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Ultrasonics Sonochemistry 15 (2008) 188194

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Intensication of esterication of acids for synthesis of biodiesel

using acoustic and hydrodynamic cavitation
Mandar A. Kelkar, Parag R. Gogate, Aniruddha B. Pandit *

Chemical Engineering Department, Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India

Received 1 January 2007; received in revised form 15 March 2007; accepted 5 April 2007
Available online 29 April 2007

Abstract

Cavitation results in conditions of turbulence and liquid circulation in the reactor which can aid in eliminating mass transfer resis-
tances. The present work illustrates the use of cavitation for intensication of biodiesel synthesis (esterication) reaction, which is mass
transfer limited reaction considering the immiscible nature of the reactants, i.e., fatty acids and alcohol. Esterication of fatty acid (FA)
odour cut (C8C10) with methanol in the presence of concentrated H2SO4 as a catalyst has been studied in hydrodynamic cavitation reac-
tor as well as in the sonochemical reactor. The dierent reaction operating parameters such as molar ratio of acid to alcohol, catalyst
quantity have been optimized under acoustic as well as hydrodynamic cavitating conditions in addition to the optimization of the geom-
etry of the orice plate in the case of hydrodynamic cavitation reactors. Few experiments have also been carried out with other acid
(lower and higher)/methanol combination viz. caprylic acid and capric acids with methanol with an aim of investigating the ecacy
of cavitation for giving the desired yields and also to quantify the degree of process intensication that can be achieved using the same.
It has been observed that ambient operating conditions of temperature and pressure and reaction times of <3 h, for all the dierent com-
binations of acid (lower and higher)/methanol studied in the present work, was sucient for giving >90% conversion (mol%). This
clearly establishes the ecacy of cavitation as an excellent way to achieve process intensication of the biodiesel synthesis process.
 2007 Elsevier B.V. All rights reserved.

Keywords: Cavitation; Sonochemistry; Hydrodynamic cavitation; Biodiesel; Process intensication

1. Introduction biodiesel refers to a catalysed chemical reaction involving

Various products derived from vegetable oils have been
proposed as an alternative fuel for diesel engines. Today
biodiesel is the term applied to the esters of simple alkyl
fatty acids used as an alternative to petroleum based diesel
fuels. Importance of biodiesel in the recent context
increases due to increasing petroleum prices; limited fossil
fuel reserves and environmental benets of biodiesel viz.
decrease in acid rain, decrease in emission of CO2, SOx
and unburnt hydrocarbons during the combustion process
[1,2]. Due to these factors, and due to its easy biodegrad-
ability, production of biodiesel is considered as an advan-
tage over that of fossil fuels. Chemical synthesis of
*
Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614.
E-mail address: abp@udct.org (A.B. Pandit).
vegetable oil and an alcohol (methyl or ethyl) to yield acid
alkali esters and glycerol. Usually waste vegetable oils as
against virgin vegetable oil have been used for the synthesis
with an aim to reduce the cost of production [1]. The con-
ventional techniques based on use of stirring typically uti-
lize temperatures in the range of 70200 C, pressures in
the range of 610 atm and reaction times of up to 70 h
for achieving conversions in the range of 9095 mol%
based on the type of raw material used, type and concen-
tration of the catalyst and the percentage excess of alcohol
[35]. At present, the high cost of biodiesel is the major
obstacle to its commercialization. It is reported that the
high cost of biodiesel is mainly due to the cost of virgin
vegetable oil [1]. Exploring ways to reduce the high cost
of biodiesel is of much interest in recent biodiesel research.
Increasing the rates of reaction can be one of the

1350-4177/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2007.04.003
 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194
approaches for cost reduction. The main reason for low
rates of trans-esterication reactions is the mass transfer
limitations since the acid and alcohol form immiscible
phases in the system. Cavitation results in conditions of
local intense turbulence and liquid circulation currents,
which should increase the rates of chemical reactions which
are limited by mass transfer resistances [6,7]. Extent of
intensication obtained in the rates of reaction will be
dependent on the number of cavitation events occurring
in the reactor and aim of the designers should be to maxi-
mize these eects. There have been some reports in the
recent past depicting the use of cavitation for synthesis
of biodiesel from pure vegetable oils [2,8,9]. However, the
use of pure vegetable oils results in higher production
costs as compared to waste oil (fatty acid odour cut).
The present work utilizes waste oil (fatty acid odour cut)
instead of virgin oil to produce biodiesel and illustrates
an eective way to reduce the raw material cost. Also,
Stavarache et al. [2,8,9] have used only ultrasonically gen-
erated cavitation which is not an energy ecient way of
generating cavitating conditions compared to hydrody-
namic cavitation, which has been investigated in the pres-
ent work.
In the present work, the esterication reaction of
C8C10 fatty acid cut has been carried out with methanol
using concentrated H2SO4 as a catalyst. Acoustic and
hydrodynamic cavitation has been investigated with an
objective of intensifying the biodiesel synthesis process
using fatty acids. Preliminary studies with virgin vegetable
oil (sunower oil and palm oil) indicated that conven-
tional approach of stirring is about 10 times slower as
compared to acoustic and hydrodynamic cavitation. Tak-
ing a lead from these results, esterication using stirring
was not investigated as it is expected to be still slower
for waste cooking oil (C8C10 fatty acid cut) and compar-
ison with literature results for conventional approach have
been done as discussed later. Use of heterogeneous cata-
lytic conditions has also been investigated since industri-
ally it is always important to use heterogeneous catalyst
as it can be easily recycled. Superacid clay has been used
as a catalyst. The main reason of using this catalyst is the
ease of regeneration and reuse so that wastage of the cat-
alyst can be minimized. To check applicability of the tech-
nique for dierent combinations of oil/alcohol systems,
additional experiments have also been performed with
caprylic acid/methanol system and capric acid/methanol
system.
2. Experimental methodology
2.1. Reactor congurations
The hydrodynamic cavitation reactor (Fig. 1) consists of
a reservoir or a collecting tank with 10 l capacity that is
connected to the multistage centrifugal pump with power
rating of 1.5 kW. Centrifugal pump is the main device for
energy dissipation in the hydrodynamic cavitation reactor.
189
Fig. 1. Schematic representation of the experimental setup for hydrody-
namic cavitation reactor.
Calorimetric studies indicated that about 65% of the sup-
plied energy is actually dissipated in the system and avail-
able for generation of cavitation events. The suction side
of the pump is connected to the bottom of tank. The dis-
charge from the pump branches into two lines which help
in control of the inlet pressure and the inlet ow rate into
the main line housing the orice with the help of valves
V2 and V3. The main line consists of a ange to accommo-
date the orice plates. The inlet pressure and the fully
recovered downstream pressure can be measured with the
pressure gauges P1 and P2, respectively. The operating tem-
perature of the reactor was maintained to near ambient
conditions (around 28 C with accuracy of 1 C) by circu-
lating water within the jacket surrounding the tank as the
energy dissipated by the pump can increase the tempera-
ture of the mixture.
The sonochemical reactor used in the present work is a
conventional cleaning tank type reactor (ultrasonic bath)
equipped with three transducers at the bottom of the tank
arranged in a triangular pitch and operates at an irradiat-
ing frequency of 20 kHz and power dissipation of 120 W
(calorimetrically measured exact power dissipation was
45 W indicating about 37.5% energy conversion and trans-
fer eciency; the transfer eciency is usually dependent
on the operating frequency, shape, size and the number
of the transducers, location of the transducers, etc., which
can be optimized to get maximum energy conversion). The
bath had dimensions of 15 cm 15 cm 15 cm. The max-
imum volume of the reaction medium that could be used
directly in the case of ultrasonic bath was 3500 ml. The
schematic representation of the ultrasonic bath is shown
in Fig. 2. The operation time was distributed in cycles of
10 min on followed by 10 min o to allow for cooling of
the reaction mass using an external heat exchanger. The
temperature was maintained around 28 C with accuracy
of 2 C.
190 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194
Fig. 2. Schematic representation of sonochemical reactor generating
acoustic cavitation.
2.2. Experimental procedure for esterication reaction of FA
with methanol under hydrodynamic cavitation reactor
Fatty acid (FA) odour cut (C8C10) was taken in a su-
cient amount and added to the hydrodynamic cavitation
reactor. The conc. H2SO4 as a catalyst (1% by weight of
the reactants FA) was mixed with a known quantity of
methanol. The excess methanol (molar ratio of methanol
to FA cut 5:1 or 10:1) was used to overcome the equilibrium
limitations. The methanolH2SO4 mixture was also added
to the reactor. The reaction mixture was then circulated
through the cavitation zone of the reactor. The samples
were taken after every 15 min and the acid value of this sam-
ple was found out. The acid value is dened as the amount
of NaOH necessary to neutralize the 1 g of the FA sample.
The decrease in the acid value showed the forward progress
of the esterication reaction. The excess methanol was dis-
tilled out and the mixture of unreacted FA cut and methyl
ester was washed with alkali (NaOH) solution to remove
the unreacted FA as soap and neutralize the sulfuric acid.
After washing to remove soap and neutral salts, the mixture
was allowed to separate in a separating funnel. The top
layer comprising mainly methyl esters, was taken for analy-
sis. The sample was then analyzed by GLC. The analysis
was done using an Agilent 6890N gas chromatograph (M/s
Agilent Technologies, USA) and a BPX 70 column with
30 m 0.32 mm 0.25 lm dimensions. The detector used
was FID with nitrogen as a carrier gas (at a ow rate of
1.2 ml/min). The bottom layer was a soapy layer, which
comprised of soap due to the saponication of the unre-
acted FA with NaOH solution and neutralized H2SO4 in
the form of Na2SO4 salt as well.
2.3. Experimental procedure for an esterication of FA
(C8C10) with methanol under acoustic cavitation reactor
FA odour cut (C8C10) in a known quantity was taken
in a round bottom ask. Methanol in excess (molar ratio
of methanol to FA cut as 5:1 or 10:1) was added to the
FA cut. The conc. sulfuric acid as a catalyst was mixed
with this reaction mixture. The mixture was then sonicated
under ultrasound. The reaction has been carried out at
temperature of about 40 C. The samples were taken for
every 30 min interval and acid value was found out every
time. In this case also, the same procedure as in hydrody-
namic cavitation has been followed regarding the removal
of unreacted methanol by distillation and unreacted FA
cut and conc. sulfuric acid catalyst by alkali washing.
Additional experiments were also performed using solid
superacid clay (chlorosulfonic acid supported on zirco-
nium) as a catalyst using similar experimental methodology
as mentioned above. Superacid clay was used in powder
form and was observed to get deactivated during the reac-
tion possibly due to the adsorption of water molecules on
the active sites. It is also expected that under the eects
of cavitation the morphology of catalyst changes though
exact quantication could not be done due to unavailabil-
ity of the surface characterization instruments. For regen-
eration of the catalyst, the used superacid initially is
reuxed with methanol at 70 C for 2 h. It is then dried
and kept at 110 C for 1 h before reuse.
Each experimental run was repeated a minimum of two
times to check the reproducibility of the obtained data and
the experimental results were found to be reproducible
within the limits of 1%.
3. Results and discussion
The initial optimization was done in terms of establish-
ing the eect of molar ratio FA to MeOH and the eect of
catalyst concentration (conc. H2SO4) on the extent of con-
version under acoustic and hydrodynamic cavitation.
3.1. Eect of molar ratio
The esterication was carried out using 1:2, 1:5 and 1:10
molar ratios of FA to MeOH with the quantity of conc.
H2SO4 kept at a concentration of 1% by weight of the reac-
tants FA under hydrodynamic cavitating conditions.
Excess methanol was used every time since the water being
formed during the esterication reaction gets dissolved in
this excess methanol. Thus, equilibrium limitation due to
the reversibility of the reaction can be shifted towards right
side of the reaction. The esterication reaction can be writ-
ten as follows:
R1 COOH CH3 OH R1 COOCH3 H2 O
FA cut Methanol Methyl esters Water
The reaction was found to proceed up to 90% conversion
(mol%) levels at appreciable rate beyond which the rate of
progress of the reaction was substantially slower. This is
due to the dilution of the acid catalyst with the water
formed in the reaction reducing its catalytic activity. Thus
for establishing the comparative eect of mole ratio of the
reactants, time required to reach near 90% conversion
 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194
(mol%) has been considered as the criteria. The results of
these runs are given in Table 1. It can be seen that the time
required for achieving 90% conversion (mol%) decreases
with an increase in the amount of methanol in the system.
This can be attributed to the fact due to higher concentra-
tion of methanol in the system (more aqueous layer), higher
intensity cavitation is generated leading to benecial eects
as well as reducing the equilibrium limitation due to a large
excess of methanol.
Under acoustic cavitation also, eect of molar ratio has
been investigated at a catalyst loading of 1% by weight of
the fatty acids. The results obtained have been given in
Fig. 3. It can be seen from the gure that the conversion
of about 98% (mol%) was achieved in 2 h with a molar
ratio of 1:10 and about 91% conversion (mol%) was
obtained in 3 h for the operating molar ratio of 1:5. Thus
in the case of acoustic cavitation also, an optimum molar
ratio of 1:10 has been observed.
It should be also noted here that using additional meth-
anol although speeds up the reaction, it also increases the
separation (methanol recovery) load on the system (only
specic amount of methanol is required for actual reaction
and hence any excess will appear as unreacted methanol
thereby increasing the separation load) and hence an opti-
mum operating ratio should be selected on the basis of
overall economics and the equilibrium conversion. Over
the range of the molar ratios investigated in the present
work, biodiesel synthesis process was signicantly aected
by the increase in the molar ratio of fatty acid to alcohol
and 1:10 molar ratio appears to be the optimum molar
ratio.
Table 1
Eect of molar ratio of FA cut to methanol under hydrodynamic
cavitating conditions at 1% by weight of catalyst conc. H2SO4
Molar ratio Time (min) % Conversion (mol%)
1:2 210 90
1:5 150 91
1:10 90 92
100
80
Conversion (mol%)
60
40
1:5 molar ratio
20
1:10 molar ratio
0 0
0 50 100 150
Time (min)
Fig. 3. Eect of molar ratio of FA cut to methanol under acoustic
cavitating conditions at 1% by weight of catalyst conc. H2SO4.
191
3.2. Eect of catalyst concentration
The amount of catalyst used, has also been optimized to
get conversion to methyl esters in the excess of 95%
(mol%). The eect of variation in the catalyst concentra-
tions (two loadings at a level of 1% and 2% by weight of
the reactants) has been studied at two dierent operating
molar ratio of FA to methanol (1:5 and 1:10). The results
obtained have been shown in Fig. 4. The results indicate
that the higher catalyst loading was benecial in both the
cases. At operating molar ratio of 1:5, the extent of conver-
sion increased from 91% (mol%) in 3 h of reaction time to
about 97% (mol%) in only 90 min of reaction time, when
the catalyst concentration was increased from 1% to 2%.
At an operating molar ratio of 1:10, the conversion
increased from 98% (mol%) in 2 h to about 100% (mol%)
in 90 min of treatment time for a similar increase in the cat-
alyst concentration from 1% to 2%. Considering the excess
cost associated with the separation of the excess methanol,
increasing catalyst loading for increasing the overall yields
of biodiesel appears to be a more attractive option.
3.3. Eect of change in type of the catalyst
To minimize the cost of the synthesis of biodiesel, some
additional experiments in terms of checking the suitability
of heterogeneous catalyst were also performed. Superacid
clay was used as a catalyst instead of conc. H2SO4. The
main reason of using clay catalyst was that it could be
regenerated and reused, as it gets deactivated due to the
water formed in the reaction. The superacid clay is a chlo-
rosulfonic acid supported on zirconium. The reaction has
been studied at two dierent catalyst loadings (1% and
2% by weight) with a molar ratio of FA:methanol as 1:10.
The extent of conversion obtained at periodic intervals of
treatment has been shown in Fig. 5. Overall it can be said
that with 1% by weight of solid catalyst loading, the extent
of conversion was about 75% (mol%) in 5 h of reaction
100
90
80
Conversion (mol%)
70
60
50
1:5 molar ratio; 1 wt% catalyst
40
1:5 molar ratio; 2 wt% catalyst
30
20 1:10 molar ratio; 1 wt% catalyst
10 1:10 molar ratio; 2 wt% catalyst
200 0 50 100 150 200
Time (min)
Fig. 4. Eect of catalyst concentration on extent of conversion at two
dierent molar ratio of FA cut to methanol using acoustic cavitation.
192 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194
100
80
Conversion (mol%)
60
40
1% by weight catalyst loading
20
2% by weight catalyst loading
0 to MeOH as 1:10, H2SO4 concentration 2% by weight)
0 100 200 300 400
Time (min)
Fig. 5. Dependency of extent of conversion on catalyst loading for the
case of heterogeneous catalyst using acoustic cavitation at FA:methanol
ratio of 1:10.
period. After 150 min of reaction time, it was observed that
the reverse reaction rate substantially increases leading to a
substantial drop in the extent of conversion and increase in
the acid value. The presence of water is known to deactivate
the solid catalyst and hence it is more likely that the reduc-
tion in the forward reaction rate could be due to the deacti-
vation of the catalyst. This process is similar to the dilution
of the H2SO4 in the use of homogeneous catalytic reaction
due to the formation of water. This equilibrium eect can be
overcome by the intermittent regeneration of the used cata-
lyst. After 150 min of reaction, the used catalyst was sub-
jected to regeneration process and partially reactivated
catalyst was again added in the reaction mass. After the
addition of the regenerated catalyst, the reaction was
observed to proceed in the forward direction until about
75% conversion (mol%) obtained at end of 5 h. Regenera-
tion of catalyst at this stage did not result in any improve-
ment in the rates of reaction. This indicates that the
regeneration treatment used in the work cannot eectively
regenerate the active sites of the catalyst after usage for
5 h and hence no increase in the rates of reaction could be
observed.
With 2% by weight loading of the catalyst, the conver-
sion of about 97% (mol%) was achieved in 7 h without sub-
stantial deactivation of the catalyst (attributed to higher
amount of catalyst present in the reaction mass) and there
was no need of intermittent regeneration. To check the
recyclability of the used catalyst, the catalyst was regener-
ated again and the fresh reaction has been carried out with
the regenerated catalyst. The conversion of about only 41%
(mol%) was achieved in similar levels of reaction time. This
indicates that the regeneration techniques used in the pres-
ent work could not remove all the water molecules from the
active sites leading to only a partial activity of the catalyst.
4. Applicability of cavitation to other combinations
of acid/alcohol
With an aim of preparing biodiesel with dierent speci-
cations and also reducing the cost of synthesis, applicabil-
ity of cavitation phenomena for dierent combinations of
fatty acids and alcohols have been investigated. The opti-
mized set of operating parameters for acoustic cavitation
reactor as obtained with FA acid odour cut and methanol
combination has been used and the experimental procedure
is similar to that described earlier.
4.1. Esterication of caprylic acid (C8) with methanol
The optimized parameters (molar ratio of FA odour cut
500 achieved during an esterication of FA odour cut with
methanol have been used to esterify pure caprylic acid
(C8) rather than a fatty acid mixture (C8 and C10) with
methanol using conc. H2SO4 as a catalyst. The results
obtained have been shown in Fig. 6. Conversion levels of
about 99% (mol%) were obtained within 75 min of treat-
ment time and the desired product obtained in this case
was methyl caprylate.
4.2. Esterication of capric acid (C10) with methanol
Keeping all the conditions, i.e., molar ratio of
FA:MeOH and the catalyst quantity, same as during
caprylic acid (C8), an esterication of pure capric acid
(C10) has also been carried out using acoustic cavitation
reactor. The results obtained have been shown in Fig. 6.
In this case also, about 98% conversion (mol%) has been
achieved again in 1 h and 15 min. On comparing the rates
of esterication reactions, it has been observed that the rate
of conversion of C8 acid is slightly higher than that of C10
acid. Though the increase is not signicant (and is within
the limits of experimental errors also), it is expected that
the caprylic acid (C8) would be more easily attacked by
the methanol to produce the corresponding esters, taking
into account the steric hindrance of organic acids. Also,
100
80
Conversion (mol%)
60
40
20 Caprylic acid
Capric acid
0
0 20 40 60 80
Time (min)
Fig. 6. Extent of conversion levels obtained for esterication of caprylic
acid and capric acid (acid:methanol ratio of 1:10; 2% by weight of catalyst
H2SO4 and using acoustic cavitation).
 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194
as discussed earlier, the extent of cavitation controls the
degree of intensication obtained. In the case of C8 acid,
which has lower boiling point as compared to C10 acid,
the ease of generation of cavities would be higher and
hence the number of cavities generated in the system is
expected to be higher. Thus the degree of intensication
observed in the case of C8 acid is expected to be higher
as compared to C10 acid. The main aim in the present work
is not to compare the rates of reaction in dierent acids but
is to show applicability of cavitation phenomena for syn-
thesis of biodiesel using dierent acids and show that the
rates of reaction are signicantly higher as compared to
the conventional approach.
It can be conclusively established that cavitation can be
eectively applied for synthesis of biodiesel using dierent
combinations of fatty acid and alcohols as the starting
raw materials. All the combinations under optimized con-
ditions result in >95% (mol%) conversion in 90 min of
the treatment time at ambient conditions of temperature
and pressure. The conventional ways of synthesis of biodie-
sel from waste cooking oil based on mechanical stirring as
the source for energy input include use of higher pressures
and temperatures and reaction times of few hours, which
clearly demonstrate the degree of process intensication
achieved using cavitation. To cite a specic illustration as
regards to the degree of process intensication achieved
in the present work; with an operating ratio of FA cut
(waste fatty acids) to methanol as 1:10, 1% by weight load-
ing of the catalyst and at operating temperature of 30 C,
92% conversion (mol%) was achieved using hydrodynamic
cavitation in only 90 min of reaction time whereas conven-
tional method [10,11] for the esterication of waste cooking
oil using methanol under stirring conditions required about
69 h to obtain >90% oil conversion to methyl esters at
65 C operating temperature and a molar ratio of methanol
to oil as 30:1. The requirement of excess methanol also
reduces from about 3050 times the fatty acid [1214] in
conventional technique to about 10 in the case of cavitation
based process as illustrated in the present work. Stavarache
et al. [2,8,9] have also shown a signicant process intensi-
cation using acoustic cavitation for these trans-esterica-
tion reactions.
5. Comparison between hydrodynamic cavitation and
acoustic cavitation
Comparison of hydrodynamic cavitation and acoustic
cavitation reactors have been done using a generalized
parameter of cavitational yield dened as the yield of prod-
uct per unit supplied energy to the system. Considering cost
of synthesis, supplied energy is important since this,
accounts for the actual cost of operation. From the sup-
plied energy, the actual energy which is available for cavi-
tation (based on the transfer cycle and eciency at each
point) will be dependent on the type of equipment used
for generation of cavitation. Calorimetric studies gives an
idea about this actual available energy as discussed earlier.
193
Appendix I gives the details of the cavitational yield calcu-
lations for a specic case of molar ratio of 1:10 and 1% by
weight loading of conc. H2SO4. It can be seen from the cal-
culations that hydrodynamic cavitation reactor is order of
magnitude more energy ecient as compared to the acous-
tic cavitation reactor. Depending on the type of acid/alco-
hol combination used in the present work the cavitational
yield for hydrodynamic cavitation varied in the range of
1 1042 104 g/J (on the basis of supplied energy)
whereas for acoustic cavitation it was order of magnitude
lower, i.e., in the range of 5 1062 105 g/J. Consider-
ing the actual energy available for generation of cavitation
events (considering the results of the calorimetric studies),
the cavitational yield for hydrodynamic cavitation reactors
work out to be in the range of 1.53 1043.1 104 g/J
whereas for acoustic cavitation it is in the range of
1.33 1055.33 105 g/J. The obtained results are quite
similar to those obtained in our earlier works for cell dis-
ruption [15], hydrolysis of fatty acids [16] and degradation
of colored dye euents [17] clearly establishing the superi-
ority of the hydrodynamic mode for generation of cavities
for the process intensication.
6. Conclusions
Cavitation can be eectively used for the intensication
of the synthesis of biodiesel with overall operation at
ambient conditions of temperature and pressures as
against the requirement of high pressures and reux condi-
tions for the conventional route of synthesis. Optimization
in terms of the operating molar ratio of the fatty acid to
alcohol (1:10 ratio is the optimum in the present case)
and catalyst loading (2% by weight of conc. H2SO4 cata-
lyst) results in >95% (mol%) conversion in about 90 min
of processing time. Use of heterogeneous clay catalyst
signicantly slows down the process and also the catalyst
cannot be eectively recycled after use (only 41 mol%
conversion is obtained with the recycled catalyst). Applica-
bility of cavitation to dierent combinations of starting
raw materials has been clearly established in the present
work which allows the exibility in terms of raw material
selection for possible lowering of the cost of production.
Hydrodynamic mode of cavitation has been found to be
more energy ecient as compared to the acoustic mode
of cavitation. The present work has clearly demonstrated
the use of cavitation as an eective tool of process intensi-
cation and the approach to be used for optimization of
the operating parameters with an aim of maximizing the
extent of intensication.
Appendix I. Calculation of cavitational yield for
hydrodynamic and acoustic cavitation reactors
(a) Hydrodynamic cavitation
XA (conversion to methyl esters) = 0.92
According to stoichiometry,
194 M.A. Kelkar et al. / Ultrasonics Sonochemistry 15 (2008) 188194

1 mol of FA  1 mol Me esters References

) With 10 mol as the initial amount of FA,
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[2] C. Stavarache, M. Vinatoru, Y. Maeda, Ultrason. Sonochem. 12
Molecular wt. of Me esters = 171 (2005) 367372.
) Amount of Me esters formed (g) = 1573.2 g [3] E.W. Eckey, JAOCS 33 (1956) 575.
Energy required for this reaction [4] E. Crabbe, C. Nolasco-Hipolito, G. Kobayashi, K. Sonomoto, A.
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[6] K.S. Suslick, J.J. Gawienowski, P.F. Schubert, H.H. Wang, Ultra-
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Amount of product g sonics 22 (1984) 3336.
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Energy supplied J
43.
1573:2
Cavitational yield 1:66  104 g=J [8] C. Stavarache, M. Vinatoru, Y. Maeda, Ultrason. Sonochem. 13
9 450 000 (2006) 401407.
(b) Ultrasonic cavitation [9] C. Stavarache, M. Vinatoru, Y. Maeda, H. Bandow, Ultrason.
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1 mol of FA  1 mol Me esters (1986) 13751380.
[11] B. Freedman, E.H. Pryde, T.L. Mounts, J. Am. Oil Chem. Soc. 61
) With 0.1 mol as the initial amount of FA,
(1984) 16381643.
Total moles of FA converted = Total moles of Me [12] E. Crabbe, C. Hipolito-Nolasco, G. Kobayashi, Process Biochem. 37
esters formed = 0.1 0.93 = 0.093 mol (2001) 6571.
Molecular wt. of Me esters = 171 [13] N. McBride, Modeling the production of biodiesel from waste frying
) Amount of Me esters formed (g) = 15.903 g oil, B.A.Sc. Thesis, Department of Chemical Engineering, University
of Ottawa, Canada, 1999.
Energy required for this reaction
[14] W.E. Ripmeester, Modeling the production of biodiesel oil from
= power supplied time waste cooking oil, B.A.Sc. Thesis, Department of Chemical Engi-
= 120 3600 1.5 neering, University of Ottawa, 1998.
= 6 48 000 J [15] S.S. Save, J.B. Joshi, A.B. Pandit, Chem. Eng. Res. Des. 75 (1997) 41.
Amount of product g [16] A.B. Pandit, J.B. Joshi, Chem. Eng. Sci. 48 (1993) 3440.
Cavitational yield
Energy supplied J [17] M. Sivakumar, A.B. Pandit, Ultrason. Sonochem. 9 (2002) 123.
15:903
Cavitational yield 2:454  105 g=J
6 48 000