ARTICLE

pubs.acs.org/IECR

Silica-Supported Tin Oxides as Heterogeneous Acid Catalysts for

Transesterification of Soybean Oil with Methanol
Wenlei Xie,* Hongyan Wang, and Hui Li
School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450052, P. R. China

ABSTRACT: In this work, the SnO2/SiO2 materials with various Sn loadings ranging from 1 to 16 wt % were prepared and used as
heterogeneous acid catalysts for soybean oil transesterification to produce biodiesel. The catalyst with 8 wt % Sn loading and calcined
at 873 K exhibited the best catalytic activity, giving an oil conversion of 81.7%. The dispersed amorphous SnO2 species on the silica
surface are considered to be active sites for the transesterification reaction. The effect of reaction parameters such as catalyst amount,
reaction temperature, reaction time, and methanol-to-oil ratio was investigated to optimize the transesterification conditions. It is
shown that the free fatty acid (FFA) and water have no significant influence on the catalytic activity to the transesterification
reaction. In addition, the heterogeneous acid catalyst was found to have high activities toward the esterification of FFAs.
Furthermore, the catalyst could be recovered with a better reusability.

1. INTRODUCTION unsuitable for the industrial process based on alkaline catalysis.

Due to depletion of fossil fuels and environmental concerns,
biodiesel fuels, consisting of methyl esters of long chain fatty
acids, have attracted much attention as a promising alternative
fuel with significantly lower exhaust emissions of particulate matter
and green-house gases such as carbon monoxide, carbon dioxide,
and sulfur oxides.1 Generally, biodiesel can be produced by
the transesterification of vegetable oils with methanol, which is
carried out in the presence of base or acid catalyst. In the con-
ventional biodiesel process, homogeneous base catalysts, such as
potassium hydroxide, sodium hydroxide, or alkoxides, are the
most preferred choice of catalysts because the rate of transester-
ification reactions catalyzed by alkaline catalysts is much faster
under moderate operating conditions than that of reactions cata-
lyzed by the acid catalysts.2,3 However, these homogeneous
catalysts suffer from various drawbacks, including sensitivity to
moisture and free fatty acid (FFA) content and the need to deal
with the waste from the neutralization processes, though they are
highly efficient and of low cost. The FFA present in the reactants
can react with the alkaline catalysts to form unwanted soap
byproduct, and these generated soaps could lead to the forma-
tion of emulsions, which inhibit the separation of biodiesel from
the reaction mixture and ultimately lowers the biodiesel yield.
Additionally, the removal of these base catalysts after the reaction
is technically difficult, and a large amount of wastewater is gen-
erated in separating and cleaning the products. Therefore, the alkali-
catalyzed procedure requires the use of higher purity vegetable
oils with less than 0.5 wt % FFA and anhydrous conditions.3
5
At present, the major hurdle in the commercialization of bio-
diesel production is the high cost of raw materials used, since the
high price of virgin oil can contribute potentially as much as 70%
of total costs of biodiesel. For this reason, an effective way of
reducing the cost of raw material is to employ low-quality oils
(such as waste cooking oils and nonedible oils), which are cheaply
available and can be regarded as attractive feedstocks for bio-
diesel production.6 However, the low-cost oils usually contain
large amounts of FFAs and water. As mentioned previously, the
presence of high percentages of FFAs makes the low-cost oils
Therefore, homogeneous acid catalysts have the potential to replace
alkali catalysts, since they show less sensitive to FFAs and able to
conduct esterification and transesterification simultaneously.7,8
As a result, biodiesel produced by the transesterification of low-cost
waste oils using an acid catalyst could make it more cost-competitive
with petroleum diesel as far as the economic benefit for biodiesel
production was concerned. Among the homogeneous catalysts,
sulfuric acid and hydrochloric acid are the most common acid
catalysts used for the transesterification process. However, several
drawbacks such as high reaction temperature, slow reaction rate,
difficulty in separation, reactor corrosion, and the incapability for
reuse have depreciated the utilization of the liquid acid catalyst
for biodiesel production.8
10
In recent years, the recyclable solid acid catalysts have attrac-
ted much attention because of their potential to replace corrosive
homogeneous acid catalysts in industrial processes.2 Hetero-
geneous acid catalysts can be easily separated from the reaction
mixture by centrifugation or filtration and do not require neu-
tralization processes, thus providing a more environmentally
benign process and reducing the cost of processing.4 In parti-
cular, they have the ability to simultaneously catalyze the tran-
sesterification of triglycerides and the esterification of FFAs.11
Thus, the utilization of solid acid catalysts for the biodiesel
preparation is expected to simplify significantly the manufactur-
ing process when the low-cost oils are employed as feedstcocks
and allows for good practices of catalyst recycling. There are
several reports about the use of heterogeneous acid catalysts to
produce biodiesel, including zeolites,12 La/zeolite β,13 tung-
stated zirconia,14 sulfated zirconia,15,16 sulfated zirconia

alumina (SZA),17 sulfated tin oxide,18 heteropoly acids,11,19 vanadyl
phosphate,20 sulfonated polystyrene compounds,21 and carbon-
based solid acid catalyst.22
Received: October 2, 2011
Accepted: November 27, 2011
Revised: November 25, 2011
Published: November 28, 2011

r 2011 American Chemical Society 225 dx.doi.org/10.1021/ie202262t | Ind. Eng. Chem. Res. 2012, 51, 225–231
Industrial & Engineering Chemistry Research
The silica used as a support presents significant advantageous
features owing to its high specific surface area, large pore size, and
high thermal stability. In the present contribution, the SnO2/
SiO2 catalysts were prepared and tested as a heterogeneous acid
catalyst for the transesterification of soybean oil with methanol.
The catalytic performance of the catalyst in the transesterification
reaction was investigated regarding the conversion to methyl
esters, and more attention was paid to the effect of calcination
temperatures and Sn loadings. Besides, the experimental variables
such as the amount of catalyst, methanol/oil molar ratio, reaction
temperature, reaction time and the presence of FFAs and water
were investigated to optimize the transesterification conditions.
Moreover, the catalysts were characterized by various physico-
chemical techniques such as powder X-ray diffractometry (XRD),
thermogravimetric and differential thermogravimetric analysis
(TG
DTG), and scanning electron microscopy (SEM). Further,
the reusability of the catalyst was checked and the catalytic acti-
vity of the catalyst toward the esterification reaction was also
investigated in terms of the FFA conversion to methyl esters.
2. EXPERIMENTAL SECTION
2.1. Materials. Commercial edible-grade soybean oil was
obtained from the local market. According to GC (Shimadzu
DC-9A) analysis, the fatty acid profiles of the soybean oil used
were as follows: palmitic acid, 12.3%; stearic acid, 5.8%; oleic
acid, 26.5%; linoleic acid, 49.4%; and linolenic acid, 5.9%. The
acid value was less than 0.1 mg KOH g
1, and the average molar
mass of triacylglycerols present in the soybean oil was 874 g
mol
1, calculated from the saponification index (SV = 192.6 mg
KOH g
1). All other employed materials were of analytical grade
and were used as received without further purification.
2.2. Catalyst Preparation. The SnO2/SiO2 catalysts with
various Sn loadings were prepared by an incipient wetness
impregnation of powdered silica (SiO2) with an acetone solution
containing an appropriate amount of dibutyltin dilaurate. Com-
mercial silica was used as the support. After impregnation, the
obtained sample was dried in an oven at 373 K, and finally, the
solid was calcined at designed temperature for 5 h under air
atmosphere in a muffle furnace before use for the transesterifica-
tion reaction. The concentration of the precursor solution was
adjusted so as to yield the desired Sn loadings in the final cata-
lysts. The tin content in the SnO2/SiO2 catalysts was varied from
1 to 16 wt % based on the Sn loading.
2.3. Catalyst Characterization. Powder X-ray diffraction
(XRD) measurements were conducted on a Rigaku D/MAX-
3B powder X-ray diffractometer using a radiation source of
Cu Kα (λ = 0.154 nm) at 40 kV and 20 mA over a 2θ range of
20°
70° at a scanning speed of 5° min
1. The XRD diffraction
patterns thus obtained were compared with references from the
Power Diffraction File (PDF) database (JCPDS, International
Centre for Diffraction Data) to identify the phase present in the
samples.
TG
DTG was carried out on a STA409PC thermal analyzer
operating under a flow of air at a 20 K min
1 heating rate up to
1273 K. The surface morphology of the catalysts was studied by
scanning electron microscopy using a JEOL JSM-6700F
instrument.
2.4. Transesterification Procedures. All the transesterifica-
tion reactions were carried out in a 250 mL stainless steel high-
pressure autoclave reactor fitted with a temperature controller
and mechanical stirrer. In a typical assay, 16.0 g of soybean oil,
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different amounts of methanol, and the catalyst (5 wt % referred
to the initial oil weight) were incorporated together inside the
reactor. To minimize mass transfer limitations, the reactants were
stirred at 350 rpm. The reactor temperature was raised to the
required value, and after running the reaction for the desired
duration, the reactor was allowed to cool to room temperature.
Afterward, the solid catalyst was separated from the product
mixture by filtration, and the excess methanol was recovered
under reduced pressure prior to the subsequent analyses. Experi-
ments were performed by varying reaction parameters such as
methanol/oil ratio, reaction temperature, reaction time, and
catalyst amount. The conversion of soybean oil to methyl esters
was determined by measuring hydroxyl content on the transester-
ified soybean oil as previously described by us in the literature.23
2.5. Esterification Reaction of FFAs. In the current work,
oleic acid was used as a model free fatty acid and was deliberately
added into the soybean oil. The liquid-phase esterfication of oleic
acid present in the feedstocks with methanol over the catalyst was
carried out in a stainless steel high-pressure vessel using 5 wt % of
catalyst in the presence of 10 wt % FFA. The acid values of the
reaction mixtures were determined by titration of the aliquots,
taken out from the reaction mixture at different time intervals
with an alkali solution. The conversion of FFAs in the reactant to
methyl esters can be determined according to the following
equation.
initial acid value
final acid value
FFA conversion ð%Þ ¼
initial acid value
ð1Þ
3. RESULTS AND DISCUSSION
3.1. Screening of the Catalyst. A screening of different
catalysts was performed under identical reaction conditions to
identify the most promising solid acid catalysts for the transes-
terification reaction. The best catalyst was selected on the basis of
maximum conversion to methyl esters. The experimental results
are listed in Table 1. From this table it was seen that the selected
support (Al2O3, ZrO2, and SiO2) showed low activities, with
conversions below 30%. However, when the metal oxides were
loaded on the supports and activated at a high temperature, the
catalytic activity of the formed solid acid catalyst was improved
in the transesterification reaction. For example, over SnO2/
γ-Al2O3, a soybean oil conversion of 68.5% was obtained, and
a conversion of 64.3% was observed with SnO2
TiO2/SiO2 cata-
lyst. Obviously, the Sn-based catalysts and the ZrO2-supported
catalysts showed higher catalytic activities. In particular, SnO2/
SiO2 solid exhibited superior catalytic activity, giving a conver-
sion of 81.6% after 5 h of reaction at a reaction temperature of
453 K, probably because of the presence of strong acid sites on
the surface of the catalyst (entry 14 in Table 1). It is expected that
the incorporation of tin oxides to SiO2 leads to the formation of
SnO2/SiO2 catalyst with an enhanced acidity in comparison with
the silica. On the basis of the above results, the SnO2/SiO2 cata-
lyst showed potential for use as a heterogeneous acid catalyst and
therefore was chosen for the subsequent study.
3.2. Catalyst Characterization. The XRD patterns for 8 wt %
SnO2/SiO2 calcined at different temperatures are illustrated in
Figure 1. For the samples calcined at temperatures below 873 K
(curves a
c in Figure 1), there was only a broad diffraction peak
centered at 2θ angles of 22°, due to the amorphous silica, to be
observed in the XRD patterns, and no diffraction peak corresponding
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Industrial & Engineering Chemistry Research ARTICLE

Table 1. Catalytic Activities of Different Catalystsa

entry catalysts Tp (K) conversion (%)

1 γ-Al2O3 873 17.8

2 ZrO2 873 10.5
3 SiO2 873 22.1
4 B2O3/γ-Al2O3 873 43.6
5 MoO3/γ-Al2O3 873 48.7
6 SnO2/γ-Al2O3 873 68.5
7 TiO2/γ-Al2O3 873 58.8
8 B2O3/ZrO2 873 61.7
9 MoO3/ZrO2 873 64.6
10 SnO2/ZrO2 873 58.6
Figure 2. XRD patterns for samples with different Sn loadings: (a) 2 wt %,
(b) 4 wt %, (c) 8 wt %, (d) 12 wt %, and (e) 16 wt %. The calcination
11 TiO2/ZrO2 873 63.3 temperature of supported catalysts was 873 K. (Δ) SiO2, (2) SnO2..
12 B2O3/SiO2 873 47.2
13 MoO3/SiO2 873 51.6
14 SnO2/SiO2 873 81.6 of the original one. This phenomenon shows that the SnO2
15 TiO2/SiO2 773 61.2
species is not changed during the transesterification processes.
Notably, the changes of XRD diffraction peaks with the calcina-
16 SnO2
TiO2/SiO2 873 64.3
tion temperature for the catalyst are in agreement with the
17 SnO2
MoO3/SiO2 873 62.1
a
changes in the catalytic activity toward the transesterification
Reaction conditions: methanol/oil molar ratio, 25:1; catalyst amount, reaction, as illustrated in the following section. In addition, all the
5 wt %; reaction temperature, 453 K; reaction time, 5 h.
catalysts maintained the amorphous structure of the support,
since their XRD patterns showed broad diffraction peaks at
2θ angles of 22°, similar to the amorphous silica. Accordingly, SnO2
amorphous species probably can be considered as catalytically
active sites for the transesterification reaction.
Figure 2 shows the XRD patterns of the catalyst with different
Sn loadings. As presented in Figure.2, when the Sn loading was
below 8 wt %, the major features of the XRD pattern basically
belonged to the amorphous silica support, and no characteristic
peak of crystalline SnO2 or another tin compound was detected
by the XRD techniques, indicating the good dispersion of tin
compounds on the silica.24,27 As the amount of Sn loading in-
creased to 12 wt %, the defined XRD peaks at 2θ angles of 26.7°,
33.9°, 37.9°, 71.8°, 54.8°, 61.8°, and 65.8° appeared on the XRD
patterns (curve e in Figure 2). These characteristic XRD peaks
Figure 1. XRD patterns for 8 wt % SnO2/SiO2 calcined at different were well-matched with the rutile cassiterte phase of SnO2
temperatures: (a) not calcined, (b) 573 K, (c) 873 K, (d) 1073 K, and (JCPDS 41-1445), and their intensities further grew with in-
(e) recovered catalyst; (Δ) SiO2, (2) SnO2.. creasing the Sn loading to 16 wt %, which suggests that a residual
crystalline phase of SnO2 is formed on the support at these
to SnO2 could be detected by XRD measurements, suggesting loadings.25 Besides, it is also shown that there is no crystallite
that tin compounds are highly dispersed on the silica at calcina- SnO2 species in the catalyst when the Sn loading amount is less
tion temperatures below 873 K.24 As expected, the incorporation than 8 wt %. Evidently, the XRD-undetectable phase of SnO2
of tin compounds into the silica and subsequent thermal treat- may have dispersed onto the support, which is important for the
ment could result in a remarkable increase in the number of acid generation of active sites in the SnO2/SiO2 catalysts. When the
sites and hence the catalytic activity. However, when the cal- Sn loading amount increases beyond a borderline, i.e., above its
cination temperature increased to 1073 K, the XRD pattern was dispersion capacity, the XRD SnO2 peaks could be detected,
completely different from the catalyst calcined at lower tempera- revealing that tin is dispersed in the form of an amorphous
tures. For the sample calcined at 1073 K, apart from the species at lower Sn loading and the SnO2 with crystal structure
diffraction peaks owing to the silica, some new diffraction peaks appears at higher Sn loading. Indeed, for those catalysts loaded
at 2θ angles of 26.7°, 33.9°, and 54.8°, which are the character- with tin oxides at more than the spontaneous dispersion capacity
istic peaks for the cassiterite SnO2 phase (curve d in Figure 1), on the silica, the residual bulk crystalline phase of SnO2 remains
emerged in the XRD pattern.25 Such a result indicates that the on the composite, which reduces the catalytic activity of the
local crystalline SnO2 is formed on the surface of the silica upon catalyst, since the crystalline SnO2 exhibits low activities for the
calcination at a temperature of 1073 K. Since the 1073 K-calcined transesterification reaction. In other words, the catalysts that con-
catalyst was found to have lower activities, the amorphous SnO2 tain only amorphous SnO2 are catalytically superior to the other
probably appeared to be catalytically better for the transester- catalysts that contain both amorphous and crystallite SnO2.
ification reaction than the SnO2 crystallites. This finding was also The thermal analysis of the catalyst was performed in an
reported in the literature.26 Besides, the XRD pattern of the re- attempt to gain information about the nature of the catalysts.
covered catalyst exhibited very similar diffraction peaks to those As shown in Figure 3, the weight loss was less than 1.5% upon
227 dx.doi.org/10.1021/ie202262t |Ind. Eng. Chem. Res. 2012, 51, 225–231
Industrial & Engineering Chemistry Research
Figure 3. TG
DTG curves of noncalcined 8 wt % SnO2/SiO2 sample.
Figure 4. SEM images of samples: (a) SiO2 and (b) 8 wt % SnO2/SiO2.
heating to 423 K, and the total weight loss value was 21%. The
low-temperature weight loss below 423 K in the TG profile could
be assigned to the loss of residual solvent or water trapped in the
silica framework. Besides, The TG curve of the original sample
showed a significant weight loss in a wide temperature between
453 and 873 K. This weight loss, accompanied by a large DTG
peak centered at 543 K, is mainly attributed to the progressively
thermal decomposition of supported dibutyltin dilaurate, produ-
cing tin oxides when the temperature is raised. After 873 K there
was no change in the weight loss value in the TG curve.
SEM analyses were used to elucidate the morphological char-
acteristics of the solid catalysts. The SEM photographs of the
samples are presented in Figure 4. The morphology of the silica
and SnO2/SiO2 samples showed well-ordered particles with a
size of about 2
12 μm and nearly polygonal and irregular in
shape with defined edges. As shown in Figure.4, no significant
morphology change was observed, except small particles (maybe
SnO2 particles) on the SnO2/SiO2 catalyst that were not seen on
the silica. On the basis of the results, after loading of tin com-
pounds, the silica retains its structure and the tin species are
distributed upon the silica.
3.3. Influence of Preparation Conditions on the Catalyst
Performance. The transesterifications catalyzed by various SnO2/
SiO2 catalysts calcined at different temperatures were carried out
using 5 wt % catalysts, and the results are illustrated in Figure 5.
It is shown that the calcination temperature is of importance in
determining the final activity of the catalysts. In the absence of
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ARTICLE
Figure 5. Influence of calcination temperature on the conversion to
methyl esters. Reaction conditions: catalyst amount, 5 wt %; reaction
time, 5 h; reaction temperature, 453 K; methanol/oil molar ratio, 24:1.
Figure 6. Influence of loading amount of Sn on the conversion to
methyl esters. Reaction conditions: catalyst amount, 5 wt %; reaction
time, 5 h; reaction temperature, 453 K; methanol/oil molar ratio, 24:1.
calcination, the catalyst was not particularly active. After calcina-
tion the catalyst showed considerable activities toward the tran-
sesterification reaction. With increasing the calcination tempera-
ture from 473 to 873 K, the conversion to methyl esters was
gradually increased. At 873 K, the conversion of soybean oil was
attained a maximum value of 81.7% over the catalyst. The en-
hancement of the catalytic activity for the solid catalyst is most
likely caused by the different decomposition extents of the pre-
cursor compound upon increasing the calcination temperature
and subsequently the different amounts of the thus generated
active species. However, as the calcination temperature increased
to 1073 K, it can be seen that the conversion was substantially
reduced. Presumably, the decrease in the catalytic activity at higher
temperatures largely results from the formation of crystalline
SnO2, as was demonstrated by the XRD measurements. Therefore,
the optimal calcinatiion temperature is set at 873 K.
The conversions to methyl esters over the catalysts with dif-
ferent Sn loadings are presented in Figure 6. As can be observed
from this figure, when the Sn loading rose from 1 to 8 wt %, the
conversion to methyl esters was gradually increased, and the best
conversion was reached at the Sn loading of 8 wt %. However,
with the further enhancement in the Sn loading from 8 to 16 wt %,
a diminishing trend in the conversion was noticed, probably due
to the formation of crystallites SnO2 that could cover the surface
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Industrial & Engineering Chemistry Research
Figure 7. Effect of methanol/oil molar ratio on the conversion to
methyl esters. Reaction conditions: catalyst amount, 5 wt %; reaction
time, 5 h; reaction temperature, 453 K.
active sites of the catalyst. As a result, the catalytic activity of the
catalyst is largely dependent on the Sn loading, and the proper Sn
loading is necessary for the catalyst to get high catalytic activity.
Thus, it may then be suggested that the amorphous SnO2 species
formed during the calcination processes could be considered to
be the mainly catalytically active phase for the reaction. Accord-
ingly, the SnO2/SiO2 catalyst with the Sn loading of 8 wt % is the
most suitable catalyst for the transesterification reaction.
3.4. Influence of Reaction Parameters on the Oil Conver-
sion. The reaction temperature is one of the important variables
affecting the transesterification reaction. Usually, higher reaction
temperature can give higher reaction rate in the transesterifica-
tion reaction, especially by using acid catalysts.2 The effect of
reaction temperature was investigated with this catalyst by vary-
ing the reaction temperature in the range of 393
493 K. The
results achieved here showed that the soybean oil conversion was
even less than 60%, though the reaction was run at 393 K.
However, it could be noted that the conversion to methyl esters
increased steadily from 56.5% to 70.8% to 81.7% upon increas-
ing the reaction temperature from 393 to 423 to 453 K. The in-
creased conversion with reaction temperature might be not only
due to the effect of the increase in reaction rate by increasing
temperature but also due to the improvement of the solubility of
methanol in soybean oil. However, the further increase in the
reaction temperature gave an insignificant increase in conversion
to methyl esters. Hence, it could be inferred that the optimum
operating temperature for the transesterification reaction is 453 K.
In the reaction sequence, triglycerides are converted stepwise
to diglyceride, monoglyceride, and finally glycerol accompanied
with the formation of methyl esters. Stoichiometrically, the tran-
sesterification reaction requires 3 mol of methanol for each mole
of triglyceride. However, the excess methanol is commonly em-
ployed for the transesterification reaction in order to shift the
reaction equilibrium toward the desired product side.28 In gen-
eral, the higher methanol/oil molar ratio is required for the acid-
catalyzed process to obtain a higher reaction rate, in comparison
with the base-catalyzed process.4 The effect of methanol/oil
molar ratio was investigated using this solid acid catalyst, and the
results are shown in Figure 7. With the increase in methanol/oil
molar ratio, the conversion was gradually enhanced and a maxi-
mum conversion after reaction for 5 h was achieved over the
catalyst at the methanol/oil molar ratio of 24:1. However, there
was no significant increase in the conversion to be observed with
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ARTICLE
Figure 8. Effect of reaction time on the conversion to methyl esters.
Reaction conditions: methanol/oil molar ratio, 24:1; reaction tempera-
ture, 453 K; catalyst amount, 5 wt %.
increasing methanol addition beyond the molar ratio of 24:1.
From the results, the optimum molar ratio of methanol/oil for
the reaction is approximately 24:1. The excess methanol can be
recovered from the reaction product by simple distillation, and
the byproduct of glycerol in the process can be gravitationally
separated by decantation without any complex process.
The influence of catalyst loadings was also investigated by
using different catalyst loadings between 1 and 7 wt %. The tran-
sesterification reactions were set at a methanol/oil molar ratio of
24:1, a temperature of 453 K, and a reaction time of 5 h. As the
catalyst loading increased from 1 to 3 to 5 wt %, the correspond-
ing conversion to methyl esters was increased from 40.8 to 68.4
to 81.7 and reached a plateau thereafter when the catalyst loading
was further increased beyond 5 wt %. The optimum catalyst
loading for obtaining high conversion to methyl esters was found
to be 5 wt %. As the catalyst loading increases, more catalytically
active sites are available to facilitate the reaction to occur, which
allows the conversion to methyl esters to increase. From the above
results, a catalyst loading of 5 wt % was chosen for subsequent
studies.
To examine the effect of reaction time on the conversion to
methyl esters, experiments were performed by using different
reaction times under the reaction conditions of 453 K and 24:1
ratio of methanol to oil. The reaction time was varied within a
range from 1 to 9 h. From the results shown in Figure 8, it was
observed that when the reaction time extended to 5 h, the con-
version to methyl esters was increased and reached the maximum
value of 81.7%, achieving the equilibrium of the reaction. The
further increase in reaction time to 9 h resulted in the small
increase in the conversion to 83.6%. Therefore, the suitable reac-
tion time for the transesterification reaction is 5 h.
The methodology based on acid-catalyzed transesterification
has raised a lot of interest because it allows for the preparation of
biodiesel by using low-cost oils as feedstocks. To study the influe-
nce of FFA and water on the activity of the catalysts, the sim-
ulated waste oils with different amounts of FFA and water were
prepared by deliberately adding oleic acid or water. Additional
experiments were performed with the simulated waste oils under
the optimized reaction conditions. When the FFA amount was
1%, 3%, 5%, 7%, and 10% (based on refined soybean oil weight),
the conversions to methyl esters were 80.1%, 78.9%, 78.2%,
77.1%, and 75.7%, respectively. Obviously, the conversion went
down slightly with the increase in the FFA amount within the
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Industrial & Engineering Chemistry Research
Figure 9. Effect of reaction time on the conversion of FFA to methyl
esters. Reaction conditions: methanol/oil molar ratio, 24:1; reaction
temperature, 453 K; catalyst amount, 5 wt %; reaction time, 5 h.
range studied, and the conversion of soybean oil could retain
75.7% even with 10% of FFA. It is reported that during the tran-
sesterification processes, the activity of solid catalysts is adversely
affected by the presence of water.4 By using the SnO2/SiO2
catalyst, the effect of the water amount on the catalytic activity
was studied. The conversions were 81.2%, 80.4%, 78.7%, 75.4%,
72.1%, and 63.2%, respectively, when the water content was
0.1%, 0.3%, 0.5%, 0.7%, 1%, and 1.5%. Clearly, the oil conversion
declined with the increase in water content. Indeed, the water
content of less than 1.0% could lead to the conversion above 70%
after 5 h of reaction. However, up to a water content higher than
1.0%, the conversion to methyl esters decreased rapidly. With
water content of 1.5%, the soybean oil conversion was low and
only attained 63.2%. Therefore, the water content in oil had
better be less than 1.0%, which is higher than the allowable water
content of the base catalyst employed.
In order to examine the catalytic activity of the catalyst toward
the esterification of FFAs, the esterification of oleic acid present
in the oils with methanol over the catalysts was carried out in a
stainless steel high-pressure vessel, using 5 wt % of catalyst at a
reaction temperature of 453 K. With the SnO2/SiO2 catalyst,
both the esterification and transesterification could be conducted
in a single process. As illustrated in Figure 9, a FFA conversion of
93.8% was attained after 3 h. When the reaction time increased to
5 h, the conversion of FFA to methyl esters over the catalyst was
increased steadily and reached as high as 94.1%, followed by a
slight increase upon a further increase of reaction time. By draw-
ing on the results, the solid catalyst also exhibited catalytic acti-
vities toward the esterification of FFAs with methanol.
3.5. Reusability of the Catalyst. The reutilization of hetero-
geneous catalyst is an important aspect that makes it economic
and preferable over a homogeneous one. For the reusability
investigation, the used catalysts were separated by filtration and
washed with petroleum ether and methanol. Before reuse in the
second reaction cycle, the recovered catalysts were dried at 393 K
and subsequently used for new reactions under the optimum
operating conditions. When the solid catalyst was used for one,
two, three, and four cycles, the conversion of soybean oil was
declined slightly from 80.2%, 78.3%, and 74.6% to 67.5%. Thus,
the catalyst retained a higher catalytic stability even after con-
tinuous use up to four cycles. It might be hypothesized that the
Sn is linked to the surface of the silica by a Si
O
Sn chemical
bond arising due to the stronger interactions between SnO2 and
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the silica, leading to the improvement of the catalyst stability.
However, when the catalyst was further used for a fifth cycle, the
conversion decreased remarkably to 54.3%. The loss of the cata-
lytic activity is probably owing to the original active sites being
blocked partially by adsorbed intermediate or product species,
which diminishes the amount of readily available catalytic sites.
In general, the acid-catalyzed transesterification usually in-
volves high reaction temperature, long reaction time, and low
conversion rate. In the present research, the SnO2/SiO2 catalyst
shows higher efficiency in biodiesel production when low-cost
feedstocks are employed. Over the catalyst, the soybean oil con-
version of 81.7% and the FFA conversion of 94.6% are obtained
under appropriate operating conditions. It is shown that the soy-
bean oil and FFA can be converted to biodiesel in a one-step
process catalyzed by the solid catalyst. Notably, the conversions
achieved in this work are relatively low and are not of commercial
interest, and thus, for the industrial production of biodiesel, the
activity of the catalyst needs to be improved considerably. Alter-
natively, another stage of transesterification after glycerol separa-
tion would be expected to complete the reaction if the solid
catalyst is to be practically employed for the biodiesel production.
4. CONCLUSIONS
The SnO2/SiO2 catalysts containing different amounts of Sn
loading were prepared by impregnation with dibutyltin dilaurate
and thermal activation at higher temperature for the production
of biodiesel. The maximum activity is found for the catalyst with
8 wt % Sn loading and calcination at 873 K, which could catalyze
the transesterification reaction of soybean oil even containing a
large amount of FFA. The soybean oil conversion of 81.7% was
obtained after 5 h of reaction, when a methanol/oil molar ratio of
24:1 and 5 wt % of catalyst loading were employed. The amor-
phous SnO2 on the silica support is shown to be catalytically
active sites for the transesterification reaction. Besides, the cata-
lyst also exhibits high catalytic activities in the esterification
reaction of FFA, with a FFA conversion of 94.6%. Further, the
SnO2/SiO2 catalyst could be easily recovered and reused without
serious loss in the catalytic activity for four cycles.
’ AUTHOR INFORMATION
Corresponding Author
*Telephone: +86-371-67756302. Fax: +86-371-67756718. E-mail:
xwenlei@163.com.
’ ACKNOWLEDGMENT
This work was financially supported by research grants from
National Science Foundation of China (project No. 21076062)
and Program for Science & Technology Innovation Talents in
Universities of Henan province in China (HASTIT).
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