Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138

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Journal of Molecular Catalysis A: Chemical

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

Catalytic performance and characterization of Cs–Ca/SiO2 –TiO2

nanocatalysts for biodiesel production
Mostafa Feyzi a,b,∗ , Esmaeil Shahbazi a
a
Faculty of Chemistry, Razi University, P. O. Box: 6714967346, Kermanshah, Iran
b
Nanoscience & Nanotechnology Research Center (NNRC), Razi University, P. O. Box: 6714967346, Kermanshah, Iran

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

Article history: In this research work, the transestrification (biodiesel production) of blend refined vegetable oil over
Received 26 January 2015 novel promoted Cs–Ca/TiO2 –SiO2 nanocatalysts was investigated. The effects of different mass ratios of
Received in revised form 23 April 2015 Ca/TiO2 –SiO2 , loading of Cs as a promoter, calcination conditions and different operational conditions on
Accepted 24 April 2015
the catalytic performance of Cs–Ca/TiO2 –SiO2 nanocatalysts were studied. The best operational condi-
Available online 27 April 2015
tions were the methanol/oil = 12/1 at 60 ◦ C with mechanical stirring of 500 rpm for 2 h. Characterization of
catalysts was carried out by using scanning electron microscopy (SEM), Transmission electron microscopy
Keywords:
(TEM), X-ray diffraction (XRD), temperature programmed desorption (TPD), Fourier transform-infrared
Nanocatalyst
Biodiesel
spectroscopy (FT-IR) and N2 adsorption–desorption measurements methods. The maximum biodiesel
Transesterification yield of 98% was obtained by using the optimal Cs–Ca/TiO2 –SiO2 nanocatalyst.
Characterization © 2015 Elsevier B.V. All rights reserved.
Operational conditions

1. Introduction
Nowadays, The increasing oil demands have created a renewed
interest in alternative fuels of biological origin. Alternative fuels,
such as biodiesel have been focused universally because of recent
energy crisis [1,2]. Biodiesel is long chain alkyl esters which can
be produced from renewable sources [3]. It is derived from the
transesterification of triglycerides such as animal fats and vegetable
oil with simple alcohols (methanol or ethanol) in the presence
of acid, base or enzyme catalyst [4–6]. Alkali-catalyzed (NaOH,
KOH) reaction is much faster than acid-catalyzed (H2 SO4 , HCl)
reaction, so it is used commercially. The homogeneous catalysts
have some serious disadvantages such as: low rate of reaction (the
contact time of reaction mixture is quite long), reactor material
corrosion and also separation of products is more difficult. The
performance of heterogeneous catalysts is generally lower than
the commonly used homogeneous catalysts [7,8]. Heterogeneous
catalysts are easy separation from the biodiesel product. In com-
parison with homogeneous catalysts, the heterogeneous catalysts
with strong basicity have similar activity, selectivity and long life-
times, so people prefer to use a heterogeneous catalyst system [9].
Yearly a huge amount of heterogeneous catalysts such as zeolites
∗ Corresponding author at: Faculty of Chemistry, Razi University, P. O. Box:
6714967346, Kermanshah, Iran. Tel.: +98 833 4274559; fax: +98 833 4274559.
E-mail addresses: m.feyzi@razi.ac.ir, Dalahoo2011@yahoo.com (M. Feyzi).
and metal catalysts have been synthesized for biodiesel production
[10–13]. Researches have focused on finding a suitable heteroge-
neous catalyst that can be easily separated and give a high yield
and conversion without compromise [14]. Since the catalytic activ-
ity of basic catalysts is higher than that of acid solids, they have
been preferably studied. Alkaline earth metal oxides such as cal-
cium oxide [15,16] and calcium methoxide [17] have been shown
to have excellent catalytic activity and stability for the production
of biodiesel [18]. Moreover, biodiesel is a liquid fuel similar to petro-
diesel fuel in combustion properties, but free of sulfur [19]. It is an
environmentally friendly fuel, biodegradable, renewable and non-
toxic [20]. Biodiesel is a biodegradable fuel, but showing a slight
increase in NOx emissions by using biodiesel fuel was reported
[21]. Nevertheless, todays many countries such as United States,
Germany, Brazil and Eastern Asia countries used biodiesel blends
for their vehicles [22]. It has been reported that the concentration
of active sites and specific surface are influences in transesterifica-
tion. Thus, it is interesting to correlate the effects of these characters
on the catalysts activity. The sulfated titania catalyst that pre-
pared using sol–gel method has the highest catalytic activity in the
methanolysis of soybean and castor oils was that which displayed
the highest specific surface area [23]. Despite of these apprecia-
ble works on TiO2 and SiO2 as commercial catalysts support for
biodiesel production, the Cs–Ca/TiO2 –SiO2 has high specific surface
and strong basicity, so it was chosen for this study.
In the present work, the Cs–Ca/TiO2 –SiO2 catalysts were pre-
pared using a combination of sol–gel and impregnation method.

http://dx.doi.org/10.1016/j.molcata.2015.04.018
1381-1169/© 2015 Elsevier B.V. All rights reserved.
132 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138
Fig. 1. Diagram of the chemical processes for catalyst preparation.
The effect of the mass ratio of catalyst to support (wt.%), loading of
promoter and calcination conditions on the catalytic performance
were investigated. The effect of reaction variables, such as methanol
to oil molar ratio, catalyst amount, reaction temperature and reac-
tion time for biodiesel production were investigated.
The prepared catalysts were characterized by FTIR, TPD, XRD,
SEM, TEM and N2 adsorption–desorption measurements methods.
2. Experimental
2.1. Synthesis of Ca/SiO2 –TiO2 catalysts
The appropriate amount of start materials Ca(NO3 )2 ·4H2 O
(Merck 99%), tetraethyl orthosilicate (TEOS, Merck 98%) and tita-
nium isopropoxide (TIP, Merck 98%) have been dissolved in ethanol
at 60 ◦ C, separately. Then, the calcium nitrate solution was added to
the mixed solution of TEOS–TIP, and subsequently oxalic acid added
under rigorous stirring at 60 ◦ C for achieving pH to 4. While the
temperature kept at 60 ◦ C, after 60 min the obtained homogenous
solutions have been left at room temperature in the air atmosphere
to jellify. The obtained gel has been dried in the oven at 120 ◦ C,
for 12 h to give a material denoted as the catalyst precursor. After
drying and milling, precursors have been thermally treated (calci-
nation) at 650 ◦ C for 6 h, to give the Ca/SiO2 –TiO2 catalyst (Fig. 1).
2.2. Synthesis of Cs–Ca/SiO2 –TiO2 catalysts
In this step, Ca/SiO2 –TiO2 as a precursor was impregnated with
aqueous solution of CsNO3 (Merck 99%). Afterward, the precursor
has been dried in the oven at 120 ◦ C, for 12 h. Finally, the catalyst
precursor was calcined at 650 ◦ C for 6 h to produce solid catalyst.
2.3. Catalyst characterization
2.3.1. X-ray diffraction (XRD)
The XRD patterns of all the precursor and calcined nanocata-
lysts were recorded with a Philips X’Pert (an accelerating voltage
of 40 kV, and an emission current of 30 mA) X-ray diffractometer,
using a Cu K␣ radiation source ( = 1.542 Å) and combined with the
nickel filter in the 2 range of 5–100◦ .
2.3.2. N2 -adsorption–desorption measurements
The specific surface area of nanocatalysts (using The
Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH)
methods), the total pore volume and the mean pore diameter were
measured using a N2 adsorption–desorption isotherm at liquid
nitrogen temperature (−196 ◦ C), using a (Quantachrome instru-
ment, model Nova 2000, USA). Prior to the adsorption–desorption
measurements, all the samples were degassed at 110 ◦ C in a N2
flow for 2 h to remove the moisture and other adsorbents.
2.3.3. Scanning electron microscopy (SEM)
The morphology of catalyst and precursor was observed by
means of an S-360 Oxford Eng scanning electron microscopy.
2.3.4. Transmission electron microscopy
TEM investigations were carried out using a Hitachi H-7500
(120 kV). The sample for TEM study was prepared by ultrasonic
dispersion of the catalyst in ethanol. The suspension was dropped
onto a carbon-coated copper grid.
2.3.5. Fourier transforms infrared (FT-IR) spectrometry
Fourier transform infrared (FT-IR) spectra of the samples were
recorded using a Bruker Vector 22 spectrometer in the region of
400–4000 cm−1 while the applied resolution was 1 cm−1 .
2.3.6. Temperature programmed desorption (TPD)
CO2 -TPD profile of CaO/TiO2 –SiO2 were recorded using a
micromeritic TPD–TPR 290 system. The TPD analysis was per-
formed using a mixture gas of 10%CO2 /90%He (v/v). The sample
were heated from 40 to 905 ◦ C at a heating rate of 10 ◦ C/min.
2.4. Kinematic viscosity measurements and evaluation
The blend refined vegetable oil was provided from Iranian Pardis
Company, and its characterization parameters are shown in Table 1.
The Cannon–Fenske Routine viscometer (Cole-Parmer Co., US) in a
glycerin bath fixed at specified temperature ±1 ◦ C which can be
used for high viscosity measurements was employed to measure
kinematic viscosity variation of samples according to ASTM D445.
2.5. Refractive index measurements
Generally, the refractive index is a physical property like melting
point and boiling point of a compound. This measurements can
be used to determine solution concentrations, ascertain purity and
identify a compound. Index of refraction is very sensitive to the
purity of the solutions. In the present paper, the refractive index
for biodiesel samples were measured by refractometer D-22976
model with an accuracy of ±0.001 at 40 ◦ C (The refractive index
should be read to at least four decimal places). The refractive index
measurements were conducted three times for each sample, and
the results were averaged.
Table 1
Composition and characterization of used vegetable oil.
Physical properties Value
Acid value (mg KOH/g) 0.15
Density at 40 ◦ C (g/cm3 ) 0.8774
Saponification index (mg KOH/g oil) 193.98
refractive index at 40 ◦ C 1.4659
Kinematic viscosity at 40 ◦ C (cSt) 24.583
Mean molecular weight (g/mol) 867.6
 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138 133

Table 2
Effect of wt.% CaO on the catalytic performance of CaO/TiO2 –SiO2 and physical
properties of biodiesel.

CaO (wt.%) K. V. D R Yeild (%)

Oil 24.583 0.8774 1.4659 -

1.0 9.287 0.8768 1.4646 38
2.0 7.752 0.8767 1.4642 40
3.0 7.208 0.8766 1.4638 41
4.0 6.495 0.8764 1.4628 44
5.0 6.289 0.8763 1.4624 45 Fig. 2. CO2 -TPD profile of Ca/TiO2 –SiO2 catalyst.
6.0 4.476 0.8760 1.4606 51
7.0 3.155 0.8757 1.4582 63
8.0 2.949 0.8754 1.4531 78
that the viscosity and density can be used as important parameters
9.0 2.807 0.8745 1.4473 89
10.0 6.552 0.8765 1.4635 62 in the production of biodiesel.
The basic property of CaO/TiO2 –SiO2 catalyst was carried out
Reaction conditions: methanol/oil = 12/1, T = 60 ◦ C, reaction time = 2 h and the stir-
ring rate of 500 rpm.
(Fig. 2). The strength of basic sites was deduced from the work by
K. V. = kinematic viscosity at 40 ◦ C (cSt). Pasupulety et al. [24], where it was suggested that desorption tem-
D = density at 40 ◦ C (g/cm3 ). perature between 400 and 600 ◦ C indicates basic sites of weak and
R = refractive index at 40 ◦ C. medium strength, and desorption temperature range of 600–850 ◦ C
indicates strong basic sites. The peak in the 780 ◦ C is the desorption
2.6. Transesterification reactions of CO2 which was adsorbed on the basic sites. It can be seen that
the total amount of CO2 desorbed is 1.6 × 1020 (atom/g). The high
The blend refined vegetable oil was used in the transesterifica- basic sites of the catalysts enabled high yield biodiesel to occur.
tion reaction. The transesterification of 30 g oil was carried out in a
250 ml round bottomed flask fitted with a condenser and magnetic 3.2. Effect of weight percent of Cs
stirring system (reaction system). At first, the reaction system was
heated to selected temperature, when the mixture of methanol and To investigate the effect of Cs as a promoter on the
the catalyst reached to desire temperature; oil was added with con- catalytic performance, a series of Cs–Ca/TiO2 –SiO2 catalysts
tinuous stirring. After completion of the reaction, the solid catalyst with different weight percentages of Cs to catalyst weight
was separated with filtration. The obtained products was heated for (Cs/(CaO/TiO2 –SiO2 ) = 0.5, 1, 1.5, 2 and 2.5 wt.%) were prepared at
remove excess methanol and then settled in a separating funnel. the following calcination conditions: T = 650 ◦ C, 6 h and heating rate
The upper phase consisted of fatty acid methyl esters (biodiesel) 5 ◦ C/min. All prepared catalysts tested under the same reaction con-
and the lower phase contained the glycerol as the by-product. ditions including: methanol/oil = 12/1, catalyst dosage 2 wt.% of oil,
reaction temperature 60 ◦ C, the stirring rate of 500 rpm and reac-
2.7. Catalytic tests tion time of 2 h. The results are shown in Fig. 3. It can be seen that
the biodiesel yield was dependent on the mass ratio of Cs. Accord-
The type and quantity of methyl esters in the biodiesel samples ing to the results, the catalyst containing 0.5 wt.% of Cs produced
were determined using gas chromatography–mass spectrometry the highest yield of biodiesel production and it was chosen as the
(GC Agilent 6890N model and Mass Agilent 5973N model) equipped optimal catalyst, so the catalyst activity is depended on the weight
with a flame ionized detector (FID). A capillary column (HP-5) with of Cs in catalysts [25,26], the correlation between the mass ratio of
60 mm column length, 0.25 mm inner diameter and 0.25 ␮m film Cs and biodiesel yield is depicted in Fig. 3. It is clearly illustrated that
thickness was used with helium as the carrier gas. The temperature by increasing weight of Cs, at first, the biodiesel yield increased and
program for the biodiesel samples started at 50 ◦ C and ramped to then decreased after addition of 0.5 wt.% of Cs. The chemical prop-
150 ◦ C at 10 ◦ C/min. The temperature was held at 150 ◦ C for 15 min erty of Cs is very active and Cs2 O is able to dissolve in methanol
and ramped to 280 ◦ C at 5 ◦ C/min. The holding time at the final in higher Cs content, in present of alkali metals such as Na and Cs
temperature (250 ◦ C) was 5 min. Also, the injector was used from formation of soap is feasible.
kind split/splitless. Dorado et al. [27] and Meher et al. [28] reported that with the
increase in the concentration of active materials of catalyst, there
was a decreased in the yield of methyl ester due to soap formation,
3. Results and discussion
which increased the viscosity of the reactants and lowered the yield
of biodiesel.
3.1. Effect of weight percent of CaO

To understand the influence of CaO loading on the catalytic per-

formance, a series of CaO/TiO2 –SiO2 catalysts with different weight
percent of CaO to TiO2 –SiO2 (CaO/TiO2 –SiO2 = 1.0, 2.0, 3.0, 4.0, 5.0,
6.0, 7.0, 8.0, 9.0 and 10.0) were prepared at the following calcination
conditions: T = 650 ◦ C, 6 h and heating rate of 5 ◦ C/min. All prepared
catalysts were tested under the same reaction conditions including:
methanol/oil = 12/1, catalyst dosage 2 wt.% of oil, reaction tempera-
ture 60 ◦ C, the stirring rate of 500 rpm and reaction time of 2 h. The
results are shown in Table 2. According to the obtained results, the
catalysts containing CaO/TiO2 –SiO2 = 9.0 wt.% showed the best cat-
alytic performance for biodiesel production. Thus, this catalyst was
chosen as the optimal catalyst for the conversion of oil to biodiesel.
As can be seen in Table 2, with increasing biodiesel yield, viscosity Fig. 3. Effect of wt.% Cs on the catalytic performance at reaction conditions:
and density of biodiesel were decreases. In fact, it can be concluded methanol/oil = 12/1, T = 60 ◦ C, reaction time = 2 h and the stirring rate of 500 rpm.
134 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138
Fig. 4. Effect of calcination temperature on the catalytic performance of
Cs–Ca/TiO2 –SiO2 nanocatalyst at reaction conditions: methanol/oil = 12/1, T = 60 ◦ C,
reaction time = 2 h and the stirring rate of 500 rpm.
3.3. Effect of calcination temperature
Calcination temperature plays an important role in physical and
chemical properties of catalyst and also catalytic performance. In
order to investigate the effect of this parameter, 5 samples of the
optimal Cs–Ca/TiO2 –SiO2 catalyst precursor were heated for 6 h
(air atmosphere and heating rate of 5 ◦ C/min) at 500, 550, 600,
650 and 700 ◦ C, separately. Then, these calcined catalysts were
tested at the same reaction conditions (methanol/oil = 12/1, cata-
lyst dosage 2 wt.% of oil, reaction temperature 60 ◦ C, the stirring rate
of 500 rpm and reaction time of 2 h). According to the results are
shown in Fig. 4, increasing calcination temperature increased the
biodiesel yield at first, and decreasing was observed above 700 ◦ C.
Hence, for the catalyst was calcined at 650 ◦ C the biodiesel yield was
higher than the other calcined catalysts under the same reaction
conditions. In high calcination temperature, the suitable phases
was formed [29]. In this condition, it is suggested that a sufficient
amount of active CaO (cubic) phase has been generated.
The XRD patterns for the precursor and calcined catalyst are
shown in Fig. 5. The precursor were largely found to be amorphous
and silicate phases. These amorphous phases make the other phases
undetectable. In contrast, the calcined catalysts contain mainly the
CaTi(SiO4 )O (monoclinic) and Cs2 O (hexagonal) and space group of
P21/a (14), P63/mcm (193), respectively.
The physical characterizes such as; specific surface area, pore
volume and pore diameter of the catalysts are given in Table 3.
According to the obtained results, the specific surface area of cat-
alysts are depend on the calcination temperature. It can be clearly
illustrated for calcined catalysts, with increasing the temperature
at first, these entire physical characteristic feature were increased
then decreased.
Fig. 5. X-ray diffraction pattern of Cs–Ca/SiO2 –TiO2 nano catalyst (precursor and
calcined catalyst).
Table 3
N2 adsorption–desorption measurements of nanocatalysts with different calcina-
tion temperatures (◦ C).
Specific surface area Pore volume Pore diameter
C.T (m2 /g) (cm3 /g) (Å)
500 150.9 0.563 45
550 158.1 0.574 46
600 168.2 0.584 47
650 169.6 0.595 51
700 164.8 0.551 47
C.T: calcination temperature (◦ C).
Previous researchers had reported that activity of catalyst
depended on BET surface area, pore diameter and pore volume
[30,31]. Jacobson et al. [32] reported that the pore structure was
a primary requirement for an ideal solid catalyst for biodiesel pro-
duction since a typical triglyceride molecule has a pore diameter of
58 Å, approximately. The larger average pore diameter and larger
interconnected pores would minimize diffusion limitations of reac-
tant molecules. Consequently, the reactants easily diffuse into the
interior of the catalyst and encounter in contact with the active
sites as the catalyst has better catalytic activity. Besides, all of the
catalyst could be defined as mesoporous catalyst since the pore
diameter of each catalyst was in intermediate range between 2 nm
(micropore) and 50 nm (macropore).
The mesoporous catalyst has been widely used for biodiesel pro-
duction in previous studies [32–35]. In addition, the specific pore
volume which represents the total internal volume per unit mass
of catalyst would facilitate the reaction by amplifying the reac-
tion surface. The N2 absorption–desorption data were shown that
the catalyst was calcined in 650 ◦ C has the higher specific surface
area, pore volume and pore diameter than the other calcined cata-
lysts. Also, the catalyst was calcined at 650 ◦ C had a larger average
pore diameter (51 Å) than the other calcined catalysts. According
to Table 3, pore volume for the optimal catalyst was larger than
the other prepared catalysts, significantly. This phenomenon is very
interesting and this might be reasons for the catalyst was calcined at
650 ◦ C shows a better catalytic performance than the other calcined
catalysts.
The SEM images of both precursor and calcined Cs–Ca/TiO2 –SiO2
catalyst are displayed in Fig. 6. SEM observations have shown dif-
ferences in morphology of precursor and calcined catalysts. The
obtained image of catalyst precursor depicts several larger agglom-
erations of particles (Fig. 6a) and shows that this material has a less
dense and homogeneous morphology. When the calcination con-
dition reached above of the 650 ◦ C, 6 h and heating rate of 5 ◦ C/min,
the morphological features are different with the precursor sample
and shows that the agglomerate size is reduced compared to the
precursor (Fig. 6b), greatly. It is obvious in Fig. 5b that the crys-
tal sizes were between 40 and 50 nm. The particle size could be
calculated by Scherer-equation [35].
It is clear that the catalyst particle size was in nano dimen-
sion (45 nm). The calcined Cs–Ca/TiO2 –SiO2 was characterized with
TEM (Fig. 7). According to this figure, the crystal sizes were between
45 and 50 nm. This result confirmed the obtained results by using
the Scherrer equation and SEM.
In order to get detailed information about the surface structure
through the modes of vibration offered by different species on the
surface of catalyst, FT-IR spectroscopic analysis of Ca–Cs/TiO2 –SiO2
sample and results are displayed in Fig. 8. The IR bands at 1031.79
and 457.98 cm−1 correspond to asymmetric stretching and bend-
ing modes of Si O Si linkage in nano catalyst [35,36]. The Ti O Si
infrared vibration is generally observed between 910 and 960 cm−1
[37,38] with the exact band position depending on the chemi-
cal composition of the sample, calibration and resolution of the
instrument. The intensity of this IR band has been used to eval-
 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138 135

Fig. 6. The SEM image of catalyst, (a) precursor and (b) calcined nano catalyst.

uate the absolute amount of Ti O Si linkages, so the IR band Table 4

Effect of calcination time on the catalytic performance of Cs–Ca/TiO2 –SiO2 and phys-
at 876.25 cm−1 attributed to the asymmetric stretching modes of
ical properties of biodiesel.
Ti O Si of nanocatalyst [39]. Fig. 7, represents that the broad peaks
at 3448.70 and 1628.44 cm−1 in the spectra are due to the stretch- Calcination time (h) K. V. D R Yeild (%)
ing and bending vibration of the OH group in nanocatalyst. In 4 2.727 0.8744 1.4459 93
the spectrum of pure TiO2 , the peak at 550 cm−1 shows stretch- 5 2.653 0.8742 1.4417 97
ing vibration of Ti O and peaks at 1450 cm−1 shows stretching 6 2.646 0.8741 1.4393 98
7 3.692 0.8742 1.4432 96
vibrations of Ti O Ti. Also, the peaks at 1400 cm−1 , 450–550 cm−1
8 2.807 0.8745 1.4473 89
exhibit stretching modes of Ti O Ti [40]. The band at 554.78 cm−1
Reaction conditions: methanol/oil = 12/1, T = 60 ◦ C, reaction time = 2 h and the stir-
can be assigned to the Ca O stretching in Ca O Si bonds in cata-
ring rate of 500 rpm.
lyst. These results suggested that the Ca–SiO2 interaction exists in K. V. = kinematic viscosity at 40 ◦ C (cSt).
the catalyst in a form of Ca O Si structure. D = density at 40 ◦ C (g/cm3 ).
R = refractive index at 40 ◦ C.

3.4. Effect of calcination time

One of the most important factors which can influence the cat-
alytic performance is the calcination time. So, the influences of
a range of the calcination time were examined. At first, 5 sam-
ples of Cs–Ca/TiO2 –SiO2 precursor were calcined in air at 650 ◦ C
with heating rate of ◦ C/min for 4, 5, 6, 7 and 8 h, respectively. The
biodiesel yield for these calcined catalysts in reaction conditions of
methanol/oil = 12/1, T = 60 ◦ C and reaction time of 2 h are shown in
Table 4. As can be seen in this table, the optimum calcination time
is 6 h at 650 ◦ C with heating rate of 5 ◦ C min−1 , at this calcination
conditions, the Cs–Ca/TiO2 –SiO2 catalyst has the highest yield of
biodiesel (98%).

3.5. Effect of reaction temperature

The effect of reaction temperature on catalytic performance of

Fig. 7. TEM image of calcined Cs–Ca/TiO2 –SiO2 nanocatalyst.
the optimal Cs–Ca/TiO2 –SiO2 catalyst studied at a range of temper-
atures between 50 and 65 ◦ C under the same reaction conditions
(methanol/oil = 12/1, the stirring rate of 500 rpm and reaction time
of 2 h). The results are presented in Table 5. According to the results,
by increasing the operating temperature, biodiesel yield increased.
In addition, for the reaction temperature at 60 ◦ C, the biodiesel yield
was higher than the other reaction temperatures under the same
reaction conditions.
Previous studies [38,41–45] had proved that the yield of
biodiesel could be increased by increasing temperature. When the
reaction was carried out at 60 ◦ C, which is above the boiling point of
methanol, the solvent vaporized and remained in the vapor phase
in the reactor causing a reduction in the methanol in the reaction
media. Because of high biodiesel yield, the temperature 60 ◦ C was
136 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138

Table 5 Table 6
Effect of reaction temperature on the catalytic performance of Cs–Ca/TiO2 –SiO2 and Effect of reaction time on the catalytic performance of Cs–Ca/TiO2 –SiO2 and physical
physical properties of biodiesel. properties of biodiesel.

Reaction temperature (◦ C) K. V. D R Yeild (%) Reaction time (h) K. V. D R Yeild (%)

50 2.934 0.8747 1.4480 88 MG DG ME (biodiesel)

55 2.915 0.8747 1.4476 89
60 2.646 0.8741 1.4393 98 1 6.412 0.8764 1.4632 5 8 43
65 2.915 0.8746 1.4476 89 2 2.646 0.8741 1.4393 – 1 98
3 2.927 0.8747 1.4474 9 7 75
Reaction conditions: methanol/oil = 12/1, reaction time = 2 h and the stirring rate of 4 2.934 0.8749 1.4479 11 8 74
500 rpm.
K. V. = kinematic viscosity at 40 ◦ C (cSt). Reaction conditions: methanol/oil = 12/1, T = 60 ◦ C and the stirring rate of 500 rpm.
D = density at 40 ◦ C (g/cm3 ). K. V. = kinematic viscosity at 40 ◦ C (cSt).
R = refractive index at 40 ◦ C. D = density at 40 ◦ C (g/cm3 ).
R = refractive index at 40 ◦ C.
MG = mono-glyceride.
DG = di-glyceride.
considered to be the optimal operating temperature. The oil con-
ME = methyl ester.
version yield increased with rising temperatures because in the
presence of heterogeneous catalyst, the reaction mixture consti-
tutes a three-phase system, oil–methanol-catalyst, in which the catalyzed by heterogeneous catalysts [49]. The transesterifica-
reaction would be slowed down because of the diffusion resis- tion consists of three step reactions for converting triglyceride to
tance between different phases. However, the reaction rate can be biodiesel and glycerol. In the first step, the triglyceride reacts with
accelerated at higher reaction temperatures and higher temper- one molecule of methanol, and it produces diglyceride and one
atures improved methanol dissolving and fastened the reaction. molecule of methyl ester. Then, the molecule of diglyceride reacts
The methanol vapor pressure rose with reaction temperatures with another molecule of methanol to produces monoglyceride and
with a rapid increase above 80 ◦ C. Taking conversion rate, reaction one molecule of methyl ester. Finally, the reaction between mono-
equipment and production operations into account, and a reaction glyceride and methanol produces methyl ester and glycerol as the
temperature of 60 ◦ C was chosen for subsequent tests, approxi- byproduct. Therefore, it is very important to select an optimal time
mately. Generally, a more fast reaction rate could be obtained at to ensure that the reaction is completed [50]. The following is the
high temperatures, but at high temperatures methanol was vapor- simplified reaction scheme:
ized and formed a large number of bubbles, which inhibited the
TG + CH3 OH ↔ DG + ME (1)
reaction on the three-phase interface. Therefore, the optimum reac-
tion temperature was chosen 60 ◦ C [46–48]. DG + CH3 OH ↔ MG + ME (2)

3.6. Effects of reaction time
A series of experiments were carried out to investigate the
performance of optimal Cs–Ca/TiO2 –SiO2 nanocatalyst with the
variation in reaction time in the range of 1–4 h, at the optimal reac-
tion conditions (methanol/oil = 12/1, T = 60 ◦ C and the stirring rate
of 500 rpm) and 2 wt.% of catalyst. As shown in Table 6, increas-
ing the reaction time has influence on the biodiesel yield. Hence,
the reaction time of 2 h is considered as the optimal reaction
time for the biodiesel production. Reaction time plays an impor-
tant role in transesterification reaction, especially the reactions
MG + CH3 OH ↔ G + ME (3)
After 2 h, the yield was decreased. Probably, the reverse reaction
of biodiesel (ME) with glycerol prevails at this stage, enabling the
decrease in reaction yield of ME.
3.7. Effect of methanol/oil molar ratio
Methanol to oil molar ratio (feed molar ratio) is an important
factor which affects the yield of biodiesel [48,45]. To fully per-
ceive the factors affecting the catalytic performance of optimal
Cs–Ca/TiO2 –SiO2 catalyst, a series of experiments were carried out

Fig. 8. FT-IR spectra of Cs–Ca/SiO2 –TiO2 nano catalyst at calcination temperature 650 ◦ C and time = 6 h.
 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138 137

Fig. 9. Effect of methanol/oil on the catalytic performance of Cs–Ca/TiO2 –SiO2 nanocatalyst at reaction conditions: T = 60 ◦ C, reaction time = 2 h and the stirring rate of 500 rpm.

at different methanol/oil molar ratios from 6/1 to 24/1 under the morphology and texture of the catalysts. The physical characteris-
reaction conditions (T = 60 ◦ C, the stirring rate of 500 rpm and reac- tic such as: viscosity, density and refractive index decreases by the
tion time of 2 h). The results are presented in the Fig. 9. According to increase of biodiesel yield. Viscosity and refractive index are rec-
the results, the highest biodiesel yield was achieved at the methanol ommended as reliable physical properties to estimate of biodiesel
to oil molar ratio of 12/1. The biodiesel yield percents are varied by yield and reduce analysis cost.
increasing methanol to oil ratio. It was found that, the feed ratio
and mixing of feed play an important role in transesterification of
Acknowledgement
oils.
When the optimal Cs–Ca/TiO2 –SiO2 catalyst was added to the
We are grateful to the Iran Nanotechnology Initiative Council
reactants, small bubbles were formed, as reported by Kim et al. [48].
(INIC) for their partial support on this project.
It was necessary to stir the mixture to enhance the contact between
reactants and active sites of the catalyst. According to the chemical
dynamics, the transesterification could be accelerated by increasing References
the amounts of methanol. The higher molar ratio of methanol to oil
could enhance the conversion yield of biodiesel. The stoichiometric [1] E. Li, Z.P. Xu, V. Rudolph, Appl. Catal. B: Environ. 88 (2009) 42–49.
[2] B.K. Barnwal, M.P. Sharma, Renew. Sustain. Energy Rev. 9 (2005) 363–378.
molar ratio of methanol to oil is 3/1. When the mass transfer was
[3] J.M. Marchetti, A.F. Errazu, Fuel 87 (2008) 3477–3480.
limited due to problems of mixing, the mass transfer rate seems to [4] K.H. Chung, D.R. Chang, B.G. Park, Bioresour. Technol. 99 (2008) 7438–7443.
be much slower than the reaction rate, so the methanol/oil molar [5] Y.C. Sharma, B. Singh, Renew. Sustain. Energy Rev. 13 (2009) 1646–1651.
[6] V. Mutreja, S. Singh, A. Ali, Renew. Sustain. Energy Rev. 36 (2011) 2253–2258.
ratio should be higher than that of stoichiometric ratio in order to
[7] G. Arzamendi, I. Campo, E. Arguinarena, M. Sanchez, M. Montes, L.M. Gandia,
drive the reaction toward completion and produce more methyl Chem. Eng. J. 134 (2007) 123–130.
esters as the product. On the other hand, increasing the amount [8] R.I. Kusuma, J.P. Hadinoto, A. Ayucitra, F.E. Soetaredjo, S. Ismadji, Appl. Clay
of methanol reduces the concentrations of catalyst and reactant, Sci. 74 (2013) 121–126.
[9] C. Ngamcharussrivichai, P. Totarat, K. Bunyakiat, Appl. Catal. A: Gen. 341
which leads to delay of the reaction and aggravates recovery of sol- (2008) 77–85.
vents. The reaction was faster with higher molar ratio of methanol [10] M. Kim, S. Yan, S.O. Salley, K.Y.S. Ng, Catal. Commun. 10 (2009) 1913–1919.
to oil, whereas a longer time was required for lower molar ratio to [11] W.N.N. Omar, S.N.A. Amin, Fuel Process. Technol. 92 (2011) 2397–2405.
[12] S. Benjapornkulaphong, C. Ngamcharussrivichai, K. Bunyakiat, Chem. Eng. J.
obtain similar conversion yields [51,52]. The recycle experiments 145 (2009) 468–474.
was performed for 4 times. It indicated that the nanocatalyst can be [13] S. Zhang, Y.G. Zu, Y.J. Fu, M. Luo, D.Y. Zhang, Bioresour. Technol. 101 (2010)
easily recycled with a little loss and can maintain catalytic activity 931–936.
[14] A. Brito, M.E. Borges, N. Otero, Energy Fuels 21 (2007) 3280–3283.
(98%). [15] H.P. Zhu, Z.B. Wu, Y.X. Chen, P. Zhang, S.J. Duan, X.H. Liu, Chin. J. Catal 27
(2006) 391–396.
[16] X.J. Liu, H.Y. He, Y.J. Wang, S.L. Zhu, X. Piao, Fuel 87 (2008) 216–221.
4. Conclusions [17] X.J. Liu, X.L. Piao, Y.J. Wang, S.L. Zhu, H.Y. He, Fuel 87 (2008) 1076–1082.
[18] C. Samart, C. Chaiya, P. Reubroycharoen, Energy Convers. Manage. 51 (2010)
1428–1431.
The Cs–Ca/SiO2 –TiO2 nanocatalysts were prepared for biodiesel
[19] J.P. Szybist, J. Song, M. Alam, A.L. Boehman, Fuel Process. Technol. 88 (2007)
production. The effects of different weight percent of Ca to 679–691.
TiO2 –SiO2 , loading of Cs as a promoter, calcination conditions [20] A.M. Dehkhoda, A.H. West, N. Ellis, Appl. Catal. A: Gen. 382 (2010) 197–204.
[21] E. Alptekin, M. Canakci, Renew. Energy 33 (2008) 2623–2630.
and different operational conditions on the catalytic perfor-
[22] L. Bournay, D. Casanave, B. Delfort, G. Hillion, J.A. Chodorge, Catal. Today 106
mance of Cs–Ca/TiO2 –SiO2 nanocatalysts were investigated. The (2005) 190–192.
results showed that the best operational conditions were the [23] R.M. de Almeida, L.K. Noda, N.S. Gonçalves, S.M.P. Meneghetti, M.R.
methanol/oil = 12/1 at 60 ◦ C with mechanical stirring 500 rpm for Meneghetti, Appl. Catal. A: Gen. 347 (2008) 100–105.
[24] N. Pasupulety, K. Gunda, Y. Liu, G.L. Rempel, F.T.T. Ng, Appl. Catal. A: Gen. 452
2 h. The optimal catalyst showed high catalytic performance for (2013) 189–202.
biodiesel production and the biodiesel yield reached to 98%. The [25] S. Yan, S.O. Salley, K.Y. Simon, Appl. Catal. A: Gen. 353 (2009) 203–212.
best calcination conditions were found to be air atmosphere at [26] N. Boz, N. Degirmenbasi, D.M. Kalyon, Appl. Catal. B: Environ. 89 (2009)
590–596.
650 ◦ C for 6 h with a heating rate of 5 ◦ C/min. Effective factors on [27] M.P. Dorado, E. Ballesteros, F.J. Lopez, M. Mittelbach, Energy Fuel 18 (2004)
catalytic activity are specific surface area, pore diameter, pore vol- 77–83.
ume and active site concentration on the surface of catalyst. The [28] L.C. Meher, V.S.S. Dharmagadda, S.N. Naik, Bioresour. Technol. 97 (2006)
1392–1397.
characterization of precursor and calcined catalysts was performed [29] R.S. Boynton, Chemistry and Technology of Lime and Limestone, 2nd ed, John
by powder XRD, TEM, SEM and N2 physisorption, also it is con- Wiley & Sons, New York, 1980.
cluded that the preparation conditions has a marked effect on the [30] W. Xie, H. Peng, L. Chen, Appl. Catal. A: Gen. 300 (2006) 67–74.
138 M. Feyzi, E. Shahbazi / Journal of Molecular Catalysis A: Chemical 404 (2015) 131–138
[31] H. Sun, Y. Ding, J. Duan, Q. Zhang, Z. Wang, H. Lou, X. Zheng, Bioresour.
Technol. 101 (2010) 953–958.
[32] K. Jacobson, R. Gopinath, L.C. Meher, A.K. Dalai, Appl. Catal. B: Environ. 85
(2008) 86–91.
[33] A.C. Alba-Rubio, J. Santamaría-González, J.M. Mérida-Robles, R. Moreno-Tost,
D. Martín-Alonso, A. Jiménez-López, P. Maireles-Torres, Catal. Today 149
(2010) 281–287.
[34] C. Samart, P. Sreetongkittikul, C. Sookman, Fuel Process. Technol. 90 (2009)
922–925.
[35] J.C. Juan, J. Zhang, M.A. Yarmo, J. Mol. Catal. A: Chem. 267 (2007) 265–271.
[36] C.H. Mauldin, D.E. Varnado, Stud. Surf. Sci. Catal. 136 (2001) 417–422.
[37] M.M. Mohamed, T.M. Salama, T. Yamaguchi, Colloid Surf. A. 207 (2002) 25–32.
[38] G.M.S. Shafei, M.M. Mokhtar, Colloid Surf. A. 94 (1995) 267–277.
[39] X. Gao, I.E. Wachs, Catal. Today 51 (1999) 233–254.
[40] H. Kochkar, F. Figueras, J. Catal. 171 (1997) 420–430.
[41] P. Felizardo, M.J. Neiva Correia, I. Raposo, J.F. Mendes, R. Berkemeier, J.M.
Bordado, Waste Manage. 26 (2006) 487–494.
[42] S. Yan, S.O. Salley, N.K.Y. Simon, Appl. Catal. A: Gen. 353 (2009)
203–212.
[43] J. Jitputti, B. Kitiyanan, P. Rangsunvigit, K. Bunyakiat, L. Attanatho, P.
Jenvanitpanjakul, Chem. Eng. J. 116 (2006) 61–66.
[44] D.Y.C. Leung, Y. Guo, Fuel Process. Technol. 87 (2006) 883–890.
[45] Y. Wang, S.P. Liu, Z. Zhang, Energy Convers. Manage. 48 (2007)
184–188.
[46] S. Zhang, Y.G. Zu, Y.J. Fu, M. Luo, D.Y. Zhang, T. Efferth, Bioresour. Technol. 101
(2010) 931–936.
[47] F. Qiu, Y. Li, D. Yang, X. Li, P. Sun, Bioresour. Technol. 102 (2011) 4150–4156.
[48] H.J. Kim, B.S. Kang, M.J. Kim, U.M. Park, D.K. Kim, J.S. Lee, Catal. Today 93
(2004) 315–320.
[49] M.K. Lam, K.T. Lee, Fuel Process. Technol. 92 (2011) 1639–1645.
[50] S.J. Yoo, H.S. Lee, B. Veriansyah, J. Kim, J.D. Kim, Y.W. Lee, Bioresour. Technol.
101 (2010) 8686–8689.
[51] A. Demirbas, Biomass Bioenergy 33 (2009) 113–118.
[52] X. Wenlei, H. Xiaoming, Catal. Lett. 107 (2006) 53–59.