Ultrasonics Sonochemistry 88 (2022) 106082

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Ultrasound-assisted solid Lewis acid-catalyzed transesterification of

Lesquerella fendleri oil for biodiesel synthesis
Mohammed Shahidul Islam, Cari Robin Hart, Dominick Casadonte *
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061 USA

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

Keywords: Biodiesel, a mixture of fatty acid methyl esters (FAME), is bio-renewable, non-toxic, biodegradable, and is an
Ultrasound attractive alternative to petroleum diesel. This work studied the sonochemical transesterification of Lesquerella
Lesquerella fendleri oil fendleri oil (LFO) using inexpensive solid Lewis acid (LA) catalysts with an aim to reduce environmental pollution
Solid Lewis acid
and dependance on non-renewable fuel sources. Due to the presence of hydroxy fatty acid methyl esters
Transesterification
Biodiesel
(HFAME) in LFO (~60%), in addition to producing biofuel it can also be used to generate chemically important
Hydroxy fatty acid methyl ester estolides and cyclic lactones. AlCl3, SnCl2, and Sn(CH3COO)2 showed catalytic activity using direct immersion
ultrasound (DI-US) among a list of LA catalysts investigated, with AlCl3 being the best catalyst. Ultrasound
increased the reaction rate by facilitating carbocation formation of glyceridic carbons. Experiments were carried
out at room temperature in a solvent range from 3:1 to 18:1 methanol-to-oil molar ratio and catalyst loading
from 1 wt% to 6 wt% over 10 to 60 min sonication time at 48% ultrasound amplitude (roughly 17 W/cm2).
Complete conversion (>99%) was achieved in 40 min with 5 wt% AlCl3 catalyst. A statistical regression analysis
with STATA 14.0 software was performed to optimize process parameters. Chemical characterizations of the
compounds were performed with nuclear magnetic resonance (NMR) spectroscopy (1H NMR & 13C NMR), and %
conversion of FAMEs was calculated from the 1H NMR spectra. The fatty acid profile was determined by GC-FID
and GC–MS analysis. FT-IR spectroscopic analysis and thermogravimetric analysis (TGA) were performed to
investigate the infrared absorption pattern of the compound and the volatility difference between Lesquerella
fendleri biodiesel and oil under nitrogen atmosphere. Results indicate that this is a fast, green, energy-efficient,
sustainable, and industrially applicable method for biodiesel production from LFO.

1. Introduction
Biodiesel fuel, made from vegetable oils, animal fats, or to some
extent from waste cooking oils, is a viable alternative to petroleum diesel
fuel [1,2]. It has been receiving a great deal of attention as an alternative
to fossil fuels since mineral or petroleum fuel sources are depleting
rapidly [3]. Moreover, because they consist of fatty acid methyl esters
(FAMEs), biodiesel fuels are safe, biodegradable, and renewable. They
can either be used in pure form or in a blend with petroleum fuel in
diesel engines [1,4]. Because biodiesel possesses fuel properties similar
to petroleum diesel but with fewer pollutants, both scientific and com­
mercial communities are giving careful consideration to biodiesel to try
to overcome the issues involved with petroleum diesel [4].
Strong Brønsted base-catalyzed transesterification of triglyceride
with short-chain alcohols like methanol, ethanol, etc. at high tempera­
ture using mechanical stirring with long reaction times is the most
widely used method for biodiesel synthesis [5]. Due to the reaction
between two immiscible liquids (the oil and short chain alcohols), it is a
slow process and requires a large amount of energy consumption to
accelerate the reaction [3].
The application of ultrasound to facilitate the transesterification re­
action is a relatively new field of interest for the conversion of tri­
glycerides to FAMEs. Sonication works through the process of acoustic
cavitation, a phenomenon that is the combination of the formation,
growth, and implosive collapse of bubbles in a liquid [6].
The implosive collapse of bubbles produces extremely high pressures
and temperatures in the microscopic region of ultrasound-irradiated
liquids that generate high-energy species inside the sonication cell [7].
Eventually, the attractive forces of the molecules in the reaction mixture
are destroyed by mechanical activation [8]. Wood and Loomis first re­
ported the effect of sound waves in a chemical process when they suc­
cessfully applied ultrasonic waves to penetrate the water barrier [9].

* Corresponding author.
E-mail address: Dominick.Casadonte@ttu.edu (D. Casadonte).

https://doi.org/10.1016/j.ultsonch.2022.106082
Received 30 January 2022; Received in revised form 17 June 2022; Accepted 20 June 2022
Available online 26 June 2022
1350-4177/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Shahidul Islam et al.
O
O R2
R1 O Catalyst
+ 3R OH
O O
O
R3
O
Triglyceride Alcohol
from vegetable oil
= Hydrocarbon chain ranging from 15 to 22 carbon atoms
R1, R2, R3
Fig. 1. General transesterification reaction scheme for the synthesis of FAMEs.
From then on, researchers have been applying ultrasound technology in
many chemical fields. Its application in transesterification and esterifi­
cation of triglycerides and free fatty acids (FFA) respectively for FAME
synthesis is an emerging technology. Base-catalyzed transesterification
of vegetable oils have been well-studied and the application of ultra­
sound reduces the reaction time by one-sixth over conventional methods
used to obtain the desired biodiesel conversion [5]. Due to the tendency
of an unavoidable saponification reaction between the free fatty acids
(FFA) of the feedstock and the base, this process requires high purity
feedstock with a minimal presence of FFAs. As a result, low-cost non-
edible FFA-rich oil cannot be used as a biofuel feedstock [10–12]. This
results in higher production costs compared to petroleum diesel fuel
[13,14]. It has been reported that the requirement of high-quality or
refined feedstock to produce ASTM-standard biodiesel (<0.5% FFA)
constitutes 80–88% of the total production cost [15].
To remove the requirements of expensive low FFA-containing refined
feedstock, acid-catalyzed transesterification is receiving attention. It is
more suitable for the conversion of unrefined oil or less expensive
feedstocks with higher FFA content than the corresponding base-
catalyzed process because the saponification reaction is unlikely. It
has not received as much attention as base-catalyzed processes due to
the slower reaction rate and the requirement of a higher amount of
solvent [16]. To hasten the reaction and reduce the dependency on oil
quality, a two-steps process has also been reported, where the first step is
acid-catalyzed esterification of FFA with methanol using H3PO4, H2SO4,
and Fe2(SO4)3 as a catalyst, followed by base-catalyzed trans­
esterification [10,17].
Lewis acid (LA) catalysts are species with an electron deficiency and
which are typically milder than Bronsted acids. Because of the presence
of an electron-deficient metal center they activate electron-rich sub­
strates [18]. Moreover, solid LA catalysts offer two specific advantages:
1) they are insensitive to FFA so soap formation is unlikely and 2) they
can be recycled and reused [19]. Catalytic activity of LAs such as Cd
(OOCCH3)2, Pb(OOCCH3)2, Zn(OOCCH3)2, FeCl3, SnCl2, and ZnCl2 for
simultaneous esterification/transesterification of vegetable oils has been
reported [20,21].
In order to lower biodiesel production cost and develop an eco-
friendly method, solid LA catalysis could provide an attractive alterna­
tive to base catalysis [22]. Additionally, to increase the reaction rate and
to make it competitive with various base-catalyzed systems, ultrasound-
assisted biodiesel production from biomaterials which are neither
human feedstocks (like soybean) nor which contain toxins (like caster)
are desirable. Unrefined Lesquerella fendleri oil (LFO), which is derived
from a plant which is easily grown and which provides leftover material
which can be used as animal feed, is of interest as a biofuel source but
2
Ultrasonics Sonochemistry 88 (2022) 106082
O
H3C
O R1
O OH
+
H3C HO
R2
O OH
H 3C
O R3
FAMEs Glycerol
(Biodiesel)
has not been reported to date. In this study, the catalytic effect of 22
(twenty-two) different laboratory-available inexpensive solid LAs were
investigated as a replacement for corrosive base catalysts for the trans­
esterification of Lesquerella oil (LFO). The purpose of this study is to use
Lewis acid catalysts with Lesquerella fendleri oil to mitigate environ­
mental hazards as well as to explore the effect from direct immersion
ultrasound to increase the reaction rate and the rate of mass transfer
between the two immiscible liquids used in the study, methanol and
LFO. Analytical methods including NMR, GC, GC–MS, FTIR, and TGA
were used to characterize the final product and feedstocks.
2. Materials and methods
Lesquerella fendleri oil, containing about 60% hydroxy fatty acids,
was used as the primary feedstock in this study. The oil was extracted
sonochemically from Lesquerella fendleri seeds (Lesquerella fendleri, a
member of the Brassicaceae family) that contain about 30% oil, 15%
gums, and 23% protein and which were obtained from local farmers. A
portion of Lesquerella fendleri oil was obtained from the Biodiesel
Research Unit, United States Department of Agriculture-ARS. Commer­
cial grade castor oil, canola oil, and glycerin were purchased locally.
Acetone-free, ACS-certified absolute methanol (99.8% purity) and n-
hexane was purchased from Fisher Scientific. The reference standards
14-hydroxy-cis-11-eicosanoic acid methyl ester and Supelco 37 compo­
nent FAME mix were purchased from Santa Cruz Biotechnology, Inc. and
Millipore Sigma respectively. All reagents, including AlCl3, SnCl2. Sn
(CH3COO)2, etc. were purchased as reagent grade and used without
further treatment.
An 8891-MTH ultrasonic cleaning bath obtained from Cole-Parmer
Instrument Company was used to extract the Lesquerella fendleri oil.
For the examination of low-power processes, the same cleaning bath was
used for transesterification reactions at a processing temperature of
25 ◦ C. A Vibra Cell VC 505 processor with a fixed frequency of 20 kHz
and 500 W power with programmable amplitude was obtained from
Sonics & Materials, Inc. and used as the direct immersion ultrasound
source in the transesterification process. The Vibra Cell VC 505 consisted
of a processor, a titanium sonotrode, and the process control unit. Lead
zirconate titanate piezoelectric material act as an ultrasonic transducer
that contracts, expands, and subsequently converts electric energy to
sound energy through a titanium horn (probe) [23]. A VWR 1156
recirculating chiller obtained from VWR Scientific was used to maintain
the temperature at 5 ◦ C (25 ◦ C cell temperature) and a PowerSpin FX
centrifuge purchased from Unico Scientific with a spin rate of 3400 rpm
was used to centrifuge the reaction mixture.
The solid Lewis acid-catalyzed transesterification reactions primarily
M. Shahidul Islam et al.
Fig. 2. Transesterification reaction set up using direct immersion ultrasound.
were carried out in a direct immersion ultrasound using the VC 505
processor at 48% amplitude (17 W/cm2 acoustic power, as measured
using calorimetry [38]). The effects of different process parameters such
as solvent-to-oil molar ratio (3:1 to 18:1), sonication time (5 min, 10
min, 15 min. 30 min, 40 min, 50 min, and 60 min), catalyst loading (1 wt
%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 6 wt%), and type of catalyst were
investigated. Reactions were carried out using 10 mL of LFO in the
presence of the various Lewis acid catalysts to synthesize Lesquerella
fendleri methyl esters by means of the transesterification reaction with
methanol (see Fig. 1). All experiments were conducted at a cell tem­
perature of 25 ◦ C which was maintained using the chiller and also at
atmospheric pressure.
A typical reaction involved a 6:1 methanol-to-oil molar ratio and 5
wt% solid catalyst with respect to the primary feedstock. The reaction
was started by transferring 2.47 mL of methanol followed by 0.5 g of
catalyst into a 25 mL sonication cell. The wt.% of catalyst was measured
with respect to the weight of the oil (wt./wt.) throughout the study. 10
mL of Lesquerella fendleri oil were transferred to the mixture and soni­
cated for the required period of time. After.
sonication, the resulting mixture was transferred to a separatory
funnel and allowed to settle overnight to form biodiesel (top layer) and
glycerol (bottom layer). The unreacted methanol stays at the top and to
some extent with glycerol at the bottom while the catalyst stays at the
bottom (see Fig. 2).
The separation and purification begins with the separation of the
FAMEs layer in a centrifuge tube followed by 10 min centrifugation to
precipitate any dissolved catalyst or glycerol present in the FAMEs layer.
The clear solution from the centrifuge tube is gently decanted into a 100
mL round bottom flask and any unreacted solvent was removed using a
rotary vacuum evaporator at 50 to 55 ◦ C. The dry FAMEs were again
centrifuged for 10 min to get clean, pure biodiesel.
The progress of reaction was monitored with thin layer chromatog­
raphy (TLC) analysis using small aliquots collected every 5 min
following the work of previous authors [24]. The NMR (1H NMR and 13C
NMR) analysis for qualitative and quantitative characterizations of
feedstocks and partial and completely converted FAMEs mixture were
performed in a 400 MHz JEOL NMR using deuterated chloroform (CDCl3
- chloroform-d) containing ≥ 99.8 D as solvent. The integration value of
the methoxy protons in the methyl ester and methyl protons of the
3
Ultrasonics Sonochemistry 88 (2022) 106082
β-carbon to the ester group were used to calculate the % conversion (%
C) of LFO to biodiesel using the following equation [16]:
2 × integration of methoxy protons
%C = × 100 (1)
3 × integration of β − methyl protons
Relaxation delay of 2 s, 5000 scans, 30◦ -degree pulse angle, and
CDCl3 solvent were used as the standard conditions for 13C NMR
analysis.
The GC–MS analysis to study the fatty acid profile of synthesized
biodiesel was performed with an Agilent 6890 N GC system coupled
with 5973 N Mass Selective Detector (MSD) over a polar SP-2380 GC
column of L × I.D. 30 m × 0.25 mm, df 0.20 µm acquired from Milli­
poreSigma. Two reference standards involving lesquerolic acid methyl
ester and a Mix 37 component mixture of FAMEs containing C12 to C30
purchased from Santa Cruz Biotechnology and MilliporeSigma respec­
tively were used to identify the positions of individual fatty acid peaks.
The percent compositions of FAMEs were calculated from the peak area
values. The GC parameters were set as follows: Nitrogen (N2) was used
as the career gas, H2 and air were used as make up gases, and the injector
and detector temperature were selected 260 ◦ C & 250 ◦ C respectively.
The column temperature was programmed as follows: start at 100 ◦ C
and hold for 2 min, then increase at 10 ◦ C/min to 270 ◦ C and hold for 20
min, and then finally back to 100 ◦ C at 20 ◦ C/min. A split mode injection
with 50:1 split ratio, 0.45 mL/min column flow, 18.7 cm/sec linear
velocity, and 100 kPa pressure was used to run the sample in the gas
chromatograph.
Thermal analysis of the products and feedstock was performed using
a high-sensitivity suspension-type thermobalance TGA-50 purchased
from Shimadzu Scientific Instruments. Analyses were conducted under a
nitrogen atmosphere with a flow rate of 80 mL/min and the temperature
was programmed to increase from room temperature to 800 ◦ C with a
constant ramp rate of 5 ◦ C/min. A NicoletTM iSTM 5 FTIR Spectrometer
with iD7 ATR (Attenuated Total Reflectance) was used to identify the
functional groups and characteristic covalent bonds.
M. Shahidul Islam et al. Ultrasonics Sonochemistry 88 (2022) 106082

Table 1
List of Lewis acid catalysts and their maximum catalytic performance on biodiesel production.
Catalyst % Conversion to biodiesel (±SD) Catalyst % Conversion to biodiesel (±SD)

SnCl2 31.3 (±1.5) AlCl3 95.5 (±4.5)

FeCl3⋅6H2O <5.0 CrCl3⋅6H2O 0.0
CoCl2⋅5H2O 0.0 SnO2 0.0
Fe3O4 0.0 SnCl2⋅2H2O 0.0
ZrO2 0.0 CaCl2 <5.0
Co(OAc)2⋅4H2O 0.0 CuFe2O4 0.0
ZnO 0.0 Cu(I)Cl 0.0
CoFe2O4 0.0 MnCl2⋅4H2O 0.0
ZnFe2O4 0.0 Sn(CH3COO)2 14.9 (±0.9)
CuCO3 0.0 MnCl2 0.0
ZnCl2 0.0 CrCl3 0.0

R'OH
O HOH

MXn R O R'' MXn

R'' MXn Methyl ester MXn O R''
O
O O R O
R O
H Step 3 R O R'' R O R'' H
O O
Step 4 Step 4 Step 3
R' H
MXn
O R''
TRANSESTERIFICATION MXn (LA) ESTERIFICATION MXn
R O O R''
H R O
OR'
Step 2 Step 2 H
OH
O O

MXn R O R' R O H MXn

R''OH O MXn MXn
Starting materials O O
O
R''OH
R O R' R O R' R O H R O H
Step 1 Step 1
MXn = Lewis acid; R = alkyl group of the fatty acid
R' = alkyl esters of triglyceride
R'' = alkyl group of alcohol

Fig. 3. Reaction mechanism of Lewis acid-catalyzed transesterification and esterification reactions.

3. Results and discussion
3.1. Lewis Acid-catalyzed transesterification reaction
The catalytic activity of 22 solid Lewis acid catalysts was investi­
gated in the transesterification of Lesquerella fendleri oil. Table 1 shows
the maximum biodiesel conversions achieved with each respective
catalyst. Only SnCl2 (31.3%), Sn(CH3COO)2 (14.9%), and AlCl3 (95.5%)
showed significant catalytic activity and studied their catalytic activity
extensively. The % values in Table 1 shows the maximum results ob­
tained using different combination of reaction parameters. All other
catalyst was used with a minimum of 5 reactions with a 6:1 methanol-to-
oil ratio and a 30 min reaction time under ultrasonic irradiation. AlCl3
was used as the standard catalyst because of its outstanding performance
in catalyzing the transesterification of LFO under ultrasonic irradiation.
The proposed chemical pathway for the Lewis acid catalyzed
simultaneous transesterification and esterification of LFO is depicted in
Fig. 3. The esterification of FFA follows an analogous mechanism as
transesterification and rationalizes the insensitivity of solid LA catalysis
on the FFA content of feedstock. The acidic site of the LA joins the ox­
ygen of the carbonyl group of the triglycerides and/or FFA and increases
the electrophilicity of that adjoining carbon [25]. The increased elec­
trophilicity makes it more susceptible to nucleophilic attack. The overall
mechanism consists of: (1) formation of a carbonyl carbocation elec­
trophile by the Lewis acid, (2) nucleophilic attack of the alcohol to the
carbocation and tetrahedral intermediate formation, (3) migration of
proton and intermediate breakdown, and (4) FAMEs formation and
regeneration of the catalyst. This phenomenon indicates that a strong
electrophile formation is a key step and easy access of solid the LA
catalyst to the triglyceride is necessary to initiate the transesterification
reaction.
3.2. SnCl2 catalyzed transesterification of Lesquerella fendleri oil
The catalytic activity of SnCl2 was studied extensively, considering
the higher Lewis acidity of Sn2+ than other transition metals that follows
the order of Sn2+ ≫ Zn2+ > Pb2+ ≈ Hg2+ [26]. It is less sensitive to
water, easy to handle, less corrosive, and overall a stable solid [18].
Several experiments were performed varying the catalyst concentration,
solvent amount, and sonication time. A better performance was antici­
pated based on its Lewis acidity and prior reported work, but a
maximum of 31.1% biodiesel conversion was achieved (Table 1) using

4
M. Shahidul Islam et al. Ultrasonics Sonochemistry 88 (2022) 106082

Table 2 3.3. Sn(CH3COO)2 catalyzed transesterification of Lesquerella fendleri

FAME yield (%) from SnCl2 catalyzed transesterification. oil
Catalyst conc. Sonication time, Methanol: L. oil molar FAME % yield
mol% min ratio (±SD) The transesterification of Lesquerella fendleri oil was conducted using
2.0 20.0 6:1 0.0 Sn(CH3COO)2 as a Lewis acid catalyst. The FAMEs contents (% con­
5.0 20.0 6:1 0.0 versions) of the Lesquerella fendleri biodiesel at different sonication times
5.0 30.0 6:1 8.3 (±0.8) from 20 to 60 min, catalyst concentration from 10 to 20 mol%, and
5.0 40.0 6:1 8.0 (±1.3) methanol-to-oil molar ratio of 10:1 were calculated using 1H NMR
5.0 50.0 6:1 5.7 (±1.5)
5.0 20.0 10:1 18.3 (±1.1)
spectra analysis and summarized in Table 3. All experiments were per­
5.0 30.0 10:1 8.5 (±1.5) formed at room temperature and ultrasound amplitude of 48%. Among
5.0 60.0 6:1 7.0 (±2.2) all the combination of reaction parameters, a maximum of 14.9% con­
5.0 90.0 10:1 9.0 (±2.5) version of LFO into FAMEs was obtained in 30 min sonication time, 15
10.0 20.0 6:1 26.0 (±1.1)
mol% catalysts, and 10:1 methanol-oil ratio. An increase in sonication
10.0 30.0 6:1 13.4 (±2.1)
10.0 30.0 10:1 31.3 (±1.5) time caused an increase in % conversion as the catalyst concentration
10.0 40.0 10:1 30.5 (±0.8) was increased to 15 mol% (4 wt%), but no improvement in biodiesel
10.0 20.0 30:1 0.0 conversion occurred when the sonication time was increased further.
10.0 40.0 30:1 0.0 Likewise, when the catalyst concentration was increased from 10 mol%
10.0 50.0 30:1 0.0
12.0 20.0 6:1 24.0 (±1.3)
to 15 mol%, a significant increase in % conversion from 2.7% to 14.9%
12.0 30.0 6:1 25.3 (±1.5) was observed but no improvement, in the same way, was achieved with
12.0 40.0 6:1 25.0 (±0.8) a further increase in catalyst concentration. The lower catalytic activity
18.0 20.0 12:1 5.0 of tin(II) acetate compared to SnCl2 could be due to both electronic and
20.0 20.0 10:1 0.0
steric factors of the anionic ligands. Moreover, it was also important to
consider the solubility of the catalysts, as tin(II) acetate was very slightly
soluble in methanol. As a result, tin(II) acetate showed lower catalytic
Table 3 activity than SnCl2. Additionally, the lower catalytic activity of tin(II)
Percent conversion of Lesquerella fendleri biodiesel with tin(II) acetate catalysis. acetate may be due to the low lability of the acetate ligand [27]. The
10:1 methanol-to-oil molar ratio was used. activation of the carbonyl group of Lesquerella fendleri triglycerides
Sonication time, min Catalyst concentration, mol% % Conversion (±SD) might be hindered by this bidentate ligand. It can be hypothesized that
20.0 10.0 2.7 (±0.3) the availability of Sn(II) cations is responsible for the activation of the
20.0 12.0 10.3 (±1.8) carbonyl group of the triglycerides.
20.0 15.0 11.7 (±0.3)
30.0 12.0 10.8 (±1.8)
30.0 15.0 14.9 (±0.9) 3.4. AlCl3 catalyzed transesterification of Lesquerella fendleri oil
40.0 15.0 9.0 (±0.9)
50.0 15.0 7.8 (±0.7) In this study AlCl3 turned out to be the best performing solid Lewis
30.0 20.0 9.5 (±0.3) acid catalyst for the sonochemical transesterification of LFO. An exten­
sive analysis was performed using this most active catalyst. The effects
SnCl2 in this study. Table 2 shows the biodiesel conversion from the of different reaction parameters such as sonication time, catalyst con­
SnCl2 catalyzed transesterification reaction. The % conversion was centration, and solvent amount, were investigated and a complete
calculated from 1H NMR spectra applying equation (1). conversion of LFO into Lesquerella fendleri biodiesel was achieved at
room temperature using direct immersion ultrasound.
Simultaneous esterification and transesterification of FFA and tri­
glycerides respectively occurred that was assumed by the appearance of

100.0

90.0

80.0
% Conversion of FAMEs

70.0 1 wt% catalyst

60.0 2 wt% catalyst
50.0 3 wt% catalyst
40.0 4 wt% catalyst

30.0 5 wt% catalyst

20.0 6 wt% catalyst

10.0

0.0
10.0 20.0 30.0 40.0 50.0 60.0
Sonicaton time, min

Fig. 4. Effect of sonication time and catalyst concentration (wt.% of oil) and sonication time. 6:1 methanol-to-oil molar ratio was used.

5
M. Shahidul Islam et al.
100
90
% Conversion of biodiesel 80
70
60
50
40
30
20
10
0
3:1
Fig. 5. The effect of methanol-to-oil molar ratio on biodiesel synthesis with 5 wt% catalyst and 40 min sonication time.
no soap formation and further demonstrated by 1H NMR analysis. Re­
sults were further analyzed by GC–MS, FT-IR, and TGA. A statistical
regression analysis of the process parameters was performed with
STATA 14 statistical software package to identify the best combination
of reaction conditions that is statistically valid.
3.5. Effect of sonication time and catalyst concentration on the
transesterification reaction
The sonication time turns out to be one of the most significant factors
besides methanol-to-oil molar ratio and catalyst loading (Shinde &
Kaliaguine, 2019). The effect of sonication time from 10 min to 60 min
in Lesquerella fendleri biodiesel conversion was investigated using the
AlCl3 catalyst. A 6:1 MeOH-to- Lesquerella fendleri oil molar ratio was
kept constant while the effect of sonication time was investigated for
each of the different catalyst concentrations from 1 wt% to 6 wt%
(Fig. 4). Over 85% conversion was observed in 20 min under direct
immersion ultrasound. The low conversion and slow reaction initially
are attributed to the poor mixing of two completely immiscible liquids
(methanol and Lesquerella fendleri oil). Therefore, poor mass transfer is a
foremost problem for such solid LA acid catalyzed transesterification
reactions.
Approximately 95% biodiesel conversion was recorded in 30 min
with 5 wt% catalyst, which is a remarkably lower time than the me­
chanical heating-stirring method reported thus far, which requires
several hours for the transesterification reaction with LA catalysts.
Soriano et al. reported a 20% conversion in 24 h using 5 wt% AlCl3
catalyst and mechanical stirring at 75 ◦ C (Soriano, Venditti, & Argyr­
opoulos, 2009). The % conversion showed continuous improvement
when the sonication time increased from 10 min to 40 min but no sig­
nificant improvement was observed when the sonication time was
increased to 60 min.
The catalyst concentration also plays a vital role in Lesquerella
fendleri biodiesel conversion. With little exception, increase in catalyst
loading from 1 wt% to 5 wt%, increases the conversion rate of LFO to
FAMEs under the same reaction conditions viz. when the sonication
time, MeOH-to-LFO molar ratio, and temperature are kept constant.
Fig. 4 shows that when the AlCl3 concentration with respect to the
volume of Lesquerella fendleri oil (wt./wt. of oil) is increased from 1 wt%
to 4 wt%, the % conversion of biodiesel increases from 20% to 95%. A
further increase to 5 wt% did not show significant improvement, while
beyond 5 wt% showed a sharp decline in biodiesel conversion. We as­
sume that the reason behind the decline could be the formation of a
more viscous mixture when a higher amount of catalyst is used,
Ultrasonics Sonochemistry 88 (2022) 106082
6:1 9:1 12:1 15:1 18:1
Methanol-to-oil molar ratio
inhibiting mass transfer between the alcohol and oil.
3.6. Effect of Methanol-to-Lesquerella fendleri oil molar ratio
The amount of methanol with respect to the Lesquerella fendleri oil is
another significant variable affecting FAMEs conversion. According to
the stoichiometry of the transesterification reaction, 3 mols of methanol
are required for 1 mol of oil to synthesize 1 mol of glycerol and 3 mol of
FAMEs. However, the stoichiometric ratio of methanol to Lesquerella
fendleri oil provided the lowest conversion (<40%). Therefore, an excess
amount of methanol was used to shift the reversible reaction forward
towards the product side. This facilitates the easy contact of methanol
molecules to triglycerides and results in improved biodiesel production.
The solvent ratio from 3:1 to 18:1 was studied keeping other parameters
(including 40 min sonication time, 48% ultrasound amplitude, and
catalyst loading at 5 wt%) constant.
Fig. 5 depicts that FAMEs conversion shows an upward trend when
the solvent ratio was increased from 3:1 to 9:1, but the conversion
declined with further increase. We hypothesized that the higher amount
of methanol increases the solubility of glycerol in methanol and subse­
quently dilutes the biodiesel and glycerol products. As a result, a back­
ward reaction might initiate that reduces biodiesel yield. This is
attributed to the reversible phenomena of the transesterification reac­
tion of triglycerides [28]. It is also important to optimize the methanol
requirements to minimize the processing steps and equipment needed
for methanol recovery [29]. Soriano and co-workers [16] reported that a
24:1 methanol: oil ratio in the presence of a co-solvent (THF with same
amount of methanol) is required for a 98% conversion under conditions
of an 18 h reaction time, 110 ◦ C temperature, and AlCl3 as catalyst using
mechanical heating and stirring. The Casas group in another study [30]
reported that a 30:1 M ratio of methanol was required for 96% biodiesel
conversion from sunflower oil with tin (II) acetate as a LA at 150 ◦ C
temperature and 3 h reaction time. Based on the results obtained in this
current study, a 9:1 solvent ratio is recommended for complete con­
version to biodiesel using 5 wt% AlCl3 as solid LA catalyst.
3.7. Effect of direct immersion ultrasound
To study the effect of direct immersion (DI-US) ultrasound in the
FAMEs synthesis from LFO with solid LA catalysts, transesterification
reactions were carried out using conventional stirring, an ultrasonic
bath, and DI-US under the same reaction conditions, which include a 9:1
methanol-to-oil molar ratio, 5 wt% catalyst concentration, and a 40 min
reaction time. The reactions using DI-US and the ultrasonic cleaning
6
M. Shahidul Islam et al. Ultrasonics Sonochemistry 88 (2022) 106082

Table 4
Ultrasonic vs mechanical reaction systems.
Reaction system Temperature Catalyst type % Conversion 2 wt.% Cat.
(◦ C) (±SD)

DI-US 25 AlCl3 95.5 (±4.5)

DI-US 25 SnCl2 30.5 (±2.5) 3 wt.% Cat.
DI-US 25 Sn 14.9 (±0.9)
(CH3COO)2
Ultrasonic Cleaning 25 SnCl2 5.8
4 wt.% Cat.
Bath
Ultrasonic Cleaning 25 Sn <5.0
Bath (CH3COO)2
Ultrasonic Cleaning 25 AlCl3 20.5 (±2.7) 5 wt.% Cat.
Bath
Conventional Method 60 AlCl3 <5.0
Conventional Method 60 SnCl2 0.0 6 wt.% Cat
Conventional Method 60 Sn 0.0
(CH3COO)2

Time

Table 5
Percentage of conversion by different concentrations of the catalyst. 0 .01 .02 .03 .04
Variable conc. Observations Mean Std. Dev. Min. Max.

1 wt% 6 15.7 9.3 6.3 32.0 Fig. 6. Comparison of p-values in model 3.

2 wt% 9 42.0 10.5 25.3 55.3
3 wt% 6 37.4 17.1 6.3 53.0
4 wt% 9 68.6 32.6 6.7 100.0
5 wt% 12 72.9 18.8 37.0 99.0
6 wt% 7 45.6 15.1 30.0 70.0 2 wt.% *Time

2 wt.% Cat.
bath were performed at room temperature (25 ◦ C), while 60 ◦ C tem­ 3 wt.% *Time
perature and 1000 rpm of magnetic stirring were used for the stirring
3 wt.% Cat.
reactions run as controls without ultrasound. Table 4 shows that in the
absence of DI-US no significant conversion of LFO to FAMEs was ob­ 4 wt.% *Time

tained, while almost complete conversion was obtained under DI-US. 4 wt.% Cat.
Due to the immiscibility of methanol with Lesquerella fendleri oil, the 5 wt.% *Time
transesterification reaction is controlled by mass transfer in the reaction
5 wt.% Cat.
system [29]. DI-US increases the rate of mass transfer between methanol
and Lesquerella fendleri oil due to cavitation. Acoustic cavitation results 6 wt.% *Time

in implosive collapse of bubbles producing high pressure, intense local 6 wt.% Cat
heating, microturbulence, microstreaming, and formation of small Time
eddies that enhance the mass transfer in the surrounding liquid.
Increased mass transfer provides a faster rate of transesterification re­ 0 .2 .4 .6 .8 1
action without requiring the severe reaction conditions of the conven­
tional system [31].
Fig. 7. Comparison of p-values in model 4.

3.8. Statistical analysis of AlCl3 catalyzed biodiesel conversion
The experimental data were statistically analyzed by a regression
analysis method using 49 (forty-nine) observations to optimize process
conditions and the interaction of process variables for the conversion of
Lesquerella fendleri to biodiesel using AlCl3 catalyst under DI-US. The
statistical analysis was performed using STATA 14.0 software and using
an Ordinary Least Square Models (OLS) to study the effect of sonication
time and catalyst concentration on the % conversion of biodiesel. The
6:1 methanol-to-oil molar ratio and ambient temperature (25 ◦ C) were
kept constant. Table 5 shows the basic summary statistics for the %
conversion by the type of catalyst concentrations. It can be inferred that
the conversion rate is high for 4 wt% and 5 wt% catalyst. However, the
spread of the data on conversion is high for 4 wt% (SD = 32.58) and a
higher mean was observed for 5 wt% catalyst.
To study the effect of individual parameters and interactions be­
tween the parameters, a regression analysis on % conversion was per­
formed on forty-nine (49) experiments with a constant 6:1 methanol-to-
Lesquerella fendleri oil ratio. Based on the different variables and in­
teractions among the variables, the analysis was categorized into four
(4) models and all models were analyzed with respect to the %
conversion with 1 wt% catalyst (1 wt% as the base category). The first
model includes only time as a variable and shows no significant impact
on the % conversion at any significance level. The second model only
uses different catalyst concentrations from 2 wt% to 6 wt% and shows
that all the catalyst concentration types work better and increase the %
conversion compared to the 1 wt% catalyst and all the coefficients are
statistically significant. The third model explains the impact of time and
different concentrations of the catalyst on the % conversion and shows
that compared to the 1 wt% catalyst, the 5 wt% catalyst has a major
impact on the improvement of % conversion followed by the 4 wt%
catalysts while everything else is kept constant. The final and last model
includes all the previous variables along with the interaction terms. The
interaction terms allow one to analyze the impact of the variables when
two variables are changing at the same time.
The coefficient of the 4 wt% catalyst*time interaction states that
with everything else constant, a 4 wt% catalyst would result in a sig­
nificant increase in the conversion rate with an increase in time
compared to the 1 wt% catalyst, which is statistically significant at a
95% confidence level. As all the other variables are kept constant in a lab
setting, no bias should be built into the statistical model. Hence, only
two variables (catalyst concentration and sonication time) are changing

7
M. Shahidul Islam et al.
Fig. 8. 1H NMR of Lesquerella fendleri biodiesel (FAMEs).
Fig. 9. 1H NMR spectra of Lesquerella fendleri oil.
in the model that would give us a causal impact on the conversion rate.
The r-squared values have increased significantly in model 3 and model
4 which means that the variations in the variable used in those models
could explain the variation in the % conversion significantly.
The corresponding p-values for models 3 and 4 are presented in
Figs. 6 and 7 respectively. The reference significance level is set to 99%
level for model 3 and 90 % level for model 4. We can state that in model
3 all the coefficients (impact on % conversion) of the variables including
time are statistically significant at a 95% level.
However, the coefficients for catalyst 4 wt%, 5 wt%, 6 wt%, and
sonication time are significant at a 99% level. In model 4, we can see that
only two coefficients of the variables are statistically significant at a 90%
level, which are the 4 wt% catalyst and the interaction term where we
multiply 5 wt% catalyst with sonication time. The statistical results are
consistent with our hypothesis that, with everything else constant, a 4 wt
8
Ultrasonics Sonochemistry 88 (2022) 106082
% catalyst can increase the conversion rate significantly compared to 1
wt% catalyst.
3.9. Nuclear magnetic resonance spectroscopy (NMR) analysis
NMR analysis was used to calculate the % conversion of triglycerides
of oil/fat to FAMEs. Figs. 8 and 9 show that the major peaks that are
different between the 1H NMR spectra of synthesized biodiesel and
Lesquerella fendleri oil involve the appearance of methoxy protons
resonated at around 3.6 ppm as a singlet, the disappearance of the
methylene glyceridic protons at 4.0–4.2 ppm, and the methine glycer­
idic protons at 5.08–5.11 ppm. The corresponding decrease in the
integration value of the 4.0–4.2 ppm peak and the increase in 3.6 ppm
peak.
corroborate the conversion of LT to FAMEs. Chemical shifts for
M. Shahidul Islam et al. Ultrasonics Sonochemistry 88 (2022) 106082

Fig. 10. Combined TGA diagrams of Lesquerella fendleri biodiesel and oil.

methylene protons and methoxy protons were analyzed for each run.
Table 6
Among the other significant peaks, the terminal methyl is observed at
Characteristic FT-IR absorption peaks of Lesquerella fendleri biodiesel and oil.
0.74 ppm with a smaller peak at 0.89 ppm because of the presence of
methyl auriculate and methyl linolenate with double bonds close to the Lesquerella fendleri oil Lesquerella fendleri biodiesel

terminal methyl group. Different olefinic protons exhibit two complex Characteristic Functional Characteristic Functional group
multiplets at 5.37–5.41 ppm and 5.17–5.28 ppm while another multiplet peaks, cm− 1 group peaks, cm− 1
for the protons on the hydroxy-containing carbons occurs at 2.7 ppm. 3456 O–H stretching 3402 O–H stretching
The % conversions of FAMEs were calculated using equation (1) where 3006 –CH2 stretching 3006 –CH2 stretching
A1 denotes the integration value of methoxy protons and A2 denotes the 2921 C3sp-H2 2922 C3sp-H2
asymmetric asymmetric
integration value of β -methylene protons to the glyceridic skeleton. 2852 C3sp-H2 2852 C3sp-H2
The major characteristic peak in the 13C NMR of biodiesel is assigned symmetric symmetric
to the methoxy carbon resonated at 51.44 ppm, which is absent for LFO 1741 C = O ester 1738 C = O ester
in figure S2 (see Supplimentary Material). The other prominent peaks stretching stretching
1455 CH2 bending 1435 Methyl ester
include peaks at 133.26 ppm and 125.19 ppm attributed to the olefinic
(CO-O-CH3)
carbons of C-11 and C-12 respectively, and numerous peaks in the range 1376 Bending of CH2 1361 Bending of CH2
of 127.05 ppm to 132.55 ppm due to the presence of other unsaturated groups groups
carbon chains in Lesquerella fendleri methyl ester. The hydroxy- 1160 C-O stretching 1170 C-O stretching
containing carbon at C-14 resonated at 71.60 ppm while the methy­ 1195 split
1118 C-O stretching
lene carbon of C-13 located between the C-OH and double bond reso­ split
nated at 35.32 ppm. Additionally, C-1 resonated at 174.50 ppm, the -O-CH2-C
peak at 22.70 ppm to CH2 proximate to the terminal CH3 resonated at 722 –CH2 rocking 722 –CH2 rocking
22.70 ppm, and the terminal carbon of CH3 group resonated at 13.93
ppm.
biodiesel and oil are shown in Figure S3 (see Supplementary Material).
Absorption peaks were assigned in the FT-IR spectra of all of the samples
3.10. Thermogravimetric analysis (TGA)
based on standard methods and previous studies [32–34].
The absorption frequency of the same functional group present in
Thermogravimetric analysis was performed to analyze the thermal
different compounds may slightly fluctuate based on the structural
profile of Lesquerella fendleri oil and Lesquerella fendleri biodiesel. The
environment [35]. Table 6 shows a detailed comparison between the IR
thermal vaporization of both Lesquerella fendleri oil and biodiesel con­
absorption peaks of Lesquerella fendleri biodiesel and LFO. A low-
tinues until complete vaporization. The thermal vaporization of Les­
intensity broad peak observed in biodiesel and LFO spectra at 3450
querella fendleri biodiesel starts at about 180 ◦ C and completes at 400 ◦ C,
cm− 1 indicates the presence of hydroxyl groups in the long fatty acid
while Lesquerella fendleri oil starts vaporization at approximately 290 ◦ C
chain. The other characterizing modes that biodiesel exhibits are C2sp-H2
and completes at about 500 ◦ C. It can be noted from Fig. 10 that, before
of vinyl hydrogens at 3006 cm− 1, C3sp-H2 symmetric at 2852 cm− 1 and
reaching the boiling temperature range of Lesquerella fendleri oil, bio­
asymmetric at 2920 cm− 1, the C–– O stretching of the ester at 1740 cm− 1,
diesel vaporizes by almost 80%. This result indicates the significantly
Csp-H3 and Csp-H2 bending at 1435 cm− 1 and 1456 cm− 1 respectively,
3 3
higher volatility of Lesquerella fendleri biodiesel than the original oil.
C–O stretching of ester at 1170 cm− 1, and C3sp-H2 rocking at 722 cm− 1.
The splitting of the 1160 cm− 1 peak of the oil into 1195 cm− 1 and 1170
3.11. Fourier transform infrared spectroscopy (FT-IR) cm− 1 in biodiesel marks the conversion of triglycerides into FAMEs. The
major difference between the two spectra is related to the trans­
The functional groups of the compounds were studied using FT-IR formation of ester groups of the triglyceride into the methyl esters of
spectroscopy. Representative FT-IR spectra for Lesquerella fendleri

9
M. Shahidul Islam et al. Ultrasonics Sonochemistry 88 (2022) 106082

Table 7
Fatty acid profile of Lesquerella fendleri oil.
Peak # FAMEs structure Name of methyl ester Retention time, min Composition (%)

1 Palmitic acid 13 1.2

2 Palmitoleic 15.1 0.5

3 Stearic acid 22.4 2.2

4 Oleic acid 24.3 17.1

5 Cis-13-octadecanoic acid 24.5 1.8

6 Linoleic acid 26.9 6.8

7 Ecosanoic acid 29 0.7

8 Linolenic acid 29.8 8.6

9 Eicosenoic acid 30.5 1.1

10 Ricinoleic acid 38.5 0.7

11 Lesquerolic acid 39.8 54.8

12 Auricolic acid 40.3 4

Fig. 11. Mass spectra of lesquerolic acid methyl ester at RT and t = 39.8 min.

FAMEs [36]. biodiesel and the results are presented in Table 7. GC–MS analyses
confirmed the presence of about 60% –OH containing fatty acid methyl
esters with about 55% lesquerolic acid methyl ester. Small amounts of
3.12. GC–MS (Electronic Ionization) analysis of Lesquerella fendleri
auricolic acid ester and ricinoleic acid ester, 9 unsaturated fatty acid
biodiesel
methyl esters, and 3 saturated fatty acid methyl esters are also observed.
The identified FAMEs composition is in line with previously reported
The fatty acid profile plays a vital role in the fuel properties of bio­
fatty acid compositions of Lesquerella fendleri oil [37].
diesel. GC–MS (Gas Chromatography-Mass Spectrometry) was used to
The mass spectrum of lesquerolic acid methyl ester from synthesized
determine the FAMEs composition of the synthesized Lesquerella fendleri
biodiesel is shown in Fig. 11 and a mass spectrum of the reference
biodiesel as well as to monitor the presence of hydroxy fatty acid-
standard of lesquerolic acid methyl ester is given in Figure S4 (see
containing lesquerolic acid methyl esters. Each peak in the gas chro­
Supplementary Material) to provide a comparison. Identical retention
matogram corresponds to a fatty acid methyl ester of the Lesquerella
times and fragmentation patterns of the molecular ions of both samples
fendleri biodiesel.
were observed. A characteristic base peak at m/z 55 occurs following a
Both reference standards and FAMEs samples were run under iden­
McLafferty rearrangement. The fragmentation of hydroxy fatty acid
tical conditions to study the FAMEs mixture of Lesquerella fendleri

10
M. Shahidul Islam et al.
methyl esters can be explained based on the TMS ether derivatives
mechanism where fragmentation happens before (m/z 255) or after (m/z
226), the position of the hydroxyl group in the carbon chain. This
fragmentation also provides an idea about the relative position of the
hydroxyl group as well as the number of hydroxyl groups in the
compound.
4. Conclusion
This study reports a direct-immersion ultrasound-assisted fast, eco-
friendly method to synthesize fatty acid methyl esters from Lesquerella
fendleri oil. A series of solid Lewis acids were studied and AlCl3 was
identified as the best catalyst among them for the complete conversion
(~99%) of Lesquerella fendleri oil into Lesquerella fendleri biodiesel. Ul­
trasonic irradiation enhanced the rate of the transesterification reaction
significantly by increasing the rate of carbocation intermediate forma­
tion of glyceridic carbons and the mass transfer rate between two
immiscible liquids (methanol and oil). It was demonstrated that the
AlCl3 catalysis is not sensitive to the FFA content and could catalyze the
esterification of FFA and the transesterification of triglycerides in LFO
simultaneously. These results suggest that AlCl3 is a potential alternative
catalyst for biodiesel synthesis from Lesquerella fendleri oil without
feedstock pretreatment. Statistical analysis showed that 5 wt% catalyst
concentration was the best in providing consistently higher yield with
different sonication times followed by 4 wt% catalyst loading. Consid­
ering the need for consistency of results and the goal of minimizing
sonication time, the 5 wt% catalyst was chosen as the optimum con­
centration, along with a 6:1 methanol-oil molar ratio and 40 min of
sonication time. We believe that the use of AlCl3 catalysis for Lesquerella
fendleri biodiesel production using ultrasound will open a window for a
more sustainable biodiesel synthesis process that could be used in both
batch and continuous processes. In summary, it has been demonstrated
that AlCl3 can catalyze the transesterification of LFO at room tempera­
ture under ultrasonic irradiation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to acknowledge the contribution of Israt
Jahan in the Department of Applied Economics at Texas Tech University
for her help with the statistical analysis. MSI would like to acknowledge
Noakhali Science and Technology University in Bangladesh for the leave
granted to perform this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ultsonch.2022.106082.
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