Applied Catalysis A: General 476 (2014) 2633

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Applied Catalysis A: General

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

Biodiesel production via transesterication of palm olein using

sodium phosphate as a heterogeneous catalyst
Khritsayaporn Thinnakorn , Jirdsak Tscheikuna
Oleochemical Laboratory, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Phayathai Road, Pathumwan,
Bangkok 10330, Thailand

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

Article history: The production of Fatty Acid Methyl Esters (FAMEs) via the transesterication reaction of palm olein and
Received 13 November 2013 methanol using sodium phosphate (Na3 PO4 ) as a heterogeneous catalyst has been investigated. This study
Received in revised form 7 February 2014 determined the inuence of various parameters, such as the methanol to oil molar ratio, the operating
Accepted 8 February 2014
temperature, the amount of catalyst, and the presence of water and free fatty acid in the raw materials,
Available online 17 February 2014
on the rate of reaction. The study demonstrated that Na3 PO4 can be used effectively as a heterogeneous
catalyst in transesterication process. It was determined that increasing the methanol to oil molar ratio
Keywords:
results in an increase in equilibrium conversion. A molar ratio of methanol to oil of 18:1 provides the
Transesterication
Palm olein
fastest rates of reaction and the highest FAME content. The operating temperatures have a strong effect
Heterogeneous catalyst on FAME yield; increasing the reaction temperature tends to accelerate the rate of reaction but reduces
Sodium phosphate the glycerol by-product quality. Under the study conditions, with a methanol to oil molar ratio of 18:1
and a reaction temperature of 210 C 98.5% FAME yield was obtained within 30 min with only 1 wt.% of
Na3 PO4 . When a large excess of methanol was used, the experimental results agreed with the irreversible
1st order kinetic model, while the activation energy was found to be 32.59 kJ/mol palm olein.
2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2. Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2. Transesterication reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.3. Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1. Transesterication reaction using Na3 PO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.2. Effect of the molar ratio of methanol to oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3. Effect of reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.4. Effect of mass ratio of catalyst to oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.5. Effect of the water and free fatty acid (FFAs) content in oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.6. Catalyst solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.7. Kinetics of transesterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Corresponding author. Tel.: +66 2 2186878; fax: +66 2 2186880.

E-mail addresses: khrits@yahoo.com, thinna1@hotmail.com (K. Thinnakorn).

http://dx.doi.org/10.1016/j.apcata.2014.02.016
0926-860X/ 2014 Elsevier B.V. All rights reserved.
 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633
1. Introduction
Biodiesel or fatty acid methyl esters (FAMEs) produced by the
transesterication of vegetable oil or animal fats with methanol
is used as a renewable diesel fuel. Biodiesel has similar proper-
ties to petroleum-based diesel but has several advantages, such
as being biodegradable and producing less harmful gas emissions
and particulate matter content. The conventional production pro-
cess for biodiesel uses homogeneous catalysts and excess methanol
to attain high yields, with the reaction products being FAME and
glycerin. The most commonly used and most active catalysts are
homogeneous alkaline catalysts such as NaOH, KOH, and their
methoxides (NaOCH3 , KOCH3 ) [1]. The production process obtains
high FAME yields (>98%) within a short reaction time at low temper-
ature. However, these processes generate large amounts of waste
water from the washing step. Moreover, the glycerin by-product
from this reaction is not pure and must go through a complex
purication process before use in industrial cosmetics [2,3].
Several types of catalysts have been developed for FAME pro-
duction to reduce the environmental impact. A homogeneous
acid-catalysed process can reduce environmental problems from
waste water emission, but acid catalysts require a high alcohol to oil
molar ratio and a long reaction time to complete the conversion [4].
A supercritical process is an alternative method for a non-catalytic
transesterication reaction. The reaction completes within a short
time, but requires high temperature (350400 C) and high pres-
sure (4565 MPa) [5]. Enzymatic processes [6] and ion-exchange
resins [7] have been the focus of interest in recent years. Because
enzymes can tolerate free fatty acid and water contents in oils while
avoiding soap formation, purication of biodiesel and glycerin is
thus easier than with the other methods. However, enzymes are
expensive and ion-exchange resins require a long reaction time to
obtain high product yields.
A production process using a heterogeneous catalyst is an alter-
native that solves these problems. It produces biodiesel in a more
environmentally friendly manner because the catalyst does not dis-
solve into the products; it can easily be separated from the product
by ltration at the end of the reaction. Thus, the catalyst does not
require a water-washing step and can be reused several times. Con-
sequently, transesterication with a heterogeneous catalyst has
the potential to be developed for use in a continuous production
process. Currently, only one industrial application of the heteroge-
neous base catalysts developed by the French Institute of Petroleum
(IFP) has been reported. This process, using a spinel mixed of Zn
and Al oxide as a solid base, operated at 200250 C [8]. On a labo-
ratory scale, the development of heterogeneous catalysts has been
extensively investigated, with many catalysts being studied and
tested in the transesterication of various types of oils and alcohols.
The most widely used catalysts were alkaline and alkaline-earth
compounds, such as metal oxides, carbonates, phosphates, and the
catalysts prepared on supported catalysts [912].
The major problem with a heterogeneous catalyst is the slow
reaction rate due to the problem of mass transfer resistance of
the 3 phases (oil, methanol, and catalyst), which are not soluble
in each other. Strong mechanical stirring and a long reaction time
are required to obtain a high product yield [13]. Additionally, it
was found that there is leaching of active species into the reac-
tion mixture after the reaction. Thus, the reusability of catalysts
without regeneration has been shown to be less than ideal. Many
studies have reported on the effect of partial dissolution of catalysts
into the product where they act as homogeneous catalysts, but the
result requires complex separation [14,15]. It has been reported
that highly active solid catalysts, such as K2 CO3 , dissolve readily
into products, and high yields (98%) were obtained within 120 min,
but it was found that 55 wt.% had dissolved [16]. The same was true
for metal oxides such as SrO, CaO, ZnO, TiO2 , and ZrO2 . SrO showed
27
highest activity but dissolved on the biodiesel during the reac-
tion because the mechanism of these catalysts are transformed to
methoxide ion [17,18]. High-activity catalysts partially dissolved,
and reutilisation of the catalyst without regeneration has shown
a loss of efciency. However, if the catalyst is not soluble or less
soluble, it will take a long time to obtain a high yield. For example,
CaO was a good catalyst in the transesterication reaction and had
low solubility, but the reaction time was up to 20 h to obtain an
80% yield of the FAME product [19]. However, the development of
heterogeneous catalysts has to be based on high activity and good
stability.
One way to reduce the catalyst dissolution under the reaction
conditions is to prepare the active components on stable mate-
rials, such as supported catalysts, to reduce the leaching of the
active components and increase the surface area of the reaction.
Moreover, the separation of the catalyst from the reaction products
is easier than in powder form. Many researchers have investi-
gated various active compounds on supported catalysts [2024].
However, the long reaction time is maintained due to the internal
diffusion of the large triglyceride molecule into the catalyst pores
[25].
Normally, accelerating the rate of reaction of a heterogeneous
system can be achieved with an increase in the amount of alcohol
and catalyst used [12,26,27]. This can also be performed by increas-
ing the reaction temperature [11,17,28,29]. The ability of CaO to
catalyse transesterication was quite weak under ambient temper-
ature, and the yield of methyl ester was only 5% over 3 h. However,
when the reaction temperature was increased to 252 C, the reac-
tion was completed within 6 min [30,31]. Transesterication is an
endothermic reaction, so increasing the reaction temperatures will
accelerate the reaction rate and reduce the amount of catalyst used
while generating a high product yield.
Among these base catalysts, Na3 PO4 appears to be a promising
candidate to develop for the transesterication reaction because it
has high activity, is insoluble in reactants, and inexpensive. Nor-
mally, it is mainly used as fertiliser in agriculture. It can be reused
in many times, which makes it easier to handle than homoge-
neous catalysts and more environmentally friendly. Na3 PO4 has
been shown to be a potential catalyst with both high activity and
good stability for the transesterication reaction [10,32,33]. It could
be used in a continuous production process. In the present work,
Na3 PO4 -catalysed transesterication reaction of palm olein and
methanol was investigated. The variables affecting the methyl ester
yield during the transesterication of palm olein and methanol,
such as the molar ratio of methanol/oil, the amounts of catalyst,
and the reaction temperature, were studied. Moreover, the pres-
ence of water and free fatty acid contents in raw materials was also
studied in this research.
2. Experiment
2.1. Materials
The rened palm olein used in this research was purchased
from the market. Industrial-grade methanol (purity: 99.86 wt.%)
was used as the reactant in this research. Na3 PO4 12H2 O (labora-
tory grade) was used as the catalyst. Prior to the transesterication
reaction, the catalyst was dried in an oven at 120 C for 24 h and
then calcined in a mufe furnace at 500 C for 5 h. The powder
particle diameter of the calcined Na3 PO4 was determined through
with a particle size analyser and ranged from 200 to 250 m. The
basic strength (H ) of the catalyst as determined using the Hammett
indicator method was 15 < H < 18.4 [34,35].
The palm olein used in this research was analysed for its phys-
ical properties and fatty acid compositions. The results are shown
28 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633

Table 1 2.2. Transesterication reaction

Physical properties of palm olein.

Physical properties The experiments were conducted in a 2-litre stainless-steel

Acid value (mgKOH /g) 0.358 autoclave equipped with a variable speed agitator (501500 rpm).
Saponication value (mgKOH /g) 197.946 The reactor could be heated while the temperature was controlled
Moisture content (wt.%) 0.104 by a jacketed heating element. The reactor pressure was maintained
Molecular weight (g/mol) 850.76 at 800 psi with nitrogen gas. The calcined sodium phosphate cat-
alyst was rst put in a stainless steel basket that was placed in
the middle of the reactor vessel. Palm olein was put into the reac-
Table 2 tor in predetermined amounts, and the feed bomb was lled with
Fatty acid composition of palm olein. methanol. The system was then purged with nitrogen. Next, the
reactor was heated to the desired temperature while the liquid was
Name Structure Composition (wt.%)
stirred at a constant speed of 600 rpm. When the reactor reached
Lauric 12:0 0.53
the reaction temperature, methanol was fed into the reactor. Sam-
Myristic 14:0 1.04
Palmitic 16:0 38.67 ples were taken at specic times, dipped into cold water to stop the
Palmitoleic 16:1 0.23 reaction, and then separated in a centrifugal separator. The prod-
Stearic 18:0 4.10 uct was separated and washed with warm water. The samples were
Oleic 18:1 42.90 analysed for FAME content using gas chromatography. A schematic
Linoleic 18:2 10.92
diagram of the experimental set up is shown in Fig. 1.
Linolenic 18:3 0.24
Arachidic 20:0 0.35
Behenic 22:0 0.80
2.3. Analysis
Erucic 22:1 0.22
Total Saturated 45.49
Total Unsaturated 54.51 The FAME products were analysed by gas chromatography
(Variance 3800). A polar capillary column (Agilent, HP-Innowax
20 M) with an internal diameter of 0.32 m, a length of 30 m, a lm
thickness of 0.25 m, and a Flame Ionisation Detector (FID) were
used. Helium was used as the carrier gas at a pressure of 10 psig. The
in Table 1 and Table 2, respectively. The results show that the injector and detector temperature were set at 260 C and 230 C,
fatty acid composition of the palm olein varied within the range respectively. The programmed temperature was set for an initial
of C12:0C22:1 and that the major fatty acid components in the temperature of 80 C for 5 min, and then the rate was increased
palm olein were palmitic and oleic acids. The total saturated fatty with the heating rate set at 20 C/min up to a nal temperature of
acids in the palm oil was 45.49 wt.%, while the total unsaturated 230 C where it was held for 5 min. Methyl decanoate, which was
fatty acids was 54.51 wt.%. The amount of unsaturated and satu- used as an internal standard, was mixed with heptane to prepare a
rated oils had an effect on the fuel properties, especially because stock solution. After a sample was accurately weighted, an internal
the presence of saturated fatty acids lowers the cloud point. standard stock solution was added to the sample. The FAME

Fig. 1. Schematic diagram of the experimental set up for the transesterication process.
 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633 29

Scheme 1. Transesterication of palm olein with methanol.

content was dened as the ratio of the weight of FAME determined

by the GC to the weight of the oil used, as shown in Eq. (1).

Wt. of FAME (g)
Yield of FAME = 100% (1)
Wt. of Palm Oil used (g)
The FAME content was calculated using the compensated nor-
malisation method with internal standardisation. A standard FAME Fig. 2. Gas chromatogram of fatty acid methyl esters (FAME) in a product sample.
mix (C8C24) from Supelco was used to identify the peaks at differ-
ent retention times and to correct the peak area using the response proportion of fatty acid content in the palm olein raw material, as
factors of the compound. Error was separated into analytical error seen in Table 2.
and experimental error. The analytical error was checked by repeat-
ing the process 7 times and was found to be less than 1.5% on
3.2. Effect of the molar ratio of methanol to oil
average (at 95% condence error). The experimental error was
determined by repeating the experiment 3 times. The errors are
The molar ratio of alcohol to oil is one of the most important
shown in the experimental results.
variables affecting transesterication reactions. In this study, the
effect of stoichiometric methanol/oil molar ratios of 3:124:1 on
3. Results and discussion the FAME yield was investigated. All experiments were conducted
at a reaction temperature of 190 C with 0.5 wt.% Na3 PO4 . The for-
3.1. Transesterication reaction using Na3 PO4 mation of FAME with different ratios of methanol as a function of
time is shown in Fig. 3. It can be seen that the reaction proceeds
Sodium phosphate-catalysed transesterication at a low tem- rapidly with an increase in the molar ratio of methanol to oil from
perature has been studied previously [32,33]. However, the 3:1 to 18:1. A higher molar ratio drastically increases the FAME
reaction mechanism of the Na3 PO4 -catalysed transesterication content over time. However, the reaction is limited by the mass
reaction is not explained well. In a homogeneous system, the alkox- transport of methanol to the oil phase. At molar ratios of higher
ide group (NaOCH3 , KOCH3 ) attacks the carbonyl carbon atom of than 18:1, the FAME contents are almost identical because further
the triglyceride molecules to form fatty acid methyl ester [36,37]. increases in methanol do not affect the reaction rate.
Many studies assumed a similar mechanism in the case of a hetero- Transesterication is a chemical equilibrium reaction. An excess
geneous Bronsted base catalyst, such as basic zeolite [37], which of methanol compared to oil is generally used to drive the reaction
formed catalytic species of homogeneous alkoxide. The formation forward, thus producing higher yields of methyl esters. However,
of alkoxide groups is also a fundamental step for heterogeneous eventually the amount of methanol had no effect on the reaction
basic catalysts [17,3840]. rate [43]. One fact to consider is that methanol and oil are insoluble
In this work, the transesterication of palm olein and methanol in each other at molar ratios higher than 3:1. In the case of a solid
catalysed by Na3 PO4 can be described as similarity to process catalyst, the existence of 3 phases at the initiation of the reaction
using a heterogeneous Bronsted basic catalyst [41]. Triglyceride limits contact between the reactant and the catalyst. It can be con-
reacts with three moles of methanol to give 3 moles of fatty acid cluded that the concentration of the alcohol has to balance between
methyl ester and one mole of glycerine through reversible reac- the rate of diffusion by the formation of two phases of uid, and
tions. The transesterication of palm olein with methanol is shown the shifting of the reaction towards products [41]. This research
in Scheme 1. shows that 18:1 is the appropriate proportion for maximum yield.
This reaction involves 3 steps that take place simultaneously.
Diasakou [42] proposed that triglycerides react with methanol to
produce diglycerides, and then diglycerides react to produce mono-
glycerides. Finally, monoglycerides react with methanol to yield
glycerin as a by-product. At each reaction step, one molecule of the
methyl ester is produced for each molecule of methanol consumed.
The analytical results showed that no side reactions occurred
and that the reaction products, FAME and glycerine, collected from
the reaction appeared to be clean and transparent. The FAME
products derived from the reaction were analysed by gas chro-
matography. Prior analytical research reported only the yield of
FAME, which ignores the complex diglyceride and monoglyceride
intermediates. Fig. 2 shows a gas chromatogram of the FAMEs
in the product sample, methyl laurate (C12:0), methyl myris-
tate (14:0), methyl palmitate (16:0), methyl palmitoleate (C16:1),
methyl stearate (18:0), methyl oleate (18:1), methyl linoleate
(C18:2), methyl linolenate (C18:3), methyl arachidate (C20:0),
methyl behenate (C22:0), and methyl erucate (C22:1), sequentially. Fig. 3. Effect of the molar ratio of methanol to oil on FAME yield. Molar ratio of
The results show that the amount of product corresponds to the methanol to oil 3:124:1. Temperature: 190 C. Amount of Na3 PO4 :0.5 wt.%.
30 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633
Fig. 4. Effect of reaction temperature on FAME yield. Temperature: 190250 C.
Molar ratio of methanol to oil: 18:1. Amount of Na3 PO4 :0.5 wt.%.
However, while higher methanol to oil molar ratios interfere with
the separation of glycerol, methanol with its polar hydroxyl group
can also work as an emulsier at the same time [44].
3.3. Effect of reaction temperature
Reaction temperature strongly affects the reaction rate. To study
the effect of the reaction temperature, the experiment was per-
formed at temperatures from of 190 to 250 C. The molar ratio of
methanol to oil was xed at a value of 18:1 with 0.5 wt.% Na3 PO4 .
Fig. 4 shows the effect of reaction temperature on FAME yield. It
was observed that the reaction rate increased with increasing reac-
tion temperature. At a reaction temperature of 210 C, the FAME
content reached equilibrium within 30 min. At a reaction temper-
ature of 250 C, the reaction proceeded very quickly, and complete
conversion of oil was observed within a 20 min period. However,
it was observed that the glycerol product under these conditions
exhibited a darker colour than the samples obtained at lower tem-
peratures.
Transesterication is an endothermic reaction, so increasing the
reaction temperature favours higher product yields. At high tem-
peratures, non-polar triglycerides can dissolve well in methanol to
form a single phase of methanol and oil, resulting in an increase in
FAME content [9]. To quantify the effects of the reaction temper-
ature on FAME content and calculate the activation energy of the
transesterication reaction with Na3 PO4 , the experimental results
were interpreted in terms of the kinetics of converting palm olein
to methyl esters. The results are shown in the next section.
3.4. Effect of mass ratio of catalyst to oil
The role of the catalyst is very important to promoting the rate
of reaction. The effect of the mass ratio of the catalyst to oil was
determined based on comparison with a non-catalytic reaction
under the same conditions. Although the transesterication reac-
tion occurs at temperatures approximately 200 C, the reaction is
very slow, and the formation of desired esters is not selective due
to incomplete alcoholysis of glyceride derivatives [42,45]. In this
research, the effect of different amounts of catalyst, varying from
0.0 to 1.0 wt.% of oil, were examined. The molar ratio of methanol
to oil was 18:1 with a reaction temperature of 210 C. The results
are shown in Fig. 5. It is clear that the transesterication reaction
of palm olein and methanol must be a catalysed reaction. Small
amounts of FAME were detected when there was no catalyst in the
reactor. When only a small amount of Na3 PO4 (0.1 wt.%) was added
to the reactor, the FAME content was greatly increased, and the
reaction rate increased with an increase in the amount of catalyst.
At the maximum amount of catalyst (1 wt.%) in the reactor, the oil
Fig. 5. Effect of the mass ratio of catalyst to oil on FAME yield. Amount of Na3 PO4 :
0.01.0 wt.%. Temperature: 210 C. Molar ratio of methanol to oil: 18:1.
was completely converted within 30 min. This study clearly showed
that sodium phosphate can be used as an effective transesterica-
tion catalyst with only 1 wt.% of catalyst sufcient to accelerate
the reaction. Catalysts work by reducing the activation energy of
the reaction, so the presence of a catalyst helps a reaction to reach
equilibrium more quickly.
3.5. Effect of the water and free fatty acid (FFAs) content in oil
In production systems using conventional catalysts, the water
and FFA content in the feedstock can signicantly affect the sys-
tem. The presence of both components causes soap formation and
reduces catalyst effectiveness. Therefore, transesterication with
an alkali catalyst is suitable for biodiesel derived from rened oil
feedstock. To ensure that a high percentage of products is obtained,
the amount of water and FFAs in the oil must not exceed 0.06 wt.%
and 0.5 wt.%, respectively [43]. Usually, the cost of biodiesel pro-
duction is dependent on the cost of the raw materials and the cost
of processing [36]. The processing cost can be reduced by using a
heterogeneous catalyst that can be recycled and eliminating the
water treatment step. The use of low-cost feedstock such as waste
oil or nonedible type oil can reduce the cost of biodiesel production.
However, waste oil contains as much as 6 wt.% water and 10 wt.%
free fatty acids [46].
The effects of water and fatty acid content in oil can be studied
by applying Na3 PO4 as a catalyst to low-quality oil. The study was
carried out with a molar ratio of methanol to oil of 18:1, a reaction
temperature of 210 C, and 1 wt.% Na3 PO4 . Different amounts of
water equivalent to 37 wt.% of the palm olein were added to the
methanol, while 310 wt.% of Palm Fatty Acid Distillate (93 wt.%
PFAD) was added to the oil. The results are shown in Figs. 6 and 7.
The results are compared with an experiment where neither FFAs
nor water was present.
Fig. 6 shows the effect of the presence of varying amounts of
water in the system. It can be seen that FAME contents decrease
with time as the amount of water increases. There was a slower
rate of reaction when the system had increased amounts of water.
However, all experiments attained equilibrium conversion to the
same extent as in the experiment without additional water within
90 min.
In Fig. 7, the effects of varying amounts of FFA content in oil
showed a similar trend to the effects of additional water. The
reactions approached equilibrium conversion in only 60 min. This
nding clearly shows that the presence of either or both compo-
nents in the reaction feedstock reduces the reaction rate, but it
does not have any effect on the equilibrium composition. The reac-
tion tends to reach its equilibrium slower in the presence of water
and/or FFAs than when these components are absent.
 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633
Fig. 6. Effect of different water contents in oil on FAME yield. Water contents in oil:
07 wt.% H2 O. Temperature: 210 C. Molar ratio of methanol to oil: 18:1. Amount of
Na3 PO4 : 1.0 wt.%.
Yin et al. [47] reported an upper limit for water and oleic acid tol-
erance in soybean oil with K3 PO4 as a catalyst of 5 wt.% and 3 wt.%,
respectively. Similarly, a study by Wang et al. [28], examined the
effect of water under reaction conditions of 0.5 wt.% NaOH and a
temperature of 250 C. They found that the water content of the
reactants had to be less than 1.5 wt.% to obtain a high yield within
10 min. Nair et al. [48] synthesised biodiesel from waste frying oil
using CaO and found that when water and FFAs were present in the
feed, three types of reactions (transesterication, hydrolysis, and
alkyl esterication of fatty acid) occurred simultaneously. Warabi
et al. [45] also found that alkyl esterication is faster than transes-
terication and that all FFAs in the feed, whether present originally
or as the products of hydrolysis, are completely transformed into
alkyl esters.
In non-catalytic processes, the amount of water present in the
feedstock did not have a signicant effect on the biodiesel yield. The
conversion tended to increase slightly with increased FFA content
in rapeseed oil [49]. However, in a catalytic system, it may be reduce
the effectiveness of the catalyst when the system contains both
components because the base catalyst dissolves in water and the
product of esterication of FFA also generates water. This decreases
the effectiveness and reusability of the catalyst. The duration of this
study was extended until the system approached equilibrium. It
can be observed that both components only had an effect at the
beginning of the reaction. Transesterication at high temperatures
has the ability to convert the FFAs in triglycerides to methyl esters,
but the reaction time must be extended. However, a catalytic sys-
tem contaminated with water and FFA operates via a complicated
Fig. 7. Effect of FFA contents in oil on FAME yield. FFA contents in oil: 010 wt.%
FFA. Temperature: 210 C. Molar ratio of methanol to oil: 18:1. Amount of Na3 PO4 :
1.0 wt.%.
31
mechanism, so more study is needed to determine the reaction
pathway.
3.6. Catalyst solubility
The solubility of the heterogeneous catalyst under reaction con-
ditions is a very important factor that has to be considered. This
factor indicates the efciency of the catalyst. However, few stud-
ies have reported the solubility of solid catalysts, which are always
assumed to be insoluble. Nevertheless, if the solid catalyst partially
dissolves, it requires purication. Normally, leaching of a catalyst is
accelerated by the presence of polar substances such as methanol,
water, and FFAs [43]. Although Na3 PO4 is insoluble in methanol, it
can be dissolved in H2 O at 8.8 wt.%.
To study catalyst reusability, Na3 PO4 separated from the reac-
tion was rinsed with methanol and dried at 120 C in an oven. The
used catalyst did not exhibit signicantly decreased activity after
3 runs. We further studied the solubility of Na3 PO4 in methanol
under the study conditions. The calcined Na3 PO4 was agitated with
methanol at a mixing speed of 600 rpm, a reaction time of 4 h,
and a temperature of 250 C. The catalyst was ltered with lter
paper and dried in an oven for 24 h. The methanol was titrated
with standard 0.1 molar HCl solution. The results showed only
a 0.14 wt.% loss of Na3 PO4 . It can be concluded that, under the
experimental conditions used, the catalyst is insoluble. The catalyst
showed potential to be developed for industrial-scale production.
However, because the catalyst is in the form of a powder, it is dif-
cult to separate out at the end of the reaction. As a result, some of the
catalyst may be lost during separation. Further research should be
performed on how to prepare Na3 PO4 on a large supported catalyst
to make separating the catalyst from the product easier.
3.7. Kinetics of transesterication
Kinetic studies under different reaction conditions carried out
by many researchers have reported that transesterication are
reversible reactions [2,15,16]. The overall reaction, shown in
Scheme 1, assumes that the reaction proceeds from triglyceride
to methyl ester by ignoring the other complex reaction steps (e.g.,
formation of diglycerides and monoglycerides). In our work, the
reaction was assumed to be a 1st order irreversible reaction as
a function of FAME products [4] because an excess of methanol
was used. The reaction rate constant was determined from the
increased amount of FAME product formed during the reaction
period. Hence, the kinetics of transesterication were studied with
respect to FAME yields as a function of time. The rst order rate
constant of the reaction can be expressed by Eq. (2).
dCFAME
rA = (2)
dt
where CFFAME represents the % FAME yield. The 1st order rate equa-
tion can be modied to
dCFAME
= k1 CFAME (3)
dt
assuming that the initial concentration of FAME at time = 0 is
FAME,0 and that it increases to FAME,t at time t. The integration
of this equation gives the following:
 FAME,t  t
dCFAME
=k dt (4)
FAME,0
CFAME 0
ln CFAME,t
= kt (5)
CFAME,0
To determine the chemical rate constant (k) and the activation
energy, the above relationship and the results from the experiments
32 K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 2633
Table 3
Chemical rate constants (k).
Temperature (o C) k (s1 )
190 0.0446
210 0.0738
230 0.0818
250 0.1267
conducted at a molar ratio of methanol to oil of 18:1 with 0.5 wt.%
Na3 PO4 and temperatures of 190250 C were used. The data were
collected at from 0 to 60 min. The chemical rate constants (k) were
determined and are reported in Table 3.
The results showed that increasing the reaction temperature
increased the reaction rate. A number of investigators studied
the kinetics of transesterication at various temperatures and
pressures. They reported that the reaction rates constants increase
with increased temperature in agreement with our work [39,50,51].
The activation energy can be determined from the plot of the
natural logarithm of initial rate against the reciprocal of the reac-
tion temperature (Arrhenius plot) as shown in Fig. 8. The activation
energy is calculated through the Arrhenius equation, which include
activation energy Ea and the frequency factor A given below
k = A eEa /RT
where R is the universal molar gas constant, and T is the tem-
perature (K). Because the activation energy is dependent on
temperature, the rate constant at any temperature can be computed
using Eq. (7).
Ea
ln k = ln A
RT
Eq. (7) is a linear equation, and therefore a plot of ln k and 1/T
given in Fig. 8 validates that it is a rst order reaction. The activation
energy (Ea ) was calculated using Fig. 8.
The apparent activation energy calculated from the slope of the
line of ln k vs. 1/T using the Arrhenius equation was 32.59 kJ/mol
palm olein. Many studies have reported the activation energy of
the transesterication reaction. Wang and Yang [18] reported an
activation energy for non-catalytic soybean oil and methanol of
92 kJ/mol in their experiments conducted at temperatures between
200 and 260 C. Wang et al. [28] also reported an activation energy
of 85.4 kJ/mol for rapeseed oil and methanol in a system with
sodium hydroxide catalyst. It was concluded that the activation
energy of a catalytic reaction was lower than that for a non-catalytic
reaction. Permsuwan et al. [19] estimated the activation energy for
a non-catalytic transesterication reaction between palm oil and
methanol at temperatures between 150 and 200 C to be in the
range of 91105 kJ/mol. In the present study, the results indicate
that in system using a catalyst, the activation energy of the sys-
tem is reduced, and the reaction proceeds quickly compared to a
Fig. 8. Arrhenius plot of the transesterication rate constant of palm olein oil in
methanol with 0.5 wt.% Na3 PO4 .
non-catalytic system. A high yield of FAMEs was obtained at milder
reaction conditions. Therefore, transesterication using Na3 PO4 as
a heterogeneous catalyst can be more protable than other pro-
cesses, including alkali-catalysed and non-catalytic processes.
4. Conclusions
Sodium phosphate can be used effectively as a heteroge-
neous catalyst in the transesterication reaction of palm olein and
methanol. The rate of reaction depends on the reaction conditions,
such as the molar ratio of methanol/oil, the operating tempera-
ture, and the amount of catalyst used. Increasing the molar ratio of
methanol/oil results in a faster rate of reaction, but at ratios higher
than 18:1, the reaction rate is identical. Higher operating tempera-
tures tend to accelerate the rate of reaction but reduce the glycerol
by-product quality. The addition of even a small amount of cat-
alyst into the system signicantly increased FAME yields. Under
suitable conditions, such as a methanol/oil molar ratio of 18:1, a
temperature of 210 C and 1 wt.% catalyst, nearly complete conver-
sion occurred with 30 min. The presence of water and FFAs affect
the system during the initial stages of the reaction, but they do
not reduce the yield of FAME at equilibrium. When large amounts
of methanol were used, the experimental results agreed with the
(6) irreversible 1st order kinetic model, and the activation energy was
found to be 32.59 kJ/mol palm olein.
Our research showed sodium phosphate is a potential catalyst
for use in transesterication reactions because it does not dissolve
in the reaction mixtures. However, it is difcult to separate from
the reaction product in powered form. Further studies should be
performed on the preparation of Na3 PO4 in the commercially use-
(7)
ful forms of pellets, pills, rings, spheres, granules, or extrudes to
facilitate the separation of the solid phase from the reactants and
products.
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