Catal Lett (2010) 134:250–257
DOI 10.1007/s10562-009-0248-9
Diesel-like Hydrocarbons from Catalytic Deoxygenation
of Stearic Acid over Supported Pd Nanoparticles
on SBA-15 Catalysts
S. Lestari • P. Mäki-Arvela • K. Eränen •
J. Beltramini • G. Q. Max Lu • D.Yu. Murzin
Received: 16 October 2009 / Accepted: 3 December 2009 / Published online: 22 December 2009
Ó Springer Science+Business Media, LLC 2009
Abstract Palladium catalysts with different loading on
SBA-15 have been prepared using a direct synthesis
method and characterized with X-ray diffraction, micro-
graph images, and X-ray photoelectron spectroscopy.
Mesoporous Pd-SBA-15 was an active and selective cata-
lyst for deoxygenation of stearic acid in dodecane as a
solvent at 300 °C under 17 bar of 5 vol% H2 in argon as a
carrier gas in a semibatch reactor.
Keywords Deoxygenation
SBA-15
Fatty acids
1 Introduction
The amount of primary energy produced in the world was
500 EJ (5 9 1024 J) in 2005 with 86.5% from fossil fuels.
The energy consumption is projected to expand by 50% in
2030, therefore demand of energy is increasing continu-
ously worldwide [1]. Since fossil fuels are non-renewable
and the source is limited, the development of new tech-
nologies for fuel production becomes a great challenge.
Apart from fossil sources, energy can be also derived from
biomass. Few technologies have been developed for the
conversion of biomass into fuels, such as pyrolysis, gasi-
fication of synthesis gas followed by Fischer–Tropsch
route, as well as transesterification of fatty acid and their
derivatives to fatty acid methyl ester (FAME) [2].
S. Lestari
J. Beltramini
G. Q. Max Lu
ARC Centre of Excellence for Functional Nanomaterials,
University of Queensland, Brisbane, QLD 4072, Australia
S. Lestari
P. Mäki-Arvela
K. Eränen
D.Yu. Murzin (&)
Process Chemistry Centre, Åbo Akademi University, 20500
Turku, Finland
e-mail: dmurzin@abo.fi
123
The next generation of biofuels focuses on diesel-like
hydrocarbons. Thus, it can be utilized directly using current
combustion engines without engine modification, as well as
avoiding the ethical issue of using biomass source compet-
ing with food sources, as is the case of ethanol derived from
agricultural crops. One possible route is via catalytic deox-
ygenation of fatty acids and their derivatives into diesel-like
hydrocarbons which have been recently developed [3–7].
The advantage of deoxygenation route is that no hydrogen is
required which makes the process more economically fea-
sible compared to an alternative hydrotreating process.
The catalytic deoxygenation of different fatty acids has
been intensively investigated, ranging from both saturated
and un-saturated C12 to C22 acids, as well as esters and
triglycerides [8, 9]. Catalyst screening experiments
revealed that Pd supported on either microporous or mes-
oporous carbon catalyst is the most promising catalyst used
in deoxygenation reaction [6]. Typically, a complete con-
version of the representative model compound of fatty
acids, i.e. stearic acid was achieved at 300 °C under 17 bar
of 5 vol% H2 in argon, producing n-heptadecane as the
main product. The off-line gas analysis showed that CO
and CO2 are the main gaseous products, confirming that
deoxygenation occurs via decarbonylation and decarbox-
ylation. Therefore, utilization of a semibatch reactor is
preferable in order to purge out the gaseous products since
CO is well known for poisoning the metal catalyst surface.
Supported metal nanoparticles (SMNPs) have attracted
attention over the past decade due to their superior physi-
cochemical properties compared to their bulk materials.
The ability to control the particle size, shape, and metal
dispersion as well as the advantage of nanoparticle aggre-
gation inhibited by immobilization/separation on the het-
erogeneous support offer the potential for enhanced
selectivity and activity in catalytic applications [10, 11].
Diesel-Like Hydrocarbons from Catalytic Deoxygenation of Stearic Acid
Many immobilization methods and support materials have
been reported in the literature. Han et al. described syn-
thesis of Pd/SBA-15 by one step synthesis method through
sol–gel reaction leading to a catalyst which exhibited high
catalytic activity and better recycling in the Suzuki and
Heck coupling reactions [12].
In this work, Pd nanoparticles on SBA-15 by direct
synthesis have been applied as a catalyst for deoxygenation
of stearic acid. The main parameter under study is the
effects of metal loading. The supported Pd nanoparticles
that have large support surface area and porosity are
reported to be more suitable for catalytic conversion of
larger fatty acid molecules [13–15].
2 Experiment Section
2.1 Materials
The following chemicals were used in preparation of SBA-
15 support and Pd/SBA-15 catalyst: Pluronic P123 triblock
copolymer (EO20PO70EO20), (Sigma–Aldrich) with aver-
age molecular weight, Mn 5,800 and tetraethyl orthosilicate
(TEOS), (Aldrich, purity [99%) as the organic template
and silica sources, respectively. Palladium chloride anhy-
drous, Fluka (purity [60% of Pd) was used as a metal
precursor. In the deoxygenation experiments, a pure, 99%
stearic acid (Sigma–Aldrich) was used as a feedstock and
dodecane (Fluka, purity [98%) was applied as a solvent.
N,O-bis(trimethyl)-trifluoroacetamide, BSTFA was used as
a silylation agent. All chemicals were used as received.
2.2 Synthesis of SBA-15
SBA-15 was synthesized according to the procedures
reported previously [16, 17]. A homogeneous mixture
containing EO20PO70EO20 and TEOS in hydrochloric acid
solution was first stirred in a beaker glass at 40 °C for 2 h.
Then the resultant gel was transferred to a Teflon-lined
autoclave. After the hydrothermal treatment at 100 °C for
24 h, the solid product was recovered by filtration, fol-
lowed by washing with de-ionized water and drying at
50 °C in vacuum. The removal of organic template was
done by ethanol-solvent extraction using an excess amount
of ethanol (1 g of SBA-15/150 mL ethanol) and the mix-
ture was stirred vigorously for 5 h at 60 °C. After being
treated with ethanol for three times, finally the powder was
dried overnight at 100 °C.
2.3 Direct Synthesis of Pd-SBA-15 (In Situ Method)
Palladium anchored SBA-15 with various palladium load-
ing were synthesized by in situ method adopted from
251
Zhang et al. and Selvaraj et al. [18, 19]. In a typical syn-
thesis, 4.0 g of P123 was dispersed in 30 g of de-ionized
water. After stirring the mixture for 4 h, 70 mL of 0.29 M
HCl were added and the solution was stirred for 2 h. Then,
9 g of TEOS and an appropriate amount of palladium
chloride were added under stirring to the above homoge-
neous solution. After further stirring at 40 °C for 24 h, the
resulted gel (molar composition of TEOS:PdCl2:P123:
HCl:H2O & 1:0.0052–0.0748:0.016:0.47:129) was trans-
ferred to a Teflon-lined autoclave for hydrothermal pro-
cessing at 100 °C for 48 h. The obtained mixtures were
washed with de-ionized water, filtered, and dried at 120 °C
overnight. The obtained powders were calcined at 550 °C
for 5 h. The nominal Pd metal loading was calculated
based on weight ratio of palladium to silica which gave
weight percentage in range 0.3–5 wt%. The final sample
then denoted as xPd-SBA-15 in which x represent Pd metal
loading in wt%.
2.4 Catalyst Characterization
The ICP-AES technique was used to determine the palla-
dium content in the final samples. Before analysis, the
samples were digested in a mixture of HF, HCl and HNO3
using a CEM MDS2000 microwave digester at 68% power
for 20 min. The digested samples were analyzed using a
Varian Vista Pro ICP-AES instrument running at 1,200 W
forward power.
The crystal phase and pore structure of samples were
determined by X-ray diffractometer (XRD, Bruker/AXS
D8 Advance) operating at 40 kV using Cu Ka irradiation
(k = 0.15406 nm). The XRD patterns were recorded in the
2h range of 0.5–6o for small angle profiles and 10–90o for
wide-angle profiles. Surface area and pore size distribu-
tions as well as adsorption–desorption isotherms were
measured via N2 adsorption using Quadrasorb with all
samples out-gassed at 120 °C for 6 h before measurement.
The images of samples were recorded by SEM F6300 and
TEM JEOL 1010 operating at 100 kV.
X-ray photoelectron spectroscopy (XPS, Kratos Axis
Ultra) was employed to determine the O 1s, Pd 3d, and Si
2p binding energies of surface oxygen, palladium, and
silicon species with Mono Al Ka (hm = 1486.6 eV) as the
excitation source. The survey and high resolution scans
done at analyzer pass energy of 160 and 20 eV, respec-
tively. The C 1s peak at 284.6 eV was taken as a reference
for binding energy calibration.
The metal dispersion of supported palladium catalysts
were investigated by CO-chemisorption. Detail procedure
and setup used in analysis are described elsewhere [23].
The molar ratio between Pd:CO assumed to be unity
[13].
123
252 S. Lestari et al.

2.5 Catalytic Deoxygenation Reaction

The catalytic deoxygenation of stearic acid was performed

in a semi batch reactor coupled with a condenser and
heating mantle with the liquid phase volume of 100 mL.
The flow of carrier gas and reaction pressure inlet and
outlet were controlled by a flow (Brookle 58505 S) and a
pressure controller (Brookle 5866), respectively. The stir-
ring speed was maintained suitably high, at 1,100 rpm to
prevent external mass transfer limitation. The catalysts
were reduced in situ by hydrogen for 1 h prior to the cat-
alytic test at constant temperature and pressure, 60 °C and
4.8 bar, respectively. In a typical reaction, the catalyst and
feed amount were used as follows: 0.5 g of catalyst;
0.05 M feed (1.4 g of stearic acid, 99% Sigma–Aldrich in
100 mL of dodecane). The reactor was then flushed thor-
oughly with an inert gas. Before the reaction started
25 mL/min of reaction atmosphere gas was passed through
the reactor until reaching the reaction pressure. Thereafter,
the reaction temperature was adjusted with heating ramp
10 °C/min to the desired reaction temperature. At this point
stirring commenced, which was considered as the begin-
ning of the reaction. After the reaction, the catalyst parti-
cles were filtered and washed with acetone for further
characterization. A schematic diagram of the semi batch
reactor used in these experiments is shown in Fig. 1.

2.6 Liquid Samples Analysis

Liquid phase samples were withdrawn from the reactor

vessel via a sampling valve during the experiment. Typi-
cally, the samples had to be dissolved in pyridine and si-
lylated with N,O-bis(trimethyl)-trifluoroacetamide, BSTFA
in order to be analyzed by GC. Generally 100 wt% excess
Fig. 2 Small (a) and wide (b) angle XRD pattern of xPd-SBA-15
synthesized by direct synthesis method with nominal palladium
loading = (a) 0.3 (b) 0.6 (c) 1.5 (d) 3 and (e) 5 wt%

Fig. 1 A schematic diagram of

semi batch reactor used for
deoxygenation experiment

123
Diesel-Like Hydrocarbons from Catalytic Deoxygenation of Stearic Acid 253

Table 1 Actual palladium content, metal dispersion and average crystallite size, and physical properties of Pd supported catalyst
Samplea Actual Pd Pd dispersionc Pd particle Pd particle SfBET (m2/g) Dgp (nm) Vgp (cm3/g)
contentb (wt%) sized (nm) sizee (nm)

SBA15 – 850 6.8 1.4

Direct synthesis
0.3 wt% Pd-SBA-15 0.26 68.0 2.0 3.5 921 5.6 1.3
0.6 wt% Pd-SBA-15 0.38 54.0 2.3 2.2 838 5.1 1.1
1.5 wt% Pd-SBA-15 1.05 30.7 4.1 3.5 934 5.3 1.2
3 wt% Pd-SBA-15 2.92 28.2 4.0 4.3 (3.9h) 870 5.6 (5h) 1.2
5 wt% Pd-SBA-15 3.74 15.0 6.4 4.3 834 5.6 1.2
a
Nominal palladium loading as denoted in sample xPd-SBA-15
b
Determined by ICP-AES
c
Measured by CO chemisorption
d
Measured by CO chemisorption
e
Calculated based on wide angle XRD using Scherrer equation
f
Calculated by BET method
g
Calculated from desorption branch by BJH method
h
Determined from TEM

of BSTFA were added to the sample. After addition of the
silylation agent, the samples were kept in an oven at 60 °C
overnight. The internal standard eicosane, C20H42 was
added for quantitative calculations. The samples were
analyzed with a gas chromatograph (GC, HP 5890)
equipped with non-polar column (HP-1, with dimension of
60 m 9 0.32 mm 9 0.5 lm) and a flame ionization
detector. About 1 lL sample was injected into the GC with
split ratio 50:1, and the carrier gas (helium) flow rate was
137 mL/min. The injector and detector temperature were
280 and 290 °C, respectively. The following temperature
program was used for analysis: 130, 169 °C (1 °C/min)
hold for 15 min, 246 °C (5 °C/min) hold for 3 min and
300 °C (10 °C/min). The gas chromatographic method was
calibrated using the following chemicals: n-heptadecane
(Acros, 99%) and stearic acid (Sigma–Aldrich, 99%). The
product identification was validated with a gas chromato-
graph-mass spectrometer (GC–MS).
3 Results and Discussion
3.1 Phase Structure and Physical Properties
of Supported Pd Catalysts
The small and wide angle of XRD patterns of xPd-SBA-15
synthesized by direct synthesis method are shown in Fig. 2.
It is observed, that almost all samples exhibit one intense
peak at 0.84–0.96o along with two peaks at 1.4–1.5o and
1.6–1.7o, which correspond to 100, 110, and 200 reflec-
tions, respectively (Fig. 2a). These XRD patterns verify the
formation of a typical hexagonal structure of mesopores
SBA-15 as reported by Zhao [17]. These peaks still could
be clearly observed at high loading of Pd although their
intensities are varied to some extent. The results indicated
that the well ordered pore structures of SBA-15 are still
retained in xPd-SBA-15 samples suggesting that the
anchoring of Pd2? during synthesis of mesoporous frame-
work has no significant effect on the formation of mesop-
ores structures.
Figure 2b shows a wide XRD pattern of xPd-SBA-15.
The results demonstrated that at wide diffraction angles,
10–70o all the samples show a relatively sharp peak at
2h = 33–34o assignable to metallic Pd. The intensity of
this peak increased with increasing of Pd content. This
peak is already observed for the sample with Pd loading as
low as 0.3 wt%, however, the exact location of Pd crys-
tallites is unclear. Therefore, more sensitive analysis such
as XPS and morphology imaging were utilized to identify
the position of Pd particles.
The physical properties of xPd-SBA-15 and SBA-15 are
summarized in Table 1. It is seen that SBA-15 sample
possesses high surface area and large pore volume of
850 m2/g and 1.4 cm3/g, respectively, with an average pore
diameter of 6.8 nm. This value is slightly higher from those
reported previously [13, 17]. For the xPd-SBA-15 samples,
with anchoring of Pd ions during synthesis, the surface area
varies in the range 834–934 m2/g, whereas pore volume
and average pore diameter seems to be quite similar,
around 1.2 cm3/g and 5.3 nm, respectively.
The N2 adsorption–desorption isotherm of xPd-SBA-15
are shown in Fig. 3a, which exhibited type-IV isotherms
with a regular type H1 hysteresis loop at relative pressure
(P/P0) of 0.6–0.8. These isotherm features are quite similar

123
254
Fig. 3 a N2 adsorption–desorption isotherm of xPd-SBA-15. Nota-
tion is the same as in Fig. 2; b Pore size distribution of xPd-SBA-15
with increasing Pd loading suggesting that anchoring of Pd
ion by direct synthesis does not affect the mesoporous
channels of SBA-15.
The pore size distributions of xPd-SBA-15 calculated
from the desorption branch by Barrett-Joiner-Halenda
method gave a narrow curve with a maximum at 7.0 nm,
although the intensity were slightly lower with the
increasing of Pd loading on the surface as shown in
Fig. 3b.
Metal dispersion of supported palladium catalysts
gradually decreased by increasing metal loading, as could
be expected (Table 1). Average metal crystallite sizes
determined from CO chemisorption, TEM and XRD agree
very well for the 3 wt% Pd-SBA-15 (Table 1), while some
discrepancy could be observed in the cases of 0.3 wt% Pd
and 5 wt% Pd supported on SBA-15. For the latter catalyst
the average Pd crystallite size was overestimated by 75%
due to the fact that the metal crystallites smaller than 3 nm
cannot be determined by XRD.
The average Pd particles size calculated by Scherrer
equation gave the range 2.2–4.3 nm. When comparing
123
S. Lestari et al.
these numbers with pore size of SBA-15, which are larger,
it can be tentatively concluded that palladium particles are
anchored inside the pore structure of SBA-15. However,
the reliability of metal particle size calculated by Scherer
equation is questionable as TEM shows bigger particle size
of Pd, ca. 7 nm.
The Si 2p, O 1s and Pd 3d XPS spectra of the xPd-SBA-
15 samples are shown in Fig. 4. For the xPd-SBA-15
samples, the symmetric signals of Si 2p remained almost
unchanged at the binding energy of 103.7 eV (Fig. 4a),
whereas the O 1s signals shifted from BE = 533.2 eV for
Pd-SBA-15 with Pd loading = 0.3 wt% to BE = 532.4 eV
for Pd-SBA-15 with Pd loading = 5 wt%. The reason for
the binding energy shift is most probably an interaction
between O and Pd. Moreover, the decline in O 1s peak is
also observed with an increase in Pd content (Fig. 4b).
According to the literature [20–22], the Pd 3d5/2 peak
binding energy at 335 eV is associated with Pd(0) whereas
the Pd 3d3/2 at 337.5–338 eV are characteristic for Pd(II).
For the xPd-SBA-15 samples, the latter two peaks of Pd are
slightly shifted for the sample with Pd loading 0.5–5 wt%.
3.2 Morphology and Pore Structure
Electron microscopic techniques were used for investiga-
tion of surface morphologies and pore structure of
supported Pd samples. Figure 5 shows the SEM images of
xPd-SBA-15, as well as parent SBA-15. It is observed that
SBA-15 possesses a typical long-chain architecture
(Fig. 5a); the pore structure is regular and highly ordered
with a pore size of ca. 5 nm and wall thickness of 6–7 nm.
There was a good correlation of the pore sizes determined
from TEM images and using BJH method (see Sect.3.1).
For xPd-SBA-15 prepared by the direct synthesis method,
the banana-like morphology was still retained in the sample
with Pd loading 3 wt% (Fig. 5c).
3.3 Catalytic Deoxygenation of Stearic Acid
As reported previously, supported palladium catalysts were
found to be the most active and selective catalyst in deox-
ygenation of fatty acid and derivatives to produces diesel-
like hydrocarbons. 6In this work, we aim to examine the
possibility of palladium supported on SBA-15 catalyst for
deoxygenation reaction of stearic acid. As mentioned above
utilization of mesoporous support SBA-15 could give a
beneficial effect for the large molecules as the fatty acids.
The catalytic deoxygenation of stearic acid over sup-
ported palladium catalyst resulted in n-heptadecane as the
main product. Trace amounts of isomer n-C17, i.e. 3-hep-
tadecene and/or 8-heptadecene were also formed in the
liquid phase. A reactant and product concentration profiles
are shown in Fig. 6.
Diesel-Like Hydrocarbons from Catalytic Deoxygenation of Stearic Acid 255

Fig. 4 XPS spectra of xPd-SBA-15 (a, b, c) with Pd loading: (a) 0.6, (b) 1.5, (c) 3, and (d) 5 wt%

Fig. 5 SEM and TEM images,

respectively of: (a, b) parent
SBA15; (c, d) 3 wt%Pd-SBA-
15

The effect of palladium metal loading was investigated metal taking into account metal dispersion were calculated.
by conducting experiments over catalysts with different The highest initial TOF was 0.72 s-1 over 3 wt% Pd,
metal loading. The initial TOFs, defined as the amount of whereas Pd 0.3, 0.6 and 5 wt% catalysts exhibited initial
converted stearic acid divided by time and mole of surface TOF values of 0.16, 0.27 and 0.14 s-1, respectively.

123
256 S. Lestari et al.

A 100

80

Conversion (%)
60

40

20

0 1 2 3 4 5 6 7 8
Time *Mass of Pd (min*g)
Fig. 6 a Kinetics in the deoxygenation of stearic acid over: 3 wt%
Pd-SBA-15. The reaction conditions as follows: Cstearic acid = B
0.049 M (1.4 g in 100 mL of dodecane); masscatalyst = 0.5 g; 100
T = 300 °C; P = 17 bar in 5 vol% H2 in argon

Selectivity to heptadecane (%)

90

The lowest TOF over palladium catalyst with the highest 80

loading of 5 wt% could be associated with the low metal
dispersion. Analogously to these results, an optimum metal 70
dispersion for deoxygenation of stearic and palmitic acid at
300 °C under 17.5 bar H2/Ar (5 vol% H2) was established 60

in [13]. It was stated in [13] that the small Pd particles

exhibited strong interaction with the support and thus their
structure was not suitable for deoxygenation of fatty acids,
while 6 nm Pd particles were too large to be very active in
fatty acid deoxygenation [13]. Comparison of the TOFs for
the 3 wt% Pd/SBA-15 with the one achieved over a
microporous Pd/C under the same reaction conditions using
5 vol% H2 in argon as a carrier gas in a semibatch reactor
3
the results were as follows: In the current case the stearic
acid to Pd mass ratio was 933 resulting in a TOF of
0.72 s-1 and 96% conversion during 300 min reaction time
whereas for 5 wt% Pd/C the mass ratio of stearic acid to Pd
was 900 giving TOF of 0.126 s-1 and 62% conversion of
stearic acid after 360 min3 thus showing that the Pd/SBA-
15 catalyst was more efficient than Pd/C in deoxygenation
of stearic acid.
The catalytic activities after prolonged reaction times
are depicted as a function of normalized time in Fig. 7a.
Stearic acid deoxygenation was very fast over 0.3 and 0.6
wt% Pd-SBA-15 catalysts, whereas lower deoxygenation
rates were achieved over 3 and 5 wt% Pd-SBA-15 cata-
lysts, respectively. The conversion levels after 5 h reaction
time decreased in the following order: 0.6 wt% Pd [ 3
wt% Pd  0.3 wt% Pd  5 wt% Pd (Table 2). In all cases
the catalysts were active after prolonged reaction times, as
can be seen from Fig. 7a. Catalyst deactivation occurred
during the deoxygenation of stearic acid mainly due to the
formation of unsaturated compounds, such as heptadecene,
50
40
0 20 40 60 80 100
Conversion (%)
Fig. 7 a Conversion of stearic acid as a function of normalized time,
b selectivity to heptadecane as a function of conversion in the
deoxygenation of stearic acid over: 3 wt% Pd-SBA-15, b) the effect of
metal loading on the deoxygenation product over supported Pd
catalysts. The reaction conditions as follows: Cstearic acid = 0.049 M
(1.4 g in 100 mL of dodecane); masscatalyst = 0.5 g; T = 300 °C;
P = 17 bar in 5 vol% H2 in argon. Symbols: (open square) 0.3 wt%,
(filled triangle) 0.6 wt%, (open circle) 3 wt% and (filled square) 5
wt% Pd
which was already confirmed in the deoxygenation of
stearic acid over microporous Pd/C [6]. In [6] the BET
surface area of the spent catalyst decreased indicating
coking of the catalyst. The formation of unsaturated C17
compounds was more prominent in ethyl stearate deoxy-
genation under hydrogen scarce conditions [5]. It should be
pointed out here that ethyl stearate deoxygenation proceeds
via formation of stearic acid. In the current work the
deoxygenation atmosphere applied was 5 vol% H2 in
argon, which thus promoted the formation of unsaturated
C17 hydrocarbons.
The selectivity to the main deoxygenation product,
n-heptadecane as a function of conversion is shown in

123
Diesel-Like Hydrocarbons from Catalytic Deoxygenation of Stearic Acid 257

Table 2 Effect of various Pd loading on selectivity and conversion of stearic acid. Reaction conditions as follow: T = 300 °C; P = 17 bar; gas
atmosphere = 5% H2/Ar; cSA,0 = 0.049 M (1.49 g in 100 mL of dodecane); masscatalyst = 0.5 g
Catalyst ConversionSAa % Selectivity (n-C17)
b
% Selectivity (X = 60%)
c
%

Direct synthesis method

0.3 wt% Pd-SBA-15 64 98 98
0.6 wt% Pd-SBA-15 96 98 96
3.0 wt% Pd-SBA-15 94 94 80
5.0 wt% Pd-SBA-15 41 95 84
a
Conversion of stearic acid after 5 h reaction
b
Selectivity to main product of n-heptadecane after 5 h reaction
c
Selectivity to main product of n-heptadecane at conversion of 60%

Fig. 7b, demonstrating that the formation of n-heptadecane
was over 95% after prolonged reaction times. Initially the
formation rate of n-heptadecene was high, but since there
was hydrogen present in the reaction atmosphere, most of
the formed n-heptadecene was hydrogenated to saturated
n-heptadecane during the course of the reaction.
4 Conclusions
The palladium nanoparticles anchored in SBA-15 with
various metal loading have been synthesized by direct in
situ method. The well ordered structures of SBA-15 were
still retained giving surface area in the range of 834–
921 m2/g and average pore size ca. 5.6 nm.
Catalytic deoxygenation of stearic acid was successfully
performed over these materials. The most active catalyst
was 3 wt% Pd-SBA-15 exhibiting high TOF of 0.72 s-1 at
300 °C, under 17 bar of 5 vol% H2 in argon, using 0.5 g of
catalyst and 0.049 M of reactant (in dodecane). The main
deoxygenation product was n-heptadecane with over 90%
selectivity above 95% conversion levels. Furthermore,
trace amounts of unsaturated C17 isomers, such as 3- and/
or 8-heptadecene were formed.
Acknowledgments Siswati Lestari gratefully acknowledges the
research facilities and funding provided by ARC Centre of Excellence
for Functional Nanomaterials, University of Queensland, Australia.
The authors are grateful to Mr. Sandy Budihartono for performing
micrographs analysis of TEM and SEM. The XPS analysis performed
by Dr. Barry Wood from Centre of Microscopy and Microanalysis,
University of Queensland is gratefully acknowledged. This work is part
of activities at the Åbo Akademi Process Chemistry Centre of Excel-
lence Programmes (2000–2011) financed by the Academy of Finland.
References
2. Gerpen JV (2005) Fuel Process Technol 86:1097
3. Kubicková I, Snåre M, Eränen K, Mäki-Arvela P, Murzin DY
(2005) Catal Today 106:197
4. Lestari S, Simakova I, Tokarev A, Mäki-Arvela P, Eränen K,
Murzin DY (2008) Catal Lett 122:247
5. Mäki-Arvela P, Kubickova I, Snåre M, Eränen K, Murzin DY
(2007) Energy Fuels 21:30
6. Snåre M, Kubickova I, Mäki-Arvela P, Eränen K, Murzin DY
(2006) Ind Eng Chem Res 45:5708
7. Snåre M, Kubicková I, Mäki-Arvela P, Eränen K, Wärnå J,
Murzin DY (2007) Chem Eng J 134:29
8. Murzin DY, Kubickova I, Snåre M, Mäki-Arvela P, Myllyoja J
(2009) Method for manufacture of hydrocarbons. US Patent
7491858, 1990
9. Snåre M, Kubicková I, Mäki-Arvela P, Chichova D, Eränen K,
Murzin DY (2008) Fuels 87:933
10. White RJ, Luque R, Budarin VL, Clark JH, Macquarrie DJ (2008)
Chem Soc Rev 38:481
11. Astruc D, Lu F, Aranzaes JR (2005) Angew Chem Int Ed 44:7852
12. Han P, Wang X, Qiu X, Ji X, Gao L (2007) J Mol Catal A Chem
272:136
13. Simakova I, Simakova O, Mäki-Arvela P, Simakov A, Estrada M,
Murzin DY (2009) Appl Catal A Gen 355:100
14. Simakova I, Simakova O, Romanenko AV, Murzin DY (2008)
Ind Eng Chem Res 47:7219
15. Mbaraka IK, Shanks BH (2005) J Catal 229:365
16. Zhao D, Chmelka BF, Stucky GD (1998) Science 279:548
17. Zhao D, Huo Q, Feng J, Chmelka BF, Stucky CD (1998) J Am
Chem Soc 120:6024
18. Selvaraj M, Kawi S (2007) Chem Mater 19:509
19. Zhang L, Zhao Y, Dai H, He H, Au CT (2008) Catal Today
131:42
20. Chen J, Zhang Q, Wang Y, Wan H (2008) Adv Synth Catal
350:453
21. Rossi LM, Silva FP, Vono LLR, Kiyohara PK, Duarte EL, Itri R,
Landers R, Machado G (2007) Green Chem 9:379
22. Wagner CD, Naumkin AV, Kraut-Vass A, Allison JW, Powell
CJ, Rumble JR (2007) NIST X-ray photoelectron spectroscopy
database. National Institute of Standard and Technology (NIST)
Technology Services, United States of America
23. Tanksale A, Beltramini J, Dumesic JA, Lu GQJ (2008) J Catal
258:366

1. International Energy Outlook (2008) Energy information admis-

tration. URL: http://www.eia.doe.gov/oiaf/ieo/

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