J. Chem. T echnol. Biotechnol.

1998, 73, 1È6

Resistance to Sulphur Poisoning of

Alumina-Supported Iridium Catalysts in Toluene
Hydrogenation and Methylcyclohexane
Dehydrogenation
Patricio Reyes,1* Javier Ferna ndez,1 Gina Pecchi1 & Jose Luis Garcia Fierro2
1 Departamento de F• sico-Qu• mica, Facultad de Ciencias Qu• micas, Universidad de Concepcion, Casilla
3-C, Concepcion, Chile
2 Instituto de Catalisis y Petroleoqu• mica, CSIC, Cantoblanco, Campus UAM, 28049 Madrid, Spain
(Received 26 June 1997 ; revised version received 21 January 1998 ; accepted 6 April 1998)

Abstract : Alumina-supported iridium catalysts were prepared with highly dis-

persed iridium particles. The surface acidity of the catalysts was varied by addi-
tion of variable amounts of HCl to the impregnating solution and also by using
an organometallic precursor. The catalysts were used in toluene hydrogenation
and in methylcyclohexane dehydrogenation reactions and the thiotolerance level
was measured with a feed containing 10 ppm of thiophene. In both reactions, it
was found that the sulphur tolerance increases with increasing acidity of the
support. ( 1998 Society of Chemical Industry

J. Chem. T echnol. Biotechnol. 73, 1È6 (1998)

Key words : iridium ; hydrogenation ; thiotolerance ; chemisorption ; XPS

INTRODUCTION It is generally believed that the sulphur resistance of

The interactions between sulphur compounds and
metallic catalysts have been widely studied. In general, a
decrease in the catalytic activity due to the decrease in
the number of active sites occurs. Review articles1h3
analyse extensively the di†erent parameters that can
a†ect the sulphur poisoning of metal catalysts. Most of
the research works devoted to this subject have focused
on the interaction of sulphur compounds, mainly H S,
2
with Ni or Pt catalysts. However, little attention has
been given to iridium catalysts. Iridium is of interest as
an additive to improve the sulphur tolerance of
Pt/Al O catalysts in hydrogenolysis4,5 and also added
2 3
to an Ni methanation catalyst.6 Also, some other
studies have been dedicated to Ir catalysts and the e†ect
of the support on the thiotolerance in the dehydroge-
nation of cyclohexane and benzene hydrogenation.7,8
* To whom correspondence should be addressed.
Contract/grant sponsor : CONICYT ; Contract/grant number :
FONDECYT 1950756.
1
( 1998 Society of Chemical Industry. J. Chem. T echnol. Biotechnol. 0268-2575/98/$17.50.
metal-supported catalysts may be a†ected by changing
the electronic properties of the metal and that this
resistance may be a result of changes in particle size,
alloying, nature of supports, surface acidity, etc.9h12
In the present work, the e†ect of the surface acidity of
Ir/alumina catalysts on the thiotolerance to thiophene
in toluene hydrogenation and in the dehydrogenation of
methylcyclohexane, both structure insensitive reac-
tions,13 has been investigated. For this purpose, the
catalysts were characterized by H chemisorption, TPR,
2
TPD or ammonia and XPS.
EXPERIMENTAL
The catalysts were prepared by impregnation of a c-
Al O (Girdler T-126, S \ 192 m2 g~1) with an
2 3
aqueous solution of H IrCl (Aldrich) containing the
2 6
appropriate amount to reach an iridium loading of
1 wt% and variable amounts of HCl in order to obtain
initial Ir/Cl ratios of 1 : 6 ; 1 : 9 ; 1 : 12 ; and 1 : 15. After
Printed in Great Britain
2 P. Reyes, J. Ferna ndez, G. Pecchi, J. L . G. Fierro

impregnation the solids were dried overnight at 393 K compounds detected in both reactions were toluene and
and calcined in air at 573 K for 4 h. Finally, they were methylcyclohexane.
reduced in hydrogen Ñow (50 cm3 min~1) at 773 K for
2 h. For comparison, another catalyst containing
1 wt% of iridium was prepared by impregnating the RESULTS AND DISCUSSION
support with a toluene solution of Ir(acac) (Aldrich),
2
with the same drying and calcination as for the previous Table 1 summarizes H/Ir ratios, the estimated particle
series. For the sake of simplicity, they will be referred to size and surface acidity evaluated from TPD of
hereafter as Ir/Al O : (0), (6), (9), (12) and (15) respec- ammonia. The average Ir particle size, d, has been cal-
2 3
tively according the initial Cl/Ir ratio. culated from the equation,15 d \ 1É11/D (nm), where D
Hydrogen chemisorption, TPR and TPD of ammonia is the dispersion degree of the metal. In all cases high
studies were carried out in a TPR/TPD Micromeritics metal dispersions and, consequently, small particle size
2900 system. Hydrogen chemisorption was performed at were found. A slight increase in metal dispersion as
298 K using a pulse method. For TPR experiments, the surface acidity increases could be noted. This behaviour
reducing gas was a mixture of 5% H in argon may be expected,16 taking into account the isoelectric
2
(40 cm3 min~1) and a heating rate of 10 K min~1. For point of 7 of the support, Al O . The interaction with
2 3
TPD of ammonia, the adsorption of NH was per- the metal precursor is higher if it is present in an acid
3
formed at 373 K by the pulse method using medium in anionic form. As this occurs in the present
40 cm3 min~1 of argon as carrier. After saturation, the case a stronger interaction between the alumina surface
sample was cooled to room temperature and once the and the anionic [PtCl ]2~ complexes will be developed
6
base line was restored, the temperature was linearly upon increasing the acidity of the aqueous medium. In
increased (10 K min~1) up to 773 K. the Ir/Al O (0) catalyst obtained from Ir(acac) , the
2 3 2
XPS spectra were recorded using an ESCALAB 200R metal dispersion seems to be slightly lower. The pres-
electron spectrometer with an Mg Ka X-ray source ence of some fragments of acac decomposition on the
(hl \ 1253É6 eV) and a hemispherical analyser. The alumina surface may alter the interaction of metal par-
X-ray source was operated at 12 kV and 10 mA. The ticles, thus changing the dispersion degree of the metal.
catalysts were pressed in a hydraulic die to form thin, Surface acidity, expressed as the amount of NH
3
smooth discs and placed in the cell. The samples were desorbed, follows the expected trend, that is higher
reduced in hydrogen at 773 K for 1 h and then trans- acidity in the samples in which higher amounts of
ported to the analysis chamber without contact with hydrochloric acid had been added.
air. The C 1s peak at 284É9 eV was used as internal Figure 1 shows TPR proÐles of Ir/Al O samples.
2 3
standard. The intensities of the XPS peaks were deter- Figure 1(A) corresponds to dried and calcined samples.
mined using S-shape background subtraction and inte- They show two peaks centred at 375 and 675 K respec-
gration of peak areas. The surface Ir/Al and Cl/Al ratios tively. The low temperature peak shifts towards higher
were estimated from the integrated intensities of Ir temperatures as chlorine content decreases. It may be
4f , Al 2p and Cl 2p lines using the sensitivity assigned to the reduction of IrO particles. The peak at
7@2 3@2 2
factors of Wagner et al.14 higher temperatures may be associated to HCl evolu-
Catalytic activity measurements were carried out in a tion. In the chlorine-free Ir/Al O (0) sample no evolu-
2 3
Ðxed-bed microcatalytic reactor working at atmospheric tion of HCl would be expected, however, it also shows
pressure. The mixture H /hydrocarbon two peaks in the TPR proÐle.
2
(H /methylcyclohexane \ 75É5 or H /toluene \ 60) was TPR-ms of two representative samples were also
2 2
Ñowed at 30 cm3 min~1 through the catalytic bed. The carried out. SigniÐcant di†erences in both proÐles were
system is equipped with a bypass to also feed with a found. Even though both samples desorb important
contaminated mixture (with 10 ppm of thiophene). The amounts of water, CO evolution was di†erent. The
2
reaction temperatures were 513 and 543 K for methyl- TABLE 1
cyclohexane dehydrogenation and 373 for toluene H/Ir Ratios, Particle Size and Surface Acidity of 1 wt%
hydrogenation. The reduced catalysts were heated in H Ir/Al O Catalysts
2 2 3
at 10 K min~1 up to the reaction temperature and kept
at this temperature for 30 min. Then the Catalyst H/Ir d (nm) NH ads
3
H /hydrocarbon mixture was Ñowed into the reactor (at/at) (kmole
2 NH m~2)
and the reaction was studied for 2 h, a period in which 3
no signiÐcant deactivation was detected. Then, the cata-
Ir/Al O (0) 0É70 1É6 1É70
lysts were regenerated at the reaction temperature for 2 3
Ir/Al O (6) 0É84 1É3 2É50
1 h in hydrogen and Ðnally, the contaminated mixture 2 3
Ir/Al O (9) 0É88 1É3 2É63
containing 10 ppm of thiophene was fed into the 2 3
Ir/Al O (12) 0É92 1É2 2É80
reactor. The analyses of reactant and products were 2 3
Ir/Al O (15) 1É00 1É1 2É95
carried out by on-line gas chromatography. The only 2 3
Resistance to sulphur poisoning by iridium catalysts 3

an easier process without signiÐcant contribution of

products of the precursors.
In Fig. 2 the Ir 4f core level spectra of the reduced
iridium catalysts are given. For the catalysts obtained
from H IrCl the position of the peak is approximately
2 6
60É9 ^ 0É1 eV corresponding to Ir0 species. However,
for the Ir/Al O (0) catalyst prepared from Ir(acac)
2 3 2
there is a shift in the binding energy, indicating the pres-
ence of Ir0 and Ird` species. These results seem to be
unusual, because it is generally accepted that catalysts
having higher surface acidity should show electron-
deÐcient metal particles. However, it may be explained
by considering that Ir particles remain in two di†erent
positions after the reduction process, one in the surface
of the support, as Ir0, and the other into the porous
structure in which Ir remains as Ird` species, the former
Fig. 1. Temperature programmed reduction proÐles of 1 wt% being mainly detected by XPS, and therefore, no signiÐ-
Ir/Al O catalysts. (A) Samples calcined at 573 K. (B) Samples cant changes are expected. In Table 2, Ir/Al and Cl/Al
2 3at 773 K and oxidized up to 773 K. (a) Ir/Al O (0) ;
reduced
2 3 atomic surface ratios obtained from XPS are given. The
(b) Ir/Al O (6) ; (c) Ir/Al O (9) ; (d) Ir/Al O (12) ; (e)
2 3 2 3
Ir/Al O (15). 2 3
2 3

ex-Cl sample shows a peak centred at 650 K (and traces

around 400 K), whereas in the ex-acac sample a peak at
370 K and a second wider peak with higher intensity
centred at 600 K appears. These results clearly show
that in the calcined sample ex-acac there are fragments
of the organometallic complex which are evolved as
CO . It may be expected that under vacuum conditions
2
and high temperatures, these residues may be quantitat-
ively eliminated. The presence of acac fragments was
also detected in Pt/Al O catalysts obtained by the
2 3
organometallic route.17
Comparing TPR proÐles of Fig. 1(A) for ex-Cl
samples (bÈe) it can be observed that the Ðrst peak is
split and one of its components is shifted towards
higher temperatures as the surface acidity increases, as
was expected. The other peak component remains
almost constant at about 400 K. These two peak com-
ponents can be attributed to two Ir species ; the one
located at low temperature corresponds to highly dis-
persed Ir placed in the external part of the support
grains, whereas the one at higher temperatures corre-
sponds also to highly dispersed Ir, located inside of the
mesoporous network, where the competition of adsorp-
tion between HCl and the Ir complex warrants a more
efficient adsorption process. For the ex-acac catalyst
(Fig. 1(A, a)) the higher intensity of the peak centred at
650 K is due to the evolution of CO as was detected
2
by mass spectrometry.
Figure 1(B) shows TPR proÐles of Ir/Al O samples
2 3
previously reduced at 773 K for 2 h and oxidized in a
TPO cycle up to 773 K. A single and very well deÐned
peak centred at 473 K can be observed. This is
explained by considering that as the samples were Fig. 2. XP spectra for Ir/Al O catalysts. (a) Ir/Al O (0) ; (b)
already reduced and calcined, the elimination of the 2 ; 3(d) Ir/Al O (12) ; (e)
Ir/Al O (6) ; (c) Ir/Al O (9) 2 Ir/Al
3 O
2 3 2 3 (15). 2 3 2 3
residues has already occurred, this second reduction is
4 P. Reyes, J. Ferna ndez, G. Pecchi, J. L . G. Fierro

TABLE 2 reaction conditions. Similar behaviour was observed for

Binding Energies (eV) and XPS Atomic Ratios of 1 wt% all catalysts. Table 3 summarizes the catalytic results in
Ir/Al O Catalysts the toluene hydrogenation at 373 K on the iridium
2 3
catalysts. The activity has also been expressed as turn-
Catalyst BE Ir 4f (Ir/Al) (Cl/Al)
(eV )
7@2
(at/at)
s
(at/at)
s over number (TON), at 120 and 220 min on-stream
operation once 10 ppm of thiophene were added to the
Ir/Al O (0)
2 3
60É9 (27) 0É0014 0É014 feed.
61É8 (73) The results compiled in Table 3 show that the TON
Ir/Al O (6) 61É0 (100) 0É0024 0É021
2 3 remains almost constant for most of the catalysts, as
Ir/Al O (9) 60É9 (100) 0É0036 0É032
2 3 expected for a structure-insensitive reaction. The excep-
Ir/Al O (12) 60É9 (100) 0É0032 0É034
2 3 tion is the catalyst prepared via Ir(acac) which exhibits
Ir/Al O (15) 60É8 (100) 0É0037 0É047
2 3 2
a lower activity compared with all the other counter-
parts. It is likely that in this catalyst some carbonaceous
Ir/Al atomic surface ratios follow the expected trend. species from the precursor remains bonded to iridium
They increase with increasing chlorine content, which is particles, decreasing the ability to adsorb and to hydro-
lower in the case of the catalyst prepared using the genate the hydrocarbon molecules. With regard to the
organometallic precursor. These results are in good thiotolerance, signiÐcant di†erences are observed again
agreement with those obtained from H chemisorption between the catalyst obtained from the organometallic
2
data. With regard to the Cl/Al ratio, values are also as precursor and those prepared from H IrCl . Thus,
2 6
expected. The Cl/Al ratios presented in Table 2 also comparison of the activity retained at 120 min on
indicate that the catalyst ex-Ir(acac) displays a minor stream upon adding thiophene in the feed reveals that
2
proportion of chlorine ions. As a similar ratio has in the Al O (0) catalyst only 24% of the original activ-
2 3
already been observed for the Al O carrier it is ity is retained whereas a fraction around 40% is kept in
2 3
inferred that this chlorine content comes from the the catalysts ex-chloride. At longer time on-stream
Al O itself. (220 min) the sulphur poisoning e†ect is more pro-
2 3
The toluene hydrogenation reaction was studied at nounced, decreasing the residual activity fraction to
373 K and methylcyclohexane was the only detected 12% in the catalyst prepared from Ir(acac) whereas it is
2
product. After 2 h on-stream almost no deactivation reduced to around 22% in those prepared from
was observed. Then, the catalysts were treated in hydro- H IrCl . Therefore, a slight increase in the thiotol-
2 6
gen at the reaction temperature for 30 min and 10 ppm erance with the acidity of the catalyst is observed. Con-
of thiophene was added to the reactant mixture. Hydro- sidering that, essentially, the particle size of Ir
genation activity was found to decrease drastically and crystallites is the same for all the catalysts, the observed
the experimental curve can be reasonably described by behaviour must be related to the acidic properties of the
an exponential delay. Figure 3 shows the variation of catalysts, as already pointed out by Guenin et al.11,18
turnover number (TON \ molecules converted per Thus, the higher the surface acidity of the catalysts, the
exposed site and unit time) with time during poisoning higher the thiotolerance to thiophene. It seems that the
with thiophene for two representative catalysts. It can thiophene is adsorbed without CwS bond cleavage on
be seen that stabilization is not achieved during the both the metal and the support. This adsorption is
rather weak and the activity may be recovered to a
great extent if the poison is removed from the stream.11
The catalytic studies in the methylcyclohexane dehy-
drogenation at 543 K showed almost constant activity
during 2 h on-stream operation. Although the samples
were treated in hydrogen at the same temperature
before bypassing the contaminated feed through the

TABLE 3
TON and Thiotolerance in Toluene Hydrogenation at 373 K
on 1 wt% Ir/Al O Catalysts
2 3
Catalyst T ON ] 102 s~1 T ON ] 102 s~1 T ON ] 102 s~1
(t \ 0) (t \ 120 min) (t \ 220 min)

Ir/Al O (0) 4É4 1É06 0É53

Fig. 3. Variation of the activity in toluene hydrogenation at 2 3
Ir/Al O (6) 16É8 6É59 3É28
373 K. The catalysts were Ðrstly contacted with toluene and 2 3
Ir/Al O (9) 16É0 6É53 3É36
hydrogen and after stabilization and regeneration in H , they 2 3
2 Ir/Al O (12) 16É5 6É88 3É68
were treated with a mixture H , toluene ( ] 10 ppm of 2 3
2 Ir/Al O (15) 15É6 6É71 3É90
thiophene). (a) Ir/Al O (0) ; (b) Ir/Al O (15). 2 3
2 3 2 3
Resistance to sulphur poisoning by iridium catalysts 5

TABLE 4 are present. The Ir/Al atomic surface ratios follow the
Turnover Number, Thiotolerance Level and Activation same trend as in the chemisorption results, being higher
Energy in Methylcyclohexane Dehydrogenation at 543 K on in the more acidic samples. Catalytic activity in toluene
1 wt% Ir/Al O Catalysts hydrogenation and methylcyclohexane dehydroge-
2 3
nation, showed that in both reactions the TON values
Catalyst T ON ] 102 T hiotolerance Activation
(s~1) level energy
do not change signiÐcantly. However, if the reaction is
(kJ mole~1) studied by adding thiophene to the feed, a drastic
decrease in the activity is produced. In toluene hydro-
Ir/Al O (0) 6É97 0É68 146 genation the thiotolerance is lower because the poison
2 3
Ir/Al O (6) 5É90 0É59 138
2 3 is adsorbed in both the support and the metallic phase.
Ir/Al O (9) 7É14 0É59 146
2 3 The catalysts with higher surface acidity display higher
Ir/Al O (12) 6É55 0É63 147
2 3 resistance to sulphur poisoning. In the dehydrogenation
Ir/Al O (15) 5É60 0É66 146
2 3
of methylcyclohexane at 543 K, deactivation of catalysts
occurs to a lesser extent. The adsorption of thiophene
reactor, a fast deactivation occurs, reaching a steady or fragments of thiophene degradation occurs mainly in
state after 2 h on-stream. However, in all the studies the the iridium particles, and the adsorption on the support
reaction in the presence of thiophene was evaluated for is almost negligible. Slight changes in thiotolerance with
on-stream periods of 4 h. The results are shown in surface acidity were also detected.
Table 4, in which the initial TON (before poisoning),
the thiotolerance level and the activation energy are
given. In all catalysts, the TON does not change signiÐ- ACKNOWLEDGEMENTS
cantly as would be expected for a structure-insensitive
reaction. Also, the thiotolerance level only increases The authors thank CONICYT (FONDECYT Grant
slightly when the surface acidity of the support 1950756) for the Ðnancial support.
increases.9,11 The only exception is catalyst Ir/Al O (0)
2 3
which exhibits the highest thiotolerance level. This can
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