RESEARCH ARTICLE

Ultrasound-assisted transesterification of refined and crude

palm oils using heterogeneous palm oil mill fly ash
supported calcium oxide catalyst
Wilson Wei Sheng Ho1, Hoon Kiat Ng1, Suyin Gan2 & Wai Loon Chan1
1
Department of Mechanical, Materials and Manufacturing Engineering, The University of Nottingham Malaysia Campus, Jalan Broga, 43500
Semenyih, Selangor Darul Ehsan, Malaysia
2
Department of Chemical and Environmental Engineering, The University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih,
Selangor Darul Ehsan, Malaysia

Keywords Abstract
Biodiesel, calcium oxide, crude palm oil, palm
oil mill fly ash, refined palm oil, ultrasound- Ultrasound-assisted transesterification of refined palm oil (RPO) and crude
assisted transesterification palm oil (CPO) to produce biodiesel using a palm oil mill fly ash supported
calcium oxide (CaO) catalyst is studied in this work. The reaction time is sig-
Correspondence nificantly reduced from a maximum of 360 min under conventional mixing to
Suyin Gan, Department of Chemical and just 30 min with the use of ultrasound. Under ultrasonic cavitation, the
Environmental Engineering, The University of
required catalyst loading and methanol to oil molar ratio to produce compara-
Nottingham Malaysia Campus, Jalan Broga,
43500 Semenyih, Selangor Darul Ehsan,
ble yields and fatty acid methyl esters (FAME) conversions as conventional
Malaysia. mixing are lower. For RPO, the ultrasound-assisted transesterification condi-
Tel: +603 8924 8162; Fax: +603 8924 8017; tions of 60% ultrasonic amplitude, 30 min reaction time, 4 wt.% catalyst load-
E-mail: [email protected] ing, and 9:1 methanol to oil molar ratio result in maximum biodiesel yield and
FAME conversion of 85.23% and 97.02%, respectively. As for CPO, maximum
Funding Information biodiesel yield of 73.23% and FAME conversion of 97.04% are obtained under
This work was supported by the Ministry of
the same conditions with the exception of a methanol to oil molar ratio of
Higher Education (MOHE), Malaysia as well
as the Faculty of Engineering at The
12:1. Key physicochemical properties of the produced biodiesels are found to
University of Nottingham Malaysia Campus. be within the limits set by EN 14214 and ASTM D 6751. Catalyst reusability
tests indicate that the catalyst can be used up to three consecutive cycles after
Received: 17 September 2014; Revised: 2 regeneration using methanol washing followed by recalcination at 850°C for 2 h.
December 2014; Accepted: 5 December
2014

Energy Science and Engineering 2014;

3(3): 257–269

doi: 10.1002/ese3.56

subsequent use. With increasing catalysis research, they

Introduction
can also be designed to give higher activity, stability, and
Heterogeneous catalyzed transesterification has emerged as selectivity, as well as longer lifetime [3–4]. Nonetheless, a
an alternative biodiesel processing route to homogeneous major drawback of heterogeneous catalyzed transesterifica-
catalyzed transesterification in light of its potential indus- tion is its low reaction rate due to weak interactions
trial applicability [1]. The heterogeneous route potentially between the oil, alcohol, and catalyst because of their
lowers the overall biodiesel production cost and minimizes mutual immiscibility. To improve mass transfer between
environmental impacts due to its simpler production and the oil and alcohol reactants, the use of ultrasound which
purification steps [2]. Heterogeneous catalysts can be easily results in conditions of intense local turbulence and liquid
separated from the reaction mixture and regenerated for circulation has been recently proposed.

ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 257
This is an open access article under the terms of the Creative Commons Attribution License, which permits use,
distribution and reproduction in any medium, provided the original work is properly cited.
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

High power ultrasound generates ultrasonic cavitation, barium oxide (BaO) [11], strontium oxide (SrO) [12],
a phenomenon that is defined as the formation, growth, and calcium oxide (CaO) [18].
and collapse of microscopic bubbles periodically in the The main aim of the present work is to investigate the
ultrasound irradiated liquid. The implosive collapse of use of ultrasound in heterogeneous catalyzed transesterifi-
the cavitation bubbles during adiabatic compression cation using palm oil mill fly ash supported CaO. Palm oil
results in formation of a high local temperature and mill fly ash supported CaO is a recently developed hetero-
pressure spot, called “hotspot.” Furthermore, the collapse geneous catalyst which has been reported as an effective
and/or formation of cavitation bubbles cause the forma- transesterification catalyst [19]. Two different feedstock,
tion of high-speed microjets, microstreaming, and gener- that is, refined palm oil (RPO) and crude palm oil (CPO)
ation of shockwaves that increase heat and mass transfer are studied in order to compare the differences in terms of
in the liquid, as well as velocity gradients that result in biodiesel yield and fatty acid methyl esters (FAME) conver-
shear stresses. These physical effects contribute to effec- sion. To the best knowledge of the authors, no attempts
tive mixing of solution, disruption of immiscible liquid have been carried out so far to convert RPO and CPO using
layers, and promotion of mass transfer at the liquid– ultrasound-assisted transesterification with this heteroge-
solid interface [5]. For instance, Deshmane and Adewuyi neous catalyst. Parametric experimental tests are carried
[6] showed that the highest soy biodiesel conversion in out to elucidate the effects of ultrasonic amplitude, reaction
excess of 90% was achieved within 90 min with the use time, catalyst loading, and methanol to oil molar ratio on
of ultrasound. In another study using Jatropha curcas oil yield and FAME conversion. In light of the relatively
[7], a conversion of 91% was achieved in just 40 min at unknown ultrasound effects on biodiesel quality, the physi-
a moderate ultrasonic amplitude of 60%. Meanwhile, [8] cochemical properties and glycerides content are analyzed.
reported that a high biodiesel conversion of approxi- Lastly, catalyst reusability is examined to determine possi-
mately 98% using J. curcas oil was obtained at an opti- ble leaching effects caused by ultrasonic cavitation.
mum condition of 3 wt.% catalyst concentration and
15 min reaction time. Nonetheless, while improvements
Experimental
in reaction rates may be addressed by the use of ultra-
sound, its effects on biodiesel quality remains relatively
Materials
unknown. Due to the high local temperature and pres-
sure, species that are present within the cavitation bub- Commercial palm cooking oil (Buruh, Malaysia) was pur-
bles may undergo pyrolysis, which adversely affects chased from a local supermarket and CPO was provided
biodiesel quality. by Havys Oil Mill Sdn. Bhd. The accompanying CPO
To date, the majority of heterogeneous ultrasound- sample analysis report recorded a FFA content of 3.7%, a
assisted transesterification studies utilize refined oils as deterioration of bleachability index (DOBI) value of 2.6%
their feedstock [1, 2, 6, 9–11]. Salamatinia et al. [12] have and a moisture content of 0.2%. Palm oil mill fly ash was
recently reported that biodiesel could be produced from collected from Seri Ulu Langat Palm Oil Mill Sdn. Bhd.,
palm, corn, canola, and sunflower oils using ultrasound. Malaysia. Methanol (CH3OH; >99% purity) and calcium
They linked the free fatty acids (FFA) content to the bio- carbonate (CaCO3; 99.95% purity) were purchased from
diesel conversions obtained. In the transesterification of Merck (Bandar Sunway, Selangor, Malaysia) and Sigma
soybean oil, it was observed that ultrasound frequency Aldrich (Subang Jaya, Selangor, Malaysia), respectively.
could enhance mass transfer as 611 kHz resulted in signif- Meanwhile, internal standard methyl heptadecanoate
icantly improved mass transfer coefficient (89%) as com- (C17:0) was purchased from Sigma Aldrich. The reference
pared to 20 kHz (48%)[6]. Notably, Badday et al. [7] and standards for FAME (FAME mix RM-6), glycerol and gly-
Kumar et al. [8] have used nonedible oil J. curcas oil as cerides contents were also obtained from Sigma Aldrich
the raw feedstock for biodiesel production using ultra- as follows: N-methyl-N-trimethysilyltrifluoroacetamide
sound-assisted transesterification. (MSTFA), n-heptane, 1,2,4-butanetriol (internal standard
Both heterogeneous acid and base catalysts have report- No. 1), tricaprin (internal standard No. 2), glycerol, 1-
edly been used in ultrasound-assisted transesterification monooleoylglycerol (monoolein), 1,3-dioleoylglycerol
processes. Heterogeneous acid catalysts used include (diolein), and 1,2,3-trioleoylglycerol (triolein).
carbon, cesium, and alumina doped heteropolyacid cata-
lysts [13–15], 3-(NN,N-triethylamino)-1-propanesulfonic
Catalyst preparation
hydrogen sulfate ionic liquid [16], and mixed sulfate zir-
conia/titania [17]. Meanwhile, heterogeneous base cata- The wet impregnation method was used to prepare the
lysts used include zeolite [1], silicon dioxide supported catalyst at a fixed composition of 45 wt.% calcined
sodium (Na/SiO2) [8], potassium phosphate (K3PO4) [9], CaCO3 loaded onto palm oil mill fly ash [20]. The palm

258 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
W. W. S. Ho et al. Ultrasonic transesterification of palm oils

oil mill fly ash was first sieved and dried at 105°C for equipped with an ultrasound transducer and a probe (Qso-
24 h to eradicate all moisture. Prior to use, CaCO3 was nica Q700 (Newtown, CT, USA); 20 kHz max. power
calcined at 800°C for 90 min to remove CO2 and gener- 700 W) as shown in Figure 1. A condenser and a thermome-
ate CaO in which the active salt precursor Ca(OH)2 will ter were inserted into the side joints. Cooling water was
be subsequently obtained. Typically, to obtain 45 wt.% allowed to flow through the jacket to control the reaction
calcined CaCO3 loaded catalyst, 13.5 g of calcined CaCO3 temperature, which was fixed at 45
2°C. Ultrasonication
was added to 200 mL of pure deionized H2O in a three- was introduced in a pulse mode with 10 sec on and 7 sec off
neck flask under magnetic stirring at 700 rpm to prepare to avoid instantaneously temperature spikes and to generate
an aqueous solution of Ca(OH)2. The solution was heated sudden impacts for better cavitation. Conventional mixing
in a closed system at 70°C. 16.5 g of fly ash was then transesterification experiments were also carried out to serve
slowly added to the solution and mixed vigorously for as a benchmark for the comparison of the presence and
another 4 h until a homogenous mixture was obtained. absence of ultrasound. For these experiments, a 250 mL
The sample was then aged for 18 h to ensure that the Ca heated three-neck round bottom flask equipped with a
(OH)2 precipitated on the fly ash carrier. The removal of reflux condenser was used [20].
adhering H2O in the mixture was accomplished using a
hot air oven at 105°C for 24 h. The dried catalyst was
Ultrasound-assisted transesterification
then calcined at temperatures of 850°C in a muffle fur-
reactions
nace for 2 h. Sufficient catalyst was produced following
the methodology described above for the entire set of sin- For all transesterification tests, 100 mL (87 g) of RPO or
gle factor transesterification parametric study and charac- CPO was measured. The desired amount of fly ash sup-
terized according to [20]. Since the parametric study was ported CaO catalyst was added to a fixed amount of
repeated thrice, three batches were made and character- methanol depending on the methanol to oil molar ratio,
ization of each batch of catalyst was carried out to ensure and was heated and premixed at 40°C and 500 rpm for
that the quality of the prepared catalyst was consistent 15 min. The catalyst–methanol mixture was then intro-
and up to the expected requirements. duced into the reactor and ultrasonication was applied.
The effects of ultrasonic amplitude, reaction time, catalyst
loading, and methanol to oil molar ratio were investigated
Experimental setup
in this work. Table 1 shows the nominal and tested para-
Ultrasound-assisted transesterification reactions were car- metric settings for the single factor transesterification
ried out in a customized three-neck jacketed reactor parametric study. All experiments were repeated thrice.

(C)
(B)

(A) (H)

(G)

(D)

(E)
(F)

Figure 1. Schematic diagram of ultrasonic reactor (A) sonicator; (B) condenser; (C) transducer; (D) cooling water outlet; (E) cooling water inlet;
(F) ultrasonic reactor; (G) thermometer and (H) retort stand.

ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 259
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

Table 1. Nominal and tested parametric settings for the ultrasound- quantitative FAME conversion was determined according to
assisted transesterification study. EN 14103 [21]. For this, 50 mg of biodiesel sample was mixed
Reaction parameters Tested settings with 1 mL of internal standard methyl heptadecanoate (C17)
solution (10 mg/mL). Similarly, 1 lL of the mixed sample
Ultrasonic amplitude (%) 20, 40, (60)1, 80, 100 was injected into the GC. The quantitative analysis provides
Reaction time (min) 15, (30)1, 45, 60
verification that the FAME conversion in biodiesel is greater
Catalyst loading (wt.%) 2, (4)1, 6, 8
Methanol to oil molar ratio (mol/mol) 6:1, 9:1, (12:1)1, 15:1, 18:1
than 96.5% (mol/mol) in accordance to the specifications
reported in EN 14214 [22]. As detailed in EN 14103, the
1
The settings in parentheses are the nominal settings. FAME conversion was calculated using Equation (2).
After the reaction, the solid catalyst was filtered out from P  
A  AIS CIS VIS
the mixture with the aid of a vacuum pump. The filtered Ester contentð%Þ ¼ 100 ; (2)
AIS m
sample was then separated by centrifugation at 4000 rpm
for 15 min. Two phases would be formed, namely an ester- P
where A is the sum of areas of all peaks ranging from
rich phase (top layer) and a glycerol-rich phase (bottom
C14:0 and C24:1; AIS is the internal standard (methyl
layer). The glycerol was removed using a separating funnel
heptadecanoate) peak area; CIS is the concentration of the
while the excess methanol in the ester-rich phase was removed
internal standard solution (mg/mL); VIS is the volume of
via a rotary evaporator. The sample from the ester-rich phase
the internal standard solution used (mL); and m is the
underwent further treatment including diluted acetic acid
mass of the sample (mg).
washing (90°C) to remove all dissolved residues and finally hot
air oven drying (65°C) to remove all H2O content. The mass of
the final product, that is, biodiesel was measured for the deter- Glyceride analysis
mination of yield according to Equation (1) and is presented
Triplicate analyses of free glycerol, monoglycerides (MG),
in this work as the average of three repeats.
diglycerides (DG), triglycerides (TG), and total glycerol
Weight of biodiesel were performed on a Perkin Elmer Clarus 680 GC equipped
Yield (%) ¼ : (1)
Weight of oil with an on-column injector, a FID, and a Supelco MET-
biodiesel capillary column (14 m 9 0.53 mm ID) coated
Conventional mixing transesterification experiments
with 0.16 lm film with an integrated 2 m 9 0.53 mm I.D.
were additionally performed as a benchmark to compare
guard. The GC operating conditions were as follows: detec-
the presence and absence of ultrasound on biodiesel yield
tor temperature 380°C; programmed-temperature split/
and FAME conversion. The nominal reaction time, cata-
splitless injector 60°C hold for 1 min, heat at 15°C/min to
lyst loading, methanol to oil molar ratio, and temperature
300°C; then heat at 30°C/min up to 380°C; oven tempera-
were set at 180 min, 4 wt.%, 12:1 and 45°C, respectively.
ture program 2 min at 50°C, heat at 15°C/min to 180°C,
then heat at 7°C/min to 230°C and finally heat at 10°C/min
Gas chromatography (GC) analyses up to 370°C and hold for 5 min. The carrier gas (He) flow
was set at 3 mL/min.
Fatty acid methyl esters analysis
100 mg of homogenized biodiesel sample was accurately
The FAME in the final biodiesel products were qualitatively measured in a vial. 80 lL of 1,2,4-butanetriol, 100 lL of
and quantitatively analyzed three times by gas chromatogra- tricaprin, and 100 lL of MSTFA were added into the vial
phy (GC). The GC used was a Perkin Elmer (Petaling Jaya, and mixed vigorously. The sample solution was silylated
Selangor, Malaysia) Clarus 500 GC equipped with a flame for 15 min before adding 8 mL of heptane [23]. The silyla-
ionization detector (FID). The capillary column used was an tion is intended to increase the volatility and stability of
Agilent (Petaling Jaya, Selangor, Malaysia) J&W HP-88 col- the hydroxyl compounds injected which therefore
umn with dimensions of 0.25 mm I.D. 9 60 m improves their detection. 1 lL injections in splitless mode
length 9 0.2 lm film thickness. Helium (He) was the carrier were carried out on the GC.
gas and its pressure was set at 32 psi. The oven temperature
was isothermally held at 185°C for 15 min. Meanwhile, the
Determination of the percentage of free glycerol
injector and detector temperatures were set at 240 and
and glycerides
250°C, respectively. For qualitative analysis, 0.1 mL of bio-
diesel sample was dissolved into 1.9 mL of hexane. 1 lL Four calibration solutions were prepared according to EN
injections with a split injection ratio of 100:1 were carried out. 14105 [23] for the determination of the percentage of free
The identification of all fatty acids composition in the sample glycerol and glycerides. The calibration solutions were
was compared to the reference FAME mix RM-6. Meanwhile, analyzed thrice under the same conditions as the sample

260 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

Table 1. Nominal and tested parametric settings for the ultrasound- quantitative FAME conversion was determined according to
assisted transesterification study. EN 14103 [21]. For this, 50 mg of biodiesel sample was mixed
Reaction parameters Tested settings with 1 mL of internal standard methyl heptadecanoate (C17)
solution (10 mg/mL). Similarly, 1 lL of the mixed sample
Ultrasonic amplitude (%) 20, 40, (60)1, 80, 100 was injected into the GC. The quantitative analysis provides
Reaction time (min) 15, (30)1, 45, 60
verification that the FAME conversion in biodiesel is greater
Catalyst loading (wt.%) 2, (4)1, 6, 8
Methanol to oil molar ratio (mol/mol) 6:1, 9:1, (12:1)1, 15:1, 18:1
than 96.5% (mol/mol) in accordance to the specifications
reported in EN 14214 [22]. As detailed in EN 14103, the
1
The settings in parentheses are the nominal settings. FAME conversion was calculated using Equation (2).
After the reaction, the solid catalyst was filtered out from P  
A  AIS CIS VIS
the mixture with the aid of a vacuum pump. The filtered Ester contentð%Þ ¼ 100 ; (2)
AIS m
sample was then separated by centrifugation at 4000 rpm
for 15 min. Two phases would be formed, namely an ester- P
where A is the sum of areas of all peaks ranging from
rich phase (top layer) and a glycerol-rich phase (bottom
C14:0 and C24:1; AIS is the internal standard (methyl
layer). The glycerol was removed using a separating funnel
heptadecanoate) peak area; CIS is the concentration of the
while the excess methanol in the ester-rich phase was removed
internal standard solution (mg/mL); VIS is the volume of
via a rotary evaporator. The sample from the ester-rich phase
the internal standard solution used (mL); and m is the
underwent further treatment including diluted acetic acid
mass of the sample (mg).
washing (90°C) to remove all dissolved residues and finally hot
air oven drying (65°C) to remove all H2O content. The mass of
the final product, that is, biodiesel was measured for the deter- Glyceride analysis
mination of yield according to Equation (1) and is presented
Triplicate analyses of free glycerol, monoglycerides (MG),
in this work as the average of three repeats.
diglycerides (DG), triglycerides (TG), and total glycerol
Weight of biodiesel were performed on a Perkin Elmer Clarus 680 GC equipped
Yield (%) ¼ : (1)
Weight of oil with an on-column injector, a FID, and a Supelco MET-
biodiesel capillary column (14 m 9 0.53 mm ID) coated
Conventional mixing transesterification experiments
with 0.16 lm film with an integrated 2 m 9 0.53 mm I.D.
were additionally performed as a benchmark to compare
guard. The GC operating conditions were as follows: detec-
the presence and absence of ultrasound on biodiesel yield
tor temperature 380°C; programmed-temperature split/
and FAME conversion. The nominal reaction time, cata-
splitless injector 60°C hold for 1 min, heat at 15°C/min to
lyst loading, methanol to oil molar ratio, and temperature
300°C; then heat at 30°C/min up to 380°C; oven tempera-
were set at 180 min, 4 wt.%, 12:1 and 45°C, respectively.
ture program 2 min at 50°C, heat at 15°C/min to 180°C,
then heat at 7°C/min to 230°C and finally heat at 10°C/min
Gas chromatography (GC) analyses up to 370°C and hold for 5 min. The carrier gas (He) flow
was set at 3 mL/min.
Fatty acid methyl esters analysis
100 mg of homogenized biodiesel sample was accurately
The FAME in the final biodiesel products were qualitatively measured in a vial. 80 lL of 1,2,4-butanetriol, 100 lL of
and quantitatively analyzed three times by gas chromatogra- tricaprin, and 100 lL of MSTFA were added into the vial
phy (GC). The GC used was a Perkin Elmer (Petaling Jaya, and mixed vigorously. The sample solution was silylated
Selangor, Malaysia) Clarus 500 GC equipped with a flame for 15 min before adding 8 mL of heptane [23]. The silyla-
ionization detector (FID). The capillary column used was an tion is intended to increase the volatility and stability of
Agilent (Petaling Jaya, Selangor, Malaysia) J&W HP-88 col- the hydroxyl compounds injected which therefore
umn with dimensions of 0.25 mm I.D. 9 60 m improves their detection. 1 lL injections in splitless mode
length 9 0.2 lm film thickness. Helium (He) was the carrier were carried out on the GC.
gas and its pressure was set at 32 psi. The oven temperature
was isothermally held at 185°C for 15 min. Meanwhile, the
Determination of the percentage of free glycerol
injector and detector temperatures were set at 240 and
and glycerides
250°C, respectively. For qualitative analysis, 0.1 mL of bio-
diesel sample was dissolved into 1.9 mL of hexane. 1 lL Four calibration solutions were prepared according to EN
injections with a split injection ratio of 100:1 were carried out. 14105 [23] for the determination of the percentage of free
The identification of all fatty acids composition in the sample glycerol and glycerides. The calibration solutions were
was compared to the reference FAME mix RM-6. Meanwhile, analyzed thrice under the same conditions as the sample

260 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

98.18 98.6 100 observed in the first 30 min. Meanwhile, for CPO, an
100
97.2
97.04 increase from 52.85% to 73.23% in yield and a high
86.73 85.26
90 90
85.74 87.55 FAME conversion of approximately 97% are attained in
80.02

Conversion (%)
80 80.94 84.72 80 the first 30 min. The observed trends can be attributed to
82.31
Yield (%)

81.38 77.34 the sonochemical effect induced by acoustic cavitation

70 75.71 70
73.23 72.60 71.08
stimulated by ultrasonic irradiation [28]. The speed of
68.71
60 60 ultrasound in a liquid medium varies with the properties
59.46 of the medium. The speed of ultrasound is 1140 m/sec in
50 Yield of RPO Yield of CPO 50
methanol, 1410 m/sec in biodiesel and 1453 m/sec in
Conversion of RPO Conversion of CPO
40 40 palm oil [25]. The change in velocity of ultrasound in
20 40 60 80 100 adjacent mediums may enhance mixing between two
Ultrasonic amplitude (%)
phases because of the changes in acoustic streaming pat-
Figure 2. Effects of ultrasonic amplitude on biodiesel yield and FAME
terns, which further reduces the mass transfer resistance
conversion under nominal parametric settings (catalyst loading and helps to speed up the reaction [25]. After 30 min,
4 wt.%, methanol to oil molar ratio 12:1, temperature 45°C, time the yield drops and the FAME conversion is lower due to
30 min). promotion of the reverse reaction. The yield and conver-
sion of RPO biodiesel drop to 66.19% and 75.93%,
respectively, while the yield and conversion of CPO bio-
yield of RPO biodiesel increases from 75.71% to 84.72%, diesel drop to 64.19% and 91.24%, respectively, at
while the yield of CPO biodiesel increases from 59.46% 60 min. These results are in line with that reported by
to 73.23%. As the amplitude increases, the size of cavita- [11] whereby only 75% conversion was detected at
tion bubbles increases leading to more intense collapse of 60 min in CaO catalyzed ultrasound-assisted transesterifi-
bubbles which form very fine and stable emulsions [25]. cation of palm oil.
This rapid emulsification accelerates the transport of reac- The results for the conventional mixing transesterifica-
tants to and from the boundary between the two phases tion experiments are shown in Figure 3B. For both RPO
of oil and methanol resulting in higher interfacial surface and CPO, the ultrasound-assisted transesterification reac-
area for mass transfer and hence higher biodiesel yield tions are very fast (15–60 min) as compared to the con-
[26]. Wu et al. [27] have proven that very fine and stable ventional mixing ones (180–360 min). The underlying
emulsions produced in the presence of ultrasound were mechanism behind the fast reactions is the collapse of ca-
approximately 2.4 times smaller in droplets size than vitational bubbles near the methanol/oil boundaries lead-
those produced in the absence of ultrasound. In this ing to ultrasonic jets of methanol impinging into oil and
work, a maximum yield is recorded at 60% ultrasonic resulting in excellent mixing. These results are in line with
amplitude and any increase beyond that causes a drop in [29–31] who reported that the conversion of biodiesel
yields for both RPO and CPO. This is because a large was complete at approximately 60 min regardless of the
number of cavitation bubbles is generated in the mixture type of oil. Figure 3B also shows that the highest RPO
with high ultrasonic amplitude. These bubbles will coa- yield of 84.61% is obtained with 360 min of conventional
lesce forming larger bubbles which will then act as a bar- mixing. In contrast, a similar RPO yield of 84.72% is
rier to the transfer of acoustic energy through the liquid achieved in just 30 min with the use of ultrasonic cavita-
phase [8]. As observed in Figure 2, FAME conversion tion. For CPO, a shorter reaction time of 180 min is
reaches a maximum above 80% in all cases. The highest required with conventional mixing to achieve the highest
FAME conversions of 98.18% and 97.04% are achieved yield of 73.48%. Compared to RPO, this represents a
with 60% ultrasonic amplitude for RPO and CPO biodie- 50% reduction in reaction time. Nevertheless, significant
sels, respectively. Thus, the recommended amplitude for reductions in reaction time of above 90% can only be
transesterification of both oils using palm oil mill fly ash achieved by using ultrasonic cavitation. In general, ultra-
supported CaO catalyst is 60% for the best yield and con- sound reduces the reaction times of conventional mixing
version. from the range of 180 to 360 min to 30 min with similar
yields and conversions.
Effects of reaction time
Effects of catalyst loading
Figure 3A shows the effects of ultrasonic reaction time on
biodiesel yield and FAME conversion for both RPO and The effects of catalyst loading on biodiesel yield and
CPO. An increase from 73.49% to 84.72% in RPO yield FAME conversion in ultrasound-assisted transesterifica-
and a high FAME conversion of more than 98% are tion for RPO and CPO can be seen in Figure 4A. The

262 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
W. W. S. Ho et al. Ultrasonic transesterification of palm oils

97.04 96.23 100 98.24 98.27 98.04 97.63 100

(A) 100 (B) 100
91.24
88.41 98.18 98.02 97.92 97.58 97.24
90 90 90 90

Conversion (%)

Conversion (%)
80 84.72 83.65 80 80 84.61 80
83.02 83.12 83.36
Yield (%)

Yield (%)
79.55
77.34 75.93
70 73.49 70 70 73.48 70
73.23
66.19
67.83 66.24
60
52.85 64.49 60 60
62.83
60
60.03
50 50 50 50

40 40 40 40
15 30 45 60 180 240 300 360
Reaction time (min) Reaction time (min)
Yield of RPO Yield of CPO
Conversion of RPO Conversion of CPO

Figure 3. Effects of reaction time on biodiesel yield and FAME conversion under nominal parametric settings of (A) ultrasonic amplitude 60%,
catalyst loading 4 wt.%, methanol to oil molar ratio 12:1, temperature 45°C; (B) stirring speed 700 rpm, catalyst loading 4 wt.%, methanol to oil
molar ratio 12:1, temperature 45°C.

RPO yields for all catalyst loadings are comparable within from 2 wt.% to 4 wt.%, the conversion increases from
the range of 81–84%. These results are supported by [11] 66.71% to 98.18% and reaches a constant beyond 4 wt.%.
in which the yields were reportedly similar with increas- Maximum FAME conversion of 97.04% for CPO is also
ing amount of heterogeneous catalysts (CaO and SrO) in obtained at a catalyst loading of 4 wt.%, but the conver-
the ultrasonic reactor. It was suggested that catalyst load- sion decreases to 80.19% when 8 wt.% catalyst loading is
ing may not be the dominant factor controlling the rate used.
of reaction in ultrasonic systems. Conversely, the CPO Figure 4B illustrates the RPO and CPO biodiesel yields
yield increases from 56.44% to 73.23% when the catalyst and FAME conversions for conventional mixing transeste-
loading increases from 2 wt.% to 4 wt.%. Further rification at different catalyst loadings. It can be observed
increase in catalyst loading reduces the yield to 53.95%. that the biodiesel yields increase with increase in catalyst
The presence of excess catalyst leads to soap formation loading, but they drop once the optimum loading of
and difficulty in esters separation [32]. In these cases, 6 wt.% is reached. The results indicate that lesser catalyst
soap formation was visually observed as a milky third loading is required to produce comparable maximum
layer which formed between the top biodiesel layer and yields with the use of ultrasound as compared to conven-
the bottom glycerol layer. In this work, a concentration tional mixing regardless of the type of oil. In ultrasonica-
of 4 wt.% gave the best biodiesel yields. As for RPO tion, for both RPO and CPO, 4 wt.% catalyst loading is
FAME conversion, when the catalyst loading increases required to achieve the highest yields while 2 wt.% lesser

98.18 97.55 95.88 97.67 98.26 98.24

(A)100 97.04
100 (B) 100 92.98
100
98.08 98.02
91.28 96.51
90 90 90 90
87.54
84.71
Conversion (%)

Conversion (%)

80 84.72 80.19 80 80 80
82.66 73.23 83.02
Yield (%)

81.42
Yield (%)

80.95 80.95 80.42

66.71 79.15
70 65.92 70 70 70
73.48
60 56.44 60
53.95 60 55.05 60
51.11 50.47
50 50 50 50

40 40 40 40
2 4 6 8 2 4 6 8
Catalyst loading (wt.%) Catalyst loading (wt.%)
Yield of RPO Yield of CPO
Conversion of RPO Conversion of CPO

Figure 4. Effects of catalyst loading on biodiesel yield and FAME conversion under nominal parametric settings of (A) ultrasonic amplitude 60%,
methanol to oil molar ratio 12:1, temperature 45°C, time 30 min; (B) stirring speed 700 rpm, methanol to oil molar ratio 12:1, temperature
45°C, time 180 min.

ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 263
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

98.18 98.6 100 observed in the first 30 min. Meanwhile, for CPO, an
100
97.2
97.04 increase from 52.85% to 73.23% in yield and a high
86.73 85.26
90 90
85.74 87.55 FAME conversion of approximately 97% are attained in
80.02

Conversion (%)
80 80.94 84.72 80 the first 30 min. The observed trends can be attributed to
82.31
Yield (%)

81.38 77.34 the sonochemical effect induced by acoustic cavitation

70 75.71 70
73.23 72.60 71.08
stimulated by ultrasonic irradiation [28]. The speed of
68.71
60 60 ultrasound in a liquid medium varies with the properties
59.46 of the medium. The speed of ultrasound is 1140 m/sec in
50 Yield of RPO Yield of CPO 50
methanol, 1410 m/sec in biodiesel and 1453 m/sec in
Conversion of RPO Conversion of CPO
40 40 palm oil [25]. The change in velocity of ultrasound in
20 40 60 80 100 adjacent mediums may enhance mixing between two
Ultrasonic amplitude (%)
phases because of the changes in acoustic streaming pat-
Figure 2. Effects of ultrasonic amplitude on biodiesel yield and FAME
terns, which further reduces the mass transfer resistance
conversion under nominal parametric settings (catalyst loading and helps to speed up the reaction [25]. After 30 min,
4 wt.%, methanol to oil molar ratio 12:1, temperature 45°C, time the yield drops and the FAME conversion is lower due to
30 min). promotion of the reverse reaction. The yield and conver-
sion of RPO biodiesel drop to 66.19% and 75.93%,
respectively, while the yield and conversion of CPO bio-
yield of RPO biodiesel increases from 75.71% to 84.72%, diesel drop to 64.19% and 91.24%, respectively, at
while the yield of CPO biodiesel increases from 59.46% 60 min. These results are in line with that reported by
to 73.23%. As the amplitude increases, the size of cavita- [11] whereby only 75% conversion was detected at
tion bubbles increases leading to more intense collapse of 60 min in CaO catalyzed ultrasound-assisted transesterifi-
bubbles which form very fine and stable emulsions [25]. cation of palm oil.
This rapid emulsification accelerates the transport of reac- The results for the conventional mixing transesterifica-
tants to and from the boundary between the two phases tion experiments are shown in Figure 3B. For both RPO
of oil and methanol resulting in higher interfacial surface and CPO, the ultrasound-assisted transesterification reac-
area for mass transfer and hence higher biodiesel yield tions are very fast (15–60 min) as compared to the con-
[26]. Wu et al. [27] have proven that very fine and stable ventional mixing ones (180–360 min). The underlying
emulsions produced in the presence of ultrasound were mechanism behind the fast reactions is the collapse of ca-
approximately 2.4 times smaller in droplets size than vitational bubbles near the methanol/oil boundaries lead-
those produced in the absence of ultrasound. In this ing to ultrasonic jets of methanol impinging into oil and
work, a maximum yield is recorded at 60% ultrasonic resulting in excellent mixing. These results are in line with
amplitude and any increase beyond that causes a drop in [29–31] who reported that the conversion of biodiesel
yields for both RPO and CPO. This is because a large was complete at approximately 60 min regardless of the
number of cavitation bubbles is generated in the mixture type of oil. Figure 3B also shows that the highest RPO
with high ultrasonic amplitude. These bubbles will coa- yield of 84.61% is obtained with 360 min of conventional
lesce forming larger bubbles which will then act as a bar- mixing. In contrast, a similar RPO yield of 84.72% is
rier to the transfer of acoustic energy through the liquid achieved in just 30 min with the use of ultrasonic cavita-
phase [8]. As observed in Figure 2, FAME conversion tion. For CPO, a shorter reaction time of 180 min is
reaches a maximum above 80% in all cases. The highest required with conventional mixing to achieve the highest
FAME conversions of 98.18% and 97.04% are achieved yield of 73.48%. Compared to RPO, this represents a
with 60% ultrasonic amplitude for RPO and CPO biodie- 50% reduction in reaction time. Nevertheless, significant
sels, respectively. Thus, the recommended amplitude for reductions in reaction time of above 90% can only be
transesterification of both oils using palm oil mill fly ash achieved by using ultrasonic cavitation. In general, ultra-
supported CaO catalyst is 60% for the best yield and con- sound reduces the reaction times of conventional mixing
version. from the range of 180 to 360 min to 30 min with similar
yields and conversions.
Effects of reaction time
Effects of catalyst loading
Figure 3A shows the effects of ultrasonic reaction time on
biodiesel yield and FAME conversion for both RPO and The effects of catalyst loading on biodiesel yield and
CPO. An increase from 73.49% to 84.72% in RPO yield FAME conversion in ultrasound-assisted transesterifica-
and a high FAME conversion of more than 98% are tion for RPO and CPO can be seen in Figure 4A. The

262 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
W. W. S. Ho et al. Ultrasonic transesterification of palm oils

in biodiesel yield and FAME conversion of 85.23% and fact that the density of CPO at 950 kg/m3 is higher than
97.02%, respectively. Meanwhile, for the ultrasound- that of RPO at 900 kg/m3 [4]. Variations in biodiesel
assisted transesterification of CPO, the optimum transe- density are mostly dependent on the feedstock used rather
sterification conditions are the same except for methanol than the production process.
to oil molar ratio, which is at 12:1. Under these condi- The flash points for biodiesels produced using conven-
tions, a yield of 73.23% and an FAME conversion of tional mixing is 168°C for RPO and 144°C for CPO.
97.04% are obtained. Meanwhile, for biodiesels produced using ultrasonication,
the flash points are 170°C for RPO and 164°C for CPO.
All the flash points are well above the specified minimum
Biodiesel properties analysis
of 130°C in ASTM D 6751, but the biodiesels produced
Table 2 summarizes the tested physicochemical properties using ultrasonication have higher flash points especially
of the biodiesels produced under optimum conditions. for CPO. Since the flash point is an indicator of the
The biodiesels produced from RPO and CPO using ultr- absence/presence of volatile alcohol, the high flash points
asonication have slightly lower viscosities (5.02 and of biodiesels as compared to diesel indicate that the bio-
5.79 mm2/sec, respectively) as compared to those pro- diesels are safer fuels [4]. From Table 2, it can be
duced using conventional mixing (5.03 and 5.98 mm2/ observed that acid values for both biodiesels produced
sec, respectively). All these viscosities remain within the using ultrasonication and conventional mixing range
standard range of 1.9 to 6.0 mm2/sec at 40°C specified in between 0.32 and 0.49 mg KOH/g, which satisfy the max-
ASTM D 6751 biodiesel standard. High viscosity results imum limit of 0.5 mg KOH/g in ASTM D 6751. It is
in poor fuel atomization, incomplete combustion, and important to meet this requirement to avoid problems
carbon deposition on the injector. Additionally, the densi- associated with deposit and corrosion of fuel injection
ties of RPO and CPO biodiesels from ultrasonication systems. For HHV, the ASTM D 6751 imposes a HHV
(862.3 and 863.9 kg/m3, respectively) are slightly lower higher than 35 MJ/kg for biodiesel. The HHV of biodie-
than the RPO and CPO biodiesels from conventional sels produced are 39.0 and 38.1 MJ/kg for RPO and CPO,
mixing (863.1 and 865.3 kg/m3), respectively. Likewise to respectively, using conventional mixing, and 38.1 and
viscosity, these densities fully conform to the limits given 37.5 MJ/kg for RPO and CPO, respectively, using ultraso-
by ASTM D 6751, that is, between 860 and 900 kg/m3 at nication. The HHV values are slightly less with ultrasoni-
15°C. A higher biodiesel density means that there is a cation, but the results are above the acceptable minimum.
delivery of a greater mass of fuel for a fixed volumetric These HHV are similar to those reported by [37] which
flowrate. Hence, CPO biodiesel has this added advantage ranged from 37.8 to 39.4 MJ/kg for used frying palm oil
over RPO biodiesel since its density is higher in both pro- biodiesel. The final measured physicochemical property is
duction methods. Its higher density can be linked to the CN which is an important indicator of the quality of the

Table 2. Physicochemical properties of biodiesels produced in comparison to standard biodiesel specifications.

Physicochemical ASTM D 6751 and

Conventional mixing Ultrasonic cavitation
property Unit Test method EN 14214 limits
RPO CPO RPO CPO
2 1
Kinematic viscosity mm /sec; 40°C ASTM D 445 1.9-6.0 5.03 5.98 5.02 5.79
Density kg/m3; 15°C ASTM D 1298 860-9001 863.1 865.3 862.3 863.9
Flash point °C ASTM D 93 130 minimum1 168 144 170 164
Acid value mg KOH/g ASTM D 664 0.5 maximum1 0.32 0.42 0.46 0.49
High heating value MJ/kg ASTM D 4868 35 minimum1 39.0 38.1 38.1 37.5
Cetane number3 – ASTM D 613 47 minimum1 50.4 48.1 49.8 49.0
FAME conversion % (mol/mol) EN 14103 96.5 minimum2 96.8 97.0 98.2 97.1
Free glycerol % EN 14105 0.02 maximum2 0.0069 0.0059 0.0068 0.0039
Total glycerol % EN 14105 0.25 maximum2 0.0604 0.0610 0.0163 0.0347
Monoglyceride % EN 14105 0.8 maximum2 0.1245 0.1722 0.0297 0.0976
Diglyceride % EN 14105 0.2 maximum2 0.1702 0.1730 0.0790 0.1660
Triglyceride % EN 14105 0.2 maximum2 0.1068 0.084 0.077 0.0344

1
Limits specified in ASTM D 6751.
2
Limits specified in EN 14214.
3
Prediction based on ANN.

ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 265
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

fuel and is usually measured using the standard engine

Catalyst reusability study
test, that is, ASTM D 613. However, CN is relatively
difficult to measure and is not always determined owing Catalyst reusability cycles
to the lack of measurement facility [38]. In this work, the
Figure 6 shows the RPO and CPO biodiesel yields and
CN is predicted using Equation 12, which has been dem-
FAME conversions for five consecutive cycles of catalyst
onstrated to produce predicted CN with a level of confi-
reuse. Both yield and conversion decrease after each sub-
dence of greater than 90% [24]. All the predicted CN
sequent cycle. For the first cycle, the yields of RPO and
ranging from 48.1 to 50.4 exceed the minimum value of
CPO are 84.72% and 73.23%, respectively. Meanwhile,
47 required by ASTM D 6751, which indicates good qual-
the conversions of RPO and CPO are 98.18% and
ity combustion in compression ignition engines.
97.04%, respectively. Significantly, both yield and conver-
Overall, the measured biodiesel physicochemical prop-
sion from the fourth cycle reduce to 56.63% and 71.72%,
erties indicate that there are no significant variations in
respectively, for RPO; and 45.91 and 51.23%, respectively,
viscosity, density, flash point, acid value, HHV, and CN
for CPO. Under ultrasonic cavitation, the microbubbles
with the use of ultrasonication as compared to conven-
of reaction products especially glycerol have more poten-
tional mixing. Additionally, all biodiesels produced meet
tial to adsorb onto the CaO surface and generate glycer-
the requirements stipulated in ASTM D 6751. The
oxides species as the alternative active sites [9]. Kouzu
results reveal that not only ultrasonication is effective
et al. [39] reported that glyceroxides species are more
in achieving significantly shorter reaction times for
active than CaO itself in transesterification. However, the
transesterification, but it does not adversely affect bio-
CaO surface does not only adsorb glycerol, but also other
diesel quality.
reaction products which lead to the deactivation of CaO
within the catalyst. Deactivation of catalyst becomes more
FAME conversion and glycerides analysis dominant than generation of glyceroxides species after
each subsequent cycle.
Table 2 also lists the FAME conversions and glycerides
analysis for both RPO and CPO biodiesels produced
under conventional mixing and ultrasonication. The Characterization of recycled catalysts
FAME conversions of all biodiesels exceed the minimum
Figure 7 depicts the SEM images of the catalyst after each
limit of 96.5% specified in EN 14214. In the presence of
cycle while Table 3 lists the BET surface areas of fresh
ultrasound, it can be observed that the FAME conversion
and recycled catalysts, and CaO and Ca concentrations.
improves from 96.8% to 98.2% for RPO, and slightly
The catalyst size increases slightly with each subsequent
improves from 97.0% to 97.1% for CPO.
cycle as shown in Figure 7. Accordingly, as listed in
Irrespective of the mixing method, the CPO biodiesel
Table 3, the BET surface area decreases after each subse-
has lower free glycerol, but higher total glycerol concen-
quent cycle. This may be caused by adsorption of com-
trations as compared to the RPO biodiesel. In addition,
pounds onto the catalyst surface. In general, a larger
higher MG and DG, but lower TG are measured in the
particle size is typically associated with a smaller surface
CPO biodiesel as compared to the RPO biodiesel. For
area which decreases the rate of reaction. As a result,
all biodiesels, both free and total glycerol concentrations
are lowered with the use of ultrasonic cavitation. This
is especially so for CPO whereby the free glycerol is 100 98.18 100
94.69
reduced from 0.0059% to 0.0039% while the total glyc- 90 97.04 91.03 90
84.32
erol is reduced from 0.0610% to 0.0347%. Both the free 80 84.72 80
81.92
71.72
Conversion (%)

and total glycerol concentrations are below the maxi- 70 69.46 70

73.23
66.79
Yield (%)

60 68.85 56.63 60
mums stipulated in EN 14105. For other by-products 51.23
50 58.27 50
including MG, DG and TG, their concentrations are 40 Yield of RPO 40
45.91
reduced under the influence of ultrasonic cavitation. 30 Yield of CPO 30
The observed reductions in these by-products can be 20 Conversion of RPO 20
linked to the good mixing of ultrasonic cavitation 10
Conversion of CPO
10
which promote mass transfer at the liquid–solid inter- 0 0
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5
faces. Due to the enhanced mass transfer, lesser by-
No of cycles
products are formed as more are converted into biodie-
sel. In short, it can be concluded that ultrasonic cavita- Figure 6. Reusability cycle of RPO and CPO biodiesel yield and FAME
tion during transesterification produces biodiesel which conversion (ultrasonic amplitude 60%, catalyst loading 4 wt.%,
meets EN standards in terms of purity. methanol to oil molar ratio 9:1, temperature 45°C, time 30 min).

266 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
W. W. S. Ho et al. Ultrasonic transesterification of palm oils

(A) (B) (C) (D)

50 µm 50 µm 50 µm 50 µm

Figure 7. SEM images (2000 9 magnification) of catalysts from (A) 1st cycle (B) 2nd cycle (C) 3rd cycle and (D) 4th cycle.

respectively. Meanwhile, for the ultrasound-assisted

Table 3. CaO and Ca concentrations, and BET surface areas of fresh
transesterification of CPO, the optimum transesterifica-
and recycled catalysts.
tion conditions are the same except for methanol to oil
CaO concentration Ca concentration BET surface molar ratio, which is at 12:1. Under these conditions, a
Catalyst (wt.%) (wt.%) area (m2/g) yield of 73.23% and an FAME conversion of 97.04% are
Fresh 83 38 3.539 obtained. With the use of ultrasonic cavitation in transe-
2nd cycle 73 34 3.499 sterification, the reaction time is significantly reduced
3rd cycle 64 26 3.423 from a maximum of 360 under conventional mixing to
4th cycle 58 17 3.385 just 30 min. Additionally, the required catalyst loading
5th cycle 53 9 3.359 and methanol to oil molar ratio are reduced as compared
to conventional mixing for comparable yields and conver-
sions. All produced biodiesels have physicochemical prop-
lower biodiesel yields and FAME conversions occur after erties such as kinematic viscosity, density, flash point,
each subsequent cycle. acid value, HHV, and CN within the limits specified in
When ultrasonic cavitation was applied to the transe- ASTM D 6751. The FAME and all glycerides contents are
sterification process, the CaO and Ca concentrations also within the limits specified in EN 14214. The catalyst
decrease after each cycle. Since the obtained Ca concen- can be reused feasibly up to three consecutive cycles after
trations are considered semiquantitative, all the associated regeneration. In conclusion, the potential of palm oil mill
discussions are relying on the figures in Table 3 to obtain fly ash supported calcium oxide (CaO) catalyst to be used
valid trends when parameters are changed. The actual in conjunction with ultrasound-assisted transesterification
magnitudes must be treated with a certain degree of con- to produce RPO and CPO biodiesels has been demon-
servatism. After the fourth cycle, the CaO concentration strated.
decreases from 83 wt.% to 53 wt.% while the Ca concen-
tration decreases from 38 wt.% to only 9 wt.%. This indi- Acknowledgments
cates that the palm oil mill fly ash supported CaO
catalyst experiences leaching in ultrasound-assisted transe- This work was supported by the Ministry of Higher Edu-
sterification. Despite dissolution of CaO and Ca into the cation (MOHE), Malaysia as well as the Faculty of Engi-
reaction mixture, the catalyst can be reasonably reused up neering at The University of Nottingham Malaysia
to three times. Campus. The authors would like to express gratitude to
Havys Oil Mill Sdn. Bhd. for providing the crude palm
oil and Seri Ulu Langat Palm Oil Mill for the supply of
Conclusions palm oil mill boiler ash.
Ultrasound-assisted transesterification of RPO and CPO
to produce biodiesel using a palm oil mill fly ash sup- Conflict of Interest
ported calcium oxide (CaO) catalyst has been investi-
gated. The optimum transesterification conditions for None declared.
RPO under ultrasonic cavitation are 60% ultrasonic
References
amplitude, 30 min reaction time, 4 wt.% catalyst loading,
and 9:1 methanol to oil molar ratio. This results in bio- 1. Georgogianni, K. G., A. K. Katsoulidis, P. J. Pomonis, G.
diesel yield and FAME conversion of 85.23% and 97.02%, Manos, and M. G. Kontominas. 2009. Transesterification

ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 267
Ultrasonic transesterification of palm oils W. W. S. Ho et al.

of rapeseed oil for the production of biodiesel using oil using cesium doped heteropolyacid catalyst:
homogeneous and heterogeneous catalysis. Fuel Process. interactions between process variables. Energy 60:283–291.
Technol. 90:1016–1022. 15. Badday, A. S., A. Z. Abdullah, and K. T. Lee. 2014.
2. Salamatinia, B., H. Mootabadi, S. Bhatia, and A. Z. Transesterification of crude Jatropha oil by activated
Abdullah. 2010. Optimisation of ultrasonic-assisted carbon-supported heteropolyacid catalyst in an ultrasound-
heterogeneous biodiesel production from palm oil: a assisted reactor system. Renew. Energy 62:10–17.
response surface methodology approach. Fuel Process. 16. Guo, W., H. Li, G. Ji, and G. Zhang. 2012. Ultrasound-
Technol. 91:441–448. assisted production of biodiesel from soybean oil using
3. Puna, J. F., J. F. Gomes, M. J. N. Correia, A. P. S. Dias, Bronsted acidic ionic liquid as catalyst. Bioresour. Technol.
and J. C. Bordado. 2010. Advances on the development of 125:332–334.
novel heterogeneous catalysts for transesterification on 17. Boffito, D. C., V. Crocella, C. Pirola, B. Neppolian, G.
triglycerides in biodiesel. Fuel 89:3602–3606. Cerrato, M. Ashokkumar, et al. 2013. Ultrasonic
4. Salamatinia, B., A. Z. Abdullah, and S. Bhatia. 2012. enhancement of the acidity, surface area and free fatty
Quality evaluation of biodiesel produced through acids esterification catalytic activity of sulphated ZrO2-
ultrasound-assisted heterogeneous catalytic system. Fuel TiO2 systems. J. Catal. 297:17–26.
Process. Technol. 97:1–8. 18. Verziu, M., S. M. Coman, R. Richards, and V. I.
5. Kojima, Y., H. Imazu, and K. Nishida. 2013. Physical Parvulescu. 2011. Transesterification of vegetable oils over
and chemical characteristics of ultrasonically-prepared CaO catalysts. Catal. Today 167:64–70.
water-in-diesel fuel: effects of ultrasonic horn position 19. Ho, W. W. S., H. K. Ng, and S. Gan. 2012. Development
and water content. Ultrason. Sonochem. 21:722–728. and characterisation of novel heterogeneous palm oil mill
6. Deshmane, V. G., and Y. G. Adewuyi. 2013. Synthesis and boiler ash-based catalysts for biodiesel production.
kinetics of biodiesel formation via calcium methoxide base Bioresour. Technol. 125:158–164.
catalysed transesterification reaction in the absence and 20. Ho, W. W. S., H. K. Ng, S. Gan, and S. H. Tan. 2014.
presence of ultrasound. Fuel 107:474–482. Evaluation of palm oil mill fly ash supported calcium
7. Badday, A. S., A. Z. Abdullah, and K.-T. Lee. 2013. oxide as a heterogeneous base catalyst in biodiesel
Optimisation of biodiesel production process from synthesis from crude palm oil. Energy Convers. Manage.
Jatropha oil using supported heteropolyacid catalyst and 88:1167–1178.
assisted by ultrasonic energy. Renew. Energy 50:427–432. 21. EN 14103. 2003. Fat and oil derivatives – Fatty Acid
8. Kumar, D., G. Kumar, Poonam, C.P. Singh. 2010. Methyl Esters (FAME) – Determination of ester and
Ultrasonic-assisted transesterification of jatropha curcas oil linolenic acid methyl esters contents.
using solid catalyst, Na/SiO2. Ultrason. Sonochem. 17:839– 22. EN 14214. 2003. Automotive fuels – Fatty Acid Methyl
844. Esters (FAME) for diesel engines – Requirements and test
9. Choedkiatsakul, I., K. Ngaosuwan, and S. Assabumrungrat. methods.
2013. Application of heterogeneous catalysts for 23. EN 14105. 2003. Fat and oil derivatives – Fatty Acid
transesterification of refined palm oil in ultrasound-assisted Methyl Esters (FAME) – Determination of free and total
reactor. Fuel Process. Technol. 111:22–28. glycerol and mono-, di- and triglyceride contents.
10. Choudhury, H. A., S. Chakma, and V. S. Moholkar. 2013. 24. Cheenkachorn, K. 2004. Prediction properties of biodiesels
Mechanistic insight into sonochemical biodiesel synthesis using statistical models and artificial neural network. Sust.
using heterogeneous base catalyst. Ultrason. Sonochem. Energy Environ. 3003:176–179.
21:169–181. 25. Naresh, N. M., and G. A. Yusuf. 2009. Optimisation of the
11. Mootabadi, H., B. Salamatinia, S. Bhatia, and A. Z. synthesis of biodiesel via ultrasound-enhanced base-
Abdullah. 2010. Ultrasonic-assisted biodiesel production catalysed transesterification of soybean oil using a
process from palm oil using alkaline earth metal oxides as multifrequency ultrasonic reactor. Energy Fuels 23:2757–
the heterogeneous catalysts. Fuel 89:1818–1825. 2766.
12. Salamatinia, B., H. Mootabadi, I. Hashemizadeh, and A. Z. 26. Naresh, N. M., and G. A. Yusuf. 2010. Application of
Abdullah. 2013. Intensification of biodiesel production taguchi method to investigate the effects of process
from vegetable oils using ultrasonic-assisted process: parameters on the transesterification of soybean oil using
optimisation and kinetic. Chem. Eng. Process. 73:135–143. high frequency ultrasound. Energy Fuels 24:2120–2126.
13. Badday, A. S., A. Z. Abdullah, and K. T. Lee. 2013. 27. Wu, P., Y. Yang, J. A. Colucci, and E. A. Grulke. 2007.
Ultrasound-assisted transesterification of crude Jatropha Effect of ultrasonication on droplet size in biodiesel
oil using alumina-supported heteropolyacid catalyst. Appl. mixtures. J. Am. Oil Chem. Soc. 84:877–884.
Energy 105:380–388. 28. Omotola, B., P. Leslie, A. Bamikole, and A. Farouk. 2009.
14. Badday, A. S., A. Z. Abdullah, and K. T. Lee. 2013. Low-cost feedstock conversion to biodiesel via ultrasound
Ultrasound-assisted transesterification of crude Jatropha technology. Energies 3:1691–1703.

268 ª 2015 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
W. W. S. Ho et al. Ultrasonic transesterification of palm oils

29. Stavarache, C., M. Vinatoru, R. Nishimura, and Y. Maeda. compounds as catalysts for the methanolysis of sunflower
2005. Fatty acids methyl esters from vegetable oil by oil. Catal. Today 133–135:305–313.
means of ultrasonic energy. Ultrason. Sonochem. 12:367– 35. Kawashima, A., K. Matsubara, and K. Honda. 2009.
372. Acceleration of catalytic activity of calcium oxide for
30. Stavarache, C., M. Vinatoru, and Y. Maeda. 2006. biodiesel production. Bioresour. Technol. 89:1818–
Ultrasonic versus silent methylation of vegetable oils. 1825.
Ultrason. Sonochem. 13:401–407. 36. Georgogianni, K. G., M. G. Kontominas, P. J. Pomonis, D.
31. Stavarache, C., M. Vinatoru, and Y. Maeda. 2007. Aspects Avlonitis, and V. Gergis. 2008. Alkaline conventional and
of ultrasonically assisted transesterification of various in situ transesterification of cottonseed oil for the
vegetable oils with methanol. Ultrason. Sonochem. 14:380– production of biodiesel. Energy Fuels 22:2110–2115.
386. 37. Encinar, J. M., J. F. Gonzalez, and A. Rodriguez-
32. Dias, A. P. S., J. Puna, M. J. N. Correia, I. Nogueira, J. Reinares. 2007. Ethanolysis of used frying oil.
Gomes, and J. Bordado. 2013. Effect of the oil acidity on Biodiesel preparation and characterization. Fuel
the metholysis performances of lime catalyst biodiesel Process. Technol. 88:513–522.
from waste frying oils (WFO). Fuel Process. Technol. 38. Encinar, J. M., J. F. Gonzalez, and A. Pardal. 2012.
116:94–100. Transesterification of castor oil under ultrasonic
33. Kotwal, M. S., P. S. Niphadkar, S. S. Deshpande, V. V. irradiation conditions. Preliminary results. Fuel Process.
Bokade, and P. N. Joshi. 2009. Transesterification of Technol. 103:9–15.
sunflower oil catalysed by flyash-based solid catalysts. Fuel 39. Kouzu, M., S.-Y. Yamanaka, J.-S. Hidaka, and M.
88:1773–1778. Tsunomori. 2009. Heterogeneous catalysis of calcium
34. Arzamendi, G., E. Arguinarena, I. Campo, S. Zabala, and oxide used for transesterification of soybean oil with
L. M. Gandia. 2008. Alkaline and alkaline earth metals refluxing methanol. Appl. Catal. A 355:94–99.

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