
performed using high temperature chromatography (HTGC),
following the method described elsewhere [12]. In brief a 20 mg
aliquot from the collected reaction products was dissolved in ethyl
acetate and ltered through magnesium sulfate lter in order to
remove moisture. From the prepared samples, 0.5 ml was injected
into the gas chromatography column. External calibration curves
were generated using 0.2e20 mg of pure standard dissolved in 1 ml
ethyl acetate. Calibration curves were generated by tting a straight
line with the y-intercept passing through zero (R2 > 0.992).
Qualitative and quantitative analyses of FAME and unreacted FA
in each sample was performed using a Shimadzu GC2010 (Kyoto,
Japan) equipped with a split-injector and a FID (ame ionization
detector). Separation was carried out on a ZB-5HT (5% phenyl)methylpolysiloxane nonpolar column (15 m  0.32 mm i.d.,
0.1 mm lm thickness) (Zebron, Phenomenex, Torrance, CA, USA).
Both injector and detector temperatures were set at 370
C. The
temperature program was set at 80
C, increase to 365
C at 15
C/
min and held for 8 min. Total analysis time was 29 min. Nitrogen
was used as the carrier gas with a linear velocity of 30 cm/s at 80
C.
Data analysis was carried out by the software GC Solution version
2.3, Shimadzu.

(100
C and 374
C, respectively). For mixture of water and methanol at temperature between 100
C and 240
C, since methanol
(200
C; 40 bar) has a much higher vapor pressure than that of
water (200
C; 15 bar), it ensures that water is at the subcritical
state.
3.1. Effects of different methanol loading on conversion
Esterication reactions are widely utilized in the production of
esters used as solvents in various applications like cosmetics and
lubricant industry [10]. These reactions are typically catalyzed using mineral acids. Esterication of FA is thermodynamically
reversible; due to the competitive formation of FA in the presence
of water the net reaction rate of ester formation is low and would
reach certain equilibrium. Since the reaction is controlled by
equilibrium, it would require certain conditions to push the reaction in favor of ester formation [16].
Ju et al. [12] reported that when palmitic acid reacts with
methanol (palmitic acid: methanol: water 1:24:0.05, w/w/w)
under subcritical water condition (175
C, 24 bar), FAME conversion
can only reach 35% after a reaction time of 4 h. According to the
esterication reaction scheme, increasing the amount of methanol
should be benecial to promote ester formation. However, when
the amount of methanol was increased, instead of increasing FAME
conversion as expected, it actually decreased as shown in Fig. 2. It
can be seen clearly from Fig. 2 that in contrary to adding more
methanol, decreasing methanol loading up to a methanol to oil
ratio of 2 improved FAME conversion. By just heating the reactor to
175
C, which took about 30 min, FAME conversion can be over 35%
when low methanol loading is used.
The difference in the highest FAME conversion that can be
attained between palmitic acid and oleic acid can be explained by
the nature of the two carboxylic acids. Reactivity of carboxylic
carbon chain in both esterication and transesterication are
related not only to its carbon chain length but also to the carboxyl

2.5. Free fatty acid analysis

Unreacted FA in the reaction products was also counter checked
and determined using the conventional titrimetric method according to AOCS ofcial methods (Method Ca 5a-40). In brief, 1 g of
sample was accurately weighed with the use of an analytical balance and dissolved in hot and neutralized ethanol (w95%);
phenolphthalein (1% in ethanol) as indicator was added (2e3
drops); and the sample was titrated with 0.1 N KOH in ethanol.
Analyzing known samples of FA with varied concentrations the
results of the two methods differ by less than 0.5%.
3. Results and discussion
In this study, the possibility of reacting free fatty acid with
methanol under subcritical water and methanol condition without
the use of conventional acid/base catalyst was investigated. Initial
reacting temperature (175
C) and the ratio of fatty acid to methanol and water used (1:24:0.05, w/w/w) in the experiment were
based on previously published results [12], obtained for a rened
soybean oil sample. However, under the above reaction conditions
low conversion of FFA into FAME was obtained. Further studies
were focused on the effect of the relative amounts of methanol,
fatty acid and water on FAME conversion. All results reported are
averaged values of at least triplicate trials.
Under subcritical condition, a substance is at temperatures
greater than its boiling point (b.p.) but below its critical temperature and with a pressure high enough to keep the substance in
liquid state. The b.p. and critical temperature of methanol (65
C
and 240
C, respectively) are considerably lower than that of water

Fig. 2. FAME (wt.%) in the product produced from palmitic acid (A) and oleic acid (B)
into their respective methyl ester. Reaction was terminated after 30 min upon heating
up from 30
C to 175
C and 0.1 MPa to 2.0 MPa with different weight ratios of MeOH/
FA. Error bars indicate the standard deviation of triplicate trials carried out in this
study.

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

moiety [17]. The study by Aranda et al. [17] showed that protonation of the carboxylic moiety for oleic acids has lower activation
energy than palmitic acid for its transition state in an acid catalyzed
reaction, which is attributed to the polarity of the double bond
present in oleic acid. Thus even at higher methanol loading oleic
acid showed higher conversion than palmitic acid. While at lower
methanol loading conversion for both fatty acids are improved,
oleic acid seemed to have slowed down reaction rate, which could
be due to the increase in the reverse reaction rate thus resulting in a
lower net reaction rate.
Further investigations were done using oleic acid to evaluate
the effect of time on conversion as it is found to be the most
abundant fatty acid in most plant oils. In Fig. 3 it can be seen that
with methanol loading less than 4 and greater than 1, >90 wt.%
FAME yield could be achieved after 4 h of reaction at 175
C.
Prolonging the reaction over 4 h had negligible effect on
increasing FAME yield. At higher methanol loading (oleic
acid:methanol 1:4, w/w), it can be observed that both lower
reaction rate and nal FAME yield were obtained. The highest
FAME yield obtained was observed at an oleic acid to methanol
ration of 1:2 (w/w). However, further decreasing in oleic acid to
methanol ratio below 1:2 (w/w) resulted in the decrease of both
reaction rate and FAME yield. From the kinetic point of view, the
use of excess methanol is to suppress the reverse reaction of FAME
to FA but adding too much methanol would dilute the FA concentration and thus decrease the rate of reaction. A similar
observation was reported by Minami and Saka [15] during esterication of oleic acid under supercritical methanol condition in
which a FAME yield of 94 wt.% was obtained when the oleic acid to
methanol ratio used was 1:0.9 (v/v), while only 80 wt.% FAME
yield was achieved when the ratio used was 1:5.4.
3.2. Effects of temperature on yield of non-catalytic esterication
Temperature not only affects the reaction rate but also equilibrium of the reaction. Fig. 4 shows the time courses of FAME yield at
different temperatures. Although increasing temperature increased
the rate of FAME formation, the esterication reaction seems to
always reach equilibrium at a FAME yield of w96%. This is in
agreement with the results reported by Kusdiana and Saka [9] and
Minami and Saka [15] on the supercritical methanol esterication

Fig. 3. Effect of methanol amount on the time courses of FAME yield in the esterication of oleic acid with methanol under subcritical water condition (175
C, 2.0 MPa).
Initial water content 0.05 g/g oleic acid. Error bars indicate the standard deviation of
triplicate trials carried out in this study.

Fig. 4. Effect of temperature on time courses of FAME yield in the esterication of oleic
acid with methanol under subcritical water condition. Oleic acid/methanol/water 1/
2/0.05 (w/w/w). Error bars indicate the standard deviation of triplicate trials carried
out in this study.

of oleic acid. Failure to achieve complete conversion not only exists

in non-catalytic esterication of fatty acid but also in catalyzed
esterication. As reported by Zhang et al. [18] the same equilibrium
conversion was obtained even in the presence of an ionic liquid
catalyst, [NMP][CH3SO3], which was found to have better catalytic
activity than sulfuric acid.
Minami and Saka [15] and Kusdiana and Saka [19] achieved
similar FAME yield (w96% and 94%, respectively) in a much shorter
reaction time (40 min and 4 min, respectively) than this study.
However, very severe reaction conditions (270
C, 20 MPa and
350
C, 43 MPa respectively) were employed in their studies as
compared to the much milder conditions (w200
C and 2.8 MPa)
used in our work.
3.3. Effects of water content on FAME yield
The presence of water is generally regarded as unfavorable in
either transesterication of acylglycerols with methanol or

Fig. 5. Effect of water amount on FAME yield in the esterication of oleic acid with
methanol under subcritical water condition. (Amount of methanol used 2 g/g oleic
acid, reaction time 4 h.) Error bars indicate the standard deviation of triplicate trials
carried out in this study.

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

Fig. 6. pH of water at different temperatures and pressure. (Data obtained from International Association for the Properties of Water and Steam.) [21].

Fig. 8. Effect of water on esterication of oleic acid in acid catalyzed and subcritical
water processes. Error bars indicate the standard deviation of triplicate trials carried
out in this study.

esterication of fatty acids with methanol. In the transesterication

reaction, the presence of water causes saponication to occur
which results in loss of catalyst and difculty in product purication. In esterication, water causes the hydrolysis of FAME favoring
the formation of FA. Raw materials (oil, alcohols and catalyst) used
in the production of FAME all contain certain level of moisture. For
instance, methanol is hygroscopic and easily absorbs water from
atmosphere. In commercial base-catalyzed biodiesel production,
moisture content of feedstock is required to be less than 0.05% [20].
In order to utilize cheap feedstock oil, which usually has high FFA
and moisture contents, for biodiesel production; there is a need to
develop a new process or improve the performance of the current
available process.
As can be seen in Fig. 5, at 175
C water up to 5% seems to shift
the reaction forward but over 5% FAME yield started to decline.
Although statistical evaluation shows that these changes are not
signicant (p 0.05), a 4% difference might already be of a significant quantity in industrial scale. However, at 205
C it is possible to
achieve high conversions for water content from 0 to 15%. Although

waters contribution in the overall reaction may not be as evident at

205
C compared to reactions carried out at 175
C, the result of this
study shows that supercritical methanol conditions are not
required in order to convert feedstock oil with high moisture
content into biodiesel, even at about 200
C water up to 15% in
feedstock oil can be tolerated.
From the results, it is clear that water plays an important role in
the esterication of fatty acids under subcritical conditions. Contrary to the general belief that water is unfavorable for the esterication of fatty acids with methanol, the presence of subcritical
water (up to 20% based on weight of fatty acid) does not hinder the
reaction. In fact it may actually act as catalyst in turning feedstock
oil into FAME [12]. It is interesting to note that oil (or fatty acid)
with 5e15% water content is 100e300 folds more than the allowed
moisture content in conventional catalytic methods.
Water under subcritical conditions can act as an acidebase
catalyst due to better dissociation of the water molecule into
hydroxonium ion (H3O) and hydroxide ion (OH). As shown in

Fig. 7. Effect of methanol on esterication of oleic acid in acid catalyzed and subcritical
water processes. Error bars indicate the standard deviation of triplicate trials carried
out in this study.

Fig. 9. pH of washing water after each stage of washing in acid catalyzed esterication
(deionized water with pH 6 was used in washing).

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

Fig. 10. Typical chromatograms showing the formation of methyl stearate under subcritical water condition (a. methyl myristoleate, b. methyl myristate, c. methyl palmitoleate, d.
methyl palmitate, e. heptadecenoate, f. methyl oleate and methyl linoleate, g. methyl stearate, h. methyl eicosenoate, i. oleic acid).

Fig. 6, the pH of water decreases from w7.4 at 0
C to w5.5 at

250
C. Hence the amount of H3O ion in subcritical water increases
with temperature up to about 250
C.
Under subcritical condition the concentrations of H3O and OH
ions is 100 times larger than for water at ambient conditions. For
every mole of H3O the same amount of OH is also present, which
technically makes subcritical water neutral rather than being acidic
or basic. Despite the fact of being neutral, the catalytic effects are
exhibited due to the presence of the ionic species. H3O having a
pKa of 1.74, is a strong acid, which could probably help push the
reaction forward as in the case of acid catalyzed esterication.
Kusdiana and Saka [19] suggested that methanol could have
acted as an acid catalyst at its supercritical state but they also
believed that water acted as a catalyst more strongly than methanol
under supercritical methanol conditions at 280e350
C in which
water is rich in ionic products. From Fig. 5, the concentrations of
H3O and OH of water at 175e205
C are comparable to that of

water under supercritical methanol conditions. This further provides evidence that the much milder subcritical water condition
than that of supercritical methanol is sufcient to drive the reaction
forward and that the ionic species of water do play a role in the
formation of FAME.
In addition to ionic species produced from water molecules at
conditions above 200
C, methanol could also have acted as an acid
catalyst as it nears its supercritical state, specially that it is the
closest analog of water in view of its molecular structure. Since it is
also available in much greater amounts than water the effects of
water as catalyst do not seem evident at temperatures higher than
200
C compared to results obtained at 175
C.
3.4. Comparison with conventional acid catalyzed esterication
Conventional esterication processes typically use mineral acids
such as sulfuric acid as catalyst. In this study, sulfuric acid at 5 wt.%

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

Table 1
Comparison of different methods for esterication of fatty acid with methanol.
Method

Temperature (
C)

Acid (H2SO4) catalyzed

conventional method
Bronsted acidic ionic liquid catalyzed
[NMP][CH3SO3]
[SO3H(CH2)3Vim][HSO4] immobilized
in PDVB
Subcritical methanol (methane sulfonic)
catalyzed
Subcritical methanol
Subcritical methanol (microwave
assisted heating)
Supercritical methanolysis
Supercritical methanolysis
Supercritical methanolysis
Subcritical ethanol
Subcritical water
Subcritical water
Subcritical water

65
C

0.1

70
C

0.1

15%

0.1

5%

70 C

Pressure (MPa)

Catalyst/FA (wt%)
3.0%

Alcohol/FA
(nA/nFA)

Water
content (%)

Time (h)

Yield (%)

Reference

10%

48

w95%

[19]

95.3%

[18]

w5.1

98.2%

[23]

4%

94%

[17]

130
C

130
C
200
C

e
2.0

e
e

3
15

e
e

1
0.75

35%
58.3%

[17]
[11]

43
42
20
2.0
2.6
2.8
2.8

e
e
e
e
e
e
e

42
42
7
10
18
18
18

10%
e
e
w10%
w5%
w5%
w15%

0.07
0.13
0.75
1.33
4.5
3.5
4.5

w97%
95.8
w94%
w88%
96.3%
w95%
w95%

[19]
[24]
[15]
[10]
This study
This study
This study

350
300
270
250
195
205
205

C
C


C


C


C


C


C

and 10 wt.% (based on fatty acid weight) was used as the catalyst to
convert oleic acid into oleic acid methyl ester. From Fig. 7, it can be
seen that at a methanol to FA weight ratio of 2, maximum FAME
was reached for both sulfuric acid catalyzed and subcritical processes. From these results it can be further seen that the subcritical
water process behaved much like an acid catalyzed reaction as
previously suspected. Moreover even with the conventional process it would require the same amount of methanol as in the
subcritical water process. At lower methanol loading longer reaction time or higher catalyst loading is required. The conventional
process is affected by the dilution effect of methanol at high
methanol loading to a lesser extent than the subcritical water
process due to the much higher catalytic activity of mineral acid it
uses. Although high methanol loading may seem to help lowering
down the amount of catalyst required for the conventional process,
it has a disadvantage of resulting in a lower overall productivity
when carried out in a reactor with xed volume.
It is generally believed that water content of more than 1%
would greatly inhibit esterication reaction, but as can be seen in
Fig. 8 the acid catalyzed esterication seems to be able to tolerate
high amounts of water. This was also reported by Kusdiana and
Saka [19] who employed 3% sulfuric acid as catalyst to esterify oleic
acid and achieved >90% FAME after 48 h with water contents up to
30%. At subcritical water conditions and at higher temperature of
about 200
C, much higher water content can be tolerated and
water seems to behave much more like an acid catalyst as previously suspected. This could be due to the higher activity of the ions
present at this state.
For the subcritical water process, washing of the product stream
would not be needed since no catalyst is being used. As for the
conventional process several washing steps are required. Fig. 9,
shows the number of washing steps required in removing the
catalyst. It requires at least 5 washings before the pH of the
water approaches neutrality and it was also noticed that up to 11%
of product could be lost after several washing steps (data not
shown).
Compared to conventional acid-catalyzed process, the subcritical water process offers several advantages: (1) no catalyst is
required; (2) no washing step is needed which reduces the product
losses due to washing; (3) no generation of wastewater; (4) ease
of methanol recovery, since during cool down methanol can be
evaporated and recovered separately. Further improvements to the
process scheme could lead to fewer steps in biodiesel production,
incorporating methanol recovery, moisture removal and cooling

0.01

down of the system in one step, which further reduces the associated production cost. A major disadvantage of the process is the
long reaction time (4 h) required to achieve conversion > 95%.
3.5. Thermal stability of oleic acid and methyl oleate under
subcritical conditions of solvent mixture (methanolewater)
To ensure that no side reaction products were formed during the
esterication of fatty acid with methanol under subcritical water
condition, detail comparisons of the product chromatograms with
that of the FAME and FA standards were conducted. The analytical
grade oleic acid used in this study was analyzed and found to have
certain peculiar peaks between 6 and 7 min as compared to standard grade oleic acid. These were suspected to be fatty acids of
shorter carbon chains since verication by titration resulted to
w99% fatty acid by weight.
Even at prolonged chromatographic analysis up to 29 min and at
365
C, no oxidative products or polymeric carbon chains were
found. Upon closer inspection there is a small peculiar peak that
appeared at a retention time of 8.4 min. The reaction products were
further veried with a 37 FAME mix and the peak at 8.5 min is
identied as methyl stearate (C18:0). Shin et al. [22] reported that
minimal degradation of oleic acid was found at temperatures from
300
C to 370
C with an operating pressure of 20 MPa. Degradation
products of oleic acid exposed to subcritical water at 300
C for
30 min were mainly positional isomers and hydrogenation of
double bonds resulting to formation of stearic acid [22]. Hydrogenation could be the probable reason for the formation of methyl
stearate under subcritical water condition, especially due to the
prolonged time of the reaction (4 h). At temperatures above 300
C
degradation of stearic acid was not observed but degradation of
unsaturated fatty acids (oleic and linoleic), even in a short reaction
time of 10 min did occur [22]. Therefore, in biodiesel production,
temperature below 300
C is recommended to avoid formation of
pyrolysis products. The other small peaks between 5.5 and 7.5 min
were identied as FAME of C14:0, C16:1, C16:0 and C17:1 (see
Fig. 10).
Oleic and linoleic acids typically comprises up to 60e70% of the
fatty acid of vegetable oil. Although supercritical methanol method
has high tolerance to water, use of high temperature results in the
degradation of unsaturated fatty acids as reported by Shin et al. [22]
in which the recovery of fatty acids (oleic and linoleic) were below
90% at temperatures higher than 300
C. From the results of the
study it is evident that the use of subcritical water process not only

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013

A.W. Go et al. / Energy xxx (2014) 1e8

provides high FAME yield but also ensures no thermal degradation

of product occurs.
3.6. Comparison with other methods of esterication
Table 1 provides a comparison of FAME yield in the esterication
of oleic acid with methanol using different methods. Although
esterication carried under subcritical condition requires higher
temperature and pressure than that needed in the conventional
acid catalyzed esterication, the subcritical process eliminates the
need of using acid catalyst and is capable of achieving high conversions. Esterication under supercritical methanol condition can
achieve high conversion in a much shorter reaction time, but it
requires very high temperatures and pressures. Esterication of
fatty acid under subcritical condition provides a milder alternative
for biodiesel production but would require relatively longer time.
4. Conclusions
It has been shown in this study the possibility of utilizing
subcritical wateremethanol in the esterication of FAs into FAMEs
(biodiesel). Water, contrary to the general belief as being an inhibitor during FAME production from FA, served as catalyst to some
extent in promoting the production of FAME. This technology
provides a milder alternative in producing biodiesel from fatty
acids, compared to conventional processes such as acid catalyzed
esterication. The subcritical water process proposed in this study
is capable of producing FAMEs from FAs with conversions as high as
93e97% even in the presence of water (w5%). Although the process
requires longer reaction time of 3e4 h, this process only requires
operating conditions at subcritical state of water (205
C 2.3 MPa),
which is far less severe than that of the supercritical methanol
method. Furthermore, this process produces high yield of FAME
without incurring any decomposition of FAs or FAMEs.
Acknowledgment
The authors would like to acknowledge the nancial supports of
the National Science Council of Taiwan (NSC 101-ET-0-E-011-003ET) and National Taiwan University of Science and Technology
(101H451403).
References
[1] Atabani AE, Silitonga AS, Badruddin IA, Mahlia TMI, Masjuki HH, Mekhilef S.
A comprehensive review on biodiesel as an alternative energy resource and its
characteristics. Renew Sustain Energy Rev 2012;16:2070e93.

[2] Dasari MA, Goff MJ, Suppes GJ. Noncatalytic alcoholysis kinetics of soybean oil.
J Am Oil Chem Soc 2003;80:189e92.
[3] Sharma YC, Singh B. Development of biodiesel: current scenario. Renew
Sustain Energy Rev 2009;13:1646e51.
[4] Atabani AE, Mahlia TMI, Masjuki HH, Badrddin IA, Yussof HW, Chong WT,
Lee KTA. Comparative evaluation of physical and chemical properties of biodiesel synthesized from edible and non-edible oils and study the effects of
biodiesel blending. Energy 2013;58:296e304.
[5] Serrano M, Oliveros R, Sanchez M, Moraschini A, Martinez M, Aracil J. Inuence of blending vegetable oil methyl ester on biodiesel fuel properties:
oxidative stability and cold ow properties. Energy 2014;65:109e15.
[6] Tomic M, Savin L, Micic R, Simikic M, Furman T. Possibility of using biodiesel
from sunower oil as additive for improvement of lubrication properties of
low-sulfur diesel fuel. Energy 2014;65:101e14.
[7] Lam MK, Lee KT, Mohamed AR. Homogeneous, heterogeneous and enzymatic
catalysis for transesterication of high free fatty acid oil (waste cooking oil) to
biodiesel: a review. Biotechnol Adv 2010;28:500e18.
[8] Tan KT, Lee KT, Mohamed AR. Potential of waste palm cooking oil for catalystfree biodiesel production. Energy 2011;26:2085e8.
[9] Kusdiana D, Saka S. Two-step preparation for catalyst-free biodiesel production. Appl Biochem Biotechnol 2004;113e116:781e91.
[10] Pinnarat T, Savage PE. Noncatalytic esterication of oleic acid in ethanol.
J Supercrit Fluid 2010;53:53e9.
[11] Melo Jnior CAR, Albuquerque CER, Carneiro JSA, Dariva C, Fortuny M, et al.
Solid-acid-catalyzed esterication of oleic acid assisted by microwave heating.
Ind Eng Chem Res 2010;49:12135e9.
[12] Ju YH, Hyunh LH, Tsigie YA, Ho QP. Synthesis of biodiesel in subcritical water
and methanol. Fuel 2013;105:266e71.
[13] Hyunh LH, Tran Nguyen PL, Ho QP, Ju YH. Catalyst-free fatty acid methyl ester
production from wet activated sludge under subcritical water and methanol
condition. Bioresour Technol 2012;123:112e6.
[14] Tsigie YA, Huynh LH, Ismadji S, Engida AM, Ju YH. In situ biodiesel production
from wet Chlorella vulgaris under subcritical condition. Chem Eng J 2012;213:
104e8.
[15] Minami E, Saka S. Kinetics of hydrolysis and methyl transesterication for
biodiesel production in two-step supercritical methanol process. Fuel
2006;85:2479e83.
[16] Schultz AK, Hass MJ, Banavali R. Biodiesel production-catalysis in biodiesel
processing. In: The biodiesel handbook; 2010. pp. 67e84.
[17] Aranda DAG, Santos RTP, Tapanes NCO, Ramos ALD, Antunes OAC. Acidcatalyzed homogeneous esterication reaction for biodiesel production from
palm fatty acid. Catal Lett 2008;122:20e5.
[18] Zhang L, Xian M, He YC, Li LZ, Yang JM, Yu ST, et al. A Bronsted acidic ionic
liquid as an efcient and environmentally benign catalyst for biodiesel synthesis from free fatty acids and alcohols. Bioresour Technol. 2009;100:4368e
73.
[19] Kusdian D, Saka S. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour Technol 2004;91:289e95.
[20] Van Gerpen J, Shanks B, Pruszko R, Clements D, Knothe G. Biodiesel production technology. National Renewable Energy Laboratory, U.S. Department of
Energy; 2004.
[21] IAWPS. Release on the ionization constant of H2O. Lucerne (CH): International
Association for the Properties of Water and Steam; 2007.
[22] Shin YH, Ryu JH, Park SY, Bae SY. Thermal stability of fatty acids in subcritical
water. J Anal Appl Pyrol 2012;98:250e3.
[23] Liang XZ. Synthesis of biodiesel from waste oil under mild conditions using
novel acidic ionic liquid immobilization on poly divinylbenzene. Energy
2013;63:103e8.
[24] Warabi Y, Kusdiana D, Saka S. Reactivity of triglycerides and fatty acids of
rapeseed oil in supercritical alcohols. Bioresour Technol 2004;91:283e7.

Please cite this article in press as: Go AW, et al., Catalyst free esterication of fatty acids with methanol under subcritical condition, Energy
(2014), http://dx.doi.org/10.1016/j.energy.2014.04.013