Applied Catalysis B: Environmental 101 (2011) 239–245

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Applied Catalysis B: Environmental

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Hydrodeoxygenation of guaiacol with CoMo catalysts. Part I: Promoting effect

of cobalt on HDO selectivity and activity
Van Ngoc Bui, Dorothée Laurenti ∗ , Pavel Afanasiev, Christophe Geantet
Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), UMR 5256, CNRS-Université Claude Bernard Lyon1, 2 av. Albert Einstein,
69626 Villeurbanne, cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Unsupported and alumina-supported MoS2 and CoMoS catalysts have been compared in the hydrodeoxy-
Received 6 July 2010 genation (HDO) reaction of guaiacol (2-methoxyphenol), a typical model molecule for bio-oils coming
Received in revised form 19 October 2010 from the pyrolysis of ligno-cellulosic biomass. The goal of this work was to understand the cobalt pro-
Accepted 21 October 2010
moting effect on MoS2 phase in this type of catalytic reaction. It appeared clearly that in the presence
Available online 28 October 2010
of the CoMoS phase, the direct deoxygenation (DDO) pathway involved in guaiacol conversion was
strongly increased as compared to the non-promoted MoS2 in the bulk or supported state. This effect
Keywords:
is similar to the well-known increase of direct desulfurization (DDS) pathway by cobalt promoter in the
Hydrodeoxygenation
Guaiacol
hydrodesulfurization (HDS) of refractory sulfur compounds over molybdenum sulfide catalysts.
MoS2 © 2010 Elsevier B.V. All rights reserved.
CoMoS
MoS2 /Al2 O3
CoMoS/Al2 O3

1. Introduction
The idea of turning farm products into fuel seemed, for a time,
to be one of the answers to high global oil prices and supply wor-
ries. This strategy was followed by many countries like USA, Brazil
or EC [1]. However, a strong reaction is growing against such pol-
icy since these fuels are driving up food prices and starving poor
people. Thus, a second generation of biofuels is under develop-
ment dealing with biomass which does not interfere with food
production. Significant quantities of such biomass are available
from timber industries, residues of pulp and paper manufacture,
by-products from fermentation and other residues [2]. One alter-
native for the transformation of this raw matter is a conversion
into “bio-liquid”, so called bio oil, by fast pyrolysis [3–5] and sub-
sequent appropriate upgrading [6]. The liquid products resulting
from such wood pyrolysis or high pressure liquefaction (bio-oils)
contain small amounts of sulfur compounds, but possess high oxy-
gen content, about 15–40% weight [7]. These feedstocks can be
used as crude oil substitute in conventional refinery units and thus
may afford significant CO2 emission abatement. The possibility
to co-process these bio oils in the refining units may provide an
Abbreviations: DME, demethylation; DMO, demethoxylation; GUA, guaiacol;
CAT, catechol; PHE, phenol; Me-CAT, methyl-catechol; Me-PHE, methyl-phenol.
∗ Corresponding author. Tel.: +33 472445327; fax: +33 4 72445399.
E-mail address: dorothee.laurenti@ircelyon.univ-lyon1.fr (D. Laurenti).
easy way to convert them into valuable fuels. In order to specifi-
cally convert the bio oils into hydrocarbons, hydrodeoxygenation
(HDO) reactions have been often considered [8]. The achievement
of these transformations with hydrotreating catalysts like sup-
ported Co(Ni)MoS, has been proposed and could provide better
solution to realize HDO-HDS co-processing [9]. Because function-
alized phenols are the main components of bio-oils obtained from
the lignin fraction of ligno-cellulosic biomass liquefaction, the
model molecules used in HDO studies were mainly guaiacol (2-
methoxyphenol), cresols or anisole [8,10–12]. From these early
HDO academic studies, mainly carried out in the 1980–1990, it
has been established that the basic reaction scheme of guaiacol
HDO on supported CoMoS catalysts involves transformation into
catechol, phenol and deoxygenated compounds (benzene, cyclo-
hexene, cyclohexane) as well as methyl-substituted compounds
[13,14]. Generally, a consecutive reaction pathway from guaiacol
to catechol and then to phenol was considered, but some authors
mentioned the possibility of direct hydrogenolysis step produc-
ing phenol from guaiacol by elimination of methanol molecule,
in the presence of carbon supported CoMoS catalysts [15,16]. It
was also reported that heavier products (coke precursors) might
be formed during the reaction especially with the acidic catalytic
systems [17]. Several ␥-alumina-supported MMo catalyst com-
positions have been already tested in HDO of diphenyl ether in
competition with hydrogenation of naphthalene and among the
promoter metals (M), Co, Ru and Rh gave highest promoting effect,
with the highest hydrogenolysis/hydrogenation ratio for Co [18].

0926-3373/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2010.10.025
240 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245
Table 1
Textural and chemical composition of catalytic systems.
Catalysts % Co (wt) % Mo (wt)
MoS2 – 55.8
CoMoS 25.8 29.5
MoS2 /␥-Al2 O3 – 7.6
CoMoS/␥-Al2 O3 1.7 7.3
a
x = Co/(Co + Mo) atomic ratio.
Furthermore, for the transformation of phenol-type molecules,
alumina-supported CoMoS phase appeared to be more efficient
than alumina-supported NiMoS [19,20]. More recently, the effect
of morphology has been investigated for bulk MoS2 in phenols con-
version and it was demonstrated that low stacking of MoS2 slabs
favored hydrogenolysis versus hydrogenation [21].
The principal objective of this work was to study the promot-
ing effect of cobalt on the molybdenum sulfide catalysts for HDO
reaction. If we can expect some similarities between the HDS and
HDO reactions, it seemed necessary to clarify the role of Co in terms
of activity and selectivity by comparing non-promoted MoS2 cat-
alysts with promoted CoMo sulfide in the unsupported state or
supported on ␥-alumina. According to the previous considerations,
guaiacol (GUA) has been chosen as a model compound. As con-
cerns reactivity, GUA molecule possesses two types of C–O bonds:
Csp2 –OH (hydroxyl) and Csp2 –OCH3 (methoxy) which can probe the
catalyst behavior with respect to these different organic functions.
In this first paper, the promoting effect in HDO reaction for the
unsupported and supported molybdenum sulfide catalysts will be
discussed in detail.
2. Experimental
2.1. Preparation of the catalysts
Bulk MoS2 was prepared by decomposition of ammonium
thiomolybdate. Unsupported CoMoS catalysts were prepared in
two stages. The pre-catalysts were first prepared in aqueous or
mixed solution and then they were sulfided under a gas flow con-
taining 15 vol% of H2 S in H2 . The details on the preparation of these
unsupported catalysts have been described elsewhere [22].
The supported catalyst MoS2 /␥-Al2 O3 was prepared by a con-
ventional incipient wetness impregnation method on ␥-Al2 O3
(Axens, 260 m2 g−1 ) with an appropriate aqueous solution of
ammonium heptamolybdate ((NH4 )6 Mo7 O24 ·4H2 O) in order to
obtain about 2.5 Mo atoms per nm2 of support. After impregna-
tion, the catalyst was matured at room temperature overnight to
achieve diffusion of the solution into the pores of support. Then the
catalyst was dried at 110 ◦ C under vacuum for 10 h and calcined at
500 ◦ C for 3 h under flowing air (4 L/h). The catalyst CoMo/␥-Al2 O3
was prepared by incipient wetness co-impregnation of a solution
of ammonium heptamolybdate and cobalt nitrate followed by mat-
uration, drying and calcination as for non-promoted counterparts.
Before each test, the catalysts were sulfided ex situ under H2 S/H2
15% (v/v) flow at 400 ◦ C for 4 h (rate 10 ◦ C/min, flow rate 4 L/h).
After sulfidation, the catalysts were cooled down under nitrogen
flow and stored under argon.
2.2. Catalysts characterization
The principal characteristics of the catalysts used in this study
are presented in Table 1. The Mo and Co contents in the solids were
analyzed by plasma coupled atomic emission spectroscopy (AES-
ICP-Horiba Jobin Yvon). Textural properties were determined after
degassing the samples at 473 K during 3 h. The specific surface areas
were determined by nitrogen adsorption at 77 K using BET equation
xa Surface area (m2 g−1 ) Mo atom nm−2
– 82 –
0.48 110 –
– 250 1.9
0.3 230 2.0
(ASAP 2020 – Micromeritics). Textural properties of bulk catalysts
were measured after sulfidation while those of alumina-supported
catalysts were measured after the calcination step.
2.3. Catalytic HDO experiments
The catalytic HDO experiments were carried out in a fixed bed
tubular reactor equipped with a Pyrex reactor inserted into stain-
less steel one [23]. This type of reactor can be easily cleaned to
avoid any deposition of metals on the frit. The operating condi-
tions were chosen in order to avoid diffusion limitations and to
obtain moderate conversions. The reaction temperature was 573 K
and the total hydrogen pressure was 4 MPa. The reactant (GUA) was
introduced with H2 flow through a saturator/condenser system at
a partial pressure of 2.7 kPa. Hydrogen sulfide (H2 S) was added to
reach a partial pressure of 400 Pa (100 ppm) in order to maintain
the catalyst in the sulfided state during the experiments. The H2 and
H2 S gas flows were measured with mass flow meters and pressure
was controlled by a back-pressure regulator. The total flow was var-
ied between 50 and 500 mL/min to obtain a contact time between
0.3 and 8 s. Catalytic activities were measured at steady state after
at least 12 h on stream at around 30% of conversion which corre-
sponds to a range between 0.3 s and 1 s for the contact time. The
accuracy of catalytic activity determination was better than 10%.
The products were analyzed online by gas chromatography with
a HP 5890 equipped with a flame ionization detector (FID) with
CP-Sil5 capillary column (50 m × 0.32 mm × 5 ␮m). The condensed
products trapped in liquid nitrogen were also analyzed by gas
chromatography coupled with mass spectrometry (GC–MS Agilent
5975B) and the product identification was confirmed by manual
injection of pure compounds on the same column. Response fac-
tors were determined experimentally using pure compounds and
they served as a basis for the determination of the molar balance
and the selectivity. The molar balance has been checked closed to
98% for each experiment.
According to the integral reactor model, and assuming a first-
order reaction, the rate constant of reaction can be expressed
according to the following equation:
Fo
k=− ln(1 − )
wCo
where  is the total conversion, w is the catalyst weight (g), Fo is
the molar flow of reactant (mol s−1 ), Co is the initial concentration
of reactant (mol L−1 ).
The specific reaction rate (r, mol g−1 s−1 ) can be expressed by
the following equation:
Fo
r = kCo = − ln(1 − )
w
and the intrinsic reaction rate ri (molec. Mo at−1 s−1 ) is expressed
by r i = (r /n) × N with n = number of Mo atoms per g of catalyst
and N = Avogadro Number.
2.4. o-Xylene transformation
The acido-basic properties of the catalytic systems under
study were evaluated in o-xylene transformation. The main
 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245 241

to catalytic reactions (Table 2). The products of thermal decomposi-

HYD ISO
o-xylene 1,2-cycloC6 trimethyl-cycloC5
methyl-ethyl-cycloC5
ISO
1,3-cycloC6 1,4-cycloC6
Fig. 1. General reaction scheme for ortho-xylene conversion.
reaction products were the hydrogenated compound 1,2-
dimethylcyclohexane and isomerized products 1,3- (or
1.4-)dimethylcyclohexane as well as C3 -cyclopentane (ring
contraction after hydrogenation) (Fig. 1). The experiments were
carried out under the same conditions and using the same appa-
ratus which have been used for HDO reactions with 2.7 kPa for
o-xylene partial pressure. Kinetic data were analyzed using the
same equation as described above and the reaction rate expressed
as rXYL for the disappearance of reactant and rISO for the production
rate of isomerized products.
3. Results
3.1. Guaiacol HDO reaction
The general reaction scheme of the transformation GUA under
H2 with transition metal sulfide catalysts is given in Fig. 2. Under our
operating conditions, the thermal conversion of GUA without any
catalyst occurred at a very low rate (4 × 10−9 mol s−1 ) as compared
tion were only catechol (CAT) and traces of phenol (PHE). Therefore,
to compare catalytic activities and selectivities, the effect of thermal
conversion was not taken into account.
3.1.1. Conversion of GUA with bulk MoS2 and CoMoS catalysts
The total conversion rate based on GUA disappearance r(GUA)
obtained with bulk CoMoS catalyst was ca. 6 times higher per gram
of solid as compared to non-promoted MoS2 . The intrinsic rate per
Mo atom showed that the CoMoS phase was 12 times more active,
attesting of the beneficial effect of cobalt. Similarly, the intrinsic
rate of formation of oxygen-free compounds (ri(HDO) ), was much
higher for bulk CoMoS catalyst (about 9 times as compared to
MoS2 ). As concerns the catalysts selectivity and the reaction path-
way, we found, with non-promoted MoS2 , that CAT was the first
product formed and then appeared consecutively phenol and O-
free products like cyclohexene, benzene, cyclohexane (Fig. 3). The
distribution of these deoxygenated products versus HDO conver-
sion is presented in Fig. 5 for the four catalysts studied. Cyclohexene
appeared as the main HDO product with MoS2 . Heavier and iso-
merized products like cyclohexylbenzene and methylcyclopentane
were detected with MoS2 attesting of a stronger acidic character of
this solid compared to CoMoS.
On the other hand, in the presence of bulk CoMoS catalyst,
PHE seems to be a primary product together with CAT. Benzene
is the major HDO product in this case and very few methylated
products have been detected. For both catalysts, light products
including methanol and methane were observed and quantified.
Fig. 6 shows the distribution of the methyl group coming from the
methoxy substituent in GUA molecule, into methane, methylmer-
captan, methanol and methylated products. Comparison of these
distributions was performed at circa 30% conversion. It appeared
clearly that methanol was formed in a larger extent with the CoMoS
catalyst than over MoS2 . On the contrary, with MoS2 , methane

HO

Me-CAT CRE
OH
OH OH
condensation and
heavier products

Me-substitution
"CH3"
OH OH OH
-CH3 DDO
OCH 3 OH
benzene
DME HYD O OH H2O
GUA CAT PHE

DMO

Fig. 2. General reaction scheme for GUA conversion.

Table 2
Conversion of GUA and HDO rates expressed as specific (mol g−1 s−1 ) and intrinsic (molec. Mo at−1 s−1 ) rates for unsupported and supported catalysts at 573 K.

Catalysts rGUA (10−7 mol g−1 s−1 ) rHDO (10−7 mol g−1 s−1 ) ri(GUA) (10−4 molec. Mo at−1 s−1 ) ri(HDO) (10−4 molec. Mo at−1 s−1 )

MoS2 35 10.1 6 1.7

CoMoS 222 49.7 72 16.2
MoS2 /␥-Al2 O3 64.2 2.3 81 2.9
CoMoS/␥-Al2 O3 71 5 93 6.6
242 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245

a 60 b 60

CAT Me-CAT CAT PHE

50 50
Me-PHE HDO
PHE Me-PHE
40 40 Lights

Products (%)
Products (%)

HDO Lights
30 30

20 20

10 10

0 0
0 20 40 60 80 100 0 20 40 60 80 100

Guaiacol Conversion (%) Guaiacol Conversion (%)

Fig. 3. Products distribution versus total conversion of GUA on (a) MoS2 , (b) CoMoS catalyst.

selectivity was higher than 80%. Methylmercaptan (CH3 SH) was in addition to the methylated products. A slight deactivation (<10%)
only observed with non-promoted catalysts. The methyl substi- was observed for both supported systems after 60 h on stream.
tuted products were obtained in higher proportion over MoS2 than
over the promoted system. Both unsupported catalysts were not 3.2. Evaluation of MoS2 and CoMoS catalysts in o-xylene
noticeably deactivated after more than 60 h on stream. transformation

3.1.2. Conversion of GUA with supported catalysts: MoS2 and
CoMoS on -Al2 O3
Alumina alone can convert GUA into CAT, PHE and methylated
oxygenated compounds (8–10 times less active than the sulfide cat-
alysts) [13]. The role of the support will be discussed in more details
in part II of this work [24]. With the ␥-alumina supported catalysts,
methyl-substitution products like methyl-catechols and methyl-
phenols were formed during the GUA transformation (Fig. 4). With
MoS2 /␥-Al2 O3, CAT and methyl-CAT were the primary products
of the reaction and then we observed the formation of PHE and
cresols. The main oxygen-free products obtained were cyclohexene
and methylcyclohexene (Fig. 4a). For alumina-supported CoMoS,
the selectivities were slightly different: CAT and PHE were the pri-
mary products and then methylated analogs were formed (Fig. 4b).
Furthermore, for the Co promoted catalyst, we observed among
deoxygenated products a larger fraction of benzene as compared
to cyclohexene which was the main product with MoS2 /␥-Al2 O3
(Fig. 4). Concerning the reactivity of the methoxy group, Fig. 6
shows that similarly to the unsupported MoS2 catalyst, MoS2 /␥-
Al2 O3 produces methane and methylmercaptan, but not methanol,
No direct isomerization products (m- and p-xylenes) were
detected in the o-xylene conversion products with unsupported
MoS2 and CoMoS under the reaction conditions similar to those
applied in the HDO experiments. We only observed hydrogenation
product (1,2-dimethyl-cyclohexane) and the products of its sub-
sequent isomerization, namely 1,3-, 1,4-dimethyl-cyclohexanes
and trimethyl- or methyl-ethyl-cyclopentanes. The selectivity
to 1,2-dimethyl-cyclohexane reached 50% on CoMoS at 25%
conversion while on MoS2 , at the same conversion, only 15%
of the direct hydrogenation product was obtained. With the
latter catalyst, the other 85% products correspond to trimethyl-
cyclopentanes (12%), methyl-ethyl-cyclopentanes (28%) and 1,3- or
1,4-dimethylcyclohexanes (39%) and 6% of non-identified products.
The total reaction and isomerization rates have been calculated
to compare the acidity strength of the two unsupported catalysts
(Table 3). According to these experiments, MoS2 catalyst would be
more acidic than CoMoS as the total rate of conversion which is
also the hydrogenation rate, was approximately the same for both
catalysts, while MoS2 produced larger amount of isomerization
products.

60 60
CAT Me-CAT CAT Me-CAT
50 PHE Me-PHE 50 PHE Me-PHE
HDO Lights HDO Lights
40 40
Products (%)

Products (%)

Heavies Heavies
30 30

20 20

10 10

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Guaiacol Conversion (%) Guaiacol Conversion (%)

Fig. 4. Products distribution versus total conversion of GUA on (a) MoS2 /␥-Al2 O3 and (b) CoMoS/␥-Al2 O3 .
 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245 243

(a) MoS 2 (b) CoMoS

50 50
Cyclohexene Benzene
Cyclohexane
40 40 Cyclohexene
Me-cyclopentane
Benzene Cyclohexane
Products (%)

Products (%)
30 Cyclohexylbenzene 30 Toluene

20 20

10 10

0 0
0 10 20 30 40 50 60 0 20 40 60
HDO Conversion (%) HDO Conversion (%)

(c) MoS2/γ-Al2O3 (d) CoMoS/γ-Al2O3

10 10
Cyclohexene Me-products Me-products

8 Cyclohexene
8 Benzene Cyclohexane
Benzene
Products (%)
Products (%)

Cyclohexylbenzene 6
6 Cyclohexane

4 4

2 2

0 0
0 5 10 15 0 5 10 15

HDO Conversion (%) HDO Conversion (%)

Fig. 5. O-free products distribution versus total deoxygenation during GUA conversion at 573 K, (a) with MoS2 , (b) with CoMoS, (c) with MoS2 /␥-Al2 O3 , (d) with CoMoS/␥-
Al2 O3 .

4. Discussion
Considering the literature and the results of this work on the
distribution of the products at various conversion levels, we pro-
pose a more complete reaction scheme for the HDO of GUA (Fig. 2).
The GUA molecule possesses three types of oxygen–carbon bonds:
C(sp3) –OAr (methoxy group), C(sp2) –OMe and C(sp2) –OH (hydroxyl)
with the bond energies about 247, 356 and 414 kJ/mol respectively
Fig. 6. Distribution of methane, methylmercaptan, methanol and methylated prod-
ucts at 30% GUA conversion.
[26]. From the thermodynamic point of view, the easiest reaction
during the HDO of GUA should be the demethylation (DME) which
is a C(sp3) –OAr cleavage. The formation of phenol directly from GUA
would originate from a direct C(sp2) –OMe cleavage, called in this
work demethoxylation step (DMO). In our case, anisole (Ph–OMe),
which would be formed by C(sp2) –OH cleavage was only detected
as traces among the products on CoMo catalysts. This finding seems
not surprising taking into account that the rupture of this bond is
the most difficult one of three possibilities offered by GUA structure.
The first stage of the reaction network (DMO or DME) differed
greatly on the non-promoted and promoted unsupported catalysts:
non-promoted catalysts preferentially lead to the demethylation
route (DME) whereas both DME and DMO routes were observed
for the promoted catalyst, as confirmed by the production of
methanol. The data on the evolution of the methyl group from
the methoxy function of the GUA molecule are highly informative
for the understanding of the reaction pathways, as illustrated in
Fig. 6. Several products are issued from the GUA methoxy group,
including methane, methanol, methylmercaptan and methylated
compounds. With the increase of conversion on unsupported
CoMoS, both methane and methanol production increased lin-
early. For unsupported catalysts, o-xylene conversion evidenced a
stronger acidity of bulk MoS2 as compared to CoMoS. Increased
acidity of MoS2 correlates with the enhanced formation of the
methyl-substitution compounds. The capability of Co promoted
MoS2 to direct the reaction pathway towards methanol produc-
244 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245
Table 3
o-Xylene conversion rate (total and part of isomerization) under HDO operating conditions with bulk catalysts.
Catalysts rXYL (10−7 mol g−1 s−1 ) rISO (10−7 mol g−1 s−1 )
MoS2 1.8 1.5
CoMoS 1.1 0.5
tion was also confirmed over supported catalysts. Indeed, with
MoS2 /Al2 O3 catalyst, the first stage of the reaction did not show
any methanol production whereas on the CoMoS/Al2 O3 catalyst
methanol was obtained in a concentration comparable to that of
methane. This evidence again that the addition of the promoter
favors the DMO route. Furthermore, with alumina-supported cat-
alysts, numerous methylated products have been detected and
obviously this is due to the acidity of the support (the role of
the support acidity will be detailed in part II of this work). On an
acidic support, after heterolytic cleavage, positively charged methyl
group may stay on the support surface instead of being converted
to methane and an electrophilic substitution may occur on aro-
matic ring of CAT (or PHE) still adsorbed, in the nearest position
which is the ortho one (Fig. 7). This phenomenon has been already
reported several times for the catalysts supported on ␥-alumina
[25] or silica–alumina [14]. Finally, the large amount of methylated
products formed over the supported MoS2 and CoMoS catalysts
comparatively to the bulk systems implied for these solids a low
selectivity towards HDO products (Figs. 3 and 4).
With MoS2 and MoS2 /Al2 O3 , CAT was formed and then PHE
appeared coming from the CAT dehydroxylation, while with CoMoS
and CoMoS/Al2 O3 , PHE was observed like a primary product of the
GUA transformation together with CAT. Therefore a part of PHE was
probably formed directly from GUA by DMO pathway in full agree-
ment with the formation of methanol. We can conclude that the
promotion by Co facilitates the C(sp2) –OMe cleavage at the expense
of the DME for the first step of the GUA conversion.
The final reaction stage is the production of oxygen-free com-
pounds. The HDO rate obtained with unsupported MoS2 and CoMoS
at 573 K, showed large differences, much higher rates being reached
for the unsupported CoMoS catalyst (Table 2). The introduction of
cobalt promoter enhanced greatly the HDO performance. In terms
of selectivity, similarly to HDS reaction [26], two routes can be
considered: a direct deoxygenation route (DDO) and a consecutive
route including hydrogenation (HYD) with subsequent elimina-
tion of oxygen. Thus, benzene could be formed by a direct C(sp2) –O
cleavage from PHE while cyclohexene and cyclohexane are issued
from hydrogenation of the aromatic cycle and elimination of water
molecule. During this latter process cyclohexanone and cyclohex-
anol have been found to be intermediate products, few traces of
them being detected by GC–MS. However these traces suggest that
the final transformation of cyclohexanol to cyclohexene by dehy-
dration should be very fast.
As represented in Fig. 5, non-promoted catalysts (supported or
unsupported but more significantly the latter) produced mainly
cyclohexene, whereas in the case of unsupported promoted
CoMoS catalyst, the major compound among the deoxygenated
products was benzene (Fig. 5b). Supported CoMoS catalyst also
produced some benzene, but in a lesser extent (Fig. 5d). This indi-
cates that the CoMoS phase favors direct cleavage of aromatic
OH
H3C O δ+
HO O CH3
Me-CAT
Fig. 7. Methyl-substitution reaction due to a heterolytic cleavage of O–Me bond.
ri(XYL) (10−5 molec. Mo at−1 s−1 ) ri(ISO) (10−5 molec. Mo at−1 s−1 )
3.1 2.6
3.6 1.6
carbon–heteroatom bond (DDO) at the expense of hydrogenation
route (HYD), similarly to the HDS reactions [27,28]. For supported
catalysts, the distribution of deoxygenated methyl-containing
products logically issued from the methyl-phenols, was different
depending on the catalysts. CoMoS/Al2 O3 mostly gave aromatic
methylated compounds like toluene whereas, over MoS2 /Al2 O3
catalyst, the main O-free product was methyl-cyclohexene. Again,
this observation goes in lines with high DDO performance of co-
promoted catalysts (either bulk or supported).
The comparison of the intrinsic reaction rates (Table 2) per
Mo atom for supported and unsupported catalysts showed that
the total rate of GUA conversion became higher by supporting
CoMoS phase on alumina but the HDO rate (ri(HDO) ) obtained for
bulk CoMoS (16 × 10−4 molec. Mo at−1 s−1 ) cannot be reached on
the alumina-supported system. Indeed, the support contributed to
the conversion of GUA into CAT and methylated compounds but not
at all to the formation of O-free compounds. Furthermore, the ortho-
methylation step observed with ␥-alumina-supported catalysts has
certainly a harmful effect on the deoxygenation reaction because
the deoxygenation of 2-methylphenol is more difficult than that of
phenol [29] and the whole HDO rate was therefore decreased.
To explain the trends of catalytic activity in HDO, Ferrari et al.
[15] have proposed four kinds of active sites on CoMoS catalysts:
three-fold coordinatively unsaturated Mo atoms for hydrogena-
tion (A), three-fold coordinatively unsaturated Mo atoms with a
sulfhydryl group (–SH) neighbour for C–X hydrogenolysis (B), acid
sites of the support (CS ), and acid sites on the metal sulfide (CM ).
Demethylation step can be achieved by support or metal sulfide
acid sites, a heterolytic scission would occur on the support while
a homolytic cleavage would be responsible of the reaction on the
metal sulfide [8,14]. Then, we can propose that CS sites on the sup-
port act for the demethylation-methyl substitutions as observed
with alumina-supported catalysts. Bulk MoS2 , would possess acid
CM sites allowing the demethylation step and especially the for-
mation of isomerized compounds like methylcyclopentane in line
with the o-xylene isomerization results. The homolytic character
of the O–Me cleavage with MoS2 is in accordance with the fact
that methane was formed as side-product to the demethylation
preferentially to methyl-transfer.
On sulfide catalysts, the problem of existence of two distinct
sites for hydrogenation and hydrogenolysis is still controversial and
this concept has been recently criticized by Massoth et al. [30] who
assumed that only one site is involved for both hydrogenation and
hydrogenolysis and that phenol was transformed exclusively via a
pre-hydrogenation step and followed by elimination of water. In
our study, CoMoS phase enhanced greatly the formation of ben-
zene from PHE as compared to non-promoted catalyst, particularly
in the case of bulk catalytic systems, and there is no necessity to
dearomatize phenol ring to eliminate oxygen. With the use of very
efficient catalyst for hydrogenolysis, such as bulk CoMoS phase, the
OH
OH OH
- H2 O - H2O
Me-PHE Toluene
 V.N. Bui et al. / Applied Catalysis B: Environmental 101 (2011) 239–245
DMO step allows GUA to be converted directly to PHE and there-
fore the deoxygenation of CAT is not anymore a limiting step. So in
order to promote deoxygenation reaction of GUA-type molecules
it appears important to find a support which does not promote
demethylation and methyl-substitution reactions as alumina does,
but which would be able to disperse efficiently the CoMoS phase.
To illustrate this, the strong support effect found for CoMoS cata-
lysts in HDO of GUA will be fully reported in the following part II
[22].
5. Conclusion
In this work, we demonstrated that the HDO transformation of
GUA-type molecules on MoS2 -based catalysts is greatly enhanced
due to promoting with cobalt. Using promoted catalytic systems,
a part of GUA was converted directly to phenol by a demethoxy-
lation (DMO) step with formation of methanol. Then the phenol
intermediate was mostly transformed to benzene via DDO pathway
involving C(sp2) –O direct hydrogenolysis. Similarly to the well-
known DDS pathway in the hydrodesulfurization studies, the main
advantage of this DDO pathway as compared to the hydrogenation
route is the hydrogen economy during the deoxygenation process.
The use of ␥-alumina as support for this promoted CoMoS phase
lead to demethylation/methyl-substitution reactions after C(sp3) –O
cleavage and the formation of the methyl-substituted products
(Me–catechols or cresols) does not facilitate the deoxygenation
process. In order to avoid these reactions we will propose other
supports for the CoMoS phase suitable for this kind of reaction in
part II of this article.
Acknowledgement
V.N. Bui is grateful to CNRS for a PVD grant.
245
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