Bio-oil hydrodeoxygenation: Adsorption of phenolic compounds on sulded

(Co)Mo catalysts
Andrey Popov, Elena Kondratieva, Laurence Mariey, Jean Michel Goupil, Jaafar El Fallah,
Jean-Pierre Gilson, Arnaud Travert, Franoise Maug

Laboratoire Catalyse et Spectrochimie, ENSICAEN, Universit de Caen, CNRS, 6 Boulevard Marchal Juin, 14050 Caen, France
a r t i c l e i n f o
Article history:
Received 11 July 2012
Revised 11 September 2012
Accepted 5 October 2012
Available online 16 November 2012
Keywords:
HDO
Phenol
Guaiacol
Sulde catalyst
IR spectroscopy
Adsorption mode
Deactivation
a b s t r a c t
This paper reports the interaction of aromatic compounds (as phenol, ethylphenols, and guaiacol) repre-
sentative of oxygenated functions of pyrolysis bio-oils, with sulded (Co)Mo/Al
2
O
3
catalyst in order to
determine the origin of catalyst deactivation in hydrodeoxygenation (HDO) reaction.
Infrared spectroscopy shows that all the studied phenolic compounds anchor on the alumina support
as phenate-type species, whereas only the most basic ones (2(4)-ethylphenol and guaiacol) interact also
with the sulde phase. At 623 K (typical temperature of the HDO reactions), only phenate species on the
support are formed that is conrmed by study of the catalyst tested in HDO reaction. Phenate-type spe-
cies anchored on alumina hinder the accessibility of the sulde edge sites. This shows that the nature of
the oxygenated compound (basicity and nature of the substituent) as well as the surface properties of the
catalyst support are crucial in the mode and extent of HDO active sites poisoning.
2012 Elsevier Inc. All rights reserved.
1. Introduction
The increase in crude oil prices and environmental concerns in
limiting carbon dioxide emissions implies the substitution of con-
ventional fuels by new products issued of renewable sources. In
European Union, 20% of the conventional fuels should be replaced
by alternative fuels in the road transport sector by 2020 [1]. Since
the development of bio-fuels should avoid competition with hu-
man food production, it is widely admitted that a sustainable route
is the use of lignocellulosic biomass issued from agricultural and
wood residues [26]. From the various thermochemical processes
developed to produce liquids from solid lignocellulosic materials,
fast-pyrolysis seems the most promising one because it does not
need neither high pressure nor H
2
supply [7,8]. However, lignocel-
lulosic-derived bio-oils resulting from fast-pyrolysis contain very
important amounts of oxygenated compounds (up to 45 wt% O)
[2,4,9]. Resasco [10] underlines that these bio-oils include three
main families of compounds: (i) small acids, aldehydes and ke-
tones, (ii) sugar-derived compounds, and (iii) lignin-derived phen-
olics. Consequently, the main challenges for production of bio-fuel
from pyrolytic bio-oils are the elimination of oxygen, while retain-
ing the carbon in the product, and with minimum hydrogen con-
sumption. In this aim, activity, selectivity, and stability of the
HDO catalyst have to be optimized.
As recently reviewed, hydrodeoxygenation (HDO) appears as a
very promising route that could produce bio-fuel at reasonable
prices compare to fossil fuel [11]. The number of papers dealing
with HDO have considerably increased in the last 10 years
[3,5,1214]. As emphasized by Hicks [7], the most important issue
is the development of highly selective and durable catalysts.
Hydrodesulfurization/hydrodenitrogenation (HDS/HDN) cata-
lysts based on mixed suldes of (Co, Ni) and (Mo, W) dispersed
on high surface area supports like c-Al
2
O
3
are interesting candi-
dates for HDO reaction. Some papers report their use in HDO of
pyrolysis bio-oils [15,16]. But, as important quantities of oxygen-
ated aromatic compounds are present in pyrolytic bio-oils [17],
and as these molecules are known to be the most refractory ones,
most of the HDO studies concentrate on oxygenated aromatics like
anisole, phenol, 2-methoxyphenol (guaiacol), and other phenolic
compounds.
It is generally reported that deoxygenation reaction occurs via
two main routes: HYDrogenation (HYD) and Direct DeOxygenation
(DDO) [18,19], this latter route allowing deoxygenation while min-
imizing H
2
consumption. Within the most recent papers, Bui et al.
[20] shows that the DDO route involved in 2-methoxyphenol con-
version is strongly increased versus HYD route after Co addition to
MoS
2
/Al
2
O
3
catalyst. Romero et al. [18] emphasize the increase in
the HDO rate with the addition of Co or Ni to Mo/Al
2
O
3
for
0021-9517/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcat.2012.10.005

Corresponding author.
E-mail address: francoise.mauge@ensicaen.fr (F. Maug).
Journal of Catalysis 297 (2013) 176186
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2-ethylphenol HDO and point out a highest DDO/HYD selectivity
for CoMo/Al
2
O
3
. Finally, Senol et al. [21] shows that CoMo catalyst
exhibits higher activity than NiMo for phenol HDO. Therefore, the
CoMo catalyst seems promising. Furthermore, on CoMo/ZrO
2
, the
DDO/HYD selectivity is even better, showing that support change
is an interesting way for H
2
economy [22].
However, deactivation of HDO catalyst is a key problem, and
deactivation mechanisms are still unclear. Deactivation can be re-
lated to water effect (that can modify active phase or support), sin-
tering of the active phase, or coking [23]. In our previous work [24],
we showed that water effect is not the main factor in the deactiva-
tion of phenol HDO, and that Co addition to Mo/Al
2
O
3
allows to re-
duce this effect.
Therefore, deactivation of HDO catalyst is likely related to active
phase sintering or poisoning by carbon deposition. Previous studies
on HDS or HDN catalysts show that carbon is deposited under the
form of polyaromatic species and can block the active sites of the
catalyst [25]. Carbon deposition strongly depends on the type of
feed. Due to their stronger interaction with the catalytic surface, al-
kenes and aromatics have the largest afnity for carbon formation
relative to saturated hydrocarbons [11]. Besides, for oxygen-
containing compounds, those with more than one oxygen atom
appear to have a higher afnity for carbon formation by polymeri-
zation reactions [25]. Indeed, it has been shown that the interaction
of phenolic compounds with sulded catalysts produces these
types of poison species [2628]. Note that coking increases with
increasing acidity of the catalyst, while acid sites are required in
the mechanism of HDO [11].
The positive effect of H
2
S against deactivation has been shown
in various papers [19,21,2932]. H
2
S allows reactivating the suld-
ed phase. H
2
S could also prevent poison species formation. But be-
sides, too much of H
2
S is known to inhibit HDO reaction [33].
To specify the role of the various components of the catalyst in
the deactivation process, in our rst work [34], we focused on the
adsorption mechanisms of phenolic model compounds on oxides
usually used as supports for hydrotreatment catalysts. Therefore,
the adsorption of phenol, anisole and 2-methoxyphenol on alu-
mina, silica, and silicaalumina was studied by IR spectroscopy.
The main results show that at room temperature (RT), while phe-
nolic-type compounds mainly interact via H-bonding with silica,
chemisorption is the main adsorption mode on alumina, probably
due to interaction of phenol with the Lewis acidbase pairs of alu-
mina. At typical temperatures of HDO operating conditions
(673 K), the phenate species cover 2/3 of the alumina surface.
These species are likely responsible for the deactivation of the cat-
alysts supported on alumina.
To validate this hypothesis, we investigate the inuence of phe-
nolic-type molecules (phenol, ethyl-phenol, anisole, 2-methoxy-
phenol) on supported sulded (Co)Mo/Al
2
O
3
catalysts. In this
aim, this paper focuses on (i) the identication of the adsorption
modes of the oxygenated molecules on catalysts, (ii) the measure-
ment of the accessibility of catalyst sites, (iii) the analysis of poison
species on spent catalysts, and (iv) the validation of these results
by a quantitative model.
2. Experimental
2.1. Materials
The c-Al
2
O
3
and (Co)Mo/Al
2
O
3
catalysts were supplied by TO-
TAL. Cobalt composition was measured by X-ray uorescence spec-
troscopy (XRF) and the molybdenum content by Inductively
Coupled Plasma (ICP) method. The origin and the properties of
the oxides studied are given in Table 1.
Commercial oxygen-containing compounds phenol, ethylphe-
nols, and 2-methoxyphenol were used (Prolabo for phenol and eth-
ylphenols with purity of 99.5 wt%, Johnson Matthey Company for
2-methoxyphenol with purity of 98 wt%).
2.2. IR spectroscopy measurements
The IR experiments were performed using a FTIR Nicolet Magna
AEM spectrometer equipped with a DTGS detector. Each spectrum
corresponds to the accumulation of 64 scans at 4 cm
1
of resolu-
tion using one zero lling level. Most of the spectra displayed cor-
respond to difference spectra, that is, spectrum after adsorption (or
desorption) minus the spectrum of the corresponding activated
sample. All spectra are normalized to a constant mass (10 mg of
dried catalysts for a disk of 2 cm
2
).
Each sample was pressed into a self-supported wafer (2 cm
2
,
between 10 and 20 mg but precisely weighed), under a pressure
of 10
7
Pa. Activation and adsorption/desorption steps of the vari-
ous experiments were performed in situ in the infrared cell accord-
ing to the procedures described in the following sections.
2.2.1. Suldation procedure
The wafer was ushed under argon gas ow for 1 h at 423 K to
remove adsorbed water and air traces and further cooled down to
RT. Then, the sample was sulded by heating from 298 K (RT) up to
623 K (ramp 3 K/min) under H
2
S/H
2
(10/90) ow at 30 mL/min.
After 2 h suldation at 623 K, the temperature was decreased to
room temperature. Then, an activation procedure was followed at
623 K (5 K/min) for 30 min to remove H
2
S.
2.2.2. Phenolic compounds adsorption
Oxygenated compounds (20 Pa) were introduced on the pellet
at RT or at 623 K maintained at this temperature for 15 min and
further evacuated the adsorption temperature for 15 min.
2.2.3. CO adsorption
2.2.3.1. Experimental protocol. In order to identify the catalyst sites
involved in the interaction of oxygenated molecules, CO adsorption
was applied before and after oxygenated compound introduction.
Firstly, CO was introduced at about 100 K at equilibrium pressure
of 133 Pa on the sulded catalyst. After desorption of CO at
298 K, oxygenated compound (pressure of 20 Pa) was introduced
on the sample at room temperature, followed by evacuation for
15 min at the adsorption temperature. Then, CO adsorption was
performed in similar conditions than previously. In a second step,
oxygenated compound was adsorbed at 623 K following the same
procedure. CO was again adsorbed in the same conditions than
previously.
2.2.3.2. Calculation of the site concentration. On sulded CoMo/
Al
2
O
3
, the adsorption of CO at 100 K gives rises to several bands
characteristic of various species: m(CO/Al
3+
) at 2185 cm
1
, m(CO/
OH) at 2154 cm
1
, m(CO
physisorbed
) at 2141 cm
1
, m(CO/MoS
2
)
at 2109 cm
1
, m(CO/CoMoS) at 2070 and 2050 cm
1
. To quan-
tify these species, spectral decomposition is required. The m(CO)
zone was tted using Gaussian/Lorentzian curves. Area of each
band was then obtained using the tting procedure of the OMNIC
Table 1
Characteristics of the support and catalysts.
Al
2
O
3
Mo/Al
2
O
3
CoMo/Al
2
O
3
Mo (wt%) 9.9 9.2
Co (wt%) 4.2
S
BET
(m
2
g
1
) 252 258 243
Average slab length (nm) 2.4 2.6
A. Popov et al. / Journal of Catalysis 297 (2013) 176186 177
software. The concentration of MoS
2
and CoMoS sites was calcu-
lated using the Beer Lambert law
A
i
e
i
n
i
S
where A
i
is the band area (cm
1
); e
i
, the molar extinction coefcient
(cm mol
1
); n
i
, the amount of adsorption sites in the disk (mol) and
S
i
is the surface of the disk (cm
2
); the values of e
i
corresponding to
CO adsorbed on MoS
2
and CoMoS sites were determined earlier in
our laboratory [35].
2.3. Analysis of catalysts after HDO test
IR analysis of catalysts tested in ethylphenol HDO by Romero
et al. [18,19] (IC2MP Poitiers, France) was performed. Three sam-
ples CoMo tested without H
2
S and CoMo tested with H
2
S and
sulded CoMo catalysts were characterized.
Before the HDO test, the catalysts were sulded in situ using a
mixture of 5.8 wt% dimethyldisulde (DMDS) in toluene, at 623 K
and under a 4.0 MPa total pressure. After lowering the temperature
to the reaction temperature (613 K), the oxygenated model com-
pound 2-ethylphenol (2-EtPh) was introduced. 2-EtPh was diluted
in toluene and DMDS (2.1 wt% S) was added to generate H
2
S in situ
during the reaction. The partial pressure of 2-EtPh was maintained
at 49 kPa, and the pressure of hydrogen was 5.8 MPa. At the end of
the test, the reactor was depressurized and then cooled from reac-
tion temperature to RT under nitrogen ow. Unloading and storage
were performed under Ar atmosphere.
For characterizing the catalyst sites accessible after HDO run,
the sulde phase sites have to be completely preserved from air
contact. Thus, the samples were pelletized inside a glove box
although this preparation is rather tricky. Pelletizing was success-
ful for the catalyst tested without H
2
S, but not for the sample
tested with H
2
S, in spite of repeated trials. Catalyst disk was trans-
ferred without air contact into the IR cell, treated under vacuum at
623 K. Then, CO adsorption (133 Pa) was performed at about 100 K.
Nevertheless, to obtain information on the nature of the poison
species formed during the HDO test, the catalyst tested with H
2
S
was pelletized under air atmosphere, transferred into the IR cell,
and treated under vacuum at 523 K.
2.4. HRTEM measurements
HRTEM analysis of the sulded catalyst was performed using a
JEOL-2010F transmission electron microscope tted with CDD
camera and an X-ray (EDX) spectrometer. The eld emission gun
was operated at 300 kV. Before HRTEM analysis, the catalysts were
sulded in the same conditions as for IR experiments or sulded
and tested in LACCO (in the case of spent catalysts). After treat-
ment, the sample was transferred under argon in a glove box and
gently crushed under argon. A drop of a suspension of the solid
sample in n-butanol was deposited on a 300 mesh (diameter
3 mm) holey carbon lm grid and dried at 298 K under argon
ow before introduction in the high vacuum chamber of the micro-
scope. For each sample, stacking degrees and lengths of 1000
MoS
2
crystallites were measured.
3. Results and discussion
3.1. Adsorption of phenolic compounds on (Co)Mo catalysts
3.1.1. Adsorption mechanism of phenolic compounds
In the following part, the IR spectra of adsorbed phenolic mole-
cules in the low frequency region, that is, 16501200 cm
1
are con-
sidered. This zone includes the bands related to stretching
vibrations of aromatic ring, bending vibrations of OH, possibly
bending vibrations of the CH
2
and CH
3
groups and stretching
CAO vibrations.
3.1.1.1. Phenol adsorption on oxidic catalyst. The IR spectra of phenol
adsorbed on pure Al
2
O
3
and on non-sulded MoOx/Al
2
O
3
at RT are
compared in Fig. 1A. Bands at 1597 and 1498/1492 cm
1
corre-
sponding to aromatic ring vibrations m(CC) are present in the spec-
tra of both samples. For MoOx/Al
2
O
3
(spectrum b), all these band
intensities are lower than those for the pure support (spectrum
a). The intensity of the shoulder at 1470 cm
1
, which character-
izes d(OH) vibrations of phenol, is negligible for the both samples.
This fact indicates the formation of phenates instead of molecular
phenol. Major differences can be observed in the 12001300 cm
1
region that characterizes m(CO) vibrations. A multi-component at
1295/1271 cm
1
is present in the spectrum of pure Al
2
O
3
(spec-
trum a). On MoOx/Al
2
O
3
, this broad component is only present as
a minor shoulder and the main band is observed at 1217 cm
1
.
After adsorption and evacuation at 623 K (Fig. 1B), all the bands re-
main present for MoOx/Al
2
O
3
, but the band at 1217 cm
1
, more
sensitive to evacuation at 623 K than that at 1295 cm
1
, is shifted
to 1234 cm
1
. It can be concluded that phenol leads to phenate
species on both pure Al
2
O
3
and MoOx/Al
2
O
3
samples as indicated
by the absence of d(OH) band. The new band (at 1217 cm
1
) de-
tected on MoOx/Al
2
O
3
in the m(CO) region corresponds to phenate
species adsorbed on molybdenum oxide phase. The marked inten-
sity decrease in m(CC) bands on MoOx/Al
2
O
3
in comparison with
alumina support can be explained by hindered access of phenol
to alumina due to support covering by oxide phase.
3.1.1.2. Phenol adsorption on sulded catalyst. The IR spectra of phe-
nol adsorbed at RT on Al
2
O
3
and on sulded CoMo/Al
2
O
3
catalyst
are presented in Fig. 2A. The spectrum of phenol on the catalyst
(spectrum b) is very similar to that obtained on pure alumina. For-
mation of phenate species on sulded catalyst is demonstrated by
the detection of bands at 1597, 1498/1492 cm
1
(m(CC)) and 1295/
1271 cm
1
(vibrations with m(CO) component), as well as by the
absence of bands assignable to m(OH) vibration. Note that the phe-
nate bands on CoMo catalyst have similar positions as those on
alumina, but present lower intensities in comparison with the alu-
mina support. The decrease in all the phenate bands that are obser-
vable on sulded catalyst in comparison with pure Al
2
O
3
can be
explained by hindered access of phenol to alumina due to sulde
phase covering of the support. The same results were obtained
with sulded Mo/Al
2
O
3
catalyst (spectra not shown).
Formation of phenate species on sulded catalyst at RT gives
rise to IR bands taking place at the same frequency as that on pure
alumina. It can be noticed that m(CC) and m(CO) phenate bands are
quite sensitive to the nature of adsorbate as seen in the previous
section for MoOx, and in Xu et al. [36] for ZrO
2
. Indeed, this last pa-
per shows that on ZrO
2,
phenate species have characteristic bands
at 1586, 1483 and 1282 cm
1
(corresponding to the bands ob-
served on alumina at 1597, 1498/1492 and 1295/1250 cm
1
). Thus,
the similar frequencies for phenates anchored on alumina and on
the sulde phase appears highly unlikely. This leads us to propose
that phenol adsorbed on the sulded CoMo/Al
2
O
3
at RT interacts
only with the alumina support and not with the sulde phase.
Moreover, we studied the effect of pre-adsorption of H
2
S on phenol
adsorption (spectra not shown), since H
2
S can be dissociatively ad-
sorbed on the Lewis sites of alumina (CUS Al
3+
, O) as well as of the
sulde phase (CUS Mo, S) [37,38]. Interaction of phenol with Lewis
paired sites leads to the formation of phenate species [34]; thus,
H
2
S pre-adsorption should poison Lewis sites and change adsorp-
tion of phenol on these phases. However, the spectral comparison
of phenol adsorbed on Al
2
O
3
before and after H
2
S pre-adsorption
does not reveal any difference. Obviously, H
2
S is weakly adsorbed
on Lewis sites of Al
2
O
3
and can be easily replaced by O-donor mol-
178 A. Popov et al. / Journal of Catalysis 297 (2013) 176186
ecules such as phenol. Regarding the CoMo/Al
2
O
3
, absence of effect
of H
2
S pre-adsorption is also observed. In that case, the replace-
ment of H
2
S in interaction with sulde phase by O-donor mole-
cules is rather unlikely due to the weaker interaction of
oxygenated molecules than sulfur containing molecule with the
sulde phase.
Spectra of phenol adsorbed on Al
2
O
3
and sulded CoMo/Al
2
O
3
catalysts at 623 K are presented in Fig. 1.
Fig. 2B shows that, at 623 K, in addition to the main m(CC
ring
)
bands at 1597 and 1498 cm
1
and at 1295/1250 cm
1
, some sup-
plementary shoulders at 1564 and 1450 cm
1
appear on the suld-
ed catalyst. Note that these bands are not detected on pure
alumina and on MoOx/Al
2
O
3
(i.e., in the absence of sulded phase)
and are not formed on sulded catalysts after phenol adsorption at
RT. Apparently, these new species correspond to reaction of phenol
with sulde phase and could correspond to the formation of carbo-
naceous species, although the exact nature of these species is not
yet established.
3.1.1.3. 2-Ethylphenol adsorption on sulded catalyst. Spectra of 2-
ethylphenol adsorbed at RT (Fig. 3A) on Al
2
O
3
(spectrum a) and
on sulded CoMo/Al
2
O
3
(spectrum b) present similar bands that
can be assigned to: m(CC) bands at 1597 (with the shoulder at
1578 cm
1
) and 1492 cm
1
, d(OH) + d(CH) band at 1454 cm
1
,
m(CO) bands at 1291 cm
1
(phenates) and 1263, 1236 cm
1
(molecular 2-ethylphenol). The intensity ratio between the
1454 cm
1
band and the 1492 cm
1
band provides evidence for a
more important fraction of molecular form in the case of sulded
catalyst than on pure support. As a supplementary indication of
this observation, one can note the increased intensity ratio be-
tween m(CO) bands at 1263, 1236 cm
1
(molecular form), and
1291 cm
1
(phenates) on sulded catalyst. Thus, at RT, 2-ethylphe-
nol adsorption on CoMo/Al
2
O
3
leads to the formation of 2-ethyl-
phenate species as well as 2-ethylphenol in molecular form. The
latter adsorbed species are present in larger quantities on CoMo/
Al
2
O
3
than on pure support. This fact can be attributed to weak
interaction of 2-ethylphenol with the sulde phase through a
molecular adsorption. Moreover, study of the H
2
S pre-adsorption
conrms the interaction of 2-ethylphenol with the sulde phase.
Comparison of the spectra of 2-ethylphenol adsorbed on CoMo/
Al
2
O
3
before and after H
2
S pre-adsorption (spectra are not shown)
indicates the decrease in the bands of molecularly adsorbed
Fig. 1. IR spectra of phenol adsorbed on Al
2
O
3
(a), MoOx/Al
2
O
3
(b) at RT (A) and at 623 K (B).
1470
1300 1400 1500 1600
0.1
1597
1498
1492
1597
1498
1295
1250
1295
1271
1450
1564
A B
1300 1400 1500 1600
(b)
(a)
cm
-1
0.1
cm
-1
(b)
(a)
Fig. 2. IR spectra of phenol adsorbed on Al
2
O
3
(a), sulded CoMo/Al
2
O
3
(b) at RT (A) and at 623 K (B).
A B
Fig. 3. IR spectra of 2-ethylphenol adsorbed on Al
2
O
3
(a) and sulded CoMo/Al
2
O
3
(b) at RT (A) and at 623 K (B).
A. Popov et al. / Journal of Catalysis 297 (2013) 176186 179
2-ethylphenol but not of 2-ethylphenates. As reported [38], H
2
S
can be dissociatively adsorbed on sulde phase by occupation of
its Lewis sites. Thus, H
2
S could poison Lewis sites of sulde phase
and so decrease the adsorption of 2-ethylphenol on this phase.
Hence, the decrease in the amount of molecularly adsorbed 2-eth-
ylphenol after addition of H
2
S conrms that these species were ad-
sorbed on sulde phase. It should be mentioned that O-donor
molecules less strongly interact with sulde phase sites than with
oxidic support ones (Al
3+
).
After adsorption of 2-ethylphenol at 623 K on CoMo/Al
2
O
3
(Fig. 3B-b), only bands characterizing 2-ethylphenate species are
detected at 1597, 1492, 1450, 1297, and 1244 cm
1
. Note that
the new band at 1512 cm
1
present on Al
2
O
3
at high temperature
(spectrum a) is not formed on sulded catalyst (spectrum b). On
sulded catalyst, the broad shoulders at 1560 and 1460 cm
1
appear, pointing out the formation of new species in the presence
of sulde phase. Similar shoulders were observed for phenol ad-
sorbed at high temperature on sulded catalysts (Figs. 1 and 2B).
3.1.1.4. Effect of the substituent on the adsorption of phenolic
compounds. The effect of the presence, nature, and position of sub-
stituent in phenolic compounds on their adsorption on sulded
CoMo/Al
2
O
3
catalyst at RT and 623 K was studied by IR spectros-
copy (spectra not shown). Table 2 summarizes the results
obtained.
Regarding the adsorption at RT, IR spectroscopy points out that
phenol, guaiacol, and 3-ethylphenol interaction with sulded
CoMo/Al
2
O
3
leads to (methoxy, ethyl)-phenate formation with
the same frequencies as on pure Al
2
O
3
. The detection of similar fre-
quencies for both phenates anchored on alumina and sulde phase
appears highly unlikely. Therefore, we propose that in these condi-
tions, phenol, guaiacol, and 3-ethylphenol only interact with the
alumina support and not with the sulde phase. Otherwise, the
adsorption of 2-ethylphenol and 4-ethylphenol on support and
on sulded CoMo/Al
2
O
3
at RT demonstrates ethylphenate forma-
tion, as well as the presence of ethylphenol under molecular form.
However, on the CoMo/Al
2
O
3
catalyst, the fraction of molecularly
adsorbed species is greater than on the pure support where ethyl-
phenates are predominant. This fact provides evidence for weak
interaction of (2-)4-ethylphenol with sulde phase through molec-
ular adsorption. H
2
S pre-adsorption decreases the amount of
molecular adsorbed 2-ethylphenol on sulded CoMo/Al
2
O
3
whereas it does not lead to any change on Al
2
O
3
. This conrms
the molecular interaction of 2-ethylphenol with the sulde phase
(Table 2). The difference between the adsorption modes of (2-)4-
ethylphenol and the other oxygenates (phenol, guaiacol, 3-ethyl-
phenol) might be explained by higher basicity of (2-)4-ethylphenol
(pK
a
, Table 2). The donor effect of ethyl group in 2 and 4 positions
facilitates the interaction of the oxygen atom of (2-)4-ethylphenol
with sulde phase vacancies through donoracceptor mechanism.
Regarding the interaction at 623 K, the adsorption of all oxygen-
ated molecules on sulded CoMo/Al
2
O
3
catalyst reveals (1) the
presence of (ethyl, methoxy-) phenate species on the support, (2)
the absence of molecular forms, and (3) the formation of new spe-
cies (X) characterized by the appearance of shoulders (1550,
1450 cm
1
) assigned to the m(CC) bands that are not detected on
pure alumina. These new species (X) correspond to reaction of oxy-
genates with the sulde phase or with species present on it, since
they are only formed in the presence of sulde phase. These spe-
cies correspond to the formation of carbonaceous species, even if
the exact nature of these species is difcult to establish.
The mechanismof interaction of the various oxygenates with sul-
ded CoMo/Al
2
O
3
catalyst at RT and 623 K is depicted in Scheme 1.
Basicity of the oxygenated molecules and temperature of adsorption
appear as key parameters that determine the mechanism of interac-
tion. Two series of oxygenated molecules can be distinguished at RT:
(i) 3-ethylphenol, guaiacol, and phenol that only interact with the
support forming (ethyl, methoxy-) phenates through dissociative
mechanism (Scheme 1A), (ii) (2-)4-ethylphenol that interact both
with the support and with the sulde phase via dissociative mecha-
nismor coordination (Scheme 1B). Interaction of all the molecules at
623 K leads to the (ethyl, methoxy-) phenate formation on the
support and some new species (X) formation, which correspond to
reaction of oxygenates with the sulde phase or with species present
on the sulde phase (Scheme 1C).
3.1.2. Inuence of phenolic compounds adsorption on the accessibility
of sulded sites
3.1.2.1. CO adsorption on sulde catalyst. CO adsorption on sulded
CoMo/Al
2
O
3
(Fig. 4) gives rise to the m(CO) bands usually reported
in the literature [35,3942]. The rst doses of CO on the sulded
CoMo/Al
2
O
3
catalyst (spectra not shown) lead to the appearance
of two bands at 2110 and 2070 cm
1
together with a shoulder at
2052 cm
1
. Upon increasing the CO coverage, other bands at
2186, 2154 cm
1
appear, whereas the intensity of the bands
at 2110, 2070, and 2052 cm
1
continues to increase. The bands at
2186 and 2154 cm
1
are due to CO adsorption on the Al
2
O
3
support
and correspond respectively to coordination on Al
3+
Lewis acid
sites (m(CO/Al
3+
)) and hydrogen bonding with the surface hydroxyl
groups (m(CO/OH)). The three components at 2110, 2070, and
2052 cm
1
correspond to CO adsorption on the sulde phase
on either Mo edge sites of the sulded MoS
2
slab (2110 cm
1

m(CO/MoS
2
)) or on promoted sites in various environments
(2070, 2052 cm
1
m(CO/CoMoS)) [42].
From the areas of CO/MoS
2
and CO/CoMoS bands obtained by
spectral decomposition (see experimental section) and taking into
account the previously determined molar absorption coefcient
values for the bands of CO/MoS
2
and CO/CoMoS species [35], the
concentration of unpromoted Mo sites and Co-promoted sites de-
tected by CO adsorption can be calculated. Thus, on sulded
Table 2
Species formed by adsorption of phenolic molecules on sulded CoMo/Al
2
O
3
catalyst.
Phenolic molecule pK
a
T
adsorption
(K) Interaction with support Interaction with sulde phase
2-Ethylphenol 10.20 298 2-Ethylphenates 2-Ethylphenol molecular
623 2-Ethylphenates X = coke. . .
4-Ethylphenol 10.00 298 4-Ethylphenates 4-Ethylphenol molecular
623 4-Ethylphenates X = coke. . .
Phenol 9.95 298 Phenates
623 Phenates X = coke. . .
Guaiacol 9.93 298 Methoxy-phenates
623 Methoxy-phenates X = coke. . .
3-Ethylphenol 9.90 298 3-Ethylphenates
623 3-Ethylphenates X = coke. . .
180 A. Popov et al. / Journal of Catalysis 297 (2013) 176186
CoMo/Al
2
O
3
catalyst, 116 lmol g
1
of sulde sites is detected cor-
responding to 59 lmol g
1
of Mo sites and 57 lmol g
1
of CoMoS
sites.
3.1.2.2. Phenol and CO co-adsorption. After phenol contact at RT
with sulded CoMo/Al
2
O
3
catalyst (Fig. 4), comparison of CO spec-
tra before and after oxygenates contact points out that phenol
completely prevents the formation of the band at 2186 cm
1
. The
intensity of the band at 2154 cm
1
is greatly decreased. Regarding
the sulde phase, all the bands characteristics of CO uptake also
markedly diminish (60% of inaccessible sulde sites Table 3).
The CoMoS band appears slightly shifted, but this effect can be ex-
plained by the stronger diminution of the band at 2070 cm
1
than
that of the component at 2052 cm
1
. Taking into account the ab-
sence of shift for Mo band at 2110 cm
1
, this hypothesis is pro-
posed instead of the shift of CoMoS bands. The effect of phenol
treatment at 623 K on the accessibility of the sites of sulded
CoMo/Al
2
O
3
is shown (Fig. 4). A decrease in the CO bands corre-
sponding both to support (2186 and 2154 cm
1
) and to sulded
phase (region 21202000 cm
1
) is observed. However, comparison
of the effect of phenol treatment at RT and 623 K shows a partial
recovering of the accessibility of alumina support Lewis acidic sites
(band at 2186 cm
1
). In the same way, the accessibility of the sul-
ded phase sites is slightly improved after phenol treatment at
623 K (44% of the inaccessible sulde sites at 623 K instead of
60% at RT Table 3). No selective poisoning of the different types
of sulde sites is observed after high temperature treatment. The
same results were obtained with sulde Mo/Al
2
O
3
catalyst (spectra
not shown), with a similar decrease in accessible sulde sites (40%)
after phenol adsorption at 623 K.
After phenol contact at both RT and 623 K, CO uptake decrease
indicates a poisoning of the support (bands at 2186 cm
1
m(CO/
Al
3+
) and 2154 cm
1
m(CO/OH)) as well as of the sulde phase
(bands at 2110 cm
1
m(CO/Mo) and 2069, 2052 cm
1
m(CO/Co-
MoS)). Regarding the support, the decrease in the accessibility of
Al
3+
sites after phenate formation is in agreement with the disso-
ciative adsorption of phenol on alumina that leads to the formation
of AlAOAPh species (under mono or bidentate forms). The forma-
tion of phenates on the support could also indirectly perturb the
OH groups and consequently limit CO/OH interaction. As for the
sulde phase, a marked decrease in the accessibility of the sulde
sites is observed. This decrease directly depends on the amount of
phenate species as shown in Fig. 5 (when the amount of phenates
increases, the accessibility of sulded sites (MoS
2
and CoMoS sites)
decreases). This linear dependence indicates that phenate species
(formed on the support) are involved in the poisoning of the sulde
sites. Our proposal is that an indirect poisoning of the sulded
phase sites by phenate species anchored on alumina support oc-
curs at RT (Scheme 2). The presence of phenate species on alumina
in the vicinity of sulde slabs would lead to a steric hindering of
the sulde sites (both Mo and CoMo sites). After phenol treatment
at 623 K, a partial recovering of the sulde site accessibility is ob-
served, which corresponds to evacuation of a fraction of phenates
from the alumina support.
The inuence of phenol on the Mo/SiO
2
catalyst has been inves-
tigated (spectra are not shown), since the use of a less acidic sup-
port can be a way to limit the formation of phenate species
anchored on the support and thus preserve the accessibility of
the active sites. Comparison of these results with phenol effect
on Mo/Al
2
O
3
shows that the accessibility of the sulde phase is less
affected by phenol adsorption on Mo/SiO
2
than on Mo/Al
2
O
3
cata-
lyst (17% of inaccessible sulde sites instead of 40%). This can be
related to the lower amount of phenates formed on Mo/SiO
2
catalyst.
3.1.2.3. 2-Ethylphenol and CO co-adsorption. The spectrum of CO
after 2-ethylphenol adsorption at RT shows hindered accessibility
of both the support and the sulded phase sites (Fig. 6A, spectrum
b). The bands of CO adsorbed on the support almost vanish.
Scheme 1. Mechanisms of interaction of phenolic molecules with sulded (Co)Mo/Al
2
O
3
catalyst: (A) phenol at RT, (B) 2-ethylphenol at RT, (C) (ethyl)phenol at 623 K.
Fig. 4. IR spectra of CO (133 Pa at equilibrium) adsorbed on sulded CoMo/Al
2
O
3
before, after phenol adsorption at RT, after phenol adsorption at 623 K.
Scheme 2. Mechanism for indirect poisoning of the sulde sites by phenol
adsorption on the support.
A. Popov et al. / Journal of Catalysis 297 (2013) 176186 181
Regarding CO interaction with sulde phase after 2-ethylphenol
adsorption at RT, the intensities of the m(CO/MoS
2
) and m(CO/Co-
MoS) bands are reduced by 78% and their maxima are shifted
downward (5 cm
1
) (Table 3). After 2-ethylphenol treatment at
623 K (Fig. 6B, spectrum b), CO adsorption shows very weak acces-
sibility of the support sites, whereas CO uptake on sulde phase is
improved (46% of the inaccessible sulde sites instead of 78% at RT
(Table 3). Nevertheless, the shift of m(CO/MoS
2
) and m(CO/CoMoS)
bands is still observed. Note that this shift is the same at RT and
623 K.
Comparison of the spectra of CO after 2-ethylphenol and phenol
contact shows the same faction of poisoned sulde sites at 623 K
(about 45% of sulde sites become inaccessible after treatment in
both ethylphenol and phenol), whereas at RT, the poisoning effect
of 2-ethylphenol on sulde phase is stronger than that of phenol
(78% of the inaccessible sulde sites after 2-ethylphenol contact
and 60% after phenol contact Table 3). 2-Ethylphenol adsorption
leads to the formation of 2-ethylphenates on the support, as well
as coordinated molecular 2-ethylphenol on the sulde phase.
Therefore, this direct adsorption on the sulde phase, in addition
to the indirect effect due to 2-ethylphenate species anchored on
the alumina support, can explain the stronger poisoning of the sul-
de sites by 2-ethylphenol than phenol. At 623 K, 2-ethylphenol is
only present under the form of 2-ethylphenate species on the sup-
port. Hence, after adsorption of 2-ethylphenol and phenol at 623 K,
the same amount of (2-ethyl)phenates is present and leads to the
same poisoning of the sulde sites.
2-Ethylphenol interaction with CoMo/Al
2
O
3
leads to some addi-
tional modication of the sulde phase. The m(CO/MoS
2
) and m(CO/
CoMoS) bands are both shifted downward by 5 cm
1
for adsorption
performed at RT and 623 K. This indicates that 2-ethylphenol leads
to a change of the electronic properties of the sulde phase. It
should be mentioned that no shift was observed in the case of
phenol.
3.1.2.4. Effect of the substituent in the phenolic compounds on CO
adsorption. Data issued from CO adsorption before and after con-
tact of oxygenates with the sulde catalyst provide evidence for
two main effects: (1) decrease in the accessibility of the sulde
sites as shown by the intensity decrease in m(CO/MoS
2
) and
m(CO/CoMoS) bands and (2) some change of the electronic proper-
ties, as shown by the shift of the CO bands in some cases. As listed
in Table 3, the extent of these effects can be related to the presence,
nature, and position of the substituent of the phenolic compounds
as well as of the temperature of adsorption.
3.1.2.4.1. Accessibility of the sulde phase after oxygenate adsorption.
Phenol adsorption on sulded CoMo/Al
2
O
3
only gives rise to phe-
nate formation on the support. The decrease in the accessibility
of sulde sites linearly depends on the amount of phenate species
anchored on the support (Fig. 5). Hence, an indirect poisoning of
the sulded sites by the presence of phenate species on the support
and in the vicinity of the sulde slabs is proposed [43].
Like for phenol, 3-ethylphenol adsorption on sulded CoMo/
Al
2
O
3
only forms phenate-type species on the support that induce
a similar decrease in the accessibility of the sulde sites (Table 3:
Table 3
Inuence of phenolic molecule adsorption on the positions and areas of IR band of CO/sulde sites on CoMo/Al
2
O
3
catalyst.
Oxygenated molecule T
adsorption
(K) Inuence on the sulde phase
Decrease in CO uptake (%) Shift of m(CO/MoS
2
) (cm
1
)
2-Ethylphenol 298 78 5
623 46 5
4-Ethylphenol 298 77 7
623 17 7
Phenol 298 60 0
623 44 0
3-Ethylphenol 298 55 0
623 10 0
Guaiacol 298 74 10
623 63 5
Fig. 5. Relationship between the areas of (m(CO/MoS2) + m(CO/CoMoS)) bands and
phenol m(CC) band (at 1600 cm
1
) on sulded CoMo/Al
2
O
3
.
2052
2110
2070
2058
2105
2186
2154
2052
2150
2110
2105
2070
2061
2186
2154
0.02
A B
(b)
(a)
0.02
2000 2100 2200 2000 2100 2200
(b)
(a)
cm
-1
Fig. 6. IR spectra of CO (133 Pa equilibrium) adsorbed on sulded CoMo/Al
2
O
3
before (a), after (b) 2-ethylphenol adsorption at RT (A) and at 623 K (B).
182 A. Popov et al. / Journal of Catalysis 297 (2013) 176186
at RT about 55% versus 60% of inaccessible sites). Note, that after
contact with 3-ethylphenol at high temperature, a recovering of al-
most all the sulde sites is observed.
Adsorption of (2-)4-ethylphenol on sulded CoMo/Al
2
O
3
at RT
forms both phenate-type species on the support and molecular
form on the sulde phase. (2-)4-Ethylphenol adsorption leads to
a similar poisoning of the sulde phase (Table 3: about 77% of inac-
cessible sites). It should be mentioned that this poisoning is signif-
icantly greater than that observed for phenol and 3-ethylphenol.
Hence, this can be explained by the two forms of adsorption of
(2-)4-ethylphenol at RT that lead to indirect poisoning (due to
(ethyl)phenate species) on the support and also to direct poisoning
(due to molecular form) on the sulde phase.
Adsorption of 2-methoxyphenol at RT leads to a similar poison-
ing of the sulde phase than for (2-)4-ethylphenol (74% of inaccessi-
ble sites). 2-Methoxyphenol interacts only with the support and not
with the sulde phase, but the strong poisoning cannot be only ex-
plained by an indirect mechanism due to the presence of phenol
group. Hence, two features canaccount for the more markedpoison-
ing of the sulde sites: (1) the stronger interaction of 2-methoxy-
phenol with alumina at high temperature than (ethyl-)phenates
[43] and(2) the presence of methoxygrouponthe aromatic ring that
can perturb more strongly the sulde sites accessibility than the
ethyl group. After treatment at 623 K, the strong poisoning effect
of 2-methoxyphenol is hardly decreased, conversely to the (ethyl-
)phenol molecules. This is in agreement with almost unchanged
amount of methoxy-phenate-type species on the support.
As a general manner, the sulde phase sites are more accessible
after treatment at 623 K than after adsorption of oxygenates at RT.
It should be noted that on sulded CoMo/Al
2
O
3
catalyst at 623 K,
new species (X species) are formed. The question of the toxicity
of the X species on the sulde sites arises. As shown for phenol
in Fig. 5, a linear dependency between the amount of phenates
and sulde sites poisoning is evidenced. Thus, the contribution of
the X species to the poisoning should be minor in the case of phe-
nol adsorption at 623 K. Consequently, the location of these carbo-
naceous X species on the edges of the sulde slabs is very unlikely.
Otherwise, the direct poisoning effect would be stronger than the
indirect poisoning. So, we propose that these carbonaceous X spe-
cies formed after high temperature treatment are located on the
basal planes of sulde slabs or on the alumina support. Anyway,
these carbonaceous species could not be the main reason of the
catalyst deactivation.
3.1.2.4.2. Electronic properties after oxygenate adsorption. It is
known [37,44] that on metallic and on sulde phases, the position
of the CO band mainly depends on the extent of backdonation of d-
electrons of the adsorption center. This means that the electronic
properties of the sites account for m(CO) wavenumber. The down-
ward shift of CO maxima after oxygenate adsorption indicates an
increase in the electronic density on the sulde phase sites (Ta-
ble 3). However, adsorption of phenol and 3-ethylphenol does
not lead to any changes of the electronic properties of the sulde
phase. By contrast, adsorption of (2-)4-ethylphenol and 2-
methoxyphenol on the sulded CoMo/Al
2
O
3
catalyst at RT as well
as at 623 K leads to a downward shift of m(CO/MoS
2
) and m(CO/Co-
MoS) bands. Thus, the effect on the electronic properties of the sul-
de phase depends on the temperature of adsorption as well as on
the nature of the oxygenate. For adsorption at RT, it follows the or-
der: 2-methoxyphenol (10 cm
1
) > 4-ethylphenol (7 cm
1
) > 2-
ethylphenol (5 cm
1
) 3-ethylphenol phenol (0 cm
1
). For
(ethyl)phenol adsorption at 623 K, the variation of m(CO/MoS
2
)
and m(CO/CoMoS) wavenumbers is equal to that measured at RT,
whereas for 2-methoxyphenol adsorption, the shift of m(CO/
MoS
2
) and m(CO/CoMoS) bands is smaller (from 10 cm
1
up to
5 cm
1
).
Modications of the electronic properties of the sulde phase
by oxygenate adsorption could have different origins:
Direct effect: After (2-)4-ethylphenol adsorption, a shift of m(CO/
MoS
2
) and m(CO/CoMoS) bands is observed. Since the same shift
is observed both after interaction at RT and 623 K when the
adsorbed species amount is different, the modication of the
electronic properties of the sulde phase cannot be due to the
direct interaction of these oxygenates with the sulde phase.
Indirect effect: In previous studies, using the IR spectroscopy of
CO adsorption on sulde catalysts supported on b-zeolite [45],
amorphous silica alumina [46] and alumina modied by boron
[37], it was found that the CO wavenumber shifts upwards
when the acidity of the support increases indicating the
enhancement of the electronic deciency properties of the sul-
de phase. In the same way, Mg addition [37], or K addition
[37], leads to a downward shift of m(CO/MoS
2
) and m(CO/
CoMoS) bands on sulded CoMo/Al
2
O
3
catalyst, while the acid
strength of Lewis and Brnsted acid sites decreases. The m(CO/
MoS
2
) band is shifted down by 3 cm
1
in the case of Mg addi-
tion and by 7 cm
1
for K modication. Thus, the electronic prop-
erties of the sulde phase vary with the acidity of the support.
In the present case, all the oxygenates form phenate-type spe-
cies on the alumina support by interaction with Al
3+
sites. Their
strong interaction with Lewis acid sites that decreases the support
acidity could explain the change of electronic properties of the sul-
de phase. However, not all the oxygenates lead to a change of
electronic properties of the sulde phase. Thus, some additional
factors, besides the decrease in the support acidity, have to be
considered.
Oxygenate basicity: Table 2 shows that adsorption of oxygenates
with ethyl group in ortho- and para-positions have a greater
impact on the shift of m(CO/MoS
2
) and m(CO/CoMoS) bands than
that observed for oxygenate with ethyl group in meta-position
or pure phenol. Consequently, there is a relation between the
basicity of (ethyl)phenol (2-ethylphenol (10.20) > 4-ethylphe-
nol (10.00) > phenol (9.95) > 3-ethylphenol (9.90)) and the
extent of the shift.
Nature of substituent: Since the intermediate basicity of 2-
methoxyphenol (pKa: 9.93) does not explain the marked shift
of the m(CO/MoS
2
) band (10 cm
1
), the nature of substituent
also inuences the interaction of oxygenated with the sulde
phase. Indeed, the lone electron pair of oxygen atom of methoxy
group of 2-methoxyphenol adsorbed in the vicinity of sulde
particles is likely to interact stronger with the sulde phase
than the ethyl group of ethylphenol. This proposal is in good
agreement with the great m(CO/MoS
2
) shift, as well as the dim-
inution of m(CO/MoS
2
) shift (5 cm
1
) observed for 2-methoxy-
phenol contact at 623 K with respect to RT. Indeed, our previous
study [34] of 2-methoxyphenol interaction with alumina shows
that at RT, methoxy phenate is formed, while at 623 K, a fraction
of methoxy groups reacts with alumina leading to the formation
of double anchored phenate species and methoxy grafted on
alumina. Therefore, the lone electron pair of the oxygen atom
of methoxy group cannot perturb any more the sulde phase.
In summary, adsorption of (2-)4-ethylphenol and 2-methoxy-
phenol on the sulded CoMo/Al
2
O
3
catalyst changes the electronic
properties of the sulde sites, whereas adsorption of 3-ethylphenol
and phenol does not lead to any changes. It should be mentioned
that the electronic properties are more sensitive to the presence
of phenate-type species on the support than to the direct interac-
tion of the oxygenates with the sulde phase. The effect of the oxy-
genated molecules on the electronic properties of the sulded
A. Popov et al. / Journal of Catalysis 297 (2013) 176186 183
phase depends on the basicity of the oxygenate that changes the
acidity of the support, as well as the nature of the substituent.
The methoxy group of 2-methoxyphenol adsorbed on alumina in
the vicinity of the sulde phase should interact more strongly with
the sulded sites than the ethyl group of ethylphenol.
3.2. CoMo catalysts after 2-ethylphenol HDO
Results of the previous section show that, for model phenolic
molecules, the species responsible of active site poisoning are phe-
nate-type species anchored on the support. In order to conrm the
nature of poison species, catalysts after HDO reaction were
analyzed.
Since catalyst deactivation is inuenced by the presence of H
2
S
during the HDO run, surface species were analyzed on CoMo/Al
2
O
3
catalysts tested with or without H
2
S addition. The activation and
test procedure as well as condition of storage and pelletizing be-
fore the IR analysis are described in the experimental section.
3.2.1. Catalyst tested without H
2
S addition
3.2.1.1. Characterization of spent catalyst. The catalyst tested in 2-
ethylphenol HDO without added H
2
S (CoMo spent without H
2
S)
is characterized by IR spectroscopy after evacuation at different
temperatures. Stretching CH bands at 31003000 cm
1
and
30002800 cm
1
specic of aromatic and aliphatic groups respec-
tively are detected (spectra not shown). In the 17001200 cm
1
re-
gion (Fig. 7A), spectrum (a) exhibits bands at 1597, 1578, 1492 and
1460 cm
1
, which are close to those observed for 2-ethylphenol
(Fig. 3). The detection of bands at 1263 and 1236 cm
1
indicates
the presence of molecular 2-ethylphenol as discussed for alumina
in Section 3.1.1.3. Increase in the evacuation temperature up to
623 K leads to changes in this zone. The bands at 1263 and
1236 cm
1
are eliminated, indicating the disappearance of molec-
ular 2-ethylphenol species. Even if the bands between 1300 and
1240 cm
1
are too broad to be assigned for sure to ethylphenate
species, variation of the intensity ratio of the m(CC) band at
1492 cm
1
versus the [d(OH) + d(CH)] band at 1460 cm
1
with in-
creased evacuation temperature conrms this point. Hence, IR
analysis points out the presence of ethylphenate species on CoMo
spent without H
2
S catalyst.
It could be surprising to observe the presence of molecular 2-
ethylphenol on the catalyst surface after the HDO reaction. This
is likely due to residual 2-ethylphenol in the catalytic reactor that
re-adsorbs on the catalyst surface at the end of the test during the
cooling period.
3.2.1.2. CO adsorption on the tested catalyst. The purpose of these
experiments was to characterize the accessibility of the sulde
phase of the CoMo spent without H
2
S catalyst. Pelletizing a com-
plete disk inside the glove box was very difcult. Consequently, the
quality of the spectra is poor and their quantication is difcult.
Fig. 7B compares spectra of CO adsorbed on the spent CoMo/
Al
2
O
3
without H
2
S and fresh sulde catalyst. After CO contact, very
low CO uptake is detected on spent CoMo/Al
2
O
3
: only bands at
2154 cm
1
(m(CO/OH)), 2140 cm
1
(physically adsorbed CO) and
a low intense band at 2070 cm
1
(CO adsorbed on sulded phase:
CoMoS sites) are formed. Even if the characterization of the sulde
phase of spent catalyst is particularly tricky, the CO spectrum re-
veals that the accessibility of both MoS
2
and CoMoS sulde sites
is strongly reduced after HDO reaction.
3.2.2. Catalyst tested with H
2
S addition
IR spectrum of CoMo spent with H
2
S catalyst is presented in
Fig. 8b. It shows a very intense band at 1094 cm
1
that was not ob-
served on the CoMo spent without H
2
S catalyst (spectrum a).
This new band at 1094 cm
1
indicates sulfate species formation.
However, according to the literature [47], a second band at
1380 cm
1
characterizing (S@O) groups must be also present. Since
the S@O species is very sensitive to water, some contamination
with H
2
O during the unloading of the HDO reactor and/or pelletiz-
ing could explain its absence. Indeed, after evacuation of the spent
CoMo spent with H
2
S catalyst for long duration (1 h) at 623 K,
the two sulfate species bands (m(SAO) at 1090 cm
1
as well as
m(S@O) at 1367 cm
1
(spectra not shown) are observed. Since
these species are not observed on CoMo spent without H
2
S cata-
lyst, the sulfate species are likely formed during pelletizing by
reaction of sulfur residue with atmospheric oxygen. Consequently,
probing the accessibility of catalyst by CO adsorption has not been
done since it would not be meaningful.
It should be noted that the comparison of the intensity of the
m(CC) band at 1492 cm
1
between spectra (a and b) provides evi-
dence that the presence of carbonaceous species is higher (about
factor 3) on CoMo spent without H
2
S than on CoMo spent with
H
2
S. This is in line with the amount of carbon detected by elemen-
tal analysis (respectively 9 and 3.3 wt%).
A
1320
cm
-1
1200 1300 1400 1500 1600
(RT)
(523 K)
(623 K)
1263
1597
1492
1460
1236
1578
0.1
B
1260
1590
After HDO test
2186
cm
-1
2050 2100 2150 2200
2154
2110
2070
2052
Before HDO test
0.02
2070
2140
2154
Fig. 7. (A) IR spectra of sulded CoMo/Al
2
O
3
after HDO test without H
2
S: catalyst evacuated at RT, 523 K, and 623 K. (B) IR spectra of CO (133 Pa equilibrium) adsorbed on
sulded CoMo/Al
2
O
3
before and after test without H
2
S.
Fig. 8. Comparison of IR spectra of sulded CoMo/Al
2
O
3
after HDO test without H
2
S
(a) or with H
2
S (b). After HDO run, the catalysts are post-treated at 523 K in the IR
cell.
184 A. Popov et al. / Journal of Catalysis 297 (2013) 176186
3.2.3. Conclusion
On the spent catalysts, IR analysis mainly detected three spe-
cies: molecular 2-ethylphenol (due to reactant re-adsorption after
reaction), sulfate species (formed during the pelletizing under air),
and 2-ethylphenate species. The two rst ones are contaminants;
only the last one is responsible of catalyst deactivation. This con-
rms the role of ethylphenate species as a poison that was sus-
pected from the study in model conditions.
3.3. Modeling of the effect of phenol adsorption on the sulde sites
accessibility
Experiments done with model oxygenates as well as after HDO
run supports the hypothesis of an indirect poisoning, that is, that
phenate species on alumina screen the edge sites of sulde slabs
leading to a poisoning of the catalyst. To validate this conclusion,
a model is developed in order to quantify the screening effect of
phenate on support.
As previously shown for phenol adsorption (Fig. 5), the accessi-
bility of sulde sites is linearly dependant on the amount of phen-
ates adsorbed on the support:
C(CO/sulde phase) = K C(Ph/alumina) with C(CO/sulde
phase) = concentration of CO adsorbed on the sulded phase,
and C(Ph/alumina) = concentration of phenate species on
alumina.
Considering the molar absorption coefcients of the phenate
band at 1600 cm
1
(e
cc
= 5 lmol
1
cm [34]) and that of CO in inter-
action with sulde sites (CO/MoS
2
at 2115 cm
1
, e
co
= 16 lmol
1
cm
and CO/CoMoS at 2065 cm
1
, e
co
= 43 lmol
1
cm[35]), and the rela-
tionship presented Fig. 5, the K factor is calculated. K value is equal
to 0.23. This value indicates that about 4 phenate species on alu-
mina are necessary to poison one site of the sulde phase. This ratio
seems rather low. Probably, it is because only few surface phenates
are close enough to sulde slabs for screening the active sites.
To clarify this point, we attempted to model the surface of the
sulde CoMo catalyst in order to quantify the fraction of phenate
on alumina and their vicinity with sulde slabs. Therefore, our
modeling consists of three stages: (a) calculation of the alumina
coverage by sulde slabs, (b) determination of the average distance
between sulde slabs, and (c) assessment of the amount of phenate
located close enough fromsulde slabs to poison their accessibility.
Two methods were used to determine the covering of alumina by
sulde phase: theoretical (method 1) and experimental (method 2).
Method 1 is based on the calculation of the surface occupied by
sulde slabs determined from an hexagonal model of the sulde
slabs, considering a slab stacking of one and taking into account
of the amount of Mo and Co atoms determined by chemical
analysis.
Method 2 is based on the analysis of the IR spectra of phenol
adsorbed on Al
2
O
3
and on sulded CoMo/Al
2
O
3
and considering
molar absorption coefcients determined previously [34,35].
The surface coverage of alumina by sulde phase and the aver-
age distances between sulde slabs of the Mo and CoMo catalysts
are calculated according to the two methods (Table 4). The calcu-
lations are detailed in Supplementary material.
Table 4 shows that, for each catalyst, there is a good agreement
between the two methods. Note that these calculations clearly
point out differences between CoMo and Mo catalysts since the
coverage of alumina by sulde CoMo slabs is greater than by
MoS
2
slabs (41% instead of 27%), which induces a distance between
sulde slabs smaller on CoMo than on Mo catalyst (1.5 nm instead
of 2.3 nm).
Taking into account the interslab distance calculated previously
for CoMo catalyst (1.4 nm in method 2), the size of phenate species
(d
Ph
= 0.64 nm) and that of CO molecule (0.44 nm), if a phenate
species is located at equal distance of two sulde slabs, it only re-
mains 0.38 nm between the phenate species and each closest
neighbor sulde slabs (Fig. 9). Thus, in that case, one phenate pre-
vents adsorption of two CO molecules on sulde sites. The location
of phenate at a different position between the two slabs (at more
than 0.06 nm of the middle of the interslab) lets CO molecule
adsorption on one sulde slab, whereas the opposite sulde sites
slab is still screened. So, each phenate blocks one or two sulde
slab sites from CO adsorption. Accurate calculations based on slab
size distribution indicate that one phenate hinders the adsorption
of 1.35 molecules of CO (screening effect = 1.35).
Comparison between theoretical screening effect and that
determined experimentally (Fig. 5) shows strong difference. In-
deed, experimental screening effect determines from phenol and
CO adsorption (K = 0.23) is clearly smaller than the calculated
one (1.35).
The smaller experimental value can be explained by the low
amount of CO adsorbed on sulde sites compared to the concentra-
tion of edge sites that can be calculated from geometrical model,
length of sulde slab (determined from HREM), and amount of
Mo and Co (determined by chemical analysis). Indeed, in the pres-
ent study, CO adsorbed on the CoMo catalyst detected
116 lmol g
1
sulde sites of edge sites (59 lmol g
1
of Mo sites
and 57 lmol g
1
of CoMoS sites, Fig. 4a), whereas the amount of
edge sites calculated by equ. 1 is about 500 lmol g
1
. Hence, CO
adsorption only probes 23% of the total sulde sites. Taking into ac-
count this limitation, the screening effect determined experimen-
tally reaches 31%. Hence, the good agreement between
Table 4
Coverage of alumina surface by the sulde slabs (C) and sulde phase interslab distance (d) calculated by methods 1 and 2.
Method MoS
2
slabs CoMoS slabs
Alumina coverage (%) Interslab distance (nm) Alumina coverage (%) Interslab distance (nm)
Method 1 24 2.6 40 1.6
Method 2 30 2.0 42 1.4
Fig. 9. Model for phenol adsorption in the interslab zone of sulde catalyst.
A. Popov et al. / Journal of Catalysis 297 (2013) 176186 185
experimental and calculated screening effect shows that one phe-
nate species can block at least 1.3 active sites of sulde phase of
the CoMo/Al
2
O
3
catalyst. Consequently, this quantitative analysis
supports the proposal of the indirect poisoning of active sites by
phenate species adsorbed on the support.
4. Conclusion
The study of the interaction of oxygenated aromatic compounds
(as phenol, ethylphenols, and guaiacol) with sulded (Co)Mo/Al
2
O
3
catalyst shows that basicity of the phenolic molecules as well as
nature of the substituent are key parameters that determine the
adsorption mechanisms.
All the phenolic compounds anchor on the alumina support as
phenate-type species, whereas only the most basic phenolic mole-
cules (as 2 and 4 ethylphenol) and guaiacol interact also with the
sulde phase. At temperature typical of the HDO operating condi-
tions (673 K), only phenate species on the support are detected.
As expected, oxygenated compounds adsorbed on the sulde
phase poison the sulde sites. But, phenate-type species anchor
on the alumina also hinder the accessibility to the sulde edge
sites. Modeling of the catalyst surface quantitatively conrms the
screening effect of these phenate species. Characterization of cata-
lysts tested in ethylphenol HDO conrms the role of poison of the
ethylphenate species that was suspected from the model condition
study. Hence, this paper points out that the nature of the oxygen-
ated aromatic compound as well as the surface properties of the
catalyst support are determining in the mode and extent of HDO
active sites poisoning.
Acknowledgments
Thanks to Prof. Xavier Portier from CIMAP (ENSICAEN, France)
for performing the HREM observations.
Thanks to Dr. Yilda Romero, Dr. Frederic Richard, and Dr. Syl-
vette Brunet from IC2MP (University of Poitiers, France) for provid-
ing the spent catalysts as well as for all the stimulating discussions.
This work has been performed within ECOHDOC, a joint project
between CNRS, Universities of Caen, Lille and Poitiers and Total
funded by the Agence Nationale de la Recherche (France).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcat.2012.10.005.
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