Applied Catalysis A: General 319 (2007) 2537

www.elsevier.com/locate/apcata

HDS, HDN, HDA, and hydrocracking of model compounds

over Mo-Ni catalysts with various acidities
Lianhui Ding a, Ying Zheng a,*, Zisheng Zhang b,*, Zbigniew Ring c, Jinwen Chen c
a
Department of Chemical Engineering, University of New Brunswick, 15 Dineen Drive, P.O. Box 4400, Fredericton, NB E3B 5A3, Canada
b
Department of Chemical Engineering, University of Ottawa, Ottawa, Ont. K1N 6N5, Canada
c
National Centre for Upgrading Technology, 1 Oil Patch Drive, Suite A202, Devon, Alta. T9G 1A8, Canada
Received 8 June 2006; received in revised form 4 October 2006; accepted 11 November 2006
Available online 14 December 2006

Abstract
The hydrogenation and hydrocracking performances of a series of MoNi/Al2O3 catalysts were evaluated with 4,6-dimethyl dibenzothiophene
(4,6-DMDBT), 1-methylnaphthalene, pyridine, and hexadecane as model compounds. Different materials which involved amorphous silica
alumina, and hydrothermally treated zeolite beta and zeolite Y were introduced as part of the catalyst supports. The catalysts were characterized by
BET, NH3 temperature programmed desorption (NH3-TPD), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission
electron microscopy (TEM). The addition of zeolites in the catalysts could greatly improve the hydrodesulfurization and hydrodenitrogenation
activities, but it had have little enhancement in the hydroconversion of 1-methylnaphalene. The comparison among zeolite beta containing catalysts
with various zeolite content (520 wt%) indicated that the optimum hydrogenation activity was achieved by the catalyst containing 10 wt% zeolite
beta. A considerable amount of hexadecane was hydrocracked on zeolite containing catalysts. The hydrocracking of hexadecane proportionally
increased with the zeolite content. Zeolite Y appeared to be more effective in enhancing the hydrotreating activity than zeolite beta. The high
hydrogen pressure not only considerably increased hydrodearomatization activity, but also greatly suppressed the cracking of hexadecane in the
feed.
# 2006 Elsevier B.V. All rights reserved.

Keywords: HDS; HDN; Zeolite beta; Hydrocracking; Mo-Ni; Zeolite Y

1. Introduction
The demand for diesel fuel is annually increasing and the
yield of the straight-run diesel fraction is decreasing due to the
yearly deterioration of crude oil quality in terms of increased
sulfur content and decreased API gravity [1]. On the other hand,
more stringent diesel fuel specifications are being phased in.
Therefore, refining industries are facing a major challenge to
meet the more stringent specifications of diesel fuel, and to
keep up with demand by producing more diesel product from
feedstocks of lower quality. As the demand for diesel fuel
increases, some of the low quality streams have to be upgraded
before blending into the diesel pool. One such low quality
* Corresponding authors.
E-mail addresses: yzheng@unb.ca (Y. Zheng), zzhang@uottawa.ca
(Z. Zhang).
0926-860X/$ see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2006.11.016
stream is light cycle oil (LCO), from fluid catalytic cracking
(FCC), which is becoming an important source to the diesel
pool. LCO is characterized by high sulfur, nitrogen, and
polyaromatics contents, and is most difficult to be converted.
LCO has historically been used as a blend-stock into heavy fuel
oil for viscosity adjustment. This opportunity is also becoming
constrained by declining demand for heavy fuel oil. The
addition of more LCO dramatically increases the contents of
sulfur and aromatics species in feed, which requires that the
hydrodesulfurization (HDS) and hydrodearomatization (HDA)
activities should simultaneously be enhanced. Meanwhile, the
hydrocracking reaction should be reduced to a minimum to
achieve a high diesel yield and a low hydrogen consumption.
Currently, the new diesel sulfur regulations require that the
sulfur content is reduced to lower than 15 ppmw [2]. Such low
sulfur content cannot be readily achieved by using conven-
tional hydrogenation catalysts and processes, because most
of the remaining sulfur species after the conventional
26 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537
hydroprocessing treatment, 4,6-substitued dibenzothiophenes
(DBTs) [3], are very difficult to be converted by hydrogenation
or hydrogenolysis, due to the steric hindrance of substituting
groups in the 4,6-position of DBT molecules [46]. However,
HDS activity of 4,6-substitued DBT can be greatly improved
by the hydroisomerization which shifts one substitutent group
from the 4 or 6-position to the 3 or 7-position, or by the
complete removal of one or both methyl groups through a
dealkylation reaction [7]. Hence, the steric hindrance can be
relieved and HDS reactions take place more easily or
completely [8]. The conventional HDS process is usually
conducted over sulfided CoMo/Al2O3 or NiMo/Al2O3 cata-
lysts. CoMo catalysts show excellent HDS activity but they are
less active for hydrodenitrogenation (HDN) and HDA than
MoNi and WNi catalysts. The hydroisomerization and
dealkylation activities of a catalyst can be imparted by the
addition of acidic component zeolites in catalysts [9]. Bej et al.
[10] gave an excellent review concerning the approaches to
increase acidity and all the acidic components already studied.
Among all the acidic components available, acidic zeolites are
demonstrated to be the most effective. Yumoto et al. [11] found
that the addition of less than 10% zeolite (no type was
mentioned in the literature) in a MoCo supported on Al2O3
catalyst can increase HDS activity by 40% compared with
conventional MoCo/Al2O3 when evaluating with straight run
gas oil (sulfur content 1.38 wt%). The lower the sulfur content
the product had, the more pronounced the difference of HDS
activity became. They attributed the discrepancy to the
promotion of the hydrogenation rate by the acidity from the
zeolite, and easier adsorption of the DBT ring with the electronic
effect from the proton of the zeolite. Kunisada et al. [12] reported
that an aluminazeolite-supported NiMo catalyst showed very
high HDS activity for refractory sulfur species even at 1.67% H2S
in H2. Furthermore, zeolite as a strong acidic support appeared to
enhance the liberation of hydrogen sulfide from the sulfided
catalyst through weakening the metal and sulfur bond. This
function gave the catalyst high tolerance against H2S. The
authors attributed the high HDS of zeolite containing catalysts to
four main reasons: (1) the hydrogenation activity of the
neighboring phenyl ring in the refractory sulfur species can be
enhanced by acidity, (2) the isomerization and transalkylation
can be promoted by the acidity in the zeolite, (3) the acidity can
increase the resistivity against H2S, and (4) the acidity can
improve HDN. With decalin and tetralin as probe molecules for
cracking and hytrotreating the LCO, Corma et al. [13] compared
a set of zeolites with medium sized, large sized (USY and beta),
and ultralarge pores, as well as a mesoporous MCM-41, and
demonstrated that pore size, topology, and the acidity of the
zeolites had a strong influence on diffusion, activity, and
selectivity in reactions such as ring opening, dealkylation,
transalkylation, hydrogen transfer, and coke formation. Accord-
ing to their results, zeolite Y and beta were believed to be most
suitable zeolite in hydrotreating LCO because of their
appropriate pore structures and acidities. Along with the
enhancement of HDS, the addition of zeolites can also
appreciably improve the HDN and HDA activities of the
catalysts [11], which is desirable in hydrotreating LCO.
Although considerable enhancement in HDS, HDN, and
HDA activities can be achieved through adding various types of
zeolites to alumina containing catalysts, too strong acidity of
zeolite can simultaneously accelerate the cracking of paraffin
substances. Subsequently, the diesel yield is significantly
reduced; the hydrogen consumption is greatly increased, and
the catalyst deactivation becomes faster. Hence, the practical
target of the zeolite support research for LCO hydroupgrading
is to reduce the deactivation and cracking activity while
maintaining high HDS activity. Meanwhile, high aromatic
content in distillate fuel makes the reduction of the aromatic
content along with the sulfur content generally desirable with
respect to diesel fuel quality, as the aromatic reduction can
increase cetane levels and greatly improve combustion
characteristics. Thus, the best catalyst for deep HDS should
be able to simultaneously enhance the hydrosaturation and ring
opening of polyaromatics. The development of such catalysts
will partly depend on the extensive studies concerning the
effect of sulfur, aromatics, and nitrogen compounds on one
another. It is also very important to study the impact of the
zeolite addition on the cracking, along with HDS, HDN, and
HDA.
Numerous studies have been conducted to investigate HDS
reaction, the reaction mechanism on various acidic zeolite
containing catalysts, or the effect of nitrogen and aromatics on
the HDS. However, few studies focus on the hydrocracking
of paraffins on the catalysts with various acidities, and the effect
of HDS and HDN on HDA. The hydrogenation mechanism of
aromatics in the presence of sulfur and nitrogen compounds on
acidic catalysts has also been less emphasized. Therefore, the
main aim of the present study is to investigate the hydrocracking
of paraffin in the presence of sulfur, nitrogen, and aromatics
compounds, and the effect of sulfur and nitrogen species on HDA
activities on MoNi sulfided catalysts supported on various acidic
components, and the zeolite beta containing catalysts with
various zeolite content.
2. Experimental
2.1. Catalyst preparation
NH4-beta (Zeolyst CP814E) was calcinated at 813 K for
10 h, and then treated under 0.2 MPa self-steam pressure in
an autoclave at 873 K for 2 h. The pore volume and surface area
of the hydrothermally treated zeolite beta were 0.36 ml/g and
636 m2/g, respectively.
The hydrothermally treated zeolite Y was prepared by
treating NH4NaY (Zeolyst CBV-300) under self-steaming
conditions in an autoclave at 823 K and 0.1 MPa for 1 h,
followed twice by ammonia exchange with 1.0 M NH4Cl
aqueous solution at 363368 K, and then dried at 383 K
overnight. The pore volume and surface area of the
hydrothermally treated zeolite Y were 0.32 ml/g and 704 m2/g.
Amorphous silicaalumina was synthesized using the
precipitation method. Ammonia aqueous solution and water
glass (Na2SiO4 solution) were added to AlCl3 aqueous solution
in sequence. The mixture was then neutralized to pH 89,
 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537
washed, and dried in an oven at 383 K overnight. The pore
volume and surface area of the as-synthesized amorphous
silicaalumina were 0.56 ml/g and 190 m2/g, respectively.
The above hydrothermally treated zeolite beta (5, 10, and
20 wt%), zeolite Y (10 wt%), and amorphous silicaalumina
(10 wt%) mixed with alumina (Sasol PURALOX TH100/150,
pore volume 0.96 ml/g, surface area 202 m2/g), MoO3, nickel
nitrate hexahydrate, and binder (patially acid-peptized alumina,
SASOL, CAPAPAL B), extruded to form extrudate in a
cylindrical shape, dried at 383 K overnight, and then calcined in
air at 773 K for 4 h. The catalysts were named as MoNi/
Beta(5), MoNi/Beta(10), MoNi/Beta(20), MoNi/Y(10), and
MoNi/SiAl(10), respectively. The number in the parentheses
is the zeolite content in the catalyst. Using the same preparation
procedure mentioned above, MoNi/Al2O3 was synthesized by
only mixing the aforementioned alumina, MoO3, nickel nitrate
hexahydrate, and binder. The nominal contents of MoO3 and
NiO in all catalysts were 15 and 5 wt%, respectively.
2.2. Catalyst characterization
2.2.1. NH3 temperature programmed desorption (NH3-
TPD)
0.5 g of 3040 mesh sample was loaded into a 5 ml tubular
reactor, and then purged for 2 h with 40 ml/min helium at 773 K
(increased from ambient temperature to 773 K at 5 K/min),
followed by lowering temperature to 353 K. Gaseous ammonia
(50 ml/min) mixed with helium (40 ml/min) was charged for
30 min at 353 K, and then purged with 40 ml/min He at 373 K
for 1 h. Under the 40 ml/min of helium, the temperature was
raised from 373 to 883 K at 15 K/min, and the desorbed
ammonia was analyzed by mass spectrometer.
2.2.2. Powder X-ray diffraction (XRD)
The crystallinity and phase purity of solid products were
characterized by using Bruker AXS D8 ADVANCE (Cu Ka
radiation provided by a graphite monochromator).
2.2.3. Transmission electron microscopy (TEM)
TEM was performed on a JEOL 2010 STEM, operated at
200 keV. Samples were prepared by the drop method. A small
amount of sulfided catalyst powder was sonicated in 100%
ethanol. One drop was removed with a micropipette and
dropped onto a copper (or nickel) support grid. The sample was
then lightly coated with carbon to reduce charging in the TEM.
The experimental error for the particle size was 3 nm.
2.2.4. X-ray photoelectron spectroscopy (XPS)
XPS spectra of the samples were taken in a VG Microtech
MultiLab ESCA 2000 system with a CLAM4 hemispherical
analyzer. The hemispherical analyzer consists of an analysis
chamber for taking the XPS spectra, which was operated under
a vacuum of lower than 4  1010 mbar, and a fast entry air
lock for sample introduction. The source was non-mono-
chromatized Mg Ka X-rays at 1253.6 eV (15 kV, 20 mA). In
order to sample a deeper depth, photoelectron detection
perpendicular to the sample surface was chosen. The high
27
resolution C 1s spectrum of the adventitious hydrocarbon (at
284.5 eV) on the sample surfaces were recorded before and
after each measurement and used as a reference for charge
correction. Quantitative information of surface composition
was obtained from integrated peak intensities and atomic
sensitivity factors using the Advantage data acquisition and
processing software supplied by Thermo VG Scientific. Peak
fits of all spectra were performed using the Shirley background
correction and GaussianLorentzian curve synthesis.
2.2.5. BET
Nitrogen adsorption measurements were performed on a
Quantachrome Autosorb-1. Before adsorption, the samples
were calcined at 823 K for 16 h. Powder samples of 3040 mg
were degassed in a sample preparation station under 473 K and
a vacuum of 1.33  103 Pa for 15 h, and then switched to the
analysis station for adsorption and desorption under a
temperature of 77 K in liquid nitrogen. Surface area was
calculated with the multipoint BET equation with linear region
in the P/Po range of 0.050.35. Pore volume was calculated
from the maximum adsorption amount of nitrogen at P/
Po = 0.99. The relative experimental error for BET measure-
ment was <5%.
2.3. Reaction performance evaluation
Catalytic activity tests were carried out in a 5 ml fix-bed
microreactor (Autoclave Engineer, BTR-Jr-PC) in a continuous
operating mode. The 3 ml 2040 mesh catalyst sample was
diluted with the same volume and size of quartz. Before each run,
the catalysts were pre-sulfided in situ in a 20 vol% H2S/H2 stream
at 593 K for 2 h and 633 K for another 2 h. The other conditions
were as follows: 1.52 MPa hydrogen pressure, 2.0 h1 liquid
hourly space velocity (LHSV), and 200 ml/min H2 flow rate.
The 4,6-dimethyl dibenzothiophene (4,6-DMDBT,
176 wppm sulfur) was taken as model compound for HDS,
pyridine (240 wppm nitrogen) for hydrodenitrogenation
(HDN), and 1-methylnaphthlene (1-MN, 20 wt%) for hydro-
dearomatization (HDA). Hexadecane (HD) was used as the
solvent for all model compounds, and also as the model
compound for cracking reaction.
The catalysts were first evaluated using a single model
compound as the feed: pyridine in HD, 4,6-DMDB in HD, and 1-
MN in HD. For each catalyst, the evaluation was initiated with
HDN activity, following by HDS and HDA activities. In HDN
reaction, the conversion of pyridine was not taken into account
until two consecutively taken samples presented the same
conversion. Then two-component model compounds, 4,6-
DMDBT + 1-MN in HD, and tri-components, 4,6-DMDBT
+ 1-MN + pyridine in HD, were used as feeds. The evaluation
conditions for HDN, HDS, and HDA are listed in Table 1.
The reaction products were condensed and periodically
separated from a gasliquid separator. The liquid products were
analyzed by GCMS. The conversion was calculated as
X = 100%  [(Cin  Cout)/Cin], where Cin and Cout stand for the
concentration (wt%) of S, N, or 1-methylnathphene in feeds and
in liquid products, respectively.
28 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537

Table 1
The evaluation conditions for HDN, HDS, and HDA
Conditions Temperature Pressure LHSV H2/liquid
(K) (MPa) (h1) feed (v/v)
Single component
HDN 533 1.52 2.0 1000
HDS 623 1.52 2.0 1000
HDA 623 1.52 2.0 1000
Bi-components 623 1.52 2.0 1000
Tri-components
Low pressure 623 1.52 2.0 1000
High pressure 623 2.84 2.0 1000

3. Results and discussion

3.1. The textural and acidity properties of the catalysts

The textural and acidity properties of the oxide catalysts are
summarized in Table 2. MoNi/Al2O3 displayed the highest pore
volume and surface area among the six catalysts. Although
zeolite beta and Y had very high surface areas, they did not
contribute to the surface areas of the final catalysts. The XRD
results showed that the crystallinity of zeolite beta and zeolite Y
remained the same before and after Mo and Ni were added. This
indicates that the lower surface area values of zeolite containing
catalysts were not caused by the collapse of part of the
framework structure.
The acidities and their distribution obtained from NH3-TPD
are listed in Table 2. The weak, medium, and strong acidities
were assigned to the peak areas of NH3-TPD curves lower than
623 K, between 623 and 773 K, and above 773 K, respectively,
and calculated according to the equation:
 
Ai
Si Stotal
Atotal
where Si stands for the acidity of weak, medium, or strong
strength, Ai the area under the TPD curve of different tem-
perature range, Atotal the total area under the TPD curve from
373 to 883 K, and Stotal stands for the total acidity. The total
acidities of the catalysts virtually increased in the same order as
Fig. 1. XRD profiles of MoNi/Al2O3, MoNi/SiAl, MoNi/Beta, and MoNi/Y.
(*) Al2O3; (#) zeolite beta; (+) zeolite Y.
their support materials, for instance, MoNi/Y(10) > MoNi/
Beta(10) > MoNi/SiAl(10) > MoNi/Al2O3. The addition of
the amorphous silicaalumina enhanced the acidity of medium
strength, while the zeolites increased the acidity at strong
strength level. The presence of 5 wt% of zeolite beta resulted
in a significant increase in total acidity from 0.35 to 0.52 mmol/
g, but the total acidity of the catalysts tended to remain the same
with the further increase in zeolite content. The acid distribu-
tion of the three catalysts with various zeolite beta content was
similar.
3.2. XRD
The XRD profiles of the oxidic samples are shown in Fig. 1.
The characteristic diffraction peaks of g-Al2O3, zeolite beta,
and zeolite Y are marked in the figure. There were no detectable
XRD diffraction peaks of any MoO3 and NiO species, which
indicates that the molybdenum and nickel species were evenly
distributed on the surface of the support, or MoO3 or NiO
crystallites were smaller than 4 nm. The characteristic
diffraction peaks of g-Al2O3 appeared in all samples, and
their intensities were virtually the same for all samples.

Table 2
Textual and acidity properties of the oxide catalysts
Catalyst MoNi/Al2O3 MoNi/SiAl(10) MoNi/Beta(5) MoNi/Beta(10) MoNi/Beta(20) MoNi/Y(10)
Pore volume (ml/g) 0.69 0.63 0.62 0.57 0.61 0.66
Surface area (m2/g) 264 207 211 193 224 233
Average pore size (nm) 10.5 12.2 11.7 11.9 10.8 11.3
Acidity (mmol/g)
Total 0.35 0.45 0.52 0.53 0.55 0.62
<623 K 0.15 0.14 0.20 0.20 0.20 0.24
623773 K 0.10 0.19 0.12 0.13 0.12 0.16
>773 K 0.10 0.11 0.18 0.22 0.23 0.22
Average length of slabsa (nm) 5.11 10.90 6.30 6.35 6.24 5.20
Average number of layersa 1.52 2.41 2.13 2.46 2.59 1.61
a
Obtained from TEM.
 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537
Fig. 2. The representative TEM images of MoNi/Al2O3 (A), MoNi/SiAl(10) (B), MoNi/Beta(10) (C), and MoNi/Y(10) (D).
Compared with the crystallinity of parent hydrothermally
treated zeolite beta and zeolite Y, the crystallinities of the
zeolite beta and zeolite Y were not influenced by the addition of
Mo and Ni hydrogenation metals.
3.3. TEM
The representative TEM images of the four sulfided catalysts
are illustrated in Fig. 2. The TEM images reveal the presence of
typical layered structures of the MoS2 phase (confirmed by
EDX). The average number of layers per slab and average slab
length were calculated based on 300 crystallites. The statistical
results of the average length and number of layers of the MoS2
slabs are given in Table 2. The distributions of the slab length
(Fig. 3A) and the layer number (Fig. 3B) of MoS2 are illustrated
in Fig. 3. The average slab length increased in the order MoNi/Si
Al(10) (10.90 nm) > MoNi/Beta(10) (6.35 nm) > MoNi/Y(10)
(5.20 nm) > MoNi/Al2O3 (5.11 nm), while the average layer
number increased in the order MoNi/Beta(10) (2.46) > MoNi/
SiAl(10) (2.41) > MoNi/Y(10) (1.61) > MoNiAl2O3 (1.52).
The smaller layer number (2.41) of MoNi/SiAl(10) than that of
MoNi/Beta(10) (2.46) was mainly due to greater centralized slab
number distribution (Fig. 3B). It is noted that the average length
of the MoS2 slabs was almost the same for the three zeolite beta
containing catalysts (about 6.30 nm), irrespective of the content
of the zeolite, while the number of average layer slightly
29
increased with the content of the zeolite. With more zeolite beta
presented in the catalysts, the slab length and the number
distributions became wider. MoNi/SiAl(10) displayed the
broadest distribution of slab length and layer number, and
MoNi/Al2O3 was the opposite representative. The Si-rich surface
of the amorphous silicaalumina virtually resulted from its
synthesis method in which the silica was precipitated onto the
already formed Al(OH)3 hydrogels, and thus an amorphous
SiO2Al2O3 with the alumina inside silica structure was formed.
The higher Si/Al ratio of the framework of zeolite beta than that
of zeolite Y resulted in a higher proportion of Si distribution on
the surface of MoNi/Beta. Therefore, the surface Si of the four
catalysts decreased in the order MoNi/SiAl(10) > MoNi/
Beta(10) > MoNi/Y(10) > MoNi/Al2O3, which is also proved
by XPS results (Table 3). Based on the aforementioned results, it
can be concluded that the more silica the surface has, the longer
and more layer number of MoS2 slabs are formed.
3.4. XPS
X-ray photoelectron spectra of all calcined (oxidic state) and
sulfided catalysts exhibited the same profile. The binding
energies (BE) and surface species distributions of the oxidic
and sulfided catalysts are summarized in Table 3.
For the oxide samples, two prominent peaks corresponding
to the spin-splitting Mo6+ 3d5/2 (BE 233 eV) and Mo6+ 3d3/2
30 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537
Fig. 3. The slab length (A) and slab number (B) distributions for the four
sulfided catalysts.
(BE 236 eV) lines of Mo oxide species appeared. The two main
peaks in the Ni 2p spectra were assigned to the spin-splitting Ni
2p3/2 (BE 857 eV) and Ni 2p1/2 (BE 874 eV) and the two broad
peaks to the envelopes of the corresponding shakeup satellite
lines.
For the sulfided samples, the Mo 3d XPS spectra were
decomposed into three sets of doublets, corresponding to Mo6+,
Mo5+, and Mo4+ species. The Mo6+ species are obviously Mo
oxide species that were not completely sulfided. The Mo5+
species may be a Mo oxy-sulfided species, and the Mo4+ species
are MoS2 and the NiMoS phase [14]. A broad peak at
226.3 eV was assigned to S 2s [15]. The Ni 2p3 XPS spectra
presented a relatively intense peak at about 853 eV, and a
second broad band (BE 854 eV) overlapped partially with the
first one. The intense peaks of Ni 2p1 appeared at 871.3
871.8 eV. The shape of the Ni 2p envelope with a satellite peak
clearly showed the presence of non-sulfided Ni2+ species in all
catalysts after sulfidation. The Ni 2p3 peak at about 854 eV was
also due to the presence of the non-sulfided Ni2+ species
[16,17]. The second Ni 2p3 peak at 852.7853.3 eV, together
with the presence of the S 2p3 peak at 162 eV, was associated
with nickel sulfides [16,18].
The S 2p spectra of all the sulfided catalysts exhibited one
peak at the binding energy value of about 162 eV, which can be
assigned to S2 [19]. No other signal was identified around BE
169 eV, indicating that no sulfate species existed, and thus no
oxidation of the catalysts occurred during the transfer of the
solid from the sulfiding reactor to the XPS chamber [20].
The similar binding energies of Mo and Ni species for all
catalysts in the oxide state indicate that there was no significant
change in the interaction between Mo or Ni and supports, or
between Mo and Ni species after adding amorphous silica
alumina, zeolite beta, or zeolite Y. However, after sulfidation,
the binding energies of Mo, Ni, and S of MoNi/SiAl(10),
MoNi/Beta(10), and MoNi/Y(10) were higher than those of
MoNi/Al2O3, suggesting that the stronger interactions between
Mo or Ni and supports, or between Mo and Ni species occurred.
For the oxidic samples, the surface Mo/Ni molar ratios of all
the catalysts were higher than the bulk Mo/Ni, indicating that
more Mo species were distributed on the surfaces of the
catalysts than in the bulk. It has been proved that Ni species
tend to be evenly distributed in the whole support, while the Mo
species would be dominantly distributed in the vacancies on the
surface of Al2O3 and the zeolite [2123]. Compared with the
value in the bulk, the lower surface Si/Al ratios of the two
zeolite containing catalysts indicated that the hydrothermal
treatment of the zeolites created an Al-rich surface. Surpris-
ingly, MoNi/SiAl(10) had an unexplainably high surface Si/Al
ratio (0.14) (Table 3). Even though the surface of amorphous
silicaalumina is completely covered with pure silica, the
surface Si/Al molar ratio of the whole catalyst (includes silica
alumina and alumina) will only be 0.12, which is far lower than
0.14.
After sulfidation, both Ni and Mo species were redistributed
[15]. The surface Mo/Si + Al, Ni/Si + Al, and Mo/Ni molar
ratios dramatically decreased, suggesting that appreciable
amounts of the surface Mo and Ni species migrated into the
bulk. The reduced amount of Mo species was much higher than
that of Ni species. Probably due to the variation of the surface
properties, the surface Si/Al ratios of the three silica containing
catalysts changed in a different way: a significant decrease for
MoNi/SiAl(10); a great increase for MoNi/Beta(10); and
almost no change for MoNi/Y(10). It is noted that the variation
of surface Mo and Ni distributions is apparently associated with
the change of Al species on the surfaces. A higher surface Si/Al
ratio also led to a lower Mo/Ni ratio.
The sulfidation degree of hydrogenation catalyst can be
roughly predicted by the atomic ratios of S/Mo + Ni.
Theoretically, if the S/Mo + Ni of the Mo-Ni catalyst with a
Mo/Ni atomic ratio of 1.557 can be fully sulfided, the S/
Mo + Ni should be equal to 1.48, corresponding to MoS2
and Ni3S2 phase formation. From the S/(Mo + Ni) ratios listed
in Table 3, it can be seen that the S/(Mo + Ni) ratios
decreased in the order MoNi/Al2O3 > MoNi/Y(10) > MoNi/
SiAl(10) > MoNi/Beta(10). The S/(Mo + Ni) ratio of MoNi/
Beta(10) was even lower than the theoretically calculated value
1.48. With the increase of the content of zeolite beta in the
 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537 31

Table 3
The binding energies of oxidic and sulfided catalysts in XPS and surface species distributions
MoNi/Al2O3 MoNi/SiAl(10) MoNi/Beta(5) MoNi/Beta(10) MoNi/Beta(20) MoNi/Y(10)
Bulk
Mo/Ni 1.557 1.557 1.577 1.557 1.557 1.557
Si/Al 0 0.056 0.053 0.113 0.181 0.103
Oxide state
BE (eV)
Mo 3d5 232.9 232.9 232.8 233.0 233.2 233.0
Mo 3d3 236.1 236.1 235.9 236.1 236.4 236.1
Ni 2p3 856.6 856.2 856.6 856.4 856.7 856.4
Ni 2p1 874.2 873.9 874.1 874.1 874.3 874.0
Surface species distribution
Mo/Al + Si 0.08 0.08 0.08 0.08 0.07 0.09
Ni/Al + Si 0.04 0.04 0.03 0.03 0.04 0.04
Mo/Ni 2.05 2.10 2.76 2.76 1.93 2.07
Si/Al 0 0.14 0.03 0.06 0.23 0.03
Sulfided state
BE (eV)
Mo 3d5 MoS2 228.4 228.8 228.8 228.8 228.9 228.6
Mo 3d3 MoS2 231.5 231.9 231.9 231.9 232.1 231.7
Mo 3d5 oxy-sulfide 230.0 230.4 230.4 230.4 230.5 230.1
Mo 3d3 oxy-sulfide 233.1 233.5 233.5 233.5 233.7 233.2
Ni 2p3 disulfide 852.7 853.3 853.4 853.1 853.9 853.3
Ni 2p1 disulfide 869.8 870.4 870.4 870.2 871.7 870.3
Ni 2p3 NiO 853.8 854.2 854.3 854.1 856.7 854.2
Ni 2p1 NiO 871.3 871.8 872.1 871.8 874.8 871.8
S 2p3 161.2 161.6 161.7 161.8 161.9 161.6
S 2p1 162.4 162.8 162.9 163.0 163.1 163.2
Surface species distribution
Mo/Al + Si 0.02 0.02 0.02 0.02 0.02 0.02
Ni/Al + Si 0.02 0.02 0.02 0.02 0.03 0.02
Mo/Ni 1.10 1.32 1.31 1.02 0.91 1.52
Si/Al 0 0.12 0.07 0.09 0.27 0.03
S/Mo + Ni 1.68 1.54 1.77 1.40 1.24 1.78

catalysts, the S/(Mo + Ni) ratios decrease from 1.770 to 1.238,
indicating that the sulfidation degree greatly decreased. The
sulfidation degree of MoNi/Beta(5) and MoNi/Al2O3 was
similar.
3.5. Reaction performance evaluation
Table 4 summarizes the HDS, HDN, and HDA activities of all
catalysts with different feeds. With a single component feed, the
addition of the zeolite could significantly enhance all the three
reactions. All activity results were obtained after the evaluated
catalyst reached its steady state. During the initial evaluation
period, coke is easily formed on the high active fresh catalyst
surface, especially on strong acid sites when aromatics are
present in feed. Coking is one of the main reasons to cause
catalyst deactivation. Even though the activity of zeolite
containing catalysts was more easily influenced by coke, they
still showed higher hydrogenation activity than MoNi/Al2O3.
Amorphous silicaalumina, on the other hand, decreased the
HDS activity of the catalyst. The HDN, HDS, and HDA activities
of the three zeolite beta containing catalysts were similar,
irrespective of the content of zeolite. Taking a closer look at
the HDA reaction of the zeolite containing catalysts, majority of
1-MN was isomerized to 2-MN without further ring opening
(Table 5). Thus, based on 1-MN and 2-MN, the conversion of
methylnaphthalene became 100%  [(20  C1-MN  C2-MN)/
20], where 20 was the 1-MN concentration in feed (wt%), and
C1-MN and C2-MN stand for the concentration (wt%) in the
product. Excluding the isomerization, the conversions of
methylnaphthalene on MoNi/Beta(10) and MoNi/Y(10) became
26.2 and 39.5%, respectively, which were similar to that on
MoNi/Al2O3. It has been demonstrated that HDS of organic
sulfur compounds generally proceeds by two parallel reaction
pathways, one by direct desulfurization (DDS) via hydrogeno-
lysis of the CS bond, and one via hydrogenation of the aromatics
ring followed by hydrogenolysis of the CS bond (HYD) [24,25].
The two reaction pathways are believed to take place on different
active sites. Due to the steric hindrance of the methyl
constituents, the reactivity of 4,6-DMDBT HDS is very slow,
and preferentially proceeds via HYD. The HDS activity of 4,6-
DMDBT can be enhanced by adding acidic zeolite, which can
lessen or eliminate the hindrance through hydroisomerizating or
dealkylating the methyl groups at 4 and 6-positions. Therefore, it
is not surprised to see that the HDS activities of MoNi/Beta(10)
and MoNi/Y(10) were higher than that of MoNi/Al2O3. On the
surface of Al2O3-amorphous SiO2Al2O3, a considerable
32 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537

Table 4
HDN, HDS, and HDA activities on all catalysts
MoNi/Al2O3 MoNi/SiAl(10) MoNi/Beta(5) MoNi/Beta(10) MoNi/Beta(20) MoNi/Y(10)
Single component
HDN 48.7 61.4 100 100 100 100
HDS 91.2 86.4 100 100 100 100
HDA
1-MN 40.2 39.7 84.2 84.8 85.9 87.3
1-MN + 2-MN 40.2 39.7 26.8 26.2 37.0 39.5
Bi-components
HDS 68.2 74.3 94.9 96.9 99.1 98.2
HDA
1-MN 28.9 39.8 80.8 80.7 80.6 84.9
1-MN + 2-MN 28.9 39.6 27.3 29.9 25.9 40.2
Tri-components
HDN 100 100 100 100 100 100
HDS
1.52 MPa 65.3 73.4 82.9 89.8 84.4 91.2
2.84 MPa 91.2 78.6 97.8 98.5 94.6 100
HDA
1.52 MPa
1-MN 20.9 34.0 81.0 80.8 80.2 82.6
1-MN + 2-MN 20.9 34.0 27.2 30.1 26.2 37.3
2.84 MPa
1-MN 75.7 70.1 92.4 94.0 93.0 95.6
1-MN + 2-MN 75.7 70.1 71.3 74.6 70.0 80.5

amount of MoS2 crystallines had very long slabs with many
layers. These large slabs can provide less active MoNiS sites.
Subsequently, the HDS activity of MoNi/SiAl(10) was lower
than that of MoNi/Al2O3. For the same reason, the HDA activity
of MoNi/SiAl(10), MoNi/Beta(10), and MoNi/Y(10) was no
higher than that of MoNi/Al2O3.
The HDS conversions of all catalysts decreased when
aromatics presented in the feed. The decrease extents of MoNi/
Beta(10), MoNi/Y(10), and MoNi/SiAl(10) were much less
than that of MoNi/Al2O3. This indicates that the aromatics have
less influence on the HDS for the catalysts with higher acidities.
In the presence of 4,6-DMDBT, the HDA activity of MoNi/
Al2O3 dramatically decreased, while the other three catalysts
were little affected. Sulfur anion vacancies on the sulfided Mo
or W, and/or Ni are considered to be the active sites for DDS
[26], on which the adsorption of sulfur compounds occurs in a
predominantly perpendicular configuration. HYD reactions
take place on the different sites more likely by a flatwise
adsorption [27]. The aromatic hydrocarbons are also believed to
adsorb on the active sites through p-bonding of the aromatic
ring at the edge vacancies of sulfided metal active sites via
flatwise adsorption [28]. Therefore, the perpendicular adsorp-
tion of the sulfur compounds will be less influenced by the
competition adsorption with the flatwisely adsorbed 1-MN.
When the tri-component feed was used, the HDS activity of
all catalysts decreased slightly further, but the extent of
reduction in conversion was much less than the change from the
single component to the bi-component feed. Pyridine led to a
greater decrease in HDS activity of the zeolite containing
catalysts than those of the other two catalysts. The HDA
activity of the two zeolite containing catalysts was not
influenced by the addition of pyridine. Compared with
MoNi/Beta(10), MoNi/Y(10) presented higher HDS and
HDA activities. WNi/Beta(10) presented the highest HDA
activity among the three zeolite beta containing catalysts for the
bi- and tri-component feeds. The extent of HDS activity
decrease on MoNi/Beta(20) with the strongest acidic sites was
more pronounced than that on the other zeolite containing
catalysts. 4,6-DMDBT seemed to have no influence on the CN
bond scission (i.e. HDN), which is in agreement with the result
in the literature [29]. The surface Mo/Ni molar ratio of MoNi/
Beta(20) was obviously lower than that of the other catalysts.
Because more Ni species are cation-exchanged into zeolite
beta, the Ni/(Al + Si) molar ratios of the three zeolite beta
containing catalysts were lower than that of MoNi/Al2O3 when
they were in the oxide states. The low Mo distribution on the
surface of MoNi/Beta(20) probably results in the deviation of
the optimum Mo/Ni ratio, and reduces the amounts of MoNi
S active sites. As a result, the hydrogenation activity of MoNi/
Beta(20) is lower than that of MoNi/Beta(10).
Due to the higher reaction temperature (623 K), 100%
conversion of pyridine was achieved with the tri-component
feed. When the reaction pressure was raised to 2.84 MPa, HDS,
especially HDA activities of all catalysts significantly
increased. The impact of the hydrogen pressure on the HDS
and HDA activities was more pronounced on MoNi/Al2O3 than
on the other catalysts.
The zeolite containing catalysts are able to isomerize or
dealkylate sterically hindered 4,6-DMDBT to favorable
configuration, and consequently increase the conversion rate
 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537 33

Table 5
The normalized product distributions of 1-MN hydrogenation on the four catalysts (wt%)
MoNi/Al2O3 MoNi/SiAl(10) MoNiBeta(5) MoNi/Beta(10) MoNi/Beta(20) MoNi/Y(10)
Single component
Tetralin 0 0 0 0.5 13.4 0.9
PB 0 0 9.4 5.9 3.3 2.7
EPB 0 0 1.0 2.0 4.5 2.3
MBB 0 0 0.3 0.7 1.2 2.7
2-MT 0 0 0.3 2.6 2.9 5.5
1-MT 0 0 3.4 0.7 0.7 0.9
6-MT 10.3 10.7 10.6 12.5 9.5 20.9
5-MT 29.9 29.0 1.8 1.3 1.4 3.6
2-MN 0 0 57.4 58.6 48.9 47.7
1-MN 59.8 60.3 15.8 15.2 14.1 12.7
2-MN/1-MN 0 0 3.6 3.9 3.5 3.8
Bi-components
Tetralin 0 0 0 0.2 0.3 0.2
PB 0 0 2.1 2.1 2.0 0.6
EPB 0 0 0.7 1.8 2.3 1.6
MBB 0 0 0.1 0.9 0.6 0.8
2-MT 0 0 4.2 4.9 4.1 6.8
1-MT 0 0 1.5 1.7 1.3 2.2
6-MT 6.6 10.5 15.0 14.5 12.4 22.1
5-MT 22.2 29.1 3.6 3.7 2.9 5.9
2-MN 0 0.2 53.5 50.8 54.7 44.6
1-MN 71.1 60.2 19.2 19.3 19.4 15.1
2-MN/1-MN 0 0 2.8 2.6 2.8 2.9
Tri-components
1.52 MPa
Tetralin 0 0 0 0.2 0 0.1
PB 0 0 1.6 2.1 2.0 0.4
EPB 0 0 0.8 1.8 2.4 0.6
MBB 0 0 0.2 0.9 0.6 0.3
2-MT 0 0 3.9 5.0 4.1 5.6
1-MT 0 0 1.5 1.7 1.5 2.7
6-MT 3.5 9.2 15.5 14.6 12.5 20.6
5-MT 14.2 24.8 3.6 3.7 3.0 7.0
2-MN 0 0 53.8 50.7 54.0 45.3
1-MN 82.3 66.0 19.0 19.2 19.8 17.4
2-MN/1-MN 0 0 2.8 2.6 2.7 2.6
2.84 MPa
Tetralin 0 0 0 0 0 1.4
PB 0 0 0.2 3.3 3.8 2.2
EPB 0 0 0.4 3.7 1.3 3.7
MBB 0 0 0.1 1.8 0.4 1.5
2-MT 0 0 8.6 9.8 9.5 13.9
1-MT 0 0 6.3 4.8 4.5 3.9
6-MT 19.4 19.8 40.3 38.8 38.3 42.4
5-MT 56.3 50.3 13.5 12.3 12.0 11.6
2-MN 0 0 21.2 19.5 23.0 15.1
1-MN 24.3 29.9 7.6 6.0 7.0 4.4
2-MN/1-MN 0 0 2.8 3.3 3.3 3.4

via the DDS pathway. HDS via DDS pathway is less inhibited
than the HYD route [3033]. By 1-MN adsorption competition
with the sulfur compounds, the HDS activity of MoNi/Si
Al(10), MoNi/Beta(10), and MoNi/Y(10) could almost be
maintained with the presence of aromatics. Nitrogen molecules
are strong inhibitors to HDS. It was reported that the adsorption
of pyridine on both DDS and HYD sites is much stronger than
that of 4,6-DMDBT [29]. In addition, basic pyridine molecules
can be strongly adsorbed on the acidic sites, especially the
strong acidic sites, and then reduce the isomerization or
dealkylation activities of the catalysts. Therefore, the extent of
HDS activity decrease on the zeolite containing catalysts was
more pronounced than on the other two catalysts.
The higher hydrogenation activity of MoNi/Y(10) than
MoNi/Beta(10) is probably caused by: (1) MoNi/Y(10) can
provide higher surface than MoNi/Beta(10) (Table 2); (2) the
shorter average slabs of MoS2 with fewer layer numbers can
provide more MoNiS active sites on MoNi/Y(10) than on
MoNi/Beta(10) (Table 2); (3) a higher sulfidation degree can be
achieved by MoNi/Y(10) (Table 3).
34 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537

The reasons of the higher hydrogenation activity that the

zeolite containing catalysts possesses cannot rule out another
possibility, e.g. the acidity of the support favors the migration of
the hydrogen spillover from the donor phase (Ni2S3) up to the
acceptor phase (MoS2). It has been demonstrated [34] that the
mobility of the spillover hydrogen occurred even if Co9S8 (or
NiSx) and MoS2 were separates 10 mm in separated beds of Co
and Ni and Mo-supported catalysts. The higher activity of
zeolite containing catalysts may be caused by the easy
migration of spillover hydrogen over acid surfaces.
In the products of 1-MN hydrogenation reaction, four groups
of products were detected and quantified (Table 5): (1) 2-
methylnaphthlene (2-MN); (2) 1-, 2-, 5-, 6-methyltetralin
(MT); (3) ring-opening products, i.e. pentylbenzene (PB),
methylbutylbenzene (MBB), 1-ethyl-2-propenylbenzene
(EPB); (4) demethylating product, i.e. tetralin. The reaction
mechanism of 1-MN hydrogenation is illustrated in Fig. 4. 2-
MN is formed by the 1-MN isomerization via the reaction route Fig. 5. Typical GCMS chromatograms of the product on MoNi/Beta(20) with
(1). According to the position that the aromatic ring is saturated, 1-methylnaphthlene and hexadecane.
the 5-methyltetralin (5-MT) and 1-methyltetralin (1-MT) are
formed from 1-MN via routes (2) and (3), respectively; 2- decreased to 2.62.9, indicating the decline of the isomerization
methyltetralin (6-MT) and 6-methyltetralin (2-MT) are formed reactivity.
from 2-MN via routes (4) and (5), respectively. Subsequently, Different from the hydrogenation of 1-MN on the
the saturated rings in the MTs are opened to form ring-opening MoNi(Co)/Al2O3 or noble metal on Al2O3 catalysts [35,36],
products, PB, MBB, and EPB. With zeolite containing considerable amounts of 2-MN were formed on the zeolite
catalysts, a small amount of tetralin was identified. The tetralin containing catalysts via hydroisomerization. From the product
was produced through MT demethylation. Taking the 1-MN distribution, it can be seen that the aromatic ring saturation of
and all its products as 100 wt%, the concentration of individual 2-MN was much slower than that of 1-MN. The reason of
product was normalized. The normalized product distributions the decrease of 2-MN hydrogenation reactivity possibly is that
are summarized in Table 5. On MoNi/Al2O3 and MoNi/Si the isomerization and hydrogenation reactions take place on the
Al(10), no 2-MN was identified, while high proportions of 2- different active sites, the former on the acidic site, and the latter
MN were registered on the zeolite containing catalysts. For the on the hydrogenation sites. Although the addition of zeolite in
single component, the 2-MN/1-MN ratios are in the range of the catalysts can greatly improve HDS and HDN performances,
3.53.9, while for the bi- and tri-component feeds, the ratios it does not favor the hydrogenation and ring opening of

Fig. 4. Reaction mechanism of 1-MN hydrogenation.

 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537
polyaromatics. The high proportions of 5-MT and 6-MT
indicate that hydrogenation reactivity of the aromatic ring
without a methyl group is higher for both 1-MN and 2-MN,
which is in good agreement with the previous results [34,37].
No ring-opening products were formed on MoNi/Al2O3 and
MoNi/SiAl(10), while appreciable amounts of the products
were produced on the two zeolite containing catalysts. It is
quite clear that strong acidity favors the opening of saturated
aromatic rings. MoNi/Beta(10) exhibited higher ring-opening
activity than MoNi/Y(10).
It is well known that the cetane number (CN) of diesel fuel
depends on the product compositions. Generally, the polyaro-
matics has the lowest CN and is the least desired product. The
CNs of the methyltetralin isomers are also less than zero. Only
after the saturated rings in the methyltetralin isomers are
cracked, can CN be significantly increased [13]. Therefore,
although the addition of zeolite in the catalysts can greatly
improve HDS and HDN performances, it does not appreciably
enhance the hydrogenation and ring opening of polyaromatics.
In order to gain insight of the effect of sulfur, nitrogen, and
polyaromatics species on the hydrocracking of hexadecane, HD
hydrocracking reactions were carried out simultaneously with
the HDS, HDN, and HDA evaluations. Fig. 5 illustrates the
representative GCMS chromatograms of the HD cracking
product. In the HD product, besides unreacted hexadecane and
its cracked products, there existed 1-MN, pyridine, or 4,6-
DMDBT, and their reacted products. To ensure the comparison
of the hydrocracking of HD to be on the same basis, the
unreacted HD and its hydrocracked products was taken as
100 wt%. Based on this, the HD conversion was calculated
(normalized conversion). The normalized product conversions
of HD hydrocracking are listed in Table 6. For all the catalysts,
no C1C3 paraffins were detected in the products. With MoNi/
Al2O3 and MoNi/SiAl, nearly no hydrocracking reaction of
HD occurred for all feeds, indicating that the acidities of the
two catalysts are not strong enough to cleave the CC bonds of
the hexadecane molecules. Contrarily, a considerable amount
of cracking products were identified when using zeolite
containing catalysts. The cracking conversion of MoNi/
Beta(10) was much higher than that of MoNi/Y(10). The
higher cracking activity of H-beta zeolite than zeolite HY has
also been found in the cracking of heptane [38], and
hydrotreating of vacuum gas oil [39]. On MoNi/Beta(10), up
to 97.5 and 54.9% of HD were hydrocracked when using the
single component feed, HD + 1-MN and HD + 4,6-DMDBT,
Table 6
Normalized hexadecane hydrocracking conversion (wt%)
Catalyst MoNi/Al2O3 MoNi/SiAl(10)
Single component
4,6-DMDBT + HD 0 0
1-MN + HD 0.2 0.3
Bi-component 0.1 0.4
Tri-component
1.52 MPa 0.1 0.3
2.84 MPa 0.1 0.2
35
respectively. On MoNi/Y(10), the values became 12.8 and
33.6%, respectively, for HD + 1-MN and HD + 4,6-DMDBT.
When the bi-component feed was used, for MoNi/Beta(10), the
hydrocracking conversion (71.8%) of HD lied between the
conversions when using HD + 1-MN and HD + 4,6-DMDBT as
feeds. However, for the MoNi/Y(10), the cracking conversion
dropped to 6.7%. For MoNi/Y(10), the hydrocracking activity
was greatly suppressed in the presence of 1-MN and 4,6-
DMDBT. The addition of pyridine in the bi-component feed
only led to a slight decrease in the HD hydrocracking. When
hydrogen pressure increased from 1.52 to 2.84 MPa, the
cracking of HD drastically decreased to less than 20 wt% for
MoNi/Beta(10), indicating that the hydrogen pressure can
significantly suppress the hydrocracking reaction of HD.
The addition of zeolite into conventional alumina-supported
catalysts generally enhances hydrocracking activity but reduces
HYD activity [40]. The mechanism of an HD hydrocracking
reaction over a bi-functional catalyst is essentially the
carbenium ion mechanism of catalytic cracking reactions
coupled with that of hydrogenation and isomerization reac-
tions. The cracking of the paraffin molecules occurs
preferentially near the centre of the hydrocarbon chain [41].
Therefore, no C1C3 paraffins were formed.
The big difference between MoNi/Beta(10) and MoNi/
Y(10) in HD hydrocracking may be closely associated with the
variations of their acidity properties and the framework
structures. Although the quantity (0.219 mmol/g) of the acidic
sites with the strong strength on MoNi/Y (Table 2) are not lower
than that (0.196 mmol/g) on MoNi/Beta, the higher acidic
density of MoNi/Y makes the strong acidic sites easily
influenced by the reactant molecule adsorption or the reaction
on the adjacent acidic sites or hydrogenation active sites. As a
subsequence, such strong acid strength is greatly weakened.
Therefore, compared with MoNi/Beta, weaker acidic sites on
MoNi/Y can participate in the hydrocracking reaction, and then
the hydrocracking activity of HD was reduced. In addition, the
framework structure of zeolite beta makes its pore channels less
efficient in diffusing reactant or product molecules than zeolite
Y. Zeolite beta has two channels 0.72 nm  0.62 nm in
diameter, and a third channel that is only 0.55 nm  0.55 nm
wide, while zeolite Y has three-dimensional uniform channels
with a size about 0.75 nm  0.75 nm. Thus, the hydrocracking,
especially the secondary cracking, of paraffin molecules more
easily occurs in the zeolite beta due to a longer resident time.
From the cracking point of view, zeolite beta is a good
MoNi/Beta(5) MoNi/Beta(10) MoNi/Beta(20) MoNi/Y(10)
38.4 54.9 96.6 33.6
85.3 97.5 94.0 12.8
54.1 71.8 89.4 6.7
41.2 73.0 82.6 4.5
13.0 18.9 26.5 3.9
36 L. Ding et al. / Applied Catalysis A: General 319 (2007) 2537

component for the hydrocracking catalysts, but it is not a good MoNi/Y(10). MoNi/Y(10) exhibited a higher hydrogenation
component when used to prepare the catalyst to hydrotreat LCO activity than MoNi/Beta(10), but MoNi/Beta(10) presented a
aiming at maximum production of diesel fuel. Zeolite Y is higher ring-opening activity than MoNi/Y(10).
superior to zeolite beta in developing the catalyst to hydrotreat Almost no hydrocracking of hexadecane took place on
inferior diesel oil. MoNi/SiAl(10) and MoNi/Al2O3. However, a considerable
When the hydrogen pressure increased from 1.52 to amount of hexadecane was hydrocracked on all zeolite
2.54 MPa, HDA activity was considerably increased. Due to containing catalysts. The hydrocracking activity of MoNi/Beta
the limitation of thermodynamic, a high temperature and low was much higher than that of MoNi/Y.
hydrogen pressure do not favor hydrogenation reaction of With the hydrogen pressure increase, the HDA and HDS
aromatic rings. On the contrary, high hydrogen pressure can activities significantly increased, and the hydrocracking of
enhance the hydrogenation of aromatic rings, and consequently hexadecane was greatly suppressed.
increase HDS and HDA activities. HDS of 4,6-DMDBT occurs
mainly via HYD route over MoNi/Al2O3, while on the zeolite
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