Journal of Cleaner Production xxx (2016) 1e9

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Journal of Cleaner Production

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Synthesis, characterization and performance of silica impregnated

calcium oxide as heterogeneous catalyst in biodiesel production
Nurul Saadiah Lani, Norzita Ngadi*, Noor Yahida Yahya, Roshanida Abd Rahman
Department of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor, Malaysia

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

Article history: Currently, biodiesel is produced by performing a transesterification reaction with homogeneous base
Received 10 January 2016 catalysts such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) dissolved in methanol. This
Received in revised form production process can provide high fatty acid methyl ester (FAME) yields under mild conditions.
7 June 2016
However, the homogeneous catalytic process suffers some drawbacks of an inevitable production of
Accepted 10 June 2016
wastewater from washing process of catalyst residues and unreusability of the catalysts. Thus, in this
Available online xxx
study, it is proposed to synthesize and characterize a renewable low cost heterogeneous hybrid catalyst
through utilization of waste material; rice husk and egg shell for transesterification reaction. The hybrid
Keywords:
Calcium oxide
catalyst was synthesized via wet impregnation method and then characterized using fourier transform
Silica infrared spectroscopy, x-ray diffraction, surface area and pore size distribution and scanning electron
Rice husk microscopy. The composition of FAME was determined by gas chromatography analysis and the prop-
Egg shell erties of biodiesel such as density, viscosity, acid value and calorific value were also analyzed. The result
Biodiesel show that the calcium oxide (CaO) supported with silica is more effective for the production of biodiesel
Transesterification reaction compared to CaO individually. Furthermore, the synthesized catalyst was able to be efficiently recyclable
and repeatedly used up to 6 times. The fuel properties of biodiesel produced in this study were found to
meet the specification of ASTM standards. Therefore, it can be concluded that the hybrid catalyst derived
from waste materials can be an excellent catalyst in biodiesel production. In addition, developing new
catalysts from rice husk and egg shell will not only solve the issue of disposal of these wastes but will
also simplify the purification process, whereby the catalysts can be separated from the product more
easily.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction transesterification reaction with homogeneous base catalysts such

Alternative fuels for diesel engines have gain importance
because of diminishing petroleum reserves and the environmental
consequences of exhaust gases from petroleum fueled engines (Xie
et al., 2007). In this respect, biodiesel is an emerging alternative to
diesel fuel derived from renewable and locally available resources
which is cleaner, biodegradable, nontoxic and environmentally
friendly. It is mainly produced via transesterification of vegetable
oil, which is a renewable and sustainable source (Kansedo et al.,
2009). In the transesterification reaction, a triglyceride reacts
with an alcohol in the presence of a catalyst, producing a mixture of
fatty acid methyl esters (FAME) and glycerol (Schuchardta et al.,
1998). Currently, biodiesel is produced by performing a
* Corresponding author.
E-mail address: norzita@cheme.utm.my (N. Ngadi).
as KOH or NaOH dissolved in methanol. However, the major
disadvantage of homogeneous catalysts is that they cannot be
reused or regenerated, because the catalyst is consumed in the
reaction (Farooq et al., 2013). Moreover the separation of catalyst
from products is difficult and requires more equipment which re-
sults in higher production costs (Freedman et al., 1984).
Based on these drawbacks, the use of heterogeneous catalysts
could be an attractive solution. Heterogeneous catalysts can be
separated more easily from reaction products and undesired
saponification reactions can be avoided (Martino-Di et al., 2008).
Biodiesel synthesis using solid catalysts could also lead to cheaper
production costs because of reuse of the catalyst and the possibility
for carrying out both transesterification and esterification simul-
taneously (Dora et al., 2005). A large variety of different heteroge-
neous catalysts have been investigated including supported
catalysts (Umdu et al., 2009), alkali earth oxides (Ilgen and Nilgun,
2009) and hydrotalcites catalyst (Liu et al., 2008). Among them, CaO

http://dx.doi.org/10.1016/j.jclepro.2016.06.058
0959-6526/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
2 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9
has been received much interest due to its long catalyst life, high
activity and requires only moderate reaction conditions (Math
et al., 2010).
Incorporating CaO on high surface area materials such as
alumina (Umdu et al., 2009), zeolite (Wu et al., 2013) and silica
(Chen et al., 2015a,b; Samart et al., 2010) was found be able to
accelerate the catalytic activity of CaO and thus improved the
biodiesel yield. Among these catalyst supports, mesoporous silica
has attracted much attention due to its many excellent properties
such as good thermal stability, high surface area and unique large
pore structure characteristic, which reduce mass transfer limita-
tions and allow high concentration of active sites per mass of ma-
terial (Melero et al., 2012).
Albuquerque et al. (2008) reported the use of CaO loaded mes-
oporous silica as base catalysts for biodiesel production. The ob-
tained catalyst has proven to be thermally more resistant and the
interaction between CaO and silica is strong enough to prevent the
lixiviation of the active phase in methanol. In another study con-
ducted by Samart et al. (2010), silica was obtained from pluronic
P123 polymer and was then impregnated with calcium acetate
solution to produce CaO-silica catalyst. The fuel properties of the
biodiesel obtained using the synthesized catalyst was found to
meet all biodiesel standards. Studies by Umdu (2008) have
demonstrated modified single step sol-gel method by using tet-
raethyl orthosilicate (TEOS) as precursor silica support oxides. It is
reported that high dispersion of active phases was achieved for CaO
based catalysts even with the high CaO loading of 80 wt%. Another
studies regarding the silica from TEOS was conducted by Mohadesi
et al. (2014), whereby the catalyst loading of 70% (CaO based on
SiO2), calcination temperature of 60
C and acid to water ratio of 0.5
were optimal values, and the purity and conversion of produced
biodiesel were 98.5 and 85.6%. Witoon et al. (2014) meanwhile
prepared CaO supported on silica catalyst using sodium silicate and
calcium nitrate tetrahydrate as a silica and CaO source, respectively.
The incorporation of silica in the structure of catalyst was found to
be enhanced diffusion of reactants to the active sites and thus
leading to a significant enhancement in FAME percentage. Recently,
Chen et al. (2015a,b) have utilized silica supported CaO catalyst
derived from Na2SiO3 as raw material in biodiesel. In their study,
the CaOeSiO2 catalysts were prepared through the biomimetic
silification approach under ambient conditions by dispersing the
powder egg shells into NaSiO3 aqueous solution. The obtained
catalyst had a better reusability as the amount of Si compound
increased. Unfortunately, absence of silica compound in the
CaOeSiO2 catalyst had a higher yield of biodiesel. It means that the
incorporation of silica, which is obtained from sodium silicate in
this study doesn't give better catalytic activity compared by using
CaO individually.
However, there has been no work done on the utilization of
silica supported-CaO catalyst from rice husk for biodiesel synthesis.
Rice husk, a waste product of the processing of grain, is normally
been used in power generation through combustion and its burning
generates another residue, the rice husk ash. The presence of high
amount of SiO2 prompts its potential applicability as a low-cost
catalyst support.
Therefore, in this study, it is aimed to synthesize and charac-
terize a new low cost, highly efficient supported base catalyst
through utilization of the two waste materials, which is rice husk
ash and egg shell for transesterification of palm oil to yield fuel
grade biodiesel. As can be highlighted, this study is focusing on the
utilization of waste materials for synthesizing of valuable hybrid
catalyst using a simple and green approach. The findings of this
study offers a more economic solution for biodiesel production and
in the same time could reduce waste disposal problems.
Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
2. Materials and method
2.1. Materials
The virgin cooking palm oil was purchased from local market
while waste cooking oil was obtained from a local restaurant in
Arked Meranti, UTM. This oil was used for the transesterification
reaction without further treatment and purification. For catalyst
production, chicken eggshell was collected from local restaurants
and raw rice husk was purchased from Qhadijah Natural Farm,
which was located at Parit Buntar, Perak. Other chemicals used in
this study were hydrochloric acid and methanol, are reagent grade
obtained commercially from MD Interactive Sdn Bhd.
2.2. Catalyst preparation
The waste egg shells were cleaned to remove sand and flesh
adhering to the shells by rinsing with distilled water several times.
Then, the shells were dried in an oven at 60
C for 24 h. After being
dried, the shells were crushed and ground to fine powder. The dried
crushed shells were then calcined in a furnace at 900
C for 6 h in
order to obtain CaO catalyst.
For silica preparation, dry raw rice husks were sieved to elimi-
nate residual rice and clay particles and then washed with distilled
water. After through washing, rice husks were filtered and dried in
an oven at 60
C overnight. The cleaned rice husks were converted
into rice husk ash by heatetreating at 700
C for 6 h, whereby the
ash was brownish in color. Subsequently, the ash was boiled in
100 mL of 3 N of hydrochloric acid (HCl) from concentrated HCl for
1 h to get impurity free ash. The ash was then filtered, washed and
dried in an oven. Finally, the ash was calcined at 700
C for 6 h.
The hybrid catalyst of CaO and silica was prepared using wet
impregnation method. A sample of approximately 5 g of CaO was
added to 100 mL water to prepare aqueous solution. Then, this
solution was added to an amount of silica and mixed vigorously
under total reflux for 4 h at 80
C. Subsequently, the mixture was
filtered and dried in an oven. The dried mass was then calcined in a
furnace at temperature of 800
C for 3 h. The calcined mass ob-
tained was referred as hybrid catalyst.
2.3. Catalyst characterization
The FTIR spectra of catalysts were obtained by using Spectrum
One-Perkin Elmer with software spectrum v5.02. The x-ray dif-
fractions (XRD) patterns of catalyst powders were recorded on a
Bruker D8 Advance diffractometer using Ni-filter Cu Ka radiation,
with a wavelength of 0.1541 nm at 40 kV and 40 mA. Powder
samples were scanned in 2q range varying from 10
to 90
. The
surface are, total pore volume and pore size distribution of the
catalyst were determined with AUTOSORB-1C, Chem-
isorptionePhysisorption analyzer. Surface area was calculated by
using BET equation from the adsorption branch of the isotherm in a
relative pressure range from 0 to 1. The total pore volume of the
catalyst was examined by N2 physisorption method while the pore
size distribution was determined form absorption branch by the
Non-Local-Density-Functional-Theory (NLDFT) method. The sur-
face morphology of the catalysts were investigated by using a JEOL
JSMe6390LV scanning electron microscope, with the accelerating
voltage of 50 kV. All specimens were coated with gold and then
observed.
2.4. Transesterification process
The transesterification was carried out in a batch reactor. A
40 mL of oil was stirred in a 500 mL round-bottom flask equipped
 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9
with a reflux condenser. A mixture of methanol and catalyst at a
designated amount was added to the oil and the transesterification
was conducted for the required reaction times. Upon the reaction
completion, phase separation was carried out in a separatory funnel
at room temperature. The influence of silica content on the bio-
diesel yield was investigated by varying the silica content from 3 to
10 wt%, whereby the catalyst dosage, methanol to oil molar ratio,
reaction time and temperature was fixed at 3 wt%, 15:1, 2 h and
60
C, respectively. The yield of biodiesel is determined according
to Eq. (1)
Weight of biodiesel
Yield of biodiesel ð%Þ ¼  100
Weight of oil
2.5. Properties of biodiesel
The composition of fatty acid methyl ester produced under the
optimal reaction conditions was determined by gas chromatograph
(GC-2010, Shimadzu) equipped with capillary column and a flame
ionization detector. Methylheptadecanoate was used as internal
standard quantification. The biodiesel sample was first diluted in
cyclohexane and then, the analysis of a sample was carried out by
injecting 1 mL of the sample solution into the GC. A digital density
hydrometer (ZEAL Made in England) with the measuring accuracy
of ±5.0  106 g/cm3 was used to measure the density of biodiesel.
Meanwhile, the viscosity of the biodiesel was measured using a
Cole-Parmer rotational viscometer with a stainless steel spindles
and viscosity measurement ranging from 20 to 2  106 mPa s. This
test was conducted under variation of temperature from 30 to
100
C. Determination of calorific value was done by using Parr
6200 bomb calorimeter. The acid value was determined by the acid
base titration technique, whereby a mixture of biodiesel sample
(5 g), ethanol (25 mL) and phenolphthalein (5 drops) were titrated
with 0.1 N potassium hydroxide solution until the appearances of
pink color. Then, the acid value was calculated according to Eq. (2)
56:1  N  V
Acid value ¼
m
where, V ¼ volume of KOH solution used in mL
N ¼ normality of KOH
M ¼ mass of biodiesel sample in g dosage
3. Results and discussion
3.1. Catalyst characterization
3.1.1. Fourier transform infrared spectroscopy
The FTIR spectra of CaO, silica and hybrid catalyst samples in the
region of 500e4000 cm1 are presented in Fig. 1. The spectra of CaO
sample displays band at 1478, 1082 and 873 cm1 are corre-
sponding to the stretching vibration of the CO2 3 group, which is
due to the chemisorption of gaseous CO2 from atmosphere over the
surface of the catalyst. An intense absorption peak of OeH bending
vibration at about 3639 cm1 was assigned to the absorption of
water molecule from atmosphere that attached to the Ca atom
(Chen et al., 2015a,b). Additionally, the characteristic band at
854 cm1 in CaO catalyst confirms the presence of CeO bond
(Suryaputra et al., 2013). The stretching vibration mode of CaeO
bond was appeared as a strong peak at 528 cm1, which provided
great evidence for the formation of Ca oxides during the calcination
procedure of waste egg shell at the temperature of 900
C in the
muffle furnace.
Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
3
For silica spectra, the broadband located in the range of 2800
and 3750 cm1 is related to the stretching vibration of the OeH
bond from the silanol groups (SieOH). The band at 3429 and
1652 cm1 can be attributed to the presence of OeH stretching and
bending mode of adsorbed water molecules bound to the silica
surface, respectively (Hindryawati and Maniam, 2015). The pre-
dominant absorbance peak of silica was indicated by the strong
band at 1053 cm1, which could be assigned to asymmetric
stretching of siloxane bond (SieOeSi). Additionally, the peak at
796 cm1 was associated to the SieOeSi symmetric stretching
while the bending mode of bulk SieOeSi lies at 482 cm1 proving
the successful production of silica from rice husk (Singh and Patel,
(1)
2014).
On the other hand, the spectra of the hybrid catalysts showed
some identical functional groups as CaO catalyst, which revealed
similar pattern at 3,651, 846 and 531 cm1 were assigned to the
stretching vibration of OeH groups, CeO and CaeO bonds,
respectively. The absorption band at 1427 cm1 that was the
asymmetric stretch of CO2 3 groups could be found. Another ab-
sorption band that was ascribed to the out-of-plane band vibration
1
mode of CO23 groups was also found at 879 cm . However, as can
be seen, the characteristic peaks of silica are totally absent. This was
suggested all the SiO2 was reacted with CaO to form a new phase
CaSiO3 and Ca2SiO4 compound. Meanwhile, the appearance of
strong band at 995 cm1 indicates the presence of SieOeCa bond
(Chen et al., 2015a,b).
3.1.2. X-ray diffraction
The findings in the FTIR spectra are also supported by XRD for
the catalysts which are presented in Fig. 2. The typical diffraction
peaks associated to calcined waste egg shell corresponding to
highly crystalline calcium oxide were observed at 2q of 18.1
, 32.3
,
37.5
, 54.0
, 64.3
, 67.5
, 79.8
and 88.6
(Chen et al., 2015a,b).
Meanwhile, the existence of low intensity peaks at 34.2
and 50.9

indicates the presence of minor amount of calcium carbonate as
well as calcium hydroxide at 2q of 47.3
(Hui et al., 2010).
In Fig. 2b, it can be seen that the silica sample exhibited only one
strong broad peak at 2q of 23
, coincident with values reported by
(2) Liu et al. (2012). The result indicates that the formed silica was
amorphous and the absence of any ordered crystalline structure
can be assigned to highly disordered structure of silica.
Hybrid catalyst exhibited the peaks associated with the calcium
oxide are observed at 2q of 18.1
, 32
, 37
, 54.4
and 64.3
, whereby
their intensity was found to be lower than CaO catalyst. It also
showed weak XRD peaks at 51
assigned to the calcium carbonate.
An additional Ca2SiO4 and CaSiO3 phase were appeared clearly in
the diffraction patterns at 2Ɵ of 34.2
and 51.5
, respectively (Chen
et al., 2015a,b).
3.1.3. N2 adsorption-desorption
The surface area, total pore volume and pore diameter of CaO,
silica and hybrid catalyst were measured and summarized in
Table 1. The BET surface area of CaO catalyst derived from waste egg
shell was found to be 6.83 m2/g. Upon impregnation with silica,
which has high surface area of 132.83 m2/g, there was an increment
of the surface area to 12.29 m2/g. The increasing surface area of the
catalyst might be due to the strong interaction of the CaO with silica
support, which reduced the surface diffusion of Ca, inhibited sin-
tering and stabilized the surface of CaO (Omar and Amin, 2011).
Thus, it can be expected that the hybrid catalyst would leads to
improve the activity of catalyst in transesterification process by
increasing the accessibility of the active sites and provide enough
attachment area as reported by Istadi et al. (2015).
The total pore volume and average pore diameter of CaO and
silica were 0.0319 cm3/g, 7.86 nm, 0.3644 cm3/g and 15.89 nm,
4 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9

Fig. 1. FTIR spectra of the (a) CaO, (b) silica and (c) CaO impregnated with 3% silica; hybrid catalyst.

respectively, while for Cao impregnated with 3% silica these pa-
rameters were 0.0429 cm3/g and 11.76 nm, respectively. In com-
parison, the pore diameter of the catalysts are somewhat larger
than the reactant molecules, whereby the dimensions of triglyc-
eride, methyl oleate and glycerin are approximately 5.8 nm, 2.5 nm
and 0.6 nm, respectively (Granados et al., 2007). It has been re-
ported that the larger average pore diameter and larger inter-
connected pores of catalyst would minimize diffusion limitations of
reactant molecules. Therefore, the reactant molecules can easily
infiltrate into the interior of the catalyst and most of the active site
will be utilized during the transesterification reaction (Wu et al.,
2014).
The porosity of the catalyst was examined by N2 physisorption
method while the pore size distribution was determined from ab-
sorption branch by the NLDFT model. Nitrogen adsorp-
tionedesorption isotherms and the corresponding pore size
distribution plots of all catalysts are shown in Fig. 3. All isotherm
curves showed a type IV profile and type H3 hysteresis loops,
except silica, whereby there was no hysteresis loop in the first
capillary condensation. The first step of capillary condensation, in a
relative pressure of 0.5, was attributed to the nitrogen condensa-
tion that took place in the internal mesopores and secondly at a
higher partial pressure (P/P
¼ 0.8), which was attributed to the
presence of interparticle porosity. Furthermore, it could be
observed that the pore size of the CaO catalyst was in the range of
3e10 nm and can be classified as mesopores. Upon introduction of
silica into CaO and following calcination, the catalyst particles
exhibited bimodal pore size distribution that consisted of a primary
pore at 7 nm and secondary pore at 13 nm.
3.2. Effect of silica on the yield of biodiesel
The influence of the amount of silica on the activity of CaO
catalyst was tested at reaction time and temperature of 2 h and

Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9 5

From Fig. 5, all images showed the significant agglomeration of

the silica particles with a heterogeneous distribution on the surface
of CaO catalysts. The pores among the agglomerates were found to
be smaller as the silica content is increased. There is apparently
more space between the agglomerates in CaO catalyst with 3 wt% of
silica (Fig. 5a) compared to CaO catalyst with 5, 7 and 10 wt% of
silica (Fig. 5b,c,d). Therefore, the surface of the CaO/3 wt% silica
catalyst can fully contact with oil ester and methanol where they
undergo transesterification reaction to produce biodiesel, resulting
in better catalytic activity.

3.3. Properties of biodiesel

Biodiesel is composed of fatty acid methyl ester and their

composition was commonly determined by GC analysis. For com-
parison, biodiesel was also synthesized from waste cooking oil
under same conditions as virgin cooking oil. The GC chromato-
grams of both biodiesels are depicted in Fig. 6 and the methyl ester
compositions are summarized in Table 2.
The results revealed that the high conversion from oil to methyl
ester was achieved, which are around 98.65 and 95.75% conversion
from virgin cooking oil and waste cooking oil, respectively. A total of
10 methyl ester compounds were identified in biodiesel from virgin
cooking oil, whereby the main methyl esters were methyl palmi-
toleate (32.14%), methyl stearate (21.62%), methyl oleate (19.84%)
and methyl linoleate (8.30%). Furthermore, the percentage of un-
saturated methyl esters (65.34%) is remarkable compared to that of
saturated methyl esters (34.65%) and the degree of unsaturation
was calculated to be 76.64%. On the other hand, seven types of
methyl esters compounds were found in biodiesel that is produced
from waste cooking oil. The synthesized biodiesel mainly consists
of four fatty acid methyl esters, which are methyl palmitoleate
(14.26%), methyl stearate (14.05%), methyl oleate (36.00%) and
methyl linoleate (24.68%). The amount of unsaturated fractions is
68.11% while that of saturated is 31.89% and the degree of unsatu-
ration was 94.36%. Overall, it can be stated that the oil was suc-
Fig. 2. XRD patterns of the (a) CaO, (b) silica and (c) CaO impregnated with 3% silica; cessfully transesterified to biodiesel using CaO impregnated silica
hybrid catalyst.
catalyst.
The application of low quality of biodiesel due to incomplete
60
C, respectively with molar ratio of methanol to oil at 20:1. Fig. 4 reaction and the existence of contaminants in a diesel engine may
shows the yield of methyl ester using different content of silica. cause a number of issues in existing engine such as precipitation of
From the result, it was found that the CaO supported with silica fuel insolubles and filter plugging. Therefore, highly purified bio-
had a higher yield of methyl ester than CaO individually. This might diesel is necessary to meet ASTM D6751 (the American Society for
be due to the solid state reaction between silica compound and the Testing and Materials) and EN 14214 (European Committee for
surface of CaO in the activation process, whereby the silica could Standardization) standard in order to evaluate the quality of bio-
have inserted in the vacant sites of CaO. Furthermore, it was noted diesel product. Table 3 shows the properties of the biodiesel ob-
that the introduction of silica in the CaO catalyst is able to improve tained from virgin cooking oil and waste cooking oil. In addition,
the surface area due to increasing total pore volume, which in turn the relevant specification of biodiesel ASTM D6751 and EN 14214
providing the opportunity to increase the number of active sites are also listed in Table 3.
that interact with the reactants and consequently facilitates the Viscosity is refers to the internal friction or resistance of oil to
biodiesel formation. However, the further increase in the amount of flow at a given temperature. Viscosity is the most important
silica leads to low yield of methyl ester. The reduction of the property of biodiesel since it can hinder the operation of fuel in-
product might be to the active sites on CaO surface was covered by jection equipment in engine. If the fuel is too viscous, it makes it
excess silica, which corresponds to lower catalytic activity. This difficult to pump and flow through pipelines, injector nozzles and
result is in well agreement with that obtained by SEM analysis as orifices, and therefore leads to the poor atomization during the
shown in Fig. 5. fuel spray due to the formation of larger droplets on injection.
From Table 3, its can be seen that the viscosity of the biodiesel
obtained from virgin cooking oil at 40
C is 3.755 mm2/s, whereas
Table 1
those of biodiesel from waste cooking oil is 2.792 mm2/s. The
The physical properties of CaO, silica and hybrid catalyst.
viscosity of biodiesel from virgin cooking oil is in the range of
Catalyst Surface Total pore Average pore American and European standards while the viscosity of biodiesel
area (m2/g) volume (cm3/g) diameter (nm)
from waste cooking oil is specified the ASTM D6751 but not
CaO 6.83 0.0319 7.86 specified a minimum value of EN14214 biodiesel standard. Vis-
Silica 132.83 0.3644 15.89 cosity data obtained for biodiesel as a function of temperature is
Hybrid catalyst 12.29 0.0429 11.76
presented in Fig. 6.

Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
6 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9

Fig. 3. N2 adsorptionedesorption isotherm and pore size distribution of the (a) CaO, (b) silica and (c) CaO impregnated with 3% silica; hybrid catalyst.

As shown in Fig. 7, the viscosity of biodiesel from both virgin and
waste cooking oil decreased non-linearly with temperature. It also
indicates that the biodiesel from virgin cooking oil can be heated up
to 67
C so that the viscosity is in the range of 1.9 and 6 mm2/s,
while 53
C for biodiesel from waste cooking oil. Corresponding to
the viscosity limit given by the EN14214 European standard for
biodiesel fuel, heating biodiesel from virgin and waste cooking oil is
allowed up to 41 and 30
C, respectively. In addition, biodiesel from
waste cooking oils were observed to have lower viscosity value
than biodiesel from virgin cooking oil. It could be due to the high
degree of unsaturation of biodiesel from waste cooking oil as the
Fig. 4. Effect of silica content on biodiesel yield.
viscosity of biodiesel fuels decreases with increase in degree of
unsaturation.
Density is another important parameter to measure when
assessing fuel quality because of its influence on the atomization
and combustion process in engine. The ASTM standard for density
of biodiesel is 860e894 kg/m3, while the European standard is in
the range of 860 and 900 kg/m3. Higher density of fuel will leads to
lower volatility and poor atomization during fuel injection and
therefore cause incomplete combustion and carbon deposits in
combustion chamber. It was observed that the density of biodiesel
from virgin cooking oil and waste cooking oil was measured to be
870 and 880 kg/m3, respectively, which was in the range recom-
mended by both standards. By comparing the density of both bio-
diesel, it is noticed that the density for biodiesel from waste
cooking oil was higher than that from virgin cooking oil. This is
because the density of biodiesel fuel increases with increase in
degree of unsaturation.
Acid value reflects the percentage of free fatty acid (FFA) in the
fuel, whereby it is defined as the amount of potassium hydroxide
needed to neutralize the free acids in biodiesel sample. Acid value
of biodiesel should be less than 0.5 mg KOH/g sample in order to
handle the fuel properly and safe. If the acid value is too high, the
fuel could cause degradation of rubber parts in engines and
therefore resulting in filter clogging. The test result for the acid

Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9
Fig. 5. Surface morphology of (a) CaO/3 wt% silica, (b) CaO/5 wt% silica, (c) CaO/7 wt% silica and (d) CaO/10 wt% silica.
Fig. 6. GC chromatogram of the synthesized biodiesel from (a) virgin cooking oil and
(b) waste cooking oil.
value for virgin cooking oil and waste cooking oil was found to be
0.21 and 0.29 mg KOH/g sample, respectively.
The calorific value is defines as the energy content of biodiesel
produced and it is another important property of biodiesel since
the power output of an engine while running under constant
conditions and with a constant ratio of fuel consumption depends
strictly by its calorific value. The calorific value of biodiesel from
Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
7
virgin cooking oil is 39.63 MJ/kg, whereas that for biodiesel from
waste cooking oil is 38.18 MJ/kg. Furthermore, the calorific value of
both biodiesel presented approximately 12% lower energy content
compared to diesel, whose energy content is around 43.33 MJ/kg.
As pointed by Demirbas (1997), the calorific value of fuel increases
with increasing carbon number in fuel molecules. Therefore, it can
be noticed that the calorific value for biodiesel from virgin cooking
oil was higher than that from waste cooking oil due to the high
amount of carbon atom present in biodiesel synthesized from vir-
gin cooking oil.
3.4. Reusability study
The recovery and reuse of catalyst for next reaction is one of the
important factors which elucidate the potential of a catalyst for its
commercial application. Upon the completion of the trans-
esterification reaction, the spent catalyst was recovered by washing
with methanol several times in order to remove the adsorbed
materials. This catalyst was later calcined at 800
C for 3 h to
reactivate it and then reused as the catalyst for the next run. The
result of biodiesel yield as a function of the number of recycling was
shown in Fig. 8.
Fig. 8 shows that the yield of biodiesel reaches to 90% in the first
run and the hybrid catalyst was found to maintain its activity even
after being used through the next three consecutive runs. This
result indicated that the CaO impregnated silica catalyst was rela-
tively stable and exhibited high catalytic, which provide the op-
portunity to apply an appropriate recycle stream in continuous
process to minimize costs in industry. However, there was a slight
decrease in the biodiesel yield from 90 to 85, 80 and 77.5% when the
catalyst is employed for the fifth, sixth and seventh time. A
remarkable reduction in the catalytic activity can be seen in the
eighth and onward runs, whereby the biodiesel yield dropped to
52.5%. The reduction in the yield of biodiesel from fifth to tenth use
of catalyst was possibly due to leaching of Ca compound during the
reaction. The leaching effect in this catalyst can be attributed to the
bond breaking and formation of intermediate species such as
Ca(OH)2 and calcium diglyceroxide on the catalyst surface, which
prevented the contact between reactants and catalyst active sites
8 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9

Table 2
FAMEs composition of the synthesized biodiesel.

Peak Biodiesel from virgin cooking oil Biodiesel from waste cooking oil

Identified compound Composition (%) Identified compound Composition (%)

1 Methyl laurate (C12:0) 0.79 Methyl palmitate (C16:0) 14.26

2 Methyl myristate (C14:0) 5.58 Methyl stearate (C18:0) 14.05
3 Methyl palmitate (C16:0) 3.61 Methyl oleate (C18:1) 2.15
4 Methyl palmitoleate (C16:1) 32.14 Methyl oleate (C18:1) 33.85
5 Methyl stearate (C18:0) 21.62 Methyl linoleate (C18:2) 24.65
6 Methyl oleate (C18:1) 9.79 Methyl linolenate (C18:3) 4.53
7 Methyl oleate (C18:1) 10.05 Methyl arachidate (C20:0) 2.23
8 Methyl linoleate (C18:2) 8.30
9 Methyl linolenate (C18:3) 4.03
10 Methyl arachidate (C22:0) 2.58

Table 3
Physicochemical properties of the synthesized biodiesel.

Properties Biodiesel (virgin cooking oil) Biodiesel (waste cooking oil) ASTM D6751 EN 14214

Viscosity, 40
C (mm2/s) 3.755 2.792 1.9e6.0 3.5e5.0

Density (kg/m3) 870 880 860e894 860e900
Acid value (mg of KOH/g of oil) 0.21 0.29 Max 0.5 Max 0.5
Calorific value (MJ/kg) 39.63 38.18 e e

4. Conclusion

In this study, the CaO supported with silica catalyst was suc-
cessfully synthesized from waste egg shell and rice husk. The
hybrid catalyst showed high catalytic activities for the trans-
esterification reaction. The biodiesel yield of transesterification
reaction over the CaO supported by silica catalyst reaches to 87.5%
at 2 h, which is higher than the biodiesel yield over CaO individu-
ally. Furthermore, the yield of biodiesel was also affected by
different silica content. As a conclusion, this waste-derived cata-
lysts showed a potential use for biodiesel production. These wastes
could stand for abundant resources of low-cost catalysts which
provides a simple and green method in order to produce biodiesel
fuel.

Fig. 7. Relationship of temperature and viscosity in biodiesel from virgin and waste Acknowledgement
cooking oil.
The authors would like to extend their sincere gratitude to the
Ministry of Higher Education Malaysia (MOHE) for the financial
by the intermediate species (Buasri et al., 2013). As a final remark, supports received under University Grant (Vote no.
the synthesized catalyst was able to efficiently recyclable and Q.J130000.2546.11H46) and FRGS (Vote no. R.J130000.7844.4F489).
repeatedly used up to 6 times while maintaining the biodiesel yield
at around 80%. References

Albuquerque, M.C.G., Jime
nez-Urbistondo, I., Santamaría-Gonza
lez, J., Me
rida-

Fig. 8. Yield of biodiesel with recycled catalyst (Reaction conditions: catalyst amount
3 wt%, methanol to oil molar ratio 20:1, reaction temperature 60
C and reaction time
2 h).
Robles, J.M., Moreno-Tost, R., Rodríguez-Castello
n, E., Jime
nez-Lo
pez, A.,
Azevedo, D.C.S., Cavalcante Jr., C.L., Maireles-Torres, 2008. CaO supported on
mesoporous silicas as basic catalysts for transesterification reactions. Appl.
Catal. A General 334, 35e43.
Buasri, A., Chaiyut, N., Loryuenyong, Y., Wongweang, C., Khamsrisuk, S., 2013.
Application of eggshell wastes as a heterogeneous catalyst for biodiesel pro-
duction. Sustain. Energy 1, 7e13.
Chen, G.Y., Shan, R., Shi, J.F., Yan, B.B., 2015a. Transesterification of palm oil to
biodiesel using rice husk ash-based catalysts. Fuel Process. Technol. 133, 8e13.
Chen, G.Y., Shan, R., Li, S., Shi, J.F., 2015b. A biomimetic silification approach to
synthesize CaOeSiO2 catalyst for the transesterification of palm oil into bio-
diesel. Fuel 153, 48e55.
Demirbas, A., 1997. Calculation of higher heating values of biomass fuels. Fuels 76,
431e434.
Dora, E.L., James Jr., G.G., David, A.B., Edgar, L., 2005. Transesterification of triacetin
with methanol on solid acid and base catalysts. Appl. Catal. A General 295,
97e105.
Farooq, M., Ramli, A., Subbarao, D., 2013. Biodiesel production from waste cooking
oil using bifunctional heterogeneous solid catalysts. J. Clean. Prod. 59, 131e140.
Freedman, B., Pryde, E.H., Mounts, T.L., 1984. Variables affecting the yields of fatty
esters from transesterified vegetable oils. J. Am. Oil Chem. Soc. 61, 1638e1643.

Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
 N.S. Lani et al. / Journal of Cleaner Production xxx (2016) 1e9
Granados, M.L., Poves, M.D.Z., Alonso, D.M., Mariscal, R., Galisteo, F.C., Moreno-
Tost, R., Santamaría, J., Fierro, J.L.G., 2007. Biodiesel from sunflower oil by using
activated calcium oxide. Appl. Catal. B Environ. 73, 317e326.
Hindryawati, N., Maniam, G.P., 2015. Novel utilization of waste marine sponge
(demospongiae) as a catalyst in ultrasoundeassisted transesterification of
waste cooking oil. Ultrason. Sonochem. 22, 454e462.
Hui, P., Meena, S., Singh, G., Agarawal, R., Prakash, S., 2010. Synthesis of hydroxy-
apatite bio-ceramic powder by hydrothermal method. J. Miner. Mater. Charact.
Eng. 9, 683e692.
Ilgen, O., Nilgun, A.A., 2009. Transesterification of canola oil to biodiesel using MgO
loaded with KOH as a heterogeneous catalyst. Energy Fuels 23, 1786e1789.
Istadi, I., Prasetyo, S.A., Nugroho, T.S., 2015. Characterization of K2O/CaO-ZnO
catalyst for transesterification of soybean oil to biodiesel. Procedia Environ. Sci.
23, 394e399.
Kansedo, J., Lee, T.K., Bhatia, S., 2009. Biodiesel production from palm oil via het-
erogeneous transesterification. Biomass Bioenergy 33, 271e276.
Liu, X., Piao, X., Wang, Y., Zhu, S., 2008. Calcium ethoxide as a solid base catalyst for
the transesterification of soybean oil to biodiesel. Energy Fuels 22, 1313e1317.
Liu, Y., Guo, Y., Gao, W., Wang, Z., Ma, Y., Wang, Z., 2012. Simultaneous preparation
of silica and activated carbon from rice husk ash. J. Clean. Prod. 32, 204e209.
Martino-Di, S., Riccardo, T., Lu, P., Elio, S., 2008. Heterogeneous catalysts for bio-
diesel production. Energy Fuels 22, 207e217.
Math, M.C., Kumar, S.P., Chetty, S.V., 2010. Technologies for biodiesel production
from used cooking oilea review. Energy Sustain. Dev. 14, 339e345.

nchez-Va
Melero, J.A., Bautista, L.F., Iglesias, J., Morales, G., Sa
zquez, R., 2012. Zr-SBA-
15 acid catalyst: optimization of the synthesis and reaction conditions for
biodiesel production from lowgrade oils and fats. Catal. Today 195, 44e53.
Mohadesi, M., Moradi, G., Hojabri, Z., 2014. Biodiesel production by CaO/SiO2
catalyst synthesized by the solegel process. React. Kinet. Mech. Catal. 113, 1e18.
Omar, W.N.N.W., Amin, N.A.S., 2011. Biodiesel production from waste cooking oil
Please cite this article in press as: Lani, N.S., et al., Synthesis, characterization and performance of silica impregnated calcium oxide as
heterogeneous catalyst in biodiesel production, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.06.058
9
over alkaline modified zirconia catalyst. Fuel Process. Technol. 92, 2397e2405.
Samart, C., Chaiya, C., Reubriycharoen, P., 2010. Biodiesel production by meth-
anolysis of soybean oil using calcium supported on mesoporous silica catalyst.
Energy Convers. Manag. 51, 1428e1431.
Singh, S., Patel, A., 2014. 12-Tungstophosphoric acid supported on mesoporous
molecular material: synthesis, characterization and performance in biodiesel
production. J. Clean. Prod. 72, 46e56.
Schuchardta, U., Serchelia, R., Vargas, M.R., 1998. Transesterification of vegetable
oils: a review. J. Braz. Chem. Soc. 9, 199e210.
Suryaputra, W., Winata, I., Indraswati, N., Ismadji, S., 2013. Water capiz (amusium
cristatum) shell as a new heterogeneous catalyst for biodiesel production.
Renew. Energy 50, 759e799.
Umdu, E.S., 2008. Methyl Ester Production from Vegetable Oils on Heterogenous
Basic Catalysts (Master thesis). Graduate School of Engineering and Sciences of
_
Izmir Institute of Technology.
Umdu, E.S., Tuncer, M., Seker, E., 2009. Transesterification of nannochloropsis
oculata microalgas lipid to biodiesel on Al2O3 supported CaO and MgO catalysts.
Bioresour. Technol. 100, 2828e2831.
Witoon, T., Bumrungsalee, S., Vathavanichkul, P., Palitsakun, S., Saisriyoot, M.,
Faungnawakij, K., 2014. Biodiesel production from transesterification of palm oil
with methanol over CaO supported on bimodal meso-macroporous silica
catalyst. Bioresour. Technol. 156, 329e334.
Wu, H., Zhang, J., Lu, Y., Zheng, J., Wei, Q., 2014. Biodiesel production from jatropha
oil using mesoporous molecular sieves supporting k2sio3 as catalysts for
transesterification. Fuel Process. Technol. 119, 114e120.
Wu, H., Zhang, J., Wei, Q., Zheng, J., Zhang, J., 2013. Transesterification of soybean oil
to biodiesel using zeolite supported CaO as strong base catalyst. Fuel Process.
Technol. 109, 13e18.
Xie, W., Yang, Z., Chun, H., 2007. Catalytic properties of lithium-doped ZnO catalysts
used for biodiesel preparations. Ind. Eng. Chem. Res. 46, 7942e7949.