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Energy Conversion and Management 93 (2015) 282288

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Transesterication of palm oil to biodiesel by using waste obtuse horn

shell-derived CaO catalyst
Seik Lih Lee, Yong Chen Wong, Yen Ping Tan , Sook Yan Yew
Centre of Excellence for Catalysis Science and Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia

a r t i c l e

i n f o

Article history:
Received 20 August 2014
Accepted 22 December 2014

Calcium oxide
Obtuse horn shell
Palm oil

a b s t r a c t
The calcium oxide catalysts derived from waste obtuse horn shells were utilized in the transesterication
of palm oil into biodiesel. This environment-friendly catalyst is thermally activated at 800 C for 3 h. The
resulting CaO catalyst was characterized using thermogravimetric analysis (TGA), X-ray diffraction (XRD),
temperature-programmed desorption of CO2 (TPD-CO2), BrunauerEmmettTeller (BET) surface area
analysis, and scanning electron microscopy (SEM). XRD patterns of calcined catalyst showed intense
peaks of calcium oxide, consistent with XRF results that revealed calcium is the major element present
in the obtuse horn shells. High calcination temperature (800 C) tended to promote agglomeration of ne
crystals, resulted in a smaller surface area (0.07 m2/g) as examined by BET. Catalytic activities in the
transesterication process had been investigated using one-variable-at-a-time technique. The optimum
palm oil conversion was 86.75% under reaction conditions of 6 h, 5 wt.% of catalyst amount and methanol
to oil ratio of 12:1. Reusability of this waste shell derived catalyst was examined and results showed that
the prepared catalysts are able to be reused up to 3 times with conversion of more than 70% after the
third cycles. Although the reusability may not be excellent at the moment, it is still in the exploratory
study. More efforts were done to improve its properties and stability.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Today, the greatest attention in the world is devoted to the
energy resources as we are experiencing non-renewable natural
resource scarcity on a global scale. Non-renewable energy sources
refer to the energy that has nite supplies and cannot be restored
or regenerated in short period of time. In fact, over 85% of global
energy demands are met through the combustion of fossil fuel
[1]. Therefore, the search for alternative energy which is sustainable is of utmost importance. Biofuel is inherently renewable as
it is derived from biomass or waste matters. There are different
types of biofuel such as biodiesel, biogas and bioalcohol [2] and
biodiesel is gaining popularity as it is renewable, biodegradable,
non-toxic, and environmentally benign due to less green-house
gases emissions [3].
In the development and commercialism of biodiesel nowadays,
it is important that the conversion of biodiesel is successfully predicted on an industrial scale based on the experimental works [4].
Corresponding author at: Centre of Excellence for Catalysis Science and
Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan,
E-mail address: (Y.P. Tan).
0196-8904/ 2014 Elsevier Ltd. All rights reserved.

Mass transfer, reaction kinetic and chemical equilibrium were

studied in the subsequent modelling in laboratory to optimize the
conversion of biodiesel before scaling up in industrial plants [5].
One of the systematic design methods, which is attainable region
method can be used to determine the reactor structure to obtain
the optimal conversion of products. Based on the graphical designs,
the reactor trajectories are plotted, so that a suitable reactor with
the complete triglycerides conversion in the chemical system can
be identied which is leading to increasing interest in industry [6].
Biomass-derived alcohol, such as bioethanol [7] and biobutanol
[8] acted as green reactants for the production of biodiesel. These
alcohols are less toxic compared to methanol and therefore reduce
the impact on human health and the environment. The development of green chemistry process was achieved by introducing
these biomass-derived alcohols in the reaction with triglyceride
in the production of biodiesel. However, the main factor that limits
their usage in the transesterication is due to the higher production costs compared with the usage of methanol in the reaction.
Large quantities of waste cooking oil and animal fats had been
used as feedstock in biodiesel production. Methyl ester conversion
was able to reach as high as 99% with the usage of very high methanol to oil ratio [9,10]. However, these sources were normally
scattered which contributed to difculty in collection [11].

S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288

Non-food feedstock such as microalgae had been used in the

biodiesel production as they are easy to cultivate, but this is not
economically viable as the process of cultivating the algae is very
expensive [12].
Various homogeneous catalysts had been used widely in biodiesel production such as potassium hydroxide, sodium hydroxide,
sulphuric acid and hydrochloric acid. Advantages of using homogeneous catalysts include high yields of methyl esters under mild
condition and shorter reaction time. However, the application of
homogeneous catalyst regardless of acidic or basic comprised of
several drawbacks such as difcult catalyst separation. This will
increase the cost of production as product purication step will
be necessary. Large volume of wastewater will be generated and
catalysts cannot be recovered. In order to overcome these problems, much attention has been drawn to heterogeneous catalysts.
Several heterogeneous catalysts had been tested and reported
Heterogeneous catalyst offer more advantages such as simple
catalyst separation, less consumption of energy and cost, as well
as easier glycerol recovery [16]. Thus, heterogeneous catalysis is
considered as a green process. Nevertheless, these catalysts also
pose some drawbacks such as slow reaction rate, dissolution in
methanol, and sensitivity to humidity.
Utilization of environment friendly and cost-effective heterogeneous catalyst has been of recent interest in the pursuit of sustainable process. Lately, many heterogeneous catalysts derived from
natural resources or waste materials had been used in the production of biodiesel. Those were waste shells of mollusc and egg [17],
Pomacea sp. Shell [18], waste eggshells [19], shrimp shell [20],
waste mud crab shell [21], waste animal bone [22], oyster shell
[23], etc. Utilization of wastes as raw materials for the synthesis
of catalyst could help to solve the waste problems and raise its
economic value [18]. Cerithidea obtusa is a marine gastropod
mollusk in the family Potamididae. This sea snail also known as
Mud Creeper as it is commonly found in muddy coastal areas.
Fleshy portion was used as food in Southeast Asia and the shells
were discarded. Consequently, a large amount of solid waste is
generated and normally disposed in the eld without any pretreatment, resulted in environmental pollution. In fact, those waste
shells can be recycled and used as catalyst as it mainly consists
of calcium carbonate that can be converted into calcium oxide
through calcination.
An important focus of this research is the usage of waste as a
cost effective catalyst in biodiesel production. The shell-derived
catalysts were characterized and utilized in the production of biodiesel using palm oil and methanol. Optimum reaction conditions
and reusability of the catalysts were also investigated.

atmosphere. Nitrogen gas with a ow rate of 50 ml min1 was used

to remove the carbon dioxide gas produced during calcination.
About 30 mg of sample was placed into the sample holder and
heated from 50 C to 1000 C with a heating rate of 10 C min1,
to ensure the reaction went to completion in 95 min.
The phase identity of the prepared catalyst from obtuse horn
shell was determined by X-ray diffraction (XRD). Shimadzu Model
XRD-6000 was used to obtain diffraction patterns with the scan
range from 2h = 10 to 60 and scan rate of 2 per minute. The
average crystallite size of the catalyst was examined by using
DebyeScherrers equation [24]. Energy dispersive X-ray uorescence (XRF) spectrometer (model EDX-720) was used to determine
the element composition of the catalyst.
BrunauerEmmettTeller (BET) surface area analysis was used
to determine the specic surface area of catalyst samples and
Sorptomatic 1990 series (Thermo Finnigan) instrument was used.
Scanning electron microscopy (SEM) was performed to investigate
the surface morphology of the prepared catalyst by JOEL SEM
Model JSM-6400 at an accelerating voltage of 15 kV and working
distance of 1415 mm. Temperature-programmed desorption
(TPD) was used to study the basic properties of catalyst. This
characterization was carried out using Thermo Finnigan TPDRO
1100 with CO2 as the probe molecule.
2.2. Transesterication reaction and biodiesel analysis
Methanolysis of triglycerides was performed in a 100 ml round
bottom ask which was equipped with a reux condenser and a
magnetic stirrer. In a typical reaction, 10 g of palm oil (Lam Soon
Edible Oils Sdn. Bhd.) was added into the round bottom ask with
various amounts of catalysts (1, 3, 5, or 7 wt.%) and methanol to oil
molar ratios (6:1, 9:1, 12:1 or 15:1). The mixture was reuxed
under magnetic stirring in a parafn oil bath. The reaction mixture
was allowed to cool upon reaction completion. The mixture was
centrifuged at 3000 rpm for 10 min to separate the layers of methyl
ester, glycerol, and catalyst. A rotary evaporator was used to
recover the excess methanol. Methyl ester and glycerol were then
separated using separating funnel. The biodiesel product was evaluated by gas chromatography-14B (GC-14B) (model Shimadzu)
equipped with a ame ionization detector (FID). A RTX-65 capillary
column with 30 m in length and 0.25 mm internal diameter was
employed. Methyl heptadecanoate was used as the internal standard while helium gas was used as the carrier gas with a ow rate

2. Experimental
2.1. Catalyst preparation and characterization
Obtuse horn shells (C. Obtusa) were collected from local restaurants at Jalan Alor, Kuala Lumpur. The shells were cleaned to
remove impurities and eshy portion adhered to the wall of shell
by rinsing with cycles of warm water and distilled water. Then,
the shells were dried in an oven at 100 C, overnight. The shells
were calcined at 800 C (pre-determined by thermogravimetric
analysis (TGA)). The shells were crushed and ground to ne powder after calcination. This catalyst was then kept in a dessicator
to prevent contact with air.
Thermogravimetric analysis (TGA) was employed to determine
the calcination temperature of the obtuse horn shells. TGA is
carried out using Mettler Toledo model 990 instrument in an inert


Fig. 1. TGA prole of the catalyst.


S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288


Tmax = 648 oC

Intensity (Arbitary Unit)











Temperature (oC)
Fig. 4. TPD prole of the catalyst.
Fig. 2. Powder XRD patterns of catalysts at different calcination temperatures.

3. Results and discussion

3.1. Characterization of obtuse horn shell and CaO catalysts
Table 1
Elemental composition of shell-derived catalyst.
Composition, weight fraction (wt.%)
98.9 0.6

0.8 0.1

0.2 0.4

0.1 0.3

of 1.5 ml min1. Temperature of injector and detector were set at

250 C and 280 C, respectively. The initial oven temperature was
set at 150 C and raised up to 250 C with the ramping rate of
5 C min1. The yield was calculated following the European
regulated procedure EN14103 [25] as below:


Weight of biodiesel produced

Weight of oil used

Thermogravimetric analysis (TGA) was performed to determine

the calcination temperature of the obtuse horn shell. Fig. 1 shows
the TGA prole of raw powdered obtuse horn shells. A relatively
small weight loss was observed at temperature range of 170
413 C which corresponded to the elimination of loosely held
water that present in the sample. Obtuse horn shell catalyst
exhibited a major weight loss of 43% as the temperature increased
from 558 C to 857 C with the peak temperature around 800 C.
The decomposition can be attributed to the evolvement of carbon
dioxide as the weight loss matched to the stoichiometrical weight
loss, which is 44% [19]. The obtuse horn shell with mainly calcium
carbonate in its composition transformed into calcium oxide and
carbon dioxide during calcination.

CaCO3 s ! CaOs CO2 g

Fig. 3. SEM images of (a) fresh calcined catalyst and (b) catalyst after 4 cycles.


S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288






Yield (%)

Yield (%)









Methanol to Oil Molar Ratio

Reaction Time (h)

Fig. 7. Biodiesel yield versus methanol to oil ratio.

Fig. 5. Biodiesel yield versus reaction time.








Yield (%)

Yield (%)








Amount of Catalyst (wt. %)


Fig. 6. Biodiesel yield versus amount of catalyst.

Fig. 8. Reusability of catalyst.

XRD patterns of calcined catalyst at different temperatures

are depicted in Fig. 2. For catalyst calcined at 700 C, strong
peaks at 2h = 23.0, 29.3, 43.2, and 48.5 were detected, corresponding to the calcium carbonate which remains unconverted
in the particle core. However, the XRD patterns of the catalyst
calcined at 800 C and 900 C for three hours showed mainly
CaO peaks that can be observed at 2h of 32.2, 37.3, and 53.9
(JCPDS File No. 37-1497). As the calcination temperature
increased, calcium carbonate completely converted into calcium
oxide [23].
The average crystallite sizes of CaO catalysts synthesized at
800 C and 900 C were 85 2 nm and 97 2 nm, respectively.
BET surface areas and pore volume of the shell-derived catalyst
at 800 C were 0.07 0.01 m2/g and 0.002 0.02 cc/g. Meanwhile,
BET surface area and pore volume of the catalyst derived at
900 C were 0.04 0.04 m2/g and 0.001 0.04 cc/g. All shellderived catalysts were regarded as less-porous materials because
of their trace pore volume in shell [17]. Lower surface area of the

shell-derived catalyst was closely related to the calcination temperature. A high calcination temperature will lead to sintering of
ne particles, promote cluster agglomeration [26] and result in a
reduction of surface area in the catalyst.
The elemental composition was evaluated using XRF. The
elemental composition of prepared catalyst is shown in Table 1.
Calcium is the major element present in obtuse horn shell and constitutes more than 98 wt.% of the total catalyst. This indicated that
the shell composed of calcium carbonate transformed completely
into calcium oxide upon calcination.
The surface morphology of the catalyst was studied by SEM.
Fig. 3(a) depicts the SEM image of fresh catalyst. At the magnication of 2000, the calcined catalyst showed stone-like particles
with irregular size. This result was consistent with previous work
on different types of shells [1723]. The calcined obtuse horn shell
showed similar morphology with the calcined golden apple snail
shell, meretrix venus shell and calcined eggshell. Aggregates with
larger sizes were also observed [17].


S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288

TPD-CO2 was employed to evaluate the basicity strength of the

catalyst. From Fig. 4, calcined catalyst showed CO2 desorption
peaks with amount of 2508 10.76 lmol/g at 648 C. A very broad
desorption band that formed from 400 to 700 C can be assigned to
the interaction of CO2 with sites of weak and medium basic
strengths. The basic sites of weak or medium strength were related
to the presence of Ca2+ and O2 [27].
3.2. Catalytic activity in transesterication
3.2.1. Effect of reaction time
The effect of reaction time on biodiesel conversion is shown in
Fig. 5. It clearly showed that the use of shell-derived catalyst
requires a longer time (6 h) to achieve the optimum reaction time.
The presence of heterogeneous mass transfer systems led to a slow
reaction within short reaction time and hence there was no biodiesel conversion for the rst 3 h [28]. Nevertheless, it can be seen
that the percentage of conversion increased gradually from 4 h to
6 h (from 34.08% to 86.75%). The maximum conversion (86.75%)
of palm oil was achieved after 6 h and declined to 73.62% at 7 h.
This result was probably due to the formation of white emulsion
and gel in the biodiesel. Consequently, the viscosity of the product
increased and eventually making the downstream purication and
separation steps more difcult [29,30].
3.2.2. Effect of catalyst amount
The effect of catalyst loading on the transesterication reaction
was studied and displayed in Fig. 6. In transesterication process,
the basic sites of calcium oxide will transform methanol into a
much more reactive nucleophile (methoxide ions). This nucleophile will attack the carbonyl carbon structure of the glycerides
molecules. As the amount of the catalyst increase, the total number
of available active basic site will increase and lead to an increase of
conversion [18]. A maximum conversion of 86.75% was achieved
using 5 wt.% of catalyst. Beyond 5 wt.%, the yield of biodiesel
started to drop due to the high viscosity of the slurry, which led
to the problem of mixing between reactant, methanol and solid
catalyst [31,32].
3.2.3. Effect of methanol to oil ratio
The effect of methanol to oil ratio was examined by varying the
ratio from 6:1 to 15:1. Fig. 7 presents the biodiesel yield against
the methanol to oil ratio. It was not possible to analyse the mixture
at methanol to oil molar ratio of 3:1. The biodiesel yield increased
signicantly as the methanol to oil ratio increased. Below the ratio
12:1, the biodiesel yield was low as lower amount of methanol was
insufcient to shift the equilibrium to the right [33]. Maximum
conversion was obtained at methanol to oil ratio of 12:1. The conversion decreased with further increase of methanol to oil ratio.
At high methanol to oil molar ratio, the glycerin would largely
dissolve in excessive methanol. Subsequently, it reduced the
amount of methanol and inhibited the reaction of methanol to
the reactants and catalyst, resulted in a lower biodiesel conversion
[17,22]. Additionally, the polar hydroxyl group in methanol acting
as emulsier making it more difcult to separate the biodiesel
product and glycerol [34], eventually reduce the yield of methyl
3.2.4. Reusability
Stability and reusability of catalyst is one of the important features in industrial application. Hence, the reusability of the catalyst
was investigated under optimum reaction condition of 6 h, 5 wt.%
catalyst amount and methanol to oil ratio of 12:1. The catalyst
was reused directly in the second cycle after the rst cycle without
post-treatment. The graph of reusability is depicted in Fig. 8.

The catalyst can be reused up to three times with conversion of

more than 70% before the conversion dropped signicantly. The
possible reason for this loss of activity was the leaching of active
species into the biodiesel phase. Dissolution of some of the bulk
calcium oxide in methanolic solution will diminish the catalyst
activity [28]. Pore blockage of the catalyst resulted in catalyst
deactivation due to the loss of active sites [35]. The catalysts were
covered by intermediates or products such as diglyceride, monoglyceride, glycerol, biodiesel and so forth as indicated in SEM
micrographs (Fig. 3(b)). This reduced the contacts between the
catalyst and the reactant mixtures.
Industrially, the catalysts used are NaOH and KOH. These catalysts are non-reusable and generate large volume of wastewater
during separation and purication steps. Boro et al. [34] revealed
that the catalyst derived from waste shells of Turbonilla striatula
can only be reused for 2 cycles. Another study done by Lee et al.
[36] revealed that all the solid base catalysts (NaOH/Al2O3, CaO,
SrO, CaMgO and CaZnO) can only be reused up to 2 cycles.
Moreover, the reusability of waste capiz (Amusium cristatum)
shell was 2 cycles before dropped to an amount of 50% [37].
While chicken bones was applied by Muhammad and Anita
[38] and its reusability was 4 cycles. In this study, the obtuse
horn shell-derived catalyst was able to reuse up to 3 cycles,
which is relative competitive economically in comparison to
other biomass-derived CaO sources and heterogeneous catalysts.
Although the reusability may not be excellent at the moment, it
is still in the exploratory study. More efforts were done to
improve its properties and stability. Since the catalyst was produced from waste shells, it would lower the cost of catalyst
and maintenance.

4. Conclusion
Calcium oxide catalyst derived from waste obtuse horn shells
was successfully utilized in production of biodiesel. The waste
shells calcined at 800 C composed of more than 98% of calcium
oxide as conrmed by XRF and XRD. It showed irregular stone-like
shape with surface area of 0.067 m2/g. Shell-derived catalyst
possessed high basic strength as indicated by TPD-CO2 result. A
maximum conversion (86.75%) was obtained under reaction conditions of 6 h, 5 wt.% catalyst amounts and methanol to oil ratio of
12:1. This catalyst can be reused up to three times with conversion of more than 70%. Shell-derived catalyst has potential applications as low cost and renewable resource of catalyst for
biodiesel production. In future studies, research that will be executed to improve the properties of this catalyst includes supporting this catalyst on different supports such as Al2O3 or ZnO.
Supported CaO will contribute a more homogenous layer of basic
sites on the surface of support and avoid agglomeration of basic
sites. Meanwhile, the basic strength and the stability will be
enhanced, thus higher conversion of biodiesel and reusability
would be predicted. This would greatly cut down the cost of catalyst. Intensive research on alternative feedstock such as waste
oils and animal fats will also be carried out as it contributes a
large portion in biodiesel production cost. By using waste oils
and animal fats, the process would be more economically viable.
Signicant technical challenges remain for biofuel production,
including the development of better catalyst systems and downstream purication processes.

The authors acknowledge the nancial support of Universiti
Putra Malaysia (UPM).


S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288

Fig. A. Gas chromatogram of (a) standard methyl esters and (b) experimental biodiesel product.

Appendix A
See Fig. A.
Appendix B. Data for optimization reactions

Reaction time (h)

Yield (%)


0.0 0.0
0.0 0.0
0.0 0.0
34.3 0.3
79.4 0.4
86.6 0.2
73.6 0.1

Amount of catalyst (wt.%)

Yield (%)


28.9 0.4
58.8 0.3
86.6 0.2
82.3 0.4

Methanol to oil molar ratio

Yield (%)


73.3 0.3
76.3 0.1
86.6 0.2
71.9 0.3


S.L. Lee et al. / Energy Conversion and Management 93 (2015) 282288


Yield (%)


86.6 0.2
73.1 0.2
72.7 0.1
30.2 0.3

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