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Fuel 87 (2008) 933–945

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Catalytic deoxygenation of unsaturated renewable feedstocks

for production of diesel fuel hydrocarbons
M. Snåre, I. Kubičková, P. Mäki-Arvela, D. Chichova, K. Eränen, D.Yu. Murzin *

Laboratory of Industrial Chemistry, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8 FIN-20500 Åbo-Turku, Finland

Received 25 October 2006; received in revised form 4 June 2007; accepted 5 June 2007
Available online 16 July 2007

Abstract

The liquid-phase deoxygenation reaction of unsaturated renewables has been investigated in a semi-batch reactor. The reactants
examined were the monounsaturated fatty acid, oleic acid, the diunsaturated fatty acid, linoleic acid and the monounsaturated fatty acid
ester, methyl oleate. The reactions were carried out over a Pd/C catalyst under constant pressure and temperature in the following
domain, 15–27 bar and 300–360 C, respectively. The influence of carrier gas was additionally investigated. The impact as solvent (mesit-
ylene) was studied as well and reaction pathways were proposed. Furthermore, continuous deoxygenation experiments were conducted,
facilitating understanding of the catalyst stability and catalyst deactivation. The deoxygenation catalyst was characterized by physisorp-
tion, temperature programmed desorption (TPD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and
scanning electron microscopy (SEM).
 2007 Elsevier Ltd. All rights reserved.

Keywords: Deoxygenation; Renewables; Diesel

1. Introduction 100,000 kg oil/km2, but oil yields of 10–20 times are

There are several reasons for the growing interest of uti-
lizing renewable feedstocks as alternative fuels for the
future, such as the rapid decrease of fossil fuel reservoirs
and currently existing major environmental concerns.
Natural oils and fats are renewable feeds that could be
used for energy utilization. Approximately 100 million tons
of oils and fats were produced worldwide in 2003 [1], from
animal and vegetable feedstocks. At that time the produc-
tion of biodiesel (defined as alkyl fatty acid esters) was,
nevertheless, relatively low, 1.4 million tons [2]. The annual
production of oils and fats, however, could be largely
increased, without touching the sensitive ethical dilemma
of using farmland for energy production. Recently, novel
solutions have been made in order to increase availability
and oil yields. Typically, an oil-bearing crop can yield ca.
*
Corresponding author. Tel.: +358 2 215 4985; fax: +358 2 215 4479.
E-mail address: dmurzin@abo.fi (D.Yu. Murzin).
reported [3]. Moreover, non-edible and high oil yielding
crops that can withstand desert like areas and grow with
a minimal amounts of water are being developed [4–7].
Natural oils and fats are complex mixtures of triglycer-
ides, which contain three fatty acids and a glycerol moiety
[8]. As it is demonstrated in Table 1 [9–11], natural oils and
fats comprise of saturated and unsaturated fatty acids with
a carbon numbers of C4 and C24, typically C16 and C18.
The high carbon numbers, hence high heating values, of
the fatty acid alkyl chains in the natural oils and fats make
them promising potential candidates as diesel fuel if selec-
tively deoxygenated. The selective deoxygenation can be
done by direct removal of the carboxyl group via carbon
dioxide and/or carbon monoxide release [12] (decarboxyl-
ation and/or decarbonylation). It has recently been demon-
strated that saturated feeds over heterogeneous catalysts in
the liquid-phase tend to deoxygenate [13–15], when the
reactants are brought together with, i.e. Pd/C catalyst
under elevated temperatures and pressures.

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.06.006
934 M. Snåre et al. / Fuel 87 (2008) 933–945

Table 1
Content of fatty acids (wt%) in typical natural oils and fats [9–11]
Natural fats and oils Fatty acids
Saturated Unsaturated
C4:0 C6:0 C8:0 C10:0 C12:0 C14:0 C16:0 C18:0 C20:0 C22:0 C24:0 C16:1 C18:1 C20:1 C22.1 C18:2 C18:3
a
Castor 1.1 3.1 4.9 1.3
Coconut 7.1 54.1 17.4 6.1 1.6 5.1 1.3
Linseed 5.1 2.5 0.3 18.9 18.1 55.1
Maize 3.9 11.2 1.8 25.4 60.3 1.1
Olive 7.3 11.0 2.2 67.0 0.3 8.9 0.6
Palm 2.5 40.8 3.6 45.2 7.9
Palm kernel 0.2 4.0 4.3 50.4 17.3 7.9 2.3 11.9 2.1
Peanut 0.1 0.7 0.4 13.7 2.3 1.3 3.0 1.2 0.1 47.8 29.2
Rapeseed 0.6 0.1 5.1 2.1 0.2 0.2 57.9 1.0 0.2 24.7 7.9
Sesame 13.1 3.9 52.8 30.2
Soybean 0.1 0.3 10.9 3.2 0.1 0.1 0.3 24.0 54.5 6.8
a
Castor oil contains ricinoleic, 89.6%, which is a fatty acid with a hydroxyl group CX:Y X and Y defines number of carbons and number of double bonds,
respectively, in the fatty acid molecule.

Nonetheless, a great portion of natural oils and fats con-
tain unsaturated compounds (Table 1) and must therefore
be taken into consideration in the deoxygenation biodiesel
technology.
Production of hydrocarbons by thermolysis of vegetable
oils was performed over metal oxide catalysts [16]. The pre-
sented results showed that during the thermolysis severe
cracking occurred. Analogously production of synthetic
crude petroleum was carried out over an alumina catalyst
[17]. Although, several other studies of hydrocarbon pro-
duction from natural oils and fats have been reported
[18–21], no selective deoxygenation of triglyceride based
feeds for the production of diesel fuel hydrocarbons,
according to our knowledge, has been demonstrated.
Studies related to hydrocarbon production from natural
oils and fats are mainly performed over homogeneous cat-
alysts [22,23]. However, gas phase selective heterogeneous
catalytic decarboxylation of carboxylic acids, such as octa-
noic, benzoic, salicylic acid, etc., has been demonstrated
over palladium and nickel catalysts [24]. Furthermore,
selective manufacture of unsaturated linear hydrocarbons
from saturated fatty acid and fatty acid esters has been
reported over a nickel type catalyst [25]. According to the
previous results obtained from a thorough catalyst screen-
ing study in the deoxygenation of stearic acid [12], palla-
dium on carbon is the catalyst of choice, since it
displayed superior deoxygenation properties.
The aim of the present work is to investigate the possi-
bility to deoxygenate unsaturated renewables yielding die-
sel-like hydrocarbons over palladium catalysts, which
were previously demonstrated to be efficient for saturated
fatty acids and esters.
metric analysis (TGA), X-ray photoelectron spectroscopy
(XPS), temperature programmed desorption of hydrogen
(TPD-H2) and scanning electron microscopy (SEM). The
analytical procedure of nitrogen physisorption technique
can be found elsewhere [12].
2.1.1. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) measurements
were utilized to determine the oxidation states of hydrogen
pretreated and non-pretreated palladium catalyst. The XPS
experiments were carried out in a Perkin-Elmer 5400 X-ray
spectrometer with a base pressure below 9.3 · 107 Pa. Mg
Ka X-rays (1253.6 eV) was used as a primary excitation at
200 W power. The hemispherical energy analyzer, with
instrumental resolution not lower than 0.53, was used with
90 angle between X-ray source and analyzer.
2.1.2. Scanning electron microscopy–energy dispersive X-ray
Analysis (SEM–EDX)
The morphology and the chemical composition of the
catalyst surface were analyzed by scanning electron micros-
copy. The LEO 1530 scanning system was equipped with a
ThermoNoran Vantage analyzer using an acceleration
voltage of 13 keV and a take-off angle of 34.5153.
2.1.3. Thermogravimetric analysis (TGA)
Analysis of coke deposits on spent catalysts was per-
formed by a thermogravimetric technique. The spent cata-
lyst (5 mg) was burnt in synthetic air with a Mettler
Toledo TGA/SDTA 851e instrument. The temperature
ramp of 10 C/min was applied and the catalyst weight loss
as a function of temperature was registered.

2. Experimental 2.1.4. Temperature programmed desorption of hydrogen

2.1. Catalyst characterization
The 5 wt% Pd on charcoal catalyst, provided by Aldrich,
was characterized by nitrogen physisorption, thermogravi-
(TPD-H2)
Temperature programmed desorption of hydrogen on
the palladium catalyst was performed with the Micromeri-
tics Autochem 2910 coupled to GC–MS (Balzers Instru-
ments, Omnistar). The catalyst was reduced with flowing
 M. Snåre et al. / Fuel 87 (2008) 933–945
hydrogen prior to TPD with flowing hydrogen with follow-
ing temperature program: 5 C/min–200 C (2 h), after
which the adsorbed hydrogen was flushed with helium for
30 min. TPD was carried out with a temperature program:
10 C/min–1000 C and a carrier gas flow rate 50 ml/min.
2.2. Experimental setup and procedure
The catalytic experiments were carried out in a 300 ml
semi-batch reactor coupled to a condenser and a heating
jacket. The reaction temperature was kept constant during
reaction at temperatures between 300 and 360 C. The
reaction pressure was adjusted in order to keep the reaction
in liquid phase, generally between 1.5 and 4.2 MPa. Stir-
ring speed was maintained suitably high, 1100 rpm, to pre-
vent external mass transfer limitations. The flow of carrier
gas and the reaction pressure were controlled by a flow
(Brooks 58505S) and a pressure controller (Brooks 5866),
respectively.
A comparison of batch and continuous operations were
performed. The continuous deoxygenation of unsaturated
renewables was carried out in a fixed bed tubular reactor
(reactor dimension: length, 175 mm; internal diameter,
4.4 mm) over the same commercial Pd catalyst. The reac-
tion was carried out in an upward two-phase system and
thus the pressurizing media (inert gas) was introduced after
the reactor.
2.2.1. Reaction chemicals
The commercial 5 wt% Pd supported on carbon
(20.568-0) was supplied by Aldrich. The model compounds
used were, oleic acid (>58% purity, Riedel-de Haën), lino-
leic acid (60–74% purity, Fluka) and methyl oleate (>70%
purity, Aldrich). Detailed composition of technical grade
feedstock as well as the influence of feed impurities on catal-
ysis will be discussed below. The reaction and the reduction
gases, argon, hydrogen (5 vol%)–argon mixture and
hydrogen were provided by AGA. The reaction solvent,
mesitylene (C9H12), was supplied by Fluka (>98% purity).
2.2.2. Reaction procedure
The Pd/C catalyst (1 g) was reduced in situ by hydrogen at
constant reduction temperature and pressure, 200 C and
2 bars, respectively. The catalyst reduction was followed by
introduction of 63 g of the solvent to the reactor via a bub-
bling unit preventing reoxidizing the catalyst. After solvent
introduction the reactor was opened and 23 g (25 wt%)
of feed was placed into it. The reactor was then flushed
thoroughly with an inert gas. Before the reaction started
25 ml/min of inert gas was passed through the reactor until
reaching the reaction pressure. Afterwards the reactor mix-
ture was heated with a temperature rate of 15 C/min to
desired reaction temperature. At this point stirring and reac-
tion time started. After the reaction the catalyst particles were
filtered with 200 ml of acetone for further characterization.
In the continuous system, the 5% Pd/C powder catalyst
was placed between a layer of quartz sand and quartz wool.
935
The catalyst reduction was followed by direct heating and
pressurizing from reduction temperature and pressure
(mentioned previously) to desired reaction temperature
and pressure, respectively. The reaction mixture was con-
tinuously fed through the catalyst bed with the volumetric
flow of 0.05 ml/min.
2.3. Product analysis
2.3.1. Liquid phase analysis
Liquid phase samples were withdrawn from the reactor
vessel via a sampling valve during the experiments. Sam-
ples were silylated with N,O-bis(trimethyl)-trifloroaceta-
mide, BSTFA (Acros Organics, 98+%) in order to
analyze by GC. Generally 100 wt% excess of BSTFA was
added to the sample. After addition of silylation agent,
the samples were kept in an oven at 60 C for 30 min.
The samples were analyzed ex situ with a gas chromato-
graph (GC, HP 6890, Series). The GC was equipped with
a non-polar colonn (DB-5) with dimensions of
60 m · 0.32 mm · 0.5 lm and with a FI- detector. One
microliter of sample was injected into the GC with a split
ratio 50:1 and the carrier gas (helium) flow rate was
137 ml/min. The injector and detector temperature were
265 C and 290 C, respectively. The following chromato-
graphic temperature program was used for analysis:
130 C (constant 5 min)–169 C (1 C/min, constant
5 min)–246 C (5 C/min)–250 C (1 C/min, constant
3 min)–300 C (5 C/min, constant 45 min). The chromato-
graphic pressure program was as well adjusted to achieve
satisfactory separation of the desired product and its iso-
mers. The initial pressure at 172.4 kPa was kept for
30 min, thereafter the pressure was ramped with
34.5 kPa/min until reaching the ending pressure 221 kPa.
A number of chemical standards were purchased enabling
product identification and calibration. Product identifica-
tion was validated with a gas chromatograph –mass spec-
trometer (GC–MS).
3. Results and discussion
3.1. Catalyst characterization
3.1.1. Temperature programmed desorption of hydrogen
Desorption of hydrogen from the Pd/C catalyst exhibits
a maximum at 200 C. This maximum amount of hydrogen
is desorbed from the catalytically active metal. Further-
more, the hydrogen desorbed above 800 C is originating
from dehydrogenation of the carbon support [26] and it
is indicating gasification of the support, i.e. aromatic com-
pounds and hydrogen are formed. Other gaseous products,
such as CO2 and H2O, have desorption maximum at 250
and 220 C, respectively, while CO has a maximum at
700 C (Fig. 1). Based on the literature [26–28] CO2 origi-
nates from lactone, anhydride and/or carboxyl groups on
the catalyst support, while formation of CO is thought
to arise from the decomposition of quinonic, phenolic,
936 M. Snåre et al. / Fuel 87 (2008) 933–945

1.00E-12 2.00E-12 Furthermore, the carbon support seems to originate from

woody raw materials, since the particles are rather irregular
8.00E-13 1.60E-12 and they exhibit a channel-shaped structure [29]. Palladium
H2 agglomerates of around 2 lm are observed (Fig. 2).
6.00E-13 1.20E-12 Predictably, the catalyst particles did not notably change
CO in their shape after pretreatment with hydrogen. Moreover,
a.u.

no sintering on micrometer scale was detected after pre-

4.00E-13 8.00E-13
treatment, hence, the visual metal particles maintained
H 2O
their original size (Fig. 3). Nevertheless, sintering in princi-
2.00E-13 4.00E-13
ple can occur, on the nanoscale, since hydrogen pretreated
CO2
CH4 palladium particles supported on an activated carbon sim-
0.00E+00 0.00E+00 ilar to those used in the present study have been reported to
0 200 400 600 800 1000
Temperature (°C)
agglomerate [30].
As expected, the palladium on carbon catalyst surface
Fig. 1. Temperature programmed desorption of hydrogen and other was mainly composed of C, O and Pd (84.2%, 8.5% and
gaseous emissions. 6.2%). The trace compounds were Na, S, Cl, Si and Fe
(Table 2).
carbonyl and/or ether groups. The carboxyl group is pro-
posed to decompose in the temperature range of 100– 3.1.3. X-ray photoelectron spectroscopy (XPS)
400 C and lactone at higher temperature. Water probably The non-pretreated and the hydrogen pretreated palla-
evolves from moisture and/or the removal of oxygen, orig- dium catalysts were examined by XPS analysis. The metal-
inating from catalyst O2-passivation (typical technique for lic Pd was observed in Pd 3d5/2 with the binding energy
commercial catalysts) and/or the carbon support, by (BE) of 335.2–335.4 eV, which is close to the values
hydrogen. reported in [31,32]. As anticipated, the relative value of
metallic palladium increased with the hydrogen pretreat-
3.1.2. Scanning electron microscopy–energy dispersive X-ray ment procedure, the non-pretreated catalyst contained
analysis (SEM–EDX) 14%, while the pretreated catalyst had 59% of metallic state
The metal supported carbon particles are in the region palladium. The palladium oxide in Pd 3d exhibited a bind-
of 20 lm and very porous based on SEM analysis, which ing energy of 336.0–336.3 eV in the Pd/C catalyst [33].
is in accordance with previously stated textural properties. PdCl2 exhibited binding energies of 336.7–337.2 eV, which

Fig. 2. SEM images of non-pretreated Pd/C catalyst at different magnifications.

Fig. 3. SEM images of a pretreated catalyst at different magnifications.

 M. Snåre et al. / Fuel 87 (2008) 933–945 937

Table 2 the average diameter of metal crystallites is 6.2 nm. How-

Surface composition of 5% palladium on carbon measured by SEM–EDX ever, an investigation of dispersion of palladium at
Element Fraction (wt%) Atom (%) 350 C reduction temperature showed that the dispersion
C 84.26 91.82 decreased to 6% [30]. Mean catalyst particle size is 15 lm
O 8.48 6.94 (Table 4) to avoid interference of internal mass transfer.
Al 0.01 0.01 A decrease of surface area was observed for all examined
S 0.26 0.1
Cl 0.13 0.05
reactants. The most severe surface area decrease of spent
Fe 0.12 0.03 catalyst, indicating coke formation and catalyst deactiva-
Na 0.36 0.2 tion, was detected in the linoleic acid experiment and for
Si 0.12 0.06 deoxygenation of oleic acid at higher temperatures. The
Mg 0.02 0.01 surface area and the pore size distribution of fresh and used
Pd 6.15 0.76
Ca 0.04 0.01
catalysts are illustrated in Table 5.
P 0.05 0.02
3.1.5. Thermogravimetric analysis (TGA)
Table 3 The spent catalysts were studied by TGA, where the cat-
State of palladium compounds supported on carbon for non-pretreated alyst was burnt in synthetic air and the weight loss was reg-
and pretreated catalyst measured by XPS istered. The catalyst used in deoxygenation of linoleic acid
State of Pd/C under Ar atmosphere demonstrated higher relative amount
palladium of weight loss in the temperature range of 200–800 C, than
Non-pretreated Pretreated
Relative area BE (eV) Relative area BE (eV) the catalyst used for oleic acid deoxygenation under
(%)a (%)a Ar + H2 atmosphere (Fig. 4). Furthermore, the catalyst
Pd(0)/C 14.5 335.3–335.4 56.0 335.3–335.4 used in deoxygenation of methyl oleate under pure hydro-
PdO (d+)/C 9.2 335.9 22.3 336.0–336.3 gen atmosphere illustrated the lowest relative amount of
PdCI2 (ll)/C 54.8 336.9–337.0 10.9 336.7–337.2 weight loss as a function of temperature, thus, indicating
337.4–337.9 337.7–338.2 that lighter coke molecules are formed in inert atmosphere
Other 21.6 339.1–339.2 10.9 339.4–339.8
than under hydrogen rich conditions. Possible explanation
a
Relative to the Pd 3d peak. is that CO, which is formed during deoxygenation, is deac-
tivating the catalyst in inert atmosphere, while under
are in accordance with the literature [32]. The total chlorine hydrogen atmosphere CO is being reduced by hydrogen
content was relatively high also according to EDXA anal- to CH4.
ysis in the non-pretreated fresh Pd/C, whereas the chlorine
content in the pretreated catalyst was much lower. Other 3.2. Catalytic deoxygenation of unsaturated renewables
binding energies observed were 337.4–338.2 and 339.1–
339 eV (Table 3). The most common unsaturated fatty acids in vegetable
oils, e.g. oleic acid and linoleic acid as well as oleic acid
3.1.4. Textural properties of the deoxygenation catalyst methyl ester were investigated (Table 1 and Fig. 5) and
The commercial palladium on carbon is a high surface methyl oleate.
area catalyst with specific pore volume of 0.43 ml/g. The The experiments were conducted under constant tem-
metal dispersion is 18% after pretreatment at 200 C, thus perature (300–360 C) and pressure (15–27 bar) with tech-

Table 4
Textural properties of fresh 5% Pd/C catalyst [14]
Metal loading Palladium metal Particle size Surface area Specific pore volume
(wt%) Surface area (m2/gmet) Dispersion (%) Mean (lm) >50 lm (%) (m2/gcal) (ml/gcat)

5 80.2 18.0 15 96.6 1214 0.431

Table 5
Physisorption results of spent 5% Pd/C catalysts used under different feeds
Reactant Reaction conditions N2-physisorption
Temperature (C) Pressure (bar) Surface area Micropore volume
2
Used (m /gcat) Decrease (%) Used (ml/gcat) Decrease (%)
Oleic acid 300 15 (Ar) 492 59.5 0.19 55.9
Oleic acid 330 21 (Ar + H2) 250 79.4 0.09 79.1
Linoleic acid 300 15 (Ar + H2) 367 69.8 0.19 55.9
Methyl-oleate 300 15 (H2) 591 51.3 0.21 51.3
938 M. Snåre et al. / Fuel 87 (2008) 933–945

100 Table 6
Oleic acid (330 C, Ar+H2)
Composition of technical grade oleic acid, linoleic acid and methyl oleate
based on GC analysis
Linoleic acid (300 C, Ar+H2)
Weight loss of combustibles (wt%)

80
Methyl oleate (300 C, H2) Fatty acid Structure Technical grade feedstocks
Oleic Linoleic Methyl
acid acid oleatea
60
Palmetic acid C16:0 4.3 8.4 4.7
Palmitoleic C16:1(cis-9) 4 0 3.8
acid
40 Stearic acid C18:0 1.1 4.8 1.7
Oleic acid C18:1(cis-9) 63.7 15.1 59.8
Elaidic acid C18:1(trans-9) 11.2 0.9 6.8
20 Vaccenic acid C18:1(cis and 0.7 0.1 0.6
trans-11)
Linoleic acid C18:2(cis–cis-9-12) 5.2 67.6 12.1
Other 9.8 3.1 10.5
0
150 250 350 450 550 650
impurities
a
Temperature (°C) Fatty acids in the methyl ester molecule.

Fig. 4. Weight loss in TGA for catalysts used in the deoxygenation of

unsaturated feeds.
CH3-(CH2)7- -(CH2)7- C
Oleic acid
CH3-(CH2)7-
Fig. 5. Chemical structure of the unsaturated model compounds, oleic
acid, linoleic acid and methyl oleate.
nical grade reactants. Notably, when using technical grade
chemicals one has to take into consideration the analytical
complexity. The three different feeds varies substantially in
purity and the impurities can be cumbersome to separate
from the main compound in the gas chromatograph
(GC) leading to a summation of isomers in order to achieve
reprocessable data. The initial concentrations of the model
compounds and the main impurities according to GC anal-
ysis are summarized in Table 6.
The catalytic performance was evaluated based on initial
rate of feed consumption after 1 min, conversion of feed
after 6 h and selectivity towards product formation. Con-
version of feed is defined as
C 0;RC18:Y  C t;RC18:Y
Xt ¼  100%
C 0;RC18:Y
where C 0;RC18:Y is initial concentration of all unsaturated
fatty acids or esters. In oleic acid experiments this includes
vaccenic acid and elaidic acid, while in linoleic acid exper-
iments, linoleic isomers are included. Similarly methyl ole-
ate isomers are incorporated in the original feed. At the
arbitrary time, t, the feed concentration is C t;RC18:Y .
3.2.1. Deoxygenation of monounsaturated fatty acid
Preliminary results indicated that direct deoxygenation
of oleic acid to olefins occured. However, the deoxygen-
ation reaction was additionally accomplished via hydroge-
nation of double bonds and further through deoxygenation
of saturated acid (Fig. 6).
O
O Under inert atmosphere the source of hydrogen for the
CH3-(CH2)4- -(CH2)7- C hydrogenation process was provided through a simulta-
Linoleic acid OH
OH neous, hydrogen re-distribution reaction, e.g. dehydroge-
O nation of the feed to unsaturated by-products such as
-(CH2)7- C diunsaturated acids, triunsaturated acids as well as aromat-
Methyl-oleate O-CH3 ics and additionally through preadsorbed H2 on the surface
(Figs. 6–8). Furthermore, positional and geometrical isom-
erization of oleic acid, e.g. to elaidic and vaccenic acid,
seems to be the intermediate reactions prior to the hydro-
genation step, which is in accordance with literature
[34,35]. Thereafter, the deoxygenation reaction is taking
place, the main deoxygenation product is n-heptadecane,
but minor amounts of unsaturated positional isomers
(1-, 3-, and 8-heptadecene) and C17 aromatics are detected.
In addition, some formation of heavier products was
observed as well as the traces of lighter products formed
by cracking. The heavier molecules could not be properly
identified, however, according to GC–MS analysis the
molecular masses were above 400.
A summary of the experiments conducted with unsatu-
rated renewables is provided in Table 7.
3.2.1.1. Effect of solvent and pretreatment under inert
atmosphere in oleic acid deoxygenation. The effect of cata-
ðIÞ
lyst pretreatment by hydrogen and the solvent nature were
investigated under inert atmosphere at 300 C. The results
showed that the pretreated catalyst, accelerated initially the
isomerisation and hydrogenation rates compared to the
non-pretreated catalyst. The higher rates are presumably
due to differences in palladium oxidation states, since the
hydrogen pretreated catalyst had a significantly higher
amount of metallic palladium than the non-pretreated
one as from XPS results. The solvent free reaction exhib-
ited the same degree of conversion even though the concen-
tration was fourfold (0.83 mol/l and 3.15 mol/l) compared
to the experiment conducted in mesitylene. Since the
 M. Snåre et al. / Fuel 87 (2008) 933–945 939

Heavy byproducts (dimers, aromatics) Light byproducts (cracking)

Polyunsaturated acids
Other C18:X acids
+H2/-H2
O
CH3-(CH2)4- -(CH2)7- C
+H2/- Linoleic acid OH +H2/-
H2
H2 O
O
CH3-(CH2)7- CH3-(CH2)5- -(CH2)9- C
-(CH2)7- C
OH cis-Vaccenic acid OH
Oleic acid

CH3-(CH2)7- O CH3-(CH2)5- O
+H2
-(CH2)7- C +H2 -(CH2)9- C
Elaidic acid OH +H2 +H2 trans-Vaccenic acid OH
O
CH3-(CH2)16- C -CO2
OH
Stearic acid
Other C17 hydrocarbons
-CO2

CH3-(CH2)15-CH3
Heptadecane

Fig. 6. Reaction scheme of oleic acid deoxygenation under inert atmosphere.

9
70 Linoleic acid
8
Oleic acid
60 7 n-heptadecane
Concentration (mol%)

Elaidic acid
Other C17-products
Vaccenic acid 6
Lighter
Concentration (mol%)

50
5 Heavier
Other C18:x -acids
40 4
Stearic acid

3
30
2
20
1

10
0
0 60 120 180 240
Reaction time (min)
Fig. 7. Typical reactant and intermediate concentration profiles in the
catalytic deoxygenation of oleic acid over 5% Pd/C. Reaction conditions:
coleic acid = 3.15 mol/l (solvent free), mcatalyst = 1 g, T = 300 C,
p = 15 bar, V_ carrier gas ¼ 25 ml=min ðArÞ.
solvent, mesitylene, is highly unsaturated it should not act
as an hydrogen donor, but on the contrary as a hydrogen
acceptor [36]. Subsequently, the deficit of hydrogen in the
solvated system retards the hydrogenation step, while the
solvent free condition enhances the reaction (Figs. 7–9b).
The presence of hydrogen is, of course, necessary in the
hydrogenation step, however, hydrogen is, as well, known
to enhance the isomerisation rate [35,37]. When comparing
selectivity towards formation of heavier products in mesit-
ylene and solvent free system, it is noticed that heavier
0
0 60 120 180 240 300 360
Reaction time (min)
300 360 Fig. 8. Typical final product concentration profiles in the catalytic
deoxygenation of oleic acid over 5% Pd/C. Reaction conditions: coleic acid =
3.15 mol/l (solvent free), mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼
25 ml=min ðArÞ.
products are not present in solvent free systems, whereas
in mesitylene a relatively high amount of heavies are
detected. Additionally, the very concentrated solvent free
mixture might be affected by mass transfer limitations
(Table 6 (runs I–III) and Fig. 9).
3.2.1.2. Effect of reaction atmosphere in oleic acid deoxy-
genation. Separate experiments were conducted under
hydrogen atmosphere in order to suppress the dehydroge-
nation step. Consequently, oleic acid was deoxygenated
under an Ar + H2 atmosphere. As expected, over Pd/C in
the presence of hydrogen the conversion of unsaturated
 940
Table 7
Summary of semi-batch deoxygenation results after 6 h reaction time
Run Reactant Reaction conditions Conversion Selectivityd
c
Temperature Pressure XMain feed XTotal feed SME-SA SSA Sn-C17 S RC17 SLight SHeavy
(C) (bar) (%) (%) X = 35% t=6h X = 35% t=6h X = 35% t=6h X = 35% t=6h X = 35% t=6h X = 35% t=6h
a
I Oleic acid 300 15 (Ar) 79 49 – – 79 77 4 6 9 9 7 7 1 0

M. Snåre et al. / Fuel 87 (2008) 933–945

IIb Oleic acid 300 15 (Ar) 93 45 – – 63 64 5 5 18 17 13 12 1 2
III Oleic acid 300 15 (Ar) 74 50 – – 61 60 4 6 20 21 12 9 3 4
IV Oleic acid 300 15 98 78 – – 57 63 4 14 20 13 7 9 12 2
(Ar + H2)
V Oleic acid 330 21 99 92 – – 54 25 8 22 23 14 13 24 3 14
(Ar + H2)
VI Oleic acid 360 27 99 91 – – 54 36 5 26 26 17 12 16 2 4
(Ar + H2)
VII Linoleic 300 15 100 34 – – 64 64 3 3 11 11 13 13 9 9
acid (Ar + H2)
VIII Methyl- 300 15 99 84 87 87 2 2 0 3 9 5 1 2 1 1
oleate (Ar + H2)
IX Methyl- 300 15 (H2) 100 96 – 71 – 0 – 26 – 2 – 1 – 0
oleate
X Methvl- 300 15 (Ar) 91 44 80 81 3 2 0 0 7 7 8 7 3 3
oleate
Reaction conditions: coleic acid in mesitylene = 0.83 mol/1 (solvent free = 3.15 mol/1), mcatalyst = l g, V_ carrier gas ¼ 25 ml=min ðArÞ.
a
No solvent, 100% oleic acid.
b
No catalyst pretreatment.
c
Conversion of total feed is defined as conversion of all identified unsaturated acids or esters.
d
Selectivity at 35% of conversion of total 1eed (linoleic acid at 34%) and after 6 h of reaction , Et-SA = methyl stearate, SA = stearic acid, n-C17 = n-heptadecane, RC17 ¼ other C17 products.
 M. Snåre et al. / Fuel 87 (2008) 933–945 941

70
a 70 Linoleic acid Linoleic acid
Oleic acid Oleic acid
Elaidic acid 60 Elaidic acid
60
Vaccenic acid Vaccenic acid
Other unsaturated acids Other unsaturated acids

Concentration (mol%)
Concentration (mol%)

50 50 Stearic acid
Stearic acid
n-heptadecane
n-heptadecane
40 Other C17 products
Other C17 products 40

30
30

20
20

10
10

0
0 60 120 180 240 300 360 0
Reaction time (min) 0 60 120 180 240 300 360
Reaction time (min)
b 70 Linoleic acid
Oleic acid Fig. 10. Deoxygenation of oleic acid over Pd/C. Reaction conditions:
60
Elaidic acid coleic acid = 0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼
Vaccenic acid 25 ml=min ðAr þ H2 -mixtureÞ.
Other unsaturated acids
Concentration (mol%)

50 Stearic acid
n-heptadecane
40 Other C17 products Conversion of unsaturated C18-acids (%)
100
30
80
20

60
10

0 40 360°C & 27 bar

0 60 120 180 240
Reaction time (min)
Fig. 9. Effect of 5% Pd/C catalyst reduction in the deoxygenation of oleic
acid. Concentration profile versus reaction time for a) non pretreated and
b) hydrogen pretreated palladium catalyst. Reaction conditions: coleic acid =
0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼
25 ml=min ðArÞ.
acids increased compared to experiments under inert atmo-
sphere. Furthermore, the formation of unwanted polyun-
saturated acids was substantially diminished, whereas the
formation of saturated hydrocarbons increased (Table 6
(runs III and IV) and Fig. 10).
3.2.1.3. Effect of reaction temperature and pressure in oleic
acid deoxygenation. The effect of temperature in oleic acid
deoxygenation was studied in the temperature range of
300–360 C. The reaction pressure was varied in accor-
dance with the vapour pressure of the reaction mixture.
Reaction rate, as expected, increased with increasing tem-
perature. At 300 C the conversion of unsaturated acids
(lumped) was 78% after 6 h, while the conversion was
approximately 93% at 330 and 360 C (Fig. 11). The visible
‘‘conversion plateau’’ appearing in the beginning of the
reaction is attributed to the internal isomerisation of unsat-
urated acids. The isomerisation step seems to be sufficiently
slower at lower temperatures. The apparent activation
energy, based on the Arrhenius equation and first order
kinetics after 45 min, is 59 kJ/mol.
300 360
330°C & 21 bar
20
300°C & 15 bar
0
0 60 120 180 240 300 360
Reaction time (min)
Fig. 11. The effect of temperature and pressure on conversion of
unsaturated C18-acids under H2:Ar (5:95 vol%) atmosphere. Reaction con-
ditions: coleic acid = 0.83 mol/l, mcatalyst = 1 g, V_ carrier gas ¼ 25 ml=min
ðAr þ H2 -mixtureÞ.
The consumption rate of unsaturated acids is more
retarded after 1 h for the reaction at higher temperatures,
implying stronger catalyst deactivation at elevated temper-
atures. Most likely, the catalyst deactivation originates
from the solvent (as depicted earlier) or from the reactant
causing coke which covers the catalyst surface. The
assumption is strengthened by the surface area measure-
ments of the spent catalysts (see Table 5). The specific sur-
face areas of the spent catalysts used at high reaction
temperatures exhibited the lowest surface areas. If the cat-
alytically active metal particle is located inside the blocked
pore the catalytic activity is decreased at the same time.
The selectivity patterns as a function of conversion
seems to be dependent on temperatures, hence the forma-
tion of products is affected by reaction temperature
(Fig. 12). At 300 C, the selectivity to stearic acid increases,
initially, up to ca. 40% of conversion, thereafter formation
of n-heptadecane is enhanced, indicating a consecutive
942 M. Snåre et al. / Fuel 87 (2008) 933–945

Stearic acid n-heptadecane reported in the deoxygenation of saturated fatty acid esters
60
[13] was not detected. One of the possible explanations is
fast deoxygenation of stearic acid compared to methyl stea-
50
rate. At the same time comparison of the reaction rates
40
indicate that more probable is the direct deoxygenation
Selectivity (%)

of methyl stearate (methyl oleate). Similarly, the deoxygen-

30
300°C & 15 bar ation of ethyl stearate was additionally suggested to pro-
330°C & 21 bar
ceed via direct formation of n-heptadecane through CO
360°C & 27 bar
20 and ethanol release [38].

10
0
0 20 40 60
Conversion of unsaturated C18-acids (%)
Fig. 12. The effect of temperature and pressure on product selectivities
versus conversion of unsaturated C18-acids under H2:Ar (5:95 vol%)
atmosphere. Reaction conditions: coleic acid = 0.83 mol/l, mcatalyst = 1 g,
V_ carrier gas ¼ 25 ml=min ðAr þ H2 -mixtureÞ.
reaction. However, formation of heavier products is pre-
dominant in the beginning of the reaction. Speculatively,
the unidentified heavier product could be intermediate acid
isomers, which could explain the observed phenomenon.
Furthermore, an increase in temperature slightly improved
the rate of the consecutive deoxygenation reaction.
3.2.2. Deoxygenation of monounsaturated fatty acid methyl
ester
The deoxygenation of the oleic acid derivative, methyl
oleate, was studied at 300 C over Pd/C. The deoxygen-
ation of methyl oleate proceeded via a similar pathway as
previously stated in oleic acid deoxygenation (Fig. 13),
i.e. the main reaction routes were isomerization and hydro-
genation. Methyl stearate was an intermediate product
formed via hydrogenation of methyl oleate and subse-
quently deoxygenation to n-heptadecane. However, the
formation of the fatty acid intermediate, previously
3.2.2.1. Effect of reaction atmosphere in methyl oleate
deoxygenation. The effect of hydrogen atmosphere in the
80 100 deoxygenation reaction of methyl oleate was investigated
by using pure hydrogen, a mixture of Ar + H2 and inert
gas, Ar. The results demonstrated that hydrogen has a con-
siderable effect on the deoxygenation reaction. Methyl ole-
ate was immediately completely converted to methyl
stearate under neat hydrogen atmosphere, while the hydro-
genation rate significantly decreased with lower partial
pressures of hydrogen (Figs. 14 and 15).
Under Ar and Ar + H2 (5%) atmosphere the formation
of C17 products was noticed at lower conversions indicat-
ing that methyl oleate is reacting directly to olefinic C17
products, which is in accordance with previous reports.
The hydrogenation and isomerisation commenced at
higher conversions. The formation of n-heptadecane was,
however, limited to the reactions taking place under pure
hydrogen atmosphere, where the hydrogenation and isom-
erisation steps were instantaneous, whereas in hydrogen
deficit conditions, under Ar and Ar + (5%)H2 atmosphere,
the formation of deoxygenation products were barely
detectable (Fig. 15).
Since the hydrogenation step was almost instantaneous
under neat hydrogen atmosphere, the deoxygenation step
could be investigated by plotting selectivity towards C17-
products versus conversion of the intermediate, methyl
stearate. Results showed high selectivity towards the
desired deoxygenation products (Fig. 16), with above

Linoleic methyl ester

100
Oleic methyl ester
70 Elaidic methyl ester
Vaccenic methyl ester
unsaturated metylesters (%)

60 Other unsaturated methyl ester 80

Stearic methyl ester
Concentration (mol%)

n-heptadecane
50 Other C17 products
Conversion of

60
40

30 40

20 Ar
20
10
Ar-5%H
Ar + 5%2
H2
Ar
0 0
0 60 120 180 240 300 360 0 60 120 180 240 300 360
Reaction time (min) Reaction time (min)

Fig. 13. Deoxygenation of methyl oleate over Pd/C. Reaction conditions: Fig. 14. The effect of reaction atmosphere on conversion of unsaturated
cmethyl oleate = 0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼ methyl-C18 esters over 5% Pd/C. Reaction conditions: coleic acid = 0.83 mol/l,
25 ml=min ðAr þ H2 -mixtureÞ. mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼ 25 ml=min.
 M. Snåre et al. / Fuel 87 (2008) 933–945 943

= methyl stearate, = n-heptadecane and = other C17 products 80 Linoleic acid

100 Oleic acid
Elaidic acid
70
80 Vaccenic acid
Other unsaturated acids
Selectivity (%)

Ar 60

Concentration (mol %)
60 Stearic acid
Ar-5%H2 n-heptadecane
Fig. 16 50 Other C17 products
40 H2
40
20
30
0
0 20 40 60 80 100 20
Conversion of unsaturated methyl esters (%)
10
Fig. 15. The effect of reaction atmosphere on product selectivities as a
function of unsaturated methyl-C18-ester over 5% Pd/C. Reaction 0
conditions: coleic acid = 0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar, 0 60 120 180 240 300 360
V_ carrier gas ¼ 25 ml=min. Reaction time (min)

Fig. 17. Deoxygenation of linoleic acid. Reaction conditions: clinoleic acid =

0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar, V_ carrier gas ¼ 25 ml=min
= n-heptadecane and = other C17 products
ðAr þ H2 -mixtureÞ.
100

80
conversion after 6 h, 78% and 84%, respectively. Under-
standably, the conversion level was lower for linoleic acid,
Selectivity (%)

60 since an additional hydrogenation step, from diunsaturated

40
20
0
0 4 8 12
Conversion of saturated methyl esters (%)
Fig. 16. The formation of C17-products versus conversion of the
saturated methyl-C18-ester, methyl stearate over 5% Pd/C. Reaction
conditions: coleic acid = 0.83 mol/l, mcatalyst = 1 g, T = 300 C, p = 15 bar,
V_ carrier gas ¼ 25 ml=min ðH2 Þ.
80% of saturated fatty acid ester was converted to n-hepta-
decane and other C17 products (1-, 3- and 8-heptadecene).
3.2.3. Deoxygenation of diunsaturated fatty acid
Deoxygenation of the diunsaturated acid, linoleic acid,
was performed under the same conditions under Ar + H2
atmosphere as in oleic acid and methyl oleate experiments
in order to obtain comparable results. The deoxygenation
of linoleic acid proceeded analogously to the previously
described feedstocks by hydrogenation to monounsatu-
rated and saturated acids and finally via deoxygenation
to hydrocarbons (Fig. 17).
3.2.4. Comparison of different unsaturated feeds
Comparison of the deoxygenation of different feeds was
performed at 300 C with Ar + H2-mixture (Table 7, runs
IV, VII and VIII). The comparison illustrated that all feeds
were completely converted after 6 h. Nonetheless, when
considering the total unsaturated acids or esters converted,
the diunsaturated linoleic acid exhibited the lowest conver-
sion level (34%) after 6 h of reaction, while monounsatu-
rated oleic acid and methyl oleate displayed higher
to monounsaturated, is included. Moreover, catalyst deac-
tivation by coke formation was more pronounced with lin-
oleic acid as the feed, according to TGA and physisorption
results (Fig. 4 and Table 3). The selectivity towards desired
products at 35% of converted total unsaturated feed was
16 20 enhanced in reactions conducted with oleic acid. Further-
more, the formation of higher products was substantially
higher for the two acids than for the methyl ester (Table 7).
3.2.5. Continuous deoxygenation of unsaturated feeds
The impact of using unsaturated feeds in an more indus-
trial like process was investigated by deoxygenating oleic
acid in solvent free conditions over the same Pd/C catalyst
in a continuous fixed bed system (residence time of 8 min).
As previously noticed in the semi-batch study the deoxy-
genation reaction proceeds via initial isomerisation and
hydrogenation step following the subsequent deoxygen-
ation of saturated acid. Simultaneously dehydrogenation
of oleic acid is taking place. The deoxygenation is as well
carried out via direct formation of olefins from unsaturated
acid. The concentrations of saturated, mono- and diunsat-
urated acids versus time-on-stream are illustrated in
Fig. 18. The catalyst behaviour seems to be fairly stable,
hence no significant catalyst deactivation was observed
under these conditions.
The product distribution is similar to those obtained in
the batch operations. The intermediate, stearic acid, is the
most abundant product formed (selectivity <70%). The
selectivity towards dehydrogenation and higher boiling
products is ca. 20%, whereas the formation of hydrocar-
bons, mainly olefins and aromatics, is moderately low
(Fig. 19).
3.2.5.1. Comparison of productivity in batch and continuous
mode. A comparison of operation modes were performed
944 M. Snåre et al. / Fuel 87 (2008) 933–945

60 reaction became predominant. Additionally, isomerisation

monounsaturated acid
(double bond migration) of oleic acid occurred prior to
50 hydrogenation and deoxygenation. Analogous isomerisa-
Concentration (mol %)

tion, hydrogenation and deoxygenation trends were

40
observed in experiments conducted under H2 atmosphere
with other unsaturated feeds. Furthermore, the deoxygen-
30
diunsaturated acid
ation of unsaturated feeds was performed in continuous
20
mode under conditions of strong mass transfer influence,
confirming, however, catalyst stability and potential indus-
10 trial applicability.
saturated acid

0 Acknowledgements
0 60 120 180 240
Time-on-stream (min)
This work is part of the activities at the Åbo Akademi
Fig. 18. Concentration of acids as a function of time-on-stream in Process Chemistry Centre (ÅA-PCC) within the Finnish
continuous deoxygenation reaction over Pd/C. The reaction conditions:
Centre of Excellence Programme (2000–2011) appointed
T = 300 C, p = 1 bar (Ar), coleic acid = 3.15 mol/l (100%), mcatalyst = 0.2 g,
V_ liquid flow ¼ 0:05 ml=min. by the Academy of Finland. Financial support from
TEKES is gratefully acknowledged. The authors express
their gratitude to Markku Reunanen for his contribution
90
to GC–MS analysis and to Clifford Ekholm for his helpful
75 SEM characterization measurements.
Selectivity (%)

n-heptadecane
60
other C17-products
45 stearic acid
dehydrogenation and heavier products
30
15
0
0 60 120 180
Time-on-stream (min)
Fig. 19. Selectivity of products as a function of time-on-stream in
continuous deoxygenation of oleic acid over Pd/C. The reaction condi-
tions: T = 300 C, p = 1 bar (Ar), coleic acid = 3.15 mol/l (100%), mcatalyst =
0.2 g, V_ liquid flow ¼ 0:05 ml=min.
at similar reaction conditions with the exception of total
pressure. The pressure of the inert gas should not, however
affect the catalytic performance significantly, hence the
pressure effect is assumed to be negligible. The productivity
in semi-batch operations under solvent free conditions is
29.2 mmol/h gcat, whereas in continuous fixed bed opera-
tions, the productivity was 2.3 mmol/h gcat. The lower pro-
ductivity of one order of magnitude detected in continuous
mode could be attributed to mass transfer limitations in the
tubular fixed bed reactor.
4. Conclusions
Deoxygenation of unsaturated renewables, such as oleic
acid, methyl oleate and linoleic acid, with high selectivity to
saturated diesel fuel range hydrocarbons, was successfully
accomplished over Pd/C, proceeding in the studied param-
eter range via initial hydrogenation of double bonds and
subsequent deoxygenation of corresponding saturated
feeds. Parallel to hydrogenation formation of diunsatu-
rated acids occurred. Under a hydrogen rich atmosphere
the hydrogenation was enhanced and the deoxygenation
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