Front. Chem. Sci. Eng.
2014, 8(2): 161–170
DOI 10.1007/s11705-014-1430-1
RESEARCH ARTICLE
Hydrotreating of light gas oil using a NiMo catalyst supported
on activated carbon produced from fluid petroleum coke
N. Rambabu1, Sandeep Badoga1, Kapil K. Soni1, A.K. Dalai (✉)1, J. Adjaye2
1 Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical and Biological Engineering,
University of Saskatchewan, Saskatoon, SK, S7N 5A9, Canada
2 Syncrude Edmonton Research Centre, Edmonton, AB, T6N 1H4, Canada
© Higher Education Press and Springer-Verlag Berlin Heidelberg 2014
Abstract Nitric acid functionalized steam activated
carbon (NAFSAC) was prepared from waste fluid
petroleum coke (FPC) and used as a support material for
the synthesis of a NiMo catalyst (2.5 wt-% Ni and 13 wt-%
Mo). The catalyst was then used for the hydrotreatment of
light gas oil. The support and catalysts were characterized
by Brunauer-Emmett-Teller (BET) gas adsorption method,
X-ray diffraction, H2-temperature programmed reduction,
NH3-temperature programmed desorption, CO-chemisorp-
tion, mass spetrography, scanning electron microscopy
(SEM), Boehm titration, and Fourier transform infrared
spectroscopy (FTIR). The SEM results showed that the
carbon material retained a needle like structure after
functionalization with HNO3. The Boehm titration, FTIR,
and BET results confirmed that the HNO3 functionalized
material had moderate acidity, surface functional groups,
and mesoporosity respectively. The produced NAFSAC
had an inert nature, exhibited the sink effect and few metal
support interactions, and contained functional groups. All
of which make it a suitable support material for the
preparation of a NiMo hydrotreating catalyst. Hydrotreat-
ing activity studies of the NiMo/NAFSAC catalyst were
carried out under industrial operating conditions in a
laboratory trickle bed reactor using coker light gas oil as
the feedstock. A parallel study was performed on the
hydrotreating activity of NiMo/γ-Al2O3 as a reference
catalyst. The hydrodesulfurization and hydrodenitrogena-
tion activities of the NiMo/NAFSAC catalyst were 62%
and 30%, respectively.
Keywords activated carbon, fluid petroleum coke, NiMo
catalyst, hydrotreating, light gas oil
Received December 30, 2013; accepted January 25, 2014
E-mail: akd983@campus.usask.ca
1 Introduction
The US Energy Information Administration (EIA) and the
2013 British Petroleum (BP) Statistical Review of World
Energy reported that global oil production in 2012 was
approximately 4,119 million tons. Due to increasingly
stringent environmental regulations, the US Environmental
Protection Agency (USEPA) limits the sulfur content in
gas oil to 15 ppm. Hydrotreating processes are widely used
in refineries for removing sulfur and nitrogen containing
compounds, as well as other contaminants, from oil
feedstocks. Sulfided Ni(Co)-Mo(W) catalysts supported
on γ-alumina have long been used commercially for
hydrotreating but efforts to develop new supports and
catalysts with improved catalytic activity are ongoing.
Various research groups have developed new support
materials for hydrotreating catalysts such as mesoporous
silica (Ti-SBA-15, MCM-41) [1], mesoporous carbon [2],
mixed oxides (ZrO2-Al2O3) [3], zeolites (ZSM-5) [4], and
MCM – 41 [5]. Recently the role of a carbon support in
improving the activity of NiMo hydrotreating catalysts has
been demonstrated [6–8].
The increasing use of oil sands derived bitumen in
refineries has produced large quantities of petroleum coke.
The global production of petroleum coke was 80 million
metric tons per annum (MMTPA) in 2000. By 2010,
petroleum coke production had increased to 123 MMTPA,
and is expected to reach 161 MMTPA by 2015. Raw
petroleum coke generally has a high content of sulfur, ash,
and metal. The steel and aluminum industries require very
pure low sulfur petroleum coke for the production of quality
electrodes. Therefore, researchers are focusing on alternate
uses for this lower quality petroleum coke. There have been
several studies on the utilization of different kinds of
petroleum coke, including delayed coke, needle coke, shot
coke, and flexi coke, for the production of activated carbon
[9–12]. However, there has been less work focused on using
fluid coke for the production of activated carbon.
162 Front. Chem. Sci. Eng. 2014, 8(2): 161–170
Fluid coke is less reactive than other petroleum cokes,
due to its stable micrographitic structure and the lack of
pores [13]. Some recent studies have utilized fluid coke for
the production of activated carbon [14], for the adsorption
of ammonium ions and for H2S oxidation [15], for the
adsorption of water vapor and acetone [16], and for the
upgradation of heavy vacuum gas oil [17] using KOH
activation.
Chemical and physical activation are two important
methods for the production of activated carbon. In
chemical activation, a dehydrating agent such as H2SO4,
ZnCl2, KOH, or H3PO4 promotes the formation of a rigid
matrix. These processes have the advantages of not being
prone to the loss of volatile materials and they help to
produce materials with large surface areas and pore
volumes. In addition, chemical activation can be done
with short activation times and at low temperatures. For
these reasons, many studies have focused on chemical
activation. However, due to environmental concerns the
USEPA recommends minimal usage of chemical agents
and zinc chloride has been banned due to environmental
concerns [18].
In contrast, physical activation uses mild oxidizing
agents such as CO2 or steam which are environmentally
friendly and can produce a high quality activated carbon at
optimum operational conditions [19]. For these reasons,
physical activation is more attractive and cost-effective
than chemical activation for the production of activated
carbon. Small et al. 2012 [20] and Rambabu et al. 2013
[15] produced activated carbon from petroleum coke using
steam activation and then used the activated carbon for the
treatment of oil sands tailings water and for the catalytic
oxidation of H2S, respectively. However, there have been
no reports on the synthesis of hydrotreating supported
catalysts using steam activated carbon produced from fluid
petroleum coke.
This work investigates the performance of nitric acid
functionalized steam activated carbon (NAFSAC) pro-
duced from fluid petroleum coke as a support material for a
NiMo hydrotreating catalyst. The support material and
catalysts were characterized using various characterization
techniques in order to understand the mechanisms
involved in the activation process. The activity of the
catalyst for the hydrotreating of coker light gas oil (KLGO)
was investigated. The main goal of this work was to utilize
waste fluid coke to synthesize a new support material for a
hydrotreating catalyst in an environmentally friendly and
cost-effective manner. In addition NiMo/γ-Al2O3 was
prepared using commercial γ-Al2O3 as a reference catalyst.
2 Experimental
2.1 Preparation of activated carbon
Fluid petroleum coke was obtained from Syncrude Canada
Ltd., and sieved to give particles in the range of 150–350
µm. Steam activation followed by functionalization with
HNO3 was used to produce activated carbon. The
experimental set-up and detailed process are described in
our earlier study [15]. For steam activation, 20.0 g of fluid
petroleum coke was placed into the reactor and the
nitrogen flow was adjusted to 100 mL/min. The activation
temperature was increased to 900 °C at a heating rate of
4 °C/min, and the steam activation was carried out for 9 h.
The sample was then cooled to ambient temperature under
a N2 flow.
The steam activated carbon (SAC, 5.0 g) was then
placed into a 500-mL three-neck round-bottom flask and
250 mL of 8 M HNO3 solution was added to this flask.
This mixture was refluxed at 90 °C, with magnetic stirring
for 2.5 h. A reflux condenser was used to recover the
evaporated HNO3 (oxidizing reagent) during the process.
The sample was washed with water to remove excess acid
(pH 7
0.5) and the product was dried overnight at 120 °C.
2.2 Catalyst preparation
To prepare the NiMo catalyst, the activated carbon support
material was prepared using a physico-chemical method.
The carbon support was first dried at 110 °C for 5 h to
remove moisture and then the support was impregnated
with 13 wt-% Mo using an ammonium heptamolybdate
solution. Next the sample was dried at 120 °C for 6 h,
calcined at 550 °C for 5 h, and 2.5 wt-% Ni was then
incorporated using nickel nitrate dissolved in an aqueous
solution. The metal impregnated sample was then dried at
120 °C for 5 h and calcined at 550 °C for 5 h. A NiMo/γ-
Al2O3 catalyst was also prepared as a reference catalyst,
using the same method. The γ-Al2O3 support material was
purchased from Sigma Aldrich. The catalyst NiMo/
NAFSAC was pelletized using 10% bentonite to maintain
its mechanical strength and the catalyst NiMo/γ-Al2O3 was
pelletized without any binding agent. The size of the
pellets were 12 mesh, US.
2.3 Characterization
2.3.1 Pore structure analysis
The pore size distributions, Brunauer-Emmett-Teller
(BET) surface areas, and pore volumes of the catalyst
and support materials were measured by a Micromeritics
ASAP 2000 instrument using low temperature N2 adsorp-
tion-desorption isotherms. The sample was first degassed
in vacuum at 200 °C. The surface area was computed using
the multi-point BET method. The value of 0.1620 nm2 was
taken for the cross-section of the physically adsorbed N2
molecule. The total pore volume was calculated from the
amount of nitrogen adsorbed at P/P0 = 0.95, assuming that
adsorption on the external surface was negligible com-
pared to the adsorption in the pores. The pore diameters
 N. Rambabu et al. Hydrotreating of light gas oil using a NiMo catalyst
and pore volumes were determined using the Barrett-
Joyner-Halenda (BJH) method.
2.3.2 SEM analysis
The morphological features of the samples were studied by
scanning electron microscopy using a JEOL 2011 Scan-
ning Electron Microscope. The sample was ground to 100
mesh and the powdered sample was dispersed in heptane in
an ultrasonic bath for several minutes. A few drops were
then deposited on 200 mesh copper grids covered with a
porous carbon film. The electron micrographs were
recorded as electron negative films.
2.3.3 FTIR analysis
Surface functional groups on the support material were
examined by FTIR spectroscopy using the KBr pellet
technique at room temperature. The spectra were recorded
from 400 to 4000 cm–1 with a resolution of 4 cm–1 by an
infrared spectrometer (PerkinElmer Spectrum 100 Series
FTIR, USA).
2.3.4 Mass spectroscopy analysis
The ash content of the raw fluid petroleum coke was
determined using an inductively coupled plasma-mass
spectrometer (ICP-MS, Model Sciex Elan 5000, manufac-
tured by Perkin Elmer, USA).
2.3.5 Temperature programmed reduction (TPR) analysis
H2-temperature programmed reduction (H2-TPR) of the
catalysts was carried out using a temperature programmed
desorption (TPD)/TPR Quantachrome autosorb-iQ instru-
ment for analyzing the nature of the reducible metal
species in the samples. A 0.1 g-sample in a quartz tube was
purged with helium at 400°C for 1 h to remove surface
impurities. After the sample was cooled to room
temperature in flowing He, TPR was carried out using a
3% H2/N2 (v/v) mixture at a flow rate of 30 mL/min. The
heating rate was 10 °C/min from room temperature to
1000°C. The TPR profiles were recorded with a thermal
conductivity detector.
2.3.6 Temperature programmed desorption (TPD) analysis
NH3-temperature programmed desorption (NH3-TPD) of
the catalysts was carried out using a TPD/TPR Quanta-
chrome autosorb-iQ instrument for analyzing the acidic
properties of the catalyst. A 0.1-g sample was purged with
helium at 200 °C prior to ammonia adsorption. NH3 was
adsorbed at 50 °C followed by purging with He for 2 h to
remove physically-adsorbed ammonia. TPD analysis was
then done up to 950 °C at a ramp rate of 10 °C/min.
163
2.3.7 CO chemisorption
The carbon monoxide uptake by the catalyst was measured
using a Micromeritics ASAP 2020 instrument. The sample
was pre-treated for moisture removal in the presence of
helium gas at 110 °C for 10 min. Prior to CO chemisorp-
tion measurements; the sample was reduced in situ in the
presence of a H2 flow at 350 °C until the static pressure was
steady at less than 6.6  10–4 Pa. The chemisorption was
performed by passing CO pulses over the samples to
measure the total gas uptake at 35 °C.
2.3.8 X-ray diffraction (XRD) analysis
The X-ray diffraction patterns of the samples were
measured using a Bruker D8 Advance Powder Diffract-
ometer with a Ge monochromator producing monochro-
matic Cu Kα radiation. In all cases, the generator was
operated at 40 kV and 30 mA. To avoid the problem of
illuminating areas at low 2θ angles, all samples were
measured using the same sample holder. Broad angle
powder X-ray diffraction patterns of all catalysts were
recorded on a Rigaku diffractometer using Cu Kα radiation
in the range 10°–80° with a scan rate of 2 °/min.
2.3.9 Boehm analysis
The concentrations of acid functional groups were
measured using the Boehm titration method [21]. Different
samples of activated carbon (0.2 g) were placed in 25 mL
of 0.05 mol/L sodium hydroxide, 0.05 mol/L sodium
bicarbonate, 0.05 mol/L sodium carbonate, and 0.05
mol/L hydrochloric acid. The vials were shaken for 24 h
and filtered. After filtration; 5 mL of each filtrate was
titrated with HCl or NaOH, depending on the soaking
solution used. The number of acidic functional groups of
various types was calculated under the assumptions that
NaOH neutralizes carboxylic, phenolic, and lactonic
groups; Na2CO3 neutralizes carboxylic and lactonic
groups; and NaHCO3 neutralizes only carboxylic groups.
The number of surface basic sites was calculated from the
amount of hydrochloric acid that reacted with the carbon.
2.3.10 Catalytic activity
Hydrodesulfurization (HDS) and hydrodenitrogenation
(HDN) reactions were performed in a trickle bed reactor
using coker light gas oil derived from Athabasca bitumen
as the feedstock. KLGO is a complex combination of
hydrocarbons produced from a thermal cracking process
(fluid coker). It consists of hydrocarbons having carbon
numbers predominantly in the range of C11–C28 with
boiling points in the range of 200–450 °C. It has a specific
gravity of 0.95 at 20 °C and it contains 0.24 wt-% and 2.30
wt-% of nitrogen and sulfur, respectively.
164 Front. Chem. Sci. Eng. 2014, 8(2): 161–170
The high pressure reaction set up consists of a liquid and
gas feed section, a reaction section, a high pressure gas-
liquid separator, and a heater with a temperature controller.
The flow of liquid and gas through the reactor is
concurrent. The length and internal diameter of the reactor
are 240 mm and 14 mm, respectively. This reactor
simulates the process that takes place in industrial hydro-
reactors.
The catalyst was diluted with silicon carbide to
minimize any problems related to axial dispersion,
channeling effects, wetting characteristics and temperature
fluctuation. In addition, silicon carbide helps to increase
the length of the catalyst bed. When the length of the
catalyst bed is increased, the axial dispersion is substan-
tially reduced since a large length (L) to particle diameter
(dp) ratio meet the Mears criterion (L/dp > 50). In the
present study, L/dp = 65 (L = 11 cm and dp = 0 0.168 cm)
which meets the Mears criterion. The details of the catalyst
loading are as described elsewhere [1].
Sulfidation of the catalyst was done by injecting 5 mL/
min of a sulfiding solution (2.9 vol-% butanethiol) into a
straight-run atmospheric gas oil at 8.8 MPa and 193 °C for
24 h. A H2/sulfiding solution ratio of 600 mL/mL was
maintained during the sulfidation. The temperature of the
reactor was then increased to 343 °C and maintained for
another 24 h. After sulfidation, the catalyst was pre-coked
with KLGO for 5 days at 370°C and 8.8 MPa with a liquid
hourly space velocity (LHSV) of 2.0 h–1. Following pre-
coking, the HDN and HDS activities of the catalysts were
studied at 370 °C using KLGO for 3 days under the same
operating conditions. The products were collected at 12 h
intervals and stripped with nitrogen for removing dissolved
ammonia and hydrogen sulfide. The total nitrogen content
of the hydrotreated product was measured using a
combustion/chemiluminescence technique (ASTM
D4629) and the sulfur content was measured using a
combustion/fluorescence technique (ASTM D5463). The
concentrations of sulfur and nitrogen were determined
using an Antek 9000 NS analyzer.
3 Results and discussion
3.1 Production of steam activated carbon
Steam activation is a more cost-effective and eco-friendly
process for the production of activated carbon than
chemical activation. In steam activation, the development
of a porous structure depends on process parameters such
as the activation temperature and time, and the steam flow-
rate. An increase in activation time leads to an increase in
surface area, but long activation periods result in the walls
of the pores becoming thin and collapsing [22,23]. An
increase in activation temperature also results in an
increase in surface area, but at temperatures above 900°C
the surface area starts to decrease, probably due to the
destruction of the pore walls under the severe conditions
[24]. A comprehensive study on the effect of process
parameters on the porous and textural properties of
activated carbon is described in our previous work [15].
Based on this research, the optimum steam conditions of an
activation temperature of 900 °C, a steam flow-rate of 15.0
g/h, and an activation time period of 9 h were used in this
work to produce activated carbon from fluid petroleum
coke.
Table 1 shows the porous characteristics of the raw fluid
coke (RFC) and the steam activated carbon. Figure 1
shows the N2 adsorption-desorption isotherm and pore size
distribution for SAC. The isotherm is type IV, which
indicates that the material is mesoporous in nature. The
BJH pore size distribution curve shows a narrow
distribution and most of the pores are in the range of 35–
45 Å. As seen in the pore size distribution curve (Fig. 1),
some of the pores are less than 20 Å, which implies that the
material is not completely mesoporous, but has some
micropores as well. Compared to RFC, the surface area
increased from 11.0 to 482 m2/g, the total pore volume
increased to 0.231 cm3/g, and the pore diameter increased
to 37.3 Å using steam activation. Therefore, SAC can be
used as a support material for preparing a hydrotreating
catalyst. Prabhu et al. [25] used mesoporous carbon with
similar pore sizes for hydrotreating light gas oil (LGO).
Surface functional groups on support materials play an
important role in anchoring the active metals onto the
supports. FTIR was employed to check for functional
groups on the SAC. The FTIR spectrum of SAC in Fig. 2
has only one broad absorption band in the fingerprint
region of 1000–1220 cm–1. This band is due C–O
stretching vibrations. It is clear from Fig. 2 that no
functional groups are present on the SAC.
Another important characteristic for hydrotreating
catalysts is the presence of acidic sites. Acidity in a
catalyst favors HDN and HDS reactions by changing the
electronic properties of the catalytically active sites. The
pore size plays an important role in facilitating the
diffusion of the feed stock molecules to the active centers
of the catalyst. To check for acidity, Boehm titrations were
performed (Table 2) and the SAC was found to have a
weak acidic strength of 0.752 mmol/g.
3.2 Effect of HNO3 treatment on the porous structure and
surface functionality of the steam activated carbon
Surface functional groups and pore structure are important
characteristics that determine the effectiveness of activated
carbons as support materials for catalysts. Functionalized
activated carbon supports exhibit higher activity than
virgin carbon supports for hydrotreating because, the
functionalized activated carbon supports have more sur-
face hydroxyl groups which can act as anchors for
interactions with metallic precursors [26]. According to
Pradhan and Sandle [27], nitric acid treatment is very
 N. Rambabu et al. Hydrotreating of light gas oil using a NiMo catalyst
Table 1 BET surface areas, total pore volumes, and average pore diameters of RFC, SAC, NAFSAC and NiMo/NAFSAC catalyst.
Sample BET surface area /(m2$g–1)
RFC 11.7
SAC 482.0
NAFSAC 280.0
NiMo/NAFSAC 90
Fig. 1 N2 adsorption-desorption isotherms and BJH pore size distributions for (A) SAC, (B) NAFSAC, and (C) NiMo/NAFSAC catalyst
effective for the formation of functional groups on the
surface of activated carbons. Ademiluyi and David-west
[28] confirmed that the HNO3 treatment is more effective
than other oxidation treatments for the removal of metal
ions from bamboo, coconut or palm kernel shell activated
carbons.
Here, the SAC was treated with 8 M HNO3 to create
functional groups and to impart acidic properties to the
material. BET analysis was carried out to determine the
textural properties of the NAFSAC. Figure 1(B) shows that
the material exhibits a Type IV isotherm with a narrow pore
size distribution. The decrease in the height of the
hysteresis loop is due to the low surface area. As seen in
Table 1, compared to SAC, the surface area of the
NAFSAC was reduced from 482 to 280 m2/g which is due
to the collapse of some of the pores in the acidic
environment. This smaller surface area led to an increase
in total pore volume (from 0.231 to 0.297 cm3/g) and an
increase in pore diameter (from 37.1 to 41.0 Å) for SAC
and NAFSAC respectively. The Boehm titration of the
HNO3-treated steam activated carbon also indicated that
the acidic strength had increased to 2.41 mmol/g (Table 2).
165
Total pore volume /(cm3$g–1) Average pore diameter /Å
– –
0.231 37.1
0.297 41.0
0.3 39.0
Figure 2 shows the FTIR spectra for the SAC and
NAFSAC activated carbons. The NAFSAC spectrum
shows that the nitric acid treatment created new functional
groups. The band at 3250–3500 cm–1 is assigned to OH
vibrations and confirms the introduction of OH functional
groups to NAFSAC. The sharp band at 2900 cm–1 is due to
asymmetric v(C–H) vibrations in methyl groups [29] and a
high intensity is indicative of the presence of a significant
amount of hydrocarbons. The shoulder peaks at 2150 and
1750 cm–1 are ascribed to (C ≡ C) alkyne vibrations and (C
= O) carbonyl vibrations in lactones or carboxylic
anhydrides, respectively. The sharp peak at 1625 cm–1 is
associated with C = O vibrations in aromatic rings such as
in quinines [30]. The small peaks at 1450, 1375 and 1050–
1175 cm–1 are attributed to C = C vibrations in aromatic
rings, C–N vibrations, and C–O–C vibrations in ethers or
lactones respectively [29].
SEM was employed to view the surface morphology of
the activated carbons. Figure 3 shows the SEM images of
fluid petroleum coke, steam activated carbon, and nitric
acid functionalized steam activated carbon. Figure 3(a)
shows that RFC has a flat surface with no pores or cracks,
166 Front. Chem. Sci. Eng. 2014, 8(2): 161–170
Table 2 Boehm titration results for RFC, SAC and NAFSAC
Sample Acidic functional groups concentration /(mmol$g–1)
RFC 1.625
SAC 0.752
NAFSAC 2.410
Fig. 2 FTIR spectra of (A) NAFSAC and (B) SAC
which was confirmed by its low BET surface area (11.7 m2/
g). SAC (Fig. 3(b)) has deeper cracks and more openings
on the surface. During the steam activation, large fissures
were formed and the surface became perforated, resulting
in a surface area increase from 11.7 to 484 m2/g. As shown
in Fig. 3 (c), the HNO3 treatment resulted in the collapse of
the pores due to the acidic environment. This reduced the
surface area to 280 m2/g. Nevertheless, as confirmed by the
BET analyses, the material still exhibited a Type IV
isotherm with a narrow pore size distribution.
It can be concluded from the BET (Table 1), FTIR (Fig.
2), Boehm titration (Table 2), and SEM (Fig. 3) results that
NAFSAC has a large surface area of 280 m2/g with an
average pore diameter of 41 Å and exhibits average acidity.
So it is suitable to be used as support material for a NiMo
hydrotreating catalyst.
Fig. 3 Scanning electron micrographs of (A) RFC, (B) SAC and (C) NAFSAC. Scale for all SEM images: 10 µm
3.3 Characterization of catalysts
3.3.1 X-ray diffraction
Figure 4 shows the XRD wide angle powder patterns of the
NiMo hydrotreating catalyst supported on NAFSAC and
the XRD profile of the NAFSAC support. The broad peaks
at 2θ = 25° and 43° correspond to the 002 planes of
activated carbon and is due to the inter-planar distance of
the graphitic microcrystallines [3,6]. The sharp diffraction
peaks at 2θ = 26°, 36.9°, and 44.3° in the XRD spectrum of
NiMo/NAFSAC correspond to β-NiMoO4 [31]. The peaks
at 2θ = 37.2° and 53.5° correspond to octahedral MoO3
and the peak at 43.9° indicates the presence of a metallic Ni
phase [32]. The sharp diffraction peaks indicate that the
molybdenum and nickel species are poorly dispersed on
the activated carbon support. The approximate crystallite
size of active species was calculated using Scherrer’s
equation (Eq. (1)).
0:9l
davg – size ¼ , (1)
βcos
where davg-size is the average crystal size, l the X-ray
wavelength, β the FWHM (full width at half max) of the
reflection peak, and θ is the Bragg angle [33]. The
crystallite size of the β-NiMoO4 species in the NiMo/
NAFSAC catalyst is 29.4 nm, whereas the crystalline size
of MoO3 species is 18 nm. The crystallites are much bigger
than the pore size of the NiMo/NAFSAC catalyst and so
these crystallites will block some of the pore openings,
which reduce the available surface area.
3.3.2 BET analysis
The pore structure parameters of the catalysts were
determined using the N2 adsorption-desorption isotherms
and the results are presented in Table 1. Figure 1 shows the
N2 adsorption-desorption isotherm for the NiMo/NAFSAC
 N. Rambabu et al. Hydrotreating of light gas oil using a NiMo catalyst
Fig. 4 Wide angle XRD pattern for (A) NiMo/NAFSAC and (B)
NAFSAC
catalyst. The material retains its porous structure even after
metal loading and exhibits a Type IV isotherm. The
decrease in the height of the hysteresis loop corresponds to
the lower surface area of the catalyst (90 m2/g) as
compared to that of the NAFSAC support (280 m2/g).
Although the surface area decreased, the pore size
remained almost the same which may be because of the
blockage of the pore openings by the large metal
crystallites. The XRD results showed that the size of the
active metal (molybdenum oxide) crystallites was 28 nm in
NiMo/NAFSAC (Table 3). However, the average pore size
in the functionalized activated carbon (NAFSAC) is 3.9
nm (see Table 1).
3.3.3 Inductively coupled plasma mass spectroscopy (ICP-
MS) analysis
The ICP-MS analysis of the NiMo/NAFSAC catalyst
indicated the catalyst contained 2.2 wt-% Ni and 12.5 wt-%
Mo compared to the targeted values of 2.5 wt-% Ni and 13
wt-% Mo. The activated carbon also contained traces of
Mg, Zn, Na, V, Al, Ca, Ti, Cr, Mn, Fe, Co, Sr, Zr, and Ba.
3.3.4 CO chemisorption
A CO chemisorption technique was employed to calculate
the percent metal dispersion in the NiMo/NAFSAC
hydrotreating catalyst and the results are presented in
Table 3. A NiMo/γ-Al2O3 hydrotreating catalyst was used
Table 3 CO uptake of the supported NiMo hydrotreating catalysts
Catalyst Metal dispersion /% Metallic surface area
/(m2$g–1), of sample
NiMo/NAFSAC 4.4 3.4
NiMo/γ-Al2O3 9.5 7.83
167
as the reference catalyst. As seen in Table 3, the amount of
CO adsorbed by the NiMo/NAFSAC catalyst was 78
μmol/g, which is less than half that adsorbed by the NiMo/
γ-Al2O3 catalyst. This indicates a poor metal dispersion of
4.4% in the NiMo/NAFSAC catalyst compared to 9.5% for
the NiMo/γ-Al2O3 catalyst. The average crystallite size for
the NiMo/NAFSAC catalyst was calculated from the CO
chemisorption data and was 28 nm which is in good
agreement with the XRD results. From both the XRD and
CO chemisorption results, it can be concluded that the
dispersion of the active metal species in NiMo/NAFSAC is
poorer than that in NiMo/γ-Al2O3.
3.3.5 Temperature programmed reduction
The TPR profiles of the NiMo/NAFSAC and NiMo/γ-
Al2O3 catalysts are shown in Fig. 5. The TPR pattern of the
NiMo/NAFSAC catalyst has a broad reduction peak in the
temperature range of 300–700 °C. Polymolybedate struc-
tures have a reduction peak for Mo6+ to Mo4+ species at
450 °C and a second reduction peak for Mo+4 to Mo at
600 °C [34,35]. The reduction of Ni species is at 350 °C so
the broad peak would contain overlapping peaks for Mo
and Ni reductions. The peak may also contain reduction
components from various other metals such as iron,
aluminum, nickel, titanium, or vanadium that are present
in the petroleum coke in small quantities (ICP-MS results,
Section 3.3.3). For the NiMo/γ-Al2O3 reference catalyst,
the first molybdenum reduction peak (Mo+6 to Mo+4) is at
600 °C and the second reduction peak (Mo+4 to Mo+0) is at
850 °C. It is clear from the TPR results that the NiMo/
NAFSAC catalyst shows better reducibility than the NiMo/
γ-Al2O3 catalyst.
3.3.6 Temperature programmed desorption
Figure 6 shows the NH3 TPD profiles for the NiMo/
NAFSAC and NiMo/γ-Al2O3 catalysts. The NiMo/NAF-
SAC catalyst exhibits a broad peak at 250–350 °C which
can be assigned mainly to carboxylic functional groups
[36]. The presence of carboxylic functional groups in
NAFSAC was also confirmed by the FTIR results (Fig. 2).
The low temperature TPD peak at 150–350 °C signifies the
weak acidity of the NiMo/NAFSAC catalyst. In contrast,
the NiMo/γ-Al2O3 catalyst has a high temperature TPD
peak at around 600–800 °C, which indicates that the
NiMo/γ-Al2O3 catalyst is more acidic than the NiMo/
NAFSAC catalyst.
Metallic surface area /(m2$g–1), Crystallite size/nm CO adsorbed
of metal /(μmol$g–1)
21.6 28 78
57.9 13 182
168 Front. Chem. Sci. Eng. 2014, 8(2): 161–170
Fig. 5 TPR profile for (A) NiMo/NAFSAC and (B) NiMo/γ-
Al2O3 catalysts
Fig. 6 NH3-TPD profile for (A) NiMo/NAFSAC and (B) NiMo/
γ-Al2O3 catalysts
3.4 Catalytic activity
The catalytic performances of NiMo/NAFSAC and NiMo/
γ-Al2O3 for the HDN and HDS activities of coker light gas
oil were evaluated under similar operating conditions. The
characteristics of the KLGO are shown in Table 4. In a
typical run, 5 mL of catalyst was loaded into the reactor
and sulfidation was carried out for 48 h. The catalyst was
then stabilized by pre-coking with LGO for 5 days (P = 8.8
MPa, t = 370 °C, LHSV = 2 h–1, and H2/oil ratio = 600
(v/v)). The initial HDN and HDS activities for both
catalysts were high on the first day of the run, indicating
that a high number of active sites were present at the initial
stage of hydrotreating. The HDS and HDN activities
decreased with time on stream and reached steady-state
after three days. The decrease in activity with time is
probably due to coking of the most acidic sites.
After precoking, the steady-state HDS and HDN
Table 4 Characteristics of coker light gas oil derived from Athabasca
bitumen
Characteristic Coker light gas oil
Nitrogen /ppm 2439
Sulfur /ppm 23420
Density /(g$mL–1) 0.95
Boiling point distribution
IBP /°C 169
FBP /°C 548
Boiling range /°C
IBP–250 6
250–300 22
300–350 31
350–400 23
401–450 9
450–500 6
500–FBP 3
activities for both catalysts were studied using the same
feed at a reaction temperature of 370 °C. The activities
were studied for three days at a constant temperature and
samples were collected every 12 h. The average N and S
conversions of the last four samples are shown in Fig. 7.
The HDS and HDN activities of the NiMo/NAFSAC
catalyst were approximately 11.5% and 35% respectively
which are lower than those of the NiMo/γ-Al2O3 catalyst.
The lower activities of NiMo/NAFSAC are due to its lower
surface area, smaller pore diameters (3.9 nm, Table 1), and
its lower metal dispersion (4.4%, Table 3, XRD results).
Acidity is one of the crucial factors that drives HDN
reactions [33]. It is clear from the FTIR and TPD analyses
that the NiMo/NAFSAC catalyst has a very weak acidic
strength and this is the main reason for its lower HDN
activity. In contrast, the NiMo/γ-Al2O3 catalyst has better
acidic strength, better dispersion and larger pore diameters
all of which result in better activity.
Nevertheless, the HDS and HDN activities of 62% and
30% respectively for the NiMo/NAFSAC catalyst are not
bad. The inert nature of the carbon support material may
play a role in these activities. The inertness of the activated
carbon helps to lower the interactions between the metal
and the support as compared to those with an alumina
support. This makes the active metals easier to reduce
which results in better activity. This is supported by the
TPR analysis (Fig. 5). In addition, the activated carbon has
a disordered structure with more edges and defects. These
edges are associated with a high concentration of unpaired
electrons and serve as surface active sites [37]. This
electronic effect favors the adsorption of sulfur containing
compounds and hence enhances activity. Another aspect of
the carbon inertness is its low propensity for coking
 N. Rambabu et al. Hydrotreating of light gas oil using a NiMo catalyst
Fig. 7 HDN and HDS activities of NiMo/NAFSAC and NiMo/γ-
Al2O3 catalysts with KLGO at 370°C (catalyst = 5 cm3, P = 8.8
MPa, LHSV = 2 h–1 and H2/oil ratio = 600 (v/v))
compared to the NiMo/γ-Al2O3 catalyst. This helps in
maintaining the activity of catalyst for a longer period of
time
Another possible reason for the reasonable hydrotreating
activity of the NiMo/NAFSAC catalyst is that there is a
correlation between the support microporosity and activity.
As shown in Fig. 1, the NiMo/NAFSAC catalyst has
micropores along with the mesopores. These narrow slit-
shaped micropores in the activated carbon are inaccessible
to bulky reactant molecules, so they lower the vapor
pressure of sulfur to such an extent that is creates a driving
force for sulfur to transfer from bulky compounds into the
micropores. This is called the sink effect [37]. Since the
pores are slit-shaped, the hydrogen can easily diffuse
through the pores from any side and remove sulfur as H2S.
In contrast to this, microporosity leads to poor metal
dispersion.
In summary, the activated carbon produced from fluid
petroleum coke is not as good as a conventional alumina-
supported catalyst for hydrotreating. On a weight basis the
density of the conventional NiMo/γ-Al2O3 catalyst was
0.67 g/cm3 compared to 0.5 g/cm3 for the NiMo/NAFSAC
catalyst. Nonetheless, if an activated carbon material with
larger pore diameters and bigger surface areas could be
developed then it would have the potential to be used as a
support material for a hydrotreating catalyst.
4 Conclusions
Activated carbon support was prepared from fluid
petroleum coke using a steam activation method and it
was then functionalized with 8 mol/L nitric acid. The FTIR
analysis showed the presence of surface functional groups
such as carboxyl, hydroxyl, and lactonic groups. The
Boehm titration confirmed that the HNO3 treatment
resulted in an increase in the acidic strength of the steam
169
activated carbon. The SEM images showed that some of
the pore walls collapsed during nitric acid treatment,
leading to an increase in pore diameters. The BET analysis
showed that nitric acid functionalized steam activated
carbon exhibited Type IV isotherms and had pores with
diameters in the range of a mesoporous material. Nitric
acid functionalized steam activated carbon (NAFSAC) was
used as a support material for a NiMo hydrotreating
catalyst and a conventional NiMo/γ-Al2O3 catalyst was
used as a reference. The HDS and HDN activities of the
NiMo/NAFSAC catalyst for hydrotreating coker light gas
oil were lower than those of the NiMo/γ-Al2O3 catalyst.
This is because of poorer dispersion of the metals as shown
by the XRD and CO chemisorption results and weaker
acidic strength as shown by TPD. The moderate HDS
(62%) and HDN (30%) activities shown by the NiMo/
NAFSAC catalyst can be attributed to the inert nature of
the carbon, weak metal-support interactions, a low coking
propensity of the catalyst, and the sink effect. The overall
results indicate that activated carbon prepared from
Syncrude fluid petroleum coke by functionalized steam
activation has the potential to be an effective and
economical support material for hydrotreating catalysts.
Acknowledgements The authors acknowledge Syncrude Canada for
providing the fluid coke and gas oil, as well as financial support, and the
Natural Sciences and Engineering Research Council of Canada (NSERC) for
their financial support.
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