Fuel 142 (2015) 38–45

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Fuel
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Synthesis of waste cooking oil-based biodiesel via effectual recyclable

bi-functional Fe2O3AMnOASO2 4 /ZrO2 nanoparticle solid catalyst

Fatah H. Alhassan a,b, Umer Rashid c, Y.H. Taufiq-Yap a,b,⇑

a
Catalysis Science and Technology Research Center, Faculty of Science, Universiti Putra Malaysia, UPM 43400, Serdang, Selangor, Malaysia
b
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, UPM 43400, Serdang, Selangor, Malaysia
c
Institute of Advanced Technology, Universiti Putra Malaysia, UPM 43400, Serdang, Selangor, Malaysia

h i g h l i g h t s g r a p h i c a l a b s t r a c t
2
 Fe2O3AMnOASO4 /ZrO2 synthesized
first time in nanoscale to produce
biodiesel.
 The catalyst was prepared by
impregnation method.
 The catalyst activity was showed by
high density of acid sites.
 The maximum yield was achieved at
96.5 ± 0.02 (wt%), under optimized
conditions.

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

Article history: The ferric–manganese doped sulfated zirconia nanoparticle solid acid catalyst was prepared through the
Received 14 August 2014 impregnation reaction followed by calcination at 600 °C for 3 h. The characterization was performed
Received in revised form 14 October 2014 using X-ray diffraction (XRD), Temperature programed desorption of NH3 (TPD-NH3/CO2), Thermal
Accepted 16 October 2014
gravimetric analysis (TGA), Fourier Transform Infrared spectrometer (FT-IR), Brunner–Emmett–Teller
Available online 4 November 2014
(BET) surface area measurement, Energy dispersive X-ray spectroscopy (EDS), Transmission electron
microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). In addition, the dependence of the bio-
Keywords:
diesel yield on the reaction variables, such as reaction temperatures, catalyst loading, as well as the molar
Ferric–manganese doped sulfated zirconia
(FMSZ)
ratio of methanol/oil and reusability, were also investigated. The catalyst was reused six times without
Waste cooking oil loss in its activity with the maximum yield of 96.5 ± 0.02% achieved under the optimized conditions of
FAME’s (fatty acid methyl esters) the reaction temperature of 180 °C; stirring speed of 600 rpm, 1:20 M ratio of oil to alcohol and 3 wt/
Crystallite size wt% catalyst loading. Additionally, the fuel properties of producing biodiesel from waste cooking oil were
Scherrer’s relationship investigated and compared with those of the American and European standards.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction owing to its typical properties, such as non-toxicity, biodegradabil-

The exploration of other energy resources has attracted a lot of
consideration due to the increase of worldwide energy demands,
green and political worries on atmosphere contamination
originated by the ignition of petroleum oils [1]. Biodiesel has
received great awareness worldwide as a source of substitute fuel
⇑ Corresponding author at: Catalysis Science and Technology Research Center,
Faculty of Science, Universiti Putra Malaysia, UPM 43400, Serdang, Selangor,
Malaysia. Tel.: + 60 3 89466809; fax: + 60 3 89466758.
E-mail address: abuohamid9090@gmail.com (Y.H. Taufiq-Yap).
ity, essentially free sulfur and less release of CO gas [2,3].
Moreover, biodiesel has a higher flash point, better cetane number
and less exhaust emission [4]. Recently, biodiesel has been
economically possible in the fuel market as a fossil-diesel alterna-
tive. In fact, it could be applied to the current compression ignition
vehicle engines with no alteration [4,5]. Yet, the raw material price
has been considered as a big percent of the direct biodiesel
manufacturing cost [3]. Hence, the low cost acidic oil feedstocks
are considered as the best sources which contribute in decreasing
the industry budget of the biodiesel.

http://dx.doi.org/10.1016/j.fuel.2014.10.038
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
 F.H. Alhassan et al. / Fuel 142 (2015) 38–45
Spent cooking oil feedstock could be a further inexpensive feed-
stock for the preparation of spent cooking oil-based biodiesel [6].
The utilization of a solid catalysis system on the way to reinstate
a liquid system would be expected to beat problems related to
liquid catalysis which contributes in the synthesization of spent
cooking oil based-biodiesel since it would offer an additional
eco-friendly and efficiently realistic procedure due to the simplic-
ity of purification and reusability [7]. Recently, solid acid catalysts
have been used widely in industry since they can overcome many
of the defects of the liquid ones. The strong acidity of the solid acid
catalysts has attracted much attention owing to their capacity to
enhance many operations, such as esterification, cracking, alkyl-
ation as well as isomerization [8,9].
However, relatively a lot of published papers about the applica-
tion of developed solid catalysis systems in the field of biofuel syn-
thesis consist of sulfated metal oxides [10], zirconia MoO3 [11],
sulfated zirconia, WO3/ZrO2, SO2 2
4 /SnO2, SO4 /SnO2ASiO2, SnO2/
SiO2, tungstated zirconia, and WO3/MCM-14 [12]. Nonetheless,
mainly almost all of the preceding investigations have been con-
centrated in the conversion of free fatty acid and little has been
carried out on the transformation of triglyceride employing the
solid acid catalysts for producing biodiesel [7].
The most important advantage of acidic heterogeneous
catalysts is a simultaneous conversion of low-priced acidic oil feed-
stock into a high quantity of biodiesel. For example, Xie and Yang
[13] investigated the activity of the silica-organo sulfur acidic cat-
alyst with the triglyceride of soybean and it has been found that a
high yield of soybean-based biodiesel was obtained within 60 h at
the reaction temperature of 150 °C. Meanwhile, Fu et al. [14] and
Jitputti et al. [15] described studies about the biodiesel preparation
via sulfated zirconia and zirconia and they found that around 86.3
and 49.3 wt% methyl ester yields were obtained, respectively.
However, the leaching of sulfur into the product was found to
reduce the stability of the catalyst.
A review of many published articles concerning the application
of acidic heterogeneous catalysts in the field of the biofuel industry
confirmed that no earlier effort was reported up to now regarding
the production of spent cooking oil based-biodiesel employing the
ferric–manganese doped sulfated zirconia solid catalyst. The key
point of this research has been the preparation of the Fe2O3-
AMnOASO2 4 /ZrO2 solid catalyst for the synthesis of used cooking
oil based-biodiesel. The Fe2O3MnOSO2 4 /ZrO2 catalyst had been
synthesized through the impregnation technique and investigated
utilizing XRD, TGA, TPD-NH3, TPD-CO2, XPS, FT-IR, BET, EDS and
TEM. Moreover, the influence of the reaction parameters contain-
ing the stoichiometric ratio of the reactants, quantity of the cata-
lyst, duration, temperature of the operation and recyclability
have also been evaluated.
2. Experimental
2.1. Materials
A sample of the waste cooking oil was obtained from a local
market in South city, Malaysia. A total of 7.5 kg of spent oil was
employed for the optimization of the biodiesel production process.
The materials: ferric nitrate nonahydrate, manganese nitrate tetra-
hydrate, ammonium sulfate, zirconium oxychloride and ammo-
nium hydroxide (30%), were obtained from (Sigma–Aldrich,
Malaysia).
2.2. Pre-treatment of waste cooking oil
Initially, the pre-treatment of the waste oil was carried out
through filtration to remove the cooking debris and then heated
39
to around 105 °C for 6 h to remove the water. Furthermore, the free
fatty acid (FFA) content was evaluated according to the standard
AOCS method (1997), F 9a-44 [16,17].
2.3. Characterization of the waste cooking oil
Evaluation of the acid number, saponification value and free
fatty acid content of the waste cooking oil was conducted accord-
ing to the standard AOCS methods [17,18].
2.4. Catalyst preparation
To prepare the catalyst, 15 g of hydrated zirconyl oxychloride
ZrOCl2 were dissolved in about 300 ml of deionized water and a
drop wise addition of 7.9 g of 30% aqueous solution of ammonia
resulted in the precipitation. A necessary amount of ammonia solu-
tion was added so that the pH value could be adjusted to be
approximately in range of 9–10.The precipitate was aging for
12 h, filtered by vacuum and washed several times until a negative
test of chloride ion was achieved and then drying for about 24 h at
120 °C.
Fe(NO3)3  9H2O (0.576 g), Mn(NO3)2  4H2O (0.1215 g) and
ammonium sulfate (0.2128 g) were dissolved in about 300 ml of
deionized water in amounts corresponding to the desired stoichi-
ometry. The solution was added dropwise under vigorous stirring
into zirconium oxyhydroxide solution. The mixture was left under
vigorous stirring at room temperature for 4 h and hence dried out
at 120 °C for 12 h finally the product calcined for 3 h to 600 °C.
[17,19].
For the preparation of the zirconia the obtained (zirconyl oxy-
hydroxide) after drying for 24 h at 120 °C is then calcined at
600 °C for 3 h. While for the preparation of the sulfated zirconia,
the same method was followed except that, the ferric nitrate and
manganese nitrate solution was not added.
2.5. Catalyst characterization
The powder X-ray diffraction analysis was performed using a
Shimadzu diffractometer model XRD 6000. The diffractometer
using Cu-Ka radiation generated by Philips glass diffraction X-ray
tube broad focus 2.7 kW type at ambient temperature. The crystal-
lite size D of the samples was calculated by the Debye–Scherrer’s
relationship [20–22].
D ¼ 0:9k=ðb cos hÞ
where D was the crystallite size, k was the incident X-ray wave
length, b was the full width at half-maximum, and h was the diffrac-
tion angle.
The density of the active sites and acid strength of the catalyst
was measured by the temperature programed desorption tech-
nique using NH3 as the probe molecule. The TPD-NH3 experiment
was performed using a Thermo Finnigan TPDRO 1100 apparatus
equipped with a thermal conductivity detector. Approximately
0.1 g of catalyst was placed in the reactor, treated under N2
(20 ml min1) at 150 °C for 45 min. NH3 in helium gas was ramped
at 1 °C min1 for 60 min. The purging with N2 was performed at
room temperature for 55 min to remove NH3 in the gas phase.
The analysis of NH3 desorption was then studied between 50 °C
and 950 °C under helium a flow (15 °C min1, 20 ml min1) and
detected by a thermal conductivity detector.
The basicity of the catalyst was measured by using carbon diox-
ide (CO2) as a probe gas. The adsorption desorption of the CO2 fol-
lowed the same steps as the TPD-NH3 procedure. The amount of
acidity-basicity of the catalyst was assessed upon the consider-
ation of the largest integrated area of the peak of the NH3/CO2
graph. However, the temperature for the maximum peak (Tmax)
40 F.H. Alhassan et al. / Fuel 142 (2015) 38–45

at which desorption of NH3/CO2 took place was used to determine
the feature and acid/basic site distribution of active centers for the
catalysts.
The thermal stability of the catalyst was examined by using a
Mettler Toledo TG-SDTA apparatus (Pt crucibles, Pt/Pt–Rh thermo-
couple), with the purge gas (nitrogen) flow rate of 30 ml min1 and
the heating rate of 10 °C min1 from room temperature to 1000 °C.
Identification of the functional group on the surface of the
catalyst was performed via the Fourier Transform Infrared (FTIR)
analysis PerkinElmer spectrometer model 100 series.
Scanning electron microscopy with energy dispersive X-ray
spectroscopy (SEM-EDS) was used to obtain information about
the morphology and chemical composition of the samples. The
quantitative chemical composition of the prepared ferric–manga-
nese doped sulfated zirconia acid catalyst was characterized using
energy dispersive X-ray spectroscopy (EDS) model (JSM-6400) for
the elemental chemical analysis.
TEM (Hitachi H-7100, Japan) was also used to observe the crys-
tal shape. For the TEM analysis, the powder was dispersed in
deionized water, dropped onto carbon-cover copper grids placed
on a filter paper and dried at room temperature.
The specific surface area of the catalysts was measured using
the Brunauer–Emmer–Teller (BET) method with nitrogen adsorp-
tion at 196 °C. The measurement was performed using a Thermo
Fisher Scientific S.p.A (model: SURFER ANALYZER) nitrogen
adsorption–desorption analyzer.
The XPS spectra were obtained using a modified AXIS ULTRA
DLD (KRATOS) photoelectron spectrometer, equipped with a hemi-
spherical analyzer. For excitation, AlKa (1486.6 eV) radiation was
used. The analyzer was operated in the fixed analyzer transmission
mode at 40 eV pass energy. The X-ray gun was operated at 4 mA
emission current and 15 kV acceleration voltages. Samples were
pre-treated under vacuum (133.32 Pa) for 2 h before measure-
ments were taken. The base pressure of the analyzer chamber
was 1  109 Torr; during data collection, the pressure was always
<133.32 Pa. Binding energy (BE) corresponding to C 1s, Zr 3d, Fe 2p,
Mn 2p, S 2p and O 1s were measured. All binding energies were
relative to the C 1s peak taken as 284.5 eV.
2.6. Simultaneous methanolysis of spent cooking oil
The simultaneous methanolysis process of waste cooking oil
containing 17.5.% free fatty acids were carried out using the
prepared zirconia, sulfated zirconia and ferric–manganese doped
sulfated zirconia acid catalyst in the BERGHOF high pressure labo-
ratory reactor. A certain amount of catalyst, methanol and oil were
added to the reactor. The reaction was started by stirring it at
600 rpm and heating it to the specified temperature and time.
The reaction mixture was then cooled to room temperature and
separated by a centrifuge (Kubota 4200) at 600 rpm for 15 min.
CHSN-932 elemental analyzer, BaCl2AKOH titration and AAS
analysis.
2.9. Fuel properties
The fuel properties of FAME’s were evaluated using the subse-
quent ASTM methods: cloud point (ASTM D2500), pour point
(ASTM D97), kinematic viscosity (ASTM D445), flash point (ASTM
D93) and density (ASTM D5002). Triplicate determinations were
performed for every experiment and the data have been presented
as mean ± standard deviation.
3. Results and discussion
3.1. Characterization of the waste cooking oil
The assessment of the physico-chemical properties of the waste
cooking oil revealed that the following values (0.920 g/cm3,
33.0 mm/s2, 17.5% and 173.0) were found for the density, kine-
matic viscosity, free fatty acid as well as saponification number,
respectively.
3.2. FAME’s determination through the GC analysis
The GC results have indicated that FAME’s showed the lowest
percentage of saturated fatty acids (42.23%) in comparison to
unsaturated fatty acids (54.27%). The fatty acids, reported in
FAME’s, included Myristic acid (C14:0), palmitic acid (C16:0), pal-
mitoleic acid (C16:1), stearic acid (C18:0), oleic acid (C18:1) and
Linoleic acid (C18:2).
3.3. Physico-chemical properties of Fe2O3AMnOASO2
4 /ZrO2
The powder X-ray diffraction technique has been employed to
investigate the crystal structure of the Fe2O3AMnOASO2 4 /ZrO2
and zirconia (Z) catalysts calcined at 600 °C for 3 h as shown in
Fig. 1, in which the monoclinic phase was dominated the tetrago-
nal phase in the XRD pattern of ZrO2. In addition, the diffraction
peaks having 2h = 17.5, 24.1, 28.2, 31.5, 34.4, 35.4, 38.6, 40.7,
44.8, 45.5, 49.3, 54.1, 55.7, 57.2, 62.8, 65.7°) (JSPDS file No: 00-
007-0343 ZrO2) were attributed to the monoclinic phase while that
located at 2h = 50.1 and 60.2° (JSPDS file No: 00-014-0534 – Zirco-
nium oxide) were assigned to the tetragonal phase. Additionally,
the pattern for the FeAMn-doped sulfated zirconia (FMSZ) catalyst
consisted of only tetragonal ZrO2 of the metastable phase located
at 2h = 30.2, 34.7, 50.1, 60.2° (JSPDS file No: 00-014-0534 – Zirco-
nium oxide) [24]. However, the peak corresponding to the

2.7. Product analysis

The analysis of the FAME’s contents was carried out using gas
chromatography (GC) as per published work [15,17,23].

2.8. Investigation of the reusability and leaching of the catalysts

The catalysts, separated from the reaction mixture through cen-

trifuge at 600 rpm for 20 min. and then filtrated, were initially
washed with hexane to remove non-polar compounds, such as
methyl esters, on the surface. Furthermore, the catalyst was
washed with methanol to remove polar compounds, such as glyc-
erol and finally dried at 105 °C for 6 h. The leaching of the catalysts Fig. 1. XRD patterns of FMSZ (FeAMnASO4/ZrO2) and Z (ZrO2) catalysts calcined at
into the reaction mixture was investigated by using the Leco 600 °C for 3 h (O) monoclinic phase; () tetragonal phase.
 F.H. Alhassan et al. / Fuel 142 (2015) 38–45
monoclinic phase was absent in the ferric–manganese doped
sulfated zirconia XRD pattern signifying the stabilization of the
tetragonal phase. The absence of the characteristic peaks matching
Fe2O3 and MnO implies that the metal oxides were well distributed
in the surface of the zirconia. The dispersion of Fe2O3 and MnO par-
ticles caused the stabilization of the tetragonal phase and also
imparted higher surface area [25].
On the other hand, to identify the influence of the sulfate
amount on the ferric–manganese-doped sulfated zirconia quanti-
tatively, the crystallite sizes of zirconia and FMSZ were obtained
based on Debye–Scherrer’s equation. The results reveal that the
crystallite sizes of the zirconia (Z) and FMSZ catalysts were
reduced upon the addition of sulfate to the zirconia to become
25.5 and 14.0 nm for zirconia (Z) and FMSZ, respectively. This
might be assigned to the sulfate species, which remains bounded
to the catalyst surface, inhibiting the development of the zirconia
and hence, is in agreement with the oxides of titanium and tin
[26]. The reduction in the size of the particles could be described
through an assumption that stated, ‘‘the dispersed ferric oxide
and manganese oxide particles, along with the sulfate species on
the surface of the zirconia, avoid the agglomeration of metal oxides
and zirconia throughout the calcination time [27].
The thermo-gravimetric curve of the FMSZ catalyst has shown
in Fig. 2, that the weight losses initiated by the thermo-gravimetric
analysis consent strongly with the products generated via the
calcination of ferric nitrate and manganese nitrate salt treated sul-
fated zirconia to the different oxides of Fe, Mn and sulfate [28].
Therefore, the heating events in the sample below 620 °C were
assigned to the elimination of the physisorbed water, dehydroxyla-
tion progression of ZrO(OH)2 and the decomposition of ferric and
manganese nitrates; while, the second major weight loss at a
higher temperature began at about 673 °C and ended at 926 °C
and referred to the decomposition of the sulfate group [29–31].
The TPD-NH3 analysis showed that, the FMSZ catalyst had two
desorption peaks. The first one appeared around 482 °C; while
the second was detected at about 761 °C, and these two classes
of temperature peaks were attributed to moderate and strong acid
strength, corresponding to a density of active centers of
4318.4 lmol as well as 630.4 lmol and 1154.0 lmol for zirconia
and sulfate zirconia, respectively.
Moreover, the ferric–manganese sulfated zirconia (FMSZ) also
showed a basic character when analyzed via the TPD-CO2 tech-
nique. The TPD-CO2 analysis revealed a temperature peak around
737 °C for the FMSZ catalyst specifying the existence of strong base
centers on the FMSZ catalyst with a density of 1519.0 lmol of CO2/
g indicating that the FMSZ catalyst was sufficiently catalyzing the
reaction for the production of biodiesel from a low grade feedstock
via simultaneous esterification and transesterification processes.
Fig. 3(a)–(e) depicts the X-ray photoelectron spectra of ferric–
manganese doped sulfated zirconia. The FMSZ catalyst exhibited
100
Weight lost (%)
80
200 400 600 800
Temperature oC
Fig. 2. TGA and DTGA of the FMSZ catalyst.
41
photoelectron peaks around 181.9–530.0 electron volts assigned
for zirconium 3d5/2 and O1s, respectively. These photoelectron
peaks taken together were due to the zirconia [32]. The higher
binding energy species (185.5 eV) matched to the development
of the zirconium (+4) component attached to a non-metal. The
entire lack of influences on the profile of the 3d-orbital of the zir-
conium emission line has been extremely remarkable and sugges-
tive of the different strength and environment of the interactions
involved between ZrO2 and the SO2 4 anion [33,34]. The S2p emis-
sion was located at about 168.6 eV (Fig. 3(c)) and implies the
existence of S+6 in agreement with that comparative to the sulfur
of the sulfates and to previous studies dealing with sulfate group
promoted zirconia catalysts [33]. Fig. 3(d) illustrates the XPS spec-
trum of the ferric–manganese doped sulfated zirconia in the zone
of Fe 2p. The ferric 2p3/2 and 2p1/2 peaks appeared around
711.3 and 724.0 eV, respectively, supporting the presence of ferric
oxide at the surface of the catalyst. Furthermore, the spectrum is
an obvious confirmation for the existence of Fe+3 which almost
matched the spectrum of the ferric oxide [22,35]. The manganese
emission could be differentiated only with a rather poor noisy sig-
nal. Fig. 3(e) shows the XPS spectrum of the ferric–manganese
doped sulfated zirconia catalyst at the 2p zone of manganese. Thus
the 2p3/2 and 2p1/2 peaks of the manganese were detected around
642.5 and 653.4 eV, respectively, which verifies the existence of
MnO at the surface of the catalyst.
Fig. 4 displays the FTIR spectra of fresh and reused FMSZ and
sulfated zirconia (SZ). From these spectra, the presence of the sul-
fate group was confirmed by the band at a range of 1225 to 1070
(cm1), which was attributed to the symmetric stretching of the
OASAO bond and the asymmetric stretching frequency of the
O@S@O bond, respectively. The peak around 1380 cm1 was attrib-
uted to the sulfate groups having an S@O bond with a covalent
character [36,37].
The specific surface area of the ferric–manganese doped
sulfated zirconia (FMSZ), sulfated zirconia and zirconia catalysts
achieved utilizing the BET method were found to be 72.0, 38.5
and 34.8 g/cm2 respectively. It had also been reported that the
incorporation of FeAMn dopants and sulfate species on the surface
of the zirconia had enhanced the BET surface area of the ferric-
manganese doped sulfated zirconia. Moreover, in contrast to the
size of the triglyceride molecule, which was around (5.8 nm), the
FMSZ average pore diameter was 39 nm. As a result, the reacted
molecules would avoid the mass transfer limitation and smoothly
pass through the pore; consequently, being attached to the more
energetic centers and the better is a performance of FMSZ.
Meanwhile, EDS spectrometer has been utilized to analyze the
elemental composition of the catalyst [38,39]. The qualitative
percentages of the ferric–manganese doped sulfated zirconia ele-
ments were found to be Ferric- (Fe) – 1.56%, manganese (Mn) –
0.48%, sulfur (S) – 0.96%, zirconium (Zr) – 50.95%, and oxygen (O)
– 46.05%.
The transition electron microscope has been employed to deter-
mine the shape and size of the FMSZ nanoparticles. Fig. 5 shows
0.05
the nanoparticle images of the ferric–manganese doped sulfated
Derivative weight lost (%)
0.00
zirconia. It is visible that the FMSZ nanoparticles are in the order
of the tetragonal system having a size in a limit of (11.5–21 nm)
-0.05 and 15.8 nm as an average diameter.
-0.10
3.4. Optimization of the FMSZ catalyst for the production of FAME’s
-0.15
Various consequences of reaction factors, such as reaction
-0.20 heating events, catalyst quantity and the stoichiometric ratio of
1000
the reactants concerning the performance of the FMSZ catalyst
on simultaneous esterification-transesterification processes for
producing FAME’s were also examined.
42 F.H. Alhassan et al. / Fuel 142 (2015) 38–45

Fig. 3. XPS spectra of FMSZ [O Is, Zr 3d5/2, S2p, Fe (2p3/2, 2p1/2) and Mn (2p3/2, 2p1/2)] (a–e), respectively.

Fig. 5. TEM of FeAMn-doped sulfated zirconia nanoparticle calcined at 600 °C for

Fig. 4. FT-IR spectra of the fresh and reused FMSZ and SZ catalysts. 3 h.
 F.H. Alhassan et al. / Fuel 142 (2015) 38–45
Fig. 6. Influence of temperature of the reaction during 4 h, catalyst quantity 3
wt/wt%, speed of mechanical mixer 600 rpm and stoichiometric ratio of methyl
alcohol/spent cooking oil 20:1.
3.4.1. Temperature of the reaction
Reaction temperature was found to have a considerable influ-
ence on the yield of biodiesel [40,41]. Thus, the experiments using
the ferric–manganese doped sulfated zirconia solid catalyst were
conducted at 120, 140, 160, 180, 200, 220 °C. The amount of
FAME’s increased through the increment of temperature until it
reached the maximum at around 180 °C, with an insignificant
increase at 200 °C, as shown in Fig. 6. Therefore, the temperature
of the reaction was optimized at 180 °C for the other study.
3.4.2. Time of the reaction
The best reaction time for the synthesis of biodiesel was deter-
mined by carrying out reaction using the ferric–manganese doped
sulfated zirconia solid acid catalyst at varying reaction times. Fig. 7
reveals the variation of the spent cooking oil-based biodiesel con-
tent with the time of processing. Furthermore, at optimized factors
of the process, the methyl ester’s yield improved during the inter-
val ranging from 1 to 4 h and subsequently kept almost steady,
with an insignificant increase of the waste cooking oil biodiesel
after 4 h. Hence, 4 h were considered as an optimum reaction time
for the synthesis of FAME’s via the FMSZ catalyst.
3.4.3. Catalyst loading
The amount of the catalyst and the stoichiometric ratio of the
reactants were the vital variables which needed a proper control
to improve the biodiesel quantity. Nonetheless, more loading of
the catalyst was essential to enlarge the density of the energetic
centers [42]. In addition, the effect of the FMSZ loading in a limit
Fig. 7. Influence of time of the reaction using 180 °C as process temperature,
quantity of catalyst 3 wt/wt% ratio of methyl alcohol/spent cooking feedstock 20:1
and speed of mechanical mixer 600 rpm.
43
Fig. 8. Influence of Fe(+3)AMnASO4/ZrO2 dosage at 4 h, ratio of methyl alcohol/
spent cooking feedstock 20/1, temperature of the process 180 °C and speed of
mechanical mixer 600 rpm.
of (1–5 wt/wt%) on the product had been investigated at the opti-
mized variables of the reaction. As displayed in Fig. 8, the rise in
the amount of the catalyst in a range of (1–5) wt/wt% resulted in
an obvious increase of biodiesel yield from 69 to 97.0 ± 0.03%.
Yet, as loading of the catalyst was improved to 6.0 wt/wt%, there
were slight increases in the FAME’s amount. Hence, it was being
obvious that the quantity of the catalyst could have a significant
effect on the product. The process was pursued further investiga-
tion using 3 wt/wt% as an optimum loading.
3.4.4. Stoichiometric ratio of the reactants (methyl alcohol to waste
cooking oil ratio)
Since a simultaneous process for biodiesel production is revers-
ible, an extra quantity of alcohol is wanted to force the process
towards completion [43]. So, as to determine the effect of the
stoichiometric ratio of the reactants on the product, experiments
using ferric–manganese doped sulfated zirconia nanoparticle were
performed by changing the ratio in the limit of (5–30) while other
variables were fixed under their optimum conditions. Based on the
results presented in Fig. 9, the transformation of the spent cooking
vegetable oil in the existence of the catalyst exhibited a clear con-
fidence on the ratio of the reactants. Once, the amount of the
methyl alcohol had improved, the formed biodiesel was improved
significantly. The greatest yield was achieved at the stoichiometric
ratio of 1:20, spent oil: methyl alcohol, further than this ratio had a
minor development to the FAME’s yield.
Fig. 9. Influence of the stoichiometric ratio of methyl alcohol/spent cooking oil,
during 4 h, temperature of the methanolysis process 180 °C, speed of mechanical
mixer 600 rpm and catalyst dosage 3 wt/wt%.
44 F.H. Alhassan et al. / Fuel 142 (2015) 38–45

3.5. Comparative study for the biodiesel synthesis via simultaneous

esterification and transesterification reaction using zirconia, sulfated
zirconia and ferric–manganese doped sulfated zirconia catalysts

The three prepared solid acid catalysts (zirconia (Z), sulfated

zirconia (SZ) and ferric–manganese doped sulfated zirconia (FMSZ)
were examined via the preparation of biodiesel, simultaneously.
The comparative operations were performed throughout 4 h, a
stoichiometric ratio of spent oil to methyl alcohol of 1:20 with
3 wt/wt%. catalyst loading, temperature at 180 °C and the
600 rpm stirrer power. As a result, the investigational methyl
esters yield (Fig. 10) gained from the Z, SZ and FMSZ catalysts
was found to be 43.3 ± 1.04%, 88.0 ± 0.17% and 96.5 ± 0.02%. Obvi-
ously, the ferric–manganese doped sulfated zirconia (FMSZ)
revealed the best catalytic activity probably owing to the existence
of both acid and base active sites on the surface of the catalyst. It
was expected that the incorporation of ferric oxide, manganese
oxide and sulfate anion to the zirconia would result in the forma-
tion of the FMSZ catalyst with improved physico-chemical proper-
ties in comparison to zirconia. Moreover, the FMSZ catalyst also
showed superior performance when compared with the previously
reported strong heterogeneous acid catalyst SnO2/SiO2 [44]. In the
present study, FMSZ exhibited superior catalytic activity for
producing FAME’s yield of 96.5% after 4 h; whereas, the SnO2/
SiO2 catalyst gave a conversion of 81.6% after 5 h [44].
3.6. Reusability of the catalyst
Catalyst reusability is an essential step for commercial feasibil-
ity since it reduces the biodiesel production budget [45]. Thus, the
reusability of the ferric–manganese doped sulfated zirconia cata-
lyst for biodiesel production was investigated for several runs after
the catalyst had been washed with both hexane and methanol to
remove non-polar and polar compounds. It was finally dried in
an oven with the temperature fixed at 120 °C during 6 h. The reus-
ability tests were performed by employing optimized variables of
the process. Fig. 11 shows that the yield remained nearly the same
up to the sixth run and then dropped sharply to around 87 ± 0.02
(%) in the seventh run suggesting the successful reusability of the
catalyst for six runs.
However, the decrease of the FAME’s yield was probably attrib-
uted to the blockage of the energetic centers as a result of the accu-
mulation of triglycerides in the pore of the catalyst [15]. A
comparison of the FTIR spectra between the fresh FeAMnASO2 4 /
ZrO2, SO2 2
4 /ZrO2 and the recovered FeAMnASO4 /ZrO2, SO4 /ZrO2
2
catalysts is presented in Fig. 4. The characteristic absorption bands
Fig. 11. Reusability of FMSZ and SZ catalysts.
of the sulfate group were distinct in the recovered FeAMnASO2 4 /
ZrO2 after seven cycles; whereas, in the spent SO2 4 /ZrO2 they were
not clear indicating that the sulfate groups have good stability on
the surface of the catalyst [46,47]. Therefore, it can be concluded that
the FeAMn-sulfated zirconia catalyst is easily regenerated and
reused without any dissolution of ferric and/or manganese and only
an insignificant loss of sulfur (50 ppm) after the seventh run com-
pared to the spent sulfated zirconia which was unable to catalyze
the reaction after the second cycle with sulfate leaching of about
145 ppm [15,48,49].
3.7. The features of FAME’s
The quality of the FAME’s production had been tested and
established as in accordance to the American Society for Testing
and Materials and EU values, and was found to be as the following:
density (0.877 ± 0.08 g/cm3), kinematic viscosity at 40 °C
(4.5 ± 0.15 mm2/s) in addition to the flash point, pour point and
cloud point with the values of (142 °C, 10 °C, 7 °C), respectively
[50].
4. Conclusion
The performance of the FMSZ nanoparticle catalyst as a new
catalyst in the field of biodiesel was evaluated via the synthesis
of biodiesel employing spent cooking vegetable oil containing free
fatty acid. Consistent with earlier reports, the iron–manganese
doped sulfated zirconia catalyst showed a higher surface area as
compared to the zirconia sample. The dispersed Fe2O3 and MnO
particles beside the sulfate group prevented the zirconia particles
agglomeration leading to an enhanced surface area, acidity and
hence its catalytic activity which was reflected by a remarkable
yield of biodiesel under an optimized condition compared to the
production of biodiesel via zirconia and sulphated zirconia and also
a reduction of the free fatty acid content to 0.300%, confirmed that
the bi-functional FMSZ catalyst was very successful for simulta-
neous synthesis of the biodiesel. Moreover, the recovery and reutil-
izations of FMSZ in successive reactions suggest that the FMSZ
catalyst could be recycled for six runs without being defeated in
its performance. The features of FAME’s fuel were tested and the
result being confinement to ASTM and EU specifications for the
biodiesel fuels. A further study on the FMSZ catalyst can be
appraised to optimize the amount of dopants (Fe2O3 and MnO)
and also the role of Fe2O3 and MnO on the activity of the catalyst.

Acknowledgements

Fig. 10. Production of biodiesel by Z – SZ – FMSZ calcined at (600 °C for 3 h) The authors acknowledge the financial support of the Interna-
at180 °C for 4 h, 3 wt/wt% catalysts loading and 1:20 oil/methanol ratio. tional Graduate Research Fellowship (IGRF) from the Universiti
 F.H. Alhassan et al. / Fuel 142 (2015) 38–45
Putra Malaysia. And also the first author would like to thank all rul-
ers, members of the Supreme Council of the United Arab Emirates
and to all people in Sudan and UAE.
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