Anda di halaman 1dari 10

Synthesis and characterization of the acidic properties and pore texture

of Al-SBA-15 supports for the canola oil transesterication


Chenju Liang
a
, Ming-Chi Wei
b
, Hui-Hsin Tseng
c,d,
, En-Chin Shu
c,d
a
Department of Environmental Engineering, National Chung Hsing University, 250 Kuo-Kuang Rd., Taichung 402, Taiwan, ROC
b
Department of Food Science, Central Taiwan University of Sciences and Technology, Taichung 402, Taiwan, ROC
c
School of Occupational Safety and Health, Chung Shan Medical University, Taichung 402, Taiwan, ROC
d
Department of Occupational Medicine, Chung Shan Medical University Hospital, Taichung 402, Taiwan, ROC
h i g h l i g h t s
Mesopore and surface acidity of Na/SBA-15 improve the transesterication activity.
Pore structure of Na/SBA-15 were altered using different aging temperature.
Surface acidity of Na/SBA-15 were modied by incorporation of heteroatom Al.
The FAME yield of Na/Al-SBA-15 was comparability with commercial support.
a r t i c l e i n f o
Article history:
Received 5 October 2012
Received in revised form 11 March 2013
Accepted 13 March 2013
Available online 25 March 2013
Keywords:
Biodiesel
Transesterication
Canola oil
Solid catalyst
SBA-15
a b s t r a c t
Ordered mesoporous SBA-15 was used as a support for the transesterication of canola oil to produce
biodiesel. The pore size and surface acidity of SBA-15 were modied by synthesis conditions using differ-
ent aging temperatures and the addition of heterogeneous Al atoms. The results of the characterization
study indicated that a large amount of mesopore and surface acidity can greatly improve the transeste-
rication reaction at a high aging temperature and with the incorporation of aluminum into the SBA-15
framework. This improvement in transesterication activity is due to the formation of more stable
SiAOAAlbonds on the surface of the framework. The transesterication reaction was also compared
with synthesis involving traditional supports such as acidic and basic c-Al
2
O
3
, hydrotalcite, and SiO
2
. The
activities of the catalysts were related to their acidic strength.
2013 Elsevier B.V. All rights reserved.
1. Introduction
The biodiesel fatty acid methyl ester (FAME) is a renewable and
clean energy source that can replace oil and has the potential to
help reduce oil dependence and global warming [1]. Biodiesel is
synthesized by the transesterication of vegetable oils or animal
fats with a short-chain alcohol in the presence of catalysts. In the
synthesis, the exchange of the organic group R
00
of an ester with
the organic group R
0
of an alcohol occurs [2,3]. Transesterication
is usually catalyzed by acid or base catalysts that donate a proton
to the carbonyl group or remove a proton from the alcohol, thereby
making them both more reactive [4,5]. Most biodiesels are cur-
rently produced in the presence of homogeneous basic catalysts,
which offer advantages such as higher reaction rates and a low
temperature requirement to obtain high biodiesel yields in a short
period of time [6]. However, the main drawback of using homoge-
neous basic catalysts is the occurrence of saponication as a side
reaction (i.e., RACOOH + NaOH ?RACOONa + H
2
O), thereby mak-
ing the process inefcient [7].
Although the reaction rate of syntheses that involve the use of
heterogeneous catalysts is slower compared to the reaction rate
of syntheses that involve homogeneous catalysts, the heteroge-
neous catalysts still offer several advantages, which include being
noncorrosive, able to regenerate, and causing fewer disposal prob-
lems [8]. The process is thus continuous. Heterogeneous catalysts
can be designed to exhibit higher activity, selectivity, and longer
lifetimes by modifying the characterization of the catalysts.
Several types of heterogeneous catalysts have been investigated
for transesterication. These catalysts include alkaline earth metal
oxides [4,8,9] or metal oxides supported on alumina [2,5,10], zeo-
lite [1], or hydrotalcite [11,12]. Zeolites were initially considered as
a promising material because of their unique porous structure,
high surface area, and high thermal stability. However, reactions
1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.03.065

Corresponding author at: School of Occupational Safety and Health, Chung Shan
Medical University, Taichung 402, Taiwan, ROC. Tel.: +886 4 24730022; fax: +886 4
23248194.
E-mail address: hhtseng@csmu.edu.tw (H.-H. Tseng).
Chemical Engineering Journal 223 (2013) 785794
Contents lists available at SciVerse ScienceDirect
Chemical Engineering Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ cej
involving zeolites were unsuccessful because larger reactive mole-
cules are involved [7]. The acidity of the support is also essential in
transesterication because solid acid catalysts can simultaneously
catalyze the transesterication of triglycerides and the esterica-
tion of free fatty acids when waste cooking oil is used to produce
second-generation biofuels [13]. Therefore, aside from the physical
texture, the surface acidity of the support is also essential in
improving the biodiesel yield rate. Based on previous studies, the
following strategies have been recommended to improve the cata-
lyst performance: (i) developing the pore structure with a large
pore diameter and surface area to improve the mass transfer and
metallic dispersion; and (ii) increasing the support surface acid/ba-
sic strength for proton donation/removal [14]. These strategies
may be accomplished by using supports with appropriate mor-
phologies and acidic surface properties.
Amorphous silicas with ordered mesoporous structures (like
MCM-41 and SBA-15) have been widely used as supports for vari-
ous metals [1518] because of their controllable molecular-sized
pores, strong surface acidity and large number of active sites
[17]. These supports are particularly attractive applied in heteroge-
neous reactions involving large organic molecules where micropo-
rous zeolites cannot be used [19]. Among different supports with
an ordered mesopore structure, SBA-15 seem to be more suited
to react in transesterication because SBA-15 has larger pore sizes
(4.630 nm), thicker pore walls (3.16.4 nm) and higher surface
area (up to 1000 m
2
/g). SBA-15 also shows a greater opportunity
to improve the hydrothermal stability [17] than the conventional
MCM-41 support. Samart et al. [1] applied mesoporous silica as a
support in transesterication, and they evaluated the reaction con-
ditions for the reaction of soybean oil with methanol. They showed
that the methyl ester yield was close to the yield produced by the
conventional homogeneous catalysis method. However, the char-
acteristics of the silica, which are important in determining the
activity of the catalysts, were not evaluated. Saravanamurugan
et al. [20] controlled the SBA-15 morphology with an amino group
and applied this support to the transesterication of diethyl mal-
onate with various aliphatic and aromatic alcohols. They found
that functionalized catalysts exhibited enhanced catalytic activity
strongly dependent on the morphologies of the support.
However, the electrically neutral framework of silica provides
SBA-15 materials with a weak acidity due to the silanol groups lo-
catedonthe porewalls. Several efforts havebeenmadetosynthesize
SBA-15 with various heteroatoms such as aluminum [15,17,18,21],
iron [15], and zirconium [16,22] to enhance its acidity by creating
Lewis acid sites. Al-SBA-15 materials with a large number of moder-
ately acidic sites are one kind of very promising catalysts and sup-
ports involving catalytic reaction. Li et al. [17] have showed that
Al-SBA-15 materials exhibit high hydrothermal stability due to the
formation of more stable SiAOAAlbonds on the surface of the
framework. Szczodrowski et al. [23] also indicated that the doping
procedure enhanced SBA-15 acidity, especially as observed with
Al-SBA-15 compared to Zr-SBA-15 or Ti-SBA-15.
This studyaims to improve the activityof NaOH/SBA-15catalysts
by altering the physicochemical properties of the support. The prop-
erties of the support can be altered by changing its pore structure
and surface acidity. The introduction of Al into the silica framework
to improve the acidity and to modify the pore texture by changing
the aging temperature was systematically investigated.
2. Experimental
2.1. Materials
Commercial chemicals with the highest purity available (>98%),
namely, NaOH (RDH, Germany), aluminum oxide (SigmaAldrich,
France), hydrotalcites (SigmaAldrich, France), silicon dioxide (Sig-
maAldrich, France), and methanol (Fluka, France) were used with-
out further purication. Canola oil (purity >99.9%) was obtained
from Tatung Chang Chi Food Stuff Factory Co., Ltd. (Taiwan).
Tetraethyl orthosilicate (TEOS), non-ionic triblock copolymer
PEOPPOPEO ((poly(ethylene oxide)poly(propylene oxide)
poly(ethylene oxide)) (pluronic P123, MW: 5800 g/mol), hydro-
chloric acid (HCl, 37%), and aluminum isopropoxide (AIP) were
purchased from SigmaAldrich (France). All chemicals were used
for the preparation of pure or Al-doped SBA-15 mesoporous
materials.
2.2. SBA-15 and Al-SBA-15 synthesis
The SBA-15 support was synthesized using pluronics P123 as a
structure-directing agent and TEOS as a silica source. In this typical
process, 4 g of P123 was dissolved in 150 mL of aqueous HCl at pH
1.5. Subsequently, 5 mL of TEOS was added dropwise to the solu-
tion. After stirring at 40 C for 24 h, the mixture was aged at
90 C, 100 C, 110 C, or 120 C for 24 h. The white precipitate
was then collected by ltration and dried at 110 C overnight.
The product was obtained by removing the template at 550 C
for 6 h at a heating rate of 1 C/min. The samples obtained were
designated as S90, S100, S110, and S120.
Al-SBA-15 was synthesized through a direct synthesis meth-
od [24] by using the same procedure and by using AIP as an Al
source. In a typical synthesis, 5 mL of TEOS and a calculated
amount of AIP were added to 10 mol of aqueous HCl at pH 1.5 to
obtain Si/Al molar ratios of 10, 30, and 50. The solution was stirred
for 3 h and then added to a second solution containing 4 g of P123
in 140 mL of 2 M HCl solution at 40 C. The mixture was stirred for
24 h at the same temperature and then aged at 110 C for 24 h in
closed Teon bottles. The solid product obtained was ltered, dried
at 110 C and nally calcined in air at 550 C for 6 h at a heating
rate of 1 C/min. The sample was designated as Al-S110(X), where
X is the theoretical Si/Al molar ratio.
Catalyst preparation
The impregnation of the supports with the Na precursor salts
was conducted using a pore volume impregnation technique. An
appropriate concentration of NaOH ethanol solution (20 g sup-
port/150 mL ethanol) was used to impregnate the support with
5 wt% loading weight of Na. After 24 h, the solution was heated
and constantly stirred until the liquid was entirely evaporated.
NaOH loaded on basic c-Al
2
O
3
, acid c-Al
2
O
3
, silica dioxide, and
hydrotalcite was also prepared for comparison with other catalysts
using the impregnation method from an aqueous solution. The pre-
pared catalysts were dried in an oven at 105 C for 2 h and calcined
at 400 C for 5 h in air.
2.3. Catalyst characterization
The crystal structure of the catalyst was determined by a small
angle X-ray diffraction system (SAXRD; Mac Science Co., M18XHF),
with a Cu Ka X-ray source. The diffraction patterns were acquired
with a 2h angle, which ranged from 0.5 to 8 and a scanning step
of 0.02.
The morphology of the supporting materials and the supported
catalysts was examined using a eld emission scanning electron
microscope (FESEM, JEOL JSM-6700F).
Fourier transform infrared (FT-IR) spectra were obtained in
the 4000400 cm
1
region with a PerkinElmer 1730 FT-IR
spectrometer.
High-resolution transmission electron micrograph (HRTEM)
images were obtained using a JEOL 2010 microscope. The solids
were ultrasonically dispersed in heptane, and the suspension was
collected on carbon-coated grids.
786 C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794
The molar ratio of silicon to alumina and the actual amount of
sodium loading weight in the materials obtained after the last cal-
cination step were evaluated using an inductively coupled plasma
mass spectrometer (PerkinElmer, SCIEX ELAN 5000). The samples
were pretreated by microwave digestion before the analysis.
The specic surface areas and pore size distributions of the cat-
alysts were determined by the multipoint BrunauerEmmetTeller
(BET) method using the PMI Automated BET Sorptometer
(201AEL). The samples were outgassed overnight down to 10
3
-
Torr at 378 K to eliminate the impurities adsorbed on the sample
surface prior to the measurements.
Pyridine adsorption was performed on the samples by using an
FT-IR spectrometer at 25 C to evaluate and analyze the strength
and type of the acid sites. The sample was heated to 400 C in a
vacuum and cooled to room temperature before pyridine adsorp-
tion. After the pyridine was adsorbed on the sample at room tem-
perature, evacuated, and heated at various temperatures, the IR
spectra of the samples were obtained.
2.4. Transesterication reaction
Transesterication experiments were carried out in a thermo-
stated glass tank reactor equipped with a stirrer, a temperature
probe, a tube for sample withdrawal, and a condenser with cooling
water. Methanol and canola oil at a 6:1 M ratio (total reaction
weight of 100 g) were added to the reactor with 10 g of the cata-
lyst. The temperature was then increased to 65 3 C with con-
stant stirring at 600 rpm. The reaction time for transesterication
was 6 h. The samples were removed from the reaction mixture,
and the biodiesel portions were separated by centrifugation. Three
phases were formed. The top layer was biodiesel, the bottom layer
was the catalyst, and a small amount of glycerol was observed.
The biodiesel concentrations were analyzed using an Agilent
6890 N gas chromatograph equipped with a ame ionization
detector and an AB-WAX 20253002 column (30 m 0.25 mm
0.25 lm). The separation was achieved using the isothermal anal-
ysis method. The oven was heated in helium gas at a rate of 10 C/
Fig. 1. SAXRD patterns of SBA-15 supports synthesized under (a) 90 C, (b) 100 C, (c) 110 C, and (d) 120 C aging temperatures.
Table 1
Textural and structural characteristics of SBA-15 and Al-SBA-15(X) supports.
Sample Si/Al molar ratio
a
d
100
a
0
b
(nm) D
pore
c
() W
d
(nm) S
BET
e
(m
2
g
1
) V
total
f
(m
3
g
1
)
S90 9.10 10.51 37.9 6.72 738.74 0.70
S100 9.30 10.74 45.1 6.23 898.21 1.01
S110 9.40 10.85 49.1 5.94 684.18 0.84
S120 9.80 11.32 49.8 6.34 585.15 0.73
Al-S110(50) 68.2 (70.3)
g
9.70 11.20 60.4 5.16 790.40 1.19
Al-S110(30) 39.1 (39.5) 9.60 11.10 59.1 5.19 711.36 1.05
Al-S110(10) 17.6 (18.1) 9.60 11.10 58.8 5.22 691.55 1.02
a
Determined by ICP analysis.
b
a
0
= 2d
100
/
p
3 is the hexagonal lattice parameter derived from the XRD data.
c
D
pore
is the mean pore diameter derived from N
2
desorption data based on the BJH method.
d
W = a
0
D is the mean pore wall thickness.
e
S is the specic surface area.
f
V is the total pore volume.
g
The values in the parentheses were the Si/Al molar ratio of spent catalysts.
C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794 787
min from 150 C to 230 C and was maintained at 230 C for
20 min. A temperature of 250 C was used for the injection port
and the detector.
The yield for conversion of oil to biodiesel was calculated from
the methyl ester content using the following equation [23]:
Yield %
m
actual
m
theoretical
100%
C
ester
V
ester
m
oil
100%

C
ester
V
m
oil
100%
C
ester
q
oil
100%
where both m
actual
(g) and m
theoretical
(g) are the methyl ester mass,
m
oil
(g) is the canola oil mass used in the reaction, C
ester
(g/mL) is the
mass concentration of methyl ester acquired by GC, q
oil
(g/mL) is
the canola oil density, and V
ester
(mL) and V
oil
(mL) are the crude es-
ter layer and canola oil volumes, respectively.
3. Results and discussion
3.1. Textural properties of SBA-15
3.1.1. Effect of aging temperature
The SAXRD patterns of the SBA-15 obtained using different
aging temperatures are shown in Fig. 1. The results exhibit an in-
tense peak lower than 1.1 at 2h, along with two other weak peaks
between 1.5 and 2.0, which were assigned to the (100), (110),
and (200) planes in a hexagonal arrangement. All SBA-15 supports
show the optimal ordering of the two-dimensional hexagonal
p6mm structure [25], which indicates that a good preservation of
the ordered mesoporous SBA-15 silica can be achieved even at
the highest aging temperature of 120 C. The peaks shifted toward
the left side after alter-aging at different temperatures. These data
can be indexed to a hexagonal lattice with a d
100
spacing ranging
from 9.1 nm to 9.8 nm and an average unit cell parameter a
0
of
10.51 nm to 11.32 nm according to the formula a
0
2d
100
=

3
p
.
The lattice parameters increased with increasing aging tempera-
ture (Table 1). Table 1 also shows that the average pore size grad-
ually increased with increasing aging temperature. However,
differences were observed in the S110 and S120 samples. The sur-
face area and total pore volume of S110 and S120 decreased when
the aging temperature was increased to 120 C. This change was
due to the decreased fraction of microporosity present in the pores,
thereby resulting in a small surface area and pore volume [26].
The TEM images also conrmed the well-ordered hexagonal
structure of the four SBA-15 samples (Fig. 2). Fig. 3 shows the FES-
EM images of the SBA-15 supports, which possess long rod-shaped
structures. The S90 had a length of about 2 lm and a diameter of
0.5 lm. S100, S110, and S120 became longer with increasing aging
temperature. After aging at a high temperature, the length in-
creased and the diameter was extended from 0.5 lm to 2 lm.
The lattice parameters and particle size expansion can be attrib-
uted to the temperature-dependent hydrophilicity of PEO. Accord-
ing to a previous study [27], the segments of the triblock
copolymer PEOPPOPEO are in a hydrophilic state at low temper-
atures, and the PEO blocks become hydrophobic at a high temper-
ature. Moreover, the PEO segment becomes longer at high
temperatures; thus, the hydrophobic volume increases and the
pore wall becomes thinner. As a result, the lattice parameters
and particle size increase rapidly with increasing aging tempera-
ture. Moreover, the pore size and pore volume also increase.
3.1.2. Effect of Si/Al ratio
The chemical compositions of the synthesized Al-SBA-15 sup-
ports are presented in Table 1. The Si/Al molar ratio of all samples
synthesized using the direct synthesis method was in close agree-
ment with the expected X value (50, 30, or 10). This result indicates
(a) (b)
(d) (c)
Fig. 2. TEM images of SBA-15 synthesized under (a) 90 C, (b) 100 C, (c) 110 C, and (d) 120 C aging temperatures.
788 C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794
that Al was mostly incorporated into the SBA-15 framework by the
procedure performed in this study. The SAXRD pattern of the Al-
S110(X) supports is shown in Fig. 4. All Al-S110(X) supports with
different Si/Al ratios consist of three well-resolved peaks that cor-
respond to the reections (100), (110), and (200) associated with
the p6mm hexagonal symmetry of SBA-15. The intensities of these
signals did not change after Al incorporation; however, their posi-
tions shifted slightly to the low-angle region compared with the
pattern of the S110 sample. These results demonstrate that the ori-
ginal long-range periodicity order of the S110 sample was wholly
preserved after Al incorporation, and the pore size increase was
due to the expansion of the aluminosilicate framework. Table 1
(a1) (a2)
(b2)
(c2)
(d2)
(b1)
(c1)
(d1)
Fig. 3. FESEM images of SBA-15 aged at (a) 90 C, (b) 100 C, (c) 110 C, and (d) 120 C. (The left side is 10 K, and the right side is 100 K.)
C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794 789
shows that the distance between the (100) plane (d
100
) shifted to
higher values with increasing Al content. The distance changed
from 9.4 nm for S110 to 9.7 nm for Al-S110(50). All results in the
literature are in agreement that the initial introduction of Al into
the SBA-15 structure increased the d spacing [28,29], which is re-
lated to the longer AlAO bond compared with the SiAO bond [28].
However, the d spacing did not show any signicant increase when
the Al content was further increased. Similar results were also
found by Vinu et al. [29]; however, the reasons for such an obser-
vation are not yet clear.
The textural characteristics of Al-containing SBA-15 are also
shown in Table 1. The results show that a high surface area and
a high pore volume of the hexagonal mesoporous Al-SBA-15 was
obtained from Al-S110(50). The pore size, surface area, and pore
volume decreased with increasing Al content, which is in good
agreement with the data reported in the literature [28]. The FESEM
images of Al-SBA-15 supports with various Si/Al ratios (Fig. 5)
show a well-organized hexagonal mesopore structure, in agree-
ment with the results of the SAXRD patterns and nitrogen sorption
isotherms. Some impurities were observed on the outer surface
when the Al content was increased to Si/Al = 10, which indicates
that further polymerization and organization of the aluminosili-
cates occurred after the Al content was increased [28].
3.2. Surface acidity of SBA-15 and Al-SBA-15
The surface acidity of SBA-15 aged at different temperatures
and with Al incorporation was determined by the FT-IR spectrum
of the pyridine adsorption technique. Fig. 6 shows that different
signals were observed in the region between 1700 and
1400 cm
1
. The bands at 1440 and 1596 cm
1
can be assigned to
hydrogen-bonded pyridine, bands at 1446 and 1621 cm
1
to the
strong Lewis acid-bound pyridine, and a band at 1580 cm
1
to
the weak Lewis acid-bound pyridine. The bands corresponding to
the vibration of the pyridinium ion ring associated with Brnsted
acid sites were observed at 1546 and 1639 cm
1
, and a band at
1492 cm
1
was assigned to the pyridine associated with both
Brnsted and Lewis sites [30].
All pure siliceous SBA-15 supports aged at different tempera-
tures exhibited signals because of the pyridine adsorption of the
hydrogen bonds with the silanol groups (a shoulder at 1440 cm
1
and a band at 1596 cm
1
) and pyridine adsorbed on Lewis acid
sites (absorption peaks at 1446, 1485, 1580, and 1639 cm
1
). The
Brnsted acid sites observed in the spectrum of the SBA-15 sup-
ports were weak.
Compared with the S110 sample, the intensity of the bands cor-
responding to the hydrogen and Lewis acid sites of the Al-incorpo-
rated S110 sample decreased remarkably. This result indicates that
Al incorporation in the S110 leaves fewer free silanol groups and
Lewis acid sites. At the expense of these bands, new signals at
1546 and 1639 cm
1
were observed in the spectra of the Al-
S110(X) samples, which suggests that Brnsted acid sites were
generated in these samples. These results indicate that the incor-
poration of Al created Brnsted acid sites and enhanced the acid
strength of both the Lewis and Brnsted acid sites.
The Al
3+
charge was lower than the charge of the Si
4+
ions. The
net negative charge of AlAOASi clearly differed from SiAOASi
when the higher charged Si
4+
was replaced by the lower charged
Al
3+
ion in the silica framework. This observation led to changes
in the electron density around Si [19], which is one of the possible
reasons for the increase in the generation of Brnsted acid sites on
the Al-S110(X) solid.
3.3. Transesterication activity
The catalytic activity of the Na catalyst supported on SBA-15
and Al-S110(X) materials with different textural structures and
acid strengths was assessed in the transesterication of canola
oil by using methanol as a short chain alcohol. Fig. 7 shows that
Na/S90 exhibited FAME yields of 16% within 6 h. Compared with
Na/S90, catalysts Na/S100, Na/S110, and Na/S120 exhibited larger
mean pore diameters, thereby improving FAME yields from 16%
to 28%. Although the FAME yields of biodiesel with Na as the cata-
lyst and a series of SBA-15 supports showed low and similar results
(from 16% to 28%), the conversion rate increased slightly with
increasing aging temperature.
In this study, the mean pore sizes of SBA-15 were enlarged by
aging at a higher temperature because of the increase in PEO vol-
ume (Table 1). The surface area and the total pore volume were
also reduced signicantly; however, this reduction did not exhibit
any signicant inuence on FAME yields. Na/S120, which has the
lowest surface area and pore volume, showed the highest activity
in FAME yields compared with Na/S90. The mean pore size of the
SBA-15 support is essential for canola oil to enter the catalytic cen-
ters of the catalysts. Therefore, the mesoporous SBA-15 materials
consisting of large mesopores can signicantly minimize the diffu-
sion resistance for reactants to obtain access to the catalytic cen-
ters of the catalyst [31].
The FAME yields of Na/Al-S110(X) catalysts, which are ex-
pressed as the Si/Al ratio, are also presented in Fig. 7. The transe-
sterication activity improved signicantly when Al-S110(X) was
used as the supporting material. The FAME yields increased signif-
icantly from 25% to approximately 99% when the Si/Al ratio de-
creased from 1 to 10. The highest yields were obtained after the
Si/Al ratio reached 30. The incorporation of alumina into the
SBA-15 framework accelerated the transesterication reaction sig-
nicantly compared with pure silica SBA-15 supports. The acidity
of the catalysts strongly inuences the catalytic activity of transe-
sterication. Jimnez-Morales et al. [14] observed a similar behav-
ior with respect to the Si/Al ratio for Al-SBA-15. They studied three
Al-SBA-15 materials with Si/Al ratios of 10, 20, and 30, which were
prepared by post-synthesis alumination for the methanolysis of
sunower oil. In their study, the catalytic activity increased with
increasing Si/Al ratio but not in proportion to the Al content in
Fig. 4. SAXRD patterns of (a) S110 and Al-S110(X) supports with various Si/Al
ratios: (b) 50, (c) 30, and (d) 10.
790 C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794
the structure, which can be attributed to the presence of the Lewis
acid site.
The increase in the formation of biodiesel can also be related to
the higher hydrophobic surface characteristic, which facilitates the
entry of hydrophobic triglyceride molecules to the active catalytic
sites. The surface hydrophobic characteristic is essential in mass
transfer for the application of Al-SBA-15(X) porous support in the
transesterication of canola oil to biodiesel and in facilitating the
diffusion of high molecular weight and hydrophobic triglyceride
molecules involved in this reaction to the catalytic centers. There-
fore, studying the hydrophobic characteristics of the Al-S110(X)
surface in the canola oil/methanol binary liquid phase is essential.
Szczodrowski et al. [23] used a liquid-ow calorimeter to measure
the integral enthalpy of the competitive adsorption of butanol from
) 2 b ( ) 1 b (
) 2 c ( ) 1 c (
(d2) (d1)
(a2)
(a1)
Fig. 5. FE-SEM image of (a) SBA-15 aged at 110 C and Al-S110(X) supports with various Si/Al ratios: (b) 50, (c) 30, and (d) 10.
C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794 791
n-heptane solution, i.e., adsorption of a bipolar solute froma binary
liquid solution in an apolar solvent. Their results indicated that the
density of the surface polar centers in Al-SBA-15 was enhanced
because of the incorporation of Al, which created additional surface
hydroxyl groups related to bridging the Si(OH)Al hydroxyl struc-
tures with strong Brnsted acidity.
Considering all the information obtained from the catalyst char-
acterization, we can conclude that the Na/Al-S110(30) and Na/Al-
S110(10) catalysts exhibit a higher formation of FAME. This high
level of FAME formation may be attributed to the surface acidity
and the hydrophobic characteristics, where triglyceride molecules
are assumed to be chemisorbed [23,32]. Surface area and pore
structure did not have a signicant effect on the formation of FAME
because the development of the Al-S110(10) pore structure was
not better than the development of the Al-S110(50) pore structure.
3.4. Comparison with other supports
In investigating the inuence of the support characteristic on
the transesterication activity with SBA-15 or Al-SBA-15 as the
support, a comparison with several commercial and widely used
materials can be helpful. Thus, the surface characteristics of acidic
and basic c-Al
2
O
3
, SiO
2
, and hydrotalcite and the transesterica-
tion activity of canola oil were investigated. Fig. 8 shows that
Al
2
O
3
, SiO
2
, and hydrotalcite have intermediate activity compared
with SBA-15 and Al-SBA-15. The pore structure and surface charac-
0 200 400 600 800 1000
20
40
60
80
100
35 40 45 50 55 60 65 70 75
0
20
40
60
80
100
0.0 0.2 0.4 0.6 0.8 1.0 1.2
20
40
60
80
100
F
A
M
E

y
i
e
l
d

(
%
)
BET surface area m
2
/g
R
2
=-0.36618
F
A
M
E

y
i
e
l
d

(
%
)
Average pore diameter (A)
R
2
=0.85764
F
A
M
E

y
i
e
l
d

(
%
)
Total pore volume cm
3
/g
R
2
=-0.08294
Fig. 8. Correlation between the total pore volume, average pore diameter, BET
surface area, and the FAME yield of supported Na catalysts.
(a) (b) (c)
Fig. 6. IR spectra of pyridine adsorbed on (a) Na/SBA-15 catalysts aged at different temperatures and (b) Na/Al-S110 (X) catalysts with various Si/Al ratio, and (c) Na/acidic
Al
2
O
3
, Na/basic Al
2
O
3
, Na/SiO
2
, and Na/hydrotalcite. H: hydrogen-bonded pyridine; B: Brnsted-bonded pyridine; L: Lewis-bound pyridine.
a b d d e f g h i j k
0
20
40
60
80
100
Y
i
e
l
d

o
f

F
A
M
E

(
%
)
Kind of catalysts
SBA-15 Al-S110(X) Commercial materials
Fig. 7. Yield of FAME transestericated from canola oil over Na catalysts supported
on (a) S90, (b) S100, (c) S110, (d) S120, (e) Al-S110(50), (f) Al-S110, (30), (g) Al-S110,
(10), (h) acidic Al
2
O
3
, (i) basic Al
2
O
3
, (j) SiO
2
, and (k) hydrotalcite.
792 C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794
teristics of acid and basic c-Al
2
O
3
, SiO
2
, and hydrotalcite supports
were noticeably distinct from a series of SBA-15 and Al-SBA-15
supports. These supports possess low surface area, large pore
diameter, low pore volume (Table 2), and stronger acidic strength
(Fig. 6) compared with SBA-15 and Al-SBA-15 supports. The corre-
lation between total pore volume, average pore diameter, BET sur-
face area, and activity with Na as the catalyst in all support
materials is plotted in Fig. 8. The most inuential parameters are
total acidity and mean pore diameter. A linear relationship was ob-
tained for the average pore diameter with a correlation coefcient
of R
2
= 0.85764. Moreover, Al-SBA-15 showed a higher acidity and
transesterication activity compared with other mesoporous
materials.
The results reported in Table 3 represent various catalysts pre-
pared and characterized by different investigators for transesteri-
cation of vegetable oil to biodiesel reported in the literature
[1,5,7,10,14,16,26]. The present work reported here shows superior
performance over Al-incorporated SBA-15 supported Na catalysts.
As shown, a biodiesel yield of as high as 99% was achieved on
the Na/Al-SBA-15 catalyst at a relative lower reaction temperature
of 65 C and lower reaction time of 6 h compared with other SBA-
15 supported catalysts. In the meantime, no deactivation was
found after three cycles of Na/Al-SBA-15 catalysts prepared in this
study in the transesterication reaction, which showed a better
stability of chemical structure.
4. Conclusions
Mesoporous SBA-15 and Al-SBA-15 supports were synthesized
through hydrothermal reaction. These pure siliceous and alu-
mina-silica SBA-15s were examined by XRD, TEM, SEM, and BET
methods. The results indicate that a hexagonal mesoporous struc-
ture was obtained for all Si/Al ratios. The pyridine adsorption anal-
ysis indicates that these materials possess a variety of Brnsted
and Lewis acid sites that vary with aging temperature and Si/Al ra-
tio of the materials. The canola oil transesterication activity of
these materials that support Na catalysts indicates that the cata-
lytic activity depends strongly on surface acidity rather than on
pore structure. Other traditional mesoporous materials, namely,
acidic and basic c-Al
2
O
3
, SiO
2
and hydrotalcite were also com-
pared. The correlation between surface area, mean pore diameter,
pore volume, acidity, and transesterication activity suggests that
the total acidity, especially on the Brnsted acid site, is responsible
for the canola oil transesterication activity. Na/Al-S110(10),
which exhibits high acid strength, provides the highest catalytic
activity, even when its pore structure is not well developed.
References
[1] C. Samart, P. Sreetongkittikul, C. Sookman, Heterogeneous catalysis of
transesterication of soybean oil using KI/mesoporous silica, Fuel Process.
Technol. 90 (2009) 922925.
[2] H.J. Kim, B.S. Kang, M.J. Kim, Y.M. Park, D.K. Kim, J.S. Lee, K.Y. Lee,
Transesterication of vegetable oil to biodiesel using heterogeneous base
catalyst, Catal. Today 935 (2004) 315320.
[3] S.P. Singh, D. Singh, Biodiesel production through the use of different sources
and characterization of oils and their esters as the substitute of diesel: a
review, Renew. Sustain. Energy Rev. 14 (2010) 200216.
[4] R. Sree, N. Seshu Babu, P.S. Sai Prasad, N. Lingaiah, P.S. Sai Prasad,
Transesterication of edible and non-edible oils over basic solid Mg/Zr
catalysts, Fuel Process. Technol. 90 (2009) 152157.
[5] A.P. Vyas, N. Subrahmanyam, P.A. Patel, Production of biodiesel through
transesterication of Jatropha oil using KNO
3
/Al
2
O
3
solid catalyst, Fuel 88
(2009) 625628.
[6] I. Jimenez-Morales, J. Santamaria-Gonzalez, P. Maireles-Torres, A. Jimenez-
Lopez, Methanolysis of sunower oil catalyzed by acidic Ta
2
O
5
supported on
SBA-15, Appl. Catal. A: General 405 (2011) 93100.
[7] H. Kazemian, B. Turowec, M.N. Siddiquee, S. Rohani, Biodiesel production using
cesium modied mesoporous ordered silica as heterogeneous base catalyst,
Fuel (2012), http://dx.doi.org/10.1016/j.fuel.2012.07.058.
[8] X. Liu, H. He, Y. Wang, S. Zhu, X. Piao, Transesterication of soybean oil to
biodiesel using CaO as a solid base catalyst, Fuel 87 (2008) 216221.
Table 2
Pore structure of acidic Al
2
O
3
, basic Al
2
O
3
, SiO
2
, and hydrotalcite materials.
Support S
BET
a
(m
2
/g) D
b
() V
total
c
BJH adsorption cumulative pore volumes of pores between 8.5 and 1500 radius (cm
3
/g)
V
micro
V
meso
V
macro
Al
2
O
3
-acidic 134 72 0.2408 0.0517 0.1801 0.0090
Al
2
O
3
-basic 150 69 0.2569 0.0567 0.1906 0.0096
SiO
2
7 208 0.0389 0.0025 0.0322 0.0043
Hydrotalcite
d

a
S
BET
is the surface area measured by the BET method.
b
D is the average pore diameter (4 V/S) determined by BET adsorption method.
c
V
total
is the total pore volume.
d
The pore structure of hydrotalcite cannot be analyzed because of the moisture release continuously during the analysis.
Table 3
Representative biodiesel conversion of various catalysts.
Catalysts Optimum reaction conditions Conversions Ref.
Oil source Methanol/oil molar
ratio
Temperature
(C)
Time
(h)
Catalyst amount (wt.% of
oil)
Metal loading weight
(wt.%)
KI/mesoporous
silica
Soybean oil 16 70 10 5 15 94 [1]
SZr-SBA-15 Triacetin oil 12 60 12 5.3 72.9 [16]
Cs/SBA-15 Canola oil 40 135 5 2 25.35 [7]
20Al-SBA-15 Sunower 12 200 6 5 92 [14]
Ca/SBA-15 Sunower
oil
27 200 8 5 0.5 (atomic ratio) 99 [26]
Na/Al-SBA-15 Canola oil 6 65 6 5 99 Present
work
KNO
3
/Al
2
O
3
Jatropha oil 12 70 8 6 35 85 [5]
KF/c-Al
2
O
3
Vegetable
oil
15 (alcohol) 65 8 3 15 97.7 [10]
C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794 793
[9] D. Vujicic, C. Comic, A. Zarubica, R. Micic, G. Boskovic, Kinetics of biodiesel
synthesis from sunower oil over CaO heterogeneous catalyst, Fuel 89 (2010)
20542061.
[10] N. Boz, N. Degirmenbasi, D.M. Kalyon, Conversion of biomass to fuel:
transesterication of vegetable oil to biodiesel using KF loaded nano-c-Al
2
O
3
as catalyst, Appl. Catal. B: Environ. 89 (2009) 590596.
[11] N. Barakos, S. Pasias, N. Papayannakos, Transesterication of triglycerides in
high and low quality oil feeds over an HT2 hydrotalcite catalyst, Bioresour.
Technol. 99 (2008) 50375042.
[12] L. Gao, G. Teng, G. Xiao, R. Wei, Biodiesel from palm oil via loading KF/CaAl
hydrotalcite catalyst, Biomass Bioenergy 34 (2010) 12831288.
[13] A. Demirbas, Biodiesel from waste cooking oil via base-catalytic and
supercritical methanol transesterication, Energy Convers. Manage. 50
(2009) 923927.
[14] I. Jimnez-Morales, J. Santamaria-Gonzalez, P. Maireles-Torres, A. Jimenez-
Lopez, Aluminum doped SBA-15 silica as acid catalyst for the methanolysis of
sunower oil, Appl. Catal. B: Environ. 105 (2011) 199205.
[15] R.V. Grieken, J.M. Escola, J. Moreno, R. Rodrguez, Direct synthesis of
mesoporous M-SBA-15 (M = Al, Fe, B, Cr) and application to 1-hexene
oligomerization, Chem. Eng. J. 155 (2009) 442450.
[16] Y. Du, S. Liu, Y. Zhang, F. Nawaz, Y. Ji, F.S. Xiao, Urea-assisted synthesis of
hydrothermally stable Zr-SBA-15 and catalytic properties over their sulfated
samples, Microporous Mesoporous Mater. 121 (2009) 185193.
[17] Q. Li, Z. Wu, B. Tu, S.S. Park, C.S. Ha, D. Zhao, Highly hydrothermal stability of
ordered mesoporous aluminosilicates Al-SBA-15 with high Si/Al ratio,
Microporous Mesoporous Mater. 135 (2010) 95104.
[18] M. Kumaran, S. Garg, K. Soni, M. Kumar, L.D. Sharma, M. Dhar, K.S. Rama Rao,
Effect of Al-SBA-15 support on catalytic functionalities of hydrotreating
catalysts: I. Effect of variation of Si/Al ratio on catalytic functionalities, Appl.
Catal. A: General 305 (2006) 123129.
[19] T. Klimova, J. Reyes, O. Gutirrez, L. Lizama, Novel bifunctional NiMo/Al-SBA-
15 catalysts for deep hydrodesulfurization: effect of support Si/Al ratio, Appl.
Catal. A: General 335 (2008) 159171.
[20] S. Saravanamurugan, Sujandi, D.S. Han, J.B. Koo, S.E. Park, Transesterication
reactions over morphology controlled amino-functionalized SBA-15 catalysts,
Catal. Commun. 9 (2008) 158163.
[21] M. Kumaran, S. Garg, K. Soni, M. Kumar, J.K. Gupta, L.D. Sharma, K.S. Rama Rao,
G. Murali Dhar, Synthesis and characterization of acidic properties of Al-SBA-
15 materials with varying Si/Al ratios, Microporous Mesoporous Mater. 114
(2008) 103109.
[22] W. Thitsartarn, S. Kawi, Transesterication of oil by sulfated Zr-supported
mesoporous silica, Ind. Eng. Chem. Res. 50 (2011) 78577865.
[23] K. Szczodrowski, B. Prlot, S. Lantenois, J.M. Douillard, J. Zajac, Effect of
heteroatom doping on surface acidity and hydrophilicity of Al, Ti, Zr-doped
mesoporous SBA-15, Microporous Mesoporous Mater. 124 (2009) 8493.
[24] P. Bhange, D.S. Bhange, S. Pradhan, V. Ramaswamy, Direct synthesis of well-
ordered mesoporous Al-SBA-15 and its correlation with the catalytic activity,
Appl. Catal. A: General 400 (2011) 176184.
[25] H.Y. He, T. Wang, S.L. Zhu, Continuous production of biodiesel fuel from
vegetable oil using supercritical methanol process, Fuel 86 (2007) 442447.
[26] H. Sun, J. Han, Y. Ding, W. Li, J. Duan, P. Chen, H. Lou, X. Zheng, One-pot
synthesized mesoporous Ca/SBA-15 solid base for transesterication of
sunower oil with methanol, Appl. Catal. A: General 390 (2010) 2634.
[27] A. Katiyar, S. Yadav, P.G. Smirniotis, N.G. Pinto, Synthesis of ordered large pore
SBA-15 spherical particles for adsorption of biomolecules, J. Chromatogr. A
1122 (2006) 1320.
[28] T.P.B. Nguyen, J.W. Lee, W.G. Shim, H.Y. Moon, Synthesis of functionalized SBA-
15 with ordered large pore size and its adsorption properties of BSA,
Microporous Mesoporous Mater. 110 (2008) 560569.
[29] R. Grieken, J.M. Escola, J. Moreno, R. Rodrguez, Direct synthesis of mesoporous
M-SBA-15 (M = Al, Fe, B, Cr) and application to 1-hexene oligomerization,
Chem. Eng. J. 155 (2009) 442450.
[30] A. Vinu, V. Murugesan, W. Bohlmann, M. Hartmann, An optimized procedure
for the synthesis of Alsba-15 with large pore diameter and high aluminum
content, J. Phys. Chem. B 108 (2004) 1149611505.
[31] L.F. Chen, L.E. Norea, J. Navarrete, J.A. Wang, Improvement of surface acidity
and structural regularity of Zr-modied mesoporous MCM-41, Mater. Chem.
Phys. 97 (2006) 236242.
[32] M.K. Lam, K.T. Lee, A.R. Mohamed, Homogeneous, heterogeneous and
enzymatic catalysis for transesterication of high free fatty acid oil (waste
cooking oil) to biodiesel: a review, Biotechnol. Adv. 28 (2010) 500518.
794 C. Liang et al. / Chemical Engineering Journal 223 (2013) 785794