Applied Catalysis A: General 234 (2002) 45–54

Characterization and reactivity of Re(x)/␥-Al2 O3 catalysts in

hydrodesulfurization and hydrodenitrogenation of gas oil:
effect of Re loading
N. Escalona a , J. Ojeda a , R. Cid b , G. Alves b , A. López Agudo c ,
J.L.G. Fierro c , F.J. Gil Llambı́as a,∗
a Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago, Chile
b Universidad de Concepción, Casilla 160c, Concepcion, Chile
c Instituto de Catálisis y Petroleoquı́mica, CSIC, Campus UAM, 28049 Madrid, Spain
Received 13 November 2001; received in revised form 4 March 2002; accepted 9 March 2002

Abstract
A series of Re(x)/␥-Al2 O3 catalysts containing 1.69–6.76 wt.% Re2 O7 were prepared by wet impregnation and charac-
terized using X-ray diffraction (XRD), BET surface area, diffuse reflectance spectroscopy (DRS), electrophoretic migration
(EM), X-ray photoelectron spectroscopy (XPS) and surface acidity techniques. The catalysts were tested for simultaneous
hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of commercial gas oil under typical industrial hydrotreating
conditions. In general, the activities for both HDS and HDN reactions increased almost linearly with increasing Re loading,
reaching maxima at about 0.5 Re atoms nm−2 and then leveled off. These activity trends resemble that observed for the Re dis-
persion as measured by EM (in the oxided state) and XPS (in the sulfide state), which resulted in a monolayer-type deposition
up to about 0.5 Re atoms nm−2 and then in multilayers or small aggregates. The magnitude of the catalytic effect was, however,
different for HDS and HDN, and strongly depends on the Re content and reaction temperature. This led to a marked increase in
the HDN/HDS selectivity with decreasing temperature (values above 1.5 at 325 ◦ C), due to the large differences in the apparent
activation energies of HDS and HDN found for all catalysts. A gradual increase in the HDN/HDS selectivity with increasing
Re loading was also found. Such selectivity increase was ascribed to the parallel increase of catalyst acidity observed.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Supported rhenium sulfide; Sulfide rhenium; Hydrodenitrogenation (HDN); Hydrodesulfurization (HDS)

1. Introduction
Several systematic studies on the catalytic proper-
ties of transition metal sulfides (TMS) for hydrotreat-
ing reactions have been reported [1–7]. Characteristic
volcano-type curves were generally observed when the
activity was plotted against the position of the tran-
∗ Corresponding author. Fax: +56-2-6812108.
E-mail address: fgil@lauca.usach.cl (F.J.G. Llambı́as).
sition metal in the periodic table, and the highest ac-
tivity was observed for the third-row TMS, compared
to the second and first rows. In these studies bulk Re
sulfide, as well as carbon-supported Re sulfide was
found to be in a position of the volcano plot of high
or good activity, depending on the reaction or reactant
and the operating conditions. Thus, the intrinsic activ-
ity of the unsupported or carbon-supported Re sulfide
for hydrotreating reactions was generally higher than
that of Mo or W sulfides.

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 1 9 7 - 7
46 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54

Despite the high hydrodesulfurization (HDS) different and strongly dependent on reaction temper-
activity of bulk Re sulfide, very limited attention ature, large differences in the HDN/HDS selectivity
has been given to alumina-supported Re sulfide. with temperature could be expected. The catalysts
Most of the studies were concerned with HDS were thoroughly characterized by BET surface area
reactions on unpromoted Re catalysts, and reported measurements, X-ray diffraction (XRD), UV-diffuse
generally that Re/␥-Al2 O3 catalysts were markedly reflectance spectroscopy (UV-DRS) and acidity mea-
more active for HDS than the Mo/␥-Al2 O3 catalysts surements. The dispersion of rhenium was evaluated
[8–12]. For hydrodenitrogenation (HDN) reactions, using electrophoretic migration (EM) measurements
alumina-supported Re sulfide catalysts have received and X-ray photoelectron spectroscopy (XPS).
even less attention than for HDS reactions. No sys-
tematic studies of the influence of Re content on 2. Experimental
HDN activity has been published; only an earlier ex-
ploratory comparison of the activity of a commercial 2.1. Preparation of catalysts
CoMo/␥-Al2 O3 catalyst and a novel CoRe/␥-Al2 O3
catalyst in the HDN of indole [13], and later a com- Rhenium-based catalysts at various metal load-
parative study of the C–N hydrogenolysis activity of ing (1.69–6.76 wt.% Re2 O7 ) were prepared by wet
alumina-supported TMS and also as promoter of Mo impregnation of the alumina support (T-126 Girdler,
catalysts [14] were reported. Studies dealing with the SBET 194 m2 g−1 , pore volume 0.365 cm3 g−1 , par-
possible promotion of Re by other metal sulfide are ticle size 0.84–1.19 mm) with aqueous solutions of
scarce [15]. appropriate amounts of NH4 ReO4 (Aldrich, p.a.) in
The reason for the limited number of studies a rotary evaporator. After impregnation, the samples
devoted to alumina-supported Re sulfide catalysts is were dried at 110 ◦ C for 12 h and then calcined at
that the Re compounds are more expensive than those 300 ◦ C for 0.5 h. The Re loading was expressed as
of Mo or W. However, the need of catalysts having atoms of the metal per support nm2 . The Re content
better hydrogenation properties would increase in the was determined by ICP using the line of emission
future, due to the necessity for hydroprocessing of the 221.426 nm of Re. The catalysts are denoted by the
heavy oil fractions of petroleum and even deeper HDS number of metal atoms nm−2 of initial support area,
reactions [16]. Since the Re sulfide has higher hydro- e.g. Re(0.53) contains 0.53 atoms of Re (3.77 wt.% of
genation activity than the Mo or W sulfides [2,12], this Re2 O7 ) per nm2 . The catalysts are listed in Table 1.
capability of the Re sulfide can greatly help in the
development of a new generation of better hydrotreat- 2.2. Catalyst characterization
ing catalysts, specially when the reaction mechanism
requires or is predominantly through a prehydro- The specific surface area and pore volume were
genation route, as it occurs in deep HDS and HDN derived from nitrogen sorption isotherms determined
reactions. This has stimulated further research on at 77 K (degassing at 110 ◦ C, 5 × 10−3 Torr) using a
Re-based catalysts. Micromeritics ASAP 2000 apparatus.
The aim of this work was to gain new insight XRD was carried out on a Siemens D5000 diffrac-
into the surface properties of Re(x)/␥-Al2 O3 catalysts tometer using the Cu K␣ radiation (λ = 1.540598 Å).
and the influence of the Re loading on the HDS and
HDN activities and selectivities measured simultane- Table 1
ously under industrial hydrotreating conditions using Composition and specific BET area of oxidic catalysts
a real feedstock. No systematic study in such con- Catalyst Re2 O7 Re surface density BET surface
ditions has been reported in the literature. For this content (%) (atoms nm−2 ) area (m2 g−1 )
purpose, the performance of Re(x)/Al2 O3 catalysts Re(0.23) 1.69 0.23 196
in the simultaneous HDS and HDN of gas oil was Re(0.49) 3.59 0.49 195
carried out at 325–375 ◦ C. In parallel HDS and HDN Re(0.53) 3.77 0.53 195
reactions, as the extent of the competitive adsorp- Re(0.70) 4.94 0.70 –
Re(0.97) 6.76 0.97 193
tion of sulfur and nitrogen compounds are probably
 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54
The tube was operated at 40 kV and 40 mA. UV-DRS
measurements were recorded in the wavelength range
240–800 nm on a Carl Zeiss DMR 22 spectrometer
equipped with a diffuse reflectance accessory with an
integrating sphere, and BaSO4 powder as reference.
EM measurements were carried out in a Zeta-Meter
Inc. Model ZM-77 equipment using a 30 mg of sam-
ple suspended in 300 ml of a 10−3 M KCl solution.
The pH was adjusted with either 0.2 M HCl or KOH
solutions. The isoelectric point (IEP) of the support
and the zero point of charge (ZPC) of the catalysts
were calculated from the EM rate. Details of the proce-
dure and application to other supported catalysts have
been described elsewhere [17–19].
XPS measurements were performed using a VG
Escalab 200R electron spectrometer equipped with
a hemispherical electron analyzer and a Mg K␣
(1253.6 eV) excitation source. Energy corrections
were performed using as internal reference the Al line
of the alumina support at 74.5 eV. The catalyst sam-
ples for XPS were pre-sulfided ex situ with a mixture
of 10% H2 S/H2 at 350 ◦ C for 4 h. After this, the sam-
ples were cooled to room temperature, flushed with
He and transferred into flasks containing iso-octane.
The intensity of the peaks was estimated by calcu-
lating the integral of each peak after substrating an
S-shaped background and fitting the experimental
curve to a combination of Gaussian/Lorentzian lines.
Surface acidity of calcined catalysts was measured
potentiometrically by titration with n-butylamine in
acetonitrile using an Ag/AgCl electrode [20].
2.3. Activity measurements
Catalytic measurements for simultaneous HDS and
HDN of gas oil were carried out in a high-pressure
continuous-flow micro-reactor. The catalyst bed con-
sisted of 1 g of catalyst diluted 1:1 (v/v) with SiC
particles to optimize hydrodynamics. The remaining
space in the reactor was filled with SiC particles. Prior
to reaction, the catalysts were sulfided with a 7 vol.%
CS2 /gas oil mixture at 350 ◦ C and 3.0 MPa total pres-
sure for 4 h. The feed for HDS and HDN was com-
mercial gas oil, containing 470 ppm S and 190 ppm
N. The performance of the catalysts was determined
in the temperatures range 325–375 ◦ C under stan-
dard conditions: 3.0 MPa total pressure, 9 h−1 LHSV,
3600 h−1 GHSV, and H2 /feed ratio of 400. Under these
47
reaction conditions, catalyst size, dilution and length
of the catalytic bed, the reaction was not controlled
by mass transfer phenomena [21], and the catalysts
were stable. For all tests, a stabilization period of at
least 2 h was allowed before the first sample was col-
lected. Total sulfur in the effluents was determined by
iodometric titration of SO2 using a LECO analyzer,
and total nitrogen was analyzed on a Antek 703C in-
strument by chemiluminescence detection. HDS and
HDN conversions were defined as percent of total
sulfur and nitrogen, respectively, removed from the
initial gas oil.
3. Results and discussion
3.1. Catalyst characterization
The specific areas of calcined Re(x)/␥-Al2 O3 cat-
alysts shown in Table 1 were very similar and did
not differ significantly from that of the support. This
means that Re species were highly dispersed into the
pores of the alumina and that pore mouth blockage
was practically absent.
Crystalline phases in oxidic Re(x)/␥-Al2 O3 cata-
lysts were characterized by XRD. No diffraction lines
corresponding to Re compounds were detected, even
for the higher Re loading catalyst, suggesting that
ReOx species are relatively highly dispersed on the
alumina surface. This information is supported by the
DR spectra of the catalysts in the oxidic state presented
in Fig. 1. All spectra exhibited a dominant band cen-
tered at 250–260 nm with a small broad shoulder in the
region between 300 and 400 nm. With increasing Re
loading the position of the bands did not change signif-
icantly, the spectra differed only in intensity. Similar
spectra have been reported in the literature for alumina
samples with increasing Re2 O7 loading [22,23]. Com-
parison with the spectra of the NH4 ReO4 and Re2 O7
reference compounds, shown also in Fig. 1, indicates
that most of Re in the calcined catalysts is present as
distorted isolated ReO4 species. A slight relative in-
crease in the intensity of the shoulder at 300–400 nm,
observed for the high Re content catalysts, suggest the
possibility that some ReO4 species could be associ-
ated or interacting between them in such catalysts.
The dispersion of Re was examined by EM mea-
surements [17–19]. Fig. 2 compares the effect of pH
48 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54

Fig. 1. DR spectra of oxidic Re(x)/␥-Al2 O3 catalysts.

Fig. 2. Effect of pH on the zeta potential of the alumina support and catalysts. Inset: variation of the zeta potential of Re(x)/␥-Al2 O3
catalysts with Re loading.
 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54 49

on the zeta potential (ZP) of the different catalysts and

the alumina support. The inset in Fig. 2 shows a plot
of the ZP of the Re(x)/␥-Al2 O3 catalysts against the
Re content. The ZP initially decreased gradually with
increasing Re content (loading <0.5 Re atoms nm−2 ),
indicating that up to such a content the Re species are
highly dispersed in a monolayer form on the alumina
surface. For higher Re loading, the ZP of the catalysts
was nearly constant around a value of 7.7. This value
is above the 3.0–4.5 theoretical value of the IEP for
Re2 O7 calculated according to the method described
by Ion et al. [24], using a Re–O distance of 1.68 Å
and assuming a Re coordination number equal to 9 or
10 [25]. The IEP of the bulk Re2 O7 could not be ex-
perimentally determined since it is deliquescent. The
observed nearly invariability of the ZPC for catalysts
with loading above 0.5 Re atoms nm−2 indicates that
the coverage of the free-surface of the alumina by Re
does not progress more because Re is likely deposited
in the form of multilayers.
Fig. 3 shows the XPS of the Re 4f region of sulfided
Re(x)/␥-Al2 O3 catalysts. Curve fitting of the spectra
revealed two partially overlapped doublets, each one
containing the Re 4f7/2 and 4f5/2 peaks. Table 2 sum-
marizes the binding energies (BE) of the most intense
Re 4f7/2 component of each doublet, their relative pro- Fig. 3. X-ray photoelectron spectra of the Re 4f region of sulfided
portion and the surface Re/Al atomic ratios. The Re Re(x)/␥-Al2 O3 catalysts.
4f7/2 component of the most intense doublet remained
constant, about 41.6 eV, over the whole Re loading
range considered, and corresponds closely to the value Fig. 4 shows the XPS Re/Al plot as a function of
reported for ReS2 [2,26,27]. The Re 4f7/2 peak of the the nominal Re content in the catalysts. Clearly, the
less intense doublet, whose position decreased gradu- sulfided Re phase appears to be monolayer-like dis-
ally from the value 45.1 eV for the lower Re content persed up to about 0.5 Re atoms nm−2 . The observed
sample up to the value 43.6 eV for the highest Re con- deviation from linearity above 0.5 Re atoms nm−2
tent sample, can be assigned to Re(VI) and Re(IV) points to the formation of multilayers or small
oxidation states [27]. In the latter peak there is a clear three-dimensional particles, in a good agreement with
shift down in BE of more 1 eV as compared to that the EM results.
(46.5 eV) of Re(VII) in calcined samples, which in-
creases up to 2.5 eV with increasing Re content. These Table 2
observations indicate that Re sulfidation was slightly XPS binding energies (eV) and surface atomic ratios of sulfided
incomplete, under the sulfidation procedure used, and catalyst
that the reducibility and sulfidation of the supported Catalyst Al 2p Re 4f7/2 (Re/Al) × 102
Re species increase with increasing Re content. Con- atomic ratio
sistently, the degree of sulfidation of Re as measured Re(0.23) 74.5 41.7 (89), 44.9 (11) 0.39
by XPS (ratio of ReS2 to the total amount of Re) in- Re(0.49) 74.5 41.6 (88), 45.1 (12) 0.69
creased slightly for the high Re-containing catalysts Re(0.53) 74.5 41.6 (88), 44.2 (12) 0.77
Re(0.70) 74.5 41.7 (89), 43.7 (11) 0.99
due to a weaker interaction of the oxide Re species
Re(0.97) 74.5 41.6 (91), 43.6 (9) 1.32
with the surface of the alumina support.
50 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54

Fig. 4. Relationship between the XPS Re/Al atomic ratio and the nominal surface density of Re for Re(x)/␥-Al2 O3 catalysts; the dashed
straight line is the best-fit linear correlation at low Re loading.

Fig. 5. Effect of Re loading on total acidity and strength of the acid sites of calcined Re(x)/␥-Al2 O3 catalysts. Acid strength estimated by
the initial electrode potential, Ei .
 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54
Fig. 5 shows the total acidity of calcined Re(x)/
␥-Al2 O3 catalysts as a function of the Re content.
It is evident that both the number of acid sites and
their strength increased gradually by increasing the Re
content.
3.2. Catalytic performance
The activity for HDS and HDN reactions of gas oil
over Re(x)/␥-Al2 O3 catalysts, expressed as a function
of the conversion versus the Re content (atoms nm−2 )
and the reaction temperature, are presented in Figs. 6
and 7, respectively. As can be seen, the conversion for
both HDS and HDN reactions varied similarly with
the Re content, although the magnitudes were differ-
ent for both reactions. Initially, the activity increased
more or less linearly with increasing Re loading up to
about 0.5 Re atoms nm−2 , and then slightly decreased.
When the specific HDS and HDN activities are
expressed per atom nm−2 and plotted versus Re load-
ing, the specific HDS and HDN activities tend also to
increase in the first Re content range (up to near 0.5
Re atoms nm−2 ), and to decrease in the high Re con-
tent range. A similar activity trend in the thiophene
Fig. 6. Gas oil HDS activity of Re(x)/␥-Al2 O3 catalysts as a function of Re loading and reaction temperature.
51
HDS was previously reported by Arnoldy et al. [10].
In general, this variation of the activities with the
Re content is closely related to the variation of the
Re dispersion on the Al2 O3 support. The initial lin-
ear increase of HDS and HDN activities reflects an
increase in the amount of well-dispersed sulfided Re
species, which is the primary factor determining the
number of sulfur vacancies created on the sulfided
catalysts, in which hydrotreating reactions take place
[28,29]. This is consistent with observation that the
Re species were deposited in a monolayer-like form
up to about 0.5 Re atoms nm−2 according to the EM
(in the oxidic state) and XPS (in the sulfided state)
results. Above this Re loading, formation of Re multi-
layers occurred and Re dispersion decreased, leading
therefore to slight decreases in the HDS and HDN
activities. This decrease in activities caused by the
loss of Re dispersion is likely attenuated by a slightly
higher sulfiding degree of Re reached in the highly
loaded Re-containing catalysts.
Comparison of Figs. 6 and 7 reveals that the changes
in HDS and HDN activities are not only dependent
on the Re content and different for both reactions, but
also strongly dependent on the reaction temperature.
52 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54

Fig. 7. Gas oil HDN activity of Re(x)/␥-Al2 O3 catalysts as a function of Re loading and reaction temperature.

Thus, it can be observed that the HDN activity tends to of the sorption capacities of catalysts for sulfur and
increase relatively more than the HDS activity when nitrogen-containing compounds in the gas oil. The
the Re content increases, and that the temperature af- observation that the apparent activation energies for
fects relatively less to the HDN than HDS reaction. each reaction is practically constant means that the Re
To illustrate better these differences, Fig. 8 shows a content did not modify the nature of the active sites
plot of the HDN/HDS selectivity as a function of the for each particular reaction but that changes only the
Re content and the reaction temperature. Clearly, the number of the active sites for each reaction. However,
HDN/HDS selectivity increased with the Re content the fact that the apparent activation energies for HDS
and relatively more at lower reaction temperature. differ notably from those for HDN demonstrates that
Apparent activation energies (Eapp ) were calcu- HDS involves different type of catalytic sites from
lated according to the Arrhenius equation and the those for HDN, as it has generally been established in
results are given in Table 3. The apparent activation
energies were, approximately around 146 kJ mol−1 Table 3
for HDS and about 29 kJ mol−1 for HDN for all the Apparent activation energy (Eapp ) in the HDS and HDN of gas oil
catalysts. This low apparent activation energy for
Catalyst Eapp (kJ mo1−1 )
HDN might suggest that under the test conditions
used pore-diffusion limitations occur. However, we HDS HDN
must note that such limitations are not observed in Re(0.23) 138 ± 4 29 ± 4
the parallel HDS reaction. Therefore, the low appar- Re(0.49) 158 ± 2 37 ± 2
ent activation energies for HDN cannot be ascribed Re(0.53) 154 ± 4 33 ± 4
to pore-diffusion limitations but to differences in the Re(0.70) 151 ± 8 25 ± 8
Re(0.97) 151 ± 8 29 ± 8
rate constant and/or in the temperature dependence
 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54
Fig. 8. HDN/HDS selectivity of Re(x)/␥-Al2 O3 catalysts as a function of Re loading and reaction temperature.
the literature [29–31]. Higher activation energies of
the HDS reaction compared to those of the HDN re-
action for all catalysts studied indicates that the HDS
reaction is relatively more favored at higher reaction
temperatures than the HDN reaction, explaining that
the HDN/HDS selectivity would be very low (<0.8)
at 350 and 375 ◦ C and substantially higher (>1.5)
at 325 ◦ C for all the catalysts. This explains results
apparently contradictory on the HDS and HDN activ-
ities of unsupported Re catalysts previously reported
in the literature [5,32], since they were obtained under
different reaction conditions, particularly temperature.
As shown in Fig. 8, the Re content induced also a
change in the HDN/HDS selectivity, which increased
gradually with increasing Re content. Since the Re
content does not modify the nature of the active sites
for each reaction, it suggests that Re content changes
the relative concentrations of the sites for HDS and
HDN reactions, increasing relatively more those for
HDN. This relative increase in global HDN activ-
ity could be, in principle, related to a change in the
size and the stacking of the ReS2 slabs and/or in
the acid sites since HDN involves two types of sites,
53
i.e. sulfur vacancies and acid sites [31,33]. Accord-
ing to Fig. 3 results, the size of the ReS2 slabs only
change at very high Re loading and only moderately.
However, the increase of the HDN/HDS selectivity
was gradual over all the Re content range studied and
followed a trend very similar to that observed for the
catalyst acidity, both the number of acid sites and their
strength (Fig. 8). Therefore, the observed increase in
the HDN/HDS selectivity seems to be associated more
with an increase in catalyst acidity than to changes
in the size and morphology of the ReS2 slabs since
the acid sites can participate in C–N bond scission
[30,31,33].
4. Conclusions
The alumina-supported Re catalysts are highly
active in the simultaneous HDS and HDN of a com-
mercial gas oil. The effect of Re loading on the activ-
ities for both HDS and HDN reactions is qualitatively
similar for the two reactions and essentially deter-
mined by the dispersion of Re on the catalyst surface.
54 N. Escalona et al. / Applied Catalysis A: General 234 (2002) 45–54
The incorporation of different Re loading does not
change the nature of the different active sites involved
in HDS and HDN, but it changes the dispersion and
the number of the active sites in the surface, as well
as the relative concentration of the active sites for the
two reactions.
In the simultaneous HDS and HDN of gas oil, the
selectivity of the Re(x)/␥-Al2 O3 catalysts for HDS
versus HDN varies considerably with the temperature
because the apparent activation energies for HDS are
much higher than those for HDN. At low reaction
temperatures (<325 ◦ C) HDN conversion prevails no-
tably over HDS conversion, and at high temperatures
(>350 ◦ C) vice versa. This temperature selectivity de-
pendence can explain some differences in the HDS,
HDN selectivity reported for unsupported Re catalysts
[5,31]. It is also concluded that the increase of the
acidic sites with Re loading is responsible for the im-
proved selectivity to HDN.
Acknowledgements
Financial support from Project 1990496-6, FONDE-
CYT (Chile), and from the Program CYTED, Subpro-
gram V (Spain) is kindly acknowledged. N. Escalona
gratefully acknowledges the fellowship from CONI-
CYT (Chile).
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