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Rice bran oil based biodiesel production using calcium oxide catalyst derived
from Chicoreus brunneus shell
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Energy
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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.
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 11
the literature that seashell-derived CaO catalyst produces optimal 2.7. Verification data
FAME yields at 65 C [24,25]. The product mixture was allowed to
settle under gravity overnight. Where required, catalyst separation The execution of the ANN model was statistically assessed using
was undertaken using centrifugation (Hettich ROTOFIX 46, Ger- the absolute average deviation (AAD) and coefficient of determi-
many) was at 2000 rpm for 7 min followed by mechanical filtration. nation (R2) determined using Eqs. (5) and (6), respectively [27].
Methanol was removed by vacuum evaporator (IKA RV 10 Control,
n !
USA). Finally, the biodiesel was washed with distilled water. 1X Ypi Ybi
AAD ¼ x 100 (5)
Transesterification reactions were undertaken using catalyst pro- n i¼1 Ybi
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), 0 2 1
catalyst loading (0.2, 0.4, 0.6, and 0.8 wt% of RBO), and reaction Xn y
B bi y pi C
times (48, 72, 96, and 120 min). R2 ¼ 1 @ 2 A (6)
i¼1 ym ypi
2.5. Modeling using ANN where n is the number of experimental data, ybi is the experimental
kinematic viscosity, ypi is the predicted kinematic viscosity, and ym
MATLAB 7.10.0 was used to train the backpropagation of ANN. A is the average value of the kinematic viscosity obtained from the
three-layer feed forward architecture and hyperbolic tangent sig- experiments.
moid (tansig) transfer function was applied for transfer from the
input to the hidden layer of the ANN. The backpropagation ANN 2.8. Transesterification of RBO with reference catalyst, catalyst
with LevenbergeMarquardt algorithm was used in this study for recycling, and leaching analysis
the hidden to the output layer purelin transfer function. ANN ar-
chitecture consisted of four inputs for the hydrolysis process (i.e. Catalyst stability and capacity for recycling are two important
reaction time, calcination temperature, catalyst ratio, and methanol factors in the operation of commercial transesterification processes
to RBO molar ratio), hidden layers with the optimum number of [23]. C. brunneus-derived CaO catalyst prepared using a calcination
neurons, and a single output variable (kinematic viscosity). The temperature of 1100 C was used in seven transesterification re-
ANN model was trained until the mean square error (MSE) reached action cycles operated at a catalyst loading of 0.4 wt %, a molar
the lowest value and the average correlation coefficient was close methanol to RBO ratio of 30:1, and reaction time of 120 min. After
or equal to 1. The trained ANN model was subsequently combined each reaction cycle, the catalyst was separated from the product
with ant colony optimisation (ACO) to predict the kinematic vis- mixture using the methods described in Section 2.4. The catalyst
cosity of RBO-derived biodiesel produced using various combina- was then washed 5 times with n-hexane (30 ml x5), dried at 70 C
tions of operating parameters. 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
2.6. Ant colony optimisation reaction cycle. Atomic absorption spectroscopy (AAS) (VARIAN
GTA-120, AA240) was used to measure the calcium content of the
In nature, ants undertake non-systematic exploration of the area biodiesel after each reaction cycle to evaluate catalyst leaching.
surrounding their nest. Chemical pheromone traces are then left on
the ground by these initial exploratory insects in order to facilitate 2.9. Biodiesel characterisation and fuel properties
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 In order to characterize the biodiesel, FTIR spectroscopy was
by: applied over a 4000 to 400 cm1 region. Moreover, fuel properties
n o.n X o such as calorific value, acid value, viscosity, density, oxidation sta-
Qr;s ¼ sar;s nbr;s sar;s nbr;s (2) bility and flash point were tested. FAME yield was calculated using
the following equation:
where sr;s is the amount of pheromone on edge r,s, a is a parameter P
A WtEI
used to control the influence of sr;s . sr;s and nr;s represent the FAME conversionð%Þ ¼ 100% (7)
AEI m
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 P
where A is the area of all peaks in chromatogram (C6-C24:1), AEI is
according to the following equation: 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
sr;s ¼ Dsr;s þ ð1 rÞsr;s (3) weight (mg).
The application of low quality biodiesel as a result of incomplete
where sr;s is the amount of pheromone on edge r,s, r is the rate of reaction and the existence of contaminants in a diesel engine may
pheromone evaporation and Dsr;s is the amount of pheromone result in different problems in existing engine such as filter plug-
deposited. ging and precipitation of fuel insoluble. Thus, biodiesel is necessary
If ant q travels on edge r,s, the amount of pheromone deposited to meet ASTM D6751 and EN 14214 standards in order to assess the
is given by: quality of biodiesel product. Viscosity as one of the most important
8 fuel properties plays role in the ease of starting engine, the spray
>
<1 quality and the size of particles. Density directly exerts influence on
Dsqr;s ¼ Lq (4) fuel performance, as some of the engine properties, such as vis-
>
:
0 cosity and cetane number are strongly connected to density.
Further, the density has impact on the quality of atomization and
where Lq is the cost of the qth ant's tour (typically length). combustion. Acid value is defined as the amount of potassium
H. Mazaheri et al. / Energy 144 (2018) 10e19 13
3.1. Analysis of CaO nanocatalyst Fig. 2. TEM images of spherical shape CaO nanocatalyst as prepared from Chicoreus
brunneus shell.
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)
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.
Table 2
FAME concentration and profile.
Table 3
Physical characteristic of the RBO and associated biodiesel.
Properties Unit ASTM standards D6751 En standards 14214 RBO RBO biodiesel
at 0.8 wt% to 6.15 mm2 s1. This was consistent with previous with a methanol to oil molar ratio of 30:1 and reaction times of 48,
studies in which increases in catalyst loading above a critical 72, 96, and 120 min, and the effect on kinematic viscosity of the
threshold had a negative impact upon mixing during the trans- resulting biodiesel was measured (Fig. 4D). Increasing trans-
esterification reaction [38]. esterification time above 48 min decreased the kinematic viscosity
Transesterfication of RBO was undertaken at 65 C using 0.4 wt% of the resulting biodiesel to a minimum of 5.89 mm2 s1 after
of C. brunneus CaO nanocatlayst produced by calcination at 1100 C 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
R2 0.9947
AAD 0.6322
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.
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