Energy Conversion and Management 151 (2017) 216–226

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Energy Conversion and Management

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

Synthesis and application of waste egg shell derived CaO supported W-Mo MARK
mixed oxide catalysts for FAME production from waste cooking oil: Effect of
stoichiometry
⁎
Nasar Mansira,b,c, Siow Hwa Teoa,b, M. Lokman Ibrahimd, Taufiq-Yap Yun Hina,b,
a
Catalysis Science and Technology Research Centre, Faculty of Science, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia
b
Department of Chemistry, Faculty of Science, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia
c
Department of Chemistry, Faculty of Science, Federal University Dutse, 7156 Dutse, Jigawa State, Nigeria
d
School of Chemistry & Environment, Faculty of Applied Science, University Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: The solid bifunctional tungsten molybdenum supported calcium mixed oxide catalyst (Wx-Moy/CaO 0.3 ≤ x,
Transesterification 0.7 ≤ y) was synthesized by simple wet impregnation method. The prepared catalyst has successfully transes-
Waste cooking oil terified waste cooking oil to biodiesel in a single step reaction process, owing to its acid-base bifunctional
Heterogeneous bifunctional catalyst capacity. Presence of acid and basic sites of the catalyst was believed to promote the catalytic activity for the
Stoichiometry effect
transesterification reaction of high FFA waste cooking oil. The stoichiometric effect of transition bimetallic oxide
Biodiesel properties
loading on acid-base properties, surface area and porosity of the catalyst were studied. The catalytic activity of
the catalyst for transesterification reaction increases with the increase in the W molar weight ratio over Mo from
0.3 to 0.7. The W0.6-Mo0.4/CaO catalyst recorded the highest biodiesel yield of 96.2% under reaction condi-
tions of 15:1 methanol to oil molar ratio, 70 °C reaction temperature, 2 wt% catalyst loading and 2 h reaction
time. The newly synthesized catalysts were characterised by X-ray diffraction (XRD), BET surface area, vapour
pressure scanning electron microscope (VP-SEM), temperature programmed desorption of CO2 and NH3 and
thermal gravimetric analysis (TGA).

1. Introduction properties to that of conventional fuel [12,13]. However, production of

High demand of energy for the production of goods and services was
as a result of rapid population growth in the developing countries and
depleting of conventional fuel reserves worldwide [1–3]. Moreover,
conventional fossil fuel is associated with the environmental issues such
as global warming and Green house gas effects, which could be harmful
to human health and distort the ecosystem [4–5]. These problems,
triggered the search for the renewable energy alternative that would
help in reducing the over dependence on fossil fuel. Biofuels have re-
cently drawn researches attention worldwide as a possible alternative
option to popular fossil fuels [6].
Biofuel is generally referred to as fuel either in liquid or gaseous
form produced from biomass and used as fuel for internal combustion
engines (cars, generators, ships and airplanes) [7]. Among the biofuels,
biodiesel or fatty acid methyl ester (FAME) is now considered as one of
the most promising alternative renewable energy sources to fossil fuel
[5,9–11]. This is due to the availability of the feedstock, biodegrad-
ability, less toxicity and possession of similar physico-chemical
biodiesel in commercial scale remains the major problem today. This is
due to the current employed conventional method, which employs the
utilization of food grade vegetable oil such as palm oil, soybean oil and
cottonseed oil as feedstock [14,15]. These feedstocks would not only
make biodiesel production expensive, but also results to food versus
fuel competition, and consequently hunger. Additionally, the conven-
tional catalytic system adopted the use of homogeneous acid/base
catalysts such potassium hydroxide (KOH), tetraoxo sulphate (vi) acid
(H2SO4) and sodium hydroxide (NaOH) [16,17], which is associated to
separation problems after the reaction.
Homogeneous basic catalysts like KOH and NaOH, though, very
active but are only suitable for food grade feedstock. Similarly, a part
from pollution of the environment through water washing of post re-
action mixture, liquid acid catalysts such as H2SO4 and hydrochloric
acid (HCl), can also cause corrosion to the biodiesel reactors despite
their ability to esterify low grade oils [6]. However, about 70–80% of
total biodiesel production cost depends on the feedstock, hence food
grade feedstock such as palm oil soybean oil are very expensive

⁎
Corresponding author at: Catalysis Science and Technology Research Centre, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
E-mail address: taufiq@upm.edu.my (T.-Y. Yun Hin).

http://dx.doi.org/10.1016/j.enconman.2017.08.069
Received 8 June 2017; Received in revised form 24 August 2017; Accepted 26 August 2017
0196-8904/ © 2017 Elsevier Ltd. All rights reserved.
N. Mansir et al.
[12,18,19]. Beside making biodiesel expensive, homogeneous acid/
base catalysts are difficult to separate from biodiesel after the reaction,
hence require large amounts of water washing, which generates waste
water and ultimately polluting the environment [20–22]. Therefore,
considering these drawbacks, homogeneous acid/base catalyst system
is no longer environmentally benign.
The heterogeneous catalytic system is now employed for biodiesel
production from low quality feedstock such as palm fatty acid distillate
(PFAD), waste cooking oil and jatropha oil [13,23,24]. However, het-
erogeneous catalysts are also far from perfection as they exhibit high
mass transfer resistance effect, hence less reaction efficiency when
compared to the homogeneous catalysts [1]. Nevertheless, hetero-
geneous solid catalysts are easy to separate after the reaction and can be
reused severally before it completely loses its catalytic activity [25,26].
Other advantages include, less corrosive to the production plant, eco-
logically benign and less disposal problem. Moreover, heterogeneous
solid catalysts could be designed to have high activity, selectivity and
stability [27,28]. The aforementioned advantages of solid hetero-
geneous catalyst system reaffirmed its economic viability and sustain-
ability for the commercialization of biodiesel. Heterogeneous catalyst
could either be acid or base. Heterogeneous solid acid catalysts are
identified by their effectiveness for catalyzing low grade feedstock such
as PFAD [29], jatropha oil [30] and waste cooking oil for FAME pro-
duction [31]. Solid acid catalyst derived from transition metal oxides
such as tungsten, molybdenum and zirconia (W Mo and Zr) were re-
ported to have excellent catalytic activity for esterification reaction of
either FFA or waste oils such as PFAD to produce biodiesel [32]. Lit-
erature reported that tungsten oxide can be impregnated on Mo-
lybdenum oxide to form effective catalyst for different reactions such as
esterification and alkylation as a result of their strong acidity [28,33].
However, these catalysts are associated with the generation of water
during the FFA’s conversion to biodiesel and subsequently, results in
leaching and deactivation of the active sites of the heterogeneous solid
acid catalysts. Excessive reaction temperature and longer reaction time
are also considered as the major drawbacks to these catalysts [4].
Moreover, the strong acidity in such catalyst could not allow them to
successfully convert the mixture of triglycerides and FFA to biodiesel
under mild reaction conditions. Heterogeneous solid base catalysts are
considered as good candidates for transesterification reaction of bio-
diesel from triglycerides as they proceeds 4000 times faster than het-
erogeneous solid acid catalysts [34,35]. However, heterogeneous base
catalysts are also limited to certain free fatty acid (FFA) composition, as
feedstock containing more than 3 wt% FFA content cannot be run in a
single transesterification process [36], consequently, two step reaction
processes are necessary before complete conversion of such feedstocks
to biodiesel. This method is considered as a waste of time and resources,
hence making biodiesel difficult and expensive.
Bifunctional heterogeneous catalyst equipped with acid and base
active phase will convert the high FFA (> 3%) feedstock in a single step
reaction through simultaneous transesterification and esterification
reaction process. Calcium oxide (CaO) is the most commonly used
heterogeneous base catalyst. It was reported to possess outstanding
catalytic performance for transesterification reaction [31]. The major
sources of naturally occurring CaO include shells, bones, rocks and
ashes [30]. Waste chicken egg shell is believed to contain more than
95% calcium carbonate (CaCO3) and therefore considered as a good
source of CaO from the biomass [32]. Conjugation of base metal oxide
(CaO) and transition metal oxides in a binary form such as W and Mo
with different acidity and basicity is believed to provide adequate basic
and acidic active sites that would enable the conversion of high FFA
feedstock such as waste cooking oil, jatropha oil, to biodiesel in a single
step reaction process. These catalysts, unlike purely basic catalysts, can
perform simultaneous esterification and transeterification of triglycer-
ides and FFA in the feedstock under mild reaction conditions [37,38].
The simultaneous esterification and transesterification reaction me-
chanism is depicted in Fig. 1.
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Energy Conversion and Management 151 (2017) 216–226
Quite a number of mixed metal oxides heterogeneous catalysts were
reported to be active for the transesterification of low grade feedstock
to biodiesel. This is due to their ability to resist moisture content and
convert high FFA feedstock to biodiesel simultaneously. Previously, it
was established that the stability of the CaO base catalyst could be
enhanced by integrating CaO with other metal oxides such as ZnO and
MgO [39]. Integrating CaO with binary transition metal oxides will
result to high catalytic activity catalyst that can synthesize high quality
FAME from low grade feedstock and significantly increase the stability
of the catalyst. Binary metal oxides have recently received attention as
active metal oxides for transesterification reaction of triglycerides to
biodiesel. This is due to the synergy occurred during the conversion
process, which result from either acidic or basic properties contribution
by the two metal oxides. Teo et al., produced biodiesel from Jatropha
curcas oil using Ca and La mixed catalyst under near supercritical
conditions recording 93% biodiesel yield in just 10 min [10]. Similar
experiment was reported by Wong et al. [15], where solid base CaO-
CeO2 mixed catalyst was synthesized and tested for biodiesel produc-
tion from palm oil achieving 95% FAME yield. Rabiah et al. [40] re-
ported high biodiesel yield of 93% using binary Bi2O3-La2O3 catalyst
from non edible Jatropha curcas oil at optimized reaction condion of
150 °C reaction temperature, 15:1 methanol to oil ratio, 2 wt% catalyst
loading and 4 h reaction time.
In this study, binary transition metal oxides supported on CaO from
waste egg shell with adequate acid and base properties were synthe-
sized using the wet impregnation method. The binary metal oxides were
supported on CaO in order to synthesize new heterogeneous catalyst
with both acid and basic sites that can conveniently convert high FFA
waste cooking oil to biodiesel under mild reaction conditions. The
synthesized catalyst consists of W3+, Mo6+ and Ca2+ ions. The Ca-O
would provide the basic site that is suitable for the conversion of tri-
glyceride to FAME, while W3+ and Mo6+ are believed to render acidic
active phase that can esterify the small amount of free fatty acid in the
waste cooking oil. The catalytic activity and physico-chemical proper-
ties of the synthesized binary oxide supported CaO catalyst were in-
vestigated. The synthesized binary mixed oxide supported CaO catalyst
samples were used for transesterification of waste cooking oil to bio-
diesel. The produce biodiesel was tested for various standard quality
specifications to meet the requirement of ASTM D6751 and EN14214
for biodiesel international standard. Meanwhile, the stability of the
prepared catalyst was investigated through the number of reusability
cycle of the catalyst.
2. Experimental
2.1. Materials
The commercial anhydrous methanol for analysis (Merck 99.7%),
potassium hydroxide pellets for analysis (Merck) and ethyl alcohol
(System 95%), H3PO4.12WO3·xH2O (Sigma Aldrich), and
(NH4)6Mo7O24·4H2O (Merck) were purchased from Fisher Scientific
company. Waste cooking oil (WCO) was obtained from the restaurant in
the Universiti Putra Malaysia. The used oil was filtered using Buchner
Funnel and filter paper to remove the food debris before used for the
reaction. Waste egg shell was obtained from night market in Seri
Serdang, Selangor, Malaysia. All solvents and reagents used were of
analytical grade. Further physico-chemical properties characterizations
of the feedstock (waste cooking oil) were performed to determine the
acid value, FFA content, saponification value, molecular weight and
moisture content based on American Society for Testing and Material
(ASTM) standard, European Standard (EN) and Malaysian palm oil
board (MPOB) official method and the values for the feedstock char-
acterization results are summarized in Table 1.
N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Fig. 1. Simultaneous esterification and transesterification reaction mechanism [1].

Table 1 furnace for 4 h. The same procedure was repeated to prepare W0.3-
Physico-chemical properties of waste cooking oil (WCO). Mo0.7/CaO, W0.4-Mo0.6/CaO, W0.5-Mo0.5/CaO, W0.6-Mo0.4/CaO and
W0.7-Mo0.3/CaO catalyst samples [41].
Description Analysis Standard method

Moisture content (wt.%) 0.6 MPOBa

Saponification value (mg KOH g−1) 187.2 ASTM (D464)b
2.3. Catalyst characterization
Molecular weight (g mol−1) 898.9 ASTM (D464)b
Acid value (%) 11.0 ASTM [D974(00)]b The structure and crystal size analysis of the synthesized hetero-
FFA content (%) 5.5 ASTM [D974(00)]b geneous solid catalyst samples were determined by X-ray diffraction
Fatty acid (XRD) technique. The analysis was performed on a Shimadzu model
XRD6000 power X-ray diffractometer, using Cu, Kα radiation (27.7 kW
Composition (wt.%)
and 30 mA) with wavelength (λ) of 1.54 A, over the 2θ range of 10–80°
Myristic acid (C14:0) 0.70
Palmitic acid (C16:1) 60.1 with a step of 0.04° at screening speed of 2° min−1. The crystallite sizes
Stearic acid (C18:0) 10.8 of the catalyst samples were determined by the Debye-Scherrer's
Oleic acid (C18:1) 27.2 equation.
Linoleic (C18:2) 1.14 The Brunauer-Emmet-Teller (BET) surface area, pore volume and
a pore size distribution analysis of the catalyst samples were performed
MPOB = Malaysian palm oil board official method.
b
ASTM = American society for testing and material. by the multi-point nitrogen adsorption-desorption isotherms (−196 °C)
using a micrometrics ASAP 2020 3Flex version 1.02.
2.2. Catalyst preparation Variable pressure Scanning electron microscope (VPSEM LEO 1455
model) was used to examine the surface morphology of the catalyst.
2.2.1. Calcium oxide catalyst The catalyst samples were coated in gold using a Sputter Coater before
The CaO catalyst was prepared by washing the waste egg shell with been analysed.
hot water to remove the waxy material and other dirt. The raw waste Temperature programmed desorption of carbon dioxide and am-
egg shell was dried in an oven at 100 °C over night. The dried waste egg monia (TPD-CO2 & TPD-NH3) technique were used to evaluate the base
shell was crushed to powder using a milling machine. The obtained and acid sites strength, density and distribution of the synthesized solid
powder was calcined in a furnace at the temperature of 900 °C for 4 h. catalysts, respectively, using a Thermo Finnigan TPD/R/O 1100 series
The obtained CaO catalyst support was kept in the air tired container apparatus equipped with thermal conductivity detector (TCD). During
for further use. acid site distribution analysis of the synthesized solid catalyst, ammonia
is used as a probe gas. The sample was pre-treated under nitrogen flow
at a temperature of 150 °C for 1 h. The NH3 absorption was carried out
2.2.2. Tungsten-Molybdenum based catalyst under the flow of the NH3 stream for 1 h, and then the sample would be
Tungsten-Molybdenum catalyst was synthesized by the wet im- pre-treated again under the flow of helium gas to remove the excess
pregnation method and subsequent calcination in a furnace at a tem- NH3 gas before subjecting to analysis. Meanwhile, the TPD-CO2 was
perature of 650 °C. In typical preparation, the total of 0.7 g in the form used to determine the basicity of the catalyst sample using CO2 as a
of Wx-Moy (x ≥ 0.3y ≤ 0.7) from H3PO4·12WO3·XH2O and probe gas. In both cases, the chemisorptions of NH3 and CO2 were
(NH4)6Mo7O24·4H2O were dissolved in a 50 mL beaker containing dis- carried out by flowing NH3 or CO2 gas at a rate of 30 mL min−1 for 1 h.
tilled water and stirred vigorously for 1 h, after which the resultant The excess NH3 or CO2 was then flushed with helium gas at a flow rate
solution was impregnated onto the powdered CaO (4.93 g) to make the of 30 mL min−1 for 30 min. The NH3 and CO2 desorption subsequently
total of 5 g. The mixture was stirred at 450 rpm for 4 h at room tem- proceeded under the flow of helium as a carrier gas from 50 °C to 900 °C
perature to ensure total homogeneity. The resultant slurry was dried in with a ramp of 10 °C min−1 and soak for 10 min. The amount of des-
an oven at 110 °C for 24 h. The catalyst was then calcined at 650 °C in a orbed NH3 and CO2 from the catalyst sample was detected and recorded

218
N. Mansir et al.
by TCD [42].
While, the thermal stability of the catalyst samples were determined
by thermal gravimetric analysis (TGA). The analysis was carried out
using TGA/SDTA 851, Mattler Toledo, Switzerland, under the air flow
condition and temperature range of 50–1000 °C at a heating rate of
10 °C min−1.
2.4. Evaluation of catalyst activity for transesterification reaction
The catalytic activity of the catalyst was determined by the trans-
esterification of waste cooking oil to biodiesel using methanol. Waste
cooking oil contains both saturated and unsaturated fatty acids
(monocarboxylic acids with trihydric alcohol glycerides). During the
transesterification reaction process, the catalyst assists the conversion
of triglycerides to diglycerides and diglycerides to monoglycerides and
then finally monoglycerides to glycerol and FAME [36].
In a typical reaction process, an appropriate amount of Wx-Moy/CaO
catalyst was added to the reaction mixture containing 10 g of waste
cooking oil and appropriate amount of methanol into the 250 mL round
bottom flask. The reaction mixture was heated to a required constant
temperature under vigorous stirring of 450 rpm for a period of time. At
the end of the reaction process, the catalyst and excess methanol were
separated from the reaction mixture using a centrifuge and a rotary
evaporator, respectively.
2.5. Biodiesel yield analysis
The biodiesel yield quantification analysis was carried out by gas
chromatography (Shimadzu GC-14C) equipped with flame ionization
detector (FID) using methyl heptadecanoate as internal standard. The
FID was connected to a HP-INNOWax polar capillary column with a
length of 30 m and the internal diameter of 0.5 mm. Helium gas with a
flow rate of 1.5 mL min−1 was used as carrier gas. The starting oven
temperature of 150 °C was set and later automatically raised up to
250 °C at a heating rate of 5 °C min−1. The injector and detector tem-
perature were set at 250 °C and 280 °C, respectively. The injector split
ratio was set at 30:1. The hydrogen and air flow rate was set at 450 mL
and 40 mL min−1, respectively. The biodiesel yield was finally com-
puted from Eq. (1) according to (EN 14103) [43].
∑ A−AIS C × VIS
FAME Yield (%) = × IS × 100%
AIS M (1)
where ∑A is the total peak area of the methyl ester in C14 – C18, AIS is
the peak area of the internal standard, Cis is the concentration of
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Energy Conversion and Management 151 (2017) 216–226
Fig. 2. XRD pattern of W-Mo/CaO synthesized catalyst and calcined at
650 °C. ★WO3, ●Ca(OH)2, CaO and ♦MoO3.
internal standard (mg mL−1), VIS stands for the volume of the internal
standard (mL) and Mis the mass of the sample (mg).
2.6. Biodiesel quality assessment
The physico-chemical properties analysis of the produced biodiesel
from the transesterification of waste cooking oil using Wx-Moy/CaO
catalyst was carried out in a chemical laboratory at the institute of
advance technology University Putra Malaysia. The properties of the
produced biodiesel including pour point, water content, flashpoint, acid
value, kinematic viscosity and density were compared with the bio-
diesel standards set by ASTM D6751 and EN 14121.
2.7. Reusability study of the catalyst
The stability of the synthesized bimetallic oxide supported calcium
oxide catalyst was studied by investigating the number of reusability
cycles. The catalyst was used for five successive reaction cycles under
the optimized reaction parameters and the yield of each cycle is re-
corded. The changes in morphology of the used catalyst and that of the
virgin catalyst were studied.
3. Results and discussion
3.1. Catalyst characterization
3.1.1. Structure and crystallography
The structure of the synthesized catalyst was determined by X-ray
diffraction machine (Model 6000, Shimadzu, Japan). The crystal size
was computed using Derby Scherer equation. The XRD patterns of
synthesized W-Mo-CaO mixed catalyst containing various stoichio-
metric compositions of Wx-Moy where x ≤ 0.3, y ≤ 0.7 wt% are de-
picted in Fig. 2. The diffraction patterns showed sharp peaks at various
2θ positions, which are attributed to high crystallinity of the material.
There was formation of W and Mo oxide when the tungsten and mo-
lybdenum were impregnated on CaO composite. The characteristic
diffraction patterns of cubic calcium oxide (JCPDS 00-82-1691) is the
major phase while hexagonal Ca(OH)2 (JCPDS 00-84-1275), tetragonal
WO3 (JCPDS 00-001-0806) and MoO3 (JCPDS files 47-1320) are the
minor phases present in the catalyst as supported by XRD spectra.
Hexagonal Ca(OH)2 was formed as a result of reaction between CaO
and H2O during catalyst synthesis.
The crystallite size of the different stoichiometric ratio of W and Mo
are within the same range with slight differences. This is attributed to
N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Table 2 samples desorbed their CO2 peaks within the strong basicity zone. The
BET surface area, pore volume and pore size and crystal size of W-Zr/CaO catalyst excellent basicity of these catalysts was due to high basic contribution
samples.
from natural CaO oxide (egg shell powder). The variation in basic
Sample BET surface Pore volume Pore size Crystal size density sites among the catalyst samples is attributed to different stoi-
area (m2/g) (cm3/g) (Å) (nm) chiometric composition of W-Mo bimetallic oxides as presented in
Table 3.
CaO 5.4 0.026 194.7 47.477
The acidity of the synthesized catalyst samples measured by TPD-
W0.3-Mo0.7/ 10.0 0.065 261.8 46.421
CaO NH3 is presented in Fig. 4. The TPD-NH3 profile depicts the NH3 des-
W0.4-Mo0.6/ 8.5 0.059 279.2 52.236 orped peaks at various temperature regions ranging from 400 to 450 °C
CaO and 600 to 700 °C. The profile peaks desorbed between 400 and 450 °C
W0.5-Mo0.5/ 7.5 0.064 339.1 52.234 temperature zones are attributed to medium acid strength. Moreover,
CaO
the distinctive NH3 desorption peaks between 600 and 700 °C are at-
W0.6-Mo0.4/ 9.4 0.058 284.1 52.225
CaO tributed to strong acid strength [33].
W0.7-Mo0.3/ 10.2 0.063 241.4 52.234 WO3 contributed in the formation of acid site in the catalyst, while
CaO MoO3 contributed both acid and base sites. W3+ and Mo6+ metal
oxides are Lewis acid sites, which favoured the esterification reaction
[33], while the binary interaction between the surface lattice oxygen
the variability in the stoichiometric composition of W and Mo over CaO
and Ca species induced the synergetic effect that assist the formation of
as shown in Table 2.
strong basic sites. W3+ and Mo6+ operate as electron donors and
therefore assisting the interaction of reactant molecules with catalyst
3.1.2. Surface area measurement surface [44]. Moreover, the amount of basicity increased when the W to
The specific surface area measurement of the prepared catalyst Mo mass ratio increases from 0.3 to 0.6 except 0.7 which shows slight
samples was performed by Brunaurer Emmet Teller technique using decline in basic site density value Table 4. W0.6-Mo0.4/CaO catalyst
micrometric instrument (3Flex Version 1.02). The analysis involved sample recorded the best FAME yield of 96.2%. This might be due to the
pore size and pore volume determination of the samples as depicted in high basic site density of 1365 µmol/g and good acid site density of
Table 2. The specific surface area of raw CaO and Wx-Moy/CaO catalyst 3738 µmol/g which were found best to achieve 96.2% FAME from
at various stoichiometric compositions (0.3 ≤ x, y ≤ 0.7) were mea- waste cooking oil.
sured. The obtained results of W0.3-Mo0.7/CaO (10.0 m2 g−1) showed
an increase in surface area of the catalyst when compared to that of raw 3.1.4. Surface morphology characteristic
CaO (5.4 m2 g−1). This might be as a result of the contribution of The micrographs of mixed Wx-Moy/CaO catalyst samples with
specific surface area from the W-Mo bimetallic oxide. Subsequent variable W to Mo mass ratio are depicted in Fig. 4(a-e). The VPSEM
loadings of W0.4-Mo0.6 and W0.5-Mo0.5 over the surface of CaO showed a images depict the agglomerated particles peculiar to cubic CaO struc-
slight decrease in specific surface area, having 8.5 m2 g−1 and ture as well as irregular shapes of WO3 and MoO3 (Fig. 5a-c). The
7.5 m2 g−1, respectively. The decrease in specific surface area of these images undergoes slight change in surface morphology from large ag-
samples might be due to high stoichiometric composition of WO3. This glomerated spheres to a bit homogeneous spherical structures when the
was supported by further decrease in the surface area to 7.5 m2 g−1, mass ratio of W-Mo over CaO surface increases from W0.5-Mo0.5
when the loading was W0.5-Mo0.5. The specific surface area increases to (Fig. 5c) to W0.6-Mo0.4 and W0.7-Mo0.3 (Fig. 5d and e). The non-uniform
9.4 m2 g−1 and 10.2 m2 g−1 when the stoichiometric compositions of structure (spherical and cubic) of the particle size distribution might
the W-Mo bimetallic oxide changes to W0.6-Mo0.4 and W0.7-Mo0.3, re- formed either as a result of high dispersion of WO3 and MoO3 particle
spectively, which might be due to high loading of W oxide. The highest size over the CaO surface or merging the particle size structures of WO3,
specific surface area recorded by W0.7-Mo0.3 sample is attributed to MoO3 and CaO together during the catalyst synthesis [41].
high surface area contribution from MoO3 and WO3. Moreover, the pore
size and pore volume of the synthesized catalyst samples follow similar 3.1.5. Thermal gravimetric analysis
variation trends to that of their respective specific surface areas. This The thermo gravimetric analysis (TGA) was carried out to measure
behaviour is attributed to variation of stoichiometric compositions of the thermal stability of the synthesized catalyst samples. Fig. 6 depicted
bimetallic oxides over the surface of CaO. the TGA profile of the catalyst samples containing five variable stoi-
chiometric compositions of W-Mo over the surface of CaO. The TGA
3.1.3. Temperature programmed desorption of carbon dioxide and patterns of all the catalyst samples followed similar trend with almost
ammonia equal weight loss at the same temperature regions. However there is
The acidity and basicity of the synthesized catalyst samples were small disparity in the thermal stability of the catalyst samples, showing
analysed by temperature programmed desorption using ammonia and W0.3-Mo0.7/CaO having least thermal stability than W0.7-Mo0.3/CaO
carbon dioxide as probe gases (TPD-NH3 and TPD-CO2), respectively. In sample. The thermal stability trend increases with the increase in mass
both cases, during the TPD analysis, the peaks desorbed at high tem- weight ratio of W to Mo over CaO as can be seen in Fig. 6.
perature regions signifies the high strength of the bonding of the active This behaviour might be as a result of thermal stability variation
sites on the support while those at lower temperature zones signifies between the chemical composition H3PO4.12WO3·xH2O and
low strength of the bonding of active sites, hence low acidity or basi- (NH4)6Mo7O24·4H2O salts. The weight loss of about 5 wt% observed
city. The peaks desorbed at the temperature region below 300 °C are between 0 and 200 °C was attributed to elimination of loosely attached
attributed to weak acid or basic strength, those desorbed between 300 water (H2O) and carbon dioxide (CO2) absorbed from the atmosphere
and 500 °C are considered as moderately basic or acid while the peaks [45–47]. There was no much weight loss observed between 200 and
observed at the temperature zone above 500 °C are regarded as strongly 400 °C. Moreover, about 18 wt% weight loss was observed by all the
acidic or basic [40]. The basic property of the synthesized catalyst catalyst samples between 400 and 650 °C temperature regions. This
samples (W0.3-Mo0.7/CaO, W0.4-Mo0.6/CaO, W0.5-Mo0.5/CaO, W0.6- behaviour is attributed to decomposition of H3PO4.12WO3·xH2O and
Mo0.4/CaO and W0.7-Mo0.3/CaO) determined by TPD-CO2 is depicted in (NH4)6Mo7O24·4H2O salts, which results in the formation of stable
Fig. 3. The TPD-CO2 profile of the synthesized samples Wx-Moy /CaO metal oxides of tungsten and molybdenum [48]. Based on the TGA
(x ≥ 0.3 and y ≤ 0.7) presented their CO2 desorption peaks at various analysis of the catalyst samples, 650 °C was found to be the suitable
temperature, ranging from 600 to 750 °C. This shows that all the five temperature for the calcination of these catalyst samples (Fig. 6).

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N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Fig. 3. TPD-CO2 of W-Mo/CaO catalysts.

Table 3 Although the W-Mo/CaO catalyst was not reported for transester-
Acid and basic site densities of the synthesized catalyst samples. ification of waste cooking oil to biodiesel before, however, the catalytic
activity of W0.6-Mo0.4/CaO catalyst was compared with similar studies
Catalyst sample Basic site density Acid site density FAME Yield
(µmol/g) (µmol/g) (%)
from related catalysts for the transesterification of waste cooking oil.
The synthesized catalysts of this study displayed better FAME yield
W0.3-Mo0.7/CaO 1334 3085 91.0 under the most economical reaction conditions (Table 4).
W0.4-Mo0.6/CaO 1336 2989 92.4
W0.5-Mo0.5/CaO 1361 3731 94.0
W0.6-Mo0.4/CaO 1365 3738 96.2
3.3. Evaluation of catalyst reusability and leaching test
W0.7-Mo0.3/CaO 1322 3901 95.0
The reusability of the catalyst was studied by employing the pre-
pared catalysts for five successive reaction cycles under the reaction
3.2. Catalytic activity in simultaneous transesterification and esterification conditions of 15:1 methanol to oil molar ratio, 2 wt% catalyst loading,
70 °C reaction temperature and 2 h reaction time (Fig. 8). Leaching test
3.2.1. Effect of stoichiometric composition of W and Mo was conducted using EDX (Table 5a) and AAS (Table 5b) analysis on
The catalytic activity of the synthesized catalyst samples with var- either catalyst or biodiesel produced in order to examine the influence
ious W to Mo stoichiometric ratio compositions were tested on trans- of W-Mo incorporation on CaO surface toward the stability of catalyst.
esterification of waste cooking oil. The various W to Mo ratios over CaO The excellent stability of these catalysts, is as a result of strong inter-
are in the form of W0.3-Mo0.7/CaO, W0.4-Mo0.6/CaO, W0.5-Mo0.5/CaO, action of transition metal oxides (i.e. W and Mo) on the surface of CaO,
W0.6-Mo0.4/CaO and W0.7-Mo0.3/CaO. The catalytic activity of these which reduces the leaching effect of Ca ion during transesterification
catalyst samples is presented in Fig. 7. Although all the catalyst samples reaction as presented in Table 5 [31]. It is evidently proved that the
recorded excellent biodiesel yield of at least 90%, moreover, W0.6- calcium active content leached away from the catalyst samples reduced
Mo0.4/CaO achieved the best biodiesel yield of 96.2% under mild re- (2.30–1.59 mg L−1) as a result of spontaneous increased in W-Mo
action parameters. oxides loading on crystal structure of CaO (Table 5b). EDX analysis of
This might be attributed to the possession of the best basic and good fresh and spent (5th run) W0.6-Mo0.4/CaO catalysts exhibited a gradual
acid site densities during the TPD-CO2 and TPD-NH3 analysis (Table 3), decrease in Ca concentration from 34.81 to 31.90%, indicating less
that are appropriate for the transesterification of the utilized waste leaching of active metal into the reaction medium, which is in the same
cooking oil to FAME. Moreover, possession of the most appropriate manner with results obtained from AAS analysis. Surprisingly, there is
dispersion of stoichiometric ratio composition of W and Mo over the no significant loss of W3+ and Mo6+ ions in the biodiesel product
surface of CaO is another probable factor for the remarkable biodiesel (Table 5a), respectively. Hence, it is implied that the presence of in-
yield recorded by this sample. The correlation of the CO2 absorbed by teraction between active phases of the WO3-CaO–MoO3 mixed metal
the catalyst samples and FAME yield is also depicted in Fig. 7. oxide could stabilize active phases of the catalyst in order to reduce its

Fig. 4. TPD-NH3 of W-Mo/CaO catalysts.

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N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Table 4
Summary of the related studies using different catalysts.

Catalyst sample Synthesis method of catalyst Feedstock and FFA level (%) Reaction conditions FAME yield Ref.

CaO Calcination Waste cooking oil (FFA < 1) 65 °C, 5 wt%, 2 h 86.0% [49]
CaO-ZrO2 Co-precipitation Waste cooking oil (FFA < 3) 65 °C, 10 wt%, 30:1, 2 h 92.1% [31]
Mo-Mn/ˠ-Al2O3-15 wt% Impregnation Waste cooking oil (FFA 1.64) 100 °C, 27:1, 4 h 91.4% [37]
W0.6-Mo0.4/CaO Impregnation Waste cooking oil (FFA 5.5) 70 °C, 2 wt% 2 h, 15:1 96.2% This study

leaching into the reaction medium. This observation was similar to
results reported [50–52].
In addition, the stability of the catalytic activity of the synthesized
W0.6-Mo0.4/CaO catalyst was evaluated by reusability method. The
reusability of the catalyst was studied by employing the catalyst sample
for five successive reaction cycles under a similar condition as
mentioned in Fig. 8. Meanwhile, at the end of each reaction cycle, the
catalyst was removed and washed thoroughly with hexane and then
methanol to clean the catalyst surface from the polar and non polar
components [53]. The catalyst was used for the subsequent biodiesel
reaction cycles, recording outstanding 90% biodiesel yield in the 5th
cycle. The biodiesel yield content was dropped by 6.2% in the fifth

Fig. 5. VPSEM images of (a) W0.3-Mo0.7/CaO (b) W0.4-Mo0.6/CaO(c) W0.5-Mo5/CaO (d) W0.6-Mo0.4/CaO (e) W0.7-Mo0.3/CaO.

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N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Fig. 6. Thermal gravimetric analysis of the synthesized

catalyst samples a = W0.3-Mo0.7/CaO, b = W0.4-Mo0.6/
CaO, c = W0.5-Mo0.5/CaO, d = W0.6-Mo0.4/CaO and
e = W0.7-Mo0.3/CaO.

FAME YIELD K2 ĂďƐŽƌƉƟŽŶ Fig. 7. Correlation between catalytic activity and CO2 gas absorbed.

100 1400
95 1350

KϮĂďƐŽƌƉƟŽŶ;ђŵŽůͬŐͿ
90 1300
85 1250
&DLJŝĞůĚ

80 1200
;йͿ

75 1150
70 1100
65 1050
60 1000
55 950
50 900
0.3 0.4 0.5 0.6 0.7
;tͬDŽDĂƐƐƌĂƟŽͿ

Fig. 8. FAME yield and reusability cycles of the synthesized W0.6-

Mo0.4/CaO catalyst.

cycle, which could be attributed to slight loss of catalytic active sites of
the catalyst through the blockage of the active sites by the FAME and
some water molecules. The results of AAS (Table 5c), depicted that the
concentration of dissolved Ca2+ from W0.6-Mo0.4/CaO catalyst (first to
fifth cycle) into biodiesel were insignificant, with concentration of
calcium in the range of 0.03–2.45 mg L−1. However, these minor lea-
ched metal ions complied with the standard EN 14214 specification,
indicating the produced biodiesel was suitable to be used as vehicle
fuel. The concentration of Ca decreased significantly in biodiesel with
subsequent reaction cycles, and reached about 0.3–2.4 ppm after the
5th batch. This decreased amount of the leached species was attributed
to the good interaction between Ca with W and Mo respectively, which
is due to the vacancies created by substitution of Ca2+ into W3+ and
Mo6+ ions via electron transfer [54–56].
On the other hand, to investigate the changes in the morphological
properties after the 5th reusability cycle, the used catalyst was char-
acterized again using VPSEM. The images of the used and virgin (W0.6-
Mo0.4/CaO) catalyst were compared as shown in Fig. 9a and b. Hence,
the stability of the catalyst was confirmed.
3.4. Biodiesel quality assessment
The fuel properties of waste cooking oil produced biodiesel were
analysed based on the accepted biodiesel standard of American Society
for Testing Materials (ASTM D6751) and European standard (EN
14214). Table 6 presented a comparison between the fuel properties of

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N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

Table 5
Leaching test of Ca2+ into the produced FAME.

(a) Concentration (%)

a b b b b b
Catalyst Ca W Mo C O

Fresh W0.6 Mo0.4/CaO 34.81 4.45 2.50 13.96 44.30

SpentW0.6-Mo0.4/CaO 31.90 4.45 2.47 14.40 47.25

(b)

a c
Fresh catalyst Absorbance Ca2+ concentration FAME yield (%)
(mg L−1)

W0.3-Mo0.7/CaO 0.045 2.30 ± 0.12 91.0

W0.4-Mo0.6/CaO 0.044 2.25 ± 0.15 92.4
W0.5-Mo0.5/CaO 0.043 2.20 ± 0.18 94.0
W0.6-Mo0.4/CaO 0.031 1.80 ± 0.11 96.2
W0.7-Mo0.3/CaO 0.030 1.59 ± 0.13 95.0

(c)

a c
Biodiesel Ca2+ concentration
(mg L−1)

First cycle 2.45 ± 0.18

Second cycle 0.45 ± 0.16
Third cycle 0.36 ± 0.21
Forth cycle 0.35 ± 0.12
Fifth cycle 0.33 ± 0.11

a
Transesterification condition: reaction temperature of 70 °C, 2 h reaction time, 2 wt% of catalyst and methanol/oil ratio of 15:1.
b
Metal dissolution in biodiesel measured by EDX.
c
Ca metal dissolution in biodiesel measured by AAS.

waste cooking oil derived biodiesel using W-Mo/CaO catalyst and the
ASTM biodiesel standard properties values reported by [57].
3.4.1. Kinematic viscosity
Biodiesel fuel is expected to have lower viscosity when compared to
vegetable oils. Lower viscosity is needed for biodiesel in order to pre-
vent or reduced engine deposition [58]. The kinematic viscosity of
biodiesel is designed to be measured at 40 °C according to ASTM and
EN international standards. The kinematic viscosity of waste cooking
oil derived biodiesel was found to be 5.63 mm2 s−1. This is within the
range (1.9–6.0 mm2s−1) specified by ASTM D6751 and EN14214 bio-
diesel standards. Meanwhile, no additional modification of viscosity is
required.
3.4.2. Pour point
The pour point is the key cold flow properties of biodiesel fuel,
which is defined as the lowest temperature at which the fluid stop
flowing. During the analysis, the biodiesel sample was heated to 45 °C
in water bath and allow to cool down at room temperature (25 °C), after
which, the sample was taken and inserted into the pour point equip-
ment at 0 °C. The temperature of the equipment will be reducing to sub
zero levels and the sample flow was been checked at different time
interval. At the end of the analysis, the temperature at which the waste
cooking oil derived biodiesel stops flowing was found to be −9 °C. The
result is in agreement with the specified range (−15 to 9) of ASTM
D6751.

Fig. 9. The VPSEM images of W0.6-Mo0.4/CaO, (a) Virgin catalyst (b) Used catalysts.

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N. Mansir et al. Energy Conversion and Management 151 (2017) 216–226

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