Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106

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Chemical Engineering & Processing: Process Intensification

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Transesterification of vegetable oil with methanol using solid base catalyst T

of calcium oxide under ultrasonication
⁎
Yoshihiro Kojimaa, , Shinya Takaib
a
Institute of Materials and Systems for Sustainability, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8603, Japan
b
Department of Chemical Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8603, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: Transesterification of vegetable oil with methanol using calcium oxide as a solid base catalyst was carried out
Transesterification under ultrasonication and mechanical stirring conditions, and the transesterification rate was compared. In
Biodiesel addition, the effects of ultrasonic power, catalyst mass and molar ratio of methanol to oil on methanolysis rate of
Calcium oxide oil under ultrasonication were investigated. The biodiesel yield reached 88% at about 2.5 and 5 hs under ul-
Ultrasonication
trasonication and mechanical stirring, respectively, thus demonstrating that ultrasonication was more effective
Methanolysis rate
method for the acceleration of transesterification rate. The increase in both the ultrasonic power per unit volume
of mixture solution and the catalyst mass resulted in an increase in the methanolysis rate. It was found that the
larger amount of methanol in an excess over the stoichiometric amount to oil played more significant role in
enhancement of production rate of biodiesel in early reaction period limited by mass transfer of oil, but was less
favorable for the enhancement of methanolysis rate in the reaction period limited by chemical reaction.

1. Introduction purification of biodiesel product by applying the heterogeneous base

Recently, biofuels have widely been used around the world, due to
the increase in energy demand and concerns about energy and en-
vironmental issues such as the depletion of fossil fuels and greenhouse
warming. Especially, fatty acid methyl esters (FAMEs), also called
“biodiesel fuel”, have become an alternative fuel for diesel engines,
because they have similar fuel properties to fossil fuel and can be used
without any modification of the engines [1]. Biodiesel is most com-
monly produced by transesterification reactions of vegetable oils with
mono-alkyl alcohol such as methanol. The formula scheme for the
production of FAMEs out of triglyceride is as shown below [2,3]
Scheme1,
In order to shift the equilibrium to the right of reaction shown in
Scheme 1, alcohol is commonly added in an excess over the stoichio-
metric amount. For the production process of FAMEs, homogeneous
catalyst such as sodium hydroxide (NaOH) or potassium hydroxide
(KOH) is commonly used [4,5]. High conversion of triglyceride can be
achieved in comparatively short reaction times under mild conditions
in the presence of homogeneous catalyst. On the contrary, its dis-
advantage is that homogenous catalysts can not be reused. Moreover,
several washing steps are usually required to remove the catalyst re-
sidues from the ester products, giving rise to increased costs of biodiesel
production [5–9]. Hence, an attempt has been made to simplify
catalyst such as calcium oxide which can be recovered from mixture
solution. However, the reaction rate of transesterification by hetero-
geneous catalyst is relatively slower compared to that by homogeneous
catalyst [5]. In order to understand characteristics of transesterification
in the presence of heterogeneous catalysts, improve the transester-
ification reaction rate and explore the reaction mechanism, many re-
searchers have studied the transesterification reaction of vegetable oil
to biodiesel for many types of heterogeneous catalysts such as MgO,
CaO, BaO, PbO, MnO2, K2CO3/c-Al2O3, KF/c-Al2O3 and CaO/SiO2
[2,5,10–18]. Singh and Fernando investigated the transesterification
kinetics of heterogeneous catalysts of MgO, CaO, BaO, PbO and MnO2,
with soybean oil and reported that heterogeneous catalysts require
much higher temperatures and pressures to achieve acceptable con-
version levels compared to homogeneous catalysts [2]. For transester-
ification of soybean oil using CaO catalyst, Kouzu et al. reported that
CaO catalyst prepared via calcination in a helium gas flow more sig-
nificantly had activity compared with that in an ambient air [13].
Granados et al. investigated the influence of H2O and CO2 on the de-
terioration of the catalytic performance by contact with room air and
reported that CO2 is the main deactivating agent [10]. Liu et al. re-
ported that water content in methanol resulted in a significant increase
in biodiesel yield in transesterification reaction process in the presence
of CaO [5]. Kouzu et al. investigated an active phase of CaO by

⁎
Corresponding author.
E-mail address: ykojima@imass.nagoya-u.ac.jp (Y. Kojima).

https://doi.org/10.1016/j.cep.2018.12.007
Received 14 March 2018; Received in revised form 15 December 2018; Accepted 16 December 2018
Available online 19 December 2018
0255-2701/ © 2018 Elsevier B.V. All rights reserved.
Y. Kojima, S. Takai
Scheme 1. Transesterification of triglyceride oil to biodiesel.
characterizing the catalyst collected after achieving the conversion of
soybean oil into its methyl ester at reflux of methanol in a glass batch
reactor and indicated that CaO combined with the by-produced glycerol
to form calcium diglyceroxide as a major component of the collected
catalyst [16,17]. They also investigated the characteristics of transes-
terification using calcium diglyceroxide [16]. In the methanolysis
process of sunflower oil using CaO calcined at various temperatures,
Veljković et al. studied the kinetics of methanolysis under mechanical
stirring condition [14]. They analyzed the kinetics of methanolysis of
sunflower oil on the following assumptions: “the overall methanolysis
rate in the initial reaction period is limited by the triglyceride mass
transfer rate towards the active sites of catalyst surface; in the later
reaction period, the overall methanolysis rate is limited by the rate of
the chemical reaction between a methoxide ion and triglyceride; and
the conversion of triglyceride follows the pseudo-first order reaction
kinetics. According to the assumptions, the rates of triglyceride mass
transfer and triglyceride reaction have about the same value:
dcA m NaOH and KOH, and have reported that the ultrasonication is useful for
(−rA ) = − = k s,A⋅θ⋅am⋅(cA − cA,s)⋅ cat = k mt,A⋅(cA − cA,s) = k⋅cA,s,
dt V the enhancement of production rate of biodiesel [30–38].
where (-rA) [mol･dm−3･min-1] is the rate of triglyceride consumption,
cA [mol･dm−3] is the triglyceride concentration in the liquid phase; t
[min] is the reaction time; ks,A [m･min-1] is the triglyceride mass
transfer coefficient; θ [-] is the fraction of the available active specific
catalyst surface; am [m2･g-1] is the active specific catalyst surface; cA,s
[mol･dm−3] is the concentration of triglyceride adsorbed on the cata-
lyst surface per liquid phase volume; mcat [g] is the catalyst mass; V
[m3] is the reaction mixture volume; kmt,A [min-1] is the volumetric
triglyceride mass transfer coefficient; and k [min-1] is the pseudo-first
order reaction rate constant. By rearranging Eq. (1), the following
equation can be obtained:
dcA k⋅k mt,A
− = ⋅cA = kapp⋅cA,
dt k mt,A + k
−1
where kapp [min ] is the apparent rate constant which is related to the
mass transfer, as well as the chemical reaction rate. When kmt,A is sig-
nificantly smaller than k in the initial phase, then
− ln(1 − xA ) = kapp t + C = k mt,A t + C ,
where xA [-] is the conversion of triglyceride and C [-] is the integration
constant. As the reaction proceeds, the amount of methanol adsorbed
on the active catalyst surface decreases, while the fraction of the
available active catalyst surface for triglyceride adsorption and the
volumetric triglyceride mass transfer coefficient increase. When kmt,A is
significantly larger than k in the initial phase, then
− ln(1 − xA ) = kapp t + C = kt + C ,
and the chemical reaction between triglyceride and methanol controls
the overall methanolysis rate. Thus, Veljković et al. applied the pseudo-
first-order reaction kinetics model to the methanolysis, and determined
the methanolysis rate constants, km (= kapp = kmt,A) and kc (= kapp =
k), in a triglyceride mass transfer controlled regime and a subsequent
chemical reaction controlled regime, respectively.
Our research interest was focused on ultrasonically assisted
Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106
synthesis of biodiesel fuel using a solid catalyst such as CaO, because it
appeared that physical/chemical and heating effects induced by ultra-
sound were capable of improving transesterification reaction rate of
vegetable oil with mono-alkyl alcohol in the presence of solid catalyst.
High power ultrasound technique has been applied for the preparation
of solution, the synthesis and destruction of chemical species, the im-
provement and acceleration of chemical reaction rate and the pre-
paration of materials [19–25]. During ultrasound propagation in a li-
quid, the liquid flow which is termed acoustic streaming would
generate in the same direction as the ultrasound wave propagation. In
addition, high power ultrasonic irradiation to a solution causes the
formation, growth and collapse of cavitation bubbles in the solution.
The implosive collapse of the cavitation bubbles during the adiabatic
compression creates a local field with an enormous temperature of ～
5000 K and pressures of ～100 MPa, also called “hotspot”. In/around
the hotspot, molecules solvent and dissolved gas species are decom-
posed pyrolytically to produce free-radicals. The chemical reactions
proceed by contact the radicals with molecule and/or the other radi-
cals; chemical effect of ultrasound arises. The compression, expansion
and collapse of the cavitation bubbles also cause the formation of mi-
crostreaming, high-speed microjets and generation of the shockwave in
the solution [26–29]. The physical effects due to acoustic streaming,
high-speed microjets, microstreaming and shockwave enable us to
agitate solution effectively. They also play an important role in not only
disruption of immiscible liquid layers but also acceleration of mass
transfer at the liquid-solid or/and liquid-liquid interface regions. Sev-
eral researchers have investigated ultrasound application for synthesis
of biodiesel fuel in the presence of homogeneous catalysts such as
(1) In this study, an attempt was made to synthesize biodiesel fuel via
the transesterification reactions of soybean oil with methanol using CaO
solid catalyst under ultrasonic irradiation. The pseudo-first-order re-
action kinetics model was applied to the methanolysis of soybean oil to
determine the respective methanolysis rate constants, km and kc, in a
triglyceride mass transfer controlled regime and a subsequent chemical
reaction controlled regime. We compared the difference in the metha-
nolysis rates of oil between ultrasonic treatment and mechanical stir-
ring treatment. In addition, the effects of ultrasonic power, catalyst
mass and molar ratio of methanol to oil on the methanolysis rate of oil
were investigated under ultrasonication.
2. Experimental
(2) 2.1. Reagents
Soybean oil, methanol (CH3OH), calcium carbonate (CaCO3), hy-
drogen chloride (1 mol･l−1 HCl aq) and heptane (CH3(CH2)5CH3, 99+
%) were purchased from Wako Chemicals. Co. Soybean oil used in this
(3) work had a saponification value of 188–195 and an iodine value of 123-
142. Density (specific gravity) of soybean oil was 0.925 g･cm-3 (298 K).
Methyl heptadecanoate (CH3(CH2)15COOCH3, 97+%) was obtained
from Tokyo Chemical Co.
2.2. Preparation of calcium oxide catalyst
To prepare calcium oxide (CaO) catalyst, CaCO3 was calcinated in a
(4)
tubular furnace under helium atmosphere. During the calcination
treatment, the temperature rose at the rate of 6 K･min−1 from room
temperature and was kept at 1273 K for 5 h, followed by cooling down
at the rate of 6 K･min−1 until room temperature. The results of XRD
analysis in Fig. 1 reveal the complete conversion of CaCO3 to CaO via
the calcination treatment. The specific surface area and mean particle
diameter of the CaO obtained after the calcination of CaCO3 was about
7.98 m2･g−1 and 18.7 μm, respectively.
102
Y. Kojima, S. Takai
Fig. 1. XRD analysis of materials prepared by calcination of CaCO3.
2.3. Experimental apparatus and operating conditions
Fig. 2 shows a schematic diagram of the experimental apparatus and
a photograph of reaction vessel. A reaction vessel consists of a stainless-
steel cylindrical vessel (Honda Electronics) and a glass cap equipped
with a reflux. The stainless-steel cylindrical vessel has a double tube
structure (inner diameter, φ50 mm and height, 115 mm). The bottom of
the vessel played a role of vibrating plate to which a Langevin type
transducer with a diameter of 45 mm is attached. A mixture of me-
thanol, soybean oil and CaO catalyst was situated in the vessel equipped
with a thermocouple (Copper and constantan, Omega Engineering Inc.)
which is connected with a temperature recorder (NR-500, NR-TH08,
Keyence Corp.) and a personal computer. Temperature of the mixture
was maintained at 333 K during reaction using a circulating water bath.
During transesterification reactions, either the mixture in a reaction
vessel was irradiated with ultrasound or it was agitated by mechanical
stirring. Ultrasound (about 43 kHz) was emitted into the mixture from
the transducer using a power amplifier (Honda Electronics L-400BM-L)
and a function generator (NF W1946B). Ultrasonic power emitted was
measured by calorimetry as recommended elsewhere [39]. The ultra-
sonic power PUS was calculated using the following equation:
ΔT
PUS = MCP
Δt
where M, CP and ΔT/Δt denote liquid mass, specific heat of liquid at
constant pressure and rate of temperature rise, respectively. For a tra-
ditional stirring process, a stirring device and rotor blades were used.
Fig. 2. Schematic diagram of the experimental apparatus and photograph of reaction vessel.
Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106
The revolution rate of rotor blades was 400 rpm.
During the reaction, the samples (0.5 mL) were removed from the
reaction mixture at 15 or 30 min time interval, immediately quenched
by adding 0.2 mL HCl solution (0.1 mol･L−1) to neutralize the CaO, and
then centrifuged (2500 rpm, 10 min). 250 mg of products mixture was
withdrawn from the upper ester layer of the centrifuged mixture and
dissolved in a 5 mL heptane solution including the 50 mg methyl hep-
tadecanoate. The prepared solution was used to determine the amount
of methyl ester formed in the transesterification reaction by gas chro-
matographic analysis.
The molar ratio of methanol to soybean oil was in the range of
6:1–18:1. The volume of soybean oil was 70 mL except when the effect
of molar ratio of methanol to soybean oil under the same mixture vo-
lume on the methanolysis rate of oil was investigated. The mass ratios
of CaO catalyst to soybean oil were 0.5, 1.0 and 1.5 wt%.
2.4. Measurement
The amount of methyl ester formed in the transesterification reac-
tion was measured by GC-FID (GC-4000, GL Sciences Inc.) equipped
with a column (Inart-cap 225, GL Sciences Inc.). Oven temperature,
injector temperature and detector temperature were set at 488, 523 and
523 K, respectively.
According to the European regulated procedure EN14103, the yield
(y [wt%]) of the FAME product was determined as follows:
(∑ Ai − AMH ) ⎤ CMH VMH × 100
y [wt%] = ⎡ ,
⎢
⎣ AMH ⎥
⎦ W (6)
where ∑ Ai is the total peak area of FAME mixture, AMH the peak area
of methyl heptadecanoate which is the internal standard, CMH the
concentration of the methyl heptadecanoate in heptane (10 g･L−1),
VMH the volume of the methyl heptadecanoate solution (5 mL) and W
the weight of the products mixture (250 mg). In this study, the con-
version of triglyceride, x[-], was calculated on the assumption that it
was equal to the y/100.
The X-ray diffraction analysis (Rint-2500TTR, Rigaku) was carried
(5)
out to identify the CaO produced by calcination of CaCO3. The specific
surface area of the CaO catalyst was measured by a surface area mea-
suring instrument (BELSORP-mini, BEL Japan Inc.). The laser diffrac-
tion particle size distribution analyzer (LA-920, HORIBA) was
103
Y. Kojima, S. Takai
Fig. 3. Time-dependent change in biodiesel yield under ultrasonic and me-
chanical stirring conditions. Oil content: 70 mL; CaO/oil mass ratio: 1 wt%;
methanol/oil molar ratio: 6/1; ultrasonic power: 5.0 W; revolution rate of
stirring: 400 rpm.
employed to measure the mean particle diameter of the CaO catalyst.
3. Results and discussion
3.1. Ultrasonic treatment and stirring treatment
Fig. 3 shows the typical time-change of yield of FAMEs produced via
transesterification reactions of soybean oil with methanol by ultra-
sonication and mechanical stirring methods at a 6:1 molar ratio of
methanol to oil. Until early about 75 min, the reaction rate under ul-
trasonication condition was slower than that under mechanical stirring
condition. However, after about 75 min, the reaction rate was ac-
celerated under ultrasonication condition compared to mechanical
stirring condition. The FAMEs yield reached 88% at about 2.5 h and 5 h
for ultrasonication and mechanical stirring, respectively; thus the re-
sults demonstrate that enhancement in the overall average transester-
ification reaction rate is achieved under ultrasonication condition.
Veljković et al. studied the kinetics of methanolysis of sunflower oil
in the presence of CaO catalyst under mechanical stirring condition
[14]. They applied the pseudo-first-order reaction kinetics model to the
methanolysis, and determined the methanolysis rate constants, km and
kc, in a triglyceride mass transfer controlled regime and a subsequent
chemical reaction controlled regime, respectively. Fig. 4 shows the
plots of [–ln(1-x)] against reaction time under ultrasonic and me-
chanical stirring treatments, where x denotes the conversion of the
Fig. 4. Plots of [–ln(1-x)] against reaction time under ultrasonic and mechan-
ical stirring conditions. Oil content: 70 mL; CaO/oil mass ratio: 1 wt%; me-
thanol/oil molar ratio: 6/1; ultrasonic power: 5.0 W; revolution rate of stirring:
400 rpm.
104
Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106
Table 1
The first-order reaction rate constants under ultrasonic and mechanical stirring
conditions. Oil content: 70 mL; CaO/oil mass ratio: 1 wt%; methanol/oil molar
ratio: 6/1; ultrasonic power: 5.0 W; revolution rate of stirring: 400 rpm.
method km×103[min−1] kc×103[min−1]
Mechanical stirring 2.1 ( ± 0.2) 13 ( ± 2)
Ultrasonication 0.5 ( ± 0.2) 30 ( ± 2)
soybean oil triglyceride via its transesterification. In both cases of ul-
trasonication and mechanical stirring, the results in Fig. 4 reveal that
the dependence of –ln(1-x) on reaction time is linear in each regime
controlled by mass transfer or chemical reaction, indicating that the
pseudo-first-order reaction kinetics model can probably be applied to
the methanolysis of soybean oil under ultrasonication condition as well
as mechanical stirring condition. According to the pseudo-first-order
reaction kinetics model, the reaction rate constants, km and kc, were
estimated from the respective slopes in the initial and latter regions in
Fig. 4. The rate constants estimated from the slopes are listed in Table 1.
The reaction rate constant, km, under mechanical stirring condition was
about 4.2 times as large as that under ultrasonication condition, sug-
gesting that the stirring treatment at 400 rpm can disturb methanol
including solid catalysts effectively in an oil layer and subsequently
contribute to the formation of methanol/oil emulsion. On the contrary,
ultrasonication at 5.0 W is not probably intensive enough to cause the
fast acoustic streaming and formation/collapse of cavitation bubbles
which are responsible for uniformly forming the methanol/oil emulsion
and dispersing CaO catalysts over the mixture solution. In addition,
when ultrasound propagates in the solution including soybean oil of the
high viscosity, it appears that it is not easy to cause the formation/
collapse of cavitation bubbles in the solution compared to liquids of the
low viscosity such as water and methanol, because cavitation threshold
increases with an increase in viscosity of liquid generally. As shown in
Table 1, however, the reaction rate constant, kc, obtained by ultra-
sonication treatment was about 2.3 times as large as that by mechanical
stirring treatment. As the methanolysis reactions progress, the amount
of formed FAMEs increases and to the contrary the amount of soybean
oil decreases; the changes in the amounts of reactants and products
with reaction time seem to cause a decrease in the viscosity of the
mixture solution, due to mutual interaction among methanol, FAMEs,
oil and others. Cavitation threshold gradually decreases with the de-
crease in viscosity of the mixture solution and is eventually equal to the
acoustic pressure equivalent to the applied ultrasound power; then the
physical effects such as microstreaming and microjet resulting from the
formation/collapse of the cavitation bubbles are immediately in-
tensified in the mixture solution, probably contributing to evolution of
emulsification, uniformly effective dispersion of CaO catalysts in the
solution, efficient cleaning of the solid catalyst surface and/or promo-
tion of mass transfer of the solution toward the solid catalyst surface. In
addition, implosive collapse of cavitation bubbles may offer the local
hot spot with enormous temperature in the mixture solution. It is
supposed that especially cavitation effects induced under ultrasonic
irradiation condition cause considerable acceleration of the reaction
rate in the chemical reaction controlled regime as well as the transition
regime which follows the initial triglyceride mass transfer controlled
region. We conclude that ultrasound is a promising technique for en-
hancement of the overall average reaction rate of biodiesel production
in the presence of inhomogeneous catalyst.
3.2. Effect of ultrasonic power
The effect of ultrasonic power on the reaction rate constants, km and
kc was investigated. The results in Table 2 demonstrate that an increase
of the ultrasonic power resulted in acceleration of the transesterifica-
tion reaction rates. The km values were about 0.6 × 10–3, 0.7 × 10–3
Y. Kojima, S. Takai
Table 2
Effect of ultrasonic power on the first-order reaction rate constants. Oil content:
70 mL; CaO/oil mass ratio: 1 wt%; methanol/oil molar ratio: 12/1.
power km×103[min−1] kc×103[min−1]
1.2W 0.6 ( ± 0.1) 19 ( ± 1)
3.0W 0.7 ( ± 0.2) 26 ( ± 2)
5.0W 1.1 ( ± 0.2) 28 ( ± 2)
and 1.1 × 10–3 min–1 at 1.2. 3.0 and 5.0 W, respectively, indicating that
the higher ultrasonic power was favarable for mass transfer. In general,
it is believed that an increase in the ultrasonic power leads to in-
tensification of acoustic streaming and cavitation effects, which may be
responsible for the effective mixing of methanol with soybean oil in a
mass transfer controlled regime. As shown in Table 2, the kc also in-
creased from 19 × 10−3 to 28 × 10−3 min-1 for an increase in the ul-
trasonic power from 1.2 to 5.0 W. In the mixture solution, implosive
collapse of cavitation bubbles can offer the local hot spot with en-
ormous temperature, which is probably higher under higher ultrasonic
power condition. Additionally, it is considered that the implosive col-
lapse of cavitation bubbles causes locally high speed flow such as mi-
crojet, which can contribute to the enhancement in collision of me-
thanol alkoxide molecule with soybean oil molecule.
3.3. Effect of CaO catalyst mass
Table 3 shows the effect of catalyst mass on the transesterification
reaction rates of oil to biodiesel product under ultrasonication. The
results demonstrate that both km and kc depended on catalyst mass. As
catalyst mass was incresed from 0.5 to 1.5 wt%, the km increased from
0.7 × 10−3 to 1.4 × 10−3 min-1, indicating that the larger catalyst
mass leads to the enhancement of transesterification reaction rate in a
triglyceride mass transfer controlled regime. The pseudo-first-order
reaction kinetics model proposed by Veljković et al. suggests that the km
increases proportionally with catalyst mass [14]. The results in Table 3
were similar to the suggestion. Veljković et al. reported that kc did not
depend on the catalyst mass, while our results demonstrate that the kc
slightly increased from 26 × 10−3 to 30 × 10−3 min-1 as catalyst mass
increased from 0.5 to 1.5 wt%. This may be because an increase in the
solid catalyst particle content causes the intensification of cavitation
effects. Tuziuti et al. studied about the enhancement of chemical re-
action with a photocatalyst of titanium dioxide by ultrasonic irradiation
and reported that the effect of titanium dioxide particle addition on the
enhancement of chemical reaction is due to the increase in the cavita-
tion bubbles [40]. Based on the results in Table 3, it is entirely fair to
say that the overall average rate of biodiesel production in the presence
of CaO solid catalyst under ultrasonication increases with the catalyst
mass. Liu et al. reported that the biodiesel yield was significantly im-
proved with the increase of CaO solid catalyst mass in the experiments
of transesterification reactions of soybean oil under magnetic stirring
condition [5]. Their results are similar to those obtained in our study.
Table 3
Effect of CaO catalyst mass on the first-order reaction rate constants. Oil con-
tent: 70 mL; CaO/oil mass ratio: 1 wt%; methanol/oil molar ratio: 12/1; ul-
trasonic power: 5.0 W.
CaO catalyst mass km×103[min−1] kc×103[min−1]
0.5 wt% 0.7 ( ± 0.2) 26 ( ± 2)
1.0 wt% 1.1 ( ± 0.2) 28 ( ± 2)
1.5 wt% 1.4 ( ± 0.2) 30 ( ± 2)
105
Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106
Table 4
Effect of molar ratio of methanol to oil on the first-order reaction rate constants
under the same oil content condition. Oil content: 70 mL; CaO/oil mass ratio:
1 wt%; ultrasonic power: 5.0 W.
molar ratio km×103[min−1] kc×103[min−1]
oil:methanol = 1:6 0.5 ( ± 0.2) 30 ( ± 2)
oil:methanol = 1:12 1.1 ( ± 0.2) 28 ( ± 2)
oil:methanol = 1:18 1.6 ( ± 0.5) 21 ( ± 2)
3.4. Effect of molar ratio of methanol to oil
3.4.1. Condition of constant amount of oil
The dependence of the reaction rate constants, km and kc, on the
molar ratio of methanol to soybean oil was investigated. The results are
summarized in Table 4. The experiments were performed under the
constant conditions of the soybean oil content (70 mL) and ultrasonic
power. Hence the total volumes of sample mixture were about 84, 105
and 121 mL for the 6:1, 12:1 and 18:1 molar ratios of methanol to oil,
respectively, thus meaning that the ultrasonic energy per unit mixture
solution volume decreased with an increase in the molar ratio of me-
thanol to oil. The ultrasonic energy per unit mixture volume at the 18:1
molar ratio of methanol to oil was about 1.15 and 1.39 times as low as
those at the molar ratios of 12:1 and 6:1, respectively. However, as can
be seen in Table 4, the rate constant, km, increased from
0.5 × 10−3 min-1 to 1.6 × 10−3 min-1 for an increase in the molar ratio
from 6:1 to 18:1. When the oil content in mixture is relatively smaller,
the viscosity of the mixture is probably lower. The acoustic streaming
accelerates more smoothly in the mixture under the lower viscosity
condition and thus can disturb the interface of oil/methanol layer,
probably leading to intensification of emulsification which can con-
tribute to enhancement of the oil mass transfer. On the other hand, as
seen in Table 4, for 6:1, 12:1 and 18:1 molar ratios of methanol to oil,
the kc values were 30 × 10–3, 28 × 10–3 and 21 × 10–3 min–1, respec-
tively, suggesting that the higher rate constant is obtained at the lower
molar ratio of methanol to oil. As the molar ratio increases, the ultra-
sonic energy per unit mixture volume decreases, resulting in a decrease
in the number of local hot spots with enormous temperature which are
formed by implosive collapse of cavitation bubbles. Additionally, an
increase in the amount of methanol in an excess over the stoichiometric
amount to oil may give rise to lowering of collision frequency between
soybean oil molecules and molecules of calcium alkoxide.
3.4.2. Condition of constant volume of methaol/oil mixture
In the Section 3.4.1, we reported the effect of the molar ratio of
methanol to soybean oil on the reaction rate under the constant
amounts of soybean oil and ultrasonic power. In this case, un-
fortunately, the ultrasonic power per unit mixture volume was different
with each molar ratio condition. Hence, to maintain the ultrasonic
power per unit mixture volume, the dependence of reaction rates on the
molar ratio of methanol to soybean oil was investigated under the
constant conditions of the methanol/oil mixture volume and ultrasonic
power. As shown in Table 5, the mass transfer controlled rate constant,
km, increased from 0.5 × 10−3 min-1 to 1.3 × 10−3 min-1 at the molar
ratio of methanol to soybean oil of 6:1-18:1 and the dependence of km
Table 5
Effect of molar ratio of methanol to soybean oil on the first-order reaction rate
constants under the same mixture volume condition. Methanol/oil mixtute
amount: 105 mL; CaO/oil mass ratio: 1 wt%; ultrasonic power: 5.0 W.
molar ratio km×103[min−1] kc×103[min−1]
oil:methanol = 1:6 0.5 ( ± 0.2) 28 ( ± 2)
oil:methanol = 1:12 1.1 ( ± 0.2) 28 ( ± 2)
oil:methanol = 1:18 1.3 ( ± 0.1) 24 ( ± 1)
Y. Kojima, S. Takai
on the molar ratio was similar to that seen in Table 4. On the other
hand, the chemical reaction controlled rate constant, kc at the higher
molar ratio of 18:1, was slightly lower, perhaps because of ineffective
impingement of the soybean oil molecules on the molecules of calcium
alkoxide due to the excess amount of methanol. However, the rate
constant, kc, at the molar ratio of 12:1 was almost the same as that at
the 6:1 molar ratio. The higher methanol content in the mixture may
have a negative effect on impingement of the soybean oil molecules on
the molecules of calcium alkoxide as described above; but it is con-
sidered that several cavitation effects which are responsible for the
acceleration of the methanolysis rate are intensified at the 12:1 molar
ratio compared to the 6:1 molar ratio, because the viscosity of mixture
under the higher molar ratio condition seems to be lower.
The comparison of the reaction times required to recach the bio-
diesel yield of about 85% showed no significant differences among the
molar ratio conditions. As a result, it was found that the amount of
biodiesel product per units reaction time and cosumption energy was
higher at the lower moalr ratio in the moalr ratio range of 6:1 to 18:1
under ultrasonication; thus it seems reasonable to conclude that ultra-
sound is a promising method for improvement in biodiesel productivity
via methanolysis in the presence of solid base catalysts.
4. Conclusions
In a transesterification reaction of soybean oil with methanol using
heterogeneous catalyst of CaO, ultrasonication was more effective for
the improvement of the production rate of biodiesel compared to tra-
ditional mechanical stirring. The transesterification reaction rate of oil
with methanol increased with the ultrasonic power and catalyst mass.
The higher molar ratio of methanol to oil allowed the enhancement of
production rate of biodiesel in an oil mass transfer controlled regime.
On the contrary, however, the lower molar ratio of methanol to oil was
found more favorable for the enhancement of methanolysis rate in a
chemical reaction controlled regime.
References
[1] M. Mittelbach, Process technologies for biodiesel production, in: W. Soetaert,
E.J. Vandamme (Eds.), Biofuel, John Wiley & Sons, Ltd., 2009, pp. 79–93.
[2] A. Singh, S.D. Fernando, Reaction kinetics of soybean oil transesterification using
heterogeneous metal oxide catalysts, Chem. Eng. Technol. 30 (12) (2007)
1716–1720.
[3] R. Abd Rabu, I. Janajreh, D. Honnery, Transesterification of waste cooking oil:
process optimization and conversion rate evaluation, Energy Convers. Manage. 65
(2013) 764–769.
[4] G. Vicente, M. Martinez, J. Aracil, Integrated biodiesel production: a comparison of
different homogeneous catalysts systems, Bioresour. Technol. 92 (2004) 297–305.
[5] X. Liu, H. He, Y. Wang, S. Zhu, X. Piao, Transesterification of soybean oil to bio-
diesel using CaO as a solid base catalyst, Fuel 87 (2008) 216–221.
[6] T. Ebiura, T. Echizen, A. Ishikawa, K. Murai, T. Baba, Selective transesterification
of triolein with methanol to methyl oleate and glycerol using alumina loaded with
alkali metal salt as a solid-base catalyst, Appl. Catal. A Gen. 283 (2005) 111–115.
[7] H. Fukuda, A. Kondo, H. Noda, Biodiesel fuel production by transesterification of
oils, J. Biosci. Bioeng. 92 (2001) 405–416.
[8] J.K. Hak, S.K. Bo, J.K. Min, M.P. Young, Transesterification of vegetable oil to
biodiesel using heterogeneous base catalysts, Catal. Today 93 (2004) 315–320.
[9] M.P. Dorado, E. Ballesteros, F.J. Lopez, M. Mittelbach, Optimization of alkali-cat-
alyzed transesterification of brassica carinata oil for biodiesel production, Energy
Fuels 18 (2004) 77–83.
[10] M.L. Granados, M.D.Z. Poves, D.M. Alonso, R. Mariscal, F.C. Galisteo, R. Moreno-
Tost, J. Santamaría, J.L.G. Fierro, Biodiesel from sunflower oil by using activated
calcium oxide, Appl. Catal. B Environ. 73 (2007) 317–326.
[11] S. Gryglewicz, Rapeseed oil methyl esterd preparation using heterogeneous cata-
lysts, Bioresour. Technol. 70 (1999) 249–253.
[12] Z. Huaping, W.U. Zongbin, C. Yuanxiong, Z. Ping, D. Shijie, L. Xiaohua,
M. Zongqiang, Preparation of biodiesel catalyzed by solid super base of calcium
oxide and its refining process, Chinese J. Catal. 27 (5) (2006) 391–396.
[13] M. Kouse, M. Umemoto, T. Kasuno, M. Tajika, Y. Aihara, Y. Sugimoto, J. Hidaka,
Biodiesel production from soybean oil using calcium oxide as s heterogeneous
106
Chemical Engineering & Processing: Process Intensification 136 (2019) 101–106
catalyst, J. Japan Inst. Energy 85 (2006) 135–141.
[14] V.B. Veljković, O.S. Stamenković, Z. Todorović, M.L. Lazić, D.U. Skala, Kinetics of
sunflower oil methanolysis catalyzed by calcium oxide, Fuel 88 (2009) 1554–1562.
[15] S. Yamanaka, M. Kouse, K. Kadota, A. Shimosaka, Y. Shirakawa, J. Hidaka, Catalysis
by CaO/SiO2 composite particle for biodiesel production, Kagaku Kougaku
Ronbunshu 33 (3) (2007) 483–489.
[16] M. Kouzu, T. Kasuno, M. Tajika, S. Yamanaka, J. Hidaka, Active phase of calcium
oxide used as solid base catalyst for transesterification of soybean oil with refluxing
methanol, Appl. Catal. A Gen. 334 (2008) 357–365.
[17] M. Kouzu, S. Yamanaka, J. Hidaka, M. Tsunomori, Heterogeneous catalysis of cal-
cium oxide used for transesterificationof soybean oil with refluxing methanol, Appl.
Catal. A Gen. 355 (2009) 94–99.
[18] M. Kouzu, T. Kasuno, M. Tajika, Y. Sugimoto, S. Yamanaka, J. Hidaka, Calcium
oxide as a solid base catalyst for transesterificationof soybean oil and its application
to biodiesel production, Fuel 87 (2008) 2798–2806.
[19] L.M. Cubillana-Aguilera, M. Franco-Romano, M.L.A. Gil, I. Naranjo-Rodríguez,
J.L. Hidalgo-Hidalgo de Cisneros, J.M. Palacios-Santander, New, fast and green
procedure for the synthesis of gold nanoparticles based on sonocatalysis, Ultrason.
Sonochem. 18 (2011) 789–794.
[20] Y. Kojima, H. Imazu, K. Nishida, Physical and chemical characteristics of ultra-
sonically-prepared water-in-diesel fuel: effects of ultrasonic horn position and water
content, Ultrason. Sonochem. 21 (2) (2014) 722–728.
[21] Y. Hirai, K. Nakabayashi, M. Kojima, M. Atobe, Size-controlled spherical polymer
nanoparticles: synthesis with tandem acoustic emulsification followed by soap-free
emulsion polymerization and one-step fabrication of colloidal crystal films of var-
ious colors, Ultrason. Sonochem. 21 (6) (2014) 1921–1927.
[22] Y. Kojima, T. Fujita, E.P. Ona, H. Matsuda, S. Koda, N. Tanahashi, Y. Asakura,
Effects of dissolved gas species on ultrasonic degradation of (4-chloro-2-methyl-
phenoxy) acetic acid (MCPA) in aqueous solution, Ultrason. Sonochem. 12 (5)
(2005) 359–365.
[23] A. Khataee, A. Karimi, S. Arefi-Oskoui, R.D.C. Soltani, Y. Hanifehpour, B. Soltani,
S.W. Joo, Sonochemical synthesis of Pr-doped ZnO nanoparticles for sonocatalytic
degradation of Acid Red 17, Ultrason. Sonochem. 22 (2015) 371–381.
[24] E. Ruiz, H. Rodríguez, J. Coro, V. Niebla, A. Rodríguez, R. Martínez-Alvarez,
H. Novoa de Armas, M. Suárez, N. Martín, Efficient sonochemical synthesis of alkyl
4-aryl-6-chloro-5-formyl-2-methyl-1,4-dihydropyridine-3-carboxylate derivatives,
Ultrason. Sonochem. 19 (2012) 221–226.
[25] T.J. Mason, Industrial sonochemistry - potential and practicality, Ultrasonics 30
(1992) 192–196.
[26] W. Lauterborn, C. Ohl, Cavitation bubble dynamics, Ultrason. Sonochem. 4 (1997)
65–75.
[27] A. Tezel, S. Mitragotri, Interactions of inertial cavitation bubbles with stratum
corneum lipid bilayers during low-frequency sonophoresis, Biophys. J. 85 (2003)
3502–3512.
[28] L. Wolloch, J. Kost, The importance of microjet vs shock wave formation in sono-
phoresis, J. Control. Release 148 (2010) 204–211.
[29] J. Wu, G. Du, Streaming generated by a bubble in an ultrasound field, J. Acoust.
Soc. Am. 101 (1997) 1899–1907.
[30] H.D. Hanh, N.T. Dong, K. Okitsu, Y. Maeda, R. Nishimura, Effects of molar ratio,
catalyst concentration and temperature on transesterification of triolein with
ethanol under ultrasonic irradiation, J. Jpn. Petrol. Inst. 50 (4) (2007) 195–199.
[31] H.D. Hanh, N.T. Dong, C. Stavarache, K. Okitsu, Y. Maeda, R. Nishimura,
Methanolysis of triolein by low frequency ultrasonic irradiation, Energy Convers.
Manage. 49 (2008) 276–280.
[32] H.D. Hanh, N.T. Dong, K. Okitsu, R. Nishimura, Y. Maeda, Biodiesel production
through transesterification of triolein with various alcohols in an ultrasonic field,
Renew. Energy 34 (2009) 766–768.
[33] H.D. Hanh, N.T. Dong, K. Okitsu, R. Nishimura, Y. Maeda, Biodiesel production by
esterification of oleic acid with short-chain alcohols under ultrasonic irradiation
condition, Renew. Energy 34 (2009) 780–783.
[34] C. Stavarache, M. Vinatoru, R. Nishimura, Y. Maeda, Conversion of vegetable oil to
biodiesel using ultrasonic irradiation, Chem. Lett. 32 (8) (2003) 716–717.
[35] C. Stavarache, M. Vinatoru, R. Nishimura, Y. Maeda, Fatty acids methyl esters from
vegetable oil by means of ultrasonic energy, Ultrason. Sonochem. 12 (5) (2005)
367–372.
[36] C. Stavarache, M. Vinatoru, Y. Maeda, Ultrasonic versus silent methylation of ve-
getable oils, Ultrason. Sonochem. 13 (2006) 401–407.
[37] N.N. Mahamuni, Y.G. Adewuyi, Application of taguchi method to investigate the
effects of process parameters on the transesterification of soybean oil using high
frequency ultrasound, Energy Fuels 24 (2010) 2120–2126.
[38] S.M. Joshi, P.R. Gogate, S.S. Kumar, Intensification of esterification of karanja oil
for production of biodiesel using ultrasound assisted approach with optimization
using response surface methodology, Chem. Eng. Process. Process Intensif. 124
(2018) 186–198.
[39] S. Koda, T. Kimura, T. Kondo, H. Mitome, A standard method to calibrate sono-
chemical efficiency of an individual reaction system, Ultrason. Sonochem. 10
(2003) 149–156.
[40] T. Tuziuti, K. Yasui, Y. Iida, H. Taoda, S. Koda, Effect of particle addition on so-
nochemical reaction, Ultrasonics 42 (1-9) (2004) 597–601.