ISSN 20700504, Catalysis in Industry, 2014, Vol. 6, No. 3, pp. 231–238. © Pleiades Publishing, Ltd., 2014.

Original Russian Text © P.P. Dik, O.V. Klimov, S.V. Budukva, K.A. Leonova, V.Yu. Pereyma, E.Yu. Gerasimov, I.G. Danilova, A.S. Noskov, 2014, published in Kataliz v Promyshlennosti.

CATALYSIS IN PETROLEUM
REFINING INDUSTRY

SilicaAlumina Based Nickel–Molybdenum Catalysts for Vacuum

Gas Oil Hydrocracking Aimed at a Higher Diesel Fraction Yield
P. P. Dik, O. V. Klimov, S. V. Budukva, K. A. Leonova, V. Yu. Pereyma,
E. Yu. Gerasimov, I. G. Danilova, and A. S. Noskov
Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk, 630090 Russia
email: dik@catalysis.ru; klm@catalysis.ru; zsm@catalysis.ru; lakmallow@catalysis.ru; pvu@catalysis.ru;
gerasimov@catalysis.ru; danig@catalysis.ru; noskov@catalysis.ru
Received December 29, 2013

Abstract—Nickel–molybdenum hydrocracking catalysts based on amorphous silicaaluminas (ASAs) with

Si/Al = 0.3–1.5 have been prepared using chemicals and methods available for catalyst plants. The acidic
properties of the ASA surface have been investigated by IR spectroscopy of adsorbed CO, and it has been
demonstrated that the Si/Al ratio has an effect on the concentration and strength of Brønsted and Lewis acid
sites in the ASA. The catalysts have been characterized by lowtemperature nitrogen adsorption and trans
mission electron microscopy, and it was found that the Si/Al ratio in the ASA has a considerable effect on the
textural properties of the catalysts and only a slight effect on the particle size of the sulfide active component.
The catalysts have been tested in vacuum gas oil hydrocracking in a laboratoryscale highpressure flow reac
tor under typical industrial hydrocracking conditions. The highest diesel fraction yield (>60 wt % at 400°C)
has been obtained with the catalyst based on the Si/Al = 0.9 ASA, which has the strongest Brønsted acid sites.
With the catalysts based on the Si/Al = 0.3 and 1.5 ASAs, the diesel fraction yield is much lower. This may be
due to the lower concentration and strength of acid sites in these catalysts and their smaller specific surface
area. The NiMo catalyst based on Si/Al ≈ 0.9 ASA is recommended for industrial use in refineries aimed at
obtaining the maximum possible yield of lowsulfur, highcetane, diesel fuels.

Keywords: hydrocracking, vacuum gas oil, diesel fraction, catalyst, amorphous silicaalumina
DOI: 10.1134/S2070050414030076

INTRODUCTION alysts and zeolitebased hydrocracking catalysts. The

At present, Russia’s petroleum refining industry
targets a deeper petroleum conversion through an
increase in the proportion of processed highboiling
petroleum fractions. At the same time, it should meet
the increasingly stringent environmental regulations
imposed on motor fuels. An analysis by Galkin et al.
[1] demonstrated that, under the presentday laws of
the Russian Federation, the most efficient petroleum
refining scheme is the scheme maximizing the output
of middle distillates. The main process of this scheme
is vacuum gas oil (VGO) hydrocracking, which is
mainly aimed at producing a lowsulfur 180–360°C
diesel fraction that does not need further processing
and is actually a finished commercial product. There
are different hydrocracking variants intended for
obtaining middle distillates, namely, one and two
step processes with feedstock recycle and singlepass
ones. Each of these variants has its own advantages and
drawbacks. The onestep singlepass process is the
technologically simplest one [2].
The onestep singlepass process needs either a
single catalyst based on amorphous silicaalumina
(ASA) or a combination (packet) of hydrorefining cat
feedstock is initially brought into contact with the
hydrorefining catalyst beds, where it is purified from
sulfur and nitrogencontaining compounds that are
poisonous to zeolitebased hydrocracking catalysts. It
was reported [3] that, although zeolitecontaining cat
alysts are more active and allow the process to be con
ducted at a lower temperature, ASAbased catalysts
afford a higher diesel fraction yield. Earlier [4], we
demonstrated that, in VGO hydrocracking over a Ni–
Mo/ASA–Al2O3 catalyst, the diesel fraction yield is
more than 10 wt % higher than in VGO hydrocracking
over conventional catalyst packets whose lower bed is
a nickel–molybdenum catalyst based on zeolite Y. In
addition, since the ASAbased catalysts are more
selective than the zeolitebased catalysts at a given
VGO conversion, the process involving the former
yields a smaller amount of undesired products (hydro
carbon gases and lowoctane gasoline fraction) and a
larger amount of lowsulfur hydrocracking residue,
which is a valuable feedstock for both lubricant pro
duction and catalytic cracking. Because Russia’s
refineries are using only imported hydrocracking cata
lysts [5], it is a challenging practical problem to

231
232
develop domestic VGO hydrocracking catalysts
affording an increased middle distillate yield.
Hydrocracking catalysts are bifunctional. In the
silicaalumina based catalysts, the cracking function is
executed by ASA and the hydrogenating and desulfur
izing functions are executed by particles of the so
called NiMoS phase, which are packets of molybde
num disulfide whose edges are decorated with nickel
cations. In recent years, deep hydrorefining catalysts
have been prepared by the codeposition of metals from
solutions containing chelating ligands. It was demon
strated earlier that, with citric acid as the chelating
agent, this approach can be successfully used to pre
pare CoMo deep hydrorefining catalysts [6]. We took
the same approach in the preparation of NiMo hydro
cracking catalysts.
Amorphous silicaaluminas are widely employed
as catalyst supports, since they have a large specific
surface area and a large pore volume and their surface
contains Brønsted and Lewis acid sites [7, 8]. The
properties of ASAs are determined by the synthetic
method and conditions and by the nature of the silicon
and aluminum precursors [9–11]. The Si/Al ratio in
ASA also has an effect on its properties, including its
acidic properties [12]. Different ASA synthesis meth
ods have been reported: coprecipitation from alumi
num and silicon alkoxide solutions [12–16], precipi
tation of aluminum compounds onto the silica surface
[13], precipitation of silicon compounds onto the alu
mina surface [17], etc. These ASA synthesis methods
require expensive, toxic, and flammable chemicals, so
it is unlikely that they will find industrial application in
the preparation of hydrocracking catalysts. Commer
cialization of methods that are free of these drawbacks
seems more likely. These methods include coprecipi
tation or successive precipitation of the components
using sodium aluminate [9, 18–24] or an aluminum
salt [11, 13, 25–29] as the source of aluminum and
sodium silicate (liquid glass) as the source of silicon.
Here, we suggest a method of preparing ASAbased
nickel–molybdenum catalysts for VGO hydrocracking
aimed at obtaining an increased yield of middle distil
late fractions. We have investigated the effect of the
atomic Si/Al ratio in the ASAs synthesized by succes
sive precipitation on the catalytic properties of the
ASAbased NiMo catalysts.
EXPERIMENTAL
Catalyst preparation included the following steps:
ASA synthesis, preparation of granular ASAbased
supports, and deposition of the active metals onto
these supports.
ASA Synthesis
Amorphous silicaaluminas were synthesized by
the successive precipitation of aluminum and silicon
containing precursors from aluminum sulfate and
DIK et al.
sodium silicate solutions. The amounts of the salts
were adjusted so as to obtain ASA with a Si/Al atomic
ratio of 0.3, 0.6, 0.9, 1.2, or 1.5. Initially, an aluminum
hydroxide sol was precipitated from an aqueous solu
tion of aluminum sulfate at pH 8.0 by adding aqueous
ammonia. The mixture was aged under stirring for
40 min at pH 8.0 and a temperature of 60°C. An
appropriate amount of an aqueous sodium silicate
solution with a Na/Si weight ratio of 0.83 was gradu
ally added to the resulting suspension at 55°C over the
course of 15 min under vigorous stirring. The acidity of
the mixture was adjusted to pH 8.5 by adding aqueous
ammonia or sulfuric acid. Next, the mixture was aged
at 55°C for 40 min. The precipitated product was col
lected on a filter and was multiply washed with dis
tilled water until the washings were free of the sulfate
anion. The latter was detected by adding a 2% barium
nitrate solution.
The resulting solid was dried at 120°C (12 h), and
was then calcined at 700°C (4 h). Hereafter, ASA pow
ders will be designated ASAX, where X = Si/Al. (For
example, ASA0.3 stands for ASA in which Si/Al = 0.3).
Support Preparation
Supports consisting of 70 wt % ASA and 30 wt %
Al2O3 were prepared from powders of the synthesized
ASA and commercial pseudoboehmite (AlOOH) as
the binder. Pseudoboehmite was purchased from the
Ishimbay Specialized Chemical Plant of Catalysts
(Russia). According to the manufacturer’s specifica
tions, pseudoboehmite had the following characteristics:
Content, wt % Na2O, <0.03; Al2O3, >70;
Al2O3 ⋅ 3H2O, <3
Specific surface area, m2/g 230
Crystal size, nm 60–70
According to transmission electron microscopy
(TEM) data, the binder particles were needlelike,
and this imparted a high mechanical strength to the
supports and supported catalysts [30]. All supports
were synthesized via the same procedure: dry ASA and
pseudoboehmite powders were mixed in a mixer with
Zshaped blades, and the mixture was then peptized
with an aqueous nitric acid solution with an acid mod
ulus of 0.05. The resulting pastes were extruded
through a fluoroplastic die on a VINCI ram extruder at
a pressure of 3.5–4.0 MPa and an extrudate outflow
velocity of 1.2 mm/s. The extrudates were dried at
120°C (4 h) in flowing air and were then calcined at
550°C (4 h). The resulting supports had the shape of a
trefoil 1.5 ± 0.1 mm in diameter and 3–9 mm in
length. These granule dimensions and shape are typi
cal of presentday deep hydrorefining and hydrocrack
ing catalysts. The supports will be designated ASAX–
Al2O3, where X is the Si/Al ratio in ASA.
CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014
 SILICAALUMINA BASED NICKEL–MOLYBDENUM CATALYSTS 233

Catalyst Preparation Table 1. Properties of the hydrocracking feedstock

A support sample was impregnated to incipient Property VGO feedstock
wetness with an aqueous solution of the bimetallic
complex [Ni(H2O)2]2[Mo4O11(C6H5O7)2] synthesized Standard according to which GOST (USSR
the distillation characteristics were State Standard)
via a patented procedure [31]. The complex concen determined 1101185
trations in the impregnating solutions were adjusted so
that the Ni and Mo contents of the finished catalyst Bubble point, °C 255
were 2.5 and 7.5 wt %, respectively. The impregnated Distillation temperature, °C
samples were held for 1 h in a tilted rotating flask, dried 15 vol % 355
at 120°C (4 h), and calcined at 550°C (4 h) in flowing 10 vol % 390
air. The catalysts prepared in this way will be desig
30 vol % 425
nated NiMo/ASAX–Al2O3, where X = Si/Al in ASA.
50 vol % 475
70 vol % 520
Catalytic Tests 80 vol % 535
The catalysts were tested in VGO hydrocracking 90 vol % 555
using the highpressure, fixedbed, flow reactor 98 vol % 580
detailed in earlier publications [32, 33]. Defectfree Sulfur content, wt % 3.39
catalyst granules 3–6 mm in length were selected for
catalytic tests. Since the bulk density of the catalysts Nitrogen content, ppm 920
depended on the Si/Al ratio, the samples placed in the Asphaltene content, ppm 590
reactor were unified according to their weight, which Density, kg/m3 (20°C) 925
was 22 g in all cases. In order to minimize the amount
of unreacted feedstock breaking through the catalyst
bed, the granules were mixed with SiC (0.25–0.63mm and a distillation residue (>360°C). The overall mate
fraction). The catalyst bed was sandwiched between rial balance and product yields were determined via
two 250cm3 beds of coarse SiC (1.25–3.15 mm frac the addition of the amounts of the fractions obtained
tion). The most important characteristics of the VGO by the fractionation of the liquid products and the
feedstock are listed in Table 1. The diesel fraction con amounts of the gaseous fractions leaving the separator.
tent of the initial VGO was 7.0 wt %, according to The sulfur content of the feedstock and products was
atmospheric fractionation data. Such VGO is typical determined on a HORIBA SLFA 2100 Xray fluores
of Russian refineries located in the Volga and Ural cence analyzer with an accuracy of 10 ppm.
regions, whose contribution to the total amount of
processed petroleum is over 100 million tons per year.
The catalysts were sulfided in the reactor with a 1.5 wt % Characterization of the ASAs, Supports,
dimethyl disulfide solution in straightrun diesel oil and Catalysts
containing 1.43% sulfur (Table 1). The sulfiding pres The elemental composition of the catalysts was
sure was 3.5 MPa, and the other process parameters determined by inductively coupled plasma atomic
were specified in an earlier study [33]. Hydrocracking emission spectroscopy (ICPAES) on an Optima 4300
was performed under conditions that are typical of DV spectrometer. Xray diffraction patterns were
industrial hydrocracking units at Russian refineries, obtained on an HZG4C diffractometer using mono
specifically, a pressure of 10 MPa, a feedstock hourly chromated CuKα radiation (λ = 1.5418 Å).
space velocity of 0.82 h–1, and an H2 : feedstock ratio The textural characteristics of the supports and cat
of 1130 NL/L. In the initial 12 h, the reactor temper alysts were derived from lowtemperature nitrogen
ature was maintained at 360°C; next, the temperature adsorption data obtained using an ASAP2400 system
was raised to 380°C, maintained at this level for 12 h, (Micromeritics, United States). The surface of the
and further raised to 390°C. The process was con catalysts was studied by highresolution transmission
ducted at this temperature for at least 30 h while sam electron microscopy (HRTEM) on a JEM2010
pling the gaseous products at 6h intervals. The liquid microscope (JEOL, Japan) with a lattice resolution of
products were collected for 6 h and were then ana 0.14 nm at an accelerating voltage of 200 kV. The cat
lyzed. The gas samples were analyzed by gas chroma alysts were examined after they were taken out of the
tography using a flameionization detector and an reactor after catalytic tests. The pores of such a catalyst
Rtx1 capillary column with a length of 60 m, an inner were filled with diesel fuel, which prevented their con
diameter of 0.25 mm, and a stationary phase layer tact with air. The specimen to be examined was
thickness of 0.5 μm. The liquid products were frac mounted on a standard copper grid, and the latter was
tionated at atmospheric pressure according to the secured in a holder and was placed in the specimen
GOST (RF State Standard) 2177–99 to obtain a gaso chamber of the electron microscope. The mean length
line fraction (<180°C), a diesel fraction (180–360°C), of the active sulfide particles and the average number

CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014

234 DIK et al.
1 CO as the probe molecule (Tables 3, 4). The surface of
2 sites (BAS’s) and Lewis acid sites (LAS’s). In the
Si/Al
1.5
1.2
0.9
0.6
0.3
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
2θ, deg
Fig. 1. Xray diffraction patterns of ASA powders.
of active sulfide layers per packet were calculated from
data obtained for more than 500 particles for each cat
alyst sample.
Infrared spectra were recorded on an FTIR8400
spectrometer (Shimadzu) in the region of 700–6000 cm–1
with a resolution of 4 cm–1 and 100 coadditions per data
point. The ASA samples to be examined were pressed
into pellets with a thickness of 0.004–0.007 g/cm2. For
adsorption measurements, an ASA sample was placed
in a quartz cell with CaF2 windows and was condi
tioned using a vacuum–adsorption setup in a vacuum
at 500°C for 1.5 h until the residual pressure was p <
10–3 Torr. The spectrum of the sample was recorded at
room temperature, and the sample was then cooled
with liquid nitrogen to 77 K. Adsorption measure
ments were performed at 77 K while elevating the CO
pressure from 0.1 to 10 Torr. The concentration and
strength of acid sites were determined using a standard
procedure [34].
RESULTS AND DISCUSSION
Properties of the ASAs
It follows from the Xray diffraction patterns of the
ASAs (Fig. 1) that the silicaaluminas that were used
in catalyst preparation were amorphous to Xrays and
contained no foreign phases. The diffraction patterns
show no peaks characteristic of quartz or γAl2O3,
which would certainly form if the initial ASA power
contained individual silicon compounds or AlOOH.
Therefore, our synthetic affords a homogenous mate
rial with a uniform silicon and aluminum distribution.
The strongest peak in the diffraction patterns (Fig. 1),
numbered 1, shifts from 22.2° to 23.9° as Si/Al is
decreased from 1.5 to 0.3, and this is accompanied by
an increase in the intensity of peak 2. The latter cannot
be assigned to γAl2O3, because the diffraction pattern
shows no noticeable peaks at 45.8° characteristic of
γAl2O3 obtained from boehmite or pseudoboehmite.
The acidic properties of the ASAs were studied by
IR spectroscopy using lowtemperature adsorption of
all of the samples examined has both Brønsted acid
region of the stretching vibrations of carbonyl com
pounds, there are three types of absorption bands
characteristic of CO–LAS complexes: NCO = 2230–
2228 cm–1 band, which is due to the complex between
CO and a strong LAS (Al3+ ion in a defective octahe
dron, which a typical defect in silicaaluminas); νCO =
2215–2212 cm–1 band, which is due to the complex
between СО and a mediumstrength LAS (presum
ably, Al3+ ion in an Al2O3 cluster); νCO = 2205 cm–1
band, which shifts to 2192 cm–1 as the CO pressure is
raised and characterizes the complex between CO and
a weak LAS (presumably, Al3+ ion in a nucleus of the
Al2O3 phase).
The total LAS concentration, like the concentra
tion of strong LAS’s, is highest in the Si/Al = 0.6 ASA
(Table 3).
The probe molecule CO, which is a weak base, can
be used to estimate the strength of BAS’s in silicaalu
minas. CO adsorption at 77 K shifts the absorption
OH⋅⋅⋅CO
bands of OH groups to lower frequencies ( Δν OH )
because of the stretching vibrations of the OH groups
being perturbed by the formation of an OH–CO
hydrogen bond. The larger this shift, the stronger the
site. The BAS strength was quantitatively estimated in
terms of proton affinity (PA) calculated using the fol
lowing correlation: PA [kJ/mol] = 1390 – 0.00226–1
OH⋅⋅⋅CO SiOH⋅⋅⋅CO SiOH⋅⋅⋅CO
log[ ( Δν OH )/ ( Δν OH )], where Δν OH is the
shift caused by the formation of a hydrogen bond
between CO and a SiCO group of fumed silica.
According to IR spectroscopic data for the interac
tion between adsorbed CO and OH groups at the liq
uidnitrogen temperature, the surface of all the ASAs
has two types of OH groups assignable to strong BAS’s:
OH groups characterized by νOH = 3740 cm–1, for
which the bathochromic shift of the OH stretching
OH⋅⋅⋅CO
band as a result of CO adsorption ( Δν OH ) is 280–
255 cm–1 (PA = 1165–1180 kJ/mol); OH groups
characterized by νOH = 3725 cm–1, for which
OH...CO
Δν OH = 230–235 cm–1 (PA ≈ 1200 kJ/mol).
Table 4 lists the total concentrations of the two
types of strong BAS’s and the PA values characterizing
the strongest BAS’s. Here, as the Si/Al ratio in the initial
BAS is varied, the BAS concentration passes through a
maximum at Si/Al = 0.6, as in the case of LAS’s. How
ever, the strongest BAS’s (PA = 1165 kJ/mol) were
detected on the surface of the Si/Al = 0.9 silicaalu
mina.
CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014
 SILICAALUMINA BASED NICKEL–MOLYBDENUM CATALYSTS 235

Table 2. Most important characteristics of the supports and catalysts prepared

NiMo/ASA NiMo/ASA NiMo/ASA NiMo/ASA NiMo/ASA
Catalyst
0.3–Al2O3 0.6–Al2O3 0.9–Al2O3 1.2–Al2O3 1.5–Al2O3
Ni content, wt % 2.5
Mo content, wt % 7.5
Support 263 349 397 337 290
Catalyst 221 282 287 258 242
Specific surface
area m2/g Difference between the –42 –67 –110 –79 –48
specific surface area
of catalyst and that
of support
Support 0.64 0.92 0.77 0.86 0.82
Catalyst 0.56 0.72 0.59 0.68 0.7
Pore volume,
cm3/g Difference between the –0.08 –0.20 –0.18 –0.18 –0.12
pore volume of catalyst
and that of support
Support 97 105 77 102 113
Catalyst 101 103 82 105 107
Average pore
diameter, Å Difference between the +4 –2 +5 +3 –6
average pore diameter
of catalyst and that
of support
Average length of the sulfide active com 31.2 32.9 33.2 39.0 37.7
ponent layer, Å
Average number of sulfide active compo 1.58 1.40 1.58 1.74 1.31
nent layers per packet

Table 3. Types and concentrations of LAS’s in ASAs according to IR spectroscopy of adsorbed CO

LAS types Strong Medium Weak
Σ LAS’s
νCO, cm–1 2230–2228 2215–2212 2192
Si/Al ratio in ASA concentration, μmol/g
1.5 21 5 137 163
1.3 19 13 143 218
0.9 22 10 220 252
0.6 36 35 328 399
0.3 14 19 271 304

Properties of the Supports and Catalysts Table 4. Strength and concentration of BAS’s in ASAs accord
ing to the IR spectroscopy of adsorbed CO
The nitrogen adsorption data for the ASAbased
supports (Table 2) suggest that, as the Si/A ratio in Si/Al BAS strength, BAS concentration,
ASA is varied, the specific surface area of the support ratio in ASA kJ/mol μmol/g
passes through a maximum at Si/Al = 0.9, while the 1.5 1180 56
average pore diameter and pore volume remain
unchanged. 1.3 1170 68
0.9 1165 87
The deposition of the active metals causes a quite
natural decrease in the specific surface area and pore 0.6 1170 120
volume of all of the supports. The decrease in the spe 0.3 1170 77

CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014

236 DIK et al.

% somewhat smaller than for the NiMo/ASA1.2–Al2O3

40 NiMo/ASA0.3–Al2O3
NiMo/ASA0.6–Al2O3
35 NiMo/ASA0.9–Al2O3
30 NiMo/ASA1.2–Al2O3
NiMo/ASA1.5–Al2O3
25
20
15
10
5 Thus, the method we chose for the codeposition of
0 active component, and the morphology and particle
<2 2–3 3–4 4–5 5–6 6–7 >7
Layer length, nm
Fig. 2. Distribution of the layers of sulfide active component
particles over their length in the sulfided catalysts.
cific surface area is 42–110 m2/g, and the total pore
volume decreases by 0.08–0.20 cm3/g (Table 2). These
changes in textural properties are typical of the depo
sition of active metals at similar concentrations onto
γAl2O3 [30, 35]. In spite of the marked decrease in the
specific surface area and pore volume, the change in
the average pore diameter is as small as ±(2–6) Å and
is within the measurement error (5%). When the sup
ported metals are mainly located in narrow pores,
clogging up these pores, the average pore diameter
increases, while when the metals are mainly located in
wide pores, the average pore diameter decreases [30].
Therefore the above textural data indicate that the
active metals are uniformly distributed over the sur
faces of all of the pores that were initially present in the
supports.
This inference is supported by HRTEM data for
the sulfided catalysts, which suggest that the sulfide
active component in all catalysts is uniformly distrib
uted on the Al2O3 and ASA surfaces and its particles
are identical in morphology (Table 2, Fig. 2). The
average layer length increases from 31.2 to 39.0 Å as
Si/Al is increased from 0.3 to 1.2; however, the average
layer length for NiMo/ASA1.5–Al2O3 is 37.7 Å,
catalyst. The average number of sulfide active compo
nent layers per packet for the catalysts examined is
1.31 to 1.74 and is not correlated with Si/Al. The dis
tribution of the layers of sulfide active component par
ticles over their length for the sulfided catalysts is
shown in Fig. 2. It can be seen that this distribution
diagram has practically the same shape for all cata
lysts. This morphology of sulfide active component
particles is typical of presentday, highly active,
hydrotreating catalysts whose active component is
mainly the type II NiMoS phase [36].
active metals ensures a high degree of dispersion of the
size of the latter do not depend significantly on the
Si/Al ratio.
Catalytic Properties of the Catalysts
The sulfided NiMo/ASAX–Al2O3 catalysts were
tested in VGO hydrocracking. No significant changes
in product proportions or yields were observed during
the experiments. Table 5 presents averaged analytical
data for five samples. Clearly, the highest diesel frac
tion yield in VGO hydrocracking, 51.5 wt %, is
attained with the NiMo/ASA0.9–Al2O3 catalyst.
However, the catalysts based on ASA with Si/Al =
0.6–1.2 differ only slightly in diesel fraction yield.
Outside this Si/Al range, the diesel fraction yield is
much lower.
As was demonstrated above, the Si/Al ratio in ASA
has only a slight effect on the particle size of the sulfide
active component, so it is natural to assume that the
observed variation of catalytic properties in VGO
hydrocracking from one sample to another is mainly
due to the difference between the acidic properties of
the catalysts. Provided that the active metal deposition
procedure and drying and calcination conditions are
identical, these properties should be completely deter
mined by the properties of the ASA used in catalyst
preparation. The highest total concentration of acid
sites is observed in ASA0.6; however, cracking activity
depends more strongly on the strength of particular
types of sites than on the total acid site concentration
[37]. This is likely the reason why the diesel fraction

Table 5. Yields of VGO hydrocracking products

Product yield, wt %
Catalyst
residue diesel fraction gasoline fraction gas
NiMo/ASA1.5–Al2O3 45.9 47.3 4.7 2.1
NiMo/ASA1.2–Al2O3 41.6 50.9 5.4 2.1
NiMo/ASA0.9–Al2O3 41.5 51.5 5.0 2.0
NiMo/ASA0.6–Al2O3 41.6 50.6 5.7 2.2
NiMo/ASA0.3–Al2O3 50.8 44.5 3.7 1.0

CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014

 SILICAALUMINA BASED NICKEL–MOLYBDENUM CATALYSTS
yield with the NiMo/ASA0.9–Al2O3 catalyst is
higher than with the other catalysts: ASA0.9 has the
strongest BAS’s.
The hydrocarbon gas and gasoline fraction yields
for the NiMo/ASA0.3–Al2O3 catalyst are 1.0% and
3.7 wt %, respectively; for the other catalysts, these
yields are 2.1 ± 0,1% and 5.2 ± 0.5 wt %, respectively.
This is likely due to the smaller specific surface area
and pore volume of the former catalyst and to the
smaller number and lower strength of acid sites in
ASA0.3. The residue yield for the catalysts supported
on ASA with Si/Al = 0.6–1.2 varies insignificantly and
is 41.5 ± 0.1 wt %. The residue yield for the catalysts
based on ASA with Si/Al beyond this range is substan
tially higher, indicating that these catalysts are less
active. This can be due to the lower concentration and
strength of acid sites and the smaller specific surface
area of these catalysts.
Thus, the highest diesel fraction yield in VGO
hydrocracking is afforded by the catalysts prepared
using ASAs with Si/Al = 0.6–1.2, the NiMo/ASA
0.9–Al2O3 catalyst having the strongest BAS’s. This
catalyst was additionally tested under varied condi
tions in order to see whether it is possible to increase
the diesel fraction yield. Because the output rate of a
hydrocracking unit and the operating pressure at a
petroleum refinery cannot be varied in a wide range
and the hydrogencontaining gas recycle ratio should
be at least 1000 Nm3/m3, the only variable process
parameter was temperature.
In deep singlepass VGO hydrocracking below
440°C, the yield of the hydrorefining residue with a
boiling point above 360°C is usually about 20%, the
hydrocarbon gas yield is usually about 4.5%, and the
total middle distillate yield is typically about 45% [38].
In our tests, the hydrocracking temperature was raised
stepwise until the residue content of the product was
below 20 wt %. At each temperature point, the process
was performed for 30 h. The analytical data averaged
over four samples at each temperature point are plot
ted in Fig. 3. Note that, when comparing experimental
data points at a given temperature, we observed no
considerable changes in product yields.
It follows from the data presented in Fig. 3 that the
20 wt % residue yield with the NiMo/ASA0.9–Al2O3
catalyst is reached at 405–410°C. The corresponding
yield of the target diesel fraction boiling at 180–360°C
is 64–66%, implying a diesel fraction selectivity of
about 80 %. As the process temperature is raised to
420°C, the diesel fuel yield increases to 70–71%, but
the diesel fuel selectivity decreases to 75%. In the
hydrocracking temperature range from 400 to 420°C,
the sulfur content of the diesel fraction and that of the
residue were practically identical and were 10–
30 ppm. The sulfur determination accuracy was lim
ited by the potential of the HORIBA SLFA 2100 ana
lyzer. The cetane number of the resulting diesel fuel is
in the 51.5–54.2 range. Note that at none of the experi
CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014
237
80
70
60
Residue (>360°C)
Yield, wt %
50 Diesel fraction (180–360°C)
Gasoline fraction (<180°C)
40 Gas
30
20
10
0
380 385 390 395 400 405 410 415 420
Reactor temperature, °C
Fig. 3. Yields of VGO hydrocracking products as a function
of reactor temperature for the NiMo/ASA0.9–Al2O3 ca
talyst.
mental data points does the yield of the hydrocarbon gas,
the least valuable hydrocracking product, exceed 3.1%.
CONCLUSIONS
The catalyst preparation method involving the
deposition of the Ni–Mo bimetallic compound onto
granular supports containing 30% Al2O3 as the binder
affords catalysts containing fineparticle sulfide active
component uniformly distributed over the surface.
The morphology of the catalysts depends only slightly
on the Si/Al ratio in ASA. Conversely, the acidic prop
erties of ASA, namely, the concentration and strength
of Brønsted and Lewis acid sites depend considerably
on the Si/Al ratio: the total concentration of acid sites
passes through a maximum at Si/Al = 0.6, and the
strongest Brønsted acid sites are observed at Si/Al = 0.9.
It was investigated how the properties of the ASA
based NiMo catalysts for VGO hydrocracking aimed at
an increased diesel fraction yield correlate with the
Si/Al ratio (0.3–1.5) in the ASA. The highest diesel
fraction yield was attained with the NiMo/ASA0.9–
Al2O3 catalyst. In the onepass hydrocracking of VGO
over this catalyst, the yield of hydrorefined diesel fuel
is up to 64–68 wt % at 75–80% selectivity and the
hydrocarbon gas yield does not exceed 3.1 wt %. The
resulting diesel fuel has a cetane number of 51.5–54.2
and contains at most 10–30 ppm residual sulfur.
The catalyst preparation method was multiply rep
licated in the laboratory and was found to be suitable
for scaling up. The results of catalytic tests were multi
ply reproduced on a pilotplant scale under the same
hydrocracking conditions as in industrial units. The
results of this study allow us to recommend the NiMo
catalyst containing the ASA with Si/Al ≈ 0.9 for indus
trial use in petroleum refineries targeting the maxi
238 DIK et al.
mum possible yield of lowsulfur, highcetane diesel
fuels.
ACKNOWLEDGMENTS
This work was supported through state contract
no. 14.516.11.0097, July 1, 2013, subject: “Develop
ment of the Theoretical Foundations of Obtaining
HighCetane Diesel Fuels with Improved Environ
mental and LowTemperature Properties and Cata
lysts for This Process.”
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Translated by D. Zvukov
CATALYSIS IN INDUSTRY Vol. 6 No. 3 2014