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Received 26 April 2002; received in revised form 26 July 2002; accepted 27 July 2002
Abstract
A series of Re-containing catalysts supported on activated carbon, with Re loading between 0.74 and 11.44 wt.% Re2 O7 , was
prepared by wet impregnation and tested in the simultaneous hydrodesulphurisation (HDS) and hydrodenitrogenation (HDN)
of a commercial gas oil. Textural analysis, XRD, X-ray photoelectron spectroscopy (XPS) and surface acidity techniques
were used for physicochemical characterisation of the catalysts. Increase in the Re concentration resulted in a rise in the HDS
and HDN activity due to the formation of a monolayer structure of Re and the higher surface acidity. At Re concentrations
>2.47 wt.% Re2 O7 (0.076 Re atoms nm2 ) the reduction in the catalytic activity was related to the loss in specific surface
area (BET) due to reduction in the microporosity of the carbon support. The magnitude of the catalytic effect was different
for HDS and HDN, and depended strongly on the Re content and reaction temperature. The apparent activation energies were
about 116156 kJ mol1 for HDS and 2430 kJ mol1 for HDN. This led to a marked increase in the HDN/HDS selectivity
with decreasing temperature (values >3 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 increased Re loading was also found and
related to the observed increase of catalyst acidity. The results are compared with those obtained for a series of Re/-Al2 O3
catalysts.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Supported Re catalysts; Re sulphide; Hydrodenitrogenation (HDN); Hydrodesulphurisation (HDS)
1. Introduction
In the future, a new generation of catalysts for
deeper hydrodesulphurisation (HDS) and hydrodenitrogenation (HDN) and major reduction of aromatic
content in diesel fuel, more efficient than the conventional alumina-supported Co (or Ni)-Mo (or W)
Corresponding author. Fax: +52-562-6812108.
E-mail address: fgil@lauca.usach.cl (F.J. Gil-Llambas).
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 4 3 0 - 1
152
and HDN reactions [8,9]. However, relatively few detailed studies on the catalytic HDS or HDN activities
of supported Re-based catalysts have been reported
[1014]. In a previous study [15], we found that the
Re/-Al2 O3 system exhibited a high selectivity for
HDN reactions relative to HDS. This behaviour is
unusual on conventional supported molybdenum or
tungsten sulphide catalysts, which have generally
higher HDS activity relative to HDN activity. Exceptional properties for HDN have been reported only
with catalysts of unconventional composition, such as
unsupported Fe-Mo or Fe-W sulphide catalysts [16],
certain noble metal sulphides supported on active carbon [17] and Mo-Ir/-Al2 O3 sulphided catalysts [18].
However, most of these catalysts gave HDN/HDS ratios generally <1, while on Re/-Al2 O3 catalysts the
HDN/HDS ratios were between 1.5 and 2.5 at 325 C,
depending on Re content, and <1 at higher reaction
temperatures [15]. This exceptional HDS selectivity
of Re/-Al2 O3 catalysts is a very promising result
for improvement of catalysts for HDN, and deserves
further research on other supports more inert than alumina, such as carbon. Metal sulphides supported on
carbon are known to have a higher intrinsic activity in
HDS, HDN and hydrogenation (HYD) reactions than
the corresponding -Al2 O3 -supported ones [6,19].
The high activity of carbon-supported Co-Mo catalysts has been usually explained in terms of a weak
catalystcarbon interaction, which leads to a higher
degree of sulphidation and formation of the more active Co-Mo-S type II structure [19], but the role of carbon is still not clear. Recently, Chianelli and Pecoraro
have claimed that carbon stabilises MoS2 particles,
keeping crystallites smaller and less stacked, leading
to a better dispersion on a carbon support [20]. In that
study, it was also suggested that the active surface
in the stabilised structure of the molybdenum sulphide phase was carbided. In the case of Re sulphide
catalysts, it has previously been reported that the thiophene HDS activity increased in the order SiO2 <
-Al2 O3 < C and the Re catalysts were 220 times
more active than molybdenum ones [10]. Thus, catalysts based on Re/C could be an interesting alternative
for hydrotreating processes, especially for HDN.
In the present study, the performance of a series of
sulphided Re catalysts supported on activated carbon
was examined in the simultaneous HDS and HDN of
a commercial gas oil. Catalysts were characterised by
several physicochemical techniques.
2. Experimental
2.1. Catalyst preparation
Re-based catalysts at various metal loadings (0.74
11.44 wt.% Re2 O7 ) were prepared by wet impregnation of the activated carbon support (SBET 817 m2 g1 ,
total pore volume 0.637 cm3 g1 , particle size
2016 mesh) with aqueous solutions of the appropriate concentrations of NH4 ReO4 (Aldrich, p.a.)
in a rotary evaporator. After impregnation, the samples were dried at 110 C for 12 h. The Re loading
was expressed as atoms nm2 of the support. The
Re content was determined by inductively coupled
plasma-atomic emission spectroscopy (ICP-AES), in
a Perkin-Elmer model Optima 3300 DV spectrometer
using the 221.426 nm Re emission line. The catalysts
listed in Table 1 are denoted by the number of metal
atoms nm2 of initial support area, e.g. Re(0.076)/C
contains 0.076 atoms of Re nm2 (2.47 wt.% Re2 O7 ).
2.2. Catalyst characterisation
The specific surface areas, micro and mesopore volumes and pore size distributions of the samples were
determined from analysis of N2 adsorptiondesorption
Table 1
Composition and physical characteristics of oxidic catalysts
Catalyst
Re loading
(wt.% Re2 O7 )
Re loading
(atoms nm2 )
SBET
(m2 g1 )
Sext
(m2 g1 )
Micro pore
diameter (nm)
Re(0.00)/C
Re(0.024)/C
Re(0.076)/C
Re(0.135)/C
Re(0.380)/C
0.74
2.47
4.29
11.44
0.024
0.076
0.135
0.380
817
795
819
704
584
44
51
51
49
47
0.637
0.739
0.776
0.684
0.593
0.865
0.847
0.941
0.954
0.954
isotherms at 196 C using a Carlo Erba 1800 Sorptomatic apparatus. The samples were previously out
gassed at 110 C to a final vacuum of <0.05 Pa. The
BET method [21] was employed to determine the specific surface areas, taking the area of the N2 molecule
as 0.162 nm2 and the thickness of the monolayer as
0.354 nm. As all of the samples were microporous, the
linear region of the BET equation was taken in the
range of relative pressures between 0.02 and 0.12 p/p .
The adsorption isotherms were also used to calculate
the micropore volume and external surface area by a
t-plot analysis [22] using the equation of Halsey [23]
to determine the thickness of the adsorbed layer at
each relative pressure value. The micropore size distributions were determined by the method developed
by Mikhail et al. applied to the corresponding t-plots
[24]. The mesoporosity was determined from the difference between the microporosity calculated from the
t-plot and the volume adsorbed at a relative pressure
of 0.96 on the desorption branch of the corresponding isotherms, equivalent to a pore diameter of 50 nm.
Mercury intrusion porosimetry (MIP) analyses were
determined on samples previously dried overnight at
110 C in a Fisons Pascal 140/240 apparatus. Starting
from vacuum and raising the pressure to 200 MPa this
technique covers the pore diameters of 300 m down
to 7.5 nm applying the Washburn equation. Summation of the micro and mesopore volumes obtained from
N2 isotherms with the pore volumes in pores >50 nm
determined by MIP lead to the total pore volume of
the sample.
The chemical state and surface composition of
the sulphided catalysts were studied by X-ray photoelectron spectroscopy (XPS). The XP spectra were
recorded in a VG Escalab 200R electron spectrometer equipped with a hemispherical electron analyser
and a Mg K (1253.6 eV) photon source. Energy
corrections were performed employing the C line of
the carbon support at 284.9 eV as internal reference.
The catalyst samples for XPS were pre-sulphided ex
situ with a mixture of 10% H2 S/H2 at 350 C for
4 h. The samples were then cooled to room temperature, flushed with He and transferred into flasks
containing iso-octane. The intensities of the peaks
were estimated by calculating the integral of each
peak after subtracting an S-shaped background and
fitting the experimental curve to a combination of
Gaussian/Lorentzian lines.
153
154
Fig. 1. Variation of the pore volume as a function of the Re content for Re(x)/C catalysts.
155
Re 4f7/2
Re(0.024)/C
Re(0.076)/C
Re(0.135)/C
Re(0.380)/C
41.4
41.9
41.9
41.8
(87),
(91),
(74),
(83),
45.5
45.2
45.2
45.5
(12 )
(9)
(26)
(17)
(Re/C) 102
atomic ratio
Resulf /
Retotal
0.117
0.233
0.434
1.018
0.77
0.84
0.80
0.89
156
157
Fig. 5. Relationship between the XPS Re/Al atom ratio and the nominal surface density of Re for Re/-Al2 O3 catalysts; the dashed straight
line is the best-fit linear correlation at low Re loading.
this content more Re enters the micropores and reduces their accessibility or blocks the narrower ones,
sterically inhibiting the diffusion of the reactants to
the active sites due to the large size of the gas oil
Fig. 6. Gas oil HDS activity of Re(x)/C catalysts as a function of Re loading and reaction temperature.
158
Fig. 7. Gas oil HDN activity of Re(x)/C catalysts as a function of Re loading and reaction temperature.
Re(0.024)/C
Re(0.076)/C
Re(0.135)/C
Re(0.380)/C
137
156
123
116
5
10
6
1
8
7
2
2
159
Fig. 8. HDN/HDS selectivity of Re(x)/C catalysts as a function of Re loading and reaction temperature.
obviously means that the former reaction was relatively more favoured at higher reaction temperatures
than the latter reaction and reflected in the change
of HDN/HDS selectivity. Accordingly, Fig. 8 shows
that the HDN/HDS selectivity increased with decreasing reaction temperature, being <0.8 at 375 C
and >3 at 325 C for all the catalysts. This may also
explain the apparently contradictory results on the
HDS and HDN activities of unsupported Re catalysts
previously reported in the literature [9,35], since they
were obtained under different reaction conditions,
particularly temperature.
Another interesting result shown in Fig. 8 is that
the HDN/HDS selectivity increased gradually with increasing Re content. Since the Re content does not
modify the nature of the active sites for either reaction
(catalyst had Eap almost constant for both reactions), 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 the overall HDN activity does not seem to
be related to a change in the size and the stacking of the
ReS2 slabs since according to the XPS results (Fig. 3)
Re dispersion only changed at very high Re loading
and then only moderately. However, the increase of the
HDN/HDS selectivity was gradual throughout the Re
160