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Rice bran oil based biodiesel production using calcium oxide catalyst derived
from Chicoreus brunneus shell

Article  in  Energy · November 2017

DOI: 10.1016/j.energy.2017.11.073

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 Energy 144 (2018) 10e19

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Rice bran oil based biodiesel production using calcium oxide catalyst
derived from Chicoreus brunneus shell
Hoora Mazaheri a, Hwai Chyuan Ong a, *, H.H. Masjuki a, Zeynab Amini b,
Mark D. Harrison b, Chin-Tsan Wang c, Fitranto Kusumo a, Azham Alwi a
a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur, Malaysia
b
Centre for Tropical Crops and Biocommodities, Queensland University of Technology, 4001, Brisbane, Australia
c
Mechanical and Electro-Mechanical Engineering, National Ilan University, Ilan, 260, Taiwan

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

Article history: Environmental pollution and the declining global supply of accessible fossil fuels are the key drivers of
Received 3 March 2017 the search for alternative sources of energy. Biodiesel, a renewable liquid transport fuel, is commercially-
Received in revised form produced using heterogeneous catalysts. Heterogeneous catalysts obtained from seashells appeared as
21 September 2017
promising alternatives thanks to their low preparation cost and increased efficiency in trans-
Accepted 12 November 2017
Available online 14 November 2017
esterification. In this study, shells from Chicoreus brunneus (known as Adusta murex) were calcined,
hydrated, and dehydrated to produce CaO heterogeneous nanocatalyst for the transesterification of rice
bran oil into biodiesel. Field emission scanning electron microscopy, Fourier transform infrared spec-
Keywords:
Biodiesel
troscopy, transmission electron microscopy, surface area measurement (Brunauer-Emmett-Teller
Rice bran oil method), and X-ray diffraction were used to characterise the seashell-derived catalyst. The properties of
Transesterification the rice bran oil-derived biodiesel (acid value, calorific value, density, oxidation stability, and flash point)
Alternative fuel conformed to the American Society of Testing and Materials (ASTM) D6751 and European EN 14214
Ant colony optimization biodiesel standards, except for kinematic viscosity. Therefore, the impact of the parameters used for
Catalyst production of the CaO heterogeneous nanocatalyst (calcination temperature and time) and the trans-
esterification reaction (catalyst loading and methanol to rice bran oil ratio) on the kinematic viscosity of
RBO-derived biodiesel were determined. A model for the transesterification process was developed using
a combination of artificial neural networking with ant colony optimisation. The model predicted that
C. brunneus-derived CaO catalyst prepared at 1100
C for 72 min could be used to produce biodiesel from
rice bran oil with a minimum kinematic viscosity (4.42 mm2 s1) confirming to both the ASTM D6751
and EN 14214 biodiesel standards in a transesterification reaction operating with a 35:1 methanol to rice
bran oil molar ratio and 0.5 wt% catalyst mass.
© 2017 Published by Elsevier Ltd.

1. Introduction engines [4,5]. Biodiesel can be used either alone or in combination

Increase in energy demand, changing climate, and a rapid
decline in accessible fossil fuel reserves are key drivers for the
development of green, renewable energy sources [1]. Lead tech-
nologies for the development of such products are based on the use
of wind, water, sunlight, or plant biomass [2,3]. Biodiesel is a plant
biomass-based, renewable alternative to diesel. Further, biodiesel is
biodegradable, has low relatively toxicity, and can result in reduced
CO2 and sulfur emissions when used in internal combustion
* Corresponding author.
E-mail addresses: onghc@um.edu.my, ong1983@yahoo.com (H.C. Ong).
with conventional diesel in diesel engines [6]. Transesterification is
the process by which biodiesel is generated from vegetable oil
feedstocks in the presence of alcohol and catalyst [7]. Inorganic
(heterogeneous or homogeneous) or organic catalysts (enzymes)
can be used to accelerate the transesterification reaction and in-
crease the efficiency with which biodiesel is produced. Inorganic
heterogeneous catalysts have distinct advantages relative to either
inorganic homogenous or organic catalyst including ease of sepa-
ration and recovery, ease of recycling, reduced cost, and reduced
corrosion [8].
Biodiesel production using inorganic heterogeneous catalysts is
well established and the most well-studied group of inorganic
heterogeneous catalysts is the alkaline metal oxides (which

https://doi.org/10.1016/j.energy.2017.11.073
0360-5442/© 2017 Published by Elsevier Ltd.
 H. Mazaheri et al. / Energy 144 (2018) 10e19
includes CaO) [9,10]. Seashells are abundant, naturally-occurring
substrates for CaO catalyst synthesis. The shells of Cyrtopleura
costata (angel wing clam) have been used to produce CaO catalyst
for the efficient transesterification of palm fatty acid distillate into
biodiesel using either supercritical methanol [11] or microwave-
assisted transesterification [12]. Mud clamshell has been used to
prepare CaO catalyst and applied successfully to the trans-
esterification of castor oil in the presence of methanol [13]. Cer-
ithidea obtusa (Obtuse horn) shell has also been investigated as a
CaO source for transesterification [14]. Importantly, 45,000 tonnes
of shells from crustaceans and shellfish are produced annually by
the seafood industry. These shells are typically burnt and buried in
landfill, a process that has significant environmental and economic
costs. Therefore, conversion of some of these waste shells into
inorganic heterogeneous catalyst is one approach to both reduce
the amount of waste being disposed of in landfill and increasing the
commercial value of seafood production.
Rice bran oil (RBO) is a non-edible oil produced from hard outer
layers of the rice grain. China and India lead global production of
RBO with annual production rates of 6,000,000 and 1,000,000
tonnes, respectively. Depending upon the variety of rice and degree
of milling, rice bran contains 16e32 wt% of oil and, because of the
presence of active lipases in bran, the free fatty acid content in rice
bran oil is comparible with other edible oils [15,16]. Therefore, there
is the potential for significant global expansion of RBO production
and application of RBO as a feedstock for biodiesel production.
Development of mathematical models for chemical reactions,
including transesterifcation of oil into biodiesel, is a valuable tool to
identify optimal reaction conditions. The use of artificial neural
networks (ANN) to model such processes is well-established and
was inspired by biological learning process consists of neurons with
the capacity to identify linear and nonlinear correlations between
variables directly from a set of examples [17]. Furthermore, ANNs
do not require any advance specification of suitable fitting function
and have a universal capability to approximate almost all kinds of
non-linear functions [18]. ANN is a well suited to the process
modeling of biofuel synthetic processes [19,20]. Ant colony opti-
misation (ACO) is a swarm intelligence technique that simulates the
foraging behavior of real ant colonies based upon the ‘principle of
communication’ mechanism (i.e., ants, as a group, are able to
communicate with each other and collectively identify the shortest
path between any two points). However, there are few studies that
report the use of ACO to develop mathematical models that identify
optimal biofuel production systems. Recently, ACO was combined
with the kernel-based extreme learning machine (KELM) model to
optimise biodiesel yield from Ceiba pentandra (also known as
Kapok, Ceiba, or White Silk-Cotton Tree) seed oil [21]. Further, ACO
was combined with ANN to identify the optimal reaction parame-
ters for bioethanol production from sorghum grains, resulting in
maximum volumetric ethanol yield per unit sugars [22].
In the present study, a novel CaO heterogeneous catalyst was
prepared from Chicoreus brunneus seashells. The catalyst was
characterised using field emission scanning electron microscopy
(FESEM), Fourier transform infrared spectroscopy (FTIR), trans-
mission electron microscope (TEM), Brunauer-Emmett-Teller (BET),
and X-ray diffraction (XRD). The C. brunneus-derived CaO catalyst
was used to convert RBO into biodiesel, and both catalyst recycling
and stability was assessed. The fuel properties of the resulting
biodiesel were determined and conformed to those specified in
biodiesel standards ASTM and EN14214, with the exception of ki-
nematic viscosity. Therefore, both CaO catalyst production and
transesterification reaction conditions were modelled and opti-
mized using a combination of ANN and ACO to produce RBO-
derived biodiesel with acceptable kinematic viscosity.
11
2. Experimental procedure
2.1. Materials and chemicals
RBO was purchased from Scienfield SDN BHD (Selangor,
Malaysia). Laboratory-grade chemicals, included methanol (>99%
pure) and distilled deionized water were purchased from Metta
Karuna Enterprise (Kuala Lumpur, Malaysia). Commercial CaO
(Sigma) was used as a reference catalyst (Molar mass of
56.08 g mol1, boiling point of 2850
C, density of 3.3 g/cm3 at 25
C).
Nonadecanoic acid methyl ester and FAME mix (C4-C24) were pur-
chased from IT Tech Research (M) SDN BHD (Selangor, Malaysia).
2.2. Synthesis of CaO nanocatalyst from C. brunneus shell
C. brunneus shells were collected from a local supplier at Central
market, Kuala Lumpur, Malaysia. CaO nanocatalyst was produced
from the shells using calcination, hydration, and dehydration based
upon the method described by ANR et al. [23]. In brief, 500 g of
C. brunneus shell was washed with aqueous solution of sulfuric acid
(2 M) to remove the dirt and debris, rinsed in distilled water, and air
dried at 70
C for 72 h. The C. brunneus shells were manually
crushed, ground using a PM 100 Planetary ball mill (using the lead
balls) (Retsch, Germany) at 200 rpm for 2 h, and then passed
through an 80 mm mesh sieve. The powdered shell was then cal-
cinated in a furnace (Nabertherm, Germany) at 900
C for 2.5 h. The
decomposition of shell powder to CaO and carbon dioxide occurs
via the following reaction:
900
C
z}|{
CaCO3 / CaO þ CO2 (1)

C
C. brunneus-derived CaO was refluxed in water at 60 for 24 h,
the solid particles were filtered using a filter paper, and then dried
in an oven at 70
C for 24 h. The resulting dry powder was ground in
a PM 100 Planetary ball mill at 200 rpm for 3 h and dehydrated by
calcination at different temperatures (800, 900, 1000, and 1100
C)
for 3 h to convert from the hydroxide form to the oxide form. The
resulting CaO was then stored in a desiccator until required to
prevent a decrease in catalyst activity from exposure to moisture.
Commercial CaO was calcined at 900
C for 2 h to eliminate any
contamination from atmospheric carbonates and hydroxides, and
the resulting material was used as a reference.
2.3. Characterisation of CaO catalysts
FTIR spectra (4000e400 cm1) of CaO catalysts were obtained
using a Shimadzu FTIR- 8300. CaO catalyst morphology was
visualised using TEM; (Libra 120, ZEISS, Germany). The surface area
of the CaO catalysts were determined using BET (micromeritics,
TriStar II). The crystal structure of the CaO catalysts were analysed
using a Shimadzu XRD 6000 X-ray diffractometer with nickel-
filtered Cu Ka (l ¼ 1.542 Å) radiation. X-ray diffraction (XRD)
analysis was carried out over 20e80
C at a rate of 2
C min1 and a
scanning angle of 2q.
2.4. C. brunneus-derived CaO catalysed transesterification of rice
bran oil
CaO catalyst produced from C. brunneus shell (0.4 g) and
methanol was used for the transesterification of RBO in a three-
neck, round-bottom flask equipped with a thermometer,
condenser, and magnetic heating mantle. The mixture was incu-
bated at 65
C for 120 min with continuous stirring at 150 rpm; the
reaction temperature was selected based upon the observation in
12 H. Mazaheri et al. / Energy 144 (2018) 10e19
the literature that seashell-derived CaO catalyst produces optimal
FAME yields at 65
C [24,25]. The product mixture was allowed to
settle under gravity overnight. Where required, catalyst separation
was undertaken using centrifugation (Hettich ROTOFIX 46, Ger-
many) was at 2000 rpm for 7 min followed by mechanical filtration.
Methanol was removed by vacuum evaporator (IKA RV 10 Control,
USA). Finally, the biodiesel was washed with distilled water.
Transesterification reactions were undertaken using catalyst pro-
duced at a range of calcination temperatures (800, 900, 1000, and
1100
C), methanol to RBO molar ratios (20:1, 25:1, 30:1, and 35:1),
catalyst loading (0.2, 0.4, 0.6, and 0.8 wt% of RBO), and reaction
times (48, 72, 96, and 120 min).
2.5. Modeling using ANN
MATLAB 7.10.0 was used to train the backpropagation of ANN. A
three-layer feed forward architecture and hyperbolic tangent sig-
moid (tansig) transfer function was applied for transfer from the
input to the hidden layer of the ANN. The backpropagation ANN
with LevenbergeMarquardt algorithm was used in this study for
the hidden to the output layer purelin transfer function. ANN ar-
chitecture consisted of four inputs for the hydrolysis process (i.e.
reaction time, calcination temperature, catalyst ratio, and methanol
to RBO molar ratio), hidden layers with the optimum number of
neurons, and a single output variable (kinematic viscosity). The
ANN model was trained until the mean square error (MSE) reached
the lowest value and the average correlation coefficient was close
or equal to 1. The trained ANN model was subsequently combined
with ant colony optimisation (ACO) to predict the kinematic vis-
cosity of RBO-derived biodiesel produced using various combina-
tions of operating parameters.
2.6. Ant colony optimisation
In nature, ants undertake non-systematic exploration of the area
surrounding their nest. Chemical pheromone traces are then left on
the ground by these initial exploratory insects in order to facilitate
the identification of food sources by other members of the colony
[26]. The probability of an ant moving from node r to node s is given
by:
n  o.n X  o
Qr;s ¼ sar;s nbr;s sar;s nbr;s
where sr;s is the amount of pheromone on edge r,s, a is a parameter
used to control the influence of sr;s . sr;s and nr;s represent the
desirability of edge r,s, and b is a parameter used to control the
influence of nr;s . The amount of chemical pheromone is predicted
according to the following equation:
sr;s ¼ Dsr;s þ ð1  rÞsr;s
where sr;s is the amount of pheromone on edge r,s, r is the rate of
pheromone evaporation and Dsr;s is the amount of pheromone
deposited.
If ant q travels on edge r,s, the amount of pheromone deposited
is given by:
8 fuel properties plays role in the ease of starting engine, the spray
>
<1
Dsqr;s ¼ Lq
>
:
0 cosity and cetane number are strongly connected to density.
where Lq is the cost of the qth ant's tour (typically length).
2.7. Verification data
The execution of the ANN model was statistically assessed using
the absolute average deviation (AAD) and coefficient of determi-
nation (R2) determined using Eqs. (5) and (6), respectively [27].
n  !
1X Ypi  Ybi
AAD ¼ x 100 (5)
n i¼1 Ybi
0 2 1
Xn y
B bi  y pi C
R2 ¼ 1  @ 2 A (6)
i¼1 ym  ypi
where n is the number of experimental data, ybi is the experimental
kinematic viscosity, ypi is the predicted kinematic viscosity, and ym
is the average value of the kinematic viscosity obtained from the
experiments.
2.8. Transesterification of RBO with reference catalyst, catalyst
recycling, and leaching analysis
Catalyst stability and capacity for recycling are two important
factors in the operation of commercial transesterification processes
[23]. C. brunneus-derived CaO catalyst prepared using a calcination
temperature of 1100
C was used in seven transesterification re-
action cycles operated at a catalyst loading of 0.4 wt %, a molar
methanol to RBO ratio of 30:1, and reaction time of 120 min. After
each reaction cycle, the catalyst was separated from the product
mixture using the methods described in Section 2.4. The catalyst
was then washed 5 times with n-hexane (30 ml x5), dried at 70
C
using the oven for 2 days, and then recalcined at 800
C for 3 h
before being used in the next reaction cycle. FESEM was undertaken
to assess any changes in the morphology of the catalyst after each
reaction cycle. Atomic absorption spectroscopy (AAS) (VARIAN
GTA-120, AA240) was used to measure the calcium content of the
biodiesel after each reaction cycle to evaluate catalyst leaching.
2.9. Biodiesel characterisation and fuel properties
In order to characterize the biodiesel, FTIR spectroscopy was
applied over a 4000 to 400 cm1 region. Moreover, fuel properties
such as calorific value, acid value, viscosity, density, oxidation sta-
(2) bility and flash point were tested. FAME yield was calculated using
the following equation:
P
A WtEI
FAME conversionð%Þ ¼   100% (7)
AEI m
P
where A is the area of all peaks in chromatogram (C6-C24:1), AEI is
the area under the curve for the internal standard (C19), WtEI is the
weight of the C19 internal standard (mg), and m is the sample
(3) weight (mg).
The application of low quality biodiesel as a result of incomplete
reaction and the existence of contaminants in a diesel engine may
result in different problems in existing engine such as filter plug-
ging and precipitation of fuel insoluble. Thus, biodiesel is necessary
to meet ASTM D6751 and EN 14214 standards in order to assess the
quality of biodiesel product. Viscosity as one of the most important
quality and the size of particles. Density directly exerts influence on
(4) fuel performance, as some of the engine properties, such as vis-
Further, the density has impact on the quality of atomization and
combustion. Acid value is defined as the amount of potassium
 H. Mazaheri et al. / Energy 144 (2018) 10e19 13

hydroxide needed to neutralize the biodiesel acid moieties. A less

than 0.5 mg KOH g1 acid value is considered safe. Calorific value is
defined as the energy content of biodiesel produced.
Oxidation stability is another important property, as oxidation
may change the physical and chemical properties of fuel and, thus
damage the motors of vehicles [28]. The flash point is the minimum
temperature calculated to a barometric pressure of 101.3 kPa at
which the fuel ignition may occur. The flash point is important in
connection with the safety precautions involved in fuel handling
and storage [29e31].

3. Results and discussion

3.1. Analysis of CaO nanocatalyst Fig. 2. TEM images of spherical shape CaO nanocatalyst as prepared from Chicoreus
brunneus shell.

The physical and chemical properties of CaO nanocatalyst pre-

pared from calcined C. brunneus shell were determined and
compared to that of CaO nanocatalyst prepared from commercial
CaO. FESEM analysis (Fig. 1) confirmed that calcination of CaO
nanocatalyst prepared from C. brunneus shell changed the
morphology of the CaO from irregular shapes to a cluster of well-
developed cubic crystal with obvious edges. TEM analysis (Fig. 2)
indicated that the majority of the CaO nanocatalyst prepared from
calcined C. brunneus shell consisted of spherical particles or ag-
glomerates of spherical particles with an average diameter of
66.2 nm. The surface area per unit mass, average pore diameter, and
pore volume of calcined C. brunneus shell was greater than that of
calcined commercial CaO (Table 1). The average pore diameters for
each nanocatalyst were between 2 and 50 nm, indicating that both
catalysts were mesoporous. In addition, it confirms its suitability as
a catalyst, for energy storage, and for adsorption, etc [23].
The FTIR spectra of natural C. brunneus shell indicates the
presence of the carbonates (859 cm 1 and 713 cm 1) and meth-
ylene groups (1456 cm 1) (see Supplementary data, Fig. S1)
[32,33]. The FTIR spectrum of calcined C. brunneus shell exhibits a
relatively strong broad absorption band at wave numbers <600 cm
1
which were attributed to CaeO group stretching in CaO [23].
Moreover, the appearance of peaks at 3641 cm 1 was attributed to
the eOH stretching vibration of Ca(OH)2 and most likely arose from
adsorption of atmospheric water. Likewise, the appearance of ab-
sorption peaks at 1072 cm1, and 1489 cm1 was attributed to the
stretching vibration of the CO3 as a result of CO2 chemisorption to
the surface of calcined C. brunneus shell (see Supplementary data,
Fig. S1). The XRD spectrum of natural C. brunneus shell (Fig. 3A)
contained peaks at 2q ¼ 27.1
, 46.4
, and 48.2
that are consistent
with the presence of CaCO3. As expected, calcination at 1100
C
resulted in the conversion of CaCO3 to CaO, as evidenced by the
appearance of peaks at 2q of 32.30
, 37.38
, 53.8
, and 54.10

(Fig. 3B) [14,25]. The pattern of peaks in the XRD spectra of calcined
C. brunneus shell (Fig. 3B) and commercially-available CaO calcined
under the same conditions (Fig. 3C) were similar.
3.2. Analysis of biodiesel
FTIR analysis allows relatively rapid analysis of liquid samples
and has the capacity to differentiate between crude oil and bio-
diesel. Therefore, in the present study, RBO-derived biodiesel pro-
duced using C. brunneus CaO nanocatalyst was evaluated using FTIR
(see Supplementary data, Fig. S2). Two peaks were present in the
FTIR spectrum of RBO-derived biodiesel that were not present in
RBO: (i) a peak at 1435 cm1, associated with an asymmetric stretch
of eCH3 [25], and (ii) a peak at 1097 cm 1 corresponding to
asymmetric axial stretching of O-CH2-Ce-CH2-OH [5]. Further, the
peak 1377 cm1 in the FTIR spectrum of RBO-derived biodiesel is
consistent with the presence of O-CH3 in glycerol, a known by-
product of biodiesel production. FAME concentration and profile
in both RBO and RBO-derived biodiesel were analysed by gas
chromatography (GC) (Table 2). A FAME yield of 93.5% was achieved
under the following condition: calcination temperature of 1100
C,
catalyst content of 0.4 wt %, the reaction time of 120 min, and a
methanol to oil ratio of 30:1.
The fuel properties of RBO and RBO-derived biodiesel were
determined (Table 3). RBO-derived biodiesel met all the EN-14214
and ASTM D6751 standards with the exception of density and vis-
cosity. While the density of RBO-derived biodiesel (896.4 kg m3)

Fig. 1. FESEM micrographs of new catalyst A) calcined Chicoreus brunneus shell and B) uncalcined Chicoreus brunneus shell.
14 H. Mazaheri et al. / Energy 144 (2018) 10e19

Table 1
Main pore properties of newly synthesized catalyst.

Sample Surface area (m2
g1) Average pore volume (cm3
g1) Average pore diameter (Å)

Calcined seashell 1.56 0.0044 112.54

Commercial CaO 1.34 0.0021 62.59

was within the range proscribed by the EN14214 standards, the ki-
nematic viscosity of this biofuel was neither within the range of
ASTM D6751 nor EN14214. Kinematic viscosity is a measure of
resistance to flow of a liquid due to internal friction and high kine-
matic viscosity results in damage to pumps, filter blockage, poor
combustion efficiency, and increased emissions [34]. Moreover, the
impact of biodiesel viscosity is exacerbated in cold weather because
kinematic viscosity is inversely proportional to temperature. Given
that CaO nanocatalyst produced from C. brunneus shell resulted in
FAME yield of >93% and recent studies using shell-derived CaO
nanocatalyst for the production of biodiesel from palm oil and
microalgae Nannochloropsis oculata oil resulted in a maximum FAME
yield of 86.8% and 84.11% respectively [14,35], the remainder of the
present study focused on the minimisation of kinematic viscosity of
RBO-derived biodiesel.

3.3. Impact of process conditions on transesterification of RBO

Three key process parameters for transesterification of oil to

Fig. 3. XRD pattern of new catalyst A) uncalcined Chicoreus brunneus shell, B) CaO
nanocatalyst as prepared from Chicoreus brunneus shell, and C) commercial calcium
oxide.
produce biodiesel are methanol to oil ratio, catalyst loading, and
reaction time. Therefore, the effect of changes in these process
parameters on the kinematic viscosity of biodiesel produced from
RBO using C. brunneus CaO nanocatalyst was assessed. In addition,
the impact of the calcination temperature used to produce
C. brunneus CaO nanocatalyst on kinematic viscosity of RBO-
derived biodiesel was also evaluated.
The ratio of alcohol to oil in a transesterification reaction has the
most significant impact on conversion efficiency [36]. While the
theoretical minimum molar ratio of alcohol to triglyceride that is
required for complete conversion of triglyceride into FAME is 3:1,
excess alcohol to oil ratios are required in practice to deliver
maximum FAME yield [37]. Therefore, transesterfication of RBO
was undertaken at 65
C for 96 min using 0.4 wt% C. brunneus CaO
nanocatlayst produced by calcination at 1100
C with methanol to
oil molar ratios of 20:1, 25:1, 30:1, and 35:1, and the effect on ki-
nematic viscosity of the resulting biodiesel was measured (Fig. 4A).
The results demonstrate that increasing the methanol to oil molar
ratio above 20:1 decreases the kinematic viscosity of RBO-derived
biodiesel to a minimum of 6.09 mm2 s1 at 35:1.
Calcination temperature has a signficant effect upon the surface
area, total pore volume, and mean pore diameter of C. brunneus CaO
nanocatalyst (Table 1). Therefore, transesterfication of RBO was
undertaken at 65
C with a methanol to oil molar ratio of 30:1, a
reaction time of 96 min, and 0.4 wt% of C. brunneus CaO nano-
catalyst produced by calcination at 800, 900, 1000, and 1100
C, and
the effect on kinematic viscosity of the resulting biodiesel was
measured (Fig. 4B). The results demonstrate that increasing the
calcination temperature above 800
C decreases the kinematic
viscosity of the resulting biodiesel to a minimum of 5.92 mm2 s1
when catalyst calcined at 1100
C was used.
Transesterfication of RBO was undertaken at 65
C for 96 min
using C. brunneus CaO nanocatlayst produced by calcination at
1100
C with a methanol to oil molar ratio of 30:1 and catalyst
loadings of 0.2, 0.4, 0.6, and 0.8 wt% 35:1, and the effect on kine-
matic viscosity of the resulting biodiesel was measured (Fig. 4C).
The kinematic viscosity of RBO-derived biodiesel was reduced to a
minimum of 5.69 mm2 s1 at 0.6 wt% catalyst loading but increased
 H. Mazaheri et al. / Energy 144 (2018) 10e19 15

Table 2
FAME concentration and profile.

FA/FAME composition Formula Number of carbons Saturation FAME %

Palmitic acid/methyl palmitate C15H31COOCH3 C16 Saturated 14.00

Palmitoleic acid/methyl palmitoleate C15H29COOCH3 C16:1 Monounsaturated 0.11
Stearic acid/methyl stearate (octadecanoate) C17H35COOCH3 C18 Saturated 1.38
Oleic acid/cis-9-oleic methyl ester C17H33COOCH3 C18:1 Monounsaturated 38.76
Linoleic acid/methyl linoleate C17H31COOCH3 C18:2 Polyunsaturated 37.00
Linolenic acid/methyl linolenate C17H29COOCH3 C18:3 Polyunsaturated 0.58
Arachidic (Eicosanoic) acid/methyl arachidate (Eicosanoic acid) C19H39COOCH3 C20 Saturated 0.55

Table 3
Physical characteristic of the RBO and associated biodiesel.

Properties Unit ASTM standards D6751 En standards 14214 RBO RBO biodiesel

Kinematic viscosity (40
C) mm2
s1 1.9e6.0 3.5e5.0 40.13 8.05

Density (15
C) kg
m3 880 860e900 902 896.4
Acid value mg KOH
g1 Max 0.5 Max 0.5 1.22 0.5
Calorific Value MJ
kg1 35 35 37.04 39.03
Oxidation stability (110
C) H 3 6 3 3.16


Flash point C >130 >101 247 173

Fig. 4. Effect of experimental parameters on kinematic viscosity.

at 0.8 wt% to 6.15 mm2 s1. This was consistent with previous
studies in which increases in catalyst loading above a critical
threshold had a negative impact upon mixing during the trans-
esterification reaction [38].
Transesterfication of RBO was undertaken at 65
C using 0.4 wt%
of C. brunneus CaO nanocatlayst produced by calcination at 1100
C
with a methanol to oil molar ratio of 30:1 and reaction times of 48,
72, 96, and 120 min, and the effect on kinematic viscosity of the
resulting biodiesel was measured (Fig. 4D). Increasing trans-
esterification time above 48 min decreased the kinematic viscosity
of the resulting biodiesel to a minimum of 5.89 mm2 s1 after
96 min.
16 H. Mazaheri et al. / Energy 144 (2018) 10e19

Table 4
Results of CaO-oxidised transesterification of RBO.

Experiment MeOH to RBO Catalyst (wt%) Calcination Time (min) Kinematic viscosity (mm2
s1)
molar ratio temperature (
C)
Experimental Predicted

1 20 0.4 1100 96 8.05 8.05

2 25 0.4 1100 96 7.02 6.81
3 30 0.4 1100 96 5.85 5.85
4 35 0.4 1100 96 6.09 6.11
5 30 0.2 1100 96 6.25 6.25
6 30 0.4 1100 96 5.81 5.85
7 30 0.6 1100 96 5.69 5.70
8 30 0.8 1100 96 6.15 6.03
9 30 0.4 800 96 7.51 7.52
10 30 0.4 900 96 7.11 7.11
11 30 0.4 1000 96 6.9 6.89
12 30 0.4 1100 96 5.92 5.85
13 30 0.4 1100 48 6.7 6.82
14 30 0.4 1100 72 5.93 5.93
15 30 0.4 1100 96 5.89 5.85
16 30 0.4 1100 120 6.78 6.79

R2 0.9947

AAD 0.6322

3.4. Optimisation correlation between experimental and predicted outcomes of

3.4.1. Modeling and optimisation
A total number of 16 experiments were used to develop a neural
network model of transesterification of RBO using C. brunneus CaO
nanocatalyst (Table 4). Four input variables (methanol to oil molar
ratio, calcination temperature, catalyst loading, and reaction time)
and one output variable (kinematic viscosity) were considered. The
experimental data was randomly divided for use in training the
model (70% of the data sets), testing the model (15% of the data
sets), and validation of the model (15% of the data sets). The opti-
mum number of hidden neurons was determined using a heuristic
procedure. The best model topology was identified to have four
input neuron, eight hidden neurons, and one output neuron (see
Supplementary data, Fig. S3). This model had the lowest mean
squared error (MSE), highest R training value (0.9997), an R vali-
dation of 1, an R test of 1, and R all of 0.9947. ANN models with
>0.80 are considered to be accurate (see Supplementary data,
Fig. S4) [39]. Given that the correlation between the experimental
and predicted kinematic viscosity of RBO-derived biodiesel
approached unity (R2 ¼ 0.9947), the model was considered to be
well suited for the accurate prediction of optimum trans-
esterification reaction conditions (see Fig. 5). Therefore, a combi-
nation of ANN modelling and ACO was implemented to predict the
transesterification reaction conditions required to achieve mini-
mum RBO-derived biodiesel kinematic viscosity. The reason behind
the combination of ANN and ACO is to use a new method with
higher convergence speed in optimizing the non-linear parameters
in the field of biodiesel production, which ease the modelling of the
problems with a complicated nature. The model predicted that the
minimum kinematic viscosity of RBO-derived biodiesel produced
using C. brunneus CaO nanocatalyst was 4.415 mm2 s1, and that his

Fig. 6. FAME conversion yield during calcium oxide nanocatalyst reusability cycle
Fig. 5. The experimental versus ANN prediction. analysis.
 H. Mazaheri et al. / Energy 144 (2018) 10e19 17

Fig. 7. FESEM micrographs of nano-CaO catalyst prepared from Chicoreus brunneus shell indicating changes on the surface of the catalyst after seven reaction cycles.

could be achieved using a methanol to oil molar ratio of 35:1,

catalyst loading of 0.5 wt%, a reaction time of 72 min, and CaO
nanocatalyst prepared by calcination at 1100
C.

3.5. Reusability and leaching study

The reusability of any catalyst is central to its application in a

commercial-scale, industrial process. Many Calcium oxides cata-
lysts derived from natural sources could be reused in multiple re-
action cycles (with or without regeneration) in industrial processes
[40,41] but the impact of C. brunneus CaO nanocatalyst reuse on the
FAME yield from RBO transesterification was unknown. Therefore,
0.4 wt% C. brunneus CaO nanocatalyst prepared at 1100
C was
reused in seven sequential 120 min transesterification reactions at
a methanol to oil ratio of 30:1. After each reaction cycle, the catalyst
was separated from the product mixture by centrifugation,
collected by vacuum filtration, and washed with n-hexane. The
washed catalyst was then dried at 100
C and calcined at 1100
C
prior to reuse. The impact of catalyst reuse on FAME yield (Fig. 6)
and the surface properties of the catalyst itself (Fig. 7) were Fig. 8. The leaching of calcium into each sample of biodiesel obtained from the reuse
determined. FAME yield decreased significantly after the 5th of catalyst.
18 H. Mazaheri et al. / Energy 144 (2018) 10e19
transesterification reaction and this was coincident with a change
in the surface morphology of the catalyst (i.e., the disappearance of
a cluster of well-developed cubic crystals with obvious edges). The
reusability of C. brunneus CaO nanocatalyst for transesterification
compares well with other CaO catalysts derived from shell for
biodiesel production. CaO catalyst produced from duck shell has
been reported to result in 80% FAME yield after five trans-
esterification reactions under optimal conditions but, after eight
reactions, FAME yield was reduce to only 60% [1]. Likewise, CaO
catalyst produced from angel wing shell could be reused three
times under optimum reaction conditions and still result in FAME
yield above 65% [35]. Interestingly, Kouzu et al. suggested that the
leaching of CaO from recycled CaO nanocatalyst was a contributing
factor to a reduction in FAME yield during transesterification [42].
Therefore, the calcium ion concentration in the product mixture
from each transesterification reaction cycle was measured using
AAS. As shown in Fig. 8, the leaching was gradually decreased with
the number of cycles.
4. Conclusion
Herein, we demonstrate the production of CaO nanocatalyst from
C. brunneus shell and its use for the production of biodiesel from RBO.
The calcium carbonate in C. brunneus shell was converted to a more
efficient catalyst at calcination temperatures higher than 800
C. The
physical and chemical properties of the resulting nanocatalyst was
determined using a combination of FTIR, TEM, XRD, and FESEM.
Transesterification of RBO using 0.4 wt% C. brunneus CaO nano-
catalyst prepared by calcination at 1100
C and 30:1 M methanol to
RBO ratio resulted in a FAME yield of 93% after 120 min. The
C. brunneus CaO nanocatalyst was stable for five reaction cycles,
suggesting that this renewable nanocatalyst has industrial applica-
tion. The fuel properties of the resulting biodiesel were within the
parameters set down in the ASTM D6751 and EN 14214 biodiesel
standard with the exception of kinematic viscosity, which was higher
than allowed. Therefore, ANN and ACO were used to identify the
combined catalyst production (calcination temperature of 1100
C)
and RBO transesterification reaction (35:1 methanol to oil molar
ratio, 0.5 wt% catalyst loading, 72 min reaction time) conditions to
reduce the kinematic viscosity of the resulting biodiesel to meet the
required values. The results of the present study identify C. brunneus
shell as a potential source of industrial CaO nanocatalyst and confirm
that marine shell is a potential renewable source of CaO nanocatalyst
for biodiesel production.
Acknowledgements
The authors would like to acknowledge the Ministry of Higher
Education, Malaysia and The University of Malaya (Malaysia) for the
financial support via the Bantuan Khas Penyelidikan (BKP special:
BKS054-2017), SATU Joint Research Scheme (ST006-2017) and
postgraduate research grant (PPP:PG040-2014B).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.energy.2017.11.073.
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