Journal of Industrial and Engineering Chemistry 17 (2011) 138–143

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Journal of Industrial and Engineering Chemistry

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

Ultrasonic energy effect on vegetable oil based biodiesel synthetic process

Seung Bum Lee a, Jae Dong Lee b, In Kwon Hong a,*
a
Department of Chemical Engineering, Dankook University, 448-701, Republic of Korea
b
Division of Energy & Biological Engineering, Kyungwon University, 461-701, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: The manufacturing process of vegetable oil based biodiesel was introduced in experimental manner.
Received 8 June 2010 Ultrasonic energy was irradiated to induce the transesterification of the vegetable oil. The ultrasonic
Accepted 23 July 2010 irradiation had two effects, those were heating and mixing of the reactants. We performed the
Available online 25 December 2010
experiment under various manufacturing parameters, viz. the ultrasonic irradiation time, sonic power,
and irradiation type at constant reaction temperature, 55 8C. The ultrasonic irradiation biodiesel
Keywords: synthetic process reduced the reaction time by 30 min or more comparing to existing processes. The
Ultrasonic energy
ultrasonic energy densities (Ua) were calculated from the experimental data. The highest yield and
Biodiesel
methyl ester content were observed at an ultrasonic power of more than 450 W. The reaction conditions
Transesterification
Methyl ester content were also adjusted to stabilize the reaction media temperature.
ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
The development of renewable energy sources that can replace
fossil fuels such as oil, coal, and natural gas, can prevent depletion
of the available energy resources and environmental pollution.
Also, it can contribute to reduce greenhouse gas emissions.
Biodiesel (BD) consisting of a mixture of alkylesters resulting from
the transesterification reaction of vegetable oil is a source of
biodegradable clean energy, and it does not produce carcinogenic
aromatic polymer compounds or sulfoxides during its combustion.
In addition, the oxygen content of 11–15% in the molecular
structure accelerates the combustion process in diesel engines and
reduces pollutants such as fine particles, soot, and carbon
monoxide when the biodiesel is used as a mixed fuel with
petroleum diesel [1–5]. Its larger cetane number and higher
lubricity than petroleum diesel in compression ignition engines
allow biodiesel to be applied to the compression ignition engine as
shown in Table 1. Also, the modification of the engine is not
required when biodiesel is mixed with petroleum diesel in small
quantities, and it reduces the lubrication properties. However, the
poor fuel stability of biodiesel may cause corrosion or damage to
the metal engine and, therefore the acid value and moisture
content must be controlled in the biodiesel synthetic process. The
use of qualified biodiesel prevents the injector of the engine from
suffering from clogging and the sedimentation of carbon. In
addition to these problems, biodiesel has some defects such as its
high fluidity compared with petroleum diesel and its competition
with edible food.
However, despite these disadvantages, the production and usage
of biodiesel will increase in near future. Vegetable oil as a raw
material for biodiesel is usually composed of free fatty acids,
phospholipids, sterol, water and other impurities. It cannot be
directly used as a fuel because it has high viscosity. Chemical
transformation must be performed, including esterification, pyroly-
sis and emulsification [6,7]. The esterification reaction was first
introduced in the form of the alcohol decomposition of castor oil by
Rochieder in 1846 and many researchers have studied the
production processes of a variety of biodiesels, such as the acid–
base catalyst reaction, enzyme esterification, ultrasonic energy
method and supercritical fluid media reaction method [8–12].
In this study, the irradiation of ultrasonic energy was used for the
esterification of vegetable oils to shorten the reaction time and to
increase the product efficiency [13–15]. Ultrasound has a short
wavelength, slow transfer rate, and high energy transmittance as the
vibrating type energy. The cavitation in the ultrasonic wavelength is
the phenomenon of expansion and contraction of the transfer media
bubbles. Then, the ultrasonic energy is propagated into the solution
by the destruction of the pressurized microbubbles. The energy is
used in the biodiesel production process, in which vegetable oil is
esterified in a short time to obtain a higher yield.
2. Experimental method

2.1. Biodiesel synthesis using ultrasonic energy

* Corresponding author. Tel.: +82 31 8005 3544; fax: +82 31 8005 3536. Esterification is the process required for the production of
E-mail address: khong@dankook.ac.kr (I.K. Hong). environmentally benign fuel from the vegetable oil and it

1226-086X/$ – see front matter ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2010.12.012
 S.B. Lee et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 138–143 139

Table 1 performed using methanol and alkaline catalysts. Canola oil,

The properties of biodiesel and petroleum diesel.
soybean oil, and corn oil were used for the synthesis of biodiesel in
Properties Biodiesel Diesel this experimental work. Ultrasound was irradiated onto a mixture
Specific gravity 0.87–0.89 0.84–0.86 of vegetable oil and methanol mixture at a mole ratio of 1:6, so that
Cetane number 46–70 47–55 then the vegetable oil was esterified at 55 8C [10]. The reaction
Cloud point (K) 262–289 256–265 temperature was controlled by the pulse time of ultrasonic
Pour point (K) 268–286 237–243 irradiation. A probe type generator (VCX-600, D = 0.5 in., threaded
Flash point (K) 408–423 325–350
end, amplitude = 124 nm, Sonics & Material Co., USA) was used for
Sulfur (wt%) 0.0000–0.0024 0.04–0.01
Ash (wt%) 0.002–0.01 0.06–0.01 the ultrasonic irradiation. The power range of ultrasound was set
Kinematic viscosity at 313 K (cSt) 3.7–5.8 1.9–3.8 from 150 to 750 W and the irradiation time was controlled from 20
Higher heating value (MJ/kg) 39.3–39.8 45.3–46.7 to 40 min. The amount of potassium hydroxide (KOH) was 1 wt% of
[()TD$FIG]

Fig. 1. GC chromatogram for identification of FAME.

140 [()TD$FIG]
S.B. Lee et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 138–143

the vegetable oil and used in the form of a mixed solution with 100

methanol. After the esterification processing,the glycerol layer was

98
removed with a separating funnel. The biodiesel was washed with
ultrapure water to remove the basic catalyst and unreacted
96
components. Finally, the fatty acid methyl ester (FAME) was
analyzed with various analytical instruments to identify its

Methyl Ester Content [%]

94
physical characteristics such as the viscosity, heat capacity, and
heating value.
92

2.2. Identification of synthetic biodiesel

90

After esterification, the composition of the biodiesel was 88

analyzed by gas chromatography (GC–FID) using a ACME 6100
model (Young-Lin, Korea). The oven temperature was elevated 86 Canola Oil
from 140 8C (1 min) to 245 8C at a heating rate of 5 8C/min during Soybean Oil
the analytical procedure. The temperature of the sample injection 84 Corn Oil
port and detection part was kept constant at 250 8C using a HP-
Innowax column with a column length of 30 m and diameter of 82
0.32 mm. The mobile phase was high-purity nitrogen, the column 20 30 40 50 60 70 80
o
flow rate was 3 mL/min, and the split ratio was 10:1. Temperature [ C]

Fig. 2. Variation of ME content with reaction temperature for vegetable oils.

2.3. Measuring of heat capacity

The heat capacity of the vegetable oils was measured by the DSC
sapphire method (DSC822e, Mettler Toledo, Switzerland). A 3 mg
sample of the vegetable oil was loaded in an aluminum pan with a
volume of 20 mL. A three step measurement process was used,
consisting of the blank test, sapphire test and sample test. Then
samples were heated from 20 to 160 8C, with the heating rate of
10 8C/min. The atmosphere was kept with nitrogen at the rate of
80 mL/min.
3. Results and discussion
3.1. FAME analysis
The fatty acid methyl ester (FAME) synthesized by the
esterification of vegetable oils was identified by GC–FID analysis
and the chromatogram of the FAME produced using ultrasound
irradiation is shown in Fig. 1. The FAME derived from the principal
component of the vegetable oil contained carbon chains ranging
from C16:0 to C18:3 in its chromatogram. From the chromatogram,
methyl ester (ME) and linolenic acid methyl ester (LAME) contents
were calculated as follows:
½SA  AEI C EI V EI
ME contentð%Þ ¼   100
AEI m
AL
LAME contentð%Þ ¼  100 (2)
½SA  AEI
P
where [ A] is the total peak area of the C14:0 to C24:1 FAME in the
chromatogram, also AEI, CEI, and VEI stand for the peak areas of the
characteristics for various reaction temperatures and stirring
speed ranges. Fig. 2 shows the temperature dependence on the
esterification of the vegetable oils. The ME content in the biodiesel
was measured at the reaction temperatures of 30–70 8C. The mole
ratio between vegetable oil and methanol was 1–6, the stirring
speed was 300 rpm, and the reaction time was 1 h. The ME content
increased with increasing reaction temperature, but slightly
decreased at the temperature higher than 55 8C. This phenomena
can be explained as evaporation of methanol due to the boiling
temperature of methanol of 64.7 8C, which results in its above
55 8C and decreases the possibility of the vegetable oil molecules
coming into contact with it. Due to this reason, the esterification
reaction time must be controlled and the reaction temperature
kept lower than 55 8C. The ME contents at 55 8C were 97.6, 96.4,
and 91.2% for canola oil, soybean oil, and corn oil, respectively. The
canola oil showed the highest conversion for biodiesel production
among the three vegetable oils. The variation of the ME content of
the vegetable oils with the stirring speed rate is presented in Fig. 3.
The ME contents of the vegetable oils increased with increasing
[()TD$FIG]
100
(1)
98
96
94
Methyl Ester Content [%]

internal standard, methylheptadecanoate (C17:0), the concentra- 92

tion, and the sample volume (mL), respectively. In addition, AL is
the peak area of linolenic acid methyl ester, and m is the amount of 90
biodiesel (mg). EU biodiesel standard (EN 14214) requires ME
content and a LAME content, more than 96.5% and less than 12%, 88
respectively, for the BD100.
86 Canola Oil
3.2. Temperature and stirring effect without ultrasound Soybean Oil
84 Corn Oil
A preliminary experiment was conducted to observe the
82
ultrasonic effect on the process in comparison with conventional 0 100 200 300 400 500 600 700
heating method. The comparison between the conventional Stirring Speed [rpm]
heating method and the ultrasonic irradiation procedure was
analyzed and was compared with in terms of the esterification Fig. 3. Variation of ME content with stirring speed for vegetable oils.
[()TD$FIG] [()TD$FIG]
S.B. Lee et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 138–143 141

110 (a) Canola oil

100

100 98

95
90
93

Percent [%]
80 90
BioDiesel Yield
Temperature [ºC]

Methylester(ME) Content
88 Linolenic acid ME Content
70
85
10
9
60 8
7
Canola Oil 6
150 300 450 600 750
50 Soybean Oil
Corn Oil (b) Soybean oil
100
40
90 120 150 180 210 240 270 300 330 360 98
Ultrasonic Irradiation Time [s]
95
Fig. 4. Temperature increase as a function of the ultrasonic irradiation time for the
vegetable oils. 93

Percent [%]
90

stirring speed up to 300 rpm and was constant at above 399 rpm of 88
stirring speed.
85
8
3.3. Ultrasonic energy density analysis 7
6
5
The ultrasonic energy density was analyzed by the method of 150 300 450 600 750
Zarzycki et al. [17]. They measured the ultrasonic energy density in
the ultrasound induced solvent extraction. According to this (c) Corn oil
reference, the temperature of vegetable oil was measured as a 100
function of the irradiation time in an insulated container. The data
98
of the temperature change with the irradiation time were
linearized by the least square method and the real ultrasonic 95
power (Pa) was calculated from the slope of the curve.
93
Percent [%]

energy
Pa ¼ (3) 90
time
If Pa is constant for the irradiation time and volume of vegetable 88
oil, the ultrasonic energy density as a function of the ultrasonic
85
power and irradiation time can be calculated as following manner: 2
1
t
U a ¼ Pa  t a ¼ Pa  (4) 0
V 150 300 450 600 750

where t is the irradiation time (s) and V is the volume of vegetable
oil (mL).
In this study, the ultrasonic energy density was calculated using
the experimental temperature change under constant vegetable oil
volume and temperature. Fig. 4 shows the irradiation time
variation on the temperature of the vegetable oil under constant
ultrasonic power of 450 W. The ultrasound was irradiated
continuously onto a fixed volume of vegetable oil, viz. 100 mL.
The reaction temperature increased according to the first order
equation with the irradiation time increment from 90 to 360 s. The
increasing rates of the vegetable oil temperature were 9.44, 9.33,
Ultrasonic Irradiation Power [W]
Fig. 5. Variation of BD properties with ultrasonic irradiation power for vegetable
oils.
and 8.67 8C/min for canola, soybean and corn oil, respectively.
Canola oil exhibited a largest temperature increase among the
vegetable oils. The heat capacity was correlated with the
temperature based on the DSC experimental data for each
vegetable oil. The mean heat capacity, Cp , was calculated by
using the following equation under temperature range from 55 to

Table 2
Energy density of various vegetable oils.

Vegetable oil r (g/cm3) A B  103 C  105 Cp (J/g K) Pa (J/s)

Canola 0.893 4.1047 10.6 1.8836 2.8055 394.35

Soybean 0.888 4.8416 13.4 2.0333 2.6989 372.81
Corn 0.828 3.7315 8.2 1.4782 2.7644 330.62
142 S.B. Lee et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 138–143

155 8C. calculated as follow.

C p ¼ A þ BT þ CT 2 (5) amount of methyl ester ðgÞ

BD yield ð%Þ ¼  100 (6)
amount of vegetable oil ðgÞ
Then, the ultrasonic power (Pa) was calculated from the average
density, mean heat capacity of the vegetable oil, and ultrasonic The esterification reaction was performed for 30 min under the
irradiation time (270 s). The results are presented in Table 2. When conditions of the molar ratio of vegetable oil to methanol of 1–6
the ultrasonic power was constant and the reaction time was fixed and 1 wt% of the alkaline catalyst, KOH. The reaction temperature
at 30 min, the ultrasonic energy densities (Ua) irradiated in the was constant at 55 8C by using the pulse type irradiation.
experiment were 6337.8, 5959.7, and 4926.5 kJ L1 for canola, The BD yield increased with increasing irradiation power from
soybean and corn oil, respectively. 150 to 450 W. However, the ME content decreased when the
irradiation power above 450 W. This phenomenon resulted from
3.4. Effect of ultrasonic irradiation power the reduction of the real reaction time by the extension of the pulse
time used for controlling the reaction temperature when the
Fig. 5 shows the ME content and BD yield for the ultrasound irradiation power was increased. However, when the reaction
[()TD$FIG]
induced vegetable oil esterification process. The BD yield was temperature was constant, a larger BD yield and ME content were
obtained comparing to the case where the pulse interval was
(a) Canola oil reduced or ultrasound was irradiated continuously. The real
100 irradiation time decreased with irradiation strength to keep the
constant reaction temperature, 55 8C. Therefore, it can be
98
concluded that the pulse type irradiation at a power of 450 W
95 was the optimum procedure.
Percent [%]

93
3.5. Effect of irradiation time
90 BioDiesel Yield
Methylester(ME) Content Fig. 6 shows the variation of the ME content and BD yield
88 Linolenic acid ME Content with the ultrasonic irradiation time for the esterification of the
vegetable oil. The other variables, viz. the ultrasound power,
85
10 reaction temperature, vegetable oil/methanol molar ratio, and
9
8 the amount of KOH, were kept constant. The ultrasound
7
6 power, reaction temperature, vegetable oil/methanol molar
15 20 25 30 35 40 45 ratio, and amount of KOH were 450 W, 55 8C, 1–6, and 1 wt%,
respectively.
(b) Soybean oil The BD yield and ME content were both 95% at the reaction time
100
of 30 min for the three vegetable oils. The canola oil showed largest
98 BD yield (97.4%) and ME content (97.5%) among three types of oils
at the reaction time of 30 min. The temperature increasing effect
95
was small for canola oil because of the large heat capacity. Then the
Percent [%]

93 ultrasound irradiation pulse interval must be reduced. This

ultrasound irradiation method shortened the reaction time more
90 than 30 min comparing to the conventional heating method and
showed an excellent conversion rate [16–18].
88

85 4. Conclusion
8
7
6 Ultrasonic energy was irradiated onto the vegetable oil during
5 biodiesel synthetic process. The ultrasonic irradiation had
15 20 25 30 35 40 45
alternating mixing and heating effect comparing to conventional
(c) Corn oil biodiesel synthetic process. The ultrasound irradiation reduced
100 reaction time and improved biodiesel properties without any
additional mixing step in the vegetable oil esterification process.
98
The results can be summarized as follows:
95
1. The BD yield increased with increasing ultrasonic power from
Percent [%]

93 150 to 450 W, but the ME content decreased at ultrasonic

90
powers over 450 W. This is due to the decrease of the real
irradiation time caused by the increase in the pulse interval
88 required for tuning the temperature due to the extension of the
irradiation power.
85
2 2. The BD yield and ME content were both 95% at the reaction time
1 of 30 min for all of the three vegetable oils. The canola oil
0 exhibited best biodiesel properties of other two oils. This
15 20 25 30 35 40 45 improvement phenomenon can be explained and was consid-
Ultrasonic Irradiation Time [min] ered to be due to the larger ultrasonic energy density, Ua of
6337.8 kJ L1, compared to the other two vegetable oils at an
Fig. 6. Variation of BD properties with ultrasonic irradiation time for vegetable oils. ultrasound irradiation time of 30 min.
 S.B. Lee et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 138–143
3. The ultrasound irradiation method enabled to reduce the
reaction time by 30 min or more comparing to conventional
heating method. Also this method improved conversion rate.
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