Journal of Industrial and Engineering Chemistry 35 (2016) 115–122

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Journal of Industrial and Engineering Chemistry

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Upgrading of vacuum residue in batch type reactor using Ni–Mo

supported on goethite catalyst
Ramakanta Sahu a,b, Byung-Jin Song a,c, Young Pyo Jeon a,d, Chul Wee Lee a,d,*
a
Division of Green Chemistry & Engineering Research, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, Republic of Korea
b
School of Applied Sciences (Chemistry), KIIT University, Patia, Bhubaneswar, Odisha 751024, India
c
Department of Chemistry, Sungkyunkwan University, Gyeonggi-do 440-746, Republic of Korea
d
University of Science and Technology(UST), Daejeon 305-333, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: It is imperative to develop an efficient catalyst to convert vacuum residue (VR) into low boiling point
Received 26 September 2015 liquid products via an environmentally benign pathway. Ni–Mo bimetal was impregnated on goethite
Received in revised form 11 December 2015 supports and well characterized using various analytical techniques. VR hydrocracking catalytic
Accepted 12 December 2015
activities were investigated in a batch reactor. The 1%Ni–4.5%Mo/Goethite catalyst showed a high yield
Available online 19 December 2015
of low boiling point liquid products, 69.8%, with 80% VR conversion at 420 8C in the presence of 70 bar
initial hydrogen pressure in 3 h. In these liquid products, 8.6% of naphtha, 51.4% of middle distillate, 9.8%
Keywords:
of vacuum gas oil (VGO) with 28.1% of saturates, 62.5% of aromatics, 8.4% of resins and >1% of
Vacuum residue
Hydrocracking
asphaltenes were confirmed by TGA and SARA analysis, respectively. The experimental findings
Catalyst indicated that the formation of low boiling point liquid products depends on physical parameters and
Process chemical composition of the catalyst. This paper describes the synthesis of the supported catalysts,
Heavy oil influences of the active metal composition, metal/support interaction, and process parameters for
hydrocracking of VR into high value, low boiling point liquid products.
ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction catalyst and hydrogen) [2]. Hydrogen addition (hydrotreating or

The availability of light petroleum is rapidly decreasing, while
demand for low boiling point liquid products is continuously
increasing with world population growth. Hence, nonconventional
sources (VR, AR, heavy oil, extra heavy oil etc.) are the remaining
options for the future production of low boiling point liquid fuels
(gasoline, diesel, jet fuel, middle distillate etc.). Currently,
petroleum refinery industries are more concerned about the
processing of vacuum residue (VR), as it is abundant and cheaply
available, the bottom product from the vacuum distillation unit. A
number of process technologies have been developed to convert
such heavy feeds, including carbon rejection, hydrogen addition or
a combination of both [1]. The processes are simple and need low
investment (feeds are decomposed thermally in the absence of
* Corresponding author at: Division of Green Chemistry & Engineering Research,
Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600,
Republic of Korea. Tel.: +82 42 860 7381; fax: +82 42 860 7388.
E-mail address: chulwee@krict.re.kr (C.W. Lee).
hydrocracking) process technologies are also available for conver-
sion of VR.
Hydrocracking processes are preferable to carbon rejection
processes because they produce more distillate liquid products
with high H/C ratios [3]. Hydrocracking mainly involves cracking
higher molecules into smaller fractions, simultaneously with
hydrogenation/hydrogenolysis at carbon–carbon unsaturation
(C55C) or carbon bonded impurities (C-S, C-N or C-Metal) in the
presence of hydrogen and catalyst [4–6]. Generally, active
hydrocracking catalysts are composed of acidic supports such as
alumina, alumina-based mixed oxide (e.g. Al2O3–TiO2, Al2O3–
ZrO2), activated carbon, modified zeolites, mesoporous silico-
aluminates etc. and active metals (Mo, W, etc.) with promoters (Ni,
Co etc.) [7–12]. These catalysts are used in various reactors such as
fixed-bed, moving-bed, ebullated-bed, slurry-phase and batch type
[13–15].
For hydrocracking VR, generally submicron particle, transition
metal sulfide dispersed catalysts of Ni, Mo, Co, W, Fe or a
combination of these elements are used [16,17]. There are
three categories of catalysts used for hydrocracking VR: (a)

http://dx.doi.org/10.1016/j.jiec.2015.12.017
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
116 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122

heterogeneous dispersed catalysts [18–20], (b) oil soluble Preparation of support

dispersed catalysts [21,22] and (c) water soluble dispersed
catalysts [23,24]. Use of water soluble and oil soluble catalysts
(homogeneous) has several drawbacks, including precursor price,
catalyst synthesis process, and the separation of the catalyst from
products. Therefore, heterogeneous dispersed catalysts have
advantages over homogenous catalysts.
Goethite (a-FeOOH) is a yellow colored material present in
nature, however, it has also been synthesized by various
researchers. Synthetic goethite is an excellent material for use
as a catalyst in a fluidized-bed reactor (FBR) and other reactors
[25]. Goethite is a suitable precursor for the preparation of iron
oxide (Fe2O3) by thermal process. Iron oxide (hematite) is a
material of great interest because it is used in ceramic humidity
sensors, catalysts, and pigments [26,27]. In our study we used
goethite as a support for the preparation of a dispersed catalyst to
convert VR.
The aim of the present work is to convert VR into low boiling
point, high value liquid products (gasoline, diesel etc.). Here we
report on the preparation of highly active Ni, Mo supported
catalysts through the wet impregnation method. After completion
of the reaction, the obtained phases (solid residue, liquid and
gases) were quantified and the liquid product was characterized
using various analytical techniques. To complement this work, we
explored the possible effect of the supports, and other physical
parameters. Catalytic activity reaction results were correlated
based on catalyst characterizations. The specific metal/support
interaction provided an improvement in catalytic activities in
comparison with conventional catalysts.
Experimental methods
Hydrocracking feed characterizations
Properties of VR used for hydrocracking experiments are given
in Table 1.
Goethite (a-FeOOH) was prepared by homogeneous precipita-
tion method using dilute aqueous solution of ferric nitrate
[Fe(NO3)39H2O] precursor and sodium hydroxide (NaOH). Typi-
cally, 40 g of ferric nitrate was dissolved in 100 mL of distilled
water. Solution was stirred for 1 h at room temperature. Under
vigorous stirring, 10 M sodium hydroxide solution was dropwise
added until a pH of 12. Stirring was continued constantly for
another 1 h in that condition. Dark brown gel was formed which
contains mostly unhydrolysed iron (III) ion [FeIII(H2O)6], iron
hydroxide [Fe(OH)3] and iron oxyhydroxide (FeOOH). The gel as
formed was kept in an electric oven at 70 8C for 24 h. Obtained gel
was filtered off and repeatedly washed with distil water until free
from nitrate and sodium ions. The wet cake resulting material was
dried at 100 8C in vacuum oven for 24 h. Dried yellow color solid
was grinded to make powder form. As synthesize goethite was
used as support for the preparation of supported catalysts.
Preparation of supported bimetallic catalysts
Ni–Mo bimetallic supported catalysts were prepared by wet
impregnation method. In a typical preparation of 1wt%Ni-
4.5wt%Mo/goethite catalyst (1%Ni–4.5%Mo/Goethite), at room
temperature 4.71 g of dried goethite was taken in a round bottom
flask and 20 mL of water was added. The gel was stirred for 1 h.
0.25 g of nickel nitrate [Ni(NO3)26H2O] and 0.43 g of ammonium
heptamolybdate [(NH4)6Mo7O244H2O] was dissolved in 10 mL of
water in separate beaker. Dissolved precursor was mixed together
and added into the support solution within 1 min or before nickel
and molybdenum complex formation. The mixture was stirred for
another 1 h. Resultant solution was dried using rotary evaporator
followed by vacuum dry at 100 8C. The dried sample was calcined at
400 8C in presence of air flow for 2 h (heating rate was 2 8C min1) in
a closed electric furnace to decompose the residual nitrates and
ammonium ion to favor the formation of the oxide phase. A similar
procedure was applied for the preparation of other catalysts.

Catalyst characterization techniques

Table 1
Basic physico-chemical properties of VR studied in this work. Powder X-ray diffraction studies were performed using Rigaku
Properties Unit Value powder X-ray diffractometer with D/Max-3c detector. Crystalline
phases were identified by matching with the International Centre
Elementary analysisa
C wt% 84.0
for Diffraction Data Powder Diffraction File (ICDD-PDF). To confirm
H wt% 10.7 the metal concentration on the supports, chemical analysis of the
S wt% 4.84 prepared samples was carried out by Thermo Scientific ICAP 6500
N wt% 0.14 duo Inductively Coupled Plasma-Atomic Emission Spectrometer
H/C Mole fraction 1.45
(ICP-AES). The textural properties (surface area) of synthesized
Metal compositionb catalysts were determined by N2 sorption isotherms. Specific
Ni ppm 36.4 surface area was calculated by Brunauer–Emmett–Teller (BET)
V ppm 151.0
methods. H2-TPR measurements were conducted with a Micro-
Fe ppm 38.3
Ca ppm 25.0 meritics AutoChem II automated catalyst characterization system.
Si ppm 198.0 The external morphology and particle size of as synthesized
catalyst was carried out by emission field image obtained by
SARA analysisc
Saturates wt% 4.0 scanning electron microscopy (SEM) in VEGA II, MIRA3 TESCAN.
Aromatics wt% 61.0 The particle size of the samples was measured using a particle size
Resins wt% 18.0 analyzer Microtrac S3000, Bluewave software. Saturates, aro-
Asphaltenes wt% 17.0
matics, resins and asphaltenes (SARA) compounds in the liquid
Fraction composition on VRd products were identified and quantified by Iatroscan MK6s
RT-120 8C wt% 0.0 instrument. Elementary analysis was carried out in Flash EA
120–380 8C wt% 11.7
1112 instrument.
380–600 8C wt% 72.8
>600 8C wt% 15.50
a
Catalytic activity and product analysis study
CHNS analysis.
b
ICP-AES analysis.
c
TLC-FID analysis. Catalytic performance of the prepared catalysts was evaluated
d
TGA analysis. in 200 mL home-made stainless steel autoclave. Typically,
 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122
hydrocracking experiments were conducted at temperature
410–430 8C in initial hydrogen pressure of 75  2 bar@70  5 8C
using catalyst 1.32  2 g of catalyst in 1–6 h time with agitation to
speed of 600 rpm. We have used constant 40 g of VR. The
temperature program applied during the reaction included three
steps: preheating at 75 8C for 0.5 h to reduce the viscosity of VR.
After the leak test of the reactor, a linear increase in temperature
was applied up to desired reaction temperature and then kept
isothermal until end of the reaction. Reaction time was counted
after reaching the desired reaction temperature. When reaction
time elapsed, the reactor was cooled to ambient temperature. Gas
product was analyzed by gas chromatography and the bottom
products (solid residue and liquid) were separated and analyzed
using various analytical techniques. Initially, VR was black in color
and almost solid at room temperature. After hydrocracking the
color of liquid product was reddish brown
Gas phase analysis
Gaseous products were induced either by the thermal process
or by the acid catalyzed reactions tempted by Lewis or Brönsted
acid sites present in the catalyst. Among our hydrocracking
experiments, we have optimized the reaction with a maximum
of 60% liquid yield with a half of mid-distillate which has a
boiling point range between 380 and 600 8C. Based on the
reaction, we refer a term ‘overcracking’ to describe higher
degree of hydrocracking reactions, which result in lower liquid
yield with higher gas fraction than the optimum hydrocracking
reaction. As the reaction time passes, the gaseous products
formation was at higher fraction. Gaseous products formation
could be associated to the cracking of paraffinic chains present
in asphaltenes and other large molecules present in VR in the
first stages of the reaction and decomposition of smaller
molecules in latter stage (liquid). At lower reaction temperature
(410 8C), this effect is not observed remarkably because of low
VR conversion.
After elapse of reaction time, reactor was cooled to ambient
temperature and pressure was slowly released. As reaction time
increases, we observed smaller amount of liquid and solid
products, which can be interpreted as higher gas product
formation as a result of overcracking due to longer reaction time.
Solid phase analysis
In VR hydrocracking, large size organic molecules are
converted into smaller fragments, and coke formation, which
trigger the deactivation of catalyst, may occur during the
reaction. On the other hand, asphaltenes in VR is believed to be
mainly soluble in resin and decreases its solubility with
decreasing in resin concentration. During hydrocracking, resin
conversion rate is much faster as compared to asphaltenes
fraction. As asphaltenes fraction is incompatible with VR, it
precipitated on catalyst surface [28,29]. Metals in VR are also
adsorbed on catalysts surface. In our experiments, we found
solid residue contains higher organic molecules, coke and
catalyst. We weighed the solid residue and calculated yield
and conversion, accordingly.
Liquid phase analysis
The liquid phase in the reactor is the most important product as
it contains the valuable fractions obtained from hydrocracking of
VR. Boiling point of liquid product was analyzed by TGA. TGA is a
versatile technique used by several authors for analysis of VR
hydrocracking liquid products [30–32]. The obtained liquid phase
was fractionated into 3 components with different interval of
boiling point, RT-120 8C (naphtha), 120–380 8C (middle distillates),
380–600 8C (vacuum gas oil: VGO) and >600 8C solid residue
(heavy hydrocarbon).
117
Results and discussion
X-ray diffraction study
The powder XRD patterns of Ni–Mo supported catalysts are
shown in Fig. 1. The XRD patterns indicate that the synthesized
materials are crystalline in nature. On curve A, X-ray diffraction
peaks appeared at 21.38, 33.38, 36.78, 53.38 and 59.98 (the
corresponding crystal planes are indicated on the curve) which
are the characteristics of a-FeOOH (iron oxyhydroxide JCPDS 81-
0464) [33]. In this curve hematite peaks also appear along with
goethite peaks. Kosmulski et al. also reported that traces of
hematite were found in a few goethite samples [34]. It is proposed
that while adding NaOH solution or during the drying process the
temperature may have been enough to transform goethite to
hematite. It has been reported that on heating at 200–300 8C, water
molecules are lost from a-FeOOH by the dehydroxylation process.
Hence, a-FeOOH transforms into pure hematite (a-Fe2O3) through
the following reaction [35,36]:
2a-FeOOH ! a-Fe2 O3 þ H2 O
Hematite converted during the heat treatment of goethite
appears as a non-uniform broadening of the XRD pattern [37]. In
our experiment we observed similar XRD broadening when the
goethite sample was calcined at 400 8C for 2 h (curve B). Curve B
indicates that the calcined goethite is converted into a form whose
XRD peak matches hematite (JCPDS 87-1166). However, no
changes of particle size or shape were observed during the
thermal treatment (as expected for a topotactic reaction) [38].
Curve C and curve D indicate 1%Ni–4.5%Mo/Fe2O3 and 1%Ni–
4.5%Mo/Goethite, respectively. The XRD pattern results show no
characteristic peaks of MoO3 and NiO for these catalysts, nor in the
1%Ni–4.5%Mo/g-Al2O3 catalyst (not shown in Fig. 1.). This suggests
that the Ni and Mo metal are highly dispersed on the supports. We
cannot rule out the formation of less crystalline MoO3, or NiO. It is
hypothesized that microcrystals or amorphous materials are
formed even though the interaction of Mo and Ni with the support
is weak; it is not weak enough to form bigger crystalline phases
which are too small to be detected by XRD. Curve E represents the
XRD pattern of 4%Ni–20%Mo/Goethite. XRD peaks at 16.18, 18.88
Fig. 1. XRD patterns of (A) goethite, (B) goethite calcined at 400 8C, (C) 1% Ni–
4.5%Mo/Fe2O3 (D) 1%Ni–4.5%Mo/goethite, and (E) 4%Ni–20%Mo/goethite.
118 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122

Fig. 2. SEM image of (A) goethite, (B) goethite calcined at 400 8C, (C) 1% Ni–4.5%Mo/Fe2O3, and (D) 1%Ni–4.5%Mo/goethite.

and 28.58 (broad) indicate that Ni and Mo are converted into
clusters of their oxide forms [39,40]. It is also difficult to find any
individual Ni or Mo XRD peaks in curve E, as its intensity is very low
and some peaks merge with the calcined goethite.
Morphology, ICP and N2 sorption analysis
SEM image of the Ni and Mo supported catalysts are shown in
Fig. 2. Particle sizes and shapes are presented in Table 2. Specific
surface area and ICP-AES results are also presented in Table 2.
The BET surface area study indicates that the supported
catalysts have low surface area. After calcination, the surface
area of the catalysts is decreased, which may be due to removal
of water molecules, and as a result the material structure
shrinks. From ICP-AES analysis it is clear that the Ni and Mo
content on the supports deviates from the calculated amount of
metal loading, but the Ni and Mo deviation is within the
experimental error range.
H2 TPR study
After characterization of the oxide forms of the supported
catalysts by XRD, N2 sorption, SEM and ICP-AES, it was decided to
investigate the reducibility of Ni and Mo oxide species impregnat-
ed on the support, using the H2-TPR method. This is a valuable
technique to determine the type of interaction that exits between
metals (Ni and Mo) and support (a-FeOOH, Fe2O3 and g-Al2O3). A
typical metal/support interaction profile is represented in Fig. 3.
Under the applied conditions, Ni and Mo species are reduced and
show the reduction temperature in the H2-TPR profile. The
reduction temperature is characteristic of the metal/support
interaction.
In the literature it is reported that the H2-TPR profile of pure
MoO3 shows two major sharp peaks at 765 and 894 8C and a
shoulder peak at 797 8C [41]. Bhaskar et al. reported two reduction
peaks at 767 and 997 8C and one minor peak at 797 8C. The sharp
peak at 767 8C corresponds to the partial reduction

Table 2
Particle shape and size, BET surface area and metal content of catalysts.

Catalysts SEM BET ICP (wt%)

Shape Size (nm) SA (m2/g) Ni Mo Fe

Goethite Needle like 100–1000 16 0.0 0.0 58.6

1%Ni–4.5%Mo/Goethite Needle like 10 1.0 4.4 57.4
1%Ni–4.5%Mo/Fe2O3 Pseudo cubic 6 1.0 4.3 60.7
4%Ni–20%Mo/Goethite Needle like 12 3.2 18.6 44.1
1%Ni–4.5%Mo/g-Al2O3 Non spherical 191 0.9 4.2 –
1%Ni/Goethite – – – 1.0 – 66.6
5%Ni/Goethite – – – 4.3 – 62.6
5%Mo/Goethite – – – – 5.0 57.4
8%Mo/Goethite – – – – 7.2 49.3
 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122
Fig. 3. H2-TPR curves of (A) 1%Ni–4.5%Mo/g-Al2O3, (B) 1%Ni–4.5%Mo/goethite, (C)
4% Ni–20%Mo/goethite, and (D) 1%Ni–4.5%Mo/Fe2O3.
(MoO3 ! MoO2) of amorphous, highly defective, multilayer Mo
oxides or heteropolymolybdates (octahedral Mo species) MoO3
species. The peak at 997 8C relates to the reduction of highly
dispersed tetrahedral MoO2 species (MoO2 ! Mo). A shoulder peak
at 797 8C can correspond to Mo4O11 species formed during the
reduction of microcrystalline MoO3 or clusters of Mo2 oxide
formed at the time of preparation [41,42].
The NiO reduction peak appears at 300 8C [43]. When
incorporating Ni and Mo on a g-Al2O3 support, the Ni reduction
temperature shifts to a higher temperature (593 8C) and the Mo
reduction temperatures are observed at a lower temperature, i.e.
370 8C and 830 8C [44]. On examining the 1%Ni–4.5%Mo/g-Al2O3
catalyst H2-TPR profile, three reduction peaks were traced at the
reduction temperature, 350 8C, 600 8C and 771 8C (curve A). If a
weak interaction between Mo and the support exits, the reduction
occurs at a lower temperature region [44].
When the same amount of Ni and Mo (1%Ni–4.5%Mo/Goethite)
were dispersed on the goethite support, a significant shifting of the
lower reduction temperature was observed. Thus the goethite
support interacts differently with Ni and Mo. For the 1%Ni–
4.5%Mo/Goethite catalyst, H2-TPR peaks were observed at 347 8C,
477 8C, 636 8C and 686 8C (curve B), which is a lower reduction
temperature than that of the 1%Ni–4.5%Mo/g-Al2O3 catalyst.
This result indicates that the number of reduction peaks and the
reduction temperature depends on the dispersion of the metal and
the nature of the support. This observation can be supported with
XRD results. It can be concluded that, compared to g-Al2O3, the
goethite support is weakly interacting with Ni and Mo. The 4%Ni–
20%Mo/Goethite (curve C) shows reduction peaks at 450, 626, 700,
780 and 894 8C. The reduction peaks observed at higher tempera-
ture correspond with higher loading on the goethite. It seems that
at higher loading a complex interaction between the goethite and
active species occurs. The shifting to a higher reduction tempera-
ture may be attributed to the formation of a large amount of bulk
crystalline MoO3 and a-NiMoO4 phase, due to poor interaction
with the goethite support during impregnation.
However, low loading with Ni and Mo on the support leads to a
highly dispersed oxide form rather than a complex form. In the
literature, it is reported that when Ni and Mo mix together at a Ni/
Mo molar ratio of 0.3, the reduction temperatures are observed at
about 500 and 700 8C, which corresponds to a-NiMoO4, and the
signals at approximately 630 8C and 750 8C can be assigned to the
MoO3 reduction peak [45]. A similar pattern was observed for the
4%Ni–20%Mo/Goethite sample. The peak at 894 8C may be the total
119
reduction of MoO3. Curve D represents the reduction temperatures
of the 1%Ni–4.5%Mo/Fe2O3 catalyst, which appear at 487, 637 and
701 8C. The reduction pattern is completely different as compared
to other supports having the same Ni and Mo loading. The 1%Ni–
4.5%Mo/Fe2O3 reduction peaks are similar to the b-NiMoO4
reduction peaks [39].
The aforementioned characterization results (XRD, N2 sorption,
ICP-AES, and H2-TPR) of Ni, Mo supported catalysts, showed that
the nickel and molybdenum species are of different type and their
dispersion on the support is strongly influenced by their
composition (NiO and MoO3) and the type of support (a-FeOOH,
Fe2O3 and g-Al2O3).
It is proposed that when Ni and Mo are added to the support,
there is an interaction between the Ni, Mo and support. The –OH
groups on the support interact with metal to form a uniform
dispersion of Ni and Mo on the support. This interaction depends
on the –OH concentration on the support and the metal
concentration. A higher amount of metal loading leads to the
formation of a metal complex and metal oxide on the support, as
does a lack of –OH groups on the support.
Hence, in the case of 4%Ni–20%Mo/Goethite, a different
reduction was observed. As iron oxide does not have sufficient –
OH groups on its surface to interact with metal ions, the metal ions
interact with each other rather than the support. As a result, the
metal forms a stable complex (b-NiMoO4) on the supports [36].
Due to the formation of a stable complex, the iron oxide shows
completely different reduction peaks, and reduced amounts of
hydrocracking liquid products were observed, as compared to the
goethite support.
Catalytic activity
This study is mainly focused on (i) identifying a catalyst for
hydrocracking VR in a batch type reactor; (ii) evaluating time on
stream (TOS); bimetal composition, the effect of temperature and
hydrocracking product distribution; (iii) recycling of the best
catalyst; (iv) optimizing the reaction parameters to achieve the
highest yield of low boiling point liquid, as well as saturates and
aromatics in liquid product.
Catalysts evaluation for the VR hydrocracking reaction performance
Fig. 4 shows the mass fractions (or yields) of gas, liquid, and
solid residue formed during the hydrocracking of VR. According to
reports, the liquid products were analyzed using TGA [30–32].
Based on the TGA analysis results, the liquid products were
classified as naphtha (IBP-120 8C), middle distillate (120–380 8C)
and VGO (380–600 8C). Initially, VR contains 11.7% of <380 8C and
88.3% of >380 8C boiling point material. In the absence of a catalyst
(W/O), liquid products were only 45.1% (8.9% naphtha, 32.4%
middle distillate and 3.8% VGO), 12.3% were gas, and 40% were
solid residue. When the goethite support itself was used as a
catalyst, 60.2% liquid (9.7% naphtha, 46.3% middle distillate and
4.2% VGO), 28.7% solid, and 11% gaseous products were obtained.
However, when bimetallic catalysts were applied, the yields of
liquid products were increased with a decreasing yield of solid
residue. Specifically, using the 1%Ni–4.5%Mo/Goethite catalyst, a
69.8% liquid products yield (8.6% naphtha, 51.4% middle distillate
and 9.8% VGO) was observed, and this was the highest yield among
the synthesized catalysts. Consequently, gas and solid residue
were decreased to 20% and 10.2%, respectively.
In the absence of catalyst (W/O), the VR hydrocracking reaction
is very poor. In the presence of 1%Ni–4.5%Mo/g-Al2O3 and 1%Ni–
4.5%Mo/Fe2O3, 63.6% (7.9% naphtha, 47% middle distillate and 8.6%
VGO) and 55.7% (9.4% naphtha, 41.9% middle distillate and 4.5%
VGO) liquid products were obtained, respectively. In the case of
iron oxide and gamma alumina supports, less liquid products and
120 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122
Fig. 4. Product distribution during hydrocracking of vacuum residue for various
catalysts. Reaction conditions: 420 8C, initial H2 70 bar, 3 h.
higher solid residue and gaseous products were observed. This may
be due to high surface acidity (in the case of g-Al2O3) and less
metal/support interaction (in the case of Fe2O3).
Using 4%Ni–20%Mo/Goethite, 62.3% liquid (8.6% naphtha, 45.2%
middle distillate and 8.4% VGO), 25% solid residue and 12.5%
gaseous product were observed. The liquid product is much less
than that obtained with the 1%Ni–4.5%Mo/Goethite catalyst. This
observation is contradictory to the expected results. Comparing
these two catalysts (1%Ni–4.5%Mo/Goethite and 4%Ni–20%Mo/
Goethite), the ratio of Mo/Ni + Mo is different in accordance with
the active phase and carrier. The metal/support interaction (H2-
TPR study) is also different in the two catalysts. This may be the
reason for the overcracking of VR by the 4%Ni–20%Mo/Goethite
catalyst. In fact, the 1%Ni–4.5%Mo/Goethite catalyst was better
than the other synthesized catalyst in terms of the liquid product
yield (find the liquid product yield in Fig. 4). The distribution of
liquid products produced by the 1%Ni–4.5%Mo/Goethite catalyst
was slightly greater in terms of the lighter oil components, than
that of other synthesized catalyst, which means that the 1%Ni–
4.5%Mo/Goethite is more active in the hydrocracking of heavy
fractions in VR.
The liquid products obtained from the hydrocracking reactor
are a complex mixture having many of organic compounds.
According to polarity, the organic components present in the liquid
products are divided into four fractions, saturates, aromatics,
resins and asphaltenes (SARA). The quality of the hydrocracking
liquid products (SARA analysis results) are compared in Fig. 5.
Initially, VR contains 4% saturates, 61% aromatics, 18% resins and
17% asphaltenes. After the hydrocracking of VR in the presence of
catalysts, 25–28% saturates, 64–70% aromatics, 3–10% resins and
>1% asphaltenes were present in the liquid products. Among the
liquid products obtained from the 1%Ni–4.5%Mo/Goethite catalytic
reaction, saturates product content was the highest. As the
asphaltenes content in the liquid products was >1%, the quality
of the liquid product was upgraded.
Effect of reaction temperature on hydrocracking of VR
It is well known that the cracking of VR in the presence of
hydrogen is endothermic. Characteristically, at room temperature,
VR is a semisolid material, and on applying heat the semisolid
material becomes liquid. The liquid diffuses on the catalyst surface
Fig. 5. SARA analysis result of liquid products during hydrocracking of vacuum
residue for various catalysts. Reaction conditions: 420 8C, initial H2 70 bar, 3 h.
which increases the interaction between the VR molecule and
catalyst. Thus, the reaction temperature has a great impact on the
formation of low boiling point liquid products. Reaction results
indicate that the trend of the weight fraction of each component
from VR hydrocracking is affected by the applied temperature.
At 410 8C, 58% of liquid products (6.8% of naphtha, 45.1% of
middle distillate and 6.2% of VGO) were obtained. With a 10 8C rise
in reaction temperature (at 420 8C), 69.8% of liquid products (8.6%
naphtha, 51.4% middle distillate and 9.8% VGO) were obtained with
20% of solid residue formation. This indicates that at 410 8C VR was
partially converted into liquid products. However, with increasing
reaction temperature, more VR was converted into low boiling
point liquid products along with 1.9% more gaseous products
formation. A further 10 8C rise in reaction temperature (at 430 8C),
resulted in 60.8% of liquid products (11% of naphtha, 44.6% of
middle distillate and 5.2% of VGO) along with progressive
production of solid residue (22.8%) and gaseous (16%) products.
The liquid products yield decreased with the increase in
hydrocracking reaction temperature due to the overcracking of
liquid products. Thus, the yield of liquid products increases up to
420 8C with 3 h reaction time, and then thermal decomposition of
the liquid products occurred with further increases in time and
temperature. Among the tested reaction temperatures, 420 8C was
found to be the best reaction temperature to obtain high yields of
low boiling point liquid products.
The effect of reaction temperature on the formation of
saturates, aromatics, resins and asphaltenes product is presented
in Table 3. It is observed that saturates product concentration is the
highest, 28.1%, at 420 8C with 3 h reaction time, and its
concentration decreases with a further rise in reaction tempera-
ture. It is proposed that at higher temperature, the saturates
product is decomposed into gaseous products (as liquid product
decreased from 69.8% to 60.8%). However, the aromatics concen-
tration was increased by the decrease in the resins products with a
rise in reaction temperature.
Effect of reaction time on the conversion of VR
Reaction time is also a factor that can influence the yield of
liquid products. In this experiment, a 2–6 h reaction time and
420 8C temperature was chosen. Normally, with increasing
reaction time, product(s) yields increase. In our study, we observed
the same phenomenon: the yield of hydrocracked liquid products
was increased by increasing the duration of reaction time from 2 to
3 h. The amount of liquid products was 61.1% (6.7% of naphtha,
 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122 121

Table 3
Influence of process parameters on vacuum residue hydrocracking into organic fractions.A

Catalyst Process parameters SARA analysis

Temperature (8C) Time (h) Sa Ab Rc Ad

Effect of temperature
1%Ni–4.5% Mo/Goethite 410 3 23 59.6 14.6 2.8
420 28.1 62.5 8.4 1
430 19.6 72.5 7.4 0.4

Time on stream
1%Ni–4.5% Mo/Goethite 420 2 24.8 67.4 7.2 0.7
3 28.1 62.5 8.4 1
4 25.9 68.3 5.7 0.2
6 23.8 69.8 5.8 0.6

Effect of single metal

1%Ni–4.5%Mo/Goethite 420 3 28.1 62.5 8.4 1
5%Mo/Goethite 28.6 65.2 5.5 0.6
8%Mo/Goethite 25.3 71.3 3.2 0.2
1%Ni/Goethite 21.2 74.7 3.9 0.3
5%Ni/Goethite 26.7 68.6 4.4 0.3

Recyclability
1%Ni–4.5%Mo/Goethite 1st run 420 3 28.1 62.5 8.4 1
1%Ni–4.5%Mo/Goethite 2nd run 24.6 67.1 7.7 0.6
1%Ni–4.5%Mo/Goethite 3rd run 18.6 73.2 8.0 0.2

Sa = Saturates, Ab = Aromatics, Rc = Resins, Ad = Asphaltenes.

A
All reactions were carried out at H2 initial pressure of 70 bar.

43.9% of middle distillate and 10.5% of VGO) at 420 8C in 2 h, and
increased to 69.8% at the end of 3 h reaction time. However, a
further increase in reaction time led to a decrease in the liquid
products’ (69.8% in 3 h and 57.6% in 6 h at 420 8C) yield. This
decrease in the liquid yield is reflected in the formation of solids
and gaseous products, whose yields increased from 20% (3 h) to
29.7% (6 h) and 10.2% (3 h) to 12.7% (6 h), respectively.
Excessive reaction time leads to a small reduction in the liquid
product yield due to overcracking of the liquid product, resulting in
a loss of liquid products. The increase in the liquid product in the
first 3 h appears to be affected by the catalytic rather than the
thermal reaction, but when prolonging the reaction time the liquid
product is more affected thermally, as the catalyst becomes
deactivated. Therefore, the liquid product formation decreased as a
function of the rate of catalyst deactivation. 3 h was determined to
be the optimum reaction time at 420 8C.
The effect of reaction time on the composition of hydrocarbon
groups (saturates, aromatics, resins and asphaltenes) in the liquid
products is indicated in Table 3 also. It shows that initially,
saturates product increases with reaction time but decreases with
the increasing operation time. The aromatics fraction increased
along with reaction time. Asphaltenes fraction was negligible in
the liquid products.
only 5% and 8% of Mo loading on goethite resulted in 66.8% (8.4%
naphtha, 50.1% middle distillate and 8.3% VGO) and 63% (12.5%
naphtha, 47% middle distillate and 3.5% VGO) of liquid products,
respectively. With 1% and 5% of Ni only, 63.1% (9.6% naphtha, 46.6%
middle distillate and 6.9% VGO) and 63.7% (8.8% naphtha, 46.7%
middle distillate and 8.2% VGO) liquid products were obtained,
respectively.
The reaction results suggest that with 8% loading of Mo on
goethite support, the liquid product yield decreased due to
overcracking of VR. 5% of Mo loading on goethite was the optimum
for obtaining a high yield of liquid products. However, Ni loading
(1–5%) on goethite did not affect liquid products yield, which
indicates that nickel promotes the hydrocracking reaction.
Using 1%Ni–4.5%Mo/Goethite, 69.8% of liquid products was
obtained. Due to the synergistic effect of Ni and Mo bimetal on
goethite, the catalyst showed better performance and a high yield
of liquid (low boiling point) products. According to the synergistic
mechanism of multi-component (Ni, Mo bimetallic) active metal
catalysts, nickel plays a role in hydrogen activation, transferring
protons and electrons to the molybdenum [48]. The synergy is

Effect of single metal on the hydrocracking of VR

Ni–Mo supported on goethite is a bifunctional catalyst which
has both cracking and hydrogenation capability. The cracking
function is provided by the support (as goethite itself gave 60.2%
liquid products, as shown in Fig. 4) and the hydrogenation function
can be attributed to Ni and Mo [3,46,47]. The hydrocracking
reactions were strongly influenced by the bimetal composition
(Mo/Ni + Mo ratio) as well as the weight of bimetal loading,
resulting in the high yield of liquid products. In order to study the
effect of a single metal and its concentration, 4 different catalysts,
5%Mo/Goethite, 8%Mo/Goethite, 1%Ni/Goethite and 5%Ni/Goe-
thite, were synthesized and used for VR hydrocracking experi-
ments. The real metal loading (ICP-AES analysis) on the goethite is
provided in Table 2.
The VR hydrocracking reaction was carried out using a single
metal loaded on goethite and the reaction results were compared Fig. 6. Product distribution during hydrocracking of vacuum residue for various
with bimetal catalysts (Fig. 6). The reactions for the catalyst with catalysts. Reaction conditions: 420 8C, initial H2 70 bar, 3 h.
122 R. Sahu et al. / Journal of Industrial and Engineering Chemistry 35 (2016) 115–122
closely related to the metals’ content ratio. Consequently, both the
total and the ratios of the metals content should be taken into
account in the process of catalyst design. With a lack of Ni for
hydrogen activation and transferring, polymerization might be the
dominant reaction over the Mo/Goethite catalyst.
Catalyst recycling test
After the first run of fresh catalyst, the solid residue was
recovered, which contains catalyst, unconverted VR and metals.
The unconverted VR and other organic carbons were removed by
washing with dichloromethane. The washed catalyst was sub-
jected to drying and used for the next run (reaction) with the same
amount of VR under similar reaction conditions. In the 2nd and 3rd
runs, 66.2% and 57.8% of liquid yield was observed, respectively.
The decrease in liquid amount may be due to the decrease in active
sites of the catalysts, or the catalyst was deactivated. The catalyst’s
deactivation may be due to the strong adsorption of carbon and
metal, which poison the catalyst during the catalytic run. Catalyst
handling loss during the recovery process could not be avoided.
That is another reason for the decrease in liquid products with each
successive run.
Conclusions
Ni–Mo was successfully supported on goethite, gamma alumina
and iron oxide supports by use of the wet impregnation method.
The impregnated catalysts were calcined to convert the metal to
oxide form on the support. The prepared catalysts were well
characterized by various analytical techniques.
Among the synthesized catalysts, the catalytic activity efficien-
cy was as follows: 1%Ni–4.5%Mo/Goethite > 1%Ni–4.5%Mo/g-
Al2O3 > 4%Ni–20%Mo/Goethite> 1%Ni–4.5%Mo/Fe2O3 at 420 8C
in 3 h reaction time under 70 bar initial hydrogen pressure.
Metal/support interaction is the main cause for the increase in
catalytic activity. Low solids (20%), high conversion (80%) and good
quality of the liquid products (8.6% of naphtha, 51.4% of middle
distillate and 9.8% of VGO) were obtained using the 1%Ni–4.5%Mo/
Goethite catalyst. 28.1% saturates, 62.5% aromatics, 8.4% resins and
>1% asphaltenes products were obtained.
Higher Ni–Mo loading on the support surface caused a decrease
in the yield of liquid products. In addition, our work also confirmed
that the amounts of naphtha and middle distillate fractions
increased with reaction time up to 3 h at 420 8C and then
decreased. VGO fraction and solid residue formation continuously
increased with increase in reactor temperature. Using a single
metal on goethite, the liquid product did not increase more than
66.8%, while using a Ni–Mo supported catalyst, 69.8% liquid
products were obtained. These results imply that the Ni and Mo
have a synergetic effect on VR conversion into liquid product. The
results of the hydrocracking VR reaction indicate that the catalyst
could be reusable.
Acknowledgments
We would like to acknowledge the financial support from the
R&D Convergence Program of MSIP (Ministry of Science, ICT and
Future Planning) and ISTK (Korea Research Council for
Industrial Science and Technology) of Republic of Korea
(Grant B551179-12-07-00). The authors also acknowledge to
KIIT University for granting of study leave.
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