Applied Catalysis A: General 251 (2003) 8592

Deactivation of Mo/Al2 O3 and NiMo/Al2 O3 catalysts

during hydrodesulfurization of thiophene
Bas M. Vogelaar a , Petr Steiner b , A. Dick van Langeveld c, ,
Sonja Eijsbouts d , Jacob A. Moulijn a
a Department of Chemical Technology, Faculty of Applied Sciences, Delft University of Technology,
Section Reactor and Catalysis Engineering, Julianalaan 136, 2628 BL Delft, The Netherlands
b Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim, Norway
c Faculty of Applied Sciences, Particle Optics Group, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands
d AKZO Nobel Chemicals BV, P.O. Box 37650, 1030 BE Amsterdam, The Netherlands

Received 23 January 2003; received in revised form 7 April 2003; accepted 8 April 2003

Abstract
A Mo/Al2 O3 and a NiMo/Al2 O3 catalyst were subjected to the gas-phase hydrodesulfurization (HDS) of thiophene. The
mechanism of catalyst deactivation was investigated. Sintering or modification of the active phase and blocking of the active
sites or the pore structure by coke deposition were considered as possible causes. The freshly sulfided and the spent catalysts
were characterized by quasi in situ TEM, IR spectroscopy on adsorbed CO, total carbon analysis, N2 chemisorption and Hg
porosimetry. For the NiMo/Al2 O3 catalyst the main cause for deactivation is loss of sulfur during the reaction. This process
is fully reversible by H2 S/H2 treatment. In contrast coke deposition on the active sites is a major cause for deactivation of the
Mo/Al2 O3 catalyst.
2003 Elsevier B.V. All rights reserved.
Keywords: Hydrodesulfurization; NiMo/Al2 O3 ; Thiophene HDS; Deactivation; Infra-red spectroscopy; FTIR

1. Introduction about the deactivation mechanism of these catalysts.

Due to ongoing changes in legislative requirements
on transportation fuels, the hydrodesulfurization
(HDS) process is currently receiving more and more
attention. Oil refiners face the challenge to meet the
new specifications by improving hydrotreating per-
formance [1]. Although the conventional NiMo and
CoMo catalysts are widely used in commercial hy-
drotreaters for decades already, only little is known
Corresponding author.
E-mail address: a.d.vanlangeveld@tnw.tudelft.nl
(A. Dick van Langeveld).
Most striking is the initial deactivation period, that is,
its severity and its relatively short time scale; up to
50% of the initial activity may be lost within a few
days on stream [2]. The aim of the present work is to
investigate this phenomenon in more detail using var-
ious quasi in situ techniques. If answers can be found
to the question why the catalyst deactivates initially,
its performance might be improved by changing the
catalyst properties or operating conditions.
There are several possible reasons for the deactiva-
tion of a catalyst. It might be loss of dispersion due
to sintering of the active phase. Also, the state of the
active sites might change during the reaction, leading

0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0926-860X(03)00305-3
86 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592
to a decreased activity. Active sites might be poisoned
or blocked by coke. Finally, the pores of the catalyst
may be blocked by coke deposition, leading to a loss
of accessible pore volume and surface area. These four
possibilities were investigated using quasi in situ trans-
mission electron microscopy, total carbon analysis, N2
adsorption, Hg porosimetry and infrared spectroscopy
on adsorbed CO. The latter is a proven method to char-
acterize the surface of the active phase at the molecular
level. CO selectively adsorbs on coordinatively unsat-
urated sites, which are believed to be the active sites
in the HDS reaction [3]. The CO adsorption process
influences the CO bond strength and, hence, changes
its vibration frequency, shifting its absorption peak po-
sition in the infrared spectrum. This way a fingerprint
is obtained of the different surface sites on the cata-
lyst [4]. The gas phase hydrodesulfurization of thio-
phene was selected as test reaction. This makes the
translation of the results to industrial conditions (liquid
phase, high pressure) more difficult but enabled us to
develop and apply a multitude of analysis techniques.
2. Experimental
2.1. Catalysts
Two catalysts were prepared for this study, a
Mo/Al2 O3 and a NiMo/Al2 O3 catalyst. Starting mate-
rial was a high purity -Al2 O3 in the form of 1.5 mm
extrudates, which was impregnated with a solution
of ammonium heptamolybdate (NH4 )6 Mo7 O24 and
nickel nitrate Ni(NO3 )2 by the incipient wetness
method, followed by drying and calcination. After pre-
paration the catalyst extrudates were crushed and sie-
ved. The resulting catalysts contained 10 wt.% MoO3
or 10 wt.% MoO3 and 2.5 wt.% NiO, respectively.
2.2. Activity measurements
The conversion the thiophene was measured in a
fixed bed flow reactor. Five hundred milligrams of
catalyst (sieve fraction 75125 m) was diluted with
an equal volume of SiC (400 m) and placed in a
10 mm i.d. glass tube reactor. The catalysts were sul-
fided in situ using a gas mixture of 5 vol.% H2 S and
50 vol.% H2 in balance Ar at a total flow of 60 ml/min.
The temperature program applied during sulfidation
had three stages: 30 min isothermal at room temper-
ature, linear temperature increase with 10 K/min, fol-
lowed by an isothermal stage at 673 K during 60 min.
Directly after sulfiding the gas flow was switched to
the reaction mixture containing 4.3 vol.% thiophene in
balance H2 with a total flow rate of 100 ml/min. This
gas mixture was prepared by flowing pure H2 through
a saturator containing liquid thiophene (Acros Organ-
ics, >99% purity) kept at a constant temperature of
283 K. Samples of the reactor outlet gas stream were
taken on-line and analyzed using a gas chromatograph
with a fused silica column and a flame ionization de-
tector. After reaching steady state (4 h), the catalyst
was cooled down in a 30 ml/min He stream, sepa-
rated from the SiC by sieving and stored for analysis.
In part of experiments after reaching steady state, the
gas stream was switched to a different composition
(H2 S/H2 /Ar, H2 or He; T = 673 K) during 60 min
to test to what extent the activity for thiophene HDS
could be recovered. After this reactivation treatment
the activity was measured again.
2.3. Spent catalyst analysis
The carbon content of the spent catalysts was mea-
sured using a Leco CS 225 analyzer. The sample is
combusted in an O2 gas stream and the CO2 produced
is quantified with an infrared detector. The BET sur-
face area was measured by means of a Quantachrome
Autosorb 6B unit using N2 physisorption at 77 K.
Prior to the analyses the samples were heated at 473 K
in vacuum during 16 h. Pore volumes were measured
by Hg porosimetry using a CE Instruments Pascal
140440 apparatus.
2.4. Quasi in situ TEM
About 10 mg of the crushed catalyst (<75 m) was
placed in a fixed bed glass tube reactor. The catalyst
was sulfided and exposed to thiophene during 4 h as
described earlier. The reactor was cooled to ambient
temperature, flushed with Ar, sealed, and transported
to a glove box. The sample was ground, suspended
in hexane, applied to a carbon polymer microgrid
supported on a copper grid and transferred to the mi-
croscope in a special vacuum-transfer sample holder
under the exclusion of air. Transmission electron
microscopy was performed using a Philips CM30T
 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592 87

electron microscope with a LaB6 filament operated at Table 1

300 kV as the electron source. For all samples several Extent of reactivation by treatment with selected gas mixtures
micrographs were recorded from which representative Catalyst Reactivating Steady state Conversion
images were selected. gas conversiona after gas
(%) treatmenta (%)
2.5. FTIR of adsorbed CO Mo/Al2 O3 H2 S/H2 50 63
Mo/Al2 O3 H2 40 47
Mo/Al2 O3 He 44 47
About 20 mg of the crushed catalyst (<75 m) NiMo/Al2 O3 H2 S/H2 49 100
was pressed into a self-supporting disk by applying a Percentage of initial conversion.
a pressure of 500 MPa during 1 min and placed in
the infrared in situ setup (IRIS) using a mobile sam-
ple holder. The NiMo catalyst was diluted with an catalyst shows a much higher activity than the un-
equal weight of the -Al2 O3 bare support material promoted Mo based catalyst. To obtain a comparable
to improve the transparency of the sample. The IRIS thiophene conversion at the same reaction tempera-
consists of a sample pretreatment chamber and a CO ture, a ten times higher WHSV was used for the NiMo
adsorption chamber between which the sample can based catalyst. For both catalysts an initial deactiva-
be transferred without exposure to air. Mariscal et al. tion of about 50% of the initial activity is observed
[5] published a detailed description of the setup. The during the first 4 h on stream. The effect of the var-
sample was pretreated using the same procedure as ious reactivation treatments on the catalysts is sum-
stated earlier. After that the system was evacuated marized in Table 1. On the Mo catalyst the effects
at room temperature during 15 h. The sample was are marginal. Treatment with H2 S/H2 /Ar shows the
cooled to 140 K and 0.1 mbar CO was admitted to largest increase in activity, although the initial activity
the chamber. Infrared transmission spectra were taken is not fully restored. In contrast, the promoted catalyst
using a Nicolet Magna-IR 550 spectrometer. (NiMo) is completely reactivated after treatment with
H2 S/H2 /Ar.
To visualize the effect of thiophene HDS on the cat-
3. Results alyst morphology, TEM micrographs of the fresh and
spent catalysts are displayed in Figs. 2 and 3 for the
Fig. 1 shows the conversion of the two catalysts dur- Mo and NiMo catalysts, respectively. For the unpro-
ing thiophene HDS at 673 K. As expected the NiMo moted catalyst mainly single slabs can be seen and no

Fig. 1. Conversion curves for Mo/Al2 O3 and NiMo/Al2 O3 (measured at a 10 times higher space velocity than Mo/Al2 O3 ) during thiophene
HDS at 673 K.
88 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592

Fig. 2. TEM micrographs of the freshly sulfided Mo/Al2 O3 catalyst (a) and after 4 h of thiophene HDS (b).

significant differences can be observed between the
fresh and the spent catalyst. In contrast, the NiMo
catalyst shows single and multiple stacked slabs and
the stacking degree is only slightly higher after the
thiophene treatment.
The amount of carbon deposited on the catalyst
is plotted as a function of time on stream in Fig. 4.
It can be seen that the carbon levels are very low
(<0.4 wt.%). Nevertheless, the carbon levels increase
with time, especially at high reaction temperature (Mo

Fig. 3. TEM micrographs of the freshly sulfided NiMo/Al2 O3 catalyst (a) and after 4 h of thiophene HDS (b).
 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592 89

Fig. 4. Carbon content versus time on stream. Note that the NiMo catalyst was deactivated at a lower temperature.

catalyst). For coke analysis the NiMo catalyst was
deactivated at lower temperature (573 K) because of
the larger amount of catalyst required for this analysis
technique. At high temperature this amount of catalyst
would cause a full conversion of the thiophene feed in
the upper part of the catalyst bed resulting in a poorly
defined spent cat. The pore volume and surface area of
both catalysts did not change during thiophene HDS,
only during sulfidation they decreased slightly due to
sulfide formation.
Elst et al. [6] extensively studied the relation be-
tween the deactivation of Mo/Al2 O3 and its corre-
sponding IR spectrum of adsorbed CO. They observed
a decrease in the number of CO adsorption sites with
increasing time on stream. A 1 h treatment in H2 S/H2
restored the original shape of the spectrum, but did

Fig. 5. IR of adsorbed CO on NiMo catalyst after consecutive treatments (from bottom to top, the spectrum marked () was taken from a
separate experiment).
90 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592
Fig. 6. IR spectra of the carbon stretching vibration region for the NiMo catalyst after consecutive treatments (from bottom to top, spectra
marked () were taken from a separate experiment).
not restore its intensity fully. Furthermore, they ob-
served an increasing intensity of the aliphatic and aro-
matic carbon stretching vibrations in the IR spectrum
when time of thiophene exposure was increased. The
intensity of these bands decreased after treatment with
H2 S/H2 .
In the present study, similar experiments were per-
formed on the NiMo catalyst, of which the IR spectra
taken after consecutive treatments are displayed in
Figs. 5 and 6. The freshly sulfided catalyst shows
a low signal with a maximum around 2125 cm1 .
The low signal intensity is caused by the fact that
most sites are fully saturated with sulfur, thus pre-
venting the adsorption of CO. Mller et al. [4] have
shown that a hydrogen treatment can remove these
sulfur species and expose more adsorption sites for
CO. Indeed, after treatment in H2 during 1 h a large
increase in signal is observed, with two major con-
tributions at 2105 and 2080 cm1 . Useful reference
data for this type of catalyst are scarce, but Angulo
et al. [7] obtained comparable spectra a freshly sul-
fided commercial NiMo catalyst. During thiophene
HDS the shoulder at 2105 cm1 slowly disappears,
but the total signal intensity does not decrease with
time on stream, in contrast to the observations for
the Mo catalyst [6]. In the experiment the catalyst
was consecutively exposed to pure H2 during 1 h,
half an hour of thiophene HDS, again 4 h in pure
H2 and finally a treatment in H2 S/Ar during 1 h. As
can be seen, prolonged treatment in hydrogen has the
same effect on the active phase as 4 h of thiophene
HDS, which was performed as a separate experiment.
After the H2 S/Ar treatment, practically the same
spectrum as that of the freshly sulfided catalyst was
obtained.
The IR spectra of the carbon stretching vibration
region are shown in Fig. 6. Clearly the two main bands
at 1575 and 1475 cm1 increase with time on stream
during thiophene HDS. After treatment in H2 during
4 h the bands have diminished. Treatment in H2 S/Ar
restores the original spectrum again.
4. Discussion
Both catalysts show identical deactivation behavior
in the HDS of thiophene. Of the initial activity, about
50% is lost during the first 4 h on stream. The results of
the TEM investigation do not indicate a significant loss
of dispersion. As can be derived easily, the percentage
edge-side exposed metal atoms in a slab is proportional
to 1/L, L being the average slab length. The observed
changes of the slab length are such that they cannot
account for the observed 50% initial deactivation.
 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592
Fig. 2 shows the amount of deposited carbon dur-
ing thiophene HDS as a function of time on stream.
Especially the Mo catalyst shows a trend similar to
the decreasing activity in Fig. 1. Despite the fact that
the carbon levels are very low (<0.4 wt.%), it cer-
tainly plays a role, especially for Mo/Al2 O3 , where
the amount of carbon atoms deposited corresponds
to about 50% of the total amount of Mo atoms.
Theoretically this amount of carbon is sufficient to
completely block all MoS2 edges. More evidence for
the role of coke formation is given in the work of
Elst et al. [6]. They observed that after treating the
deactivated Mo/Al2 O3 catalyst with H2 S/H2 , the total
amount of adsorbed CO remained lower than that of
the freshly sulfided catalyst. It was concluded that
coke was selectively deposited on the active phase
of the catalyst, causing a permanent loss in the num-
ber of adsorption sites. Part of this coke could be
removed by a H2 S/H2 treatment, evidenced by the
decreased IR bands corresponding to carbonaceous
species. A pure H2 treatment was found to be much
less effective. Both conclusions agree well with the
reactivation data presented in Table 1.
On NiMo/Al2 O3 , the effect of coke deposition is
much less pronounced. Although the IR spectra in
the carbon stretching vibration regime indicate that
the amount of carbonaceous species increases on the
catalyst surface, this has no effect on the number of
adsorption sites. No decrease in total CO signal is
observed, in contrast to the results on the Mo catalyst.
What does change during thiophene HDS is the shape
of the spectrum of the adsorbed CO; the 2105 cm1
shoulder decreases and the 2080 cm1 band slightly
increases in intensity.
The fact that prolonged H2 treatment yields exactly
the same spectrum as 4 h of thiophene HDS indicates
that a loss of sulfur atoms is causing this change of the
active phase, probably due to the high H2 partial pres-
sure under thiophene HDS conditions. This process
leads to the formation of Ni or Mo sites with a lower
coordination number, which in general shift the vibra-
tion frequency of CO to lower wavenumbers. Travert
et al. [8] reported this shift for a Mo/Al2 O3 catalyst
after treatment in H2 at 673 K. The possibility of the
generation of sulfur vacancies under HDS working
conditions was confirmed recently by Helveg et al. [9]
using STM imaging techniques and by Li et al. [10]
and Schweiger et al. [11] by ab initio calculations.
91
A H2 S treatment fully restored the NiMo catalyst
to the freshly sulfided state, showing no permanent
loss in the number of adsorption sites. Moreover, the
number of adsorption sites did not decrease during
the HDS reaction, indicating no blocking of sites by
coke. This may be explained by the much higher hy-
drogenation activity of NiMo, enabling the continuous
removal of coke precursors during the reaction, in line
with the observation that H2 treatment reduces the in-
tensity of the IR bands of the carbonaceous species
(Fig. 6). Combined with the fact that the activity fully
recovered after a resulfidation treatment it is concluded
that the loss of sulfur during thiophene HDS is the
main cause of the deactivation of the NiMo/Al2 O3
catalyst.
5. Conclusions
During the gas phase desulfurization of thiophene,
both Mo/Al2 O3 and NiMo/Al2 O3 showed similar de-
activation behavior. About 50% of the initial activity
was lost during the first 4 h on stream. Sintering of
the active phase was ruled out as a possible cause, as
TEM analysis showed no significant changes of the
morphology before and after the thiophene reaction.
The total amount of coke deposition was low on both
catalysts, and no loss of pore volume or surface area
was found.
For the Mo/Al2 O3 catalyst it is concluded that the
blocking of the active sites by carbonaceous species
is a major cause of the initial deactivation during
thiophene HDS. Part of these coke deposits can be
removed by a H2 S/H2 treatment, which partially re-
activates the catalyst. There is, however, a permanent
loss of active sites due to the coke deposition. This
was not observed for the NiMo catalyst.
The major cause of deactivation for the NiMo/Al2 O3
catalyst during thiophene HDS is a loss of sulfur
atoms from the active phase during the reaction with
thiophene. This can be caused by the high H2 partial
pressure under reaction conditions. The process can
be completely reversed using a H2 S/H2 treatment,
leading to a full reactivation of the catalyst.
As this study was performed in the gas phase, the
question remains how to translate these findings to the
catalyst performance in an industrial (liquid phase)
process. To answer this question further studies will
92 B.M. Vogelaar et al. / Applied Catalysis A: General 251 (2003) 8592
be necessary in which the catalyst is subjected to the
liquid phase desulfurization of model compounds or
real feedstocks, and new methods should be developed
to enable spent catalyst analysis using the same quasi
in situ techniques.
Acknowledgements
Dr. P.J. Kooyman of the National Center for High
Resolution Electron Microscopy, Delft University of
Technology, is gratefully acknowledged for perform-
ing the electron microscopy investigations. J.C. Groen
and P. Boeser of the Practical Analytical Services
and Business Research Laboratory, Delft University of
Technology, are gratefully acknowledged for perform-
ing the nitrogen adsorption and mercury porosimetry
analyses. This work is sponsored by AKZO Nobel
Chemicals, The Netherlands, and the Dutch Organi-
zation for Scientific Research (NWO).
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