Energy Conversion and Management 196 (2019) 739–750

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Synthesis of Na+ trapped bentonite/zeolite-P composite as a novel catalyst T

for effective production of biodiesel from palm oil; Effect of ultrasonic
irradiation and mechanism
⁎
Mostafa R. Abukhadraa,b, , Sherouk M. Ibrahima,c, Sobhy M. Yakoutd,e, Mohamed E. El-Zaidyf,
Ahmed A. Abdeltawabg
a
Materials Technologies and Their Applications Lab, Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt
b
Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt
c
Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef City, Egypt
d
Department of Biochemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
e
Department of Analytical Chemistry and Control, Hot Laboratories and Waste Management Center, Atomic Energy Authority, Cairo 13759, Egypt
f
Department of Botany and Microbiology, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
g
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

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

Keywords: Bentonite/zeolite-P composite (B/ZP) was synthesized by simple alkaline hydrothermal treatment at 150 °C for
Bentonite 4 h and characterized by different analytical techniques. The composite was introduced as a low-cost catalyst of
Zeolite enhanced physiochemical properties and catalytic activity in the transesterification of palm oil into biodiesel.
Heterogeneous catalyst The catalytic activity of B/ZP catalyst was inspected by normal stirring mixing and under ultrasonic irradiation
Palm oil
of different powers (20–60%). The best biodiesel yield by normal stirring (96.2%) was achieved at operating
Biodiesel
Ultrasonic
conditions of 210 min as conversion time, 20:1 as a methanol-to-oil molar ratio, 5 wt% as a catalyst loading,
90 °C as temperature and 900 rpm as stirring speed. The conversion reaction under the ultrasonic irradiation
(power 60%) gives biodiesel yield of 98.8% after 120 min as reaction time using 5 wt% as catalyst loading, 20:1
as a methanol-to-oil ratio, and 90 °C as temperature. The ultrasonic irradiation is of positive impacts in reducing
the conversion time interval, reaction temperature, catalyst loading, and methanol-to-oil molar ratio with bio-
diesel yield similar to that obtained by normal stirring at its best conditions. The catalyst is of higher activities
than several homogenous and heterogeneous catalysts and can be reused several times with high catalytic ac-
tivity especially using an organic solvent either by normal stirring or under the ultrasonic irradiation. The
physicochemical specification of the obtained biodiesel by both methods matches the requirements of STM D-
6571 and EN 14214 international standards.

1. Introduction
The renewable and clean energy resource attracted the considera-
tions of the responsible energy and environmental organizations as a
potential solution for the future energy shortage problems and the as-
sociated hazardous emissions of traditional fuels [1–4]. In the later
years, biodiesel and biofuels were suggested as an effective and eco-
friendly alternative for traditional fuels [6,7]. It was reported that the
produced biodiesel from the transesterification of vegetable oil and
animal fats is of biodegradable properties, no toxic emissions and ex-
cellent diesel technical properties [8–11]. This qualifies it to be used
directly in the engines or integrated into a blend with petroleum diesel
[11–14].
The transesterification reaction for oil into biodiesel performed
mainly in the existence of a potential catalyst either homogenous cat-
alyst or heterogeneous catalyst to accelerate the process [14,15,3]. The
previous literature reported that the applying of homogenous catalysts
is of high catalytic activities but they suffer from non-reusability, high
separation costs, high corrosion properties, and of toxic residuals
[5,16]. However the heterogeneous catalysts are of lower catalytic ac-
tivities than homogenous catalysts, they are environmental materials of
low fabrication cost and can be reused several times with simple se-
paration and recovery techniques [1,14].
The recorded low catalytic activities of heterogeneous catalysts

⁎
Corresponding author.
E-mail address: Abukhadra89@Science.bsu.edu.eg (M.R. Abukhadra).

https://doi.org/10.1016/j.enconman.2019.06.027
Received 1 April 2019; Received in revised form 31 May 2019; Accepted 14 June 2019
0196-8904/ © 2019 Elsevier Ltd. All rights reserved.
M.R. Abukhadra, et al.
related to the weak interactions between them and the liquid phases of
the transesterification system (oil and alcohol). This assigned mainly to
the high immiscibility between such components which result in high
mass transfer resistance and in turn low activity rates [11,17]. The
incorporation of an ultrasonic source as mixing technique during the
transesterification reactions can provide high mixing properties and
enhance the catalytic activities of heterogeneous catalysts by the as-
sociated activation energy and cavitation phenomenon [11,18]. The
cavitation phenomenon associated with continuous generation of fine
emulsion droplets between the liquid phases and collapse of such dro-
plets results in the generation of continuous micro-streams, microjets,
and shockwaves in the system [17,19]. This provides effective mixing
properties between the immiscible liquids; reduce the mass transfer
resistance, and enhance velocity gradients [2]. The previous effects
cause an increase in the interaction area between the present phases
which promotes the transformation rates at low temperature, short time
intervals, and low alcohol-to-oil molar ratio [20]. Moreover, the ul-
trasonic waves are of impressive effect in reducing the particle size of
the solid catalyst which can increase the exposed active catalytic sites
and the surface area [2].
Fabrication of the heterogeneous catalysts from natural materials
became the main interest of the researchers in the later periods to re-
duce the total production cost and for their environmental properties
[3,21]. From the known natural materials, clay and zeolite materials
were applied widely as a heterogeneous catalyst in the biodiesel pro-
duction after their functionalization by acidic and basic chemical
groups or by supporting their structures with alkali elements (sodium
and potassium) and metal oxide [1,22,23]. Zeolite either in synthetic or
natural forms is of alkali aluminosilicate chemical composition, micro-
porous properties, extraordinary ion-exchange capacities, and eco-
friendly properties which are vital properties for superior catalytic ac-
tivities [23–28]. This also was recorded for clay minerals as they exhibit
flexible chemical structure, low cost, high ion replacement capacities
[4,28]. The commonly studied clay and zeolite based catalysts are
natural zeolite, mordenite, Zeolite-A, zeolite-X, zeolite-Y, sodalite,
bentonite, kaolinite and chrysotile [13,23,30–38]
Recently novel hybrid products between natural clays and synthetic
zeolite were produced as composites and evaluated as promising ma-
terials of superior physicochemical properties [28,37,38]. Bentonite/
zeolite-P composite was synthesized by Shaban et al., [28] as a hybrid
product of enhanced surface area, ion exchange capacity, porous
structures, and of good swelling properties. Unfortunately, the catalytic
activities of such hybrid materials in the transesterification of oil into
biodiesel have not been investigated. Thus, this study aims to synthesis
a novel composite of bentonite/synthetic zeolite-P (B/ZP) as a catalyst
in the transformation of palm oil into biodiesel by normal stirring
mixing and under ultrasonic irradiation in a comparison study. The
conversion reactions were accomplished based on the commonly stu-
died factors as conversion time, temperature, catalyst loading, me-
thanol-to-oil molar ratio, stirring speed and the reusability of the cat-
alyst.
2. Experimental method
2.1. Materials
Raw bentonite (SiO2 (54.82%), Al2O3 (17.56%), Fe2O3 (9.5%),
Na2O (2.6%), MgO (2.5%), CaO (2.4%), TiO2 (1.45%), and LOI (9.2%))
from Western desert bentonite quarry and NaOH (97%) was used in the
preparation of Na+ trapped bentonite/zeolite-P catalyst. Commercial
palm oil, pure methanol of chemical analytical grade (99.8%, Sigma
Aldrich) was used in the transesterification system.
2.2. Preparation of the catalyst
The raw bentonite sample was ground extensively to be less than
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Energy Conversion and Management 196 (2019) 739–750
70 µm and then was activated by thermal treatment in an electric
muffle furnace at an activation temperature of 750 °C for 4 h to obtain a
product of high chemical reactivity and open crystalline structure [28].
After that, 6 g of the thermally activated sample was incorporated in an
alkaline solution (12 g of NaOH + 100 mL distilled water) under stir-
ring (500 rpm) at a reaction temperature of 70 °C for 2 h. Then, the
alkaline activated bentonite was transferred into conversion reactor
consist of Teflon autoclave lined by stainless to complete the hydro-
thermal conversion of it at a reaction temperature of 150 °C for 4 h. By
the end of the conversion process, the sample was cooled, separated by
centrifugation, washed and finally dried for 24 h at 65 °C. The final
product was labeled as B/ZP and kept for further characterization and
applications.
2.3. Characterization of the catalyst
The structural properties of the investigated bentonite, as well as the
synthetic B/ZP composite, were inspected from the XRD patterns ob-
tained by a PANalytical X-ray diffractometer (Empyrean). The surficial
morphological features were inspected by field emission Scanning
electron microscope (Gemini, Zeiss-Ultra 55). The possible alteration in
the chemical functional groups from bentonite to B/ZP composite be-
fore and after the conversion reactions was studied using FTIR-FT
Raman spectrometer (Vertex 70). The textural properties including BET
surface area and pore size distribution were studied using
Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH)
methods, respectively.
2.4. Transesterification system
The used transesterification system was designed for two mixing
technologies (normal magnetic stirring and ultrasonic irradiation). The
system consists of three-necked glass bottom-flask (250 mL) as a con-
version reactor equipped with water-cooled glass condenser as a reflux
system in addition to and a thermocouple thermometer. For the de-
signed system by normal stirring, the reactor was connected with an
electric magnetic stirrer with a digital heater to control the reaction
temperature (Fig. S1 in the supplementary data). The typical experi-
mental procedures involved mixing of 40 mL palm oil with a certain
amount of B/ZP catalyst under stirring till attending the selected re-
action temperature. This followed by the addition of preheated me-
thanol to the mixture and confirming the very high sealing for the inlet
and outlet parts. The values of the controlling factors were adjusted to
be within a range from 30 min to 300 min for the time interval, from
2 wt% to 6 wt% for the used catalyst quantity, from 5:1 to 30:1 as
methanol-to-oil ratio, from 40 °C to 120 °C as temperature, and from
200 rpm to 1300 rpm as stirring speed.
For the ultrasonic assist transesterification system, it was built by
fixing the reactor parts into an ultrasonic bath (2L capacity) of 20 kHz
frequency, and 400 W full power (Branson ultrasonic processor) (Fig. S2
in the supplementary data). The effect of the ultrasonic waves was
studied within a power range from 20% (80 W) to 60% (240 W) and the
transferring of the ultrasonic waves was performed by filling the bath
volume by distilled water. The experimental procedures were accom-
plished by the same steps which were used in the normal stirring system
but without magnetic stirring and within the time range from 30 min to
150 min.
By the end of each conversion test, the resulted oil samples were
poured into the separating funnel after filtration above Whitman filter
paper and left till the complete separating of dense glycerol layers from
the yield biodiesel. After that, the yielded biodiesel was heated for
240 min at 70 °C to achieve successful evaporation for any excess in the
incorporated methanol and washed by sodium sulfate to remove the
residual water molecules.
M.R. Abukhadra, et al.
2.5. Analysis of the biodiesel samples
Gas chromatography (Agilent 7890A) device was used to determine
the quantities of fatty acid methyl ester (FAME) in the biodiesel sam-
ples. The analytical procedures involved dilution of the obtained bio-
diesel sample by n-hexane and the FAME content was inspected by an
Agilent-7890A Series gas-chromatograph system connected with flame
ionization detector, split/splitless injection system, and capillary
column (DB WAX, 30 m × 0.25 m × 0.25 µm) with inert hydrogen gas
as carrier and 100:1 split ratio. The detector and the injector tem-
perature values were fixed at about 280 °C during the analysis of the
samples. The starting temperature of the oven is 120 °C and increased
regularly by 10 °C per min for 50 min till attained 260 °C. An internal
standard of methyl heptadecanoate was used during the analysis of the
sample to quantify the FAME content in the biodiesel samples by in-
jection of 1 µl of the samples into the system. After that, total biodiesel
yields were calculated considering the quantity of the formed fatty acid
methyl based on Eq. (1) [6]:
(Weight of biodiesel x % FAME )
Biodiesel yield (%) = × 100
Weight of oil (1)
3. Result and discussion
3.1. Characterizations
3.1.1. Structural properties
The bentonite precursor showed the existence of montmorillonite
clay mineral as the dominant type of smectite clay groups (Fig. 1A). The
other crystalline phases as kaolinite, calcite, and quartz were identified
as associated impurities. The characteristic XRD peaks of montmor-
illonite were recognized at 2θ angles of 6.55°, 19.85°, 25.1° and 28.35°
which were assigned to (0 0 2), (0 2 0) and (1 0 5) lattice planes, re-
spectively (card No: 00-003-0010 and No: 00-058-2010). The present
montmorillonite is of 12.96 nm average crystallite size and 13.48 Å d-
spacing. The thermal activation resulted in a significant reduction in the
intensities of the montmorillonite peaks and the d-spacing value
12.85 Å (Fig. 1B) which related to the partial dehydration and de-
struction of the montmorillonite structure during the activation process.
Additionally, most of the impurities related peaks were disappeared
after the thermal activation.
Fig. 1. XRD patterns of raw bentonite (A), calcinated bentonite (B), synthetic
bentonite/zeolite (B/ZP) catalyst (C), and the spent B/ZP catalyst after the
reaction (D).
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Energy Conversion and Management 196 (2019) 739–750
The obtained pattern of B/ZP declared the distinctive peaks of
zeolite-P at about 12.46°, 16.6°, 21.66°, 28.1°, 33.38° and 38° [28]
(Fig. 1C). This associated with disappearance for several montmor-
illonite peaks as well as obvious reducing and shifting for its main peak
as it appeared at 2Theta angle of 6.73° (Fig. 1C). This reduced peak was
defined by Ma et al., [39] as an indicator peak of montmorillonite
mineral which confirming the synthesis of hybrid material from ben-
tonite and synthetic zeolite-P [28]. The XRD pattern of the catalyst after
the transesterification reaction showed no variation in the main peaks
of B/ZP catalyst except a slight reduction in the intensities of the peaks
which can be related to the possible coating of the catalyst particles
with glycerol and methyl ester molecules (Fig. 1D).
3.1.2. Morphological features
The morphological features of bentonite, B/ZP catalyst, and the
spent catalyst were inspected from SEM images in Fig. 2. Bentonite
appears as clusters of agglomerated particles composed of stacked
layers and decorated by tiny chunks related to the associated mineral
(Fig. 2A). The SEM images of B/ZP showed massive grains of bentonite
disseminated by tiny grains of nearly cubic form and distributed ran-
domly throughout the bentonite surface (Fig. 2B and C). The present
cubic grains are well developed zeolite-P crystals and their distribution
on the bentonite grains as substrate reflected the successful fabrication
of composite from bentonite and zeolite-P without destruction for the
characteristic morphology of bentonite. The spent B/ZP catalyst ex-
hibits no changes in its morphology after the transesterification reac-
tion by normal stirring except small distortion for the particles
(Fig. 2D). While the spent catalyst after the ultrasonic assist transes-
terification showed obvious disintegration of it into finer grains with
destruction for its original morphology (Fig. S3 in the supplementary
data).
3.1.3. Textural properties and catalyst mechanism
Table 1 showed the textural properties of B/ZP composite in com-
parison with raw bentonite and commercial synthetic zeolite-P. The
specific surface area of the synthetic composite is 512 m2/g which is
higher than that of raw bentonite (91 m2/g) and zeolite-P (123 m2/g).
Moreover, the composite emphasized enhanced porous structure with
an average pore diameter of 5.8 nm as compared to 10.4 nm and 1.2 nm
for bentonite and zeolite-P, respectively. Also, the ion exchange capa-
city enhanced greatly to be 387 meq/100 g which is higher than the
estimated values for bentonite and zeolite-P (Table 1).
3.1.4. Chemical properties
The change in the functional groups with the fabrication steps of the
composite was evaluated based on the FT-IR spectra of them (Fig. 3).
The spectrum of bentonite showed the bands of structural OH within
the area from 3100 cm−1 to 3700 cm−1 in addition to a band at
16406 cm−1 related to the interlayer water molecules [28,40,41]
(Fig. 3A). The structural SieO and AleO groups were identified by their
bands at 1000 cm−1 and 918 cm−1, respectively [40]. The observed
bands from nearly 400 cm−1 to 1000 cm−1 related to MgeFeeOH,
SieO–Mg, and Si–O–Al groups [36] (Fig. 3A).
The FT-IR spectrum of B/ZB catalyst showed a clear deviation for
the main bands of OH groups and bending water molecules with a
noticeable increase in their intensities (Fig. 3B). Additionally, two ab-
sorption bands at 3625 cm−1 and 918 cm−1 were disappeared which
confirmed the successful activation of bentonite by NaOH and effective
hydration of its layer during the transformation reactions. The new
detected band at 1429 cm−1 related to the coordinated water molecules
within the pores of the synthetic zeolite [25]. This supported by the
chemical composition of the synthetic B/ZP catalyst (SiO2 (51.46%),
Al2O3 (14.52%), Fe2O3 (7.5%), Na2O (10.3%), MgO (1.52%), CaO
(1.62%), TiO2 (0.77%), and LOI (12.6%)). The enrichment in the so-
dium content related mainly to the synthetic zeolite and reflected the
effect of the alkaline alteration on the structure of bentonite.
M.R. Abukhadra, et al. Energy Conversion and Management 196 (2019) 739–750

Fig. 2. SEM images of raw bentonite at magnification of 2000×, scale bar = 10 µm, and accelerating voltage = 30 kV (A), bentonite/zeolite-P catalyst at magni-
fication of 500X, scale bar = 500 µm, and accelerating voltage = 15 kV for (B) and 1400×, scale bar = 10 µm, and accelerating voltage = 30 kV for (C), and spent
bentonite/zeolite-P catalyst after transesterification reaction at magnification of 1700×, scale bar = 10 µm, and accelerating voltage = 30 kV (D). The SEM images
were taken by Gemini, Zeiss-Ultra 55-high filed emission Scanning electron microscope.

The FT-IR spectrum of the spent catalyst after the conversion re-
actions showed the main groups of B/ZP with noticeable changes in
their positions and intensities in addition to the appearance of other
new bands (Fig. 3C). The detected new bands at about 2950 cm−1 and
1320 cm−1 were assigned to the CeH bond in methyl and/or methylene
groups of methyl esters that were adsorbed by the composite particles
[1,32].
3.2. Catalytic transformation of palm oil
3.2.1. The conversion reactions by normal stirring mixing
3.2.1.1. Effect of conversion time intervals. The transesterification period
is a vital parameter due to the immiscibility nature of reactants in the
system. The influence of time intervals on the catalytic conversion of
palm oil by B/ZP catalyst was studied within a range from 30 min to
300 min (Fig. 4A). The other controlling parameters were fixed at 70 °C
as temperature, 15:1 as an alcohol-to-oil molar ratio, 4 wt% as catalyst
loading, and 500 rpm as stirring speed (Fig. 4A). There is a gradual
increment in the obtained biodiesel yield with expanding the time
interval from 30 min to 210 min achieving the best biodiesel yield
(87%) at this time (Fig. 4). The results revealed slow changes in
transesterification rate during the initial stages of the reactions and a
significant increase in the rate with the gradual increase in the time
intervals [42]. This was emphasized to be a logic result for the high
immiscibility between methanol and palm oil at the initial stages (low
conversion time intervals) which cause an incomplete transformation of
the present FAME into biodiesel and this can be avoided by expanding
the time interval [3,43].
The further increment in the time intervals is of a reversible effect
which resulted in decreasing the biodiesel yield (%) to be 84% after
300 min (Fig. 4A). This behavior was assigned to the reversible nature
of such reactions in addition to the possible hydrolysis of the formed
esters to free fatty acids [44,45]. Therefore, 210 min was selected as the
best time for the transformation of palm oil into biodiesel in the pre-
sences of B/ZP as a basic heterogeneous catalyst.
3.2.1.2. Effect of methanol-to-oil molar ratio. Evaluation of methanol-to-
oil-ratio as a vital factor in the transesterification of palm oil was
studied within a range from 5:1 to 30:1. The other factors were adjusted
at 210 min as time, 70 °C as temperature, 4 wt% as catalyst loading, and
500 rpm as stirring speed (Fig. 4B). The presence of methanol in the
transesterification reaction is a critical component as each one mole of
triglyceride interacts with three moles of alcohol to generate three
moles of FAME and one mole of glycerol [16,46]. The presence of

Table 1
Textual and physical properties of B/ZP catalyst in comparison with bentonite and zeolite-P.
Sample Cation exchange Swelling Specific Surface Micropores volume Mesopores volume Total volume Average pore size
capacity (meq/100 g) capacity area (m2/g) (ml/g) (ml/g) (ml/g) (nm)

Bentonite 104 8.37 91 0.013 0.262 0.312 10.4

Zeolite-NaP 320 2.54 123 0.36 0.01 0.37 1.2
Bentonite/Zeolite- 387 5.62 512 0.244 0.175 0.422 5.8
NaP

742
M.R. Abukhadra, et al.
Fig. 3. FTIR spectra of raw bentonite (A), bentonite/zeolite-P catalyst (B), and
the spent catalyst after the transesterification reactions (C).
methanol in a sufficient ratio accelerates the solubility of the present
phases, reduces the mixture viscosity, improves the mixing
homogeneity and reduces the mass transfer resistance which induces
the transesterification reaction in the forward direction with high
biodiesel yield [3,6,44]. Furthermore, the interfacial area between
the present immiscible liquids does not affect by increasing the
methanol-to-oil ratio. This provides a high-frequency passage for the
solid catalyst through it which causes a considerable increase in the
exposed surface area and the catalytic activity of it [1,47,48].
In the studied B/ZP system, the resulted biodiesel yield from palm
oil increased from 71% to 90.3% with increasing the methanol-to-oil
molar ratio from 5:1 to 20:1 (Fig. 4B). The further augmentation in the
ratio to be higher than 20:1 is of reversible effect and resulted in a
noticeable reduction in the obtained biodiesel yield (Fig. 4B). The ex-
cessive methanol content is of several negative impacts including (1)
the deactivation of B/ZP catalyst, (2) the dilution of the reactants
mixture, (3) the change in the polar groups of methanol which con-
verting them to emulsifiers, and (4) the significant dissolution of the
formed glycerol byproducts by it which can shift the reaction towards
the reversible side [6,49]. Thus the excessive methanol content reduces
the transesterification rate, raises the total production cost and com-
plicates the recovering processes [3,48,50].
3.2.1.3. Effect of the reaction temperature. Investigation of the catalytic
activity as a function of the operating temperature was performed at
fixed values of 210 min as time, 20:1 as alcohol-to-oil ratio, 4 wt% as B/
ZP catalyst loading and 500 rpm as stirring speed (Fig. 4C). The
influence of temperature was studied within a range from 40 °C and
120 °C. The plotted results showed an increase in biodiesel yield with
the increment in the reaction temperature from 40 °C to 90 °C achieving
the best value at 90 °C (92.8%) (Fig. 4C). This behavior can be
explained based on the nature of the transesterification processes as
endothermic reactions [6,51]. The operation of the reaction at high
temperature gives the reactants high kinetic energies and increases the
interaction chances between alcohol and triglyceride molecules which
induce the mass transfer and promotes the solubility of the present
liquid phases which in turn enhances the catalytic conversion reactions
[1,10,16,52,53].
Performing the reaction at a temperature above 90 °C is of slight
effect and of negative effect with temperatures above 100 °C (Fig. 4C).
The over increasing in the temperature can increase the escaping
chances of the evaporated methanol from the system which hinders the
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Energy Conversion and Management 196 (2019) 739–750
predicted mass transfer of the reactants (B/ZP catalyst, palm oil, and
methanol) and impacts the used methanol-to-oil molar ratio [54]. Thus,
the best results can be obtained at a reaction temperature of 90 °C.
3.2.1.4. Effect of catalyst loading. The quantity of the used catalyst is an
effective parameter either for its economic value or for its impact on the
conversion efficiency of palm oil. The vital effect of B/ZP loading was
studied within a range from 2 wt% to 6 wt% after fixing the other
conditions at 210 min as time, 20:1 as a methanol-to-oil ratio, 90 °C as
temperature, and 500 rpm as stirring speed (Fig. 4D). The obtained
biodiesel yields declared a gradual enhancement in the percentages
with using higher catalyst loading from 2 wt% (74.5%) till 5 wt%
(93.6%) (Fig. 4D). The recorded increment in the biodiesel yield with
increasing the used B/ZP mass attributed to the associated increase the
total surface area and the quantities of the exposed active catalytic sites
[3,55].
The observed reduction in the biodiesel yield with using catalyst
loading of 6 wt% (92.4%) related to the possible formation of dense
slurry of high viscosity with using high quantities of the solid catalyst.
This reduces homogeneity between the mixed reactants and reduces the
interaction chances between them [16,56] (Fig. 7). Moreover, the rest
un-reacted catalyst particles increase the mass transfer resistance which
reduces the conversion rate of palm oil [1,52].
3.2.1.5. Effect of stirring speed. The stirring speed is a critical parameter
in all the heterogeneous catalytic transesterification reactions as it
controls the immiscibility between the reactants and preserves
homogenous mixture within the reaction period [57]. The stirring
speed as transesterification parameter was studied within a range from
200 rpm to 1300 rpm at fixed values of 210 min as time, 90 °C as
temperature, 20:1 as methanol-to-oil ratio and 5 wt% as catalyst
loading (Fig. 4E). The catalytic activity of B/ZP increased linearly
with increasing the stirring speed from 200 rpm to 900 rpm which
reflected in increasing the biodiesel yield from 88.6% to 96.2%
(Fig. 4E). Increasing the stirring speed assists greatly to wipe out the
mass transfer resistance between the liquid phases (palm oil and
methanol) and preserves high mixing homogeneity between all the
solid and liquid reactants which ensures effective conversion reactions
with high yields [57,58]. The further increase in the stirring speed
above 900 rpm is of slight negative effect on the resulted biodiesel yield
as it decreased only by 0.5% and 1% with increasing the speed by
1000 rpm and 1300 rpm, respectively. The previous behavior might be
related to the role of the high stirring speed in increasing the turbidity
between the reactants which reduce the homogenous mixing between
them and cause random dispersion of them on the walls of the system.
The previous effects are of negative impacts on the equilibrium balance
of the reaction and reduce the transesterification efficiency.
3.2.2. The conversion reactions under ultrasonic irradiation
3.2.2.1. Effect of ultrasonic irradiation time. The influence of ultrasonic
irradiation on enhancing the catalytic activity of synthetic B/ZP during
the transesterification of palm oil into biodiesel was studied within time
range from 30 min to 150 min and under ultrasonic irradiation of
different powers (20% (80 W), 30% (120 W), 40% (160 W), 50%
(200 W), and 60% (240 W)). The other parameters were adjusted to
be at 5 wt% as catalyst loading, 90 °C as temperature and 20:1 as a
methanol-to-oil ratio (Fig. 5A).
The obtained results revealed a continuous increment in the bio-
diesel yield with the gradual augmentation in the time intervals from
30 min to 150 min with clear enhancement in the values with in-
creasing the ultrasonic powers. Using ultrasonic irradiation of 20%,
30% and 40% powers resulted in biodiesel yields of 96%, 96.5%, and
97.5% after 150 min, respectively (Fig. 5A). The applying of the highest
ultrasonic powers of 50% and 60% resulted in superior conversion ef-
ficiency of very high biodiesel yields within short time intervals
(Fig. 5A). For the ultrasonic power of 50%, the obtained biodiesel yields
M.R. Abukhadra, et al. Energy Conversion and Management 196 (2019) 739–750

Fig. 4. influence of the operating parameters on the conversion of palm oil into biodiesel using B/ZP catalyst, (A) time intervals, (B) methanol-to-oil molar ratio, (C)
temperature, (D) catalyst loading, and (E) stirring speed.

enhanced to about 98.5% after 90 min as a reaction time interval. Using of palm oil in the presence of B/ZP as a heterogeneous catalyst can give
ultrasonic irradiation at 60% power achieved the best biodiesel yields higher biodiesel yield than by normal stirring method within short time
as the obtained percentages are 96.5%, 98.7% and 98.8% after 60 min, intervals.
90 min, and 120 min, respectively.
The noticeable enhancement in the biodiesel yield with raising the
3.2.2.2. The ultrasonic effect at a different catalyst loading. Investigation
ultrasonic power can be assigned to the effect of high ultrasonic waves
of the positive influences of the ultrasonic irradiation in enhancing the
in inducing the acoustic movements and the formation of numerous
effectiveness of the applied B/ZP masses was inspected in the presences
cavitation bubble of low stability [19,59]. The collapse of such less
of an ultrasonic source of different powers (from 20% to 60%) using
stable cavitation bubbles resulted in high micro-mixing processes and
different masses of the catalyst (2–6 wt%). The other parameters were
increases the jet velocities between the boundaries of the reacting liquid
adjusted at 90 °C as temperature, 20:1 as methanol-to-oil ratio and
phases. This promotes the effective formation of fine emulsions that
120 min as the time interval (Fig. 5B). As appeared in the plotted
accelerate the mass transfer and enhance the efficiency of the transes-
curves, the yield percentage increases by increasing the applied catalyst
terification reaction [2,59].
loading and the influence of catalyst loading showed great
It is worth to be mentioned that, the further increment in conversion
enhancement with increasing the ultrasonic power from 20% to 60%.
time intervals above 120 min is of slight or negative impact on the
(Fig. 5B). Biodiesel yields of 95.3%, 95.8%, 97.3%, 98%, and 98.5%
obtained biodiesel yield for all the studied ultrasonic powers (Fig. 5A).
were obtained using 4 wt% of B/ZP as catalyst loading under ultrasonic
Thus, applying the ultrasonic irradiation during the transesterification
irradiation of 20%, 30%, 40%, 50%, and 60% powers, respectively.

744
M.R. Abukhadra, et al.
Fig. 5. Influence of ultrasonic irradiation of different powers on the conversion of palm oil into biodiesel by B/ZP catalyst at different reaction parameters, (A)
conversion time intervals, (B) catalyst loading, (C) methanol-to-oil molar ratio, and (D) the reaction temperature.
The obtained values showed a slight increase with increasing the
applied catalyst loading by 5 wt%, and 6 wt% for all the inspected ul-
trasonic powers. This can be assigned to predict scattering of ultrasonic
irradiation which can be resulted in weak cavitation effects [17].The
best biodiesel yields for ultrasonic irradiations of 20% power, 30%
power, and 40% power are 96%, 96.5% and 97.8%, respectively; and
were obtained using 6 wt% B/ZP as catalyst loading (Fig. 5B). For the
reactions which were conducted using ultrasonic irradiation of 50% and
60% powers, the best biodiesel yields of 98.6% and 98.8% were
achieved using 5 wt% B/ZP as catalyst loading. Therefore, the used
masses of B/ZP catalyst can be reduced and give high biodiesel yields
by applying the ultrasonic irradiation as mixing technique instead of a
normal stirring method.
3.2.2.3. The ultrasonic effect at a different methanol-to-oil ratio. The role
of ultrasonic treatment in enhancing the catalytic activity of B/ZP as a
function of the methanol-to-oil molar ratio was investigated at a fixed
time interval (120 min), 90 °C as temperature and 5 wt% as catalyst
loading (Fig. 5C). The methanol-to-oil molar ratio was studied within a
range from 5:1 to 30:1 using different powers of ultrasonic irradiation
(20–60%).
The obtained results reflected the possible production of biodiesel
with yields higher than 90% using 10:1 as a methanol-to-oil molar ratio
under ultrasonic irradiation of powers 40%, 50%, and 60% (Fig. 5C).
Increasing the ratio to 15 (methanol):1 (oil), resulted in increasing the
biodiesel yield by 94.2%, 94.6%, 95.4%, 96.3%, and 96.8% with the
increment in the ultrasonic power by 20%, 30%, 40%, 50% and 60%,
respectively. The best catalytic performance was obtained at methanol-
745
Energy Conversion and Management 196 (2019) 739–750
to-oil ratio of 20:1 as the biodiesel yields increased to 96%, 96.5%,
97.8%, 98.6% and 98.8% with increasing the ultrasonic power by the
previous order (Fig. 5C). The further increase in the molar ratio above
20:1 is of a negative impact and resulted in the reduction of the ob-
tained biodiesel yields at all the studied ultrasonic powers. Therefore
the ultrasonic irradiation can improve the obtained biodiesel yields (%)
but has no effect on the optimization of methanol/oil ratio which is of
agreement with the previous literature [17,19,59].
3.2.2.4. The ultrasonic effect at a different reaction temperature. The role
of ultrasonic irradiation in enhancing the role of temperature and/or
reducing the required temperature for effective conversion reactions
was investigated within a temperature range from 40 °C to 120 °C. The
operating parameters were selected to be 120 min as transesterification
time, 20:1 as methanol-to-oil ratio and 5 wt% as catalyst loading
(Fig. 5D).
The biodiesel yield showed gradual increment with increasing the
temperature till 90 °C for all the studied ultrasonic powers with sig-
nificant enhancement with the augmentation of power from 20% to
60% (Fig. 5D). Under ultrasonic irradiation of 50% power, the biodiesel
increased by 90.3%, 93.6%, 95.4%, 97.4%, and 98.6% with the gradual
increment in temperature by 50 °C, 60 °C, 70 °C, 80 °C, and 90 °C, re-
spectively (Fig. 5D). With using ultrasonic irradiation of 60% power,
the biodiesel yield increased to 91.5%, 94.7%, 96.2%, 97.5%, and
98.8% at reaction temperature of 50 °C, 60 °C, 70 °C, 80 °C and 90 °C,
respectively. This gives other advantages for using ultrasonic irradia-
tion in the heterogeneous catalytic conversion of palm oil as it can
reduce the required temperature for effective production of biodiesel as
M.R. Abukhadra, et al.
Fig. 6. The reusability studies of B/ZP catalyst in the transesterification of palm
oil using different solvents (distilled water, methanol and acetone).
compared to normal stirring.
3.2.3. The catalyst reusability
The suitability of the catalyst be used for several rounds were stu-
died for eight runs either by normal stirring mixing or under ultrasonic
irradiation. The operating conditions for normal stirring tests were
fixed at 210 min as a reaction time, 20:1 as a methanol-to-oil molar
ratio, 5 wt% as catalyst loading, 90 °C as a reaction temperature and
900 rpm as stirring speed (Fig. 6). The reusability tests under the ul-
trasonic irradiation were performed at a fixed time of 120 min, me-
thanol-to-oil ratio of 20:1, temperature of 90 °C and ultrasonic irra-
diation of 60% power (Fig. 6). After each run, the solid catalyst was
separated and washed extensively by three different solvents including
distilled water, methanol, and acetone. Then the washed solid fractions
were dried in an electric oven at 70 °C for 5 h.
The reusability results using the inspected three solvents revealed
the suitability of B/ZP as a catalyst to be used for eight times with
significant biodiesel yields (Fig. 6). The catalytic activity of B/ZP
showed considerable reduction with increasing the reusability cycles
from cycle1 to cycle 8 either by normal stirring or under ultrasonic
Fig. 7. Schematic diagram for the formation B/ZP catalyst and the effect of alkaline activation on it.
746
Energy Conversion and Management 196 (2019) 739–750
irradiation (Fig. 6). This related to the predicted leaching of the present
catalytic sites (sodium ions) from B/ZP composite and the deactivation
of it by the over adsorbed transesterification by-products during the
reaction which reduce the possible interaction between the reactants
and the basic catalytic sites [1,2,22]. This assumption was confirmed by
the FT-IR spectra of the spent catalyst as it showed several functional
groups related to the adsorbed oil byproducts (Fig. 3).
For using distilled water as solvent, the obtained biodiesel yields are
96.2% (cycle 1), 94.3% (cycle 2), 91.6% (cycle 3), 85% (cycle 4), 78.4%
(cycle 5), 72% (cycle 6), 67.4% (cycle 7), and 62% (cycle8) under
normal mixing stirring. Under ultrasonic irradiation, the obtained va-
lues for the same cycles in order are 98.8%, 95.3%, 91%, 85.4%, 74%,
69%, 63% and 57.4%. For applying methanol in the regeneration of the
catalyst, the resulted yields are 96.2% (cycle 1), 95.7% (cycle 2), 93.4%
(cycle 3), 90.2%, (cycle 4), 87.3% (cycle 5), 83.5% (cycle 6), 78.4%
(cycle 7), and 72% (cycle8) by normal stirring mixing. While the ob-
tained values under the ultrasonic irradiation are 98.8% (cycle 1),
97.2% (cycle2), 93% (cycle 3), 87.5% (cycle 4), 80% (cycle 5), 74.2%
(cycle 6), 67% (cycle 7), and 61% (cycle 8). For the reusability results
after washing by acetone, the conversion processes resulted in biodiesel
yields of 96.2% (cycle1), 96% (cycle 2), 94.8% (cycle 3), 90.5% (cycle
4), 88% (cycle 5), 85% (cycle 6), 79.6% (cycle 7), and 71.8% (cycle 8)
by stirring mixing processes. Under the ultrasonic effects, the obtained
yields at the studied reusability cycles are 98.8% (cycle1), 97.5% (cycle
2), 94.3% (cycle 3), 88% (cycle 4), 81% (cycle 5), 73.5% (cycle 6), 65%
(cycle 7), and 60% (cycle 8). The results revealed that using organic
solvents (methanol and acetone) can achieves better results in reusa-
bility tests than distilled water which can credit mainly to the high
efficiency of organic solvents in the removal of the adsorbed transes-
terification by-products on the surface of the catalyst. Additionally, the
catalyst showed higher stability by normal stirring mixing processes
than under the ultrasonic irradiation which is of great agreement with
other studies [2].
3.2.4. Mechanisms of catalyst formation and biodiesel generation
The synthetic catalyst is a hybrid material composed of two silicate
minerals with different crystal structures; montmorillonite with a
layered structure and zeolite-P with tectosilicate structure (Fig. 7). The
composite was synthesized by the partial hydrothermal transformation
of bentonite in an alkaline solution. The resulted hybrid product ap-
peared as bentonite aggregates decorated by tiny cubic zeolite crystals
M.R. Abukhadra, et al. Energy Conversion and Management 196 (2019) 739–750

which give it numerous advantages represented by the formation of a Table 2

product with a highly porous structure, high surface area, ion exchange Physicochemical properties of the produced biodiesel in comparison with the
capacity, and basicity. Additionally, the bentonite sample still shows its international standards.
characterization properties of the amazing layered structure and ion Contents Unit ASTM D- EN 14214 Biodiesel Biodiesel
exchange properties. Moreover, the alkaline activation of montmor- 6751 (Ultrasonic) (Stirring)
illonite mineral affected greatly the crystal structure of it as it became
Viscosity mm2/s 1.9–6 3.5–5 3.84 4.12
saturated by sodium ions as replaceable ions or as trapped ions.
Moisture Wt. (%) < 0.05 < 0.05 0.041 0.034
Structurally, montmorillonite composed mainly of an octahedral sheet content
between two tetrahedron sheets [41] (Fig. 7). The corner sharing of the Flash point °C > 120 > 120 178.5 176
structural silica tetrahedrons results in the formation of structural open Cloud point °C −3 to 15 – 6.4 5.8
Pour point pp −5 to 10 – 5.4 5.7
molecular cavities that can act as traps for the sodium ions during the
Cetane 47–65 51–120 53.7 55.3
alkaline activation [28,60] (Fig. 7). Also, sodium ions can be inserted number
within the structure of montmorillonite by partial replacement of Si and Density g/cm3 0.82–0.9 0.86–0.9 0.872 0.864
Al ions and as trapped free ions within the interlayer water molecules
[1,22] (Fig. 7). Moreover, the alkaline activation is of etching effect on
the surficial siloxane groups and cause hydration for the montmor- glycerol [6] (Fig. 8).
illonite sheets [28]. All the previous effects enhance the ion exchange
properties, the total basicity, the surface area and cause more exposing 3.2.5. Physicochemical properties of the final biodiesel yield
for the functional groups that are of high catalytic activities [40,60] The resulted biodiesel at the best transesterification conditions was
(Fig. 7). evaluated based on the required specifications of the international
The catalytic conversion of oil into biodiesel in presence of alcohol standards (EN 14214 and ASTM D-6751) (Table 2). The properties of
(methanol) accomplished mainly by two steps; (1) cracking of the ester the finally generated biodiesel either by normal stirring or by ultrasonic
bonds between the triglyceride molecules, and (2) effective substitution irradiation strongly match the requirements of the international stan-
with the alcohol short chains producing the biodiesel [3] (Fig. 8). B/ZP dards. The measured cetane indexes are higher than 45 for both sam-
catalyst is a basic catalyst and enriched in alkaline catalytic sites that ples which give a strong recommendation for the possible using of the
play vital roles during the cleavage processes of the oil triglycerides as obtained biodiesel directly as fuels in diesel engines [1]. Generally, the
well as the alcohol (methanol) molecules [61]. The alkaline treatment production of biofuels with low cetane index is of high difficulty to be
enhances the exchangeable properties of the incorporated sodium ions used in the engines and associated with the releasing of hazardous
and the presences of sodium ions as structural elements induced the gasses and emissions [66]. Moreover, the viscosity of the produced
formation of negative charges on the present oxygen atoms. This en- biodiesel samples is of significant values to be used effectively in the
hances the alkalinity of the product and its catalytic activity during the lubrication applications, fuel injectors, and fuel atomization. Finally,
alkaline hydrolytic mechanism [62,63]. Additionally, the previous ef- the determined high flash points give the products high safety proper-
fects can cause an increase in the stability of the formed polarized ties for handling, storing and transportation [3].
molecules as alkali methoxides and fatty acid salts [3].
The catalytic conversion reactions start by the polarization of the
present triglycerides ester groups in the C-O bonds between the glycerol 3.2.6. Comparison study between the catalytic activity of B/ZP and other
groups and the fatty acid moieties [64]. Also, the used methanol mo- heterogeneous and homogenous catalysts
lecules affected by the polarization processes under the catalytic in- The catalytic activity of B/ZP composite as compared to other het-
teractions of the basic sodium sites of B/ZP composite (Fig. 8). The erogeneous and homogenous catalysts was accomplished as a function
polarization step followed by cracking processes for both the methanol of the obtained biodiesel yields at the best transesterification conditions
and triglyceride molecules. This followed by integration between the of palm oil (Table 3). For the heterogeneous catalysts, the obtained
produced methoxy groups and the fatty acids alkyl chains [65] (Fig. 8). biodiesel yield by normal stirring is of higher percentage (96.2%) than
The possible interactions between the generated intermediates during several types of the presented catalysts in Table 3 as KOH/bentonite,
the catalytic transesterification of oil resulted in the formation of me- SrO, BaO, CaO, activated carbon/CaO, Sr/ZrO2, SO4-ZrO2, CaO–CeO2,
thyl esters with various types of fatty acid moieties (biodiesel) and cesium/silica, and coconut coir husk derived catalyst (Table 3). Ad-
ditionally, the catalyst can give such high biodiesel yields by normal

Fig. 8. Schematic diagram for transesterification of palm oil into biodiesel by the synthetic B/ZP catalyst.

747
M.R. Abukhadra, et al. Energy Conversion and Management 196 (2019) 739–750

Table 3
Comparison between the obtained biodiesel yield by B/ZP catalyst and other heterogeneous and homogenous catalysts in literature.
Catalyst Time T (°C) Methanol-to-oil ratio Catalyst loading (wt.%) Stirring speed (rpm) Ultrasonic power Yield (%) References

Heterogeneous catalysts
Coconut coir husk derived catalyst 3h 130 12:1 10 500 0 89.8 [67]
Cesium/silica 3h 65 20:1 3 – 0 90 [68]
K2CO3/palygorskite 3.5 h 65 12:1 5 800 0 97
Seashell-derived Ca, Zn and Al compounds 3h 60 30:1 10 – 0 98 [69]
Sulfonated graphene 10 h 100 20:1 10 – 0 98 [70]
Rice husk ash-based catalysts 4h 65 9:1 7 800 0 91.5 [71]
CaO–CeO2 4h 65 12:1 5 – 0 95 [72]
Ostrich eggshell- CaO 1h 60 9:1 8 – 120 W 92.7 [73]
KF/Ca-Al hydrotalcite 5h 65 12:1 5 – 0 97.98 [74]
SO4-ZrO2 10 min 250 25:1 0.5 – 0 90 [75]
Sr/ZrO2 87 min 115 29:1 2.7 – 0 79.7 [76]
Activated carbon/CaO 80 min 190 15:1 5.5 0 80.9 [77]
BrO and SrO 50 min 65 9:1 2.8 – 200 W 95 [59]
CaO 1h 65 15:1 3 – 120 W 77.3 [78]
BaO 1h 65 15:1 3 – 120 W 95 [78]
SrO 1h 65 15:1 3 – 120 W 95 [78]
KOH bentonite 3h 60 6:1 3 – 0 90.7 [66]
SrO 3h 80 12:1 5 – 0 98.2 [79]

Homogenous catalysts
CyN1,1PrSO3H][p-TSA] 2.5 h 120 21:1 3 – 0 98.7 [80]
NaOH 30 min 60 6:1 1 250 0 97 [46]
KOH 15 min 60 9:1 1 – 28–70 kHz 93 [81]
KOH 15 min 60 9:1 1 – 0 89 [81]
Et3NHSO4 3h 170 15:1 5.2 – 0 82.1 [82]
KOH 50 min 60 15:1 1 600 0 96.9 [82]
Na+ trapped B/ZP 3.5 h 90 20:1 5 900 0 96.2 This study
Na+ trapped B/ZP 2h 90 20:1 5 0 240 W 98.8 This study
Na+ trapped B/ZP 1.5 h 90 20 :1 5 0 240 W 98.7 This study
Na+ trapped B/ZP 2h 90 20 :1 4 0 240 W 98.5 This study
Na+ trapped B/ZP 2h 90 15:1 5 0 240 W 97 This study
Na+ trapped B/ZP 1h 90 20:1 5 0 240 W 96.5 This study
Na+ trapped B/ZP 2h 70 20:1 5 0 240 W 96.2 This study
Na+ trapped B/ZP 2h 60 20:1 5 0 240 W 94.7 This study

stirring at lower temperature values than SO4-ZrO2, Sr/ZrO2, activated
carbon/CaO, sulfonated graphene, and coconut coir husk derived cat-
alyst; and at lower time interval than KF/Ca-Al hydrotalcite, rice husk
ash-based catalysts, sulfonated graphene, and CaO-CeO2.
Applying the ultrasonic irradiation resulted in enhancing the cata-
lytic activity of B/ZB and achieved higher biodiesel yield than all the
presented catalysts in Table 3, and within short time interval than most
of them. Additionally, the B/ZB catalyst can achieve better results at a
temperature value lower than that used for SO4-ZrO2, Sr/ZrO2, acti-
vated carbon/CaO, coconut coir husk derived catalyst, cesium/silica,
sulfonated graphene, CaO–CeO2, BrO, CaO, and SrO. This gives the
synthetic composite high technical and economic value as it is of simple
preparation processes and of lower cost than most of the presented solid
heterogeneous catalysts in the transesterification of palm oil.
Regarding the homogenous catalysts, the best biodiesel yield was
obtained by CyN1,1PrSO3H][p-TSA] (98.7%) and achieved after 2.5 h
using 20:1 methanol-to-oil molar ratio and 3 wt% catalyst loading at a
temperature value of 120 °C (Table 3). The previous makes a preference
for B/ZB catalyst under ultrasonic irradiation of 60% power as 98.8%
biodiesel was obtained after only 2 h using 20:1 methanol-to-oil ratio at
90 °C as reaction temperature. However, the alkaline solutions of NaOH
and KOH resulted in significant biodiesel yields within short time in-
tervals, the synthetic B/ZP catalyst is of higher yield than them at its
best conditions
normal stirring resulted in biodiesel yield of 96.2% after 210 min using
5 wt% as catalyst loading, 20:1 as a methanol-to-oil ratio, 90 °C as
temperature, and stirring speed of 900 rpm. The conversion reaction
under the ultrasonic irradiation (power 60%) gives biodiesel yield of
98.8% after 120 min as a reaction time using 5 wt% as catalyst loading,
20:1 as a methanol-to-oil ratio, and 90 °C as temperature. The ultrasonic
irradiation is of positive impacts in reducing the conversion time in-
terval, reaction temperature, catalyst loading, and methanol-to-oil
molar ratio with biodiesel yield similar to that obtained by normal
stirring at its best conditions. The catalyst is of higher activities than
several homogenous and heterogeneous catalysts, and can be reused
several times with high catalytic activity specially using an organic
solvent. The specifications of the final produced biodiesel by both
methods match the requirements of STM D-6571 and EN 14214 inter-
national standards.
Recommendation
Further studies will be conducted to investigate the catalytic activity
of B/ZP catalyst at the pilot scale and using the chemicals at their
commercial grades
Declaration of Competing Interest

The authors declared that there is no conflict of interest.

4. Conclusion
Bentonite/zeolite-P composite (B/ZP) was synthesized and char-
acterized as a heterogeneous catalyst of basic properties. It was applied
effectively in the transformation of palm oil into biodiesel by normal
stirring and under ultrasonic irradiation. The conversion reaction by
Acknowledgments
The authors extend their appreciation to the Deanship of Scientific
Research at King Saud University for funding this work through re-
search group No. RG-1440-043.

748
M.R. Abukhadra, et al.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.enconman.2019.06.027.
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