Article

pubs.acs.org/IECR

Biodiesel Production by Esterification of Oleic Acid and

Transesterification of Soybean Oil Using a New Solid Acid Catalyst
Comprising 12-Tungstosilicic Acid and Zeolite Hβ
Nilesh Narkhede and Anjali Patel*
Polyoxometalate and Catalysis Laboratory, Department of Chemistry, Faculty of Science, The M. S. University of Baroda, Vadodara,
Gujarat 390002, India
*
S Supporting Information

ABSTRACT: A series of catalysts containing 10−40 wt % of 12-tungstosilicic acid anchored to zeolite Hβ were synthesized and
characterized by different physicochemical techniques. Their catalytic activity was evaluated for esterification of free fatty acid and
oleic acid as well as transesterification of soybean oil with methanol. The effects of reaction variables such as catalyst loading,
methanol to acid ratio, reaction time, and temperature on the conversion were studied. The kinetic study was carried out for
esterification of oleic acid, and its Arrhenius constant (A) and activation energy (Ea) were evaluated. The maximum conversion
obtained for esterification of oleic acid and transesterification of soybean oil were 86% and 95%, respectively. Also the catalyst
was recycled up to four cycles without any loss in the conversion.

1. INTRODUCTION enhanced catalytic performance by introduction of hydrophobic

Recently, fatty acid methyl esters, FAME (biodiesel), have
attained great importance, and research has intensified for the
use of plant/tree oil and animal fat as a source of fatty acids. In
addition to known advantages, biodiesel offers the same
performance and engine durability as petroleum diesel fuel
and has almost the same flow properties (density and viscosity)
as diesel fuel.1
The esterification reaction of long chain carboxylic acids such
as oleic acid is interesting in the context of biodiesel
production. Oleic acid is present in different extensions in
vegetable oils like soybean, jatropha curcas, sunflower, rapeseed,
pongamia, palm, and sea mango. Even though oleic acid is so
important in the context of biodiesel production, not much
work has been carried out for the same.
Soybean oil is a vegetable oil extracted from the seeds of the
soybean (Glycine max). It is one of the most widely consumed
cooking oils. As a drying oil, processed soybean oil is also used
as a base for printing inks (soy ink) and oil paints. The main
free fatty acid (FFA) constituents of soybean oil are palmitic
acid (11%), stearic acid (4%), oleic acid (23%), linoleic acid
(54%), and linolenic acid (8%).2 This suggests that soybean oil
possesses triglyceride esters of both saturated and unsaturated
FFA and is perfect feedstock to study the catalytic behavior.
Recently, supported heteropoly acids have gained tremen-
dous interest in the synthesis of biodiesel.3−9 A literature survey
shows that reports on biodiesel synthesis by esterification of
oleic acid and transesterification of soybean oil over anchored
heteropoly acids are few. Esterification of oleic acid has been
successfully carried out over 12-tungstophosphoric acid and 12-
tungstosilicic acid supported on zirconia,10 Palygorskite,11
silica,12 and SBA-15.13 Guo et al.14 reported synthesis of
mesoporous 12-tungstophosphoric acid-tantalum pentoxide
(Ta2O5) composite catalyst, H3PW12O40/Ta2O5. The catalyst
showed 76% soybean oil transesterification yield in 24 h with
methanol to oil ratio of 90 at 65 °C. The same group reported
character in the catalyst Ta2O5/SiO2-[H3PW12O40/R] (R = Me
or Ph).15−17
In our previous work we have reported the synthesis of
biodiesel by esterification of oleic acid over 12-tungstophos-
phoric acid anchored to Hβ zeolite.18 The obtained results
encourage us to extend our work for 12-tungstosilicic acid, next
acidic heteropoly acid in Keggin series. Here we are reporting
biodiesel production by esterification of oleic acid; in addition,
we are also reporting transesterification of soybean oil over 12-
tungstosilicic acid anchored to zeolite Hβ.
A series of catalysts containing 10−40 wt % 12-tungstosilicic
acid (SiW12) and Hβ were synthesized. The support and 30%
loaded catalyst were characterized by various thermal and
spectral techniques such as elemental analysis (EDX),
thermogravimetric analysis (TGA), surface area measurement
(BET method), Fourier transform infrared spectroscopy (FT-
IR), and powder X-ray diffraction (XRD). The surface
morphology of the support and catalyst was studied by
scanning electron microscopy (SEM). The acidity values were
measured by NH3-TPD technique. The catalytic activity was
evaluated for esterification of oleic acid with methanol. Also the
catalyst was regenerated and reused up to four cycles. A
detailed kinetic study was carried out, and it was found that the
esterification reaction of oleic acid with methanol follows a first-
order dependency on the concentration of oleic acid and the
catalyst. As an application of the above studies, detailed catalytic
studies were carried out for biodiesel production from soybean
oil without any pretreatment, with methanol over the present
catalyst.
Received: July 12, 2013
Revised: August 24, 2013
Accepted: August 27, 2013
Published: August 27, 2013

© 2013 American Chemical Society 13637 dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research
2. EXPERIMENTAL SECTION
2.1. Materials. The chemicals used were of A.R. grade. 12-
Tungstosilicic acid was purchased from Merck. Sodium forms
of zeolite beta (β) with an Si/Al ratio of 10 was procured from
zeolites and Allied Products, Bombay, India, and used as
received. Oleic acid, methanol, and ammonium chloride were
purchased from Merck. Soybean oil was purchased from local
market.
2.2. Treatment of the Support (Hβ). The zeolite support
(Naβ) was converted into NH4+ form by a conventional ion
exchange method19 using a 10 wt %, 1 M NH4Cl aqueous
solution. The resulting NH4+ type zeolite was further converted
to H+ type by calcination in air at 550 °C for 6 h.
2.3. Synthesis of the Catalyst (SiW12 Anchored to Hβ).
A series of catalysts containing 10−40% of SiW12 anchored to
Hβ were synthesized by an impregnation method. One gram of
Hβ was impregnated with an aqueous solution of SiW12 (0.1/
10−0.4/40 g/mL of double distilled water) and dried at 100 °C
for 10 h. The obtained materials were labeled as 10% SiW12/
Hβ, 20% SiW12/Hβ, 30% SiW12/Hβ, and 40% SiW12/Hβ,
respectively.
2.4. Catalyst Characterization. Energy Dispersive X-ray
Analysis (EDX) analysis was carried out using JSM 5910 LV
mutual with INCA instrument for EDX-SEM. Thermogravi-
metric analysis (TGA) was executed on METTLER TOLEDO
STAR SW 7.01 instrument. BET surface area of the samples
was computed on a Micromeritics ASAP 2010 surface area
analyzer. The FT-IR data were noted on Perkin-Elmer. The
Raman spectra were recorded on a FT-Raman spectropho-
tometer Model Bruker FRA 106. The XRD patterns of the
samples were recorded on PHILIPS PW-1830 at Cu Kα:
1.5417 Å. Scanning electron microscope depictions were
recorded on a JEOL-SEM instrument (model-JSM-5610LV).
NH3 chemisorption studies were carried out using Micro-
meritics Pulse Chemisorb-2705.
2.5. Catalytic Reaction. The esterification of (0.01 mol)
oleic acid with (0.2 mol) methanol was executed in a 50 mL
batch reactor provided with Dean−Stark apparatus, double
walled air condenser, a guard tube, and magnetic stirrer. The
apparatus was attached with the round-bottom flask to separate
the water from the reaction mixture. The reaction mixture was
refluxed for 10 h at 60 °C. The products were estimated on a
gas chromatograph (Nucon-5700) by using a BP1 capillary
column. All the products were recognized by comparison with
authentic samples.
The typical transesterification of soybean oil (5 g) with a
corresponding amount of methanol was carried out in a 100
mL round reactor, provided with thermometer, mechanical
stirring, and condenser. The reaction mixture was held at 65 °C
for 20 h with stirring at 800 rpm in order to keep the system
uniform in temperature and suspension. After the reaction is
completed, the mixture was rotary evaporated at 50 °C to
separate the methyl esters. The conversion of FFA to biodiesel
was calculated by means of the acid value (AV) of the oil layer
with the following equation
⎛ AVOL ⎞
Conversion (%) = ⎜1 − ⎟ × 100
⎝ AVSO ⎠
where AVOL is acid value of biodiesel (oil layer), and AVSO
refers to acid value of soybean oil.
2.6. Leaching Test. Any leaching of the active species from
the support makes the catalyst unattractive, and hence, it is
13638
Article
necessary to study the stability as well as leaching of SiW12 from
the support. Heteropoly acids can be quantitatively charac-
terized by the heteropoly blue color, which is observed when it
reacted with a mild reducing agent such as ascorbic acid. In the
present study, this method was used for determining the
leaching of SiW12 from the support. One gram of catalyst with
10 mL of conductivity water was refluxed for 24 h. Then, 1 mL
of the supernatant solution was treated with 10% ascorbic acid.
Development of blue color was not observed, indicating that
there was no leaching. The same procedure was repeated with
alcohols and the filtrate of the reaction mixture after
completion of reaction in order to check the presence of any
leached SiW12. The absence of blue color indicates no leaching
of SiW12.
3. RESULTS AND DISCUSSION
The analytically computed percentages of elements for 30%
SiW12/Hβ are as follows, (%): W, 17.66; Si, 26; Al, 2.5. Values
acquired from EDX are as follows (%): W, 18.5; Si, 26.6; Al,
2.2. The EDX results were comparable with the expected ones.
TGA-DTA curves of Hβ and 30% SiW12/Hβ are displayed in
Supporting Information, Figure S1. A unique weight loss of
13−15% was observed up to 250 °C for zeolite support, which
is attributed to desorption of physically adsorbed water. No
further weight loss was observed beyond 250 °C which
indicates zeolite Hβ retains its framework structure up to 600
°C. For the catalyst 30% SiW12/Hβ, a similar weight loss of
10−12% up to 200 °C assigned to adsorbed water was
detected. A second weight loss of 1.2−1.5% was observed
between 200 and 300 °C due to the loss of water of
crystallization of the Keggin anion. After 480 °C gradual weight
loss was observed for 30% SiW12/Hβ . TGA analysis suggests
that catalyst is stable up to 480 °C.
Textural properties of Hβ and 30% SiW12/Hβ like surface
area, pore diameter, and pore volumes are presented in
Supporting Information, Table S3. Specific surface area, pore
diameter, and pore volume all strongly decreased for the
catalyst relative to the support. This indicates that SiW12
occupies sites inside the zeolite framework. Also the decrease
in surface area is the first evidence of chemical interaction
between SiW12 and Hβ.
The N2 adsorption isotherms of support and catalyst are
displayed in Supporting Information, Figures S2a and S2b.
Both isotherms showed a Type (IV) pattern with three stages:
monolayer adsorption of nitrogen on the walls of pores at P/Po
< 0.4, the part characterized by a sharp increase in adsorption
due to capillary condensation in mesopores with hysteresis at
P/Po = 0.4−0.8, and multilayer adsorption on the outer surface
of the particles. It is seen from the Figure S2b that the pore
diameter of the catalyst is decreased after anchoring SiW12
inside the zeolite framework, as anticipated.
FT-IR of SiW12 (Figure 1) has four characteristic bands at
1020, 926, 878, and 779 cm−1 corresponding to W=Od
asymmetrical, Si−Oa asymmetrical, W−Ob−W asymmetrical,
and W−Oc−W asymmetrical, respectively, where Oa, Ob, Oc,
and Od attributed to the oxygen atoms connected to silicon, to
oxygen atoms bridging to two tungsten (from two different
triads for Ob and from the same triad for Oc), and to the
terminal oxygen W=O, respectively.20 FT-IR spectra for Hβ
and 30% SiW12/Hβ (Figure 1) shows a large and broad peak
appearing in the range of 1020−1090 cm−1 is due to
asymmetric stretching vibration O−T−O (νasym), which is
sensitive to the silicon and aluminum contents in the zeolite Hβ
dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research
Figure 1. FT-IR spectra of (a) Hβ, (b) 30% SiW12/Hβ, and c) SiW12.
framework. A broad band between 3700 and 3200 cm−1 is
assigned as hydrogen bonds of silanol groups. The typical band
for SiW12, at 920 cm−1 corresponding to Si−Oa (νasym), is
clearly observed in 30% SiW12/Hβ. FT-IR spectra indicate that
the SiW12 anions preserve the Keggin unit even after anchoring
to the support.
FT-Raman spectra of SiW12 and 30% SiW12/Hβ are
displayed in Figure 2. FT-Raman of SiW12 shows bands at
Figure 2. Raman spectra of (a) Hβ, (b) 30% SiW12/Hβ, and (c)
SiW12.
1054, 976, 888, 565, and 208 which are attributed to
νs(W=Od), νas(W=Od), νas(W−Ob−W), νs(W−Oc−W), and
νs(W−Oa), respectively. The Raman spectrum of 30% SiW12/
Hβ shows the retention of all the typical bands of SiW12 at
1020, 973, 911, 521, and 231 due to νs(W=Od), νas(W=Od),
νas(W−Ob−W), νs(W−Oc−W), and νs(W−Oa), respectively. A
remarkable shift in the band νs(W=Od) confirms the presence
of a strong hydrogen bond through terminal oxygen Od of
SiW12 with the silanol group of Hβ.
To study the dispersion of SiW12 species inside the zeolite
framework, XRD and SEM were carried out.
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Crystalline peaks for 30% SiW12/Hβ (Figure 3) suggests that
zeolite framework has been retained after incorporation of
Figure 3. X-ray diffraction patterns of (a) Hβ and (b) 30% SiW12/Hβ.
SiW12. The reflections at 2θ = 26 and 29° indicate the presence
of the crystalline phase of SiW12 onto the support.21 The
catalyst shows reflections of SiW12 with very low intensity
indicating a well dispersion of SiW12 inside the channels of
support.22
The SEM images show that the surface morphology of 30%
SiW12/Hβ (Figure 4b) is identical to that of Hβ (Figure 4a).
This indicates that the framework structure of Hβ is retained
after incorporation of SiW12.
Thus, XRD and SEM confirm the uniform distribution of
SiW12 inside the framework of zeolite Hβ.
NH3-TPD is a useful tool for determining the surface acid
sites of the catalyst. The concentration of acid sites was
estimated by quantity of NH3 adsorbed, and the strength of the
acid strength was evaluated by the desorption temperature. The
NH3-TPD profile of both support (Figure 5a) and catalyst
(Figure 5b) exhibits two types of acid sites, weak (<200 °C)
and medium strength (<450 °C). After incorporation of SiW12,
a strong acidic site at 528 °C has been observed. NH3-TPD
acidity values (Table 1) indicate an increase in acidity of Hβ
after anchoring SiW12. The presence of strong acidity is due to
the presence of SiW12, known to be Bronsted acid, only.
The results suggest that presence of SiW12 enhances strength
as well as concentration of acid sites of the catalyst.
3.1. Esterification Reaction. The esterification of oleic
acid is an equilibrium-limited reaction. In order to overcome
the equilibrium limitation, the reaction was carried out by
taking alcohol in excess.
The effect of different reaction variables such as % SiW12
loading, acid/alcohol molar ratio, amount of catalyst, reaction
time, and temperature were studied to optimize the conditions
for the maximum conversion.
The effect of % loading (Figure 6) shows that % conversion
increases with the loading of SiW12. No significant increase in
the conversion was observed after 30% loading. Therefore, 30%
loaded catalyst (30% SiW12/Hβ) was considered for the further
studies.
The effect of oleic acid to methanol mole ratio was studied
by varying the mole ratio of oleic acid to methanol from 1:10 to
dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research Article

Figure 4. SEM images of a) Hβ and b) 30% SiW12/Hβ.

Figure 5. NH3-TPD profiles of a) Hβ and b) 30% SiW12/Hβ. Figure 6. Effect of % loading, catalyst amount, reaction time, and
temperature on esterification of oleic acid over 30% SiW12/Hβ.

1:40, with 0.1 g of the catalyst for 10 h at 60 °C. It was

observed from Figure 7 that the oleic acid conversion increases
with an increase in the oleic acid/methanol ratio and reaches a
maximum of 86% at the mole ratio of 1:20. With a further
increase in the molar ratio, conversion remains constant.
Hence, the molar ratio of 1:20 is optimum for obtaining high
conversion products.
The effect of the catalyst concentration on oleic acid
conversion was studied by varying the catalyst amount in the
range 50−150 mg. As shown in Figure 6, the oleic acid
conversion increases with an increase in concentration of 30%
SiW12/Hβ and reaches to 86% at 100 mg of catalyst
concentration. The conversion remains almost constant on
increasing the catalyst concentration from 100 mg to 150 mg.
Hence, 100 mg of the catalyst was considered to be optimum Figure 7. Effect of oleic acid/methanol mole ratio. Reaction
for maximum conversion. conditions: amount of catalyst, 100 mg; reaction temperature, 60
The effect of reaction time was investigated (Figure 6). It was °C; reaction time, 10 h. Amount of catalyst, 0.1 g for Hβ and 23 mg
for SiW12.
observed that the conversion increases with an increase in

Table 1. NH3-TPD Acidity of Support Hβ and 30% SiW12/Hβ

NH3 acidity, mmol/g acid strength, °C

material total NH3 acidity, mmol/g weak medium strong weak medium strong
Hβ 1.035 0.677 0.358 - 195 389 -
30% SiW12/Hβ 1.358 0.648 0.605 0.105 198 415 528

13640 dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644

Industrial & Engineering Chemistry Research Article

Figure 8. a) FT-IR and b) XRD of fresh and recycled catalyst.

reaction time. The maximum of 86% conversion was achieved retention of both zeolite framework and Keggin unit in the
in 10 h of reaction time. recycled catalyst. BET surface area and pore diameter of the
The effect of reaction temperature on oleic acid conversion reused catalyst were found to be 416.3 m2/g and 1.67 nm,
was studied, and it was found that with an increase in reaction respectively, which is quite comparable with the fresh catalyst
temperature % conversion increases (Figure 6). At 60 °C, a (419 m2/g and 1.68 nm).
maximum of 86% conversion was achieved. Therefore 60 °C 3.1.3. Comparison of Oleic Acid Conversion with Reported
was considered the optimum temperature for maximum Catalysts. It is observed from Table 2 that sulfated CMK-3-
conversion.
The optimized conditions for esterification of oleic acid over Table 2. Comparison of Oleic Acid Conversion with
30% SiW12/Hβ are as follows: mole ratio of acid to alcohol, Reported Catalysts
1:20; amount of catalyst, 100 mg; reaction temperature, 60 °C;
reaction conversion
reaction time, 10 h. catalyst conditionsa (%) remarks ref
The control experiments by using only Hβ and SiW12 were CMK-3-873- 0.43:10:80:10 52 low conversion 24
carried out under optimized conditions. It can be seen from SO3H
Figure 7 that Hβ is not much active toward the esterification of protonated- 1.25:10:80:10 59 low conversion 24
oleic acid indicating catalytic activity is due to SiW12. Thus, we nafion
were successful in the synthesis of a heterogeneous catalyst and 6% WO3/ 0.28:6:200:2 80 very high 25
USY temperature
in overcoming the traditional problems of a homogeneous
20% H3PW/ 0.1:6:100:4 88 high temperature, 10
catalyst. ZrO2 use of nitrogen
3.1.1. Heterogeneity Test. A rigorous proof of heterogeneity atmosphere
can be obtained by filtering the catalysts at the reaction TPA3/Hβ 0.1:20:60:6 84 mild reaction 18
temperature before completion of the reaction and testing the conditions
filtrate for activity.23 A test was performed by filtering the 30% SiW12/
Hβ
0.1:20:60:10 86 high conversion
under mild
this
work
catalyst from the reaction mixture at 60 °C after 6 h, and the conditions
filtrate was allowed to react up to 10 h. The product of 10 h and a
Reaction conditions = amount of catalyst (g): mole ratio of alcohol/
the filtrate were analyzed by gas chromatogram. The oleic acid oleic acid: reaction temperature °C: reaction time (h).
conversion of both the samples was 74%, indicating the present
catalyst falls into the category C.23 On the basis of these results,
it can be concluded that there is no leaching of SiW12 species 873-SO3H24 and protonated nafion24 offered very low
from the support, and the present catalyst is truly conversion for esterification of oleic acid. Both WO3/USY25
heterogeneous in nature. and 20% H3PW/ZrO210 showed conversion of 80% and 88%,
3.1.2. Recycling of the Catalyst. The catalyst was recycled in respectively, at relatively high temperatures. TPA supported on
order to test its reusability as well as stability. The catalyst was zeolite Hβ18 showed better conversions of oleic acid under mild
separated from the reaction mixture only by simple reaction conditions. The superiority of the present catalyst lies
centrifugation; the first washing was given with methanol to in obtaining high conversion of oleic acid under mild reaction
remove unreacted oleic acid, then the subsequent washings conditions.
were done by conductivity water and then dried at 100 °C, and 3.1.4. Kinetic Study. A detailed study on the kinetic behavior
the recovered catalyst was charged for the further run. The was carried out for esterification of oleic acid over 30% SiW12/
successive cycles of catalyst run provided 86, 85, 82, and 80% Hβ. In all the experiments, reaction mixtures were analyzed at a
conversion, respectively. This suggests that catalyst retains its fixed interval of time. Esterification of oleic acid with methanol
activity up to four cycles. was carried with a 1:20 molar ratio; since methanol was taken
The reused catalyst was further characterized by FT-IR, in large excess, the rate law is expected to follow first-order
XRD, and BET surface area analysis. FT-IR spectrum of the dependence.
used catalyst (Figure 8a) shows the retention of typical band The plot of ln Co/C vs time (Figure 9) shows a linear
for SiW12, indicating that SiW12 retains its Keggin unit in the relationship of oleic acid consumption with respect to time.
recycled catalyst. The XRD pattern of the recycled catalyst With an increase in reaction time, there is a gradual and linear
(Figure 8b) was also identical with a fresh one suggesting the increase in the oleic acid conversion over the catalyst. This
13641 dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research Article

of oleic acid with methanol by using 30% SiW12/Hβ at 60 °C

was found to be 2.94 × 10−3 min−1. The pre-exponential factor
(A) and activation energy (Ea) were found to be 2.3× 104
min−1 and 49.8 kJ mol−1, respectively.
It is required to recognize whether the rate is diffusion
limited/mass transfer limited or it is truly governed by the
chemical step where the catalyst is being used to its maximum
capacity. The activation energy for diffusion limited reactions is
as low as 10−15 kJ mol−1, and reactions whose rate is governed
by a truly chemical step usually show activation energy excess of
25 kJ mol−1.26 In the present case, the observed activation
energy is 49.8 kJ mol−1, and, hence, the rate is truly governed
by the chemical step.
Figure 9. First-order plot for esterification of oleic acid over 30% 3.1.6. Comparison of Activation Energy with Reported
SiW12/Hβ. Catalysts. Comparison of activation energies obtained for
esterification of oleic acid for the reported catalysts with the
observation indicates that esterification of oleic acid follows present catalyst is shown in Table 3. The observed activation
first-order dependence with respect to time.
This was further supported by the study of the effect of Table 3. Comparison of Activation Energy with the
catalyst concentration on the rate of esterification of oleic acid. Reported Catalysts
The catalyst concentration was varied from 15 × 10−3 to 55 ×
10−3 mmol at a fixed substrate concentration of 10 mmol and at catalyst free fatty acid Ea, kJ/mol ref
a temperature of 60 °C. It can be observed from Figure 10 that H2SO4 oleic acid 42.0 27
the rate of reaction increases linearly with an increase in the double metal cyanide oleic acid 52.8 28
catalyst concentration. Amberlyst 15 oleic acid 74.4 28
PW(20)MFS oleic acid 44.7 22
TPA3/SBA-15 oleic acid 44.6 13
30% SiW12/Hβ oleic acid 49.8 this work

energy value (49.8 kJ mol−1) for esterification of oleic acid with

Figure 10. Plot of reaction rate vs catalyst concentrations.
3.1.5. Estimation of Activation Energy (Ea). The graph of ln
k vs 1/T was plotted (Figure 11), and the value of activation
energy (Ea) was determined from the plot. The value of Ea and
the pre-exponential factor (A) were determined using the
Arrhenius equation. The rate constant, k, for the esterification
Figure 11. Arrhenius plot for determination of activation energy.
13642
methanol over 30% SiW12/Hβ is comparable to the activation
energy obtained by using commercial solid acid catalysts.27,28
Further, comparing with other reported solid acid catalysts,13,22
the present catalyst exhibits higher activation energy but
operates under mild conditions.
3.2. Transesterification Reaction. Transesterification is a
universal and established method for biodiesel production from
vegetable and other fatty oils. Application of the present catalyst
was extended for the synthesis of biodiesel via trans-
esterification of soybean oil. The properties such as acid
value, saponification value, and average molecular weight for
different oils are given in Supporting Information, Table S4.
Acid values and saponification values were determined by acid−
base titration, and from these values average molecular weight
was determined using the following equation
⎛ 56.1 × 1000 × 3 ⎞
M= ⎜ ⎟
⎝ SV − AV ⎠
where SV denotes saponification value, and AV denotes to acid
value.
The effect of various reaction parameters such as oil/alcohol
ratio, amount of catalyst, reaction time, and temperature were
studied to optimize the conditions for maximum conversion
(Figure 12).
The optimized conditions for transesterification of soybean
oil over 30% SiW12/Hβ are as follows: ratio of oil to alcohol
1:4; amount of catalyst 200 mg; reaction temperature 65 °C;
and reaction time 8 h. Maximum soybean oil conversion
achieved was 95%.
The control experiments were carried out under optimized
conditions with Hβ (25% conversion) and SiW12 (97%
conversion). Almost the same activity was obtained for 30%
dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research Article

Table 4. Comparison of Soybean Oil Conversion with

Reported Catalysts
reaction conversion
catalyst conditionsa (%) remarks ref
H3PW12O40 / 2wt.%: 75 prolonged reaction 17
Ta2O5 90:65:24 time, low
conversion
slag HC(800) 0.1:12:60:6 97 decrease in 29
conversion for
successive cycles
SnO2/SiO2 5Wt.%: 82 very high 30
25:180:5 temperature, low
conversion
30% SiW12/ 0.2:4:65:8 95 high conversion this
Hβ under mild work
conditions
a
Reaction conditions = amount of catalyst (g): ratio of alcohol/oil:
reaction temperature °C: reaction time (h).

Figure 12. Effect of % loading, oil/methanol ratio, catalyst amount,

reaction time, and temperature on transesterification of soybean oil
over 30% SiW12/Hβ.
SiW12/Hβ catalyst (95% conversion) indicates that SiW12 is the
real active species.
The present catalyst was recycled under optimized
conditions for four cycles. The % conversion of soybean oil
for successive cycles are 95%, 95%, 94%, and 93%. The results
suggest that the catalyst can be reused without significant loss
in the conversion.
Further the activity of the catalyst for transesterification of
acid oil has been checked. The acid oil used was prepared in the
laboratory by mixing measured amounts of oleic acid (10 wt. %
of soybean oil) and soybean oil. The transesterification reaction
was carried out under optimized conditions. The % conversion
observed for acid oil was 92%. The result suggests that there is
no significant decrease in the transesterification activity, and the
water formed during the esterification reaction does not affect
the transesterification reaction.
3.2.1. Heterogeneity Test. The catalyst 30% SiW12/Hβ
showed consistent activity up to four cycles for trans-
esterification of soybean oil. The regenerated catalyst was
characterized for FT-IR, XRD, and heterogeneity test, in order
to confirm the retention of the Keggin structure in the recycled
catalyst as discussed earlier. The results are the same and hence
are not included.
A heterogeneity test was carried out as described before, and
it was found that a catalyst is truly heterogeneous in nature.
3.2.2. Comparison of with the Reported Catalysts. Table 4
shows comparison of conversion of soybean oil with the
transesterification. They have proposed a mechanism for
esterification as well as transesterification, and we expect the
same mechanism in the present case. The interaction of the
carbonyl oxygen of free fatty acid or monoglyceride with acidic
site of the catalyst forms carbocation. The nucleophilic attack of
alcohol to the carbocation produces a tetrahedral intermediate.
During esterification the tetrahedral intermediate eliminates
H2O or R′OH molecule to form one mole of methyl ester
(RCOOCH3). The transesterification mechanism can be
extended to di- and triglyceride.
4. CONCLUSION
The present study demonstrate the synthesis and character-
ization of solid acid catalyst comprising of SiW12 and zeolite
Hβ. BET surface area, FT-IR, and FT-Raman spectra show
strong hydrogen bonding between terminal oxygens of SiW12
with the surface silanol groups of Hβ.
The present catalyst exhibits excellent activity for ester-
ification of oleic acid with maximum of 86% conversion with
activation energy of 49.8 kJ mol−1. Studies also reveal that the
catalyst can be used for biodiesel production via trans-
esterification of soybean oil without any pretreatment. The
present catalyst showed a maximum of 95% conversion of
soybean oil with oil:alcohol ratio of just 1:4 in 8 h at 65 °C.
Also the catalyst was recycled up to four times without any
significant loss in the conversion. Thus, the present catalyst can
be employed as an efficient environmentally benign catalyst, for
the feedstocks that are rich in FFAs where simultaneous
esterification of FFAs and transesterification of triglycerides
provide an alternative single step process for biodiesel
production.

■
reported catalysts. H3PW12O40/Ta2O5 offered 75% conversion
for transesterification of soybean oil but suffered from
prolonged reaction time.17 Slag HC (800) catalyzed trans-
ASSOCIATED CONTENT
esterification offered 97% conversion under very mild *
S Supporting Information

conditions, but there was a decrease in the conversion for DT-TGA curves, N2 adsorption isotherms, and textural
successive cycles.29 SnO2/SiO2 composite showed 82% properties of the catalyst. This material is available free of
charge via the Internet at http://pubs.acs.org.

■
conversion with very high alcohol content and very high
reaction temperature.30 The superiority of the present catalyst
lies in obtaining high conversion of oleic acid under mild AUTHOR INFORMATION
reaction conditions. Corresponding Author
3.3. Proposed Mechanism for Transesterification. Guo *Phone: +91- 265 2795552. E-mail: aupatel_chem@yahoo.
et al.14 reported synthesis of mesoporous polyoxometalate- com.
tantalum pentoxide composite catalyst, H3PW12O40/Ta2O5, and Notes
its application for biodiesel production by esterification and The authors declare no competing financial interest.
13643 dx.doi.org/10.1021/ie402230v | Ind. Eng. Chem. Res. 2013, 52, 13637−13644
Industrial & Engineering Chemistry Research
■
ACKNOWLEDGMENTS
We are thankful to University Grants Commission, New Delhi
(39-837/2010 (SR)) for the financial support. One of the
authors, Mr. Nilesh Narkhede, is also thankful to UGC, New
Delhi for the award of Research Fellowship.
■
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