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I. S enol
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I. S enol).
immiscibility with hydrocarbon fuels [35]. The oxygen content
of biofuels needs to be reduced, therefore.
The traditional hydrotreating processes used in oil rening
can provide a solution for the upgrading of bio-oils [3,5]. As the
heteroatomto be removed fromthe oil is oxygen, and the oxygen
is eliminated in the form of water in the presence of hydrogen,
the process is called hydrodeoxygenation (HDO). The typi-
cal catalysts, such as alumina-supported nickel-molybdenum or
cobalt-molybdenum, are more active in sulphided form than in
oxide form, and oxygenates present in bio-oils affect the sul-
phide structure negatively. Moreover, since the sulphur content
of bio-oils is low, a sulphiding agent must be added to the feed
to maintain the sulphidation degree of the catalyst [4]. Various
studies have indicated that sulphiding agents affect the HDO
process differently depending on feed composition and process
conditions. For example, the addition of a sulphiding agent to a
bio-oil has generally been found to suppress the HDO of phe-
nolic and furanic compounds on sulphided NiMo/Al
2
O
3
and
CoMo/Al
2
O
3
catalysts [610], but a promoting effect has been
demonstrated in HDO studies with aliphatic oxygenates, such
as esters and carboxylic acids on similar catalysts [11,12].
1381-1169/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2007.07.033
108 O.
C
under atmospheric pressure, as described previously [13]. The
reactants and their concentrations in the reaction mixture (vol-
ume 16 ml) are listed in Table 1. Experiments were carried out
at 250
I. Senol et al. / Journal of Molecular Catalysis A: Chemical 277 (2007) 107112 109
Fig. 1. Concentration proles of phenol (), benzene (), cyclohexane () and
cyclohexene () in the absence of H
2
S at 250
I. Senol et al. / Journal of Molecular Catalysis A: Chemical 277 (2007) 107112 111
Scheme 2. Formations of cyclohexene and cyclohexanethiol by elimination and nucleophilic substitution reactions, respectively.
Cyclohexanethiol can be formed by acid-catalysed S
N
1 and
S
N
2 nucleophilic substitution reactions, as shown in Scheme 2,
and it may react very quickly to cyclohexene via elimination
of H
2
S. The SH
I. S enol, T.-R. Viljava, A.O.I. Krause, Appl. Catal. A: Gen. 326 (2007)
236.
[13] O.