Professional Documents
Culture Documents
Chenguang Liu1 ,
Fei Wei2
1. State Key Laboratory of Heavy Oil Processing, Key Laboratory of Catalysis, CNPC, University of Petroleum,
Dongying 257061, China; 2. Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
[Manuscript received April 28, 2004; revised May 25, 2004]
Abstract: In this paper, adsorption properties of dibenzothiophene (DBT) on carbon nanotube, carbon
nanotube supported oxide state and sulfide state CoMo catalysts are studied by using thermal gravimetric analysis (TGA) technique and FT-IR spectroscopy. Activated carbon support, -Al 2 O3 support
and supported CoMo catalysts are also subjected to studies for comparison. It was found that sulfide
state CoMoS/MWCNT, CoMoS/AC and CoMoS/-Al2 O3 catalysts adsorbed much more DBT molecules
than their corresponding oxide state catalysts, as well as their corresponding supports. The chemically
adsorbed DBT aromatic molecules did not undergo decomposition on the surface of supports, supported
oxide state CoMo catalysts and sulfide state CoMo catalysts when out-gassing at 373 K. FT-IR results
indicated that DBT molecules mainly stand upright on the active sites (acid sites and/or transition active
phases) of CoMoS/MWCNT catalyst. However, DBT aromatic molecules mainly lie flat on MWCNT and
CoMoO/MWCNT.
Key words: FT-IR, dibenzothiophene, carbon nanotube, adsorption
1. Introduction
Recently, carbon materials including carbon nanotube have received increased attention as supports
for catalytic systems [1,2]. Potential advantages include easy metal recovery, low propensity of coke formation and the nanometer dimensions of carbon nanotube. In the system of heterogeneous catalysis, main
catalytic reactions are carried out on the surface of
catalysts, therefore, the adsorption properties, especially the chemical adsorption of reactants on the surface of catalysts play a very important role in the process of catalysis.
Hydrodeseulfurization (HDS) is critical in the production of clean oil and Dibenzothiophene (DBT) is
the most common sulfur containing organic molecules
existing in the petroleum-derived feed-stocks which is
hard to be removed from the feed stocks [35]. Farag
[6] studied the adsorption of DBT on carbon sup
ported Co-Mo catalysts and some surface characteristics from the adsorption and desorption techniques,
following the concepts of physical adsorption and surface science to get useful information on the dispersion
nature of the catalyst dispersed on the support by the
application of thermal gravimetric technique. Larrubia [7] studied the adsorption of benzothiophene,
dibenzothiophene and 4,6-dimenthylbenzothiophene
on catalytic supports such as alumina, zirconia and
magnesia by IR spectroscopy and the results show
that DBT and 4,6-DBT do not undergo decomposition during the desorption process because of the
stability of the aromatic rings. Up to now, few studies have been done on the adsorption states of DBT
on carbon nanotube and carbon nanotube supported
Co-Mo catalysts.
In this paper, the adsorption states of DBT aromatic molecules on carbon nanotube support, supported oxide Co-Mo catalyst and sulfide Co-Mo cat-
96
Hongyan Shang et al./ Journal of Natural Gas Chemistry Vol. 13 No. 2 2004
2. Experimental
2.1. Adsorption of pyridine
A kind of multi-walled carbon nanotube
(MWCNT) supplied by Tsinghua University was used
as-received. A pillar activated carbon (AC) offered
by the Beijing Institute of Coal Science was also used
as-received. The samples were put into a desiccator
filled with pyridine vapor for 24 h at room temperature in a high vacuum system (0.1 mPa).
After adsorption with pyridine, the samples were
subjected to analysis by using FT-IR technique to
characterize the surface acidic property.
2.2. Preparation of Co-Mo catalyst
The supported catalysts with Co/Mo atomic ratio of 0.35 were prepared by pore volume impregnation using aqueous solutions of (NH4 )6 Mo7 O24 24H2 O
and Co (NO3 )2 6H2 O (both A. R.). The Mo phase
was introduced first and dried in air at 383 K for 12
h, then Co precursor was introduced with pore volume impregnation followed by drying at 383 K for 12
h, finally the bimetallic catalysts were heat-treated
at 773 K for 4 h in the flow of nitrogen. In case of
alumina, the catalyst was calcinated in air at 773 K
for 4 h. The oxide state catalyst was labeled as CoMoO/MWCNT, CoMoO/AC and CoMoO/-Al2O3 ,
respectively.
In the preparation of sulfide state Co-Mo catalysts, sulfide Mo phase was provided by ammo-
97
of
Where A is the total specific area (m2 /g) of adsorbed DBT, M is the molar weight (g/mol) of DBT,
m represents the total weight (mg) of sample after
the adsorption of DBT, m1 represents the amount of
weight loss of DBT during TGA process. 66.51020
is the surface area of DBT per molecule, m2 .
The specific surface areas of adsorbed DBT on
supports and catalysts calculated according to formula (1) are listed in Table 2. According to the
BET data, the BET specific surface area of MWCNT
(189.6 m2 /g) is much larger than the surface area
(53.56 m2 /g) of DBT molecules which are adsorbed on
the MWCNT, it can be deduced that the surface of
CNT is not thoroughly covered by DBT molecules.
It is also the case with CoMoO/MWCNT. As for
CoMoS/MWCNT, its specific surface area coincides
with that of adsorbed DBT molecules. In general,
the sulfide state catalyst adsorbs much more DBT
molecules than the corresponding oxide state catalyst and corresponding support (see Table 2). DBT
molecules can adsorb on two kinds of sites, one is the
acidic sites and another is on the transition metals
with vacant orbits which can accept electrons. The
great increase of DBT adsorption on sulfide state catalysts may be the result of newly produced active sites
(edges of active phases) in the sulfide state catalysts
compared with oxide state catalysts.
98
Hongyan Shang et al./ Journal of Natural Gas Chemistry Vol. 13 No. 2 2004
of DBT (mg/g)
MWCNT
2.47
53.56
AC
3.13
67.91
-Al2 O3
2.01
43.59
20.1
CoMoO/MWCNT
2.15
46.69
28.5
CoMoO/AC
7.81
169.63
19.7
Sample
28.2
6.75
CoMoO/-Al2 O3
1.71
37.08
21.2
CoMoS/MWCNT
4.97
107.92
100.8
CoMoS/AC
8.11
176.18
19.1
CoMoS/-Al2 O3
6.91
150.22
77.8
a Calculated specific surface area of adsorbed DBT molecules (m2 /g) / specific surface area of catalysts or supports(m2 /g)
The band at around 3384 cm1 may be the stretching vibration of coordinated surface hydroxyl OH,
a significant shift from the region 36403610 cm1 ,
indicating that at least part of DBT molecules interact with surface OH via H-bonding. In addition, the
absence of bands in the region 30002800 cm1 (2969
and 2933 cm1 , typical vibrations of aliphatic methyl
and methylene groups) indicates that DBT decomposition does not take place under out-gassing at 373
99
100
Hongyan Shang et al./ Journal of Natural Gas Chemistry Vol. 13 No. 2 2004
30002800 cm1 representing methyl and/or methylene groups are not found in all the nine samples, it
is thus concluded that the chemically adsorbed DBT
aromatic molecules undergo no decomposition when
out-gassing at 373 K for all the samples studied.
(3) Based on the fact that the absence of shift
of the band at 739 cm1 (out-of-plane deformation
mode of DBT aromatic molecules), it is suggested
that DBT molecules mainly stand upright on the
surface of CoMoS/MWCNT catalyst. Significant
shift from 739 to 731 cm1 for MWCNT and 737
cm1 for CoMoO/MWCNT indicate that DBT aromatic molecules mainly lie flat on MWCNT and CoMoO/MWCNT. The slight shift of a band from 739
cm1 to 740 cm1 indicates that DBT molecules
mainly stand upright on the surface of CoMoS/AC,
and that at least a small portion of DBT molecules
lie flat on the surface of CoMoS/AC. The slight shift
from 739 to 737 cm1 for CoMoO/AC suggests that
a portion of DBT molecules possibly lie flat on the
surface, and the rest stands upright on the surface of
CoMoO/AC.
Acknowledgements
The Nano-Material Research Center of Tsinghua
University is gratefully acknowledged for supplying us
with different kinds of carbon nanotubes with high
quality.
References
Figure 7. IR spectra of the adsorbed species arising from contact of DBT molecules with
-Al2 O3 and supported catalysts
(1) -Al2 O3 , (2) CoMoO/-Al2 O3 , (3) CoMoS/-Al2 O3
4. Conclusions
(1) Sulfide state CoMoS/MWCNT, CoMoS/AC
and CoMoS/-Al2O3 catalysts adsorb much more
DBT molecules than their corresponding oxide state
catalyst, as well as the corresponding supports. AC
has the strongest adsorption ability to DBT molecules
among MWCNT, AC and -Al2 O3 support.
(2) Based on fact that vibrations in the region