Chapter 7

Hydrodesulfurization (HDS) Process Based

on Nano-catalysts: The Role of Supports

Alimorad Rashidi, Fatemeh Mohammadzadeh,

and Sedigheh Sadegh Hassani

Abstract Nowadays, market demand of middle distillate such as naphtha, kero-

sene, and diesel fractions with low sulfur content is augmented. Sulfur oxides which
are released to the air by combustion of this kind of fuels are one of the critical
problems of the environment. Hydrodesulfurization (HDS) is one of the most
important catalytic processes which have been offered for solving these kinds of
difficulties.
Conventional HDS catalysts are MoS2 together with some metals from the
transition metal series supported on γ-Al2O3 that are promoted by either cobalt or
nickel.
A lot of research has been focused on HDS catalysts improvement for different
industries, where they investigated various catalyst supports, active phases, and
catalyst synthesis methods.
Recently, nano-materials are extensively used for catalytic HDS process. Carbon
nanostructures such as carbon nanotubes (CNTs) draw scientists’ attention because
of their high mechanical strengths, purities, and thermal stability.
In this work, an overview of HDS process and various types of catalysts for
removal of sulfur compounds from fuels is indicated. In addition, improved cata-
lysts using nanotechnology including carbon nanotubes, graphene, and nano-
alumina are investigated.

Keywords Hydrodesulfurization • Nano-catalyst • Carbon nanotubes • Graphene •

Nano-alumina • Sulfur compounds

A. Rashidi (*) • S. Sadegh Hassani

Nanotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran
e-mail: rashidiam@[Link]
F. Mohammadzadeh
Process Engineering Section, Petroleum Engineering Department, Iranian Offshore Oil
Company, Tehran, Iran

© Springer International Publishing AG 2018 193

T.A. Saleh (ed.), Nanotechnology in Oil and Gas Industries, Topics in Mining,
Metallurgy and Materials Engineering, DOI 10.1007/978-3-319-60630-9_7
194 A. Rashidi et al.

1 Introduction

In the last few decades, requirements to healthier and cleaner transportation fuels
have become one of the most important subjects of discussion. Natural gas, fossil
fuel, and some refined petroleum products (gasoline, kerosene, fuel oils, and diesel
fuel) contain various sulfur compounds such as sulfides, thiols, thiophenes,
benzothiophenes, and alkyl-substituted derivatives, most of which come from
fluid catalytic cracking (FCC) unit (Babich and Moulijn 2003). These compounds
not only are dangerous for the environment but could also poison the reforming
catalyst and corrode the refinery equipment. In 2005, the European Union and US
regulation restricted the sulfur content in gasoline and diesel to 30–50 ppm, while
this amount was reduced to 10 ppm in 2010 (Deng et al. 2010) and it is expected to
be less than 5 ppm in 2020 (Castillo-Araiza et al. 2015). On the other hand, the
demand for high-quality petroleum grows up increasingly.
Implementation of environmental legislation to enhance the quality of oil along
with market demand for low sulfur gasoline and high octane number has made great
efforts to improve the quality of fuels. Hydrotreating process (HDT) which includes
a sequence of important processes such as hydrodesulfurization (HDS),
hydrodenitrogenation (HDN), and hydrodearomatization (HAD) for light and mid-
dle distillates, and hydrodemetallization (HDM) and hydrodeasphaltenization
(HDAs) for heavy oils are fundamental techniques to remove or decrease sulfur
components. These processes lead to more qualified productions and feedstocks
(Nikulshin et al. 2016).
Middle distillate fraction has been more interest due to the importance of
producing clean gasoline, jet and diesel fuels, and kerosene for the environment.
Hence, many researchers have been focused on the sulfur removal from engine fuel
using catalytic hydrodesulfurization process.

2 Hydrodesulfurization Process

Hydrodesulfurization (HDS) is an important catalytic process in which the sulfur

compounds are converted to hydrocarbons and hydrogen sulfide that can easily be
separated from natural gas and refined petroleum products; in this way, sulfur
dioxide (SO2) emissions from fuel combustion can be decreased.
Sulfur, even in low concentrations, poisons the precious metal catalysts (plati-
num and rhenium) in the catalytic reforming units which are used to upgrade the
octane rating of the naphtha streams.
In this regard, in the industrial HDS process, the resulted hydrogen sulfide (H2S)
gas has been converted to sulfuric acid (H2SO4) and elemental sulfur.
The general conditions for HDS process are, temperature: 500–825  F, hydrogen
pressure: 150–3000 psig, hydrogen flows: 250–10000 SCF/bbl, feed space velocity:
0.5–5.0 volumes of liquid per volume of catalyst per hour (Schuman and Shalit
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 195

1971). The process conditions depending on the type of cutting oil and its sulfur
compounds will be different. The fraction boiling up to 160  C usually contains
alkane thiols, aliphatic sulfides, and alicyclic sulfides that easily react with hydro-
gen in conventional hydrotreating process and completely removed. More complex
thiophenes and bicyclic sulfides are found in higher boiling fractions. These
compounds are more difficult to convert via hydrotreating. Hydrodesulfurization
mechanism of thiophenic compounds is carried out via two pathways. In a first way,
the sulfur atoms are directly removed from the ring and in this way, the ring is
broken (hydrogenolysis pathway). In a second way, the aromatic ring is hydroge-
nated and then sulfur atoms are removed (hydrogenation pathway). Both pathways
occur simultaneously and some parameters such as feed compound, reaction con-
dition, and type of catalyst determine the predominant reaction (Babich and
Moulijn 2003). Experimental results show that acidic supports facilitate the ring
opening of hydrogenated intermediates and thus are suitable for this procedure
(Santes et al. 2005). Many studies have been conducted to investigate the mecha-
nism of HDS reactions through the integration of experimental results with the
theoretical models (Krebs et al. 2008).
Thermodynamic data for the hydrogenation of sulfur compound which leads to
the production of hydrocarbons and hydrogen sulfide shows that this reaction is
possible thermodynamically over a wide range of temperatures. Nevertheless, the
hydrogenation behavior of various sulfur compounds is probably different from the
standpoint of thermodynamic, for example, the hydrogenation of saturated sulfur
compound is favored at high temperature while increasing the temperature will
decrease the thermodynamic driving force for thiophens. However, there is no
thermodynamic limitation for hydrogenation of diverse sulfide compounds,
although decreasing the reaction rate and the interference of competitor reactions
cause problems in the implementation of the process (Schuman and Shalit 1971).
In this conventional process which is run out industrially, the warm oil fraction is
mixed with hydrogen gas and then passed through the catalytic reactor; in this way
the sulfur compounds with various structures and molecular weight are
hydrogenated.
In the most usual cases, HDS process is carried out in fixed bed reactors with the
cocurrent supply of oil stream and hydrogen. This reactor structure design causes to
produce a mixed gas with inappropriate relative concentration. The high concen-
tration of H2S at the outlet reactor inhibits the complete sulfur removal (Babich and
Moulijn 2003). Furthermore, the relatively large size of catalyst used in fixed bed
reactor causes pressure drop and decreasing the internal diffusion and production of
extreme heat because of exothermic reactions which can lead to creating hot spots
and catalyst deactivation consequently.
In the recent years, some of the refining units exploit slurry reactors due to some
advantages including simple construction and lower cost, efficient temperature
control, less pressure drop, better performance of the catalyst, discharging the
used catalysts, and bringing the fresh catalysts concurrently (Deng et al. 2010).
Countercurrent operation is another new reactor system that could provide a
preferable concentration profile. In this system, the oil feed is entered into the
196 A. Rashidi et al.

reactor at the top and the hydrogen gas at the bottom and H2S gas is removed at the
top that prevents the reentry at the reactor outlet. The ebullated bed reactor is
another type of HDS reactor that is designed especially for heavy refinery steams.
This reactor benefit is good heat transfer and less coke formation. In another new
approach, a combination of hydrotreating with other reactions as aromatizing and
octane boosting is taken into consideration (Babich and Moulijn 2003).
Non-HDS based desulfurization technology is another approach that does not
use hydrogen for desulfurization of sulfur compound from oil. In this way, sulfur is
removed by shifting the boiling point through alkylation, extraction, adsorption,
precipitation, and selective oxidation methods (Babich and Moulijn 2003).
Researchers try to promote the HDS process via different aspects such as
construction of catalysts with high activity and lifetime, improving the design of
reactors, and recently using a new internal catalyst to realize countercurrent flow
(Deng et al. 2010; Song and Ma 2003).

3 Industrial HDS Catalysts and Their Activity

A well-known catalyst which is traditionally used in HDS process is Co–Mo, Ni–

Mo or W crystallites that are well dispersed over alumina support (El Kady et al.
2010). The binary sulfide catalysts are highly regarded too because these systems
cause very strong catalytic synergies. For example, individual Mo or Co sulfides
shows very low activity as an HDS catalyst, but when combine to each other present
very high activity (Okamoto 2008). A complete review of preparation of catalyst
methods for HDS process is presented in some papers (Toulhoat and Raybaud 2013;
Souchay 1969; Von Pope 1983; Campos-Martin et al. 2009; Vrinat et al. 2005; Dhar
et al. 2003). In order to reduce the sulfur content of diesel and gas oil fuels, less than
15 ppm and 10 ppm, respectively (Bigdeli and Fatemi 2015; Michel et al. 2012),
catalysts with higher strength are required.
The development of new catalysts is required for the optimization of HDS
process. The synthesis method, activation procedure, type of support and active
compound, promoter and posttreatment can affect the catalyst performance.
It is proven that sulfur and olefin compounds compete with each other on the
catalyst and this is while hydrogenation of olefins causes to drop in octane number.
Therefore, to keep a high octane number it is necessary to eliminate or limit the
olefins reaction by using selective catalysts (Fontaine et al. 2010).
Improving selectivity has a key role in catalyst performance and could be
fulfilled by adding diverse promoters to the catalyst composition (Mey et al.
2004), poisoning the hydrogenation sites selectively (Hatanaka 2005), balancing
the basic–acidic properties of the support, and the amount of H2S in feed (Fontaine
et al. 2010). However, it should be noted that increasing the amount of H2S has an
inhibiting effect on both hydrodesulfurization and hydrogenation of olefins.
Type and quality of support also lead difference in catalyst performance via
dispersing active component over and affecting the metal–support interaction
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 197

which in turn influence the catalyst functionalities. In order to select of an appro-

priate catalyst some criteria such as promoting effect on the active phase are
important. For example, Co and Ni sulfides effects on active phase of MoS2 lead
to the formation of “CoMoS” or “NiMoS” phases, respectively (Toledo-Antonio
et al. 2009).
Moreover, surface area, thermal stability, pore diameter, pore volume, geomet-
rical functions, acidity, and mechanical strength are considered as key parameters
for catalyst performances. Many materials were studied and experimental results
showed that γ-Al2O3 is an ideal support with favorable characteristics, because it
possesses high surface area, thermal stability, and regeneration. Also, its pore
structures can be controlled simply (Nikulshin et al. 2014). However, the severe
interaction between alumina and catalytic metals occurs that causes difficult
sulfidation of components. Furthermore, acidic and basic sites on this support
form coke (Stanislaus et al. 2010).
Generally, two types of sites are observed on traditional catalysts based on Al2O3
support: monolayer MoS2 slabs that are so-called Type I and multilayer or highly
stacked MoS2 slabs which named Type II (Toledo-Antonio et al. 2009). Type II of
CoMoS or NiMoS is a highly active site (Nikulshin et al. 2014) because strong
bonds between molybdenum and the support are observed (Coelho et al. 2014)
while the majority of sites belongs to the type I in alumina-supported catalysts.
However, it is extremely complicated to constitute them.
In order to form these active slabs, increase Mo oxides dispersion, improve
catalyst acidic characteristics, and reduce the interaction between catalysts compo-
nents and supports, some additives like P and B are applied (Villarroel et al. 2009;
Klimova et al. 2010; Dumeignil et al. 2006; Ferdous et al. 2004; Robles et al. 1999).
The other materials like MgO (Trejo et al. 2008), C (Nikulshin et al. 2014), TiO2
(Guo et al. 2013), SiO2 (Valencia and Klimova 2011; Gutiérrez and Klimova 2011),
ZrO2 (Vrinat et al. 1994), zeolite-like Na-Y, USY, and hybrid of alumina with them
(Saih et al. 2005; Ren et al. 2016; Cui et al. 2013) exhibit superior performance as a
support. Some of these oxides such as ZrO2 and TiO2 represent good reactivity
(Escobar et al. 2008). For example, in Mo/TiO2 catalysts, TiO2 has a role as an
accelerator in reduction and sulfidation of Mo because of its redox and semicon-
ducting characteristics (Caero et al. 2003). However, because of their low surface
area, weak thermal stability, and unfavorable mechanical characteristics, their
commercial application is restricted (Faro and dos Santos 2006).
Investigation shows that mixed oxides (TiO2/Al2O3 and ZrO2/Al2O3) are suit-
able as a support due to their larger surface area than the oxides alone (Robles et al.
1999). However, catalysts based on mixed oxides are deactivated fast.
198 A. Rashidi et al.

4 Nano-catalyst in HDS Process

Recently, nanotechnology has been extensively considered as a useful technology

in various industries and preparation of nano-materials has attracted more and more
attention (Gutiérrez and Klimova 2011; Mohammadi Meman et al. 2014; Morales-
Ortũno et al. 2015). Thus, many reports have been published about the synthesis of
nano-materials and many kinds of nano-catalysts for developing the HDS process.
Nano-particles with the high surface area as active phase of catalysts are
extensively used for catalytic reactions (Aghabozorg et al. 2015).
Parviz et al. (2011) reported preparation of unsupported MoO3 and Co–MoO3
catalysts in the presence of different organic additives such as urea (CO(NH2)2),
PEG200 (HO(C2H4O)nH), EDTA (C10H16N2O8), and sorbitol (C6H14O6). Various
kinds of MoO3 microstructures and nanostructures were obtained by utilizing
different additives. They clearly showed that nanostructure and promoted catalysts
had excellent response in the hydrodesulfurization reaction of naphtha than micro-
structure catalysts. They observed that the amount of sulfur of the feed was reduced
from 2420 to 24 ppm when urea-prepared promoted catalyst was utilized.
Ren et al. (2016) studied HDS of dibenzothiophene and
4,6-dimethyldibenzothiophene feed on NiW-ETS-10/Al2O3 and NiW-ETS–Ti
Reach /Al2O3 (ETS-10 is the microporous titanosilicate) catalysts at 260  C.
They recognized the WS2 slabs of NiW-AT-ETS/Al2O3 had an average length of
2.66 nm and layer number of 3.3 nm which showed more slabs and shorter slab
length than the original one. They demonstrated that weak interaction between WS2
as active phase and alumina supports was due to the presence of Ti species. They
also reported that NiW-ETS–Ti Reach/Al2O3, which was named as NiW-AT-ETS/
Al2O3, had higher activity in HDS of DBT and 4,6-DMDBT. They supposed that
shorter length of WS2 active phase leads to higher stacked layers and better
dispersion of active sites on support in comparison of NiW-ETS-10/Al2O3 which
was named as NiW-ETS-origin/Al2O3 were the reasons for 96.5% and 86.9%
activities of DBT and 4,6-DMDBT hydrodesulfurization, respectively.

5 Types and Roles of Supports

5.1 Nano-alumina Support

The potential of alumina support in catalytic activity can be improved by control-

ling its size and morphology in the mesopore size (Lee et al. 2016; Rashidi et al.
2010, 2012). In this regard, by altering the physical and chemical properties of
support, the activity and selectivity of prepared catalysts can be optimized
(Aghabozorg et al. 2015).
F. Rashidi et al. have prepared some new catalysts using micro- and nano-
alumina support with CoMoP and CoMoB active metals in hydrodesulfurization
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 199

Fig. 7.1 TEM micrograph of the nano-γ-Al2O3 prepared with 2-propanol and sulfuric acid

Fig. 7.2 HRTEM images on nano-catalysts Co–Mo/nano-alumina

of straight-run light gas oil (SRLGO) with 13500 ppm sulfur compounds (Rashidi
et al. 2013). TEM micrographs of the nano-γ-Al2O3 prepared with 2-propanol and
sulfuric acid are shown in Fig. 7.1. Also, Fig. 7.2 shows HRTEM images on nano-
catalysts Co–Mo/nano-alumina.
Synthesized nano-alumina support was characterized using Accelerated Surface
Area and Porosimetry System (ASAP), where the surface area, pore size, and pore
volume are compared with commercial alumina support and presented in Table 7.1.
Also, the synthesized catalyst performance was investigated and compared with
the commercial catalyst. They stated that presence of P and B in the catalyst
structure increased the acidity of the catalyst by diminishing the interaction
between metals and support and also caused Co metals placed on the edge of
MoS2 particles.
200 A. Rashidi et al.

Table 7.1 Physical properties of the supports

Sample Surface area (m2/g) Pore volume (cm3/g) Pore size (Å)
New nano-γ-Al2O3 403.05 1.69 104.59
Commercial-γ-Al2O3 246.20 0.50 70.30

They claimed that among the prepared catalysts, CoMoPB/nanoAl2O3 with a

better dispersion of Mo and Co showed the higher activity than others and was able
to decrease the sulfur content of diesel fuel to below 10 ppm.
They attributed the gasoil HDS activity to the stacking number and Co/Mo ratios
of the CoMoS sites of the catalysts. They deduced that the active species of CoMoS
II placed on the edges of MoS2 slabs. In addition, they found that higher Co/Mo
ratio caused higher Co efficiency. These results lead to the further HDS respon-
siveness. Also, Co and Mo dispersion and the stabilization of metals were improved
via acidic nature of nano-alumina.
Liu and coworkers’ (2012) experiments displayed higher HDS response for
4,6-DMDBT when bimodal mesoporous nanorod γ-Al2O3 support was prepared
by the hydrothermal process. They used different quantities of PEG for better
γ-Al2O3 crystal growth. Their studies indicated that supports with a higher amount
of PEG (24 g PEG) had higher stacking layer number and higher activity. Their
experiments revealed that bimodal mesoporous nanorod alumina had high surface
area, lower lattice defects, and lower support interactions. This reason led to the
higher dispersion of active phases and increasing the acidic sites. They reported that
CoMo-BMA-4 had 98.5% conversion.
Wang and coworkers (2016) synthesized mesoporous alumina supports with
crystal forms of γ, θ, and δ using boehmite sol and PEG and tested them in
hydrodesulfurization of DBT and 4,6-DMDBT and compared their activities with
commercial one. The θ and δ were obtained by thermal treatment of γ-alumina at
high temperatures. They discovered that NiMo/δ-Al2O3 had higher conversion and
catalytic response in all cases (99.6% conversion of DBT and 65.8% conversion of
4,6-DMDBT) at 613 K, 4.0 MPa, 200 ml/ml (Hydrogen/oil), and 150/h. They
expressed several reasons for these phenomena. For example, characterization
results declared δ-Al2O3 supports had a larger pore size (18.3 nm), surface area
(114 m2/g), and pore volume (0.56 cm3/g) than the other supports. They had open
pore channel so Ni–Mo metals could be impregnated easier in these channels. It
caused better dispersion and stacking of a number of active sites over these
catalysts.
This kind of prepared catalyst with moderate acid sites could facilitated the
transformation of the reactants to the active sites and thus improved HDS of DBT
and 4,6-DMDBT. Also, appropriate textural properties and suitable metal support
interaction (MSI) of NiMo/δ-Al2O3 were reported.
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 201

5.2 Carbon Nanotubes Support

Also, carbon nanotubes (CNTs) as a novel nano-material are promising candidates

because of their special properties such as high surface area (300–1500 m2/g),
thermal stability, high mechanical strength, electronic properties, and several
adsorption sites (Thi Vu et al. 2012; Nakhaei Pour et al. 2010; Graham et al. 2009).
Generally, they are classified in two groups, single-walled which are monolayer
graphene sheets that are rolled into a cylinder and multiwalled carbon nanotubes
that contain rolled up multilayer graphene with diameters from 2 to 25 nm. Before
hydrogenation process, the ends of the multiwall or single wall CNTs are opened
for catalyst application (Yu et al. 2008). Several kinds of nano-particle such as Pt
and Pd (Kiani et al. 2013) can be entered in and/or deposited on the CNTs structure
to improve their activity as catalysts.
In Pawelec et al. article (2006), CNT supported CoMo catalysts performance had
comprised with activated carbon or γ-Al2O3 supported catalysts in HDS of thio-
phene or dibenzothiophene. It was reported that CoMo/CNT had supreme activity
due to their nanosized and electron donor aspects.
Nakhaei Pour et al. (2010) compared Co–Mo/SWCNT and alumina
Co–Mo/γ-Al2O3 as the catalyst supports during hydrodesulfurization process of
naphtha. They characterized synthesized SWNT using BET and XRD, which are
shown in Fig. 7.3. and Table 7.2.

180

160

140

120
Intensity

100

80

60

40

20

0
10 20 30 40 50 60 70 80
Angel (2θ)

Fig. 7.3 XRD of Co–Mo/SWCNT catalysts after reaction

Table 7.2 Physical properties of SWCNT support

Sample Surface area BET (m2/g) Pore volume (cm3/g) Pore size (Å)
SWCNT 303.25 0.76 10.02
202 A. Rashidi et al.

XRD graph showed carbon as catalysts support and molybdenum sulfide of

consumed catalysts after reaction. They deduced Mo contents were converted to
the molybdenum sulfide.
They observed that MoO2 and MoO3 were the active sites on the CNT and
γ-Al2O3 supports, respectively. They reported that carbon nanotubes had hydro-
phobic nature which resulted in weak interaction between Co/Mo and support. In
calcinations stage, CNT caused reduction of Mo through heat treatment because Mo
oxides gathered on the surface of support preliminary.
They claimed that comfortable reduction of active metals on the CNT supports
was performed which facilitated the dispersion of Co–Mo particles on support and
improved the acidity of CNT. Therefore, high isomerization and the cracking
reaction of sulfur compounds could be observed in these kinds of catalyst that
leads to the enormous HDS responsible behavior.
Results showed that CNT supported catalysts adsorbed high quantity of sulfur at
operating temperature above 583 K since active phases on this catalyst were
reduced more comfortably.
Khorami and Kalbasi (2011) investigated on the HDS of naphtha by multiwall
carbon nanotube supported Co–Mo catalyst in a fixed bed reactor. The operational
condition of the reactor was reported as below: 310  C, 15 bar and liquid hourly
space velocity: 4/h. They acquired catalyst with 10–20 nm clusters and support with
10 nm pore diameters that improved Co/Mo particles dispersion on the support. The
activity of catalyst with total amounts of Co and Mo about 7% weight percent was
examined for HDS of naphtha with 1270 ppm sulfur species like
methylisopropylsulfide, t-amylmercaptan, isoamylmercaptan, ethyl sec butyl sul-
fide, etc. It was observed that all of the sulfur compounds displayed 88% conversion
regardless of their molecular weights.
Shang et al. (2007) synthesized MoO3/CNT, Co–Mo/CNT with different atomic
ratio of Co/Mo and γ-Al2O3 supports and examined their behavior in
hydrodesulfurization of dibenzothiophene. As the other researchers’ reports, they
revealed that Co–Mo/CNT had higher activity than Co–Mo based γ-Al2O3 catalyst
due to the weak interaction of CNT support with metals spices, unlike γ-Al2O3
supports. They also postulated that reducibility of catalysts was depended on the
atomic ratios of Co/Mo. They tested their catalysts with 0–1 atomic ratios of Co/Mo
and concluded that the more atomic ratio, hence 0.7, lead to the more active spices
in the catalysts. For MoO3/CNT catalysts, they observed well dispersion of Mo on
CNT catalysts when the catalyst loading was lower than 6% and proper scattering
of MoO2 particles when catalyst loading was 8%. MoO2 particles have a more
effective role on sulfidation process than MoO3 because of their comfortable
conversion capability.
In another research (Chen et al. 2004), DBT adsorption on sulfide and oxide of
Co–Mo catalysts on CNT, activated carbon (AC) and γ-Al2O3 were studied.
Characterization using NH3-TPD technique indicated the higher activity of sulfide
catalyst than oxides since a number of acidic sites on sulfide compounds were more
than ones on oxide catalysts. Moreover, despite AC has higher surface area and pore
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 203

volume than CNT and γ-Al2O3, CoMoS/AC showed weaker acidity because a
number of acidic sites were decreased after CoMoS and CoMoO loading on the
AC. They found that the activity of CoMoS/CNT was about 97%. It means that
almost all (90%<) of the DBT molecules were adsorbed on CoMoS/CNT. They
deduced it may be related to the CoMoS/CNT end-on mode and presence of several
onion vacancies (vacant orbit which is electron acceptor) in the MoO2 metals as
active phases.
Soghrati et al. (2012) prepared Co–Mo catalyst supported on CNT-coated
cordierite monoliths (2Al2O3: 5SiO2: 2MgO) and tested them in HDS of naphtha.
FESEM results of CNT-coated monolith determined the good distribution of
CNTs on the monolith which caused to attain catalysts with the higher surface area,
pore volume and mesoporous layer of CNTs with adhesion properties. A compar-
ison of CoMo/monolith (A), CoMo/CNT, and CoMo/FACNT (CNT-coated mono-
liths) revealed that FACNT supported CoMo catalysts had higher activity than the
others. Besides, when the metal content of the catalysts (CoMo) was increased to
10 wt%, the S conversion reached to 98.08%. It means that sulfur content of
naphtha declined from 2670 to 53 ppm at 310  C.
Eswaramoorthi et al. (2008) survived the effect of NiMo/MWCNTs catalysts on
gas oil which was obtained from Athabasca bitumen. They evaluated their catalysts
in different Ni and Mo contents of catalysts in various temperatures which showed
different results in HDN and HDS of gas oil. Experimental results illustrated the
reduction of Mo elements from Mo6+ to Mo4+ and Mo0 in two steps and different
temperatures. By increasing the amount of Ni, for example, for 0–4.5 wt% Ni/12 wt
% Mo/MWCNTs, well dispersion of MoO3 particles was seen. In addition, when Ni
content increased to 3 wt% over 12 wt% Mo/MWCNTs, the number of active sites
of MoS2 enhanced. In addition, the catalysts activity of MWCNT support was
higher than that of Al2O3 at low temperatures (345–360  C) but at higher temper-
atures (375  C) they displayed equal value. They believed that it was due to the
catalysts tendency to have maximum activity at higher temperatures.

5.3 Graphene Support

In the recent years, graphene as a new carbon material with a planar sheet with sp2
carbon–carbon bonds attracts the scientist attentions due to their high specific
surface area, supreme mechanical, electronic and thermal properties, high elastic-
ity, and good mobility (Rao et al. 2009; Zhu et al. 2010).
Some articles investigate graphene performance as catalyst support (Hajjar et al.
2016a) in HDS process. Z. Hajjar et al. (2016b) have synthesized graphene by CVD
technique in atmospheric pressure and 900–1000  C and with solid camphor
(C10H16O), hydrocarbon source that contains hexagonal and pentagonal rings like
methyl carbon, and methane gas as carbon precursors. They obtained a 5-layer
graphene with a high yield of 90%. They conclude from BET results that obtained
graphene from camphor had higher specific surface area and pore volume than
204 A. Rashidi et al.

Table 7.3 Physical properties of the graphene support

Sample Surface area (m2/g) Pore volume (cm3/g) Pore size (Å)
Graphene 850 2.11 100

Fig. 7.4 XRD pattern of Graphene

methane precursor. They declared that more acidic sites were observed on the
camphoric based catalysts. The physical characterization of the synthesized
graphene is shown in Table 7.3.
Furthermore, from XRD patterns (Fig. 7.4), it could be observed, the graphene
sample clearly shows the (002) reflection associated to 2Ө about ~29.8 which
indicate graphene sheet and (100) and (101) reflections associated to 2Ө about
46 that overlap together.
Also, the Raman spectrum of graphene, Fig. 7.5, shows three main peaks G, D,
and 2D. The ID/IG, the ratio D and G band intensities, is an important parameter to
show carbon structure disordering and heteroatom doping, which higher value is
reflective of more defects formation in graphene structure and heteroatom existence
(Sun et al. 2015; Yuezeng et al. 2013).
They have also expanded their studies on the other synthesis methods of
graphene (Hajjar et al. 2015). They have employed in situ and simultaneous
chemical exfoliation method in graphene oxide–MoS2 composite synthesis in
order to accelerate the synthesis procedure. They claimed that smaller and more
uniformly dispersed particles and higher and stronger acidic sites were obtained via
this method.
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 205

Fig. 7.5 Raman spectra of porous graphene

206 A. Rashidi et al.

In both cases, catalysts were compared with industrial Co–Mo/γ-Al2O3

supported catalysts for HDS of naphtha with 1350 ppm sulfur content. The obtained
results showed better reduction of active materials on graphene-based catalysts at
lower temperature due to the weaker interaction between supports and Co–Mo
metals. Their experience revealed that graphene-based catalyst had higher activity
than industrial ones in hydrodesulfurization. Results showed that catalytic conver-
sion of both cases was 100% while industrial catalyst had 92.6% conversion. BET
results were obviously showed that specific surface area and pore size of graphene
were higher than γ-Al2O3. In the first case, the number of active species on
graphene-based catalysts perceived to be decreased at a lower temperature which
was attributed to the weaker interaction of carbon-based supports with metals as
catalysts. In the second article, sulfidation was performed by feed at first and so
MoS2 was formed initially and could act as active phase. Graphene oxides have
weak interaction between supports and catalyst.

6 Conclusion

Sulfur compounds which are released to the air by combustion of fuels are one of
the critical problems of the environment. Hydrodesulfurization as an important
catalytic process is used to solve this problem. To reduce a number of sulfur
compounds in oil stocks, improved processes and novel active catalysts have
been introduced. The improved catalysts activity can be achieved by controlling
the size, surface area, porosity, active phase dispersion, morphology, surface
composition, and thermal stability.
In the HDS process, the most important applicable supports are nano- and
mesoporous materials such as carbon nanotubes, graphene, and γ-Al2O3.
The γ-Al2O3 is an important support for HDS process. It has bimodal pore
structures, i.e., the smaller pore with high surface area for HDS reactions and the
larger pores for bulky reactants to diffuse in pores. In these supports, it is significant
to produce fourfold (AlIV) and fivefold (AlV) aluminum acid centers in order to
have better chemical reactions. By controlling the size of them in nano or meso
scale, a lower amount of coke is obtained. By controlling the morphology and slab
stacking numbers of active species in alumina-supported catalysts in nano and
meso scales, suitable MoS2 slab layers can be obtained and complete conversion
achieved
Moreover, graphene and CNT supports have high surface area. Therefore,
dispersion of nanoclusters over catalysts is increased and lower loading of metals
on catalysts surfaces is needed which leads to economical costs.
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 207

References

Aghabozorg HR, Sadegh Hassani S, Rashidi AM (2015) Nanocatalysts preparation, characteriza-

tion, and their application in oil and gas processes. In: Kharisov BI, Kharissova OV, Ortiz-
Mendez U (eds) CRC encyclopedia. Taylor and Fransis, Boca Raton, FL, pp 100–107
Babich IV, Moulijn JA (2003) Science and technology of novel processes for deep desulfurization
of oil refinery streams: a review. Fuel 82:607–631
Bigdeli S, Fatemi S (2015) Fast carbon nanofiber growth on the surface of activated carbon by
microwave irradiation; a modified nano-adsorbent for deep desulfurization of liquid fuels.
Chem Eng J 269:306–315
Caero LC, Romero AR, Ramirez J (2003) Niobium sulfide as a dopant for Mo/TiO2 catalysts. Catal
Today 78:513–518
Campos-Martin JM, Rojas S, Oyama ST, Gott T, Zhao H, Lee Y-K (2009) Transition metal
phosphide hydroprocessing catalysts: a review. Catal Today 143:94–107
Castillo-Araiza CO, Chávez G, Dutta A, de los Reyes JA, Nu~ nez S, Garcı́a-Martı́nez JC (2015)
Role of Pt–Pd/γ-Al2O3on the HDS of 4,6-DMBT: Kinetic modeling & contribution analysis.
Fuel Process Technol 132:164–172
Chen H, Zhou X, Shang H, Liu C, Qiu J, Wei F (2004) Study of dibenzothiophene adsorption over
carbon nanotube supported CoMo HDS catalysts. J Nat Gas Chem 13:209–217
Coelho TL, Licea YE, Palacio LA, Faro AC Jr (2014) Heptamolybdate-intercalated CoMgAl
hydrotalcites as precursors for HDS selective hydrotreating catalysts. Catal Today 250:38–46
Cui Q, Zhou Y, Wei Q, Yu G, Zhu L (2013) Performance of Zr- and P-modified USY-based
catalyst in hydrocracking of vacuum gas oil. Fuel Process Technol 106:439–446
Deng Z, Wang T, Wang Z (2010) Hydrodesulfurization of diesel in a slurry reactor. Chem Eng Sci
65:480–486
Dhar GM, Srinivas BN, Rana MS, Kumar M, Maity SK (2003) Mixed oxide supported
hydrodesulfurization catalysts—a review. Catal Today 86:45–60
Dumeignil F, Sato K, Imamura M, Matsubayashi N, Payen E, Shimada H (2006) Characterization
and hydrodesulfurization activity of CoMo catalysts supported on sol-gel prepared Al2O3.
Appl Catal A Gen 315:18–28
El Kady FYA, Abd El Wahed MG, Shaban S, Abo El Naga AO (2010) Hydrotreating of heavy gas
oil using CoMoc-Al2O3 catalyst prepared by equilibrium deposition filtration. Fuel
89:3193–3206
Escobar J, Barrera MC, De Los Reyes JA, Cortés MA, Santes V, Gómez E, Pacheco JG (2008)
Effect of Mo and Co loading in HDS catalysts supported on solvo-thermally treated ZrO2–TiO2
mixed oxides. Catal Today 133–135:282–291
Eswaramoorthi I, Sundaramurthy V, Das N, Dalai AK, Adjaye J (2008) Application of multi-
walled carbon nanotubes as efficient support to NiMo hydrotreating catalyst. Appl Catal A Gen
339:187–195
Faro AC Jr, dos Santos ACB (2006) Cumene hydrocracking and thiophene HDS on niobia-
supported Ni, Mo and Ni–Mo catalysts. Catal Today 118:402–409
Ferdous D, Dalai AK, Adjaye J (2004) A series of NiMo/Al2O3 catalysts containing boron and
phosphorus Part I. Synthesis and characterization. Appl Catal A Gen 260:137–151
Fontaine C, Romero Y, Daudin A, Devers E, Bouchy C, Brunet S (2010) Insight into sulphur
compounds and promoter effects on Molybdenum-based catalysts for selective HDS of FCC
gasoline. Appl Catal A Gen 388:188–195
Graham UM, Dozier A, Khatri RA, Bahome MC, Jewell LL, Mhlanga SD, Coville NJ, Davis BH
(2009) Carbon nanotube docking stations: a new concept in catalysis. Catal Lett 129:39–45
Guo C, Wu Y, Wang X, Yang B (2013) Effect of the support calcination temperature on selective
hydrodesulfurization of TiO2 nanotubes supported CoMo catalysts. J Energy Chem
22:517–523
208 A. Rashidi et al.

Gutiérrez OY, Klimova T (2011) Effect of the support on the high activity of the (Ni)Mo/ZrO2–
SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT. J Catal
281:50–62
Hajjar Z, Kazemeini M, Rashidi AM, Bazmi M (2015) In situ and simultaneous synthesis of a
novel graphene-based catalyst for deep hydrodesulfurization of naphtha. Catal Lett
145:1660–1672
Hajjar Z, Kazemeini M, Rashidi A, Tayyebi S (2016a) Artificial intelligence techniques for
modeling and optimization of the HDS process over a new graphene based catalyst. Phospho-
rus Sulfur Silicon Relat Elem 191:1256–1261
Hajjar Z, Kazemeini M, Rashidi AM, Bazmi M (2016b) Graphene based catalysts for deep
hydrodesulfurization of naphtha and diesel fuels: a physiochemical study. Fuel 165:468–476
Hatanaka S (2005) Hydrodesulfurization of selective catalytic cracked gasoline. Catal Surv Asia
9:87–93
Khorami P, Kalbasi M (2011) Hydrodesulfurization activity of CoMo catalyst supported on multi
wall carbon nanotube: sulphur species study. J Exp Nanosci 6:349–361
Kiani M, Aghabozorg H, Jafari Jozani K, Rashidi AM, Mohsennia M (2013) Preparation and
characterization of carbon nanotubes supported Ni2P for hydrodesulfurization (HDS) of
naphtha. Phosphorus Sulfur Silicon 188:1254–1261
Klimova T, Vara PM, Lee IP (2010) Development of new NiMo/g-alumina catalysts doped with
noble metals for deep HDS. Cataly Today 150:171–178
Krebs E, Silvi B, Daudin A, Raybaud P (2008) A DFT study of the origin of the HDS/HydO
selectivity on Co(Ni)MoS active phases. J Catal 260:276–287
Lee X, Feng J, Guo J, Wang A, Prins R, Duan X, Chen Y (2016) Preparation of Ni2P/ Al2O3 by
temperature programmed reduction of a phosphate precursor with a low P/Ni ratio. J Catal
334:116–119
Liu X, Li X, Yan Z (2012) Facile route to prepare bimodal mesoporous γ-Al2O3 as support for
highly active CoMo-based hydrodesulfurization catalyst. Appl Catal B Environ
121–122:50–56
Mey D, Brunet S, Canaff C, Maugé F, Bouchy C, Diehl F (2004) HDS of a model FCC gasoline
over a sulfided CoMo/Al2O3 catalyst: effect of the addition of potassium. J Catal 227:436–447
Michel V, Dorothée L, Christophe G (2012) Use of competitive kinetics for the understanding of
deep hydrodesulfurization and sulfide catalysts behavior. Appl Catal B Environ 128:3–9
Mohammadi Meman N, Pourkhalil M, Rashidi AM, Zare Nezhad B (2014) Synthesis, character-
ization and operation of a functionalized multi-walled CNT supported MnOx nanocatalyst for
deep oxidative desulfurization of sour petroleum fractions. J Ind Eng Chem 20:4054–4058
Morales-Ortũno JC, Ortega-Domı́nguez RA, Hernández-Hipólito P, Bokhimi X, Klimova TE
(2015) HDS performance of NiMo catalysts supported on nanostructured materials containing
titania. Catal Today 271:127–139
Nakhaei Pour A, Rashidi AM, Jafari Jozani K, Mohajeri A, Khorami P (2010) Support effects on
the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery. J Nat
Gas Chem 19:91–95
Nikulshin PA, Salnikov VA, Mozhaev AV, Minaev PP, Kogan VM, Pimerzin AA (2014) Rela-
tionship between active phase morphology and catalytic properties of the carbon–alumina-
supported Co(Ni)Mo catalysts in HDS and HYD reactions. J Catal 309:386–396
Nikulshin P, Mozhaev A, Lancelot C, Blanchard P, Payen E, Lamonier C (2016) Hydroprocessing
catalysts based on transition metal sulfides prepared from Anderson and dimeric Co2Mo10-
heteropolyanions, a review. C R Chim 19:1276–1285
Okamoto Y (2008) A novel preparation-characterization technique of hydrodesulfurization cata-
lysts for cleaner fuels. Catal Today 132:9–17
Parviz D, Kazemeini M, Rashidi AM, Jafari Jozani K (2011) Naphtha hydrodesulfurization over
micro and nanostructure MoO3 catalysts. Sci Iran C 18:479–485
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 209

Pawelec B, La Parola V, Navarro RM, Murcia-Mascarós S, Fierro JLG (2006) On the origin of the
high performance of MWNT-supported PtPd catalysts for the hydrogenation of aromatics.
Carbon 44:84–98
Rao CNR, Sood AK, Subrahmanyam KS, Govindaraj A (2009) Graphene: the new
two-dimensional nanomaterial. Angew Chem Int Ed 48:7752–7777
Rashidi F, Nemati Kharat A, Rashidi AM, Lima E, Lara V, Valente JS (2010) Fractal geometry
approach to describe mesostructured boehmite and Gamma-alumina nanorods. Eur J Inorg
Chem:1544–1551
Rashidi F, Lima E, Rashidi H, Rashidi AM, Guzmane A (2012) Cooperative effect of gold
nanoparticles with CUS aluminum from nanoalumina support in the catalysis of an electron
transfer reaction. Appl Catal A Gen 417–418:129–136
Rashidi F, Sasakia T, Rashidi AM, Nemati Kharat A, Jafari Jozani K (2013) Ultra deep
hydrodesulfurization of diesel fuels using highly efficient nanoalumina-supported catalysts:
impact of support, phosphorus, and/or boron on the structure and catalytic activity. J Catal
299:321–335
Ren S, Li J, Feng B, Wang Y, Zhang W, Wen G, Zhang Z, Shen B (2016) A novel catalyst of Ni,
W-surface-Ti-rich-ETS-10/Al2O3: its role and potential of HDS performance for steric hin-
dered sulfur compound 4,6-DMDBT. Catalysis Today 263:136–140
Robles JM, Castellón ER, López AJ (1999) Characterization of Ni, Mo and Ni–Mo catalysts
supported on alumina-pillared a-zirconium phosphate and reactivity for the thiophene HDS
reaction. J Mol Catal A Chem 145:169–181
Saih Y, Nagata M, Funamoto T, Masuyama Y, Segawa K (2005) Ultra deep hydrodesulfurization
of dibenzothiophene derivatives over NiMo/TiO2-Al2O3. Appl Catal A 295:11–22
Santes V, Herbert J, Cortez MT, Zárate R, Dı́az L, Swamy PN, Aouine M, Vrinat M (2005)
Catalytic hydrotreating of heavy gasoil FCC feed on alumina–titania-supported NiMo cata-
lysts. Appl Catal A Gen 281:121–128
Schuman SC, Shalit H (1971) Hydrodesulfurization. Catal Rev Sci Eng 4(1):245–318
Shang H, Liu C, Xu Y, Qiu J, Wei F (2007) States of carbon nanotube supported Mo-based HDS
catalysts. Fuel Process Technol 88:117–123
Soghrati E, Kazemeini M, Rashidi AM, Jafari Jozani K (2012) Preparation and characterization of
Co-Mo catalyst supported on CNT coated cordierite monoliths utilized for naphtha HDS
process. Proc Eng 42:1484–1492
Song CS, Ma XL (2003) New design approaches to ultra-clean diesel fuels by deep desulfurization
and deep dearomatization. Appl Catal B Environ 41:207–238
Souchay P (1969) Ions mineraux condenses. Masson
Stanislaus A, Marafi A, Rana MS (2010) Recent advances in the science and technology of ultra
sulfur diesel (ULSD) production. Catal Today 153:1
Sun Z, Masa J, Weide P, Fairclough SM, Robertson AW, Ebbinghaus P, Warner JH, Tsang SCE,
Muhlerb M, Schuhmann W (2015) High-quality functionalized few-layer graphene: facile
fabrication and doping with nitrogen as a metal-free catalyst for the oxygen reduction reaction.
J Mater Chem A 3:15444–15450
Thi Vu TH, Thi Nguyen TT, Thi Nguyen PH, Do MH, Au HT, Nguyen TB, Nguyen DL, Park JS
(2012) Fabrication of photo catalytic composite of multi-walled carbon nanotubes/TiO2 and its
application for desulfurization of diesel. Mater Res Bull 47:308–314
Toledo-Antonio JA, Cotres-Jacome MA, Angeles-Chavez C, Escobar J, Barrera MC, Lopez-
Salinas E (2009) Highly active CoMoS phase on titania nanotubes as new hydrodesulfurization
catalysts. Appl Catal B Environ 90:213–223
Toulhoat H, Raybaud P (2013) Catalysis by transition metal sulfides, from molecular theory to
industrial application. Editions Technip, Paris, p 151
Trejo F, Rana MS, Ancheyta J (2008) CoMo/MgO–Al2O3 supported catalysts: an alternative
approach to prepare HDS catalysts. Catal Today 130:327–336
210 A. Rashidi et al.

Valencia D, Klimova T (2011) Effect of the support composition on the characteristics of NiMo
and CoMo/(Zr)SBA-15 catalysts and their performance in deep hydrodesulfurization. Catal
Today 166:91–101
Villarroel M, Baeza P, Gracia F, Escalona N, Avila P, Gil-Llambı́as FJ (2009) Phosphorus effect
on Co//Mo and Ni//Mo synergism in hydrodesulphurization catalysts. Appl Catal A Gen
364:75–79
Von Pope MT (1983) Heteropoly and isopoly oxometalates. Springer, Berlin
Vrinat M, Hamon D, Breysse M, Durand D, Courieres T (1994) Zirconia and alumina supported
molebdenum based catalysts: a comparative study in hydrodesulfurization and hydrogenation
reactions. Catal Today 20:273–282
Vrinat M, Bacaud R, Laurenti D, Cattenot M, Escalona N, Gamez S (2005) New trends in the
concept of catalytic sites over sulfide catalysts. Catal Today 107–108:570–577
Wang X, Zhao Z, Zheng P, Chen Z, Duan A, Xu C, Jiao J, Zhang H, Cao Z, Ge B (2016) Synthesis
of NiMo catalysts supported on mesoporous Al2O3 with different crystal forms and superior
catalytic performance for the hydrodesulfurization of dibenzothiophene and
4,6-dimethyldibenzothiophene. J Catal 344:680–691
Yu Z, Fareid LE, Moljord K, Blekkan EA, Walmsley JC, Chen D (2008) Hydrodesulfurization of
thiophene on carbon nanofiber supported Co/Ni/Mo catalysts. Appl Catal B Environ
84:482–489
Yuezeng S, Zhang Y, Zhuang X, Li S, Wu D, Zhang F, Feng X (2013) Low-temperature synthesis
of nitrogen/sulfur co-doped three-dimensional graphene frameworks as efficient metal-free
electrocatalyst for oxygen reduction reaction. Carbon 62:296–301
Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, Ruoff RS (2010) Graphene and Graphene Oxide:
Synthesis, Properties, and Applications. Adv. Mater. 22:3906–3924