ORI GI NAL PAPER

HDS of DBT with Molybdenum Disulde Catalysts Prepared

by In Situ Decomposition of Alkyltrimethylammonium
Thiomolybdates
R. Romero-Rivera

A. G. Camacho

M. Del Valle

G. Alonso

S. Fuentes

J. Cruz-Reyes
Published online: 2 April 2011
Springer Science+Business Media, LLC 2011
Abstract Three alkyltrimethylammonium thiomolyb-
dates, [RN(CH
3
)
3
]
2
MoS
4
(where R = lauryl, myristyl or
cetyl) were synthesized in aqueous solution, and character-
ized by
1
H-NMR spectroscopy. These alkyltrimethylam-
monium thiomolybdates were used (the lauryl and myristyl
thiomolybdates for the rst time) as precursors for in situ
prepared MoS
2
catalysts, activated during the hydrodesul-
furization of dibenzothiophene. The catalysts were analyzed
by EDX, showing large voids and a S/Mo ratio around 2.
High surface areas up to 443 m
2
/g and type IV adsorption
desorption nitrogen isotherms were obtained. X-ray dif-
fraction showed that the catalysts are poorly crystalline, with
a very weak (002) peak intensity for all samples except the
MoS
2
catalyst prepared from pure ammonium tetrathiomo-
lybdate precursor. A high dibenzothiophene conversion
(74%) was observed with the catalyst obtained from the
lauryltrimethylammonium thiomolybdate precursor, attrib-
uted mainly to its high specic surface area. Selectivity
results showed that all the prepared catalysts strongly
favored the hydrogenation pathway.
Keywords Molybdenum disulde HDS of DBT
Tetraalkylammonium thiomolybdates
1 Introduction
The use of transition metal sulde (TMS) catalysts in oil
renery hydrotreating has helped reduce the toxic SOx and
NOx atmospheric emissions of internal combustion engines
for several decades. Hydrotreating involves a variety of
reactions, among them, hydrodesulfurization (HDS), hyd-
rodenitrogenation, hydrodeoxygenation, and hydrogenation
[14].
Several methods have been used to prepare sulde cat-
alysts: suldation of coprecipitated oxides [5, 6] coma-
ceration [7, 8], homogeneous sulde precipitation [9],
ceramic method [10], impregnated thiosalt decomposition
[11], all of which yield compounds with surface areas in
the order of 550 m
2
/g.
Tetraalkylammonium thiometallates have been synthe-
sized by the metathesis reaction between ammonium
tetrathiomolybdate (ATTM) with tetraalkylammonium
chlorides [12] or tetraalkylammonium hydroxides using
acetonitrile as solvent [13]. Transition metal sulde pre-
cursors (NR
4
)
2
MS
4
, where R = H, CH
3
, or C
4
H
9
(butyl)
and M = Mo or W, have been prepared by reacting
ammonium tetrathiomolybdate with the corresponding
tetraalkylammonium bromide in an aqueous medium, fol-
lowed by in situ decomposition [14, 15].
The in situ decomposition of tetraalkylammonium
thiomolybdates yields unsupported (bulk) molybdenum
sulde catalysts with high surface area and improved cat-
alytic properties in the HDS of dibenzothiophene (DBT),
which has been associated with the presence of carbon
in substitution of sulfur atoms, generating systems like
MoS
2-x
C
y
(0 \y \1) [16]. In the synthesis of ruthenium
suldes, carbon content has also been observed according
to the formula: RuS
2-x
C
x
[17, 18]. After suldation, both
Ru and Mo sulde catalysts present excess sulfur, MS
2?x
R. Romero-Rivera A. G. Camacho M. Del Valle
J. Cruz-Reyes (&)
Facultad de Ciencias Qu micas e Ingenier a, Universidad
Autonoma de Baja California, Tijuana, B.C, Mexico
e-mail: [email protected]
G. Alonso S. Fuentes
Centro de Nanociencias y Nanotecnolog a, Universidad
Nacional Autonoma de Mexico, Ensenada, B.C, Mexico
1 3
Top Catal (2011) 54:561567
DOI 10.1007/s11244-011-9620-2
(0 \x \0.5) [16], and have been found to yield a greater
carbon content MoS
2-x
C
x
after HDS in organic solvents
[19]. Researchers have also found that metal suldes sup-
ported on carbon show a much greater activity than the
same suldes when supported in alumina [20, 21].
This work studies the properties of MoS
2
catalysts
obtained from the in situ decomposition of two new
alkyltrimethylthiomolybdates: [RN(CH
3
)
3
]
2
MoS
4
lauryl-
trimethylammonium thiomolybdate (LTAT) and myristyl-
trimethylammonium thiomolybdate (MTAT), with R
groups containing 12 and 14 carbon atoms, respec-
tively. ATTM and cetyltrimethylammonium thiomolybdate
(CTAT), with the later containing R = 16 carbon atoms,
were used as references. Catalytic activity was tested for
the model dibenzothiophene hydrodesulfurization.
2 Experimental
2.1 Preparation of Ammonium
Tetrathiomolybdate(ATTM)
(NH
4
)
2
MoS
4
, was prepared according to the method
described by G. Berhault et al. [22] which requires adding
(NH
4
)
2
S, 42.5% in aqueous solution to (NH
4
)
6
[Mo
7
O
24
]
4

4H
2
O diluted in a minimum amount of water to produce a
dark red crystalline precipitate.
2.2 Preparation of Lauryltrimethyl-, Myristyltrimethyl-,
and Cetyltrimethyl-ammonium
Tetrathiomolybdate
Freshly prepared (NH
4
)
2
MoS
4
(1.62 g, 6.22 mmol) was
dissolved in water (50 mL) with stirring. An aqueous
solution (12.44 mmol in 50 mL water) of R(CH
3
)
3
NX,
where R = lauryl (dodecyl), myristyl (tetradecyl), cetyl
(hexadecyl) was then added and the mixture stirred for 1 h
at room temperature. The resulting precipitate was isolated
by vacuum ltration, washed rst with cold water and then
with isopropyl alcohol. The solid was dried at room tem-
perature and kept under N
2
atmosphere.
2.3 Characterization of Samples
1
H-NMR spectra were recorded in DMSO-d
6
solutions
using a Gemini 200 Varian spectrometer, and were refer-
enced to SiMe
4
(
1
H).
Specic surface areas were measured with a Quanta-
chrome AUTOSORB-1 by N
2
absorption at 77 K, using the
BET isotherm and a sample mass of 0.20.3 g. Samples
were degassed under owing argon at 473 K for 2 h before
N
2
adsorption. The pore size distribution was obtained
from the desorption data, following the BJH method. The
mean standard deviation for the surface area measurements
was about 2%.
The X-ray diffraction patterns of the prepared samples
were obtained with a Philips X
0
Pert analytical diffractom-
eter for powder samples using Cu Ka radiation. Their
phases were identied with reference to the data base of the
International Centre for Diffraction Data.
A Jeol JSM5800 IV scanning electron microscope was
used to perform morphology and EDX elemental analysis.
Several elds were analyzed at different magnications in
order to recognize the prevalent features. EDX analysis
were performed with an eBX-ZAF system, using an MoS
2
reference sample to deconvolute the L lines of S and Mo.
All the catalyst samples were separated from the reaction
mixture by ltration, washed with isopropyl alcohol to
remove residual hydrocarbons, and dried in air at room
temperature before EDX analysis.
Transmission electron microscopy was done on a Philips
FEG TECNAI F20 transmission electron microscope
operated at 200 kV.
2.4 Catalytic Activity and Selectivity
The HDS of DBT was tested in a high pressure 300 mL
Parr reactor by placing 4.4 g DBT, 100 mL of decalin
and the calculated amount of precursor needed to pro-
duce 0.68 g of catalyst. The reactor was purged of
residual air, pressurized with H
2
to 3.1 MPa (450 psi)
and then heated to the reaction temperature of 623 K in
about 10 min. A stirring rate of 600 rpm was used. The
advance of the reaction was monitored by gas chroma-
tography with a HP 6890 gas chromatograph, using
samples taken every 20 min during the rst hour, then
every 30 min for the next 4 h. Reduction of sample
volume due to sampling was B5% of total volume. The
identity of the reaction products was conrmed by mass
spectrometry with a HP 6890 GCMS, using a HP-5MS
capillary column (30 m 9 0.25 mm 9 0.25 lm). Cata-
lytic activity was expressed in terms of % conversion of
DBT versus reaction time, and from these data, the
reaction rates were calculated for each catalyst. The
mean standard deviation for catalytic measurements was
about 2.5%.
The HDS of DBT yields biphenyl (BP) through the
direct desulfurization pathway (DDS), and cyclohexyl-
benzene (CHB) and tetrahydrodibenzothiophene (THDBT)
through the hydrogenation pathway (HYD). Since these
two pathways are parallel [23], the selectivity (HYD)/
(DDS) was calculated by the equation:
HYD=DDS CHB THDBT = BP
562 Top Catal (2011) 54:561567
1 3
.
3 Results and Discussion
3.1 Precursor Characterization by
1
H-NMR
The synthesis of the three alkyltrimethylammonium thio-
molybdates used as MoS
2
catalyst precursors involves the
reaction in aqueous solution of (NH
4
)
2
MoS
4
(ATTM) with
stoichiometric amounts of the corresponding alkyltryme-
thylammonium halide, according to the metathesis reac-
tion 1
NH
4

2
MoS
4
2 R N CH
3

3
X
! R N CH
3

3

2
MoS
4
2 NH
4
X 1
where R = lauryl, myristyl and cetyl
The
1
H-NMR spectra (Fig. 1ac) for the resulting
lauryltrimethylammonium thiomolybdate (LTAT), myr-
istyltrimethylammonium thiomolybdate (MTAT), and
cetyltrimethylammonium thiomolybdate (CTAT) showed
signals associated with ve different groups of protons that
are present in their chemical structures. Figure 1a shows the
NMR spectrum for LTAT, where the broad singlet at
3.42 ppm is assigned to 18 protons in the (CH
3
)
3
N groups;
the singlet at 3.14 ppm (J = 7.4 MHz), to 4 protons in the
CH
2
N groups; the signal at 1.74 ppm, to 4 protons in the
CH
2
groups in beta position from the N atom; the broad
singlet at 1.36 ppm, to 36 protons attributed to the follow-
ing CH
2
groups in the alkyl chain. The triplet at 0.96 ppm
(J = 7 Hz), is assigned to 6 protons belonging to the CH
3
groups located at the end of the C12 hydrocarbon chain. The
interpretation of the NMR spectra of MTAT and CTAT,
shown in Fig. 1b, c respectively, was analogous to that of
the NMR spectrum of LTAT. The
1
H-NMR data for the
three synthesized thiomolybdates is found in Table 1.
3.2 Catalyst Characterization
3.2.1 X-ray Diffraction
The diffraction patterns of the prepared MoS
2
catalysts are
compared in Fig. 2. While the samples obtained by in situ
decomposition are all microcrystalline, the pattern for the
MSH sample, Fig. 2a, is composed of several broad
peaks, corresponding to the (002), (100), (103), (110) and
(008) reections reported for the structure of poorly crys-
talline MoS
2
2H [2426]. The broad peaks indicate a
microcrystalline, nearly amorphous material. However, the
peak at 2h = 14 corresponds to the well dened (002)
reection of MoS
2
2H, which implies a signicant amount
of basal layer stacking in the c direction of the catalyst
particles. The reections corresponding to the (100) and
(103) planes are less intense than in MoS
2
2H crystals. The
asymmetric form of the (100) family is a characteristic of
random layered structures [26].
The XRD patterns shown in Fig. 2bd correspond to the
MoS
2
catalysts MSC12, MSC14, and MSC16, prepared
by in situ decomposition of LTAT, MTAT and CTAT
precursors. Analysis of these patterns identies the (002),
(100), (103), and (110) reections of MoS
2
2H. The low
intensity of the (002) reection suggests high dispersion
due to crystallites of only a few atomic layers, attributed to
the presence of carbon derived from the decomposition of
the organic solvent decalin and the carbon containing
precursors, in a way analogous to the high dispersion of
MoS
2
reported by others for carbon-supported MoS
2
cat-
alysts [20, 21]. Similar XRD patterns have been obtained
for chemically exfoliated MoS
2
and WS
2
catalysts [27, 28].
3.2.2 Elemental Analysis
The EDX analysis for all the in situ prepared molybdenum
disulde catalysts are reported in Table 2. The S/Mo
atomic ratio for all samples is around two (1.972.40),
which is consistent with a MoS
2
phase. High amounts of
carbon (3.80 B C/Mo B 6.50) are found in all the MoS
2
catalysts. The prime source of this carbon is most probably
the decalin solvent [29], especially in the case of the
catalyst prepared from ATTM, since it contains no carbon;
the greater carbon content of the MSC14 and MSC16
catalysts is thought to derive from the availability of the
precursors alkyl chains [15].
3.2.3 Surface Area and Pore Size Distribution
Table 2 lists the specic surface areas and total pore vol-
umes for MoS
2
catalysts produced by in situ decomposition
of the precursor series. All four catalysts present high
surface areas: the lowest surface area is 79 m
2
/g for the
MSC14 catalyst derived from MTAT, and the highest is
443 m
2
/g for MSC12, obtained from LTAT.
According to Table 2, the carbon content of the MoS
2
precursors has an important effect on the surface area and
the total pore volume of the catalysts. MoS
2
catalysts MS
C16 and MSC12 show surface areas 1.44.2 times greater
than that of MSH (104 m
2
/g) obtained from pure ATTM,
while total pore volume is 2.25.3 times greater than that of
MSH (0.09 cm
3
/g). Similar pore volume distributions,
centered on different pore sizes have been reported for
MoS
2
catalysts obtained from other alkyl-thiosalts [30].
The adsorption isotherms and pore volume distributions
for the prepared catalysts are shown in Figs. 3, 4, respec-
tively. All catalysts exhibit a Type IV isotherm with
desorption curves characteristic of mesoporous materials.
The MSH catalyst prepared from pure ATTM has a
poorly developed porous system. The MSC12, MSC14,
and MSC16 catalysts obtained from carbon-containing
precursors have better developed porous systems, with an
Top Catal (2011) 54:561567 563
1 3
average pore diameter of around 36 A

(Fig. 4). The hys-

teresis loop of MSC14 appears to be less developed and
has a narrower pore size distribution than MSC12 and
MSC16. The MSC12 catalyst has the widest hysteresis
loop and broadest pore size distribution. The hysteresis
loops shown by these catalysts correspond mainly to
cylindrical pores open at both ends [31].
3.2.4 Scanning Electron Microscopy
SEM micrographs for the in situ prepared MoS
2
catalysts
are reported in Fig. 5. Relatively few cavities are observed
in MSH, while the rest of the catalysts appear to be more
porous, with some cavities probably resulting from the
elimination of hydrocarbon gases from the alkylammonium
precursors during the course of the in situ decomposition
process.
3.3 Catalytic Activity and Selectivity
Previous HDS studies of MoS
2
catalysts obtained from
ATTM and CTAT using DBT as the parent molecule have
reported the presence of tetrahydrodibenzothiophene
(THDBT), biphenyl (BP), cyclohexylbenzene (CHB), and
dicyclohexyl (DCH) [3236] in the reaction mixture. In
this work, analysis of the reaction products for all in
Fig. 1 a
1
H-NMR of precursor lauryltrimethylammonium thiomolybdate (LTAT). b
1
H-NMR of precursor myristyltrimethylammonium
thiomolybdate (MTAT). c
1
H-NMR of precursor cetyltrimethylammonium thiomolybdate (CTAT)
Table 1
1
H-NMR data for the synthesized MoS
2
catalyst precursors
Precursor
1
H-NMR (d ppm, DMSO-d
6
)
LTAT 3.42 (s, 18H, (CH
3
)
3
N), 3.14 (s, 4H, CH
2
N), 1.74 (s, 4H, CH
2
CH
2
N) 1.36 (bs, 36H, (CH
2
)
9
CH
2
CH
2
N), 0.96 (t, 6H, CH
3
termini).
MTAT 3.42 (s, 18H, (CH
3
)
3
N), 3.13 (s, 4H, CH
2
N), 1.74 (s, 4H, CH
2
CH
2
N) 1.36 (bs, 44H, (CH
2
)
9
CH
2
CH
2
N), 0.96 (t, 6H, CH
3
termini).
CTAT 3.42 (s, 18H, (CH
3
)
3
N), 3.13 (s, 4H, CH
2
N), 1.74 (s, 4H, CH
2
CH
2
N), 1.36 (bs, 52H, (CH
2
)
9
CH
2
CH
2
N), 0.96 (t, 6H, CH
3
termini).
564 Top Catal (2011) 54:561567
1 3
situ-prepared catalysts also nds signicant amounts
of cyclohexylcyclopentylmethane (CHCPM), a reaction
product which is reported here for the rst time. The
identity of CHCPM (MW = 166) was conrmed by GC
MS analysis by comparison with the mass spectra NIST
library, obtaining a quality match (Q = 95). Recently,
CHCPM has been observed during the hydrodenitrogen-
ation (HDN) of carbazole with Mo and W carbides as cat-
alysts [37]. The CHCPM and DCH products may derive
from the cyclohexyl cyclohexene (CHCHE) intermediate.
While the formation of CHCPM would occur by rear-
rangement of CHCHE and further hydrogenation of the
resulting cyclohexyl-cyclopentene (CHCPE), hydrogena-
tion of CHCHE would yield dicyclohexyl (DCH), as shown
in Fig. 6.
Analysis of the kinetic data by the integration method
for the HDS of DBT using the prepared catalysts nds that
the HDS reaction closely follows a pseudo-rst order rate
law during the 5 h reaction time. The GC analysis of HDS
reaction products, HYD/DDS selectivity and kinetic data
for the prepared MoS
2
catalysts are listed in Table 3.
Reaction rate constants are over two orders of magnitude
greater than the k = 1.5 9 10
-8
mol s
-1
g
-1
reported by
Luis et al. [38] and over two to four times greater than the
k = 6 9 10
-7
mol s
-1
g
-1
reported by Camacho-Bragado
et al. [39] for MoS
2
catalysts under similar reaction con-
ditions; also around one order of magnitude greater than
the k = 2.1 9 10
-7
mol s
-1
g
-1
reported by Berhault
et al. [40] for MoS
2
/Al
2
O
3
catalysts, also under similar
reaction conditions. The HYD/DDS ratios (3.08.2) are
also considerably greater than those of other unsupported
MoS
2
catalysts (0.41.8) and CoMo catalysts (0.10.6)
[30, 39].
The DBT conversions after 5 h for the MSH and MS
C16 catalysts are nearly the same (57.4 and 54.5, respec-
tively), which means that the precursor consisting of CTAT,
compared to ATTM, does not give a higher activity MoS
2
catalyst. In contrast, conversions of up to 74% are found for
MoS
2
catalysts MSC12 and MSC14 obtained from pre-
cursors LTAT and MTAT, respectively. According to the
data in Table 3, the reaction rate ratios with respect to the
MSH reference catalyst reaction are k
MSC16
/k
MSH
=
0.94, k
MSC14
/k
MSH
= 0.83, and k
MSC12
/k
MSH
= 1.35.
This increase in the reaction rate for the MSC12 catalyst is
Fig. 2 XRD patterns of the in situ prepared MoS
2
catalysts: (a) MS
H; (b) MSC12; (c) MSC14, and (d) MSC16
Table 2 Specic surface area, total pore volume and atomic ratios
determined by EDX elemental analysis for the in situ prepared MoS
2
catalysts
Catalyst Surface
area (m
2
/g)
Total pore
volume (cm
3
/g)
S/Mo C/Mo
MSH 104 0.09 2.06 4.10
MSC12 443 0.48 1.97 3.80
MSC14 149 0.38 2.40 5.04
MSC16 79 0.20 2.20 6.50
Fig. 3 Adsorption-desorption isotherms of the in situ prepared MoS
2
catalysts: (a) MSH, (b) MSC12, (c) MSC14, and (d) MSC16
Fig. 4 BJH pore size distribution of the in situ prepared MoS
2
catalysts: (a) MSH, (b) MSC12, (c) MSC14, and (d) MSC16
Top Catal (2011) 54:561567 565
1 3
attributed to a better dispersion of the catalyst, induced by
the presence of carbon and perhaps organic matter derived
from the in situ decomposition of the LTAT precursor,
while the MTAT and CTAT precursors may generate
enough surface carbon in the MSC14 and MSC16 cata-
lysts to counter the increased activity of the catalysts. Some
authors have reported that amorphous carbon resulting from
the decomposition of carbon-containing precursors during
the HDS of DBT affected both the activity and selectivity of
the catalysts [19, 41, 42].
According to the rim-edge model developed by Daage
and Chianelli [34], the high catalytic activity of MSC12 is
due to a greater amount of active rim and edge sites in the
catalyst crystallites. All the prepared MoS
2
catalysts show
a greater selectivity toward hydrogenation (HYD) during
the HDS of DBT, as observed in Table 3, which is attrib-
uted to the prevalence of rim sites over edge sites. The rim-
edge model explains selectivity in terms of the ratio
between rim and edge sites: rim sites are active for both
hydrogenation and CS breaking reactions, while edge
sites are only active for CS rupture.
4 Conclusions
Two new MoS
2
catalyst precursors, LTAT and MTAT,
containing a long hydrocarbon chain with 12 and 14 carbon
atoms respectively are synthesized. These thiomolybdates
Fig. 5 SEM micrographs of the
in situ prepared MoS
2
catalysts:
a MSH; b MSC12; c MS
C14 y d MSC16
Fig. 6 Reaction pathway for the MoS
2
-catalyzed HDS of DBT
566 Top Catal (2011) 54:561567
1 3
are decomposed in situ during the HDS of DBT, producing
catalytic materials with high specic surface areas and high
catalytic activities. XRD patterns for the prepared catalysts
showed broad peaks and weak (002) reections. The
highest DBT % conversions and surface areas are observed
for the MSC12 catalyst prepared from LTAT precursor,
74% and 443 m
2
/g, respectively. Selectivity results showed
that all the prepared catalysts strongly favored the HYD
pathway. Cyclohexylcyclopenthylmethane (CHCPM) is
identied as a reaction product of the MoS
2
-catalyzed HDS
of DBT for the rst time.
Ackowledgements We gratefully acknowledge the technical assis-
tance of Carlos Ornelas and Francisco Paraguay (CIMAV), as well as
that of Elo sa Aparicio Ceja (UNAM). We also acknowledge the
support of CONACYT under Grants No. 55490 and 58280-Y.
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Table 3 Gas chromatography analysis of HDS reaction products, HYD/DDS selectivity and kinetic data for the prepared MoS
2
catalysts
Catalyst CHCPM (%) DCH (%) PCH (%) BP (%) THDBT (%) DBT (%) DBT conversion (%) [HYD]
[DDS]
k 9 10
6
(mol s
-1
g
-1
)
MSH 11.47 10.87 11.50 7.31 16.42 42.64 57.36 3.8 1.9
MSC12 20.00 21.1 18.0 8.16 6.75 26.00 74.0 3.0 2.6
MSC14 9.79 9.16 35.77 5.51 9.04 30.32 69.68 8.2 1.6
MSC16 10.65 9.82 13.17 7.72 13.15 45.46 54.54 3.4 1.8
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