Journal of Cleaner Production 205 (2018) 1094e1101

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Journal of Cleaner Production

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Performance comparison of different cavitation reactors for biodiesel

production via transesterification of palm oil
Tanutporn Laosuttiwong a, Kanokwan Ngaosuwan b, *, Worapon Kiatkittipong c,
Doonyapong Wongsawaeng d, Pattaraporn Kim-Lohsoontorn a,
Suttichai Assabumrungrat a
a
Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn
University, Bangkok 10330, Thailand
b
Division of Chemical Engineering, Faculty of Engineering, Rajamangala University of Technology Krungthep, Bangkok 10120, Thailand
c
Department of Chemical Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University, Nakhon Pathom 73000, Thailand
d
Department of Nuclear Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand

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

Article history: This study compares performance of different cavitation reactors for biodiesel production from palm oil
Received 9 March 2018 using homogeneous and heterogeneous reaction systems. In addition, the effect of reaction volume of
Received in revised form each reactor type was also investigated. For the smallest reaction volume of 165 mL, homogenizer and
17 September 2018
20 kHz ultrasonic reactors offered the highest fatty acid methyl ester yield for both sodium hydroxide
Accepted 18 September 2018
Available online 21 September 2018
and calcium oxide catalysts. When the reaction volume was increased from 165 to 500 and 1000 mL with
constant power input (80 W), homogenizer reactor did not significantly alter the rate of fatty acid methyl
ester formation, unlike the other reactors which showed the decrease in the reaction rate. The reactor
Keywords:
Biodiesel
performance was evaluated in term of yield efficiency which was based on the amount of fatty acid
Ultrasonic reactor methyl ester production, power consumption and reaction time. The increase of the reaction volume
Homogenizer reactor increased the yield efficiency of both the cavitation reactors and the mechanical stirred reactor. The
Cavitation reactor highest yield efficiencies of 169.46
104 and 8.27
104 g/J were obtained from homogenizer reactor
Yield efficiency using sodium hydroxide and calcium oxide catalysts, respectively, using the reaction volume of 1000 mL.
The homogenizer reactor also shows high flexibility of reaction volume usage with high biodiesel pro-
duction performance in a batch system.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction leading to a slow reaction rate. Many researchers have studied

Biodiesel is classified as a qualified alternative energy that can
be used with diesel engines. Transesterification of vegetable oil or
animal fats with a short chain alcohol such as methanol and ethanol
using a catalyst is the most common way to produce biodiesel
(Ramachandran et al., 2013). Actually, there are at least three types
of catalysts widely investigated in the scientific community: alka-
line, acid and enzymatic catalysts, which can form two types of
reaction systems in the process (homogeneous and heterogeneous
systems) (Abbaszaadeh et al., 2012). However, the biodiesel pro-
duction rate is typically limited by mass transfer. A mixture of
vegetable oil or animal fats with alcohol is not totally miscible
* Corresponding author.
E-mail address: kanokwan.n@rmutk.ac.th (K. Ngaosuwan).
various intensification technologies for multiphase reactors to
improve mixing between the two immiscible reactants. Cavitation
phenomena have been applied to increase the mixing efficiency
(Gogate, 2008). There are four methods to produce cavitation
phenomena as follows: (1) acoustic cavitation using ultrasonic
irradiation, (2) hydrodynamic cavitation using the geometry of the
system to create velocity variation, (3) optic cavitation using high-
intensity light (laser) to rupture liquid continuum and (4) particle
cavitation using a beam of elementary particles (neutron beam) to
rupture liquid. However, ultrasonic irradiation and hydrodynamic
cavitation are the two major methods appropriately used for bio-
diesel production (Chuah et al., 2017a; Gogate, 2008). Ultrasonic
irradiation is known to enhance the rate of chemical reaction
through cavitation bubbles. Radicals such as H* , OH* and HO*2 that
are produced during transient collapse of bubbles accelerate

https://doi.org/10.1016/j.jclepro.2018.09.159
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101
chemical reactions in a liquid medium. In addition, through phys-
ical effect, the micro-turbulence is generated due to radial motion
of bubbles, creating an intimate mixing of the immiscible reactants
resulting in increased interfacial area and faster reaction kinetics
(Kalva et al., 2009). On the other hand, hydrodynamic cavitation is
known to enhance biodiesel production by using the system ge-
ometry to create velocity variation as the following three steps: (1)
velocity of the liquid is increased with the corresponding decrease
in local pressure; (2) when the velocity is sufficient, the pressure
around the point of vena contracta falls below the vapor pressure
threshold resulting in generation of the cavitation and (3) when the
liquid jet expands, the pressure recovers, resulting in the collapse of
the cavities, with intensity depending on the geometry of the
constriction and the flow conditions of the liquid (Ciriminna et al.,
2016; Gogate and Kabadi, 2009).
It was demonstrated in earlier studies that ultrasonic irradiation
can increase interphase mixing between the phases at the desired
reaction conditions by producing high temperature and high
pressure (Gupta et al., 2015). Hingu et al. (2010) synthesized bio-
diesel from waste cooking oil using potassium hydroxide in a
sonochemical reactor. Improvement of mass transfer was achieved
from enhancement of interphase mixing between the reactants.
This can reduce the values of the required reaction parameters such
as the amount of methanol and energy consumption. It was found
that 89.5 and 57.5% of oil conversion were obtained from the
sonochemical reactor and the conventional stirred reactor,
respectively. Gogate (2008) reported the use of 4 mL of methanol
with 4 g of vegetable oil and a catalyst concentration (sodium hy-
droxide, NaOH) of 0.5 wt% in an ultrasonic bath reactor with 20 kHz
and 85 W of power dissipation. The results indicated the yield ef-
ficiency of 8.6
105 g/J in 10 min of reaction time with 99% of
biodiesel yield.
Hydrodynamic cavitation is generated from liquid passing
through a contraction such as an orifice plate, a Venturi nozzle or a
valve resulting in an increase of kinetic energy at the expense of
pressure (Ghayal et al., 2013). Hydrodynamic cavitation can also be
produced in a rotating machinery such as a high-speed homoge-
nizer with an adjustment of its rotating speed and geometry
(Gogate, 2008). Using a homogenizer which is based on the rotor/
stator principle to generate shear force is another interesting
approach to form fine emulsions of reactants. In addition, a high
turbulence occurs in the shear gap between the rotor and stator,
which provides the optimum mixing of suspension (Divyalakshmi
et al., 2015). Crudo et al. (2016) reported that using the rotor-
stator coupling could generate hydrodynamic cavitation in trans-
esterification of refined/bleached palm oil and waste cooking oil.
The high-speed rotation creates micron-sized droplets of the
immiscible mixture to enhance mass and heat transfer in the sys-
tem. More than 99% of fatty acid methyl ester content in the oil was
obtained. Pal et al. (2010) synthesized biodiesel from Thumba oil
through hydrodynamic cavitation using a methanol to oil molar
ratio of 4.5:1, NaOH loading of 1 wt%, reactor capacity of 10 L, power
consumption of 2.2 kW and reaction temperatures between 45 and
55  C. A biodiesel yield of 80% was obtained under this condition in
45 min.
Based on the literature review, most of the studies have been
carried out to determine the suitable operating parameters to
obtain the highest biodiesel yield for each cavitation reactor. In
comparison of acoustic and hydrodynamic cavitation for any
application, Gogate and Pandit (2005) found that the ratio of pro-
cess yields observed from hydrodynamic cavitation and acoustic
cavitation devices in the biodiesel synthesis was about 4. For other
application fields, Rajoriya et al. (2016) found that the same ratio
was about 13 for the degradation of bio-refractory pollutants, and
Agrawal et al. (2017) found the value of 3.5 for the formulations of
1095
citronella oil nanoemulsion. In general, Albanese et al. (2017) stated
that in hydrodynamic-assisted beer brewing, the hydrodynamic
cavitation outperformed acoustic cavitation “under virtually any
aspect, namely energy efficiency, cavitation yield and scalability.”
Also, Carpenter et al. (2017) stated about the acoustic cavitation
that “despite extensive research performed at laboratory scale, this
technique has found few takers on an industrial scale because of
some limitations, such as poor transmission of acoustic energy in
large volume of liquid, higher operational cost and low energy ef-
ficiencies, and poor spatiotemporal distribution in the liquid vol-
ume.” However, these previous works have been dealing with
applications on liquid or liquid-liquid phase in the absence of a
solid particle.
This work, therefore, aims at comparing the performance of
biodiesel production among different reactors (direct ultrasonic
(US), homogenizer (HZ) and mechanical stirred (MS) reactors) at
different reactor volumes. It should be noted that the catalysts used
in this work are classified within the same category (alkaline cat-
alysts) and, in fact, what was studied is the performance of the
reactors for different reaction systems (homogeneous and hetero-
geneous). NaOH as a conventional catalyst was selected for the
homogeneous system in biodiesel production, while the calcium
oxide (CaO) catalyst was selected for the heterogeneous system
because this catalyst provides a high catalytic activity under mild
condition in a short reaction time for biodiesel production via
transesterification (Lani et al., 2017).
2. Materials and methods
2.1. Materials
Refined palm oil was purchased from a local market in Thailand.
Methanol (99.8% purity) was purchased from Avantor Perfor-
mance Materials, Inc. Heptane (99.5% purity) was purchased from
Ajax Finechem Pty Ltd. Methyl heptadecanoate (99.0% purity) was
purchased from Sigma-Aldrich. Sodium hydroxide (NaOH, 99.0%
purity) was purchased from Merck Company Limited. Calcium ox-
ide (CaO, 96% purity) fine powder provided by Sigma-Aldrich was
calcined in a muffle furnace with a heating rate of 10  C/min and
holding at 900  C for 5 h. US was performed using AKVRBT-Super/
Probe-30420K (ultrasonic processor at 20 kHz) and AKVRBT-
Super/Probe-30440K (ultrasonic processor at 40 kHz) with a full
power of 400 W. The ultrasonic transducer was AK 35420-4 HQ
400 W with a tip diameter of 20 mm. HZ was performed using IKA
ULTRA-TURRAX T 25 digital (rotor-stator type) with a maximum
performance output of 500 W at 25,000 rpm and the shaft bearing
of the dispersion tool consisted of a side bearing made of poly-
tetrafluoroethylene (PTFE). The experiments were performed using
a stirring speed of 800 rpm for the MS reactor. The mixing and
heating power consumption was measured using a plug-in meter.
2.2. Transesterification
The desired amount of methanol was mixed with 1 wt% of NaOH
or 10 wt% of CaO catalyst (based on oil) before being transferred
into preheated oil. A 3-neck-bottom flask (165, 500 and 1000 mL)
was immersed in an oil bath to control the reaction mixture tem-
perature at 60  C. The 3-neck-bottom flask was plugged with a
condenser and a thermometer. A magnetic stirrer was used to
provide a stirring speed of 800 rpm. The obtained fatty acid methyl
ester (FAME) yields at various speeds from 700 to 900 rpm showed
no significant difference, which proved the lack of external mass
transfer. Subsequently, direct ultrasonic transducers with 20 and
40 kHz frequencies and a homogenizer were used to study the ef-
fect of different types of mixing under the similar reaction
1096 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101

condition. For US and HZ, the power was kept constant at 80 W for
all experiments. The longest observed reaction time was 3 and 4 h
for the homogeneous catalyst (NaOH) and the heterogeneous
catalyst (CaO), respectively. Triplicate experiments were performed
and the error bars of the results were provided. The reaction
product in the reaction mixture was transferred and centrifuged to
separate fatty acid methyl ester out from the reaction mixture
before being analyzed by gas chromatography (GC).

2.3. FAME yield calculation

The FAME yield was analyzed by Shimadzu GC-2010 Plus with

DB-WAX capillary column and detected by a flame ionization de-
tector (FID). Methyl heptadecanoate was used as an internal stan-
dard and the FAME yield was determined according to the EN14103
Fig. 1. Effect of mixing type on FAME yield using reaction volume of 165 mL (NaOH
standard (EN14103, 2011) as shown in Eq. (1). catalyst).
P
ð AÞ  AIS C
VIS
FAME yield ð%Þ ¼
IS
100% (1)
AIS mS 2012). The FAME yield obtained from MS was similar to that of
P 20 kHz US while exhibiting a slower reaction rate compared to HZ.
where A ¼ Total area of peak. However, the FAME yield obtained from all reactors reached equi-
librium at 60 min except for 40 kHz US. Based on this reaction
AIS ¼ Area of methyl heptadecanoate volume (165 mL), there was no significant difference in FAME yield
CIS ¼ Concentration of methyl heptadecanoate (mg/mL) because at this period of time, all reactors provided the sufficient
VIS ¼ Volume of methyl heptadecanoate (mL) degree of mixing to overcome the mass transfer limitation between
mS ¼ Mass of FAME sample (mg). the two immiscible liquids (palm oil and methanol), and there was
also no obstacle by using the NaOH catalyst.
The reactor performance in terms of FAME yield along the re-
2.4. Yield efficiency calculation action time was also investigated by using the CaO catalyst for the
heterogeneous system. The experiments were carried out at a re-
The yield efficiency defined in Eq. (2) is used to compare the action temperature of 60  C, a methanol to oil molar ratio of 9:1 and
performance of different reactors (US, HZ and MS) (Maddikeri et al., a catalyst loading of 10 wt% within 4 h. This condition was selected
2014). It shows the amount of FAME produced per unit energy due to the major problems of using the CaO catalyst, which formed
consumed. The energy consumption included both energy for a three-phase zone (methanol, oil and solid phase) leading to a slow
mixing and heating. reaction rate (Zabeti et al., 2009). Increasing the amount of catalyst
can accelerate the rate as well as increasing the amount of meth-
WFAME anol, which in turn shifts the equilibrium to the right-hand side
Yield eff iciency ¼ (2)
P
t providing more contact with the catalyst (Chen et al., 2014). Liu
et al. (2008) investigated transesterification of soybean oil to
where WFAME ¼ Amount of FAME produced (g).
FAME using CaO catalyst. It was found that the FAME yield
increased from 55 to 90% when the amount of CaO was increased
P ¼ Power supplied (J/s)
from 2 to 12 wt%. Although increasing the amount of catalyst could
t ¼ Reaction time (s)
promote more active sites, the excess amount of catalyst also limits
mass transfer in the reaction mixture.
3. Results and discussion Fig. 2 indicates that the induction period was still observed for
all reactors. The FAME yield obtained from all reactors from 0 to
3.1. Effect of mixing type on FAME yield

The effect on FAME yield of various cavitation reactors

compared to the conventional reactor (MS) for the reaction volume
of 165 mL using NaOH as a catalyst via transesterification of palm
oil was investigated as illustrated in Fig. 1. The reaction was carried
out at a reaction temperature of 60  C, a methanol to oil molar ratio
of 6:1, NaOH loading of 1 wt% and reaction time of 3 h in the testing
reactors including HZ, 20 kHz US, 40 kHz US and MS.
It can be noticed that the induction period was observed in the
initial reaction (5 min for all reactors except HZ). Moreover, HZ can
produce high FAME yields of 87.06 and 92.71% in a short reaction
time of 5 and 15 min, respectively, while 90.98% of FAME yield was
obtained in 20 kHz US for 30 min. 40 kHz US provided a lower FAME
yield compared to 20 kHz US. This was because, with the increase of
the ultrasonic frequency from 20 to 40 kHz, the bubble size
decreased. The controlled input power of 80 W was probably
insufficient to generate cavitation collapse resulting in lower shear Fig. 2. Effect of mixing type on FAME yield using reaction volume of 165 mL (CaO
force and the reduction in the cavitation intensity (Gole and Gogate, catalyst).
 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101 1097

240 min exhibited a similar trend. The FAME yield obtained from
40 kHz US was the lowest, similar to the NaOH catalyzed trans-
esterification (Fig. 1) likely due to the same reasons. The highest
FAME yield was found in 20 kHz US and was slightly higher than
that of HZ. This is most likely due to the fact that an ultrasonic
reactor can accelerate the reaction rate by increasing the level of
mixing due to the cavitation phenomena in the bulk fluid (external
mass transfer) and by carrying reactants to the active site of the
catalyst (internal mass transfer) (Carcel et al., 2010). On the con-
trary, based on the hydrodynamic cavitation principle, small
amounts of fluid are sucked through the gap between the rotor and
the stator providing shear force to generate small bubbles. Using
the CaO catalyst might reduce the velocity of the reaction mixture
in HZ, decreasing the generation of cavitation resulting in a lower
degree of mixing (Gogate and Kabadi, 2009). However, at 240 min
of reaction time, the FAME yield obtained in all reactors reached the Fig. 3. Effect of reaction volume on FAME yield using homogenizer reactor (NaOH
catalyst).
similar equilibrium. In addition, the induction period of trans-
esterification was expected when using calcium oxide as a solid
catalyst. Two hypotheses are provided to explain this behavior.
First, the induction period occurred from the internal mass transfer
between the active site and the reaction mixture (Vujicic et al.,
2010). Second, calcium oxide was an active phase of trans-
esterification at the first reaction period. Then, glycerol was pro-
duced during the reaction and reacted with calcium oxide to form a
new active phase (calcium diglyceroxide) to accelerate the trans-
esterification rate (Kouzu et al., 2008). Moreover, FAME produced
during the reaction could behave as a co-solvent to increase the
miscibility between oil and methanol. Then, the reaction mixture
was activated to increase the reaction rate on biodiesel production
(Lam and Lee, 2010).
Using cavitation reactors for biodiesel production can overcome
the hindrance of mass transfer between the two immiscible liquids
(methanol and oil) because of the presence of cavitation phenom-
ena. Moreover, methanol as a reactant for transesterification has a Fig. 4. Effect of reaction volume on FAME yield using homogenizer reactor (CaO
high vapor pressure which assists the cavitation phenomena in the catalyst).
reaction mixture. By using NaOH and CaO (representing homoge-
neous and heterogeneous systems, respectively) to catalyze trans-
esterification in all the studied reactors, the obtained FAME yield The results showed that the FAME yields from NaOH catalyzed
using NaOH is higher than that of the CaO catalyst. This is most transesterification along the reaction time carried out in HZ were
likely because there was less diffusion mass transfer resistance similar for all reaction volumes from 165 to 1000 mL. This was
from bulk liquid to the surface active site. However, the drawbacks attributable to the fact that the rotor/stator principle generates high
of the NaOH catalyst are the difficulty to separate as well as the shear force which occurs in the shear gap between the rotor and the
required large amount of water for washing (Xie et al., 2006). Using stator leading to emulsification of the suspension. The high velocity
HZ was appropriate for NaOH catalyzed transesterification of palm of the liquid causes a decrease in the local pressure, and if the local
oil while using 20 kHz US was suitable for CaO catalyzed trans- pressure is less than the vapor pressure of methanol, then the
esterification. From 120 to 180 min, 20 kHz US, HZ and MS provided cavitation is generated (Chuah et al., 2015). This result was also
the similar FAME yield using the NaOH catalyst. On the other hand, comparable to the results obtained by Mohod et al. (2017) who
for the heterogeneous system, the reaction carried out in US as well studied the high-speed homogenizer to produce FAME with yield of
as in HZ appears to exhibit a faster reaction rate than that of MS 92.3% using sunflower oil with 3% KOH, a molar ratio of methanol to
because ultrasound produces small bubbles of methanol which are oil of 12:1 and reaction temperature of 50  C along the reaction
easy to be adsorbed on the active site of CaO and because the time of 2 h.
drastic increase in an interfacial area between the two reactants Interestingly, the triplicate reaction test confirmed that for CaO
results in an improved mass transfer and the transesterification catalyzed transesterification of palm oil, when the reaction mixture
rate (Mootabadi et al., 2010). volume was increased to 500 and 1000 mL, the FAME yield was
slightly higher than that of 165 mL, despite a slower start (Fig. 4).
Joshi et al. (2017) reported that by using a high-speed homogenizer
3.2. Effect of reaction mixture volume on FAME yield to produce FAME in the presence of a CaO catalyst, the maximum
FAME yield was 84% using the catalyst loading of 3 wt%, a molar
The aim of this experiment was to illustrate the highest per- ratio of methanol to oil of 10:1, reaction temperature of 50  C and
formance of each reactor type for FAME production when using the reactor size of 300 mL with the rotation speed of 12,000 rpm. It
NaOH and CaO catalysts. The effect of reaction volume on the FAME can be seen that all previous studies (Chuah et al., 2017a) presented
yield was investigated under the similar condition and input power. only the obtained biodiesel yield in various operating conditions
The reaction volume was increased from 165 to 500 and 1000 mL. (methanol to oil molar ratio, reaction temperature and the catalyst
Figs. 3 and 4 demonstrate the effect of reaction mixture volume loading while fixing reaction volume). These results indicated that,
using HZ for NaOH and CaO catalysts. with the increase of the reaction mixture volume from 165 to
1098 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101
1000 mL while maintaining the same electrical power input, uti-
lizing the homogenizer (hydrodynamics equipment) provides a
higher FAME yield when using larger reaction mixture volume.
Fig. 5 demonstrates the effect of reaction mixture volume on
FAME yield using 20 kHz US and the NaOH catalyst. The results
illustrated that increasing the mixture volume to 3 and 6 times
resulted in a decrease in the transesterification rate at the begin-
ning of the reaction time. However, the FAME yield reached equi-
librium at the same time of 60 min for 500 and 1000 mL, except for
the small mixture volume of 165 mL, which reached equilibrium at
30 min. It should be noted that there were no further significant
increases in the FAME yields for the homogenous system (Figs. 1, 3
and 5); therefore, the transesterification time longer than 60 min
was energetically wasteful. On the other hand, the CaO catalyst
exhibited a very different FAME yield along the reaction time
(Fig. 6). During the initial period (at 60 min), the increase in the
mixture volume to 3 and 6 times reduced the FAME yield by 3.6 and
6 times, respectively. However, it can be noticed that FAME yields
obtained from 165, 500 and 1000 mL of reaction volume at the
reaction time of 240 min were similar. This indicated that the
effectiveness of the cavitation processes was slower with larger
reaction volume. Results of FAME production using 40 kHz US with
the NaOH catalyst were also depicted in Fig. 7.
The results showed that with the increase of the reaction
mixture volume, the FAME yield decreased due to the smaller
bubble size when increasing the ultrasonic frequency, which in turn
reduced the intensity and shear forces generated by the cavitation
Fig. 5. Effect of reaction volume on FAME yield using 20 kHz ultrasonic reactor (NaOH
catalyst).
Fig. 6. Effect of reaction volume on FAME yield using 20 kHz ultrasonic reactor (CaO
catalyst).
Fig. 7. Effect of reaction volume on FAME yield using 40 kHz ultrasonic reactor (NaOH
catalyst).
collapse at the beginning stage, and also possibly due to lower
penetration through the reaction mixture. The effect of reaction
mixture volume was tremendous for the CaO catalyst (Fig. 8). The
FAME yield decreased 8 times with the 3 times increase in the re-
action volume. Furthermore, higher frequency required higher
power to obtain the maximum FAME yield and the correlation
between the ultrasonic power input and the amplitude of the wave
can be seen in our previous research (Poosumas et al., 2016). Kumar
et al. (2010) reported that when increasing the ultrasonic power,
more cavitation bubbles are generated leading to increased FAME
yield. Mahamuni and Adewuyi (2009) have investigated the effect
of ultrasonic frequency. The increased frequency of ultrasonic
decreased the size of bubbles leading to a decreased implosion time
of cavitation bubbles resulting in slower reaction rate. The
conclusion can be advanced that the mixing efficiency by using
ultrasonic irradiation to produce cavitation phenomena in the short
duration is still restricted by the volume of the reaction mixture
due to requirements for ultrasonic irradiation intensity. With the
optimal frequency, the power density (power/volume) should not
be less than 1.58 W/mL to provide an efficient biodiesel production
(Poosumas et al., 2016). In this work, the ultrasonic irradiation in-
tensity was only 0.48, 0.16 and 0.08 W/mL for 165, 500 and
1000 mL, respectively.
Figs. 9 and 10 illustrate the effect of reaction mixture volume
using MS. The results showed that the FAME yield decreased with
the increase in reaction mixture volume, especially with the het-
erogeneous catalyst. The time to reach equilibrium (complete
mixing) in the reaction mixture of 165, 500 and 1000 mL was 30, 60
Fig. 8. Effect of reaction volume on FAME yield using 40 kHz ultrasonic reactor (CaO
catalyst).
 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101 1099

Fig. 9. Effect of reaction volume on FAME yield using mechanical stirrer reactor (NaOH
catalyst).
included the electrical power input from each mixing type of the
reactor and the heater. Figs. 11 and 12 illustrate the effect of the
different considered reactors on the yield efficiency using the NaOH
catalyst at 80 and 90% FAME yield, respectively. The selection of
these FAME yield values to calculate the yield efficiency refers to
the maximum FAME yield from previous studies on NaOH and CaO
catalyzed transesterification (Hanh et al., 2009; Joshi et al., 2017).
The yield efficiency for the cavitation reactors (HZ and 20 kHz
US) was increased when the reaction mixture volume increased.
The maximum yield efficiencies of 401.67
104 and 169.46

104 g/J for the reaction mixture of 1000 mL with 80 and 90% FAME
yield, respectively, were obtained in HZ. This result was attributable
to the fact that HZ can enhance mass transfer due to the immiscible
property of oil and methanol, which provided the homogeneity of
the reaction mixture as seen in Fig. 3. The FAME yield of 87% was
achieved in 5 min for all reaction volumes. The higher yield effi-
ciency was obtained compared to the work of Chuah's group who
reported the FAME yield efficiency of 12.50
104 g/J in a hydro-
dynamic cavitation batch reactor using KOH as a catalyst with the
maximum input power of 4 kW (Chuah et al., 2016, 2017b). Ghayal
et al. (2013) reported that FAME yield efficiency was 12.8
104 g/J
using a methanol to oil molar ratio of 6:1, catalyst loading of 1 wt%,
reaction temperature of 60  C, reaction time of 10 min and power of
7.5 kW. However, these experiments were carried out in a labora-
tory scale which was in different scales of operation compared to
the above previous works. The scale-up issues should be further
addressed in terms of operational parameters using different
cavitation geometries such as Venturi tubes or orifice plates.

Fig. 10. Effect of reaction volume on FAME yield using mechanical stirrer reactor (CaO
catalyst).

and 120 min, respectively. The mechanism of mechanical mixing

can be described as a combination of three physical steps: 1) dis-
tribution of the media transport to all regions of the vessel by bulk
circulation currents, 2) turbulent fluid dispersion with the gener-
ation of various eddy sizes, with subsequent breaking down to ever
smaller sizes and 3) diffusion by concentration gradient. Therefore,
when the reaction mixture volume increased, the velocity of the
media transport decreased, and the diffusion dominated to slow
down the mixing process. Moreover, the effectiveness of the use of Fig. 11. Effect of mixing type of reactor on yield efficiency based on 80% FAME yield
(NaOH catalyst).
conventional mixing such as a blade, a turbine or a magnetic bar
depends on the correct ratio of the liquid level to the blade diam-
eter. Since the increase in the reaction mixture volume increased
the liquid level, the ratio of the liquid level to the blade diameter
was altered resulting in the lower FAME yield in the specific reac-
tion time.

3.3. Energy, time and yield efficiency of various mixing types of

reactors

From the above section, FAME yield was the major parameter for
evaluation of FAME production efficiency in various mixing types
using both NaOH and CaO catalysts. To produce economical bio-
diesel, FAME yield cannot be the only parameter for the consider-
ation. The other parameters such as reaction time and input energy
are required to evaluate the costs of biodiesel production. There-
fore, yield efficiency was used to evaluate the reactor performance
based on energy consumption, amount of FAME production and Fig. 12. Effect of mixing type on yield efficiency based on 90% FAME yield (NaOH
also reaction time. The measurement of total energy consumption catalyst).
1100 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101
The yield efficiency of 20 kHz US with the requirement of 90%
FAME yield was lower than that of 80% FAME yield, and this was
due to the fact that higher FAME yield required not only more re-
action time but also more input energy. The yield efficiencies with
80% FAME yield were 13.26, 17.68 and 36.52
104 g/J and the yield
efficiencies with 90% FAME yield were 7.71, 10.91 and 21.52

104 g/J for the reaction mixture of 165, 500 and 1000 mL, respec-
tively. It can be confirmed that hydrodynamic cavitation-assisted
transesterification is a more promising technology which can
accommodate larger reaction mixture volume to produce
economical biodiesel based on the considerations of biodiesel yield
and yield efficiency. Gole et al. (2013) reported that hydrodynamic
cavitation has been more efficient as compared to an ultrasonic
reactor. The yield efficiency was 0.16
104 g/J for an ultrasonic
reactor and 13.5
104 g/J for hydrodynamic cavitation. Gogate
(2008) also reported the yield efficiency of an ultrasonic reactor
to be 0.86
104 g/J and 33.7
104 g/J for a hydrodynamic cavi-
tation reactor. The obtained yield efficiency was 1.37
104 g/J for
40 kHz US with 165 mL reaction volume. When the reaction volume
was increased up to 500 mL, the yield efficiency was not calculated
because the maximum yield achieved was only 69.17%, which was
less than the limit of 80%.
For the yield efficiency of MS with the requirement of 80 and
90% FAME yield, the results revealed that the yield efficiency
decreased when the reaction mixture volume increased. This is due
to the mechanism of conventional mixing which requires turbu-
lence to produce small eddies resulting in the homogeneity of re-
action mixture. The increase in the reaction mixture volume with
the same mixing blade size resulted in an increase of the drag force
in the reaction media. A small blade might not provide sufficient
fluid velocity to overcome the drag force. Therefore, the use of a
conventional mixing blade, a turbine or a magnetic bar was
appropriate with the correct ratio of the liquid level to the blade
diameter to provide efficient mixing. For example, placing the
agitator at a higher or lower level in the tank can affect the swirling
flow pattern and it might become difficult to achieve the desired
process result (McCabe et al., 2005).
The yield efficiency using the CaO catalyst was depicted in
Figs. 13 and 14 based on the requirement of 70 and 80% FAME yield,
respectively. Lower yield efficiencies as compared to the NaOH
catalyst were considered because of the presence of the induction
period for all mixer types. The yield efficiency obtained in HZ and
US 20 kHz was enhanced when the reaction mixture volume
increased. However, the yield efficiency obtained from CaO cata-
lyzed transesterification of palm oil in HZ was higher than those of
other testing reactors. These results also confirm that HZ exhibits
Fig. 13. Effect of mixing type on yield efficiency based on 70% FAME yield (CaO
catalyst).
Fig. 14. Effect of mixing type on yield efficiency based on 80% FAME yield (CaO
catalyst).
the highest biodiesel production performance in terms of small
energy input, short reaction time and large reaction mixture
volume.
In addition, the cost analysis was also preliminarily introduced
as a comparative analysis of the technologies to emphasize that
different cavitation methods have different economic advantages
due to different requirements of reactor volume, energy demand
and investment costs as presented in the supplementary material.
It was found that, although the reactor volume could be reduced in
cavitation reactors, the fixed capital cost increased when applying
the costs of the ultrasonic transducer and the homogenizer. How-
ever, the smaller reactor-volume requirement in the cavitation
reactor in turn reduces the overall energy input and, thus, mini-
mizes the production cost, especially in the case of HZ.
Based on this finding, the cavitation reactor has the potential to
be applied in the economical biodiesel production with the flexi-
bility in the quantity of feedstocks. It should be noted that the
performed cost analysis of an industrial-scale production based
directly on the laboratory-scale results could introduce uncertainty
in the analysis, likely due to problems of process scale up. There-
fore, scaling up for cavitation reactors need to be explored through
future research because these laboratory-scale maximum volumes
tested were only 1000 mL.
4. Conclusions
The process intensification has been applied to improve mixing
and heat/mass transfer between the two immiscible liquid phases
for biodiesel production, especially using cavitation technology.
Using HZ to carry out homogeneous (NaOH) catalyzed trans-
esterification of palm oil is preferred while 20 kHz US is slightly
more favorable for heterogeneous (CaO) catalyzed trans-
esterification for only the small reaction volume because of its
cavitation intensity. The initial rate of CaO catalyzed trans-
esterification decreased with increasing reaction volume. Yield ef-
ficiency is one of performance indices for biodiesel production
consideration which can be a guideline to select the optimum
condition to produce biodiesel. HZ showed the highest yield effi-
ciency based on energy consumption and reaction mixture volume
compared to the other reactors. At 80% FAME yield, 400
104 g/J
of yield efficiency using the reaction mixture of 1000 mL was ob-
tained from HZ for NaOH catalyzed transesterification. On the other
hand, only 8.27
104 g/J of yield efficiency was obtained in CaO
catalyzed heterogeneous systems using the similar reaction vol-
ume. This is due to the limited internal mass transfer, resulting in
the lower yield efficiency than that of the homogeneous system
 T. Laosuttiwong et al. / Journal of Cleaner Production 205 (2018) 1094e1101
(NaOH). HZ required relatively lowest power consumption and
exhibited the lowest production cost compared to US and MS. From
this finding, HZ is more suitable for biodiesel production with
various amounts of feedstock in a batch system. However, the
recommendations for future research should be more focused on
the pilot scale of a cavitation reactor restricted to operational pa-
rameters, using different cavitation geometries such as Venturi
tubes or orifice plates.
Acknowledgement
This work was financially supported by the Thailand Research
Fund through grant number DPG5880003.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2018.09.159.
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