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Intensified synthesis of biodiesel using hydrodynamic cavitation reactors

based on the interesterification of waste cooking oil

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DOI: 10.1016/j.fuel.2014.08.013

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 Fuel 137 (2014) 285–292

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Intensified synthesis of biodiesel using hydrodynamic cavitation reactors

based on the interesterification of waste cooking oil
Ganesh L. Maddikeri, Parag R. Gogate ⇑, Aniruddha B. Pandit
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai 40019, India

h i g h l i g h t s

 Hydrodynamic cavitation results in significant process intensification.

 Waste cooking oil is a good sustainable feedstock for interesterification.
 Slit venturi is the best cavitating device.
 Better properties of the final synthesized biodiesel.

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

Article history: In the present work, hydrodynamic cavitation reactor has been used for the intensification of synthesis of
Received 8 June 2014 biodiesel from waste cooking oil (WCO) based on the interesterification reaction. Experiments have been
Received in revised form 14 July 2014 performed using different cavitating devices such as orifice plate, circular and slit venturi and under vary-
Accepted 5 August 2014
ing operating parameters viz. inlet pressure (2–5 bar), molar ratio of oil to methyl acetate (over the range
Available online 17 August 2014
of 1:10–1:14) and catalyst loading over the range of 0.5–1.25% by weight of oil. Maximum yield (90%) of
biodiesel from WCO was obtained at oil to methyl acetate ratio of 1:12 and catalyst loading of 1.0% using
Keywords:
slit venturi at the inlet pressure of 3 bar. Also, higher cavitational yield (biodiesel produced per unit
Biodiesel synthesis
Sustainable feedstock
energy consumed) was obtained for the hydrodynamic cavitation based approach as compared to the
Interesterification ultrasound based approach and conventional method. The observed intensification is attributed to the
Hydrodynamic cavitation microscale turbulence generated due to the cavitational effects that help in intensifying the transfer
Cavitating device processes. Overall, the potential of WCO to produce good quality methyl esters in energy efficient manner
using hydrodynamic cavitation reactor has been demonstrated based on the cavitational yield calcula-
tions and properties of synthesized biodiesel.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction petroleum based diesel such as biodegradability, non toxic nature,

Enormous increase in the fuel consumption due to increase in
the population and industrialization has resulted in considerable
stress on the fossil fuel production, also having significant impact
on economies of many countries. The use of petroleum based prod-
ucts creates substantial air pollution problems all over the world [1]
and different alternatives are being explored currently to develop
synthesis routes for alternate fuels such as biodiesel. Biodiesel is
similar to the petroleum based diesel in many aspects and can be
synthesized by chemical reaction involving any oil or fat with alco-
hol. The sources of oil or fat can vary from sustainable sources such
as animal fats, waste cooking oil, non-edible oils, and agricultural
residues to food grade vegetable oils. Biodiesel has advantages over
⇑ Corresponding author. Tel.: +91 22 3361 2024; fax: +91 22 3361 1020.
E-mail address: pr.gogate@ictmumbai.edu.in (P.R. Gogate).
high flash point, excellent lubricity, higher cetane number, no sul-
phur content and lesser pollution [2,3]. Biodiesel can be used neat
(complete replacement) or as a diesel additive and hence has a good
potential to replace the fossil fuel [4]. Apart from the advantages of
biodiesel, there are some limitations to the use of biodiesel as a fuel
and most important one is the higher cost of production. The cost of
biodiesel is almost two times as compared to the cost of petroleum
based diesel fuel [5], which is typically attributed to higher costs of
feedstock [6], lower conversion rates and higher reaction time as
well as significant costs associated with the downstream separa-
tions. The production cost can be reduced by using sustainable
feedstock such as WCO and also based on the use of interesterifica-
tion reaction instead of transesterification. Interesterification reac-
tion between oils/fats and methyl acetate [7] results in the
formation of triacetin, which has higher value (significant use as a
plasticizer, a gelatinizing agent in polymers and as an additive in

http://dx.doi.org/10.1016/j.fuel.2014.08.013
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
286 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292
pharmaceutical, tobacco and cosmetics industries) as compared to
the glycerol produced in transesterification. Triacetin can also be
blended with biodiesel up to 20% by weight matching the quality
standards set by ASTM D6451 [8].
Interesterification has been mostly studied so far using the
enzymatic route [9–11] or based on the supercritical conditions
[12–15], but both these approaches offer significant disadvan-
tages. On one side where the enzymatic approach require consid-
erable processing time and higher production costs [15,16], the
supercritical methods require significantly high pressures (20–
40 MPa) and temperatures (350–400 °C) as well as significant
excess of methyl acetate (usually reactant ratio of oil to methyl
acetate is set at 1:42) [13]. Overall, it can be said that though
interesterification based approach is good for synthesis of biodie-
sel with a value added product, use of process intensifying
approach is required for possible reduction in the production cost
and for enabling the use of ambient conditions. Cavitational reac-
tors can be used for intensification of interesterification reaction
very similar to more deeply investigated transesterification
approaches. There are also other approaches for biodiesel pro-
duction such as microwave, oscillatory baffle reactors, microreac-
tors, and supercritical method [1,17] as well as the use of
reactive distillation [18]. The rate of biodiesel production is con-
trolled by the mass transfer limitations associated with the reac-
tant phases and the physical effects of cavitation such as intense
turbulence (generated at microscale) and streaming can be effec-
tive in eliminating these resistances. These effects are responsible
for generation of fine emulsions which provide large area for
reaction leading to intensified operations. Indeed, cavitational
reactors have been used for the intensification of the biodiesel
production from waste cooking oil [19], palm fatty acid [20]
and Nagchampa oil [21] though based on the esterification/
transesterification reactions, however the present work is the
first attempt for the application of hydrodynamic cavitation for
the intensification of interesterification based synthesis of biodie-
sel. Cavitational effects can be produced using two routes of
acoustic cavitation (passage of high intensity ultrasound through
the liquid medium) and hydrodynamic cavitation (passage of
liquid at high flow rates through a constriction). When the liquid
passes through the constriction, there is a sudden increase in the
velocity of liquid at the expense of the local pressure and if this
local pressure falls below the vapour pressure, number of cavities
will be generated that subsequently collapse with the recovery of
pressure downstream of the mechanical constriction [22–24].
Hydrodynamic cavitation has been widely used for the wastewa-
ter treatment or esterification/transesterification reactions, but
there has been absolutely no study reporting the use of hydrody-
namic cavitation for intensification of interesterification based
synthesis of biodiesel. The current work reports the novel study
of intensification of interesterification reaction of pretreated
waste cooking oil in the presence of potassium methoxide using
hydrodynamic cavitation. Potassium methoxide has been selected
on the basis of results presented by Casas et al. [7] for the inter-
esterification reaction where the effect of type of catalyst was
investigated using different catalysts such as potassium hydrox-
ide, potassium methoxide and polyethylene glycolate. It was
reported that higher biodiesel yield is obtained in the presence
of potassium methoxide and hence potassium methoxide has
been used in the present work instead of more commonly used
potassium hydroxide or sodium hydroxide. Experiments have
been performed using different geometries of cavitating device
and effect of inlet pressure, methyl acetate to oil molar ratio
and catalyst concentration on the biodiesel yield has also been
investigated. Kinetic analysis for the interesterification reaction
has also been presented with estimation of the properties of syn-
thesized biodiesel.
2. Materials and methods
2.1. Materials
Methyl acetate, potassium methoxide pellets, ortho phosphoric
acid and molecular sieves (3°A) were procured from S.D. Fine
Chem. Ltd., Mumbai whereas weak anion-exchange resin (Indion
860) was obtained from Ion Exchange Ltd., Mumbai. Acetonitrile
and acetone (HPLC grade) used as solvent for HPLC analysis were
obtained from Hi Media, Mumbai whereas methanolic potassium
methoxide (33% by wt.) was procured from Spectrochem Pvt.
Ltd., Mumbai. The standards of methyl oleate and methyl linoleate
were obtained from Sigma Aldrich. Waste cooking oil (WCO) was
procured from a local restaurant and was subjected to initial phys-
ical treatment and repeated water washing as per the details pro-
vided in the earlier work [1]. The properties of treated WCO used as
the starting raw material have been given in Table 1. As the initial
acid value of the WCO was high at 3.89 which is unsuitable for use
in the presence of alkaline catalyst, deacidification of WCO has
been performed. Weak anion exchange resin (Indion 860, 1 wt.%)
has been used for the removal of free acid content under conditions
of stirring at 800 rpm and 273 K where the acid value was reduced
from 3.89 to 0.4 in 3 h of treatment.
2.2. Reactor configuration
The schematic of the experimental setup is shown in Fig. 1. The
basic setup is similar to that used in the earlier work [25], but the
present work also uses different geometries of cavitating device
such as slit venturi, circular venturi in addition to the more com-
monly used orifice plate. The setup consists of a holding tank of
15 L volume, a multistage centrifugal booster pump of power rat-
ing 1.5 kW and a recirculation loop provided with control valves,
main line which accommodates the cavitating device and a bypass
line to control the flow. The range of inlet pressure used in the
work was 1–5 bar with the inlet flow rate varying over the range
1.58–5.83 LPM (2.63  105 m3/s to 9.72  105 m3/s). The pres-
sure gauge P1 is used to measure the inlet pressure of the liquid.
In this system, the reactants flow continuously from the tank to
cavitating device and is introduced back into the tank (recircula-
tion mode of operation) using a centrifugal pump. Due to these
effects, it is expected that uniform mixing of the reactants occurs
in the tank. The recirculation through the cavitation chamber is
intensifying the reaction due to the cavitational effects leading to
the creation of fine emulsion and generating large interfacial area
for the reaction. Depending on the increase in the flow rate, the
number of passes experienced by the reactant mixture through
the cavitation chamber will increase. For example, when the flow
rate is at minimum of 1.58 LPM, the number of recirculation of
the entire reactant mixture would be around 6 during the entire
Table 1
Physical and chemical properties of waste cooking oil.
Property Value
Physical
Saponification value (mg kOH/g of oil) 207.7
Density (kg/m3) 928
Acid value (mg KOH/g oil) 3.89
Viscosity (mm2/s) 96.5
Water content (%) 0.7
Chemical
Linoleic acid (%) 73.4
Oleic acid (%) 18.3
Palmitic acid (%) 6.7
Stearic acid (%) 1.6
 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292 287

Fig. 1. Schematic representation of hydrodynamic cavitation reactor set-up and cavitating devices.

A jacket was provided to the tank to control the operating temper-

Table 2
Dimensions of circular and slit venturi.
ature below the boiling point of methyl acetate. Cooling water was
circulated in the surrounding jacket to counter the heat dissipation
Dimension Circular venturi Slit venturi arising from the cavitational events.
Dimension of throat Circular hole of 2 mm W = 3.7 mm
diameter H = 0.92 mm
L = 0.92 mm 2.3. Experimental methodology
Venturi length 106 mm 86 mm
Length of convergent section 18 mm 18 mm
Length of divergent section 67 mm 65 mm The reactor was initially charged with known amount of WCO
Half angle of convergent 22.6° 22.6° and methyl acetate, and the mixture was circulated through the
section closed loop for achieving near uniform mixing of the contents.
Half angle of divergent 6.5° 6.5°
The upstream pressure was adjusted using the valve on the bypass
section
a (perimeter/area) 2 mm 1
2.71 mm1 line and after achieving the desired pressure, catalyst was added to
the reactor which is considered as the starting point of the reac-
tion. Samples were collected at pre-designated times and were
immediately quenched using equimolar amount of ortho-phospho-
ric acid to arrest the progress of the reaction in the withdrawn
reaction time which increases to around 23 at maximum flow rate. samples. After this treatment, water washing was performed for
In the experimental setup, there is a sample collection port in the removal of the excess catalyst from the mixture followed by the
main line (Fig. 1 gives the location) (S1) where the liquid mixture use of a molecular sieve (3°A) to remove the trace amount of mois-
coming out immediately after the cavitating device will be col- ture. Samples were then analysed using HPLC. The different oper-
lected. Fig. 1 also shows three cavitating devices used in this work ating parameters used in the present work, to optimize the yield
viz. orifice plate (1 mm thickness with 2 mm hole at the centre), of biodiesel from waste cooking oil, include geometry of cavitating
circular and slit venturi (dimensions have been given in Table 2). device (orifice plate, circular and slit venturi), inlet pressure
288 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292
(1–5 bar), oil to methyl acetate molar ratio (OMAMR) (1:10, 1:12
and 1:14) and catalyst concentration (0.75%, 1% and 1.25% by
weight of the charged oil). All the experiments were repeated at
least two times and the reported data is the average of the
obtained datasets. The experimental errors were typically found
to be within limits of 2% of the reported average values.
2.4. Method of analysis
The progress of reaction was monitored by estimation of the
methyl ester formation using high-performance liquid chromatog-
raphy (HPLC). The details of analysis methods have been described
in the earlier work [26].
3. Results and discussions
3.1. Hydraulic characteristics
Initially the measurements of flow rate and power dissipation
into the system have been performed for understanding the
hydraulic characteristics for all the cavitating devices. The actual
power dissipated (PD) into the system was calculated based on
the pressure drop and volumetric flow rate as per the following
equation
Power dissipated into the system ðPD ; J=SÞ
¼ Pressure drop across the cavitating device ðDP; PaÞ
 Volumetric flow rate through the cavitating device ðV 0 ; m3 =sÞ
ð1Þ
Cavitation number (CV) is a dimensionless number used to char-
acterize the cavitational intensity and degree of cavitation in
hydraulic devices [27,28] and was estimated based on the pressure
drop across the constriction and the velocity at the throat. The
degree of cavitation and its intensity generated by cavitating
device which is responsible for intensification of biodiesel produc-
tion [20] is dependent on cavitation number and hence it is impor-
tant to perform calculations of cavitation number and power
dissipation level. Fig. 2 depicts the effect of the inlet pressure to
the cavitating device on the cavitation number over the range of
1–5 bars. It is evident that cavitation number decreases with an
increase in the pump discharge pressure, which can be attributed
to the increase in the velocity at the throat of the venturi, which
subsequently reduces the cavitation number leading to more
intense cavitating conditions. It was also observed from Fig. 2 that
the cavitation number in the slit venturi is less as compared to cir-
cular venturi and orifice plate attributed to the higher volumetric
flow rate obtained in the slit venturi which correspond to lower
cavitation number. The obtained result can also be explained on
the basis of the ratio of the perimeter of cavitating holes to its cross
sectional area (a) as mentioned in Table 2, which is an important
parameter determining the number density of cavities generated
in the system. Moholkar et al. [29] have reported that an increased
cavitation yield (the ratio of the amount of decomposition of potas-
sium iodide to the actual energy input to the system) is obtained
with an increase in the value of a. Increase in the ratio results in
a corresponding increase in the area of the shear layer in the flow
giving higher cavitationally active volume in the reactor. In the
present case, it has been also established that value of a is higher
for the slit venturi as compared to circular venturi (Table 2), which
should give higher cavitational intensity.
The calculations of ratio of the actually dissipated power to the
supplied power (1.5 kW in all the cases) also confirmed that the
ratio was the maximum for the slit venturi as compared to other
devices viz. orifice plate and circular venturi. The power dissipated
4
Orifice
3 Circular venturi
Cavitaon number Cv
Slit venturi
2
1
0
0 1 2 3 4 5 6
Inlet pressure (bar)
Fig. 2. Effect of inlet pressure on cavitation number (CV).
into the system for the slit venturi was almost 1.1 times higher
than circular venturi and 1.5 times higher than orifice plate.
Saharan et al. [30] have also carried out geometric optimization
of different cavitating devices such as orifice plate, circular and slit
venturi for the specific case of degradation of orange-G dye as a
model pollutant, and reported similar results for higher power
dissipation into the system for the slit venturi.
3.2. Effect of type of cavitating device on the yield of biodiesel
The effect of type of cavitating device on biodiesel yield in inter-
esterification reaction between WCO and methyl acetate has been
investigated using different cavitating device such as orifice plate,
circular and slit venturi under the fixed conditions of reactant
molar ratio (1:12 of OMAMR), catalyst loading (1% by weight of
oil) and inlet pressure of 3 bar. The obtained results have been pre-
sented in Fig. 3, where it can be seen that biodiesel yield of 64% for
the orifice plate, 82% for the circular and 89% for the slit venturi
was obtained. The observed results can be explained on the basis
of the higher volumetric flow rate for a given pressure drop and
lower cavitation number being obtained in slit venturi as com-
pared to orifice plate and circular venturi. The number of cavita-
tional events and the intensity increases with a decrease in
cavitation number and these cavitational events are responsible
for formation of local turbulence, liquid micro-circulation and
micro-emulsion ultimately enhancing the biodiesel yield. Bashir
et al. [31] have reported the optimization of the important geomet-
100
80
60
% Yield
40
20
0
0 10 20 30 40 50 60 70
Time (min)
Fig. 3. Effect of geometry on yield of biodiesel (reaction conditions:
OMAMR = 1:12; catalyst concentration = 1% (by wt. of oil); inlet pressure = 3 bar).
 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292
rical parameters of a cavitating device in terms of the perimeter
ratio (a) and the ratio of the throat length to its height (in the case
of a slit venturi). These geometrical parameters control the maxi-
mum size of the cavity, the number of cavities generated and the
rate of collapse of a cavity. It was reported that the slit venturi hav-
ing a of 2.7, slit length to height ratio as 0.5 and a half angle of
divergence section of 5.5° is an optimum geometry for the best
cavitational activity as compared to circular venturi and orifice.
Also the dimensions of the cavitational zone and the number of
cavities are higher [31] in the case of slit venturi yielding the max-
imum cavitational events. The higher biodiesel yield obtained in
the current work for the slit venturi as compared to the other
two geometries can be thus confirmed on the basis of the CFD
results for cavitational intensity [31]. Similar results for the effect
of geometry of cavitating device on the degradation of orange-G
has been reported by Saharan et al. [30] where the cavitational
yield was quantified in terms of total organic carbon reduced per
unit energy supplied. It was reported that slit venturi gives almost
50% higher degradation rate and cavitational yield. It is also impor-
tant to note here that the extent of increase in the final cavitational
yield would also be dependent on the specific application (as also
confirmed here; about 10% increase in the biodiesel yield as against
about 50% increase observed in the case of orange-G degradation).
Overall it can be concluded that in the case of slit venturi, number
of cavitational event are more as compared to orifice plate and cir-
cular venturi giving beneficial effects and hence slit venturi has
been used as cavitating device for the further set of experiments
related to optimization of interesterification reactions. It is also
important to note here that there would be some mixing effects
and reaction occurring without the presence of any cavitating
device, though the extent of yields would be much lower as com-
pared to that obtained in the presence of cavitating device. The
results for such control experiments has been presented in the
work of Ghayal et al. [32] which confirmed that significantly lower
extent of conversion (only around 40%) is obtained in the absence
of cavitating device as compared to the presence of cavitating
device (90%). The results can be attributed to existence of only
macro-level mixing in absence of cavitating device which is due
to the recirculation of the reactants.
3.3. Effect of inlet pressure
The effect of inlet pressure on biodiesel yield has been investi-
gated over inlet pressure ranging from 2 to 5 bars using slit venturi
as cavitating device under the fixed conditions of reactant molar
ratio (1:12 of OMAMR) and catalyst loading (1% by weight of oil).
The obtained results have been depicted in Fig. 4. From Fig. 4, it
can been seen that as the inlet pressure increases from 2 to 3 bars,
the biodiesel yield increases from 79 to 89 but with further
increase in inlet pressure from 3 to 4 bar, there is no significant
increase in the biodiesel yield. A subsequent increase in inlet pres-
sure from 4 to 5 bar resulted in a marginal decrease in the biodiesel
yield from 89% to 85%. The obtained results can be attributed to the
fact that, increase in the inlet pressure leads to an increase in num-
ber of cavitational events and overall cavitational activity giving
increase in the biodiesel yield. The observed decrease in the biodie-
sel yield beyond inlet pressure of 4 bar can be due to the condition
called chocked cavitation where the downstream is completely
filled with a large cavity cloud, which escape the liquid without
collapsing giving reduced cavitational intensity and hence
decrease in the biodiesel yield. Ghayal et al. [32] have studied
the effect of the inlet pressure on the production of biodiesel based
on the transesterification reaction between used frying oil as a
feedstock and methanol and reported similar beneficial results
up to an optimum value of inlet pressure. Based on the obtained
results with varying pressure, an inlet pressure of 3 bar has been
289
Fig. 4. Effect of inlet pressure on yield of biodiesel (reaction conditions: cavitating
device = slit venturi; OMAMR = 1:12; catalyst concentration = 1% (by wt. of oil)).
used for further studies, as maximum biodiesel yield of 89% was
obtained at 3 bar in the case of slit venturi.
3.4. Effect of molar ratio
To study the effect of oil to methyl acetate molar ratio
(OMAMR) on biodiesel yield, experiments were conducted over
the range of molar ratio from 1:10 to 1:14. As per the reaction
stoichiometry, the required value of OMAMR is 1:3. As interesteri-
fication reaction is reversible in nature, higher oil to methyl acetate
molar ratio favours the forward reaction for the production of
desired product. In our previous study [26] for ultrasound assisted
interesterification, reaction was carried at OMAMR from 1:4 to
1:14, where obtained optimum molar ratio was 1:12. Based on
these results, significantly lower ratios have not been selected in
the present work as it is expected that the conversions will be
lower. The obtained results are shown in Fig. 5 where it can be seen
that the biodiesel yield increases from 83% to 89% with an increase
in the molar ratio from 1:10 to 1:12. An excess of methyl acetate
results in limiting the backward reaction giving an increase in
the equilibrium conversion of WCO to biodiesel. A further increase
in the OMAMR from 1:12 to 1:14 did not give significant beneficial
effects in terms of the enhanced conversion of oil. Using too much
excess of reactants also increases the load on separation and needs
to be avoided. It is worthwhile to compare the yields of biodiesel
using interesterification based on different approaches to establish
the dependency of optimum molar ratio on the synthesis approach.
Casas et al. [7] reported the biodiesel yield of 76.7% at OMAMR
of 1:50 using the conventional approach of only mechanical stir-
ring which is lower than that obtained using hydrodynamic cavita-
tion in the present work at molar ratio of 1:12. The obtained
intensification in the present work (both enhanced yield and lower
requirement of excess reactants) can be attributed to the cavita-
tional effects of micro-emulsification and streaming [24]. Usai
et al. [9] studied enzymatic interesterification reaction of triglycer-
ides such as olive oils with methyl acetate and reported yields of
about 80% at OMAMR of 1:20 using immobilized lipase candida
Antarctica over a reaction time of 24 h. Campanelli et al. [13]
reported that different oils as edible oils (soybean and sunflower
seed oil), non-edible oils (Jatropha curcas) and waste oil gave com-
plete conversion after 50 min at 345 °C and 20 MPa pressure with
oil to methyl acetate molar ratio equal to 1:42. Comparison with
the literature data confirms requirement of significantly higher
molar ratios for synthesis based on supercritical conditions and
substantially higher reactions times for the enzymatic reactions
as compared to the present approach based on the hydrodynamic
cavitation reactors. Thus, hydrodynamic cavitation based conver-
sion of WCO to biodiesel is a sustainable approach reducing the
290 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292
Fig. 5. Effect of molar ratio on yield of biodiesel (reaction conditions: cavitating
device = slit venturi; inlet pressure = 3 bar; catalyst concentration = 1% (by wt. of
oil)).
requirement of methyl acetate with lower reaction times and
milder ambient conditions. All these factors also strongly influence
the energy requirement for the overall synthesis process in a
favourable manner and hence the approach can be very promising.
3.5. Effect of catalyst concentration
Any use of excess catalyst with an objective of increasing reac-
tion rates also increases the load on the catalyst separation process
and hence understanding the effect of catalyst concentration is
very important. The effect of potassium methoxide concentration
on the biodiesel yields has been investigated over a concentration
range of 0.75–1.25% and the results have been shown in Fig. 6. It
has been observed that an increase in the catalyst concentration
from 0.75% to 1% results in increased biodiesel yield from 79% to
89%. Initially, the increase in the catalyst loading provides
enhanced active sites for reaction giving higher conversion of tri-
glycerides into the corresponding methyl esters i.e., biodiesel.
However, a further increase in the catalyst concentration from 1
to 1.25 wt.% does not show any significant increase in the biodiesel
yield and hence it can be concluded that 1% catalyst loading is the
optimum. Casas et al. [33] have investigated the interesterification
reaction of sunflower oil and methyl acetate for biodiesel
production and reported that a maximum conversion of 76.7%
was obtained at an optimized catalyst loading of 1.04% by weight
of the catalyst. Similar existence of optimum catalyst loading has
been reported by Suppalakpanya et al. [34] for the transesterifica-
Fig. 6. Effect of catalyst concentration on yield of biodiesel (reaction conditions:
cavitating device = slit venturi; OMAMR = 1:12; inlet pressure = 3 bar).
tion reaction of crude palm oil with potassium hydroxide as the
catalyst. The studies clearly establish the requirement of selecting
optimum loading of catalyst. The optimum amount of catalyst
established in the present work was 1 wt.%, which is based on
the fact that a further increase to 1.25% results in only marginal
increase in the biodiesel yields but the separation costs are on a
higher side as compared to the benefits.
3.6. Biodiesel properties
The biodiesel properties such as kinematic viscosity, density,
pour point, flash point and acid value of the final dried product
were obtained for the biodiesel synthesized at optimum condition
of oil to methyl acetate molar ratio of 1:12 and catalyst concentra-
tion of 1% by wt. of WCO. In our pervious study [26] of ultrasound
assisted interesterification reaction, we have established the bio-
diesel properties obtained by conventional and ultrasound method
at similar reaction conditions of molar ratio and catalyst concen-
tration. Biodiesel properties obtained using all the approaches
i.e., conventional, ultrasound and hydrodynamic cavitation are
shown in Table 3. It was observed that the biodiesel properties
match with the ASTM D6751 standards. The kinematic viscosity
and acid value of biodiesel obtained from hydrodynamic cavitation
method is lower as compared to conventional and ultrasound
method. The flash point of the biodiesel synthesized from hydrody-
namic cavitation method (151 °C) is also lower than that obtained
using the conventional method (190 °C) and ultrasound (155 °C)
which can be attributed to higher purity of the final product.
Higher flash point in the case of conventional method as compared
to hydrodynamic cavitation and ultrasound method is due to the
presence of unreacted oil in the final product which corresponds
to lower conversion of WCO into biodiesel. Flash point of biodiesel
obtained using hydrodynamic cavitation based synthesis was also
lower as compared to biodiesel produced from other sources such
as Nagchampa (177 °C) [35], Karanja (230 °C) [36] and Madhuca
indica (208 °C) [37]. Based on this comparison of product
properties, the superiority of the hydrodynamic cavitation assisted
synthesis of biodiesel can be clearly established.
4. Comparison between cavitational and conventional method
for biodiesel synthesis
It is worthwhile to summarize the extent of intensification
obtained using cavitation based technique such as hydrodynamic
cavitation and ultrasound irradiation also comparing with conven-
tional stirring method for biodiesel production. Biodiesel yield,
cavitational yield (yield of product per unit supplied energy to
the system) and kinetic rate constants for hydrodynamic cavitation
(based on present work), conventional reflux heating method and
ultrasound assisted synthesis (based on the earlier work [26]) have
been reported in Table 3 under the fixed reaction condition of
OMAMR of 1:12 and the catalyst concentration of 1% by wt. of
WCO. Cavitational yield was calculated based on procedure sug-
gested by Saharan et al. [30] whereas the second order kinetic rate
constants have been obtained as per the procedure explained in
the earlier work [26]. The biodiesel yield is higher for the cavitation
based technique as compared to the conventional method. In the
case of cavitation technique, higher reaction rate was observed in
the case of ultrasound as compared to hydrodynamic cavitation.
The obtained result is attributed to the fact that amount of energy
dissipated per unit of reaction volume as well as the cavitational
intensity is high in case of ultrasound technique as compared to
hydrodynamic cavitation. It is important to note that hydrody-
namic cavitation is more energy efficient compared to both the
approaches of ultrasound assisted synthesis and conventional
 G.L. Maddikeri et al. / Fuel 137 (2014) 285–292
Table 3
Characteristics of biodiesel synthesis process.
Property Conventional
Biodiesel properties
Density (g/cm3) 0.8637
Kinematic viscosity, (40 °C, mm2/s) 3.64
Flash point (°C) 168
Acid value (mg of KOH/g of oil) 0.71
Characteristics of synthesis process
Parameter Conventional
Cavitational yield (kg/kJ) 3.22  1005
Rate constant k (lit/mole. min) 1.56  1001
Biodiesel yield (%) 70
reflux heating. The cavitational yield for hydrodynamic cavitation
was 1.22  103 kg/kJ whereas the value of cavitational yield was
4.76  105 kg/kJ for the ultrasound based operation and the value
for the conventional approach was 3.22  105 kg/kJ. Comparison
with the literature illustrations [33] have also enabled to confirm
that hydrodynamic cavitation based approach gives higher biodie-
sel yields at significantly lower molar ratios of the reactants and
also the required reaction time is lower. Similar superiority of
the use of cavitation technique has been reported commonly in
the literature for the transesterification reactions [20,21] though
not much illustration can be obtained for the interesterification
reaction and hence the novelty of the present work can be
established.
4. Conclusions
Hydrodynamic cavitation can be effectively used for the
intensification of interesterification reaction for the synthesis of
biodiesel and triacetin from WCO. The presented results in the cur-
rent work are very important in the context of current scenario as
it has focused on one of the cheaper synthesis routes based on the
use of hydrodynamic cavitation for biodiesel production from
waste oils. The study using different cavitating device confirmed
that slit venturi gives better biodiesel yield as compared to orifice
plate and circular venturi. Biodiesel yield of 89.24% has been
obtained at optimized operating parameters viz. use of slit venturi;
OMAMR of 1:12; catalyst concentration of 1% by weight of WCO
and inlet pressure to the cavitating device as 3 bar. The energy effi-
cient approach based on the use of hydrodynamic cavitation (slit
venturi as the cavitating device) as compared to the conventional
method and ultrasound assisted synthesis has also been confirmed.
The micro level turbulence generated by the dynamic behaviour of
the cavitation bubbles assist in intensifying interesterification
reaction by formation of a fine emulsion providing enhanced
reaction area and turbulence which reduces the mass transfer
resistance. The properties of biodiesel match with the ASTM stan-
dards and superior properties of final product are obtained for the
hydrodynamic cavitation assisted approach. Overall, the approach
based on hydrodynamic cavitation gives intensified processing
with higher biodiesel yield and also offers various improvements
such as use of ambient conditions, requirement of lower excess
of reactants and higher cavitation yield.
Acknowledgments
GLM is thankful to the University Grants Commission, Govern-
ment of India for the financial assistance. GLM would also like to
acknowledge the help of M.P. Badve and Virendra Saharan in the
preparation of the manuscript.
291
Ultrasound Hydrodynamic ASTM D6751
0.871 0.865 0.86–0.9
3.78 3.67 1.9–6.0
155 151 100–170 °C
0.28 0.26 0.5 max
Ultrasound Hydrodynamic
4.74  1005 1.22  1003
6.03  1001 3.22  1001
90 89.24
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