672 Ind. Eng. Chem. Res.

1996, 35, 672-682

Comparative Effect of Organosulfur Compounds on Catalysts for the

n-Heptane Isomerization Reaction at Medium Pressure:
Mo2C-Oxygen-Modified, MoO3-Carbon-Modified, Pt/γ-Al2O3, and
Pt/β-Zeolite Catalysts
Andrew P. E. York, Cuong Pham-Huu, Pascal Del Gallo, Edd A. Blekkan,† and
Marc J. Ledoux*
Laboratoire de Chimie des Matériaux Catalytiques, ECPM, Université Louis Pasteur, 1 rue Blaise Pascal,
67008 Strasbourg Cedex, France

Molybdenum oxycarbide formed from oxidized Mo2C or reduced MoO3 is an active and very
selective catalyst for the isomerization of n-heptane compared to supported Pt. Deactivation
experiments performed on the catalysts with different concentrations of organosulfur compounds
show that molybdenum oxycarbide exhibits a very high resistance to deactivation, whereas with
platinum-based catalysts deactivation occurs even at low sulfur concentration in the feed.
Deactivation can be slowed by increasing the hydrogen partial pressure from 6 to 20 bar. In
these conditions, the molybdenum oxycarbide shows no deactivation with sulfur concentrations
up to 120 ppm of S. In addition, the deactivated molybdenum catalysts can be easily regenerated
by mild oxidative treatment under flowing air at atmospheric pressure and 723 K for 2 h followed
by a reactivation period under the hydrogen and hydrocarbon mixture.

I. Introduction under a mixture of hydrogen and hydrocarbon. More

In the past 20 years, a number of researchers have
shown that some transition metal carbides, such as
those of molybdenum (Lee et al., 1990) and tungsten
(Muller and Gault, 1970; Boudart and Levy, 1973) can
show catalytic behavior similar to that of the noble
metals. A further development in the use of group VI
metal carbides as selective catalysts for the alkane
isomerization reaction was the discovery that, while
clean carbide surfaces, obtained by reductive treatment
after synthesis, gave predominantly hydrogenolysis
products, modification by oxidation gave a material
which was active and highly selective for the formation
of isomers. Iglesia and co-workers (Ribeiro et al.,
1991a,b; Iglesia et al., 1991, 1992) reported that oxida-
tive treatment of a WC or β-W2C catalyst prepared by
temperature-programmed carburization of WO3 under
CH4/H2 mixtures gave a catalyst capable of alkane
isomerization without extensive hydrogenolysis.
Independent work by Ledoux and co-workers (Ledoux
et al., 1993a; Pham-Huu et al., 1993) described a similar
effect over a high surface area Mo2C, oxidized under
flowing air at 623 K, for the isomerization of n-hexane.
This was attributed to the formation of a new catalyti-
cally active phase formed during the first few hours of
the hydrocarbon reaction; this phase is an oxycarbide
consisting of a MoO3 lattice (at the surface of the
carbide) where carbon atoms replace some oxygen atoms
in the vacancies formed by partial reduction and block
the collapse of the oxide to MoO2 (Delporte et al., 1995).
It was proposed that over the molybdenum catalyst a
metallacyclobutane mechanism was responsible for the
alkane isomerization. Later work reported that the
molybdenum oxycarbide phase could be synthesized
directly from molybdenum metal or molybdenum oxide
* To whom correspondence should be addressed. Fax: 33
88 41 68 09. E-mail: ledoux@cournot.u-strasbg.fr.
† Department of Industrial Chemistry, The Norwegian
Institute of Technology (NTH), The University of Trondheim,
N7034 Trondheim, Norway. Fax: 47 735 94157.
0888-5885/96/2635-0672$12.00/0
recently, the same group (Ledoux et al., 1993b; Blekkan
et al., 1994) has shown that the isomerization of
n-heptane can be carried out without cyclization or
aromatization over oxygen-modified Mo2C or carbon-
modified MoO3 catalysts, even at high conversion; this
is a reaction of great interest to industry since, cur-
rently, alkanes higher than hexane cannot be isomer-
ized over the conventional platinum catalyst at high
conversion, due to the efficiency of this catalyst for the
cracking reactions.
In addition, a major problem for the reforming
catalysts based on Pt, is the presence of permanent
poisons, i.e., arsenic, lead, and mercury, and reversible
poisons, i.e., nitrogen, halogens, and sulfur (Chauvel et
al., 1985). Sulfur poisoning is one of the most severe
and commonly encountered poisoning problems, since
sulfur-containing compounds are present to some extent
in all crude oil. These sulfur compounds can be present
in the form of thiols, dithioalkanes, and heterocyclic
compounds such as thiophene and its analogs (Kao et
al., 1993). Because the presence of sulfur can cause a
complete loss of activity, sulfur concentrations must be
kept below a few parts per million in the feed. A
number of advances have been made over the years in
reducing the sensitivity of the supported platinum
catalysts, for example the addition of dopants such as
rhenium, iridium, and tin, but deactivation is still a
major problem. More detailed results were summarized
in a review by Biswas et al. (Biswas et al., 1988).
The aim of this article is to report the high resistance
of the Mo2C-oxygen-modified and MoO3-carbon-modified
catalysts, formed after an activation period (Ledoux et
al., 1993a; Pham-Huu et al., 1993; Delporte et al., 1995),
to different concentrations of thiophene present as
impurities during the n-heptane reaction at medium
pressure (6-20 bar) when compared to conventional Pt-
based catalysts supported either on alumina or on
β-zeolite. The influence of the nature of the sulfur
source and of the total pressure on the deactivation rate
are also investigated. Finally, the effect of an oxidative
regeneration under mild conditions was studied over
© 1996 American Chemical Society

Figure 1. Schematic diagram of the experimental setup.
completely deactivated catalysts. Structural modifica-
tions of the catalysts during the course of the reaction
were followed using powder X-ray diffraction (XRD).
II. Experimental Section
II.1. Materials and Catalysts. High specific sur-
face area molybdenum carbide (Mo2C) was synthesized
in a high temperature reaction between MoO3 (Fluka,
purity >99.5%) vapor and a high surface area carbon
(Fluka Puriss, 1150 m2 g-1, 0.250-0.425 µm) as de-
scribed previously by Ledoux et al. (Ledoux et al., 1995a,
1992a,b). Before catalytic use, the carbide (60 m2 g-1)
was oxidized under flowing air (15 cm3 min-1, 623 K,
14 h) in order to oxidize its surface and thus form the
Mo2C-oxygen-modified material. Activation of the ma-
terial was then carried out by passing a mixture of
hydrogen and n-heptane over the catalyst at 623 K for
around 2 h (Figure 2), leading to the active molybdenum
oxycarbide phase. The unmodified Mo2C was not active
and selective for the isomerization reaction (Ledoux et
al., 1993) and was not tested.
The high specific surface area MoO3-carbon-modified
catalyst (145 m2 g-1) was synthesized from the low
specific surface area MoO3 (4 m2 g-1) at low temperature
(623 K) under a mixture of n-heptane and hydrogen
under medium pressure according to Ledoux et al.
(Ledoux et al. 1993c, 1995b) and Delporte et al. (Delporte
et al., 1995).
High-purity γ-alumina (Ketjen CK-300B) was used in
the preparation of the Pt-supported sample. This had
a BET surface area of 187 m2 g-1, a pore volume of 0.63
cm3 g-1, and impurities in weight percent of Na2O <
0.002, SO4 < 0.001, Fe < 0.004, NiO < 0.001, and MoO3
< 0.001. Before impregnation the support was im-
mersed in a mixture of ethanol:water (50:50 v/v), kept
at room temperature for 14 h, and then calcined at 673
K for 2 h. Platinum was added by incipient wetness
impregnation of γ-alumina with a water solution of
(NH3)4PtCl2‚H2O such that the content of Pt after
impregnation was 2% by weight. The impregnated
sample was dried at room temperature for 12 h in air
and at 393 K for 12 h in an oven. Finally, the catalyst
was calcined at 673 K for 2 h. Before the catalytic tests,
Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996 673
the catalyst was reduced in situ with H2 (40 cm3 min-1)
at 673 K for 2 h. The Cl content was 0.8%.
A typical bifunctional catalyst was also used for
comparison. A β-zeolite support (650 m2 g-1) with a Si/
Al ratio of 12.5 was ion-exchanged three times with
NH4NO3 (aqueous 1 M), before drying, calcining in air
(813 K, 3 h) and impregnation with (NH3)4PtCl2‚H2O
to give a Pt load of 1.5% using the incipient wetness
technique. After impregnation the catalyst was dried
and subsequently calcined in air (573 K, 3 h). Before
use the catalyst was reduced in situ at 773 K for 3 h
and then cooled to the reaction temperature in flowing
H2 before introducing the hydrocarbon feed. The Cl
content was 0.5%.
The n-heptane (Prolabo) was used as received with a
purity of >99.5%. The major organic impurities were
methylcyclohexane (0.3%), 3-methylhexane (3MHex)
(0.1%), ethylcyclopentane (ECyclPen) (0.06%), 2-meth-
ylhexane (2MHex) (0.04%), and 3-ethylpentane (3EPen)
(0.04%). These were subtracted from the exit gas
analysis before calculating the product distribution.
Thiophene, sulfolane and 1-propanethiol were all from
Fluka (puriss grade) and hydrogen was obtained from
Air Liquide (U grade).
II.2. Apparatus. The schematic drawing of the
medium pressure micropilot used for the isomerization
experiments is shown in Figure 1. Most of the tubing
and valves (gray shading in Figure 1) were kept above
423 K in order to avoid any condensation. Reactions
were performed in a microreactor consisting of 1/4 in.
316-stainless steel with the catalyst placed between
quartz wool plugs in the center of a copper-lined steel
tube (4 mm i.d. × 300 mm). The tube furnace temper-
ature was controlled by a Minicor temperature control-
ler and the reactor temperature was monitored using a
second thermocouple placed along the side of the reac-
tor. The hydrogen flow rate was controlled using a
Brooks 5850 TR mass flow controller monitored by a
Brooks 5876 control unit, and the hydrocarbon was
delivered via a Gilson 302 HPLC pump. The reactant
was passed downward through the catalyst bed. The
reactor pressure was regulated using a Grove mem-
brane back pressure regulator and a micrometering
valve. Samples were analyzed off-line via a septum.
674 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996
Figure 2. Isomerization of n-heptane over Mo2C-oxygen-modified
catalyst. Conditions: 6 bar, 623 K, H2:HC ) 30.
Figure 3. Isomerization of n-heptane over MoO3-carbon-modified
catalyst. Conditions: 6 bar, 623 K, H2:HC ) 30.
II.3. Product Analysis. Product analysis was car-
ried out on a Hewlett-Packard 5890 Series II gas
chromatograph fitted with a flame ionization detector.
Separation of the C1 to C7 hydrocarbons was achieved
using a HP-PONA capillary column coated with meth-
ylsiloxane (50 m × 0.2 mm i.d., film thickness 0.5 mm),
and the response factors for the various products were
determined and taken into account. Negligible traces
of alkenes were detected in the reactor exit gas, and
these were therefore omitted from the final data analy-
sis.
Kinetic data are reported as reaction rates (mol g-1
s-1) calculated assuming a differential reactor (conver-
sion < 10%) or using pseudo first order kinetics for
experiments with higher conversions.
The reaction was carried out over a large range of
operating conditions: catalyst weight, 0.1-0.3 g; weight
hourly space velocity (WHSV), 6-18 h-1; total pressure,
6-20 bar; contact time, 8 × 10-4 to 20 × 10-4 s; total
flow rate, 200-700 mL min-1.
III. Results
III.1. Standard n-Heptane Isomerization With-
out Sulfur. III.1.1. Mo2C-Oxygen-Modified and
MoO3-Carbon-Modified. Figures 2 and 3 show the
development of the isomerization activity and the C7
selectivity of the Mo2C-oxygen-modified and the MoO3-
carbon-modified catalysts as a function of time on
stream at 6 bar and 623 K. Over both catalysts the
activity is initially low and increases with time on
stream to reach a steady state of 28.5 × 10-7 and 53.2
× 10-7 mol g-1 s-1, respectively. The selectivity to the
C7 isomers is initially low but rapidly increases with
Figure 4. Isomerization of n-heptane over Pt-1.5 wt %/β-zeolite
catalyst. Conditions: 6 bar, 563 K, H2:HC ) 30.
Figure 5. Isomerization of n-heptane over Pt-2 wt %/γ-Al2O3
catalyst. Conditions: 6 bar, 623 K, H2:HC ) 30.
time on stream to reach a value of ca. 90% for conver-
sions in the range 37-45% (Tables 1 and 2). Over the
two catalysts, no deactivation is observed as a function
of time as shown in Figures 2 and 3. The main products
from the isomerization of n-heptane are 2-methylhexane
(2MHex) and 3-methylhexane (3MHex). Dimethylpen-
tane products contribute to around 13% of the C7
isomers, and only traces of cyclic molecules are detected
among the reaction products (ca. 0.4%). Tables 1 and
2 give detailed product distributions over both catalysts.
In both cases, the cracking products are initially mainly
C3 and C4, but the C6 + C1 fraction increases with time,
at the expense of C4 + C3.
III.1.2. Pt-1.5 wt %/β-Zeolite. The experiment with
the Pt-1.5 wt %/β-zeolite at 6 bar and 563 K presented
in Figure 4 shows that the isomerization activity and
selectivity are stable over the duration of the experi-
ment. This catalyst is more active than the molybdenum-
based catalysts (rate ) 150.0 × 10-7 mol g-1 s-1) and
shows a similar selectivity to isomers, i.e., mono-
branched and dibranched molecules, of about 92% at
conversions below 40%; only traces of cyclic molecules
are observed. The detailed product distribution is given
in Table 3.
III.1.3. Pt-2 wt %/γ-Al2O3. Figure 5 shows the
development of activity and selectivity over the plati-
num catalyst at 6 bar and 673 K. The activity and
selectivity are stable over the duration of the experiment
meaning that, under the reaction conditions, no other
deactivation (coking or metal sintering) occurs on the
catalyst. The activity is equivalent to the activity
observed on Mo2C-oxygen-modified catalyst, i.e., 24.7 ×
10-7 mol g-1 s-1. The detailed product distribution is
 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996 675
Table 1. Isomerization of n-Heptane at 6 bar Total Pressure over MoC-Oxygen-Modified Catalyst in the Presence of
Different Concentrations of Sulfur in Thiophene Form (Conditions: 623 K, Total Flow 200 cm3 min-1, H2:HC ) 30)
sulfur concentration, ppm 0 0 0 30 30 30 120 120 120
time on stream, h 0.5 8 26 0 6 24 0 8 26
conversion, % 15.6 37.8 36.6 39.8 39.0 39.7 50.9 40.2 21.9
rate, 10-7 mol g-1 s-1 14.2 28.8 28.5 32.0 31.6 32.0 34.3 30.3 19.1
C7 selectivity, % 83 92 90 87 89 88 85 87 85
∑light products, % 17 8 10 13 11 12 15 13 15
C7-isomer distribution, %
dimethylpentanes 14.6 11.4 10.5 10.6 11.7 11.5 12.4 10.6 7.7
2MHex 40.4 39.8 39.4 39.4 38.8 38.2 37.9 38.2 38.5
3MHex 41.4 45.1 46.4 46.2 45.7 46.3 45.7 47.1 49.6
3EPen 3.0 3.1 3.3 3.4 3.4 3.6 3.6 3.6 3.7
ECycPen 0.0 0.0 0.0 0.0 0.0 0.0 0 0.1 0.2
MCyHex + toluene 0.6 0.6 0.4 0.4 0.4 0.4 0.4 0.4 0.3
light products distribution, %
C 6 + C1 19.4 30.0 37.7 40.7 39.2 43.5 43.1 45.7 46.1
C5 + C2 11.4 16.8 20.0 21.6 19.2 20.4 21.2 21.1 22.6
C4 + C3 61.7 47.2 34.4 30.6 34.0 29.2 27.9 26.5 23.8
others 7.5 6.0 7.9 7.1 7.6 6.9 7.8 6.7 7.5

Table 2. Isomerization of n-Heptane at 6 bar Total Pressure over MoO3-Carbon-Modified Catalyst in the Presence of
Different Concentrations of Sulfur in Thiophene Form (Conditions: 623 K, Total Flow 200 cm3 min-1, H2:HC ) 30)
sulfur concentration, ppm 0 0 0 30 30 30 120 120 120 500 500 500
time on stream, h 2 10 25 0 8 34 0 5 30 0 8 27
conversion, % 26.5 43.0 43.2 55.0 55.4 56.8 59.3 55.2 49.8 44.3 34.2 10.6
rate, 10-7 mol g-1 s-1 37.3 53.1 53.2 57.6 58.0 58.2 60.2 59.1 56.9 53.8 27.4 10.0
C7 selectivity, % 93 93 94 94 94 94 88 87 86 88 88 86
∑light products, % 7 7 6 6 6 6 12 13 14 12 12 14
C7-isomer distribution, %
dimethylpentanes 13.3 13.5 13.4 16.0 16.2 16.4 19.4 19.1 19.5 17.6 16.6 17.0
2MHex 41.4 39.2 39.1 38.9 38.7 38.6 36.7 37.3 37.0 37.4 38.2 37.6
3MHex 42.4 44.1 44.2 41.9 41.8 41.7 40.0 40.0 40.1 41.2 41.4 41.0
3EPen 2.9 3.2 3.2 3.0 3.1 3.1 3.1 3.1 3.0 3.0 2.9 3.1
ECycPen 0.0 0.0 0.0 0.0 0.0 0.0 0 0.1 0.0 0.0 0.0 0.0
MCyHex + toluene 0.0 0.0 0.0 0.2 0.2 0.2 0.8 0.4 0.4 0.8 0.9 1.3
light products distribution, %
C 6 + C1 20.1 24.9 25.4 11.4 12.3 12.0 8.7 6.6 10.0 7.7 6.0 5.0
C5 + C2 11.1 14.0 16.0 9.3 9.3 9.5 5.1 5.3 8.7 6.9 6.0 6.6
C4 + C3 66.8 58.4 56.3 75.0 74.2 73.2 82.3 83.5 77.6 81.9 85.8 86.4
others 2.0 2.7 2.3 4.3 4.2 5.3 3.9 4.6 3.7 3.5 2.2 2.0

Table 3. Isomerization of n-Heptane at 6 bar Total Pressure over Pt-1.5 wt %/β-Zeolite Catalyst in the Presence of
Different Concentrations of Sulfur in Thiophene Form (Conditions: 563 K, Total Flow 200 cm3 min-1, H2:HC ) 30)
sulfur concentration, ppm 0 0 0 30 30 30 120 120 120 500 500 500
time on stream, h 3 10 22 0 7.5 25 0 7 24 0 7 24
conversion, % 45.0 41.0 40.5 38.3 33.2 32.6 43.4 23.1 21.8 44.9 12.8 11.1
rate, 10-7 mol g-1 s-1 162.4 152.0 150.0 147.0 133.1 131.1 159.6 100.3 95.3 162.7 59.0 51.8
C7 selectivity, % 91 92 92 97 93 93 95 81 80 98 64 59
∑light products, % 9 8 8 3 7 7 5 19 20 2 36 41
C7-isomer distribution, %
dimethylpentanes 15.5 14.9 14.8 12.1 13.5 13.4 16.2 15.2 15.1 13.7 13.4 13.8
2MHex 40.5 41.0 41.2 40.9 42.8 42.6 38.7 42.1 42.0 40.0 44.2 44.5
3MHex 40.8 40.8 40.9 43.5 40.8 41.1 41.4 39.8 39.5 42.7 37.7 37.3
3EPen 2.7 2.7 2.6 3.1 2.5 2.5 3.0 2.5 2.5 3.1 2.2 2.4
ECycPen 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MCyHex + toluene 0.5 0.6 0.5 0.4 0.4 0.4 0.7 0.4 0.9 0.5 2.5 2
light products distribution, %
C 6 + C1 5.8 6.0 6.5 8.4 8.0 7.6 0.0 0.0 0.0 0.0 0.0 0.0
C5 + C2 0.8 0.6 0.5 0.0 0.0 0.0 0.5 0.3 0.6 1.1 0.6 1.0
C4 + C3 91.6 91.4 91 87.7 87.3 88.3 98.2 97.6 97.3 98.2 97.9 98
others 1.8 2.0 2.0 3.9 4.7 4.2 1.3 2.1 2.1 0.7 1.5 1.0
given in Table 4. The C7-isomer selectivity observed followed with time on stream, and the deactivation rate
over this platinum catalyst is rather low (60%) com- expressed as relative rate: ratewith sulfur/ratewithout sulfur,
pared to the one observed on molybdenum-based cata- with “rate without sulfur” corresponding to the rate
lysts (85-95%). Along with the monobranched mol- measured at time “zero” in the presence of sulfur.
ecules a large fraction of cyclic molecules are observed Sometimes (see Tables 1-4) this value is higher (or
(25%). The fraction of light products remains stable lower) than the rate at steady state without sulfur
over the duration of the experiment. because the catalyst was removed for characterization
III.2. Effect of Thiophene Concentration. Pure or was regenerated in between.
n-heptane was passed over the catalysts under the III.2.1. Mo2C-Oxygen-Modified Catalyst. Figure
appropriate conditions until the steady state was reached. 6 shows the relative rate over the Mo2C-oxygen-modified
Then n-heptane containing 30, 120, or 500 ppm of S catalyst as a function of the thiophene concentration
under the thiophene form was introduced in place of with time on stream. The catalyst remains stable up
pure n-heptane. The activity of the catalysts was to 30 ppm of S in the feed during more than 25 h of
676 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996

Table 4. Isomerization of n-Heptane at 6 bar Total Pressure over Pt-2 wt %/γ-Al2O3 Catalyst in the Presence of Different
Concentrations of Sulfur in Thiophene Form (Conditions: 673 K, Total Flow 200 cm3 min-1, H2:HC ) 30)
sulfur concentration, ppm 0 0 0 30 30 30 120 120 120
time on stream, h 2 24 48 0 6 26 0 4,5 22
conversion, % 19.7 28.7 30.0 30.5 12.9 13.8 26.3 7.6 8.2
rate, 10-7 mol g-1 s-1 17.4 23.8 24.7 24.9 11.9 12.7 22.2 7.2 7.7
C7 selectivity, % 58. 52 59 58 87 89 84 91 93
∑light products, % 42 48 41 42 13 11 16 9 7
C7-isomer distribution, %
dimethylpentanes 10.6 9.3 9.9 9.8 6.5 4.0 13.0 8.0 7.6
2MHex 22.5 23.5 22.3 22.4 31.3 34.7 33.1 30.3 30.3
3MHex 40.0 39.8 38.7 38.9 53.6 54.1 43.6 57.0 56.9
3EPen 1.2 1.4 1.4 1.4 0.8 0.7 1.3 0.7 0.9
ECycPen 0.7 0.3 0.3 0.3 0.2 0.5 5.0 3.0 3.3
MCyHex + toluene 25.0 25.7 27.4 27.2 7.6 6.0 4.0 1.0 1.0
light products distribution, %
C 6 + C1 26.0 21.5 24.3 23.6 21.8 24.0 26.0 44.0 49.8
C5 + C2 21.6 21.8 22.7 22.4 20.5 21.8 21.5 16.0 11.0
C4 + C3 48.0 53.5 50.1 50.5 51.3 49.8 46.9 38.3 36.4
others 4.4 2.1 2.9 3.5 6.4 4.4 5.6 1.7 2.8

Figure 6. Effect of sulfur concentrations on isomerization of

n-heptane over Mo2C-oxygen-modified catalyst. Conditions: 6 bar,
623 K, H2:HC ) 30. Figure 7. Effect of sulfur concentrations on isomerization of
n-heptane over MoO3-carbon-modified catalyst. Conditions: 6 bar,
reaction. However, when the concentration of sulfur is 623 K, H2:HC ) 30.
increased to 120 ppm deactivation occurs and the
catalyst loses about half its activity after 25 h of
reaction. The deactivation observed here is not ac-
companied by a loss of C7-isomer selectivity (see Table
1) meaning that deactivation is only due to the loss of
active sites and not to a modification of the nature of
the active phase. Deactivation observed at 120 ppm of
S could be due to the formation of some MoS2 on the
catalyst surface. Catalytic tests performed over MoS2
(not shown) under similar reaction conditions show that
MoS2 exhibits no isomerization activity. Detailed prod-
uct distributions in the presence of different concentra-
tions of S are given in Table 1.
III.2.2. MoO3-Carbon-Modified Catalyst. The
effect of sulfur on MoO3-carbon-modified catalyst at 6
bar is presented in Figure 7. As can be seen, the
catalyst exhibits a very high thio resistance and almost
no deactivation occurs even in the presence of 120 ppm
of S in the feed. The isomer selectivity remains un-
changed at around 90%. The product distribution as a
function of time on stream and as a function of sulfur Figure 8. Effect of sulfur concentrations on isomerization of
concentration is given in Table 2. n-heptane over Pt-1.5 wt %/β-zeolite catalyst. Conditions: 6 bar,
563 K, H2:HC ) 30.
III.2.3. Pt-1.5 wt %/β-Zeolite. The deactivation
occurs whatever the sulfur concentration as shown in
Figure 8. However, after a rapid deactivation the in Table 3. At low sulfur concentration (e30 ppm of S)
catalyst isomerization activity reaches a steady state the total isomer selectivity remains stable around 92-
and remains unchanged within the duration of the 93%. At high sulfur concentration both the isomeriza-
experiment. The detailed product distribution is given tion activity and selectivity decrease meaning that the
 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996 677
Table 5. Isomerization of n-Heptane at 20 bar Total
Pressure over MoO3-Carbon-Modified and Pt-1.5 wt
%/β-Zeolite Catalysts in the Presence of Different
Concentrations of Sulfur in Thiophene Form (Conditions
for MoO3-Carbon-Modified Catalyst: 623 K; For Pt-1.5 wt
%/β-Zeolite Catalyst: 573 K, Total Flow 660 cm3 min-1,
H2:HC ) 99)a
MoO3 Pt-1.5
carbon modified wt %/β-zeolite
120b 500 120 500
ppm ppm ppm ppm
conversion, % 43.4 23.3 31.3 25.6
rate, 10-7 mol g-1 s-1 53.3 33.7 127.9 109.1
C7 selectivity, % 94 94 88 75
∑light products, % 6 6 12 25
C7-isomer distribution, %
dimethylpentanes 13.9 12.9 15.3 14.6
2MHex 36.5 37.2 41.0 41.8
3MHex 44.4 45.7 40.8 40.3
3EPen 3.5 3.2 2.8 2.5
ECycPen 0.0 0.0 0.0 0.0
Figure 9. Effect of sulfur concentrations on isomerization of MCyHex + toluene 1.7 1.0 0.1 0.8
n-heptane over Pt-2 wt %/γ-Al2O3 catalyst. Conditions: 6 bar, 623 light products distribution, %
K, H2:HC ) 30. C 6 + C1 34.4 30.0 0.0 0.0
C5 + C2 15.9 7.4 0.0 0.2
number and the nature of the active sites are changed C4 + C3 48.0 56.9 98.2 97.8
others 1.7 5.7 1.8 2.0
as a function of deactivation.
a The results are given after 24 h under time on stream. b Sulfur
III.2.4. Pt-2 wt %/γ-Al2O3. The experiment with the
Pt-2 wt %/γ-Al2O3 catalyst at 6 bar, in the presence of concentration.
different concentrations of thiophene (Figure 9), shows
an important deactivation phenomenon even at 30 ppm after about 25 h of reaction, almost 60% of the initial
of S. At 30 ppm of S the catalyst remains stable during activity has been lost meaning that the platinum
the first 3 h of reaction and then a rapid deactivation supported on alumina catalyst is less resistant com-
occurs whereas at higher concentrations of sulfur the pared to the molybdenum-based and the Pt-1.5 wt %/β-
deactivation starts after 0.25 h on stream. The catalyst zeolite catalysts under similar conditions and with
rapidly reaches a steady state, 50% for 30 ppm and 30% higher sulfur concentration (500 instead of 120 ppm of
for 120 ppm of the original rate, and almost no ad- S). It should be noted that the two best catalysts (MoO3-
ditional deactivation occurs as shown in Figure 9. Table carbon-modified and Pt-1.5 wt %/β-zeolite) maintain
4 reports the product distribution as a function of the 60% of their initial activity after 30 h under 500 ppm
deactivation. It is interesting to note that a large of sulfur at 20 bar. This means that the new catalyst
improvment in C7 selectivity is observed in the presence based on molybdenum oxycarbide is at least as good as
of sulfur, from ∼60% to ∼90%. This phenomenon is the platinum catalyst on this point.
well-known and explains why, in many industrial III.4. Effect of Sulfur Source. Because a large
processes, Pt catalysts are sulfided before extensive use. variety of sulfur compounds can be present in industrial
III.3. Effect of Total Pressure. Results obtained feedstocks, variations of the poisoning effect as a func-
at 20 bar total pressure in the presence of g120 ppm of tion of the sulfur compound type have also been
S over the MoO3-carbon-modified catalyst and the two investigated over the molybdenum-based catalysts in
platinum-based catalysts as a function of time on stream order to check the performance of this new material.
are presented in Figure 10. Table 5 reports the product Figures 11 and 12 show the poisoning effects of these
distribution over the MoO3-carbon-modified and the Pt- compounds at a constant 120 ppm sulfur level on Mo2C-
1.5 wt %/β-zeolite catalysts only after 24 h on stream oxygen-modified and MoO3-carbon-modified catalysts,
in the presence of different concentrations of sulfur respectively, at 6 bar. It can be seen that the MoO3-
compounds in the feed at 20 bar total pressure. The carbon-modified catalyst exhibits higher resistance than
Mo2C-oxygen-modified catalyst was not tested because Mo2C-oxygen-modified catalyst for all the tested sulfur
it has been shown that this catalyst is not stable at 20 molecules (Pt-based catalysts were not tested according
bar (Blekkan et al., 1994). For comparison, the results to the nature of the sulfur compounds). On Mo2C-
already shown at 6 bar (Figures 7-9) are repeated. For oxygen-modified catalyst, the worst poison is thiophene.
MoO3-carbon-modified catalyst, no deactivation is ob- III.5. Regeneration. Regeneration has been carried
served at 120 ppm of S at high pressure, 20 bar. out for the MoO3-carbon-modified and platinum-based
Increasing the concentration of sulfur from 120 to 500 catalysts. Regeneration of the catalyst is very impor-
ppm led to a loss of about 50% of the initial rate of the tant not only in the development of practical methods
catalyst (Figure 10a). For Pt-1.5%/β-zeolite (Figure 10b) to restore catalyst activity, but also to obtain funda-
the effect of the pressure is also very positive, but mental knowledge about the cause of catalyst deactiva-
contrary to what is observed on the Mo-based catalyst, tion. Since the MoO3-carbon-modified and the Pt-1.5
120 ppm of S whatever the pressure considerably wt %/β-zeolite catalysts exhibit a very high thio resis-
poisons the catalyst. For the Pt-2 wt %/γ-Al2O3 catalyst tance, the deactivation performed at high concentration
(Figure 10c), only the deactivation at 120 ppm of S is of thiophene was used in order to obtain a more
reported due to the very fast deactivation observed at pronounced effect between the deactivated catalyst and
500 ppm. Over all the catalysts the decrease in rate the regenerated one. Therefore, the deactivated catalyst
due to deactivation is slower when increasing the total after reaction in the presence of 500 ppm of thiophene
pressure. However, over the Pt-2 wt %/γ-Al2O3 catalyst was submitted to a different regeneration treatment in
678 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996
b Conditions: 623 K, H2:HC ) 30, 120 ppm of S.
c
Figure 10. (a) Effect of total pressure on deactivation rate for
n-heptane isomerization over MoO3-carbon-modified catalyst.
Conditions: 623 K, H2:HC ) 30. (b) Effect of total pressure on
deactivation rate for n-heptane isomerization over Pt-1.5 wt %/β-
zeolite catalyst. Conditions: 563 K, H2:HC ) 30. (c) Effect of total
pressure on deactivation rate for n-heptane isomerization over Pt-2
wt %/γ-Al2O3 catalyst. Conditions: 623 K, H2:HC ) 30.
order to recover the initial activity. Over the Pt-2 wt
%/γ-Al2O3 catalyst, the deactivation was performed in
the presence of only 120 ppm of S due to the low thio
resistance of the catalyst. Mo2C-oxygen-modified cata-
lyst was not tested according to regeneration.
Figure 11. Effect of sulfur source on deactivation rate for
n-heptane isomerization over Mo2C-oxygen-modified catalyst.
Figure 12. Effect of sulfur source on deactivation rate for
n-heptane isomerization over MoO3-carbon-modified catalyst.
Conditions: 623 K, H2:HC ) 30, 120 ppm of S.
Figure 13 reports the effect of regeneration of the
deactivated catalysts after reaction under air flow at 723
K for 2 h at atmospheric pressure. Over MoO3-carbon-
modified catalyst, oxidative treatment followed by an
activation period allows the complete recovery of the
isomerization activity (Figure 13a). The XRD patterns
of MoO3-carbon-modified catalyst are presented in
Figure 14. After deactivation under 500 ppm of S
(Figure 14B), the diagram shows the diffraction lines
of MoO2, MoS2, and Mo3S4; the reflections due to the
oxycarbide phase have almost disappeared. After an
oxidative regeneration under air flowing at atmospheric
pressure and 723 K for 2 h, the XRD pattern (not shown)
mostly shows diffraction lines corresponding to MoO3
and no traces of other phases are detected. Activation
applied to the regenerated catalyst allows the complete
recovery of the isomerization activity and the XRD
pattern (Figure 14C) is similar to the one obtained on
the fresh catalyst after activation (Figure 14A).
Whereas oxidative regeneration allows the almost
complete recovery of the isomerization activity of the
molybdenum-based catalysts, only 85% of the initial
isomerization activity is recovered, after oxidative treat-

c
Figure 13. Effect of oxidative regeneration for n-heptane isomer-
ization over (a) MoO3-carbon-modified catalyst and (b) Pt-2 wt %/γ-
Al2O3 at conditions of 623 K, H2:HC ) 30; (c) Pt-1.5 wt %/β-zeolite
at conditions of 563 K, H2:HC ) 30.
ment followed by a reduction under hydrogen at 773 K
for 3 h, over the platinum catalysts (Figure 13b,c)
meaning either that over platinum some sulfur is
irreversibly adsorbed according to the results reported
in the literature or that sintering occurs during the
Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996 679
Figure 14. XRD patterns of (A) MoO3-carbon-modified catalyst
after activation under pure n-heptane and hydrogen at 20 bar,
(B) after reaction in the presence of 500 ppm of S, and (C) after
an oxidative regeneration followed by an activation under pure
n-heptane and hydrogen.
regeneration leading to less dispersed catalysts. The
XRD analysis was not performed over the platinum-
based catalysts due to the high dispersion of the metal.
IV. Discussion
The high thioresistance observed on the Mo-based
catalysts can be attributed to the presence of molybde-
num oxycarbide phase, which mitigates sulfidation of
the catalyst. The molybdenum oxycarbide, as explained
by Delporte et al. (1995), is formed by reduction of MoO3
via crystallographic shear and lattice contraction where
some oxygen atoms are replaced by carbon atoms which
stabilize a stable intermediate and stop the process of
reduction; similarly the first step of the sulfidation of
MoO3 by H2S (Wang et al., 1982) corresponds to the
formation of an oxysulfide (Mo4+OxSy) (De Jong et al.,
1993). It has been shown that pre-reduction of MoO3
into MoO2 renders the formation of MoS2 very difficult.
Similarly Spevack and McIntyre (Spevack et al., 1993)
during their investigation of the sulfidation of molyb-
denum oxide by H2S has reported that MoO2 is more
difficult to sulfide even after 2 h of sulfidation. In the
present study where almost no Mo(VI) is present
(Delporte et al., 1995), the sulfidation of the catalyst is
very difficult because of the reduced character of the
catalyst, i.e., Mo4+OxCy, Mo5+Ox′Cy′, and MoO2. This
hypothesis is verified by performing the activation
680 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996

Table 6. Isomerization of n-Heptane at 6 bar Total Pressure over MoO3-Carbon-Modified Catalyst and
MoO3-Carbon-Modified Catalyst with and without Sulfur in an Activation Feed at Different Times on Stream
(Conditions: 623 K, Total Flow 200 cm3 min-1, H2:HC ) 30)
activation under pure n-C7 activated directly under n-C7
followed addn of 120 ppm of S and 120 ppm of S
0.5a h 3.5 h 7h 25 h 1h 4h 10 h 24 h
conversion, % 59.3 53.2 56.3 49.6 7.1 6.1 16.6 14.3
rate, 10-7 mol g-1 s-1 60.2 58.4 59.5 56.8 11.3 24.3 25.0 21.8
C7 selectivity, % 88 88 86 86 82 79 74 72
∑light products, % 12 12 14 14 18 21 26 28
C7-isomer distribution, %
dimethylpentanes 19.4 18.8 19.5 19.6 16.2 17.7 19.4 20.1
2MHex 36.7 37.5 37.0 36.9 38.5 37.8 36.8 36.1
3MHex 40.0 40.0 39.9 39.8 40.4 40.7 39.7 39.1
3EPen 3.1 2.9 2.9 2.9 2.9 2.9 3.1 3.1
ECycPen 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MCyHex + toluene 0.8 0.8 0.7 0.8 2.0 0.9 1.0 1.6
light products distribution, %
C 6 + C1 8.7 7.6 6.6 11.1 4.1 6.3 4.5 3.8
C5 + C2 5.1 4.7 5.3 8.7 8.5 7.3 5.1 4.4
C4 + C3 82.3 83.9 84.4 78.8 80.8 81.4 84.2 85.5
others 3.9 3.6 3.7 1.4 6.6 5.0 6.2 6.3
a Time on stream.

Figure 16. XRD patterns of MoO3-carbon-modified catalyts (A)

after direct activation in the presence of 120 ppm of S at 6 bar
and (B) after activation under pure n-heptane and hydrogen
followed by reaction in the presence of 120 ppm of S.

catalyst after 24 h of reaction is presented in Figure 16A

Figure 15. Effect of nature of feed during activation period for
n-heptane isomerization over MoO3-carbon-modified catalyst: (a)
isomerization activity; (b) isomerization selectivity. Conditions:
623 K, H2:HC ) 30.
treatment with feed containing 120 ppm of S instead of
pure hydrocarbon. According to the results presented
in Figure 15 and Table 6, a lower isomerization activity
is obtained when compared to the activity obtained after
an activation period under pure n-heptane feed, under
otherwise similar conditions. At the beginning of the
reaction, sulfur and carbon are in competition to diffuse
and replace oxygen, leading to the formation of both
molybdenum oxycarbide (Mo4+OxCy) and oxysulfide or
sulfide which diminishes the overall activity of the
catalyst for isomerization. The XRD pattern of the
and reveals the presence of small amounts of MoS2 and
Mo3S4 along with diffraction lines corresponding to
MoO2 and oxycarbide, while the catalyst activated under
the pure hydrocarbon and hydrogen mixture, followed
by reaction in the presence of 120 ppm of S (Figure 16b),
shows no evidence of the formation of MoS2 or Mo3S4.
However, the XRD technique is not a very appropriate
analytical tool to investigate such a transformation.
New experiments are in progress using X-ray photo-
electron spectroscopy (XPS) in order to provide a better
description of the nature of the catalyst surface.
At high concentrations of sulfur, deactivation occurs
on both Mo2C-oxygen-modified and MoO3-carbon-modi-
fied catalysts. However, the first one is more affected
than the second. On Mo2C-oxygen-modified catalyst the

thin layer of oxycarbide, probably highly dispersed, is
much more sensitive to sulfidation than the bulky
structure obtained on MoO3-carbon-modified catalyst.
This is equivalent to what was observed on metal
catalysts where big particles are more sulfur tolerant
than small ones (Apesteguia and Barbier, 1982).
On Pt-based catalysts the strong decrease in isomer-
ization activity during the first hours is attributed to
the suppression of adsorption sites on the Pt surface by
formation of surface sulfide. It has been reported by
Wang et al. (1982) that sulfidation begins upon exposure
to H2S at room temperature on Pt. As shown in Table
4, the decrease in isomerization rate over Pt-2 wt %/γ-
Al2O3 catalyst, whatever the sulfur concentration, is
accompanied by an increase of isomerization selectivity
as opposed to Mo-based catalysts where isomerization
selectivity remains stable as a function of deactivation.
Similar results on Pt-2 wt %/γ-Al2O3 have already been
reported by several authors in the literature (Maurel
et al., 1975; Biloen et al., 1980) and would be due to a
size decrease of the active hydrogenolysis ensembles on
the catalyst surface, as well as to the blocking of the
highly coordinated atoms considered as active for hy-
drogenolysis. Similarly Dess and Ponec (1989) have
observed that modification of the Pt-Ir/γ-Al2O3 catalyst
by treatment with thiophene/hydrogen greatly changes
the activity and selectivity of the catalyst: almost
complete suppression of hydrogenolysis while isomer-
ization increased to a large extent. Actually, this
behavior is used by the industrial reformers to improve
the selectivity of the industrial catalysts; before running
the reforming process, the catalyst is presulfided. As a
function of time, the catalysts reaches a steady state
whatever the concentration of sulfur as shown in
Figures 8 and 9. This result could be due to the
equilibrium relationship between the rate of adsorption
and the rate of desorption of sulfur species (S + H2 f
H2S) at the reaction conditions used here (high H2/
hydrocarbon ratio and medium total pressure).
The deactivation observed for all the catalysts is
attributed to the formation of H2S by hydrogenolysis of
thiophene which can alter the active phase by formation
of sulfides. A similar result was observed by Dhainaut
et al. (Dhainaut et al., 1982) during dibenzothiophene
hydrodesulfurization over supported platinum catalysts
where specific activity decreased as the H2S pressure
increased. Deactivation is attributed to the decrease
of accessible Pt sites by formation of a surface sulfide
according to the balanced reaction M + H2S f MS +
H2 (where M ) Pt, Mo). Because of the equilibrium
relationship, one would expect a greater amount of free
surface at high pressures, and thus a lower toxicity
effect on reaction rate. Merbott (1954) reported that a
high level of sulfur (50-100 ppm) could be used at 20
bar, while high toxicity at pressures of 7-10 bar was
achieved with 5 ppm of sulfur in the feed. This is indeed
the case: increasing hydrogen partial pressure leads to
a decrease in the deactivation rate by sulfur for all the
catalysts (Figure 10). Almost no deactivation is ob-
served over molybdenum-based catalysts even in the
presence of 120 ppm of S at 20 bar while isomerization
activity loss is observed at 120 ppm of S over both the
catalysts at 6 bar. MoO3-carbon-modified catalyst
shows more thio resistance, and under 500 ppm of S
the loss of isomerization activity is only 45% after 25 h
of reaction.
Oxidative treatment followed by an activation period
under the hydrocarbon and hydrogen mixture allows the
Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996 681
complete recovery of the deactivated molybdenum-based
catalysts (Figure 13a). It is expected that sulfur poisons
present on the catalysts are oxidized during regenera-
tion treatment, leaving the active sites free for the
isomerization reaction. The activity and isomer selec-
tivity of MoO3-carbon-modified catalyst were completely
recovered after multiple regeneration cycles (three at
least). Over the Pt-2 wt %/γ-Al2O3 and Pt-1.5 wt %/β-
zeolite catalysts, regeneration is not sufficient to allow
the complete recovery of the initial activity. In the case
of platinum supported on alumina it has been shown
that at 773 K under H2 only a fraction of the adsorbed
sulfur is rapidly desorbed (Apesteguia et al., 1981),
whereas over an alumina support without platinum, the
adsorption of H2S is wholly reversible, under otherwise
similar conditions. The amount of “irreversible” sulfur
is attributed to that in strong interaction with the metal
resulting in the incomplete recovery of the isomerization
activity over the platinum-based catalysts.
V. Conclusion
Molybdenum-based catalysts formed either from Mo2C
or MoO3 exhibited a very high thio resistance even at a
sulfur concentration level of 120 ppm of S. The reduced
state of molybdenum (oxycarbide) present in these
catalysts is proposed to explain the observed result. As
the structure of the oxycarbide comes from the collapse
of the layers of the starting MoO3 during an activation
period due to carbon incorporation, this results in the
formation of a structure into which S diffusion occurs
less easily and results in a high thio resistance where
the oxycarbide is compared to MoO3. At higher con-
centrations of sulfur (>120 ppm of, S), sulfidation
occurs, resulting in a loss of isomerization activity.
Nevertheless, deactivated catalysts are easily regener-
ated under mild conditions, whereas over the platinum
catalyst regeneration, the recovery of only 85% of the
initial isomerization activity is possible. In addition,
deactivation observed over molybdenum-based catalysts
can be lowered or suppressed by increasing the total
pressure of the reaction from 6 to 20 bar. This is
attributed to the removal of adsorbed sulfur by hydro-
gen, freeing the active sites.
Among the sulfur compounds tested, thiophene is by
far the most virulent poison source. However, it is
important to note that the experiments carried out in
this work involved a high concentration of sulfur in the
feed, while in industrial conditions these concentrations
are lower, i.e., e10-30 ppm of S. Thus, under real
conditions the deactivation of the molybdenum-based
catalysts due to sulfur should be negligible.
In addition, these new oxycarbide phases allow isomer-
ization of n-alkanes containing more than six carbon
atoms with high selectivity (90%) even at high total
conversion (70-80%), which is desirable for the en-
hancement of the octane number of fuel. A further use
for isomerization over these materials would be for
decreasing the freezing point of gas-oil and lubricant
oil fractions (dewaxing) by conversion of the straight-
chain hydrocarbons into the methyl isomers without
cyclic molecules, in line with the new legislation for
restriction of aromatic compounds.
Acknowledgment
This work was supported by the Péchiney Company.
A.P.E.Y. wishes to thank the Royal Society for an ESEP
682 Ind. Eng. Chem. Res., Vol. 35, No. 3, 1996
fellowship, and E.A.B. wishes to thank NTH for finan-
cial support.
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Revised manuscript received October 30, 1995
Accepted November 14, 1995X
IE950409A
X Abstract published in Advance ACS Abstracts, January 15,
1996.