Rev Chem Eng 2018; aop

Prerana Sikarwar, Vijayalakshmi Gosu and Verraboina Subbaramaiah*

An overview of conventional and alternative

technologies for the production of ultra-low-sulfur
fuels
https://doi.org/10.1515/revce-2017-0082 for the generation of electricity and driving of vehicles.
Received September 2, 2017; accepted May 1, 2018 Further, approximately 95% of motorized transportation
is dependent on fossil fuels (Pawelec et al. 2011). Hence,
Abstract: Environmental concerns have given a great deal
an increase in usage of hydrocarbon fuels due to its wide
of attention for the production of ultra-low-sulfur fuels.
applications in the transportation sector, thereby, release
The conventional hydrodesulfurization (HDS) process
of harmful sulfur and nitrogenous compound, which act
has high operating cost and also encounters difficulty in
as a serious threat to the environment.
removing sulfur compound with steric hindrance. Con-
Sulfur compounds are the most obnoxious contami-
sequently, various research efforts have been made to
nant present in transportation fuels and occur naturally
overcome the limitation of conventional HDS process and
in liquid fuels derived from crude oil such as gasoline,
exploring the alternative technologies for deep desulfuri-
diesel, and jet fuel. The amount of sulfur in crude oil is
zation. The alternative processes being explored for the
represented as a percent of sulfur by weight, and it gen-
production of ultra-low-sulfur content fuel are adsorptive
erally varies from less than 0.1% to more than 5%. These
desulfurization (ADS), biodesulfurization (BDS), oxida-
compounds can be categorized into four major categories,
tive desulfurization (ODS), and extractive desulfurization
namely, mercaptans, sulfides, disulfides, and thiophenes.
(EDS). The present article provided the comprehensive
The combustion of these compounds releases toxic gases
information on the basic principle, reaction mechanism,
into the atmosphere (Palomino et al. 2014), which causes
workability, advantages, and disadvantages of conven-
both environmental pollution and serious health hazards.
tional and alternative technologies. This review article
During combustion, sulfur compounds are transformed
aims to provide valuable insight into the recent advances
into sulfur oxides and, thereby, transform to acid rain,
made in conventional HDS process and alternative tech-
sulfates, or other airborne particulates, which are detri-
niques. For deep desulfurization of liquid fuels, integra-
mental to the environment (Bhutto et al. 2016). Moreover,
tion of conventional HDS with an alternative technique is
a higher level of sulfur compounds in fuels adversely
also proposed.
affects the automobiles by reducing the efficiency of the
Keywords: ADS; BDS; desulfurization; ODS; ultra-low catalytic converter. As a result, strict legislation has been
sulfur. enforced to reduce the content of sulfur in the liquid fuel.
According to the US and European Union regulations, the
maximum allowable sulfur content in fuel is 15 and 10

1 Introduction parts per million (ppm), respectively. Stringent environ-

In today’s modern world, energy consumption is increas-
ing day by day, and one of the major sources of energy
is fossil fuels, which satisfy the requirement of energy
demand. Hydrocarbon fuels derived from fossil fuels
are indispensable elements of today’s progressive world
and also persist for forthcoming decades. These are used
*Corresponding author: Verraboina Subbaramaiah, Department of
Chemical Engineering, MNIT Jaipur, Jaipur-302017, India,
e-mail: vsr.chem@mnit.ac.in, vijaya.che@gmail.com
Prerana Sikarwar and Vijayalakshmi Gosu: Department of Chemical
Engineering, MNIT Jaipur, Jaipur-302017, India
mental rules and regulations as well as the application
of cleaner fuels in refinery operations and fuel cells are
putting immense pressure on refineries to produce fuels
of lower sulfur content (Sarda et  al. 2012, Rashidi et  al.
2015). Consequently, various methods for the removal of
aromatic sulfur compounds such as thiophene (Th), ben-
zothiophene (BT), dibenzothiophene (DBT), and their
alkylated derivatives have attracted considerable atten-
tion in order to produce ultra-low-sulfur fuels.
Currently, the conventional technology, hydrodesul-
furization (HDS) is used for the treatment of sulfur com-
pounds present in transportation fuels. This technology
employs high temperature (300–400°C), high pressure
(3–6 MPa), and a huge amount of hydrogen in the presence

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2      P. Sikarwar et al.: Desulfurization
of a catalyst (Sentorun-Shalaby et al. 2011). Further, more
than 30 bar pressures are required for the production
of light oil such as jet fuel or diesel (Song 2003). Hence,
HDS is an expensive choice for desulfurization due to the
requirement of high pressure, temperature, and a huge
amount of catalyst. In addition to that, this process is not
able to reduce thiophenic sulfur compounds present in
fuels such as BT, DBT, alkylated DBTs such as 4,6-dimeth-
yledibenzothiophene (DMDBT) (Song 2003, Kilbane and
Le Borgne 2004, Jeevanandam et al. 2005). In order to over-
come the drawbacks of the HDS process, various alterna-
tive techniques were explored to produce ultra-low-sulfur
fuels. These techniques include adsorptive desulfurization
(ADS), biodesulfurization (BDS), oxidative desulfurization
(ODS), and extractive desulfurization (EDS). In the ADS
process, sulfur compounds are specifically adsorbed on
the adsorbent; both surface area and the functional group
present on the surface of the adsorbent plays a significant
role in the adsorption of sulfur molecules (Ruthven 1984,
Al-Ghouti and Al-Degs 2014). Therefore, it is considered as
an economical alternative for the deep desulfurization of
fuels owing to its simplicity in operation and mild operat-
ing conditions. Most of the research work in the last two
decades is dedicated to the development of adsorbents,
which exhibit high surface area, high selectivity, and
are easy to regenerate. In the BDS process, sulfur con-
taminants are removed with the aid of microorganisms at
moderate temperature and pressure (Monticello 2000). In
this process, microorganisms need sulfur as a significant
element for their physiological activities and as a growth
factor (Boniek et  al. 2014). BDS is not commercialized
yet; therefore, most of the recent work is focused on the
development of effective biocatalyst for treating the large
volume of liquid fuels. In the ODS technique, organosulfur
compounds are oxidized to their corresponding sulfoxides
and sulfones and, thus, the removal of these compounds
with the aid of extraction, adsorption, or distillation (Fraile
et al. 2016). In recent years, enormous research has been
carried out on the usage of both oil-soluble and -insolu-
ble oxidants. Oxidation with the help of ultrasound irra-
diation has emerged as a potential technique for reducing
the sulfur content due to shorter reaction time under mild
operating conditions. In EDS process, sulfur compounds
are specifically extracted from the fuel with the help of
a solvent. Previously, researchers have focused on EDS
with organic solvents. Nowadays, a new class of solvents,
including ionic liquids and deep eutectic solvents, has
been investigated for the efficient EDS process. The present
review paper emphasizes on the potential techniques
used for desulfurization of liquid fuels and deliberates on
the advancements of desulfurization processes in order
to obtain ultra-low-level-sulfur fuels. Furthermore, the
harmful effect of sulfur compounds on the environment
and its upper limit in various countries are also included.
1.1 N
 eed of deep desulfurization
Sulfur compounds are the most undesirable and poison-
ous impurities present in transportation fuels. During
combustion, the sulfur compound containing fuels pro-
duces SOx and another airborne particulate, which are
released into the atmosphere and cause severe water and
air pollution (Ahmed and Jhung 2015). Furthermore, SOx
emissions combine with moisture present in the atmos-
phere to generate acid rain, which severely harms the
man-made structure and forests (Pawelec et  al. 2011,
Ahmed and Jhung 2016). It has been also found from
several studies that the quantity of sulfur compounds in
diesel is directly proportional to the particulate matter
(PM) emissions (Ristovski et al. 2006). PM emissions from
a diesel engine can cause adverse effects on human health
owing to their potential of penetrating deeply into the
human lungs, causes various respiratory problems, and
also, it is known to be carcinogenic (Stanislaus et al. 2010,
Mjalli et al. 2014). Sulfur compounds are also responsible
for corrosion of the combustion engine and deactivation
of the catalyst present in the catalytic converter, which is
responsible for reducing emissions of CO, NOx, and, thus,
affecting the overall performance of the engine (Campos-
Martin et al. 2010, Dasgupta et al. 2013, Jeong et al. 2013,
Safa et al. 2016). In addition, sulfur compounds also deac-
tivate the catalysts used in various refinery operations
(Gary and Handwerk 2001). Thus, strict environmental
rules and regulations have been established in the recent
past in order to limit the amount of sulfur. Table 1 depicts
the upper limit of sulfur content in various countries due
to stringent legislations. In 2006, The United States Envi-
ronmental Protection Agency (USEPA) has decreased the
amount of sulfur in gasoline and diesel from 300 to 30
parts per million by weight (ppmw) and 500 to 15 ppmw,
respectively (Ma et al. 2002). In Europe, Germany imposed
a limit of 10 ppm on sulfur content since 2001 (Babich and
Moulijn 2003). In India, BS IV was implemented since
April 2010 in 13  major cities, according to which sulfur
content in diesel and petrol has been reduced from 350
to 50  ppm and 150  ppm to 50  ppm, respectively. Since
then, it has been expanded to 26 more cities. In the rest of
the nation, BS III was implemented from September 2011
(Ministry of Petroleum and Natural Gas 2014).
Production of ultra-low-level transportation fuels by
reducing the sulfur content in diesel, gasoline, and jet
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 P. Sikarwar et al.: Desulfurization      3

Table 1: Current sulfur specification for diesel and gasoline in some countries and their year of implementation.

Country 2005 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017

US1 30 ppm
US2 15 ppm
EU1 10 ppm
EU2 10 ppm
Japan1 10 ppm
Japan2 10 ppm
Australia1 10 ppm
Australia2 10 ppm
China1 10 ppm
China2 10 ppm
Korea1, Republic of 10 ppm
Korea2, Republic of 10 ppm
India1 (selected cities) 50 ppm
India1 (rest of the nation) 150 ppm
India2 (selected cities) 350 ppm
India2 (rest of the nation) 50 ppm
Brazil1 500 ppm
Brazil2 50 ppm
Singapore1 50 ppm
Singapore2 10 ppm
Thailand1 50 ppm
Thailand2 50 ppm

Data extracted from the Ministry of Petroleum and Natural Gas 2014, ASEAN 2016, International Energy Agency 2016.
1
Sulfur content in gasoline.
2
Sulfur content in diesel.

fuel has gained more attention in recent years owing to
the stringent legal requirements as well as the intense
demand for liquid hydrocarbon fuels with less than
1  ppmw sulfur content for their application as a fuel in
fuel cells (Song and Ma 2003, Sentorun-Shalaby et  al.
2011). A fuel cell is a device, which converts hydrocarbons
into electricity without any emission of pollutants, and it
will be a potential alternative for the purpose of on-board
electricity supply in aircraft, transport vehicles, and ships
(Aicher et al. 2006, Wang et al. 2012). The current flexible
infrastructure of hydrocarbon storage, transportation,
and their special features such as high energy density and
readily availability made them a promising candidate for
their usage as a fuel in fuel cells (Hernández-Maldonado
and Yang 2004). The application of fuel cell-based auxil-
iary power units in navigation and aircraft can decrease
the emissions when the airplanes are on the ground, and
ships are on the port, as the driving engine is not in oper-
ating mode (Wang et al. 2012).
However, hydrocarbon fuels such as natural gas,
naphtha, methane, etc., contain the sulfur compounds,
which are very harmful to the catalysts used in the fuel
cell system and also tend to deactivate the electrode in
fuel cell stack (Ma et al. 2002). Therefore, the amount of
sulfur in fuel should be very less (<0.1  ppm) in order to
protect the electrodes and catalyst of the fuel cell system
from deactivation (Petzold et al. 2012).
2 Hydrodesulfurization (HDS)
Hydrodesulfurization is used in refineries to convert orga-
nosulfur compounds present in crude oil and refinery
streams into hydrogen sulfide and corresponding hydro-
carbons at higher temperatures and partial pressure of
hydrogen in the presence of a catalyst (Srivastava 2012).
2.1 R
 eaction pathways and reactivity
of organosulfur compounds
Nearly all fractions of crude oil distillation comprise
of organosulfur compounds. A high amount of sulfur
compounds are present in high-boiling point fractions
compared to low-boiling point fractions. Organosulfur
compounds present in oil fractions can be categorized
into aliphatic and aromatic organosulfur compounds.
Aliphatic organosulfur compounds such as mercaptans,

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4      P. Sikarwar et al.: Desulfurization
sulfides, and disulfides are usually present in low-boiling
point fractions. These compounds are highly reactive and
can be easily removed by the HDS process, whereas aro-
matic organosulfur compounds such as Th, BT, DBT, and
their alkyl derivatives are hard to desulfurize by hydrodes-
ulfurization (Babich and Moulijn 2003, Wang et al. 2017).
Mercaptans, sulfides, and disulfides react directly with
hydrogen and give sulfur-free products. Reaction mecha-
nism of the HDS of mercaptans, sulfides, and disulfides
are depicted in Table 2 (Gary and Handwerk 2001).
Thiophenic compounds are desulfurized via HDS by
two different routes depending on the complexity of the
structure of the sulfur-containing organic compound,
namely, direct desulfurization (DDS) and hydrogenation
followed by desulfurization (HYD). Th and BT are more
reactive than DBT and DMDBT, and are hydrodesulfurized
through the DDS path. However, DBT and its alkyl deriva-
tives are transformed through two parallel pathways,
namely, DDS and HYD. Formation of biphenyl or alkyl-
substituted biphenyl (BP) takes place in the DDS route. In
the HYD path, formation of hydrogenated intermediates
is followed by production of cyclohexylbenzene (CHB)
or alkyl-substituted cyclohexylbenzene (Castillo-Villalón
et al. 2016).
Houalla et  al. (1978) described the reaction mecha-
nism of HDS of DBT via two pathways, i.e. DDS and HYD.
Table 2: HDS reaction mechanism for aliphatic sulfur compounds.
Type of aliphatic sulfur compounds HDS reaction mechanism
Mercaptans RSH + H2→RH + H2S
Sulfides R2S + 2H2→2RH + H2S
Disulfides (RS)2 + 3H2→2RH + 2H2S
Figure 1: DBT reaction pathway for HDS over sulfided CoMo/Al2O3 catalyst.
Adapted from Houalla et al. (1978), with permission from John Wiley & Sons.
The reaction mechanism proposed by Houalla et al. (1978)
for the HDS of DBT at 300°C and 102 atm in the presence
of CoMo/Al2O3 by these two routes are shown in Figure 1.
The DDS path involves removal of sulfur with no hydro-
genation of aromatic rings, while the HYD path requires
hydrogenation of aromatic rings prior to the desulfuri-
zation process (Lara et  al. 2005). In the DDS route, the
reaction of DBT with hydrogen produces biphenyl as a
primary organic product. In the HYD route, DBT reacts
with hydrogen and gives very reactive intermediates such
as tetrahydrodibenzothiophene and/or hexahydrodiben-
zothiophene (HDBT), and these compounds are sub-
sequently desulfurized to produce CHB as a secondary
product. Further hydrogenation of CHB into the tertiary
product (bicyclohexyl) by slow hydrogenation of CHB is
via any two of the reaction routes (Srivastava 2012).
Moses et  al. (2007) reported that the HYD pathway
mechanism is more significant for the removal of DMDBT
than the DDS pathway mechanism. The HYD reac-
tion pathway is a better pathway for desulfurization of
alkyl-substituted DBTs such as DMDBT because partial
saturation of these molecules transforms the spatial con-
figuration of the compound and, thus, makes it more
reachable for adsorption on the active site before the reac-
tion (Kabe et al. 1993, Knudsen et al. 1999).
2.2 Catalyst used in HDS process
Production of ultra-low-sulfur fuels through the HDS
process mainly depends on the type of catalyst used in
the process. In order to get the desired amount of sulfur
in liquid fuels, it is very necessary to enhance the catalytic
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properties of the catalyst used in the HDS. The HDS
­technique has a high activation barrier for the hydrogen-
olysis of the C-S bond, and this barrier can be reduced by
employing a higher reaction temperature (>275°C), higher
pressure (>30 bars), and potent catalyst (Singh et al. 2016).
Typically, the HDS catalyst is composed of transition
metals with vacant d orbitals such as cobalt (3d7), nickel
(3d8), rhodium (4d8), palladium (4d10), and platinum
(5d9) on various supports and modified with the help of
promoters (Petzold et  al. 2012). The conventional HDS
process employs Co(Ni)Mo supported on alumina or silica
as a catalyst. Ni-promoted catalyst favors the HYD route
for the DBT removal, whereas Co-promoted catalyst favors
the DDS route (Saleh 2015).
Further, the conventional catalyst suffers difficulty
in removing alkyl-substituted DBTs because interaction
between the sulfur atom and the active site is hindered
due to the steric hindrance of alkyl groups (Pawelec et al.
2008). Therefore, these catalysts are not sufficient enough
to produce fuels with sulfur content of less than 15 ppm.
In order to obtain ultra-low-sulfur fuel, development of a
highly active catalyst for the removal of aromatic sulfur
compounds is required. Various catalytic systems such as
NiMo/SiO2-Al2O3 (Xu et al. 2017), NiMoW/SBA-15 (Mendoza-
Nieto et al. 2013), NiMo/mesoporous alumina (Wang et al.
2016), Pd/USY (Zhang et al. 2012a,b) have been reported in
the literature for the enhancement of the catalytic proper-
ties, and are focused on synthesis method, generation of
active phase, and properties of support (Chen et al. 2013,
Li et al. 2014).
Transition metal sulfides exhibit unique properties
that are beneficial in the HDS process and are found to
be the known class of active phases (Wajnert et al. 2008).
Pecoraro and Chianelli (1981) conducted the first organ-
ized study on the catalytic activity of transition metal
sulfides for the HDS of DBT and found the relationship
between the activity and position of the corresponding
metal in the periodic table of elements. The catalytic
activity of the iridium sulfide phase as an active compo-
nent and a mixed system of magnesium oxide and mag-
nesium fluoride as a support showed higher catalytic
activity in comparison to the CoMo/Al2O3 catalyst (used
in industry) for the HDS of thiophenes (Wajnert et  al.
2008). Liu et al. (2015) studied on unsupported Ni/Zn/Mo
sulfide catalysts for the HDS of DBT. In their observation,
9.5Ni0.5Zn10Mo catalyst gave a higher HDS activity for
DBT compared to other synthesized nickel-zinc-molyb-
denum catalysts, and this higher activity may be contrib-
uted to the complete sulfidation of the Mo species and
effortless reduction of oxide precursors as well as sulfide
catalyst.
P. Sikarwar et al.: Desulfurization      5
In 2001, new generation of commercial bulk catalyst
known as NEBULA (New Bulk Activity) was introduced
by ExxonMobil, Akzo Nobel, and Nippon Ketjen. It is
a trimetallic (Mo-W-Ni) unsupported catalyst that pos-
sesses superior HDS activity in comparison with other
catalysts available for HDS (Gochi et al. 2005). Neverthe-
less, these trimetallic catalysts are very costly owing to
their high metal content and high consumption of hydro-
gen (Morales-Ortuño et  al. 2016). In order to replace the
expensive bulk catalyst, researchers also explored cata-
lysts with low metal content and better textural proper-
ties. Most of the refineries employed a catalyst based on
BRIM™ hydroprocessing technology developed by Haldor
and Topsøe, while others used NEBULA (Saleh 2015).
Nanostructured materials have drawn considerable
attention during the last decade owing to their distinctive
physical and chemical characteristics and better textural
properties. Various types of nanostructure material have
been explored for the HDS process. For example, nano-
structured titania powder and nanotubes were used as
a support material for the HDS of DBT. Titania powder
showed two times higher HDS activity than commercially
available CoMo/Al2O3 catalyst (Escobar et al. 2005). Titania
nanotube-supported NiW showed better HDS activity in
comparison with alumina and titania-supported NiW
(Palcheva et al. 2013). A few researchers have also inves-
tigated combined/hybrid materials with different proper-
ties to use as a support of the active phase for HDS. As
an example, titanium-incorporated SBA-15 and alumina
were combined together to use as a support material in
order to obtain the benefits of both materials (Morales-
Ortuño and Klimova 2017). The hybrid catalyst showed
higher HDS activity for alkylated DBT in comparison with
NiMo/γ-Al2O3. Metal phosphides are a novel class of HDS
catalyst and exhibits superior activity. It was reported
that among all the metal phosphides, nickel phosphide is
highly active and showed a better HDS activity than the
commercially available sulfide catalysts (Lee and Oyama
2017).
Researchers have also studied the influence of the
catalyst’s synthesis procedure on HDS activity, and it has
been found that the catalyst’s synthesis procedure has
an immense effect on the catalytic activity. For example,
Singh et  al. (2016) reported the synthesis of γ-alumina-
supported NiMo (ultra-small), NiMo bimetallic metal
oxide (nanoclusters) for the HDS technique by two differ-
ent procedures, namely, colloidal synthesis and conven-
tional wet impregnation method. They observed that the
nanoclusters prepared using colloidal synthesis showed
enhanced catalytic activity for the HDS of DBT in com-
parison with the catalyst synthesized using conventional
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wet impregnation technique. A series of CoMo/γ -Al2O3

Castillo-Villalón et al. (2015)

Mendoza-Nieto et al. (2013)

Solís-Casados et al. (2016)
catalysts were prepared using various techniques such as

Zhang et al. (2012a,b)

equilibrium deposition filtration (EDF), wet impregnation,

Guzmán et al. (2013)

Zhang et al. (2017)

Liu et al. (2014a,b)

dry impregnation, successive dry impregnations (Papado-

Wang et al. (2016)

Xu et al. (2015)
poulou et al. 2003). Among these, the catalyst synthesized
through the EDF method shown a higher activity in HDS.

Reference
2.3 Effect of support

% Removal

99

88, 77
–
99
99, 99

73
85
99, 65
79, 77
Effects of support have been investigated by many
researchers to better understand the importance of support
in the dispersion of active components or promoters, and

7.3
Pressure (MPa)

8.963
5
2.5
8

5.59
5
4
5
metal-support interaction for altering the catalytic func-

BR, Batch reactor; FBR, fixed bed reactor; MAR, micro-autoclave reactor; CFFBR, continuous-flow fixed-bed reactor; SBR, slurry batch reactor.
tionalities and stability. Numerous support materials such
as Al2O3 (Ferdous et al. 2004, Liu et al. 2007), zeolites (Lee
et  al. 2007), mesoporous materials (MCM-41 and SBA-15)
(Vradman et al. 2003, Wang et al. 2004, Oyama and Lee

300
Temperature (°C)

320
350
360
315

320
230
340
320
2008, Li et al. 2012), TiO2, ZrO2, SiO2 (Okamoto et al. 2002),
and mixed metal oxides (TiO2-Al2O3 and MgO-Al2O3) (Trejo
et  al. 2008, Wang et  al. 2009a,b) have been utilized in
order to enhance the HDS process efficiency.
Many HDS studies utilized the oxides as a support
Reactor

material, which includes titania, alumina, silica, and

CFFBR
MAR

SBR
FBR
FBR

FBR
zirconia. γ-Alumina was used as a support in many HDS
BR

BR
BR
studies due to its chemical, mechanical, and thermal sta-

1,300,500
1000 each

259,1126

bility (Xia et al. 2003). Alumina with different crystal struc-

500,300
Co (ppm)

10637

tures (γ-alumina, θ-alumina, δ-alumina) were also used to

2400
500
500
study the effect of a crystal structure on the HDS process
–

(Zhang et al. 2017). δ-Alumina gave the highest percentage

NiY/Carbon nanotubes

removal of sulfur compounds. The details of the process

Table 3: HDS of organosulfur compounds under optimum reaction condition.

CoMo/Al2O3MgOLi

NiMoW/P-SBA-16

conditions can be seen in Table 3. This higher removal rate

NiMoW/SBA-15
NiMo/δ-Al2O3

NiMo/δ-Al2O3

is contributed to the concentrated pore-size distribution,

adequate interaction between support and active species,
Mo/TiO2
Catalyst

NiCuMo

Pd/USY

and superior sulfidation degree. It can be seen n Table 3

that the researchers have employed δ-alumina for the HDS
of both model oil and FCC diesel. Catalytic activities of the
trimethyldibenzothiophene

catalyst can be influenced by the morphology also. For

example, the use of nanorod γ-alumina can give a bimodal
MDBT, DMDBT, 2,4,6-

mesoporous structure to enhance the HDS activity of

Th, DBT, DMDBT

CoMo-based catalysts (Liu et  al. 2012a,b), and the cata-

S-compound

DBT, DMDBT
DBT, DMDBT
DBT, DMDBT
Th, BT, DBT

lysts supported with lath-like mesostructured γ-alumina

DMDBT

provides a good dispersion of the active phase, which aids

DBT

in increasing the conversion of DBT in HDS (Hicks et al.

–

2003). Li et al. (2014) investigated the HDS of DMDBT over

FCC gasoline, FCC diesel

Hexadecane, dodecane

CoMo catalysts supported on nanostructured γ-alumina

with two different morphologies (rod and cube type). They
reported that the activity and selectivity of the synthe-
Cyclohexane
Hexadecane

Hexadecane

sized CoMo catalyst were influenced by the morphology

FCC diesel

FCC diesel
Model oil

Decalin
Decane

of γ-alumina. Surface acidity is also one of the significant

properties of support, which affect the dispersion of active

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phases and adjust the interaction of metal and support
(Chen et al. 2013). The commercial usage of some oxides
(titania and zirconia) is expelled because of their unfa-
vorable characteristics such as inappropriate mechanical
properties, low surface area, and limited thermal stabil-
ity. In order to overcome these drawbacks, combinations
of mixed oxides with γ-aluminas was used as supports to
take benefit of the favorable features of both the systems
(Dhar et al. 2003).
Nanostructured molecular sieves such as MCM-41
and MCM-48 were first developed by a scientist of Mobil
Oil Corporation (Saleh and Gupta 2016). These molecular
sieves have attracted the attention of many researchers for
use as a support material in the HDS owing to their good
thermal stability, high surface area, novel morphology,
fascinating texture, uniform pore size, and pore volume
(Mendoza-Nieto et  al. 2013, Subbaramaiah et  al. 2013a).
SBA-15 and SBA-16 are mesoporous forms of silica. SBA-15
is a more common support for the active species in the
HDS process rather than SBA-16. Table 3 shows the HDS
performance of both SBA-15 and phosphorous-incorpo-
rated SBA-16. SBA-15 exhibits higher pore diameter and
surface area than the conventional γ-alumina (Mouli et al.
2011). Application of mesoporous silica is limited to some
extent owing to the shortage of active sites. This problem
can be overcome by the incorporation of Ti and Al in the
framework of mesoporous silica. For example, a series
of Al containing mesoporous SBA-15  with various Si/Al
ratios (50, 30, 20, and 10) was synthesized by employing a
chemical grafting technique (Klimova et al. 2008). It was
observed that catalytic activity was enhanced by incorpo-
rating aluminum in the structure of support. Song et  al.
(2014) investigated the catalytic activity of Ni2P/Ti-MCM-41
for HDS. It was found that incorporation of Ti can increase
both the Lewis and Bronsted acidity of MCM-41 supports,
and a proper quantity of Ti can encourage the formation
of the Ni2P phase and instigate a better Ni2P dispersion.
2.4 E
 ffect of nitrogen compounds on HDS
process
Nitrogen compounds act as an inhibitor in the HDS
process by competing with sulfur compounds to get
adsorbed on the active sites of the catalyst. The extent of
inhibition in HDS is influenced by both type and concen-
tration of nitrogen compounds. HDS is not only affected
by the presence of non-heterocyclic nitrogenous com-
pounds but severely inhibited by the presence of hetero-
cyclic compounds such as pyridine, quinoline, indole, etc.
The heterocyclic nitrogen compounds can be divided into
P. Sikarwar et al.: Desulfurization      7
two categories, namely, basic (quinoline, pyridine) and
neutral (­carbazole, indole). It was reported in the litera-
ture that basic nitrogen compounds strongly inhibited the
HDS process compared to neutral nitrogen compound. For
example, Kwak et al. (2001) studied the inhibition effect
of nitrogen compounds (quinoline and carbazole) on the
HDS of DBT and alkylated DBT, and it was reported that
quinoline acts as a strong inhibiting agent compared to
carbazole. Farag et al. (2014) also reported that the addi-
tion of quinoline strongly inhibited the HDS of DBT in
the initial stages, and this poisonous effect continued
to remain until the concentration of quinoline became
very low. The HDS of the straight-run diesel fraction over
CoMoP/γ-Al2O3 catalyst was inhibited even by trace quan-
tity of nitrogen (García-Gutiérrez et al. 2014). It has been
shown in the few studies that the HDS of sulfur com-
pounds with steric hindrance was enhanced by nitrogen
removal (Sano et al. 2004, Laredo et al. 2013).
3 Desulfurization through
adsorption
3.1 Adsorptive desulfurization (ADS)
ADS has been studied worldwide and implemented for
abatement of refractory sulfur compounds from liquid
fuels. Various sorbents such as zeolites (Chica et  al.
2005, Tang et  al. 2008), activated carbon (Alhamed and
Bamufleh 2009, Nunthaprechachan et  al. 2013, Saleh
and Danmaliki 2016a, Danmaliki and Saleh 2017), metal
oxides (Turk and Gupta 2001, Zhang et al. 2013a,b, Xiao
et  al. 2015), mesoporous silicas (Sentorun-Shalaby et  al.
2011, Teymouri et  al. 2013) have been studied widely for
the removal of Th, BT, DBT, and DMDBT from hydrocar-
bon streams. In the following section, different sorbents
employed for ADS are discussed.
3.1.1 Activated carbon
Activated carbon has been widely used in the ADS process
due to its excessive surface area, good porosity, and easy
functionalization with different types of functional groups.
Adsorption capacities of activated carbon are directly con-
nected to the surface area and functional group. Activated
carbon exhibits higher adsorption capacity for aromatic
sulfur compounds owing to the existence of hydrogen
bonding interactions with their surface functional groups
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8      P. Sikarwar et al.: Desulfurization
(Kim et al. 2006). The adsorptive p
­ henomenon depends on
textural as well as on surface properties of activated carbon
(Triantafyllidis and Deliyanni 2014). In order to improve its
capacity, various modifications of activated carbon have
been done by researchers. It has been found from the liter-
ature data that the treatment of activated carbon with acid
or base can improve the adsorption capacity of activated
carbon, and the acid-treated activated carbon shows more
adsorption capacity compared to base-treated activated
carbon and virgin activated carbon (Jung and Jhung 2015,
Saleh and Danmaliki 2016b). Modifications of activated
carbon with metal species and metal oxides have been
also studied in order to enhance the adsorption capacity
of activated carbon (Xiong et al. 2010, Thaligari et al. 2015,
Danmaliki et  al. 2017, Saleh et  al. 2017). Desulfurization
performance of the modified activated carbon along with
the optimum condition is given in Table 4.
It was found that incorporation of aluminum on
activated carbon increased the adsorption capacity com-
pared to virgin activated carbon (Ganiyu et  al. 2016). A
few investigators have also made an attempt to derive
activated carbon from waste sources (Nunthaprechachan
et al. 2013, Saleh and Danmaliki 2016b). Nejad et al. (2013)
synthesized ordered mesoporous carbons such as CMK 5
and CMK 3 for the removal of DBT. In their outcome, CMK
5 acquired more sorption capacity compared to CMK 3,
and this higher sorption capacity of CMK 5 was ascribed
to its exclusive structure composed of ordered cluster of
carbon nanopipes, which are isolated by ordered arrays
of mesoporous channels in a system of the bimodal pore.
3.1.2 Metal-organic frameworks (MOFs)
MOFs are crystalline solids of three-dimensional frame-
work, which is formed by the reaction between organic and
inorganic species and where an organic linker connects
the metal ion or cluster of metal ions (Perry Iv et al. 2009,
Gomes Silva et al. 2010). The unique feature of MOFs is its
broad span of chemical and physical properties. MOFs have
been attracting the attention of many researchers for their
use as a support material for catalysts and as adsorbents
because of its special features such as easy to tailor the
pore size, shape from microporous to mesoporous range,
designable crystalline structure, and high and regular
porosity (Khan and Jhung 2012). MOFs have been used
for desulfurization and denitrogenation of liquid fuels
(Khan and Jhung 2012, Ahmed et al. 2013). Cychosz et al.
(2008) used MOFs first for the desulfurization of liquid
fuel, and a series of MOFs that included HKUST-1, UMCM-
150, MOF-5, MOF-505, and MOF-177 was utilized to remove
BT, DBT, and DMDBT. It is well known that materials with
high porosity and pore volume possess superior adsorp-
tion capacity. Nevertheless, in this research, a different
pattern was observed, which indicates that adsorption of
organosulfur compounds on MOFs slightly depend on the
porosity of MOFs. In addition, the adsorption capacity of
MOFs for organosulfur removal depends on the function-
ality of the active sites rather than its porosity (Cychosz
et al. 2008). Khan et al. (2011) studied three similar MOFs,
namely, MIL-53(Al), MIL-53(Cr), and MIL-47(V) for removal
of BT. Among these, MIL-47(V) has a higher adsorption
capacity approximately up to 1.6 mmol/g. Many research-
ers have also made an attempt to modify the MOFs by
immobilizing the functional groups for better ADS. Khan
and Jhung (2012) synthesized Cu+ (active phase) sup-
ported on MIL-100(Fe) under mild conditions. It was
observed that pore volume and surface area declined
with Cu+ species loading. However, with the loading of
Cu+ species, maximum adsorption capacity increased due
to the formation of π-complexation between Cu+ species
and the BT molecules. It can be seen from Table 4 that
Cu+/MIL-100(Fe) showed a very high adsorption capacity
(154 mg/g) for BT.
3.1.3 Mesoporous silica
Mesoporous materials are those materials having a pore
diameter in the range of 2–50 nm. Among the mesoporous
materials, mesoporous silicas MCM-41 and SBA-15  have
gained remarkable recognition in the field of adsorption
due to its high surface area, high thermal stability, and
a larger pore size, which encourages the easier diffusion
of larger molecules into pores (Wan and Zhao 2007, Tey-
mouri et  al. 2013). The main drawback associated with
these materials is the low adsorption capacity and selec-
tivity, and this problem can be tackled by incorporation
of metal into nanochannels. The size of incorporated
metal also plays a crucial role in the ADS process; the
adsorption capacity of the adsorbent for the removal of
organosulfur compounds with high steric hindrance can
be enhanced by reducing the size of metal nanoparticles
(Teymouri et al. 2013). Several d-block metal cations such
as Cu+, Ag+, Pd2+, and Pt2+ are capable of π complexation
bonding (Hernández-Maldonado et  al. 2005, Jayaraman
et  al. 2006, Zhang et  al. 2008, Khan and Jhung 2012).
Yang et al. (2003) developed sorbents, which can form π
complexation for ADS. Numerous researchers studied the
π complexation mechanism for the adsorption of sulfur
compounds onto the metal species-incorporated mesopo-
rus material. In this bonding, organosulfur compounds are
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 Table 4: ADS of organosulfur compounds under optimum reaction condition.

Model oil S-compound Adsorbent Reactor Temperature (°C) Pressure (atm) Co (ppm) % Removal Reference

Activated carbon
 Iso-octane DBT Al/activated carbon BR Room temperature – 50–200 95 Ganiyu et al. (2016)
 Hexane Th, BT, DBT Activated carbon from waste BR 25 – 50 100, 30, 20 Saleh et al. (2016a,b)
(85%) + toluene (15%) rubber tires
 Cyclohexane DBT Sn/activated charcoal BR 60 – 1000 99.4 Shah et al. (2016)
 Iso-octane DBT Zn/granular activated carbon BR 30 – 574 96.8 Thaligari et al. (2016)

Mesoporous silica
 Octane Th MoO3/MCM-41 BR 30 – 300 68 Shao et al. (2012)
 JP-8 – Ag/DDA-15 BR Room temperature 1 734 46 Palomino et al. (2015)
 JP-5 light – PdCl2/SBA-15 FBR Room temperature – 841 50 Wang et al. (2008)

Adsorption capacity (mg/g)

Metal organic frameworks

 n-Octane + p-xylene BT MIL-100(Cr) BR 25 – 400 28 Ahmed et al.(2013)
 n-octane BT Cu+/MIL-100-Fe BR 25 – 1000 154 Khan and Jhung (2012)

% Removal

Others
 Kerosene, Diesel, DBT Zn/MMT Clay BR 25 1 1000 76, 77, 81 Ahmad et al. (2017)
Cyclohexane
 Iso-octane Th AgCl Nanoparticles BR Room temperature – 550 95 Li et al. (2015)
 Hexadecane DBT Ni-Cu/γ Al2O3 BR 150 – 250 97 Mansouri et al. (2017)
 Isooctane Th Ga/Y zeolite BR 60 – 500 97 Tang et al. (2008)
 Hexane DBT Activated alumina BR 30 – 500 60 Srivastav and
Srivastava (2009)
 Hexane Th, BT Zeolites (from coal fly ash) BR 30 1 500 63 Ngamcharussrivichai
et al. (2008)

BR, Batch reactor; FBR, fixed bed reactor.

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P. Sikarwar et al.: Desulfurization      9
10      P. Sikarwar et al.: Desulfurization
adsorbed in a flat, facew down orientation, which helps
in adsorbing the alkylated DBTs with steric hindrance
(Ahmed and Jhung 2016). Wang et  al. (2008) conducted
desulfurization of the JP-5 light fraction (841  ppmw) by
π-complexation adsorption mechanism with CuCl and
PdCl2 supported on the MCM-41 and SBA-15  mesoporous
materials. It was found that Pd2+ gives better π complexa-
tion bonding compared to Cu+ for the benzothiophene and
its derivatives. Optimum operating conditions for ADS of
JP-5 light fraction using PdCl2/SBA-15 is presented in Table
4. Many researchers have used nickel-based mesoporous
silicas for the adsorption of aromatic sulfur compounds.
Dasgupta et  al. (2013) studied vapor phase ADS process
for diesel fuel with the help of Ni/MCM-41 and Ni/Y sorb-
ents. Among these, Ni/Y performed slightly better than Ni/
MCM-41, and both sorbents were regenerable under con-
trolled oxidation of air without any considerable change
in desulfurization capacity.
3.1.4 Other adsorbents
Alumina has been widely employed as a catalyst and an
adsorbent both owing to its high specific surface area,
regular pore size distribution, and it is also quite stable
within a wide range of temperature. It has the capability
to stabilize, disperse the active component very well, and
also exhibits moderate acidity (Bazyari et  al. 2016a,b).
The IRVAD process uses alumina-based adsorbents.
Alumina is modified with an inorganic promoter in this
process to increase the adsorption capacity and selectivity
(Irvine 1998). This process was used commercially in the
past to decrease the amount of sulfur in the fuel. It was
reported in the literature that presence of carbon-oxygen
functional groups on the surface of alumina was proved
to be very effective in the adsorptive removal of DBT onto
alumina (Srivastav and Srivastava 2009). Alumina has
been reportedly used in conjunction with other oxide sup-
ports in order to overcome the drawback of other oxides
and to give high desulfurization efficiency. For, example,
titanium oxide contains a large number of acidic sites
and provides better dispersion of the active phase than
other surfaces. However, it is not commercially available
in the high surface area, which results into lower adsorp-
tion capacity (Nair and Tatarchuk 2010, Hussain and
Tatarchuk 2013). One way to tackle down this obstacle
is to disperse the titanium oxide onto the surface of the
higher surface area supports such as alumina. Metal oxide
and mixed metal oxide supports have also been employed
for the ADS. Graphene oxide as a support framework
for nanoparticles has been used in various field due to
its high specific area, light weight, good thermal and
­electrical conductivity (Menzel et  al. 2016, Saleh et  al.
2016a,b). A series of mixed metal oxides and mixed metal
oxides supported on graphene oxide was studied for the
adsorption of DBT from dodecane (Menzel et al. 2016). It
was shown that DBT uptake was increased up to 170% by
incorporating only 5% of graphene oxide in mixed metal
oxides. Zirconia-based materials exhibit better adsorption
characteristics and has been utilized for the adsorption
of sulfur compounds such as thiophene and DBT. Kumar
et  al. (2011) demonstrated the desulfurization ability of
the zirconia-based catalyst (normal dried zirconia, zir-
conia calcined at 893  K, zirconia sulfated and calcined
at 893  K) for the removal of DBT from iso-octane. It was
reported that the adsorption process of DBT was exo-
thermic in nature. Further, copper supported on zirconia
proved to be very effective for the removal of DBT (Baeza
et  al. 2008). Modifications of mesoporous frameworks
with zirconia have also been explored for ADS. Kwon et al.
(2008) achieved 20% more sulfur adsorption capacity on
mesoporous silica modified with zirconia compared to the
pure silica. Palomino et al. (2015) synthesized a series of
zirconium-doped silver-loaded mesoporous silica mate-
rials with varying zirconia content and surfactant chain
length. Different adsorbents used for ADS of liquid fuels
are shown in Table 4.
3.2 Regeneration of adsorbents
Regeneration of adsorbents is the prime concern of the
ADS process because it assesses whether the developed
adsorbent is feasible for industrial scale or not. Regener-
able adsorbents not only make the process economic but
also make the process environmentally friendly. Different
regeneration methods have been adopted by the research-
ers such as thermal regeneration and chemical regenera-
tion (Xiong et al. 2012, Saleh et al. 2016a,b, Danmaliki and
Saleh 2017). In the thermal regeneration process, the spent
adsorbent is treated at higher temperature. Employed tem-
perature was higher than the boiling point of adsorbed
compounds so that the all adsorbed compounds desorbed
from the adsorbent. In chemical regeneration method,
various types of solvents such as methanol, acetonitrile,
chloroform, and toluene have been utilized for the regen-
eration of spent adsorbents (Shah et  al. 2017). Palomino
et  al. (2015) employed the solvent-rinsing procedure to
regenerate spent adsorbents. Diethyl ether was used as the
solvent to regenerate adsorbent. It removed both sulfur
compounds and some of the hydrocarbons, which are
adsorbed due to Van der Waals interactions. Regeneration
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of saturated sorbents with solvent is beneficial compared
to the thermal method because it overcomes the drawback
of using a high temperature for regeneration and also
avoids oxidation of metal species (Palomino et al. 2015).
3.3 R
 eactive adsorption desulfurization
(RADS)
Reactive adsorption desulfurization is a technique where
sulfur compounds in the fuel are adsorbed on the metal-
based sorbent and reacts with it to produce metal sulfides
in the presence of hydrogen; sulfur atoms are trapped by
the sorbent, whereas the sulfur-free hydrocarbon part
is released back into the fuel. This technique takes the
benefit of both HDS and ADS; therefore it is an efficient
technique for producing ultra-low-sulfur fuels (Tawara
et al. 2000, 2001). The RADS has been commercialized by
Conoco Phillips Petroleum Company, and the technology is
named as Phillips S Zorb sulfur removal technology (Khare
2001). The process takes place in a fluidized bed reactor
in a temperature range between 377°C and 502°C under H2
pressures in the range of 0.344–3.44 MPa and utilizes the
mixed catalyst composed mainly of silica, alumina, and
zinc oxide with a few wt.% of nickel and/or cobalt (Brunet
et al. 2005, Ito and van Veen 2006, Zhang et al. 2012a,b). It
provides high-octane retention fuels and found to be very
efficient in reducing the sulfur content of liquid fuels.
Several efforts have been made by the researchers
to understand the reaction mechanism of RADS. Most of
the researchers have studied the reaction mechanism of
RADS over Ni/ZnO. Babich and Moulijn (2003) reported
the overall mechanism of the RADS process in three steps.
First, NiS was formed upon contact with the sulfur-con-
taining compound, and then the Ni sites were regenerated
by reaction with H2, and released H2S. In the last step, ZnS
was formed by the reaction of ZnO with H2S. The overall
reaction mechanism of RADS on Ni/ZnO as an adsorbent
in the presence of hydrogen is illustrated below (Huang
et al. 2011). The overall reaction takes place in three steps:
in the first step, sulfur compounds are decomposed on the
Ni surface and generate Ni3S2. Further, reduction of Ni3S2
takes place to produce hydrogen sulfide in the presence
of hydrogen. Finally, hydrogen sulfide combined with the
support material (ZnO) to form ZnS as shown below in
equations (1)–(3):
2C mHnS+3Ni+2H2 → Ni 3S2 + 2C mH n+2 (1)
Ni3S2 + 2H2 ↔ 3Ni + 2H2S (2)
ZnO+H2S ↔ ZnS+H2O (3)
P. Sikarwar et al.: Desulfurization      11
Sentorun-Shalaby et  al. (2011) also reported the
adsorption mechanism of organosulfur compounds on Ni/
MCM-48. It was observed that the adsorption mechanism
involves direct interaction between the sulfur atom of
organosulfur compounds and the available nickel atom,
and a fraction of the adsorbed sulfur compounds on the
sorbent reacts further with nickel metal to generate nickel
sulfide and releases back the corresponding hydrocarbon
molecule free from sulfur in the fuel. The support mate-
rial accepts sulfur obtained from sulfur-containing com-
pounds adsorbed on metal species, and the metal species
are recommended to be “continuously regenerated”
during the reaction (Tawara et al. 2000). Regeneration of
sorbent is carried out when the active component trans-
formed completely into sulfides. Regeneration takes place
in two stages: first calcination of a mixture of sulfides was
carried out to obtain the oxide form of metal, and then, in
the next stage, these oxides are treated with hydrogen in
order to reduce the active phase.
Tawara et  al. (2000) systematically associated the
deep hydrodesulfurization capabilities of nickel metal
(active component) supported on various supports such as
ZnO, Al2O3, CuO, Ca(OH)2, and Fe2O3. ZnO was found to be
the finest sulfur-adsorptive support to use as a catalyst in
RADS. Ni supported on zinc oxide is the most widely used
catalyst in the RADS technology (Tawara et al. 2000, Meng
et al. 2013). Hence, many studies have been performed in
order to improve its desulfurization activity or to explore
its mechanism of desulfurization. Zhang et  al. (2013a,b)
studied the doping of Mn on 5% Ni/ZnO sorbent for the
adsorption of thiophene in a model gasoline in a fixed bed
reactor. Introduction of Mn in the sorbent significantly
improved the adsorption capacity and also showed high
adsorption capacity after regeneration. Because ZnO has
the best sulfur adsorption capacity, numerous researchers
have employed ZnO as a support in their studies. Research-
ers have also explored the effect of support size on des-
ulfurization activity. For example, Zhang et  al. (2012a,b)
studied the effect of ZnO particle size for the RADS of thio-
phene using Ni/ZnO. It was reported that a smaller size
of ZnO provided better removal of thiophene compared
to a larger particle size of ZnO. This high desulfurization
efficiency is attributed to the higher dispersion of active
species (Ni) on ZnO and lower mass transfer resistance for
transfer of sulfur to ZnO. Figure 2 depicts the RADS mech-
anism of the Ni/ZnO catalyst with a different particle size
of ZnO. It can be clearly seen in Figure 2 that NiO is highly
dispersed on the smaller particle size of ZnO. Further, ZnO
is completely converted into ZnS for a smaller particle size
of ZnO. Complete transformation of ZnO to ZnS leads to
better sulfur removal for a smaller particle size of ZnO.
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12      P. Sikarwar et al.: Desulfurization
Figure 2: Proposed scheme for RADS in the presence of Ni/ZnO with a different particle size of ZnO.
Adapted from Zhang et al. (2012a), with permission from Elsevier.
4 Biodesulfurization
BDS is an environmental friendly technique, where the
removal of refractory sulfur compounds takes place by
biological activity under mild operating conditions. It is
one of the low-cost alternatives to HDS and offers various
advantages over conventional HDS such as lower operat-
ing, capital costs, and lesser greenhouse gas emissions
(Labana et  al. 2005). Sulfur is present in bacterial cells,
and its amount is around 0.5–1% of the bacterial cell
dry weight; microorganisms assimilate sulfur in very
low amounts for their metabolism and growth (Soleim-
ani et  al. 2007). In nature, various microorganisms are
present, which are capable of altering the organic sulfur
molecule for usage of either the sulfur or the carbon skel-
eton (Le Borgne and Ayala 2010), and therefore, it can be
used as an efficient source to remove organosulfur com-
pounds from refinery streams. In this method, microor-
ganisms either biotransform sulfur compounds or utilize
sulfur-containing compounds as a sole source for growing
purposes under ambient pressure and temperature.
4.1 M
 echanism of BDS
Generally, the metabolic pathways for BDS of DBT and
alkyl-substituted DBTs can be classified into two catego-
ries, namely, ring destructive and sulfur specific. Among
them, the sulfur-specific pathway has gained more
attention.
4.1.1 Ring-destructive metabolic pathways
BDS, which employs this metabolic pathway, is known
as destructive BDS as sulfur is not specifically detached
from the parental organic sulfur molecules. This bio-
catalytic route constitutes of the following major steps:
hydroxylation, ring cleavage, and hydrolysis (Gupta et al.
2005). The most common pathway for the metabolism of
DBT is the Kodama pathway; DBT degradation through
this pathway is shown in Figure 3. In the first step, oxida-
tion of one of the rings of DBT takes place and results into
the destruction of one bond or a fragment of DBT by enzy-
matic action (McFarland et al. 1998). As can be seen from
Figure 3, the initial oxidation takes place at the peripheric
aromatic ring followed by the destruction of the ring. The
final products of oxidation are 3-hydroxy-2-formyl ben-
zothiophene (HFBT) and pyruvic acid (PA) as shown in
Figure 3. These compounds are water soluble, and accu-
mulation of these compounds leads to the inhibition of
oxidation of DBT and microbial growth (Soleimani et al.
2007). HFBT was not identified after the reaction because
HFBT is a chemically unstable compound and most likely
to be mineralized in nature. Several bacterial genera such
as Rhizobium and Pseudomonas have been reported in the
literature, which degrades DBT via the Kodama metabolic
pathway (Monticello et  al. 1985, Frassinetti et  al. 1998,
Hou et al. 2005). This biological pathway has not gained
much attention due to unwanted breakage of C-C bonds,
which leads to the decrease in the calorific value of the
fuel.
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 P. Sikarwar et al.: Desulfurization      13

(Ohshiro and Izumi 1999). Four enzymes, which includes

Figure 3: Kodama metabolic pathway for desulfurization of DBT.
Adapted from Soleimani et al. (2007), with permission from Elsevier.
Afferden et  al. (1990) described another pathway for
DBT, in which DBT is converted into dibenzothiophene-
sulfoxide (DBTO) and then into dibenzothiophene-sulfone
(DBTO2), and further, DBTO2 was transformed into benzo-
ate after the removal of sulfur from it, and then it was min-
eralized into water and CO2. This biocatalytic route is also
known as the ring-destructive pathway as all the aromatic
compounds were mineralized during this process.
two monooxygenases (DszC and DszA), one desulfinase
(DszB), and one NADH:FMN oxidoreductase (DszD), are
responsible for the specific oxidative pathway. The conver-
sion of DBT into DBTO and further into DBTO2 is catalyzed
by DszC, and these two steps need FMNH2 and oxygen for
activity (Oldfield et al. 1997, Mohebali and Ball 2016). The
conversion of the sulfone to a sulfinate (HPBS) is cata-
lyzed by DszA, and the conversion step also needs mole-
cular oxygen and is NADH dependent (Oldfield et al. 1997,
Mohebali and Ball 2016). Finally, the fourth enzyme HPBS
desulfinase (DszB, encoded by the dszB), an aromatic
sulfinic acid hydrolase, is required to complete the reac-
tion sequence (Gray et  al. 2003), and the base-activated
water molecule stages a nuclophillic attack on HPBS,
which transforms it into 2-HBP. The consumption rate of
HPBS to 2-HBP, which is catalyzed by dszB, is very slow
(five times) compared to its production rate. Hence, the
conversion of HPBS to 2-HBP is considered as the slowest
step in this metabolic pathway. SOP requires approxi-
mately 4 mol of NADH to desulfurize 1 mol of DBT, which
makes it an energy-demanding process (Oldfield et  al.
1997). The mechanism of SOP for DBT is shown in Figure 4.
Many researchers have made an attempt to isolate the

4.1.2 Sulfur-specific pathway

In this metabolic pathway, sulfur is specifically removed

from the substrate, and this route can be divided into two
major pathways, namely, specific oxidative and anaerobic
metabolic pathways.

4.1.2.1 Specific oxidative pathway (SOP)

In the specific oxidative metabolic route, the carbon skel-
eton of the DBT remains intact, which results into no loss
of calorific value of the fuel. This metabolic route is also
known as the 4S pathway, and it involves four consecutive
reaction steps. In the first step, DBT is oxidized to DBTO,
further converted into DBTO2, and thereafter, it is trans-
formed into sulfinate, and finally into hydroxybiphenyl
(Kilbane 1989). This metabolic route requires four enzymes Figure 4: The 4S metabolic route for desulfurization of DBT.
for the transformation of DBT into 2-­ hydroxybiphenyl Adapted from Alcon et al. (2005), with permission from Elsevier.

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14      P. Sikarwar et al.: Desulfurization
microorganisms, which can remove s­ulfur-bearing com-
pounds without destruction of the aromatic ring; however,
it ends up with insignificant results (Afferden et al. 1990).
Consequently, in the year 1990, the Institute of Gas Techno-
logy (IGT), Chicago, made an effort to grow novel strains
through a selection of mutagens. Thus, model mixed
culture soil was adulterated with hydrocarbons comprised
of sulfur molecules and, thereafter, kept in a continuous
coal bioreactor where these samples were introduced to
mutagenic agents. Some species remained in the bioreac-
tor after several months, and these showed a specific C-S
incision activity and were capable of removing 90% of the
organic sulfur present in the given sample (Kilbane and
Bielaga 1990, Kilbane and Jackowsky 1992). This certain
microbial group was named as IGTS7. The name was given
for the minimum seven different types of the colony with
different populations. Among these seven, two mutant
strains, namely, Rhodococcus rhodochrocus (IGTS8) and
Bacillus sphaericus (IGTS9) had higher desulfurization
capabilities (Monticello and Kilbane 1994, Ohshiro et  al.
1994, Kilbane 1996).
4.1.2.2 Anaerobic metabolic pathway (AMP)
In this pathway, sulfur compounds are decomposed
with the help of certain microorganisms in the absence
of oxygen (Saleh 2018). Several anaerobic strains have
been reported in the literature, which can remove organic
sulfur compounds from liquid fuels by reductive C-S bond
cleavage (Lizama et al. 1995). For example, the reduction
of DBT by a thermophilic mixed culture was investigated
by Bahrami et  al. (2001), where H2S and biphenyl were
detected as an end product in the desulfurization process.
Kim et  al. (1995) found that Desulfovibrio de-sulfuricans
M6 can reduce DBT anaerobically to produce biphenyl and
H2S. AMP offers a few advantages such as less aeration
cost, and formation of undesired compounds (colored and
gum-forming products) is very low under anaerobic oper-
ating conditions (McFarland 1999). The major drawback of
AMP is the maintenance of the anaerobic process, low rate
of reaction, protection, and price issues (Gupta et al. 2005).
4.2 B
 DS at a glance
The BDS system is composed of three main components,
namely, aqueous, oil, and cellular. Further, the cells
are dispersed into three regions: cells in aggregates in
the aqueous phase, free cells in the aqueous phase, oil-
drop-adhered cells (Abin-Fuentes et  al. 2013), and it is a
two-phase system in which the oil phase interacts with
whole cells (biocatalyst) in the aqueous phase (Takada
et  al.  2005). The BDS of liquid fuels is usually accompa-
nied by employing the entire cell as a biocatalyst, which
facilitates the industrialization of BDS (Honda et al. 1998,
Chang et  al. 2000, Li et  al. 2005). Various desulfurizing
microorganisms have been used as a biocatalyst in the
BDS process such as Rhodococcus sp. IGTS8 (Oldfield et al.
1997), Rhodococcus erythropolis H-2 (Ohshiro et al. 1996),
Mycobacterium sp. G3 (Nekodzuka et  al. 1997), Gordo-
nia sp. CYKS1 (Rhee et al. 1998), Pseudomonas delafieldii
R-8 (Luo et al. 2003), Microbacterium sp. ZD-M2 (Li et al.
2005), Bacillus subtilis WU-S28 (Kirimura et  al. 2001), R.
erythropolis SHT87 (Davoodi-Dehaghani et al. 2010); Myco-
bacterium pheli WU-F1 (Furuya et al. 2001), Pantoea agglo-
merans D23W3 (Bhatia and Sharma 2010), Lysinibacillus
sphaericus (Bahuguna et  al. 2011), and Desulfobacterium
indolicum (Kareem et  al. 2012). However, the Rhodococ-
cus sp. bacteria have been used widely by the researchers
for the BDS process as they utilize 4S metabolic route to
degrade DBT. Moreover, the Rhodococcus sp. possesses
hydrophobic properties, which help in increasing the
contact between the cell and the organosulfur compounds,
and eventually increases sulfur removal (Monticello 2000).
The high desulfurization ability of newly isolated Rhodoc-
occus sp. P32C1 was reported by Maghsoudi et al. (2001) for
the desulfurization of middle distillate fractions like diesel
oils and model oil (n-hexadecane) containing DBT. The
desulfurization ability of the Rhodococcus sp. with model
oil and real oil system is shown in Table 5.
The conventional HDS process is carried out at ele-
vated temperature, and in order to incorporate BDS in the
petroleum-refining process, it is desirable to perform BDS
at a higher temperature with microorganisms that which
are able to withstand higher temperatures (Campos-Martin
et  al. 2010). A higher temperature offers various benefits
such as decrease in oil viscosity, which enables the easier
displacement of molecules, enhances enzymic rates, and
reduces contamination of bacteria (Gray et al. 2003, Soleim-
ani et al. 2007, Campos-Martin et al. 2010). A few research-
ers have studied the desulfurization capability of various
thermophilic microorganisms such as Paenibacillus sp.
A11-2, Klebsiella sp., and athermophilic bacterium (Konishi
et  al. 2000, Torkamani et  al. 2008, Bhatia and Sharma
2012). Ishii et  al. (2000) first studied the desulfurization
abilities of isolated Paenibacillus sp. A11-2 thermophilic
strain. Bhatia and Sharma (2012) reported the isolation of
a thermophilic bacterium Klebsiella sp. 13T and tested its
desulfurization ability for different petroleum oils. They
found that the Klebsiella sp. 13T was capable of removing
22–53% of sulfur from d ­ ifferent ­petroleum oils, and the
highest sulfur was obtained for light crude oil.
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 P. Sikarwar et al.: Desulfurization      15

Numerous BDS studies have been given in literature,

Bhatia and Sharma (2010)

Maghsoudi et al. (2001)

which employed growing and resting cells in aqueous or
Rashtchi et al. (2006)

Bordoloi et al. (2014)

Kareem et al. (2012)
Guobin et al. (2006)
bi-phasic media (Gunam et al. 2006, Rashtchi et al. 2006,
Davoodi-Dehaghani et al. 2010). Resting cells are consid-

Ma et al. (2006)
Yu et al. (2006)

Li et al. (2003)
Li et al. (2007) ered as the finest biocatalyst as the 4s metabolic route is a
Reference

difficult enzyme system, and its cofactor necessity restrict

the consumption of purified enzyme system rather than
whole cells for a real microbial desulfurization process
% Removal

48,23
94, 62, 47

78

79
95
86
50, 86
93, 26–71
77
47

(Mohebali and Ball 2016). These cells were prepared by

culturing specific species of bacteria in media with DBT
as the sulfur source. Huge generation of cells by consum-
– ing DBT is not commercially feasible owing to the high
–
–

1
–
–
–
–
Pressure
(atm)

–
–

price of DBT (Yan et al. 2000, Yoshikawa et al. 2002, Ma

et  al. 2006). Ma et  al. (2006) prepared bioactive catalyst
using dimethylsulfoxide as the only source of sulfur, and
24
–

72
24
24
24, 120
24, 72
Time (h)

7
16
96

it removed sulfur efficiently from HDS-treated diesel oil.

Immobilized microbial cells as a biocatalyst have been
used in many BDS studies owing to their better operational
45
30
30
37
30
30

30
Temperature
(°C)

30
30

stability, high oil/water volumetric ratios, continuous

use, less contamination, better efficiency in catalysis in
comparison to free cells, easier separation from the reac-
tion mixture, and good storage ability (Shan et al. 2005).
303, 1000
166.037
420
535
259, 321,
1237
200
Co (ppm)

–
591
554, 150
100

However, the free dispersion of microbial cells with hydro-

carbons minimizes the mass transfer resistance in the BDS
process, but the separation of microbial cells from the
reaction mixture becomes difficult. The entrapment and
Reactor

adsorption method have been used by many researchers

BR
BR
BR
BR
BR
BR
BR
BR
BR

for the immobilization of cells (Chang et  al. 2000, Naito

et  al. 2001). Naito et  al. (2001) studied BDS using immo-
Rhodococcus erythropolis NCC-1
Pantoea agglomerans D23W3,
Pseudomonas delafieldii R-8

Desulfobacterium indolicum

bilized Rhodococcus erythropolis KA2-5-1 on photo-cross

linkable resin prepolymers (ENT-4000 and ENTP-4000),
Rhodococcus sp. P32C1
Mycobacterium sp. X7B
Rhodococcus sp. 1awq,
Table 5: BDS of organosulfur compounds under optimum reaction conditions.

urethane prepolymers, calcium alginate, and agar for the

Achromobacter sp.
R. erythropolis XP

removal of DBT in n-tetradecane. They reported that the

Microorganism

highest desulfurization activity was achieved with ENT-

4000 immobilized cells with no loss of cells from the
RIPI-22

support. It was found that recovery of biocatalysts from

oil was easy. Immobilization of microbial cells on inor-
ganic support enhances the interaction between reactants
DBT, alkylated DBT
Alkylated DBT, BT
substituted DBTs

substituted DBTs

present in the two-phase system (Feng et al. 2006). It has

DBT and alkyl-
DBT and alkyl
S-compound

been found in the literature data that immobilization of

microbial cells using the adsorption technique possess
BT, DBT
DBT
DBT
DBT

more advantages than the cell-entrapment technique as it

–

aids in reducing the mass transfer and the steric hindrance

effect (Hou et al. 2005, Shan et al. 2005). Researchers have
Desulfurize diesel oil, Fushun
crude oil, Sudanese crude oil

also studied BDS by decorating the surface of bacterial

HDS diesel, hexadecane
Hexane, petroleum oils

cells with magnetic nanoparticles to tackle the difficulties

that arise in the conventional adsorption method such as
loss of cells and mass transfer problems (Shan et al. 2005).
Sample diesel
Hexadecane

HDS diesel
HDS diesel
HDS diesel
HDS diesel

For example, Ansari et al. (2009) and Karimi et al. (2017)

Model oil

decorated the surface of R. erythropolis IGTS8  with mag-

Diesel
Diesel

netic Fe3O4 nanoparticles. They reported that decorated

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16      P. Sikarwar et al.: Desulfurization
cells showed higher desulfurization activity (56%) than
non-decorated cells in the basic salt medium. The rate of
transfer of organosulfur compounds to the cell membrane
is limited as BDS usually takes place in organic phases.
This problem can be overcome by assembling the bacteria
(stable in oil) with the sorbents, which can adsorb orga-
nosulfur compounds (Montalvan-Sorrosa et al. 2016). For
example, Guobin et al. (2005) reported that the desulfuri-
zation rate increased two times when cells were used in
combination with alumina compared to only cells. In order
to enhance the efficiency of the BDS system, it has been
studied with several reactor setups. For example, McFarald
et al. (1998) investigated the BDS of diesel oil in continuous
stirred tank reactor using Rhodococcus sp. and reported a
50–70% reduction in total sulfur content. An airlift reactor
containing immobilized Gordonia nitida CYKS1 cells on a
fibrous support for the BDS of diesel oil was proposed by
Lee et al. (2005). Its performance at different phase ratios
of the oil to the aqueous medium and different sucrose con-
centrations was analyzed, and it was found that when the
reaction mixture contained 10% diesel oil (v/v), 61–67%
of sulfur removal was achieved in 72 h. Maass et al. (2014)
demonstrated the desulfurization ability of R. erythropolis
ATCC 4277 in a batch system for synthetic diesel. It was
found that the microbial strain was able to remove 93%,
98%, and 95% of the DBT in the presence of 20%, 80%,
and 100% (v/v) of dodecane, respectively.
Various researchers have made an attempt to examine
the abilities of microbial strain in the real liquid fuel
system. Labana et al. (2005) reported the desulfurization
of DBT by two different bacteria, namely, Rhodococcus
sp. and Arthrobacter sulfureus, isolated from oil-contam-
inated soil/sludge samples. Both microorganisms could
significantly reduce the total amount of sulfur in diesel
samples. Adlakha et al. (2016) investigated the desulfuri-
zation ability of Gordonia sp. IITR100 for the BDS of heavy
crude oil and hydrodesulfurized oil. It was found that this
microorganism was able to reduce 98% and 70% sulfur
from two different diesel oils. They reported around 76%
of sulfur removal in heavy crude oil. In addition, viscosity
of this heavy crude oil was also decreased by 31%. Table 5
sums up the research conducted for the reduction of sulfur
content in liquid fuels using the BDS process.
5 Oxidative desulfurization (ODS)
ODS is considered as a promising alternative for the
removal of refractory sulfur compounds from liquid
fuels. In this process, sulfur compounds in liquid fuels
are oxidized into their corresponding sulfoxides and
­sulfones with the help of a selective oxidant. This process
is highly advantageous in comparison to the conventional
HDS, which can occur at a mild condition with no use of
hydrogen (Dehkordi et  al. 2009). It is conducted in two
steps: oxidation in the first stage followed by removal of
oxidized sulfur compounds. The ODS process possesses a
reaction mechanism that enhances the polarity of sulfur
compounds and enables easier separation from the fuel.
During the ODS, sulfur-containing molecules in liquid
fuels are oxidized into their corresponding sulfoxides and
sulfones with the help of a selective oxidant. These oxi-
dized compounds possess enhanced relative polarity due
to which they can be easily extracted from the fuel (Aitani
et al. 2000, Gore 2001, Ali et al. 2009).
Oxidation of the organosulfur compound (DBT) to the
corresponding sulfone is shown in Figure 5.
5.1 Oxidants
A wide variety of oxidants were used for the desulfuriza-
tion of liquid fuels, i.e. hydrogen peroxide (Fox et al. 2015,
Fraile et al. 2016, Leng et al. 2016), molecular oxygen (Sam-
panthar et al. 2006, Ma et al. 2007), and organic hydroper-
oxides (Chang et al. 2010, Saha and Sengupta 2015).
5.1.1 Hydrogen peroxide
Hydrogen peroxide is one of the fascinating oxidants
because of its low cost, easy availability, and environ-
mental friendliness. It is one of the most chosen oxidants
for ODS studies as it only produces water as a by-product
(Fraile et  al. 2016). Various researchers have investi-
gated the ODS process by employing H2O2 as an oxidant
(Ribeiro et al. 2013, Krivtsov and Golovko 2014). ODS has
been studied with H2O2 in the presence of various catalyst
such as various acidic catalysts (Te et  al. 2001, Duarte
et  al. 2011, Krivtsov and Golovko 2014), ionic liquids
(He et al. 2008, Gao et al. 2010), polyoxometalate (POM)
catalysts (Ribeiro et  al. 2013), supported and unsup-
ported metal oxides (Sampanthar et  al. 2006, Huang
et al. 2008, Kumar et al. 2012), etc. Table 6 presents the
Figure 5: Oxidation of DBT into the corresponding sulfone.
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 Table 6: ODS of organosulfur compounds under the optimum reaction condition.

Model oil S-compound Oxidant Catalyst System Co (ppm) Temperature Pressure % Removal Reference
(°C) (atm)

Oil-soluble oxidant
 n-Octane DBT CHP Mo/MMS BR 500 103 1 98 Qiu et al. (2016)
 n-Tetradecane +  DBT, MDBT, DMDBT CHP MoO3/Al2O3 BR 820, 806, 879 75 – <95 Safa and Ma (2016)
n-Hexane + toluene
 Decalin DBT, DMDBT TBHP MCM-41,MCM-48 and SBA-15 BR/FBR 500, 5000, 300 80 1 – Wang et al. (2014)
 Kerosene DBT TBHP 16 wt.% Mo/Al2O3 FBFR 55 110 1 86 Wang et al. (2003)
 Decalin DBT CHP Phosphorous-modified MoO3/SiO2 FBR 298 each 50 1 92 Han et al. (2013)
 Kerosene DBT TBHP 16 wt.% Mo/Al2O3 FBFR 55 110 1 86 Wang et al. (2003)
 Toluene DBT CHP MoO3-CeO2-SiO2 FBR – 40 1 97 Zhang et al. (2009)

Oil insoluble oxidant

 n-Decane DBT, BT, DMDBT H2O2 NaHCO3, bicarbonate-functionalized BR 500, 250, 250 25 1 >99 Bokare and Choi
resin (2016)
 n-Octane DBT, DMDBT H2O2 Ti-modified hierarchical mordenites BR 1000, 300 60 – 98, 61 Leng et al. (2016)
 Diesel – H2O2 Mo/γ Al2O3 BR 320 each 80 1 96 García-Gutiérrez
et al. (2008)
 Gasoline, diesel, DBT H2O2 H2SO4 + acetic acid – 670, 1045, 500 80 – 84, 92, 98 Ali et al. (2009)
toluene + hexane
 Iso-octane DBT H2O2 Chromium promoted sulfated zirconia BR 800 60 – 79 Kumar et al. (2011)
 n-Octane DBT H2O2 C18H37N(CH3)3]4[H2SeIV3W6O34]/ BR 500 45 – 98 Xie et al. (2015)
MCM-41
 Petroleum ether DBT, DMDBT, BT H2O2 HPW/TiO2 BR 500 60 1 100, 97, 94 Yan et al. (2009)

BR, Batch reactor; FBR, fixed bed reactor; FBFR, fixed bed flow reactor.

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18      P. Sikarwar et al.: Desulfurization
ODS performance of the different catalytic systems when
H2O2 is used as an oxidant. The conversion process of
DBT to its corresponding sulfoxides and sulfones can be
catalyzed with the help of an acidic catalyst (Ali et  al.
2006). Acidic catalysts polarize the O-O bond present in
hydrogen peroxide. When the oxidation system consists
of hydrogen peroxide and carboxylic acids (formic and
acetic acid), it generates in situ peracid radicals, which
are efficient for the fast oxidation of organosulfur com-
pounds (Yan et al. 2009). The effect of stronger (hydro-
chloric acid) and weaker acids (acetic acid) compared
to formic acid on the ODS process is also investigated.
Formic acid gave better oxidation results compared to
both HCl and acetic acid (Ali et al. 2006). Ali et al. (2009)
studied ODS of thiophene sulfur compounds from hydro-
treated diesel oil in the presence of H2O2 and acetic acid
using H2SO4 as a catalyst. Their finding shows that the
highest DBT conversion was achieved when the acetic
acid and sulfuric acid ratios enhanced from 1:0 to 2:1 mol
ratios, and similarly, the sulfone content in the oxidation
product was enhanced quickly. In addition, de-Souza
et  al. (2009) studied the catalytic oxidation of nitrogen
and sulfur organic model compounds using an equimo-
lar mixture of H2O2 and HCOOH as an oxidant, and they
monitored it with the help of electrospray ionization
mass spectrometry. It was found that DBT, quinoline,
and methylene blue were oxidized through a mecha-
nism of successive hydroxylation. Experimental find-
ings showed that the reaction of H2O2 on the surface of
the catalyst produced highly reactive hydroxyl radicals,
which are responsible for the oxidation process. The oxi-
dation reactivity pattern for the sulfur-containing fuel in
a formic acid-catalyzed system with H2O2 was reported
by Otsuki et  al. (2000) at a temperature of 50°C and
atmospheric pressure. Transition metal-based catalysts
along with H2O2 as an oxidizing agent are investigated
widely by the researchers for ODS. Capel-Sanchez et al.
(2010) studied the removal of BT, DBT, and DMDBT via
oxidation using H2O2, amorphous silica-loaded titanium
oxide as an oxidant and catalyst, respectively. Leng et al.
(2016) reported on ODS for the removal of DBT with Ti-
modified hierarchical mordenite as a catalyst and H2O2
as an oxidant; 98% of the removal of sulfur was achieved
at 333 K in 120 min. Kumar et al. (2012) and Franco et al.
(2013) studied ODS for the removal of DBT using H2O2 as
an oxidant. One of the major issues associated with the
use of H2O2 is that it is an oil-insoluble oxidant due to
which it forms a biphasic liquid system. The interface
establishment between aqueous and oil phases causes
a low mass transfer rate, which eventually results into
the excessive requirement of an oxidant. Phase t­ ransfer
agents are also added in order to improve the mass
­transfer coefficient (­diffusion), but the addition of these
agents create hurdles in separating the oil phase from
the aqueous phase owing to the formation of the emul-
sion, and hence, reduces the overall oil yield. Moreover,
the aqueous phase (H2O2) creates several other problems
such as corrosion of equipment; the high volume ratio of
aqueous phase to oil phase leads to a low efficiency of
the reactor (Fraile et al. 2016) and production of oil with
high moisture content.
5.1.2 Organic hydroperoxides
Organic hydroperoxides, particularly tertbutyl hydrop-
eroxides (TBHP), have been widely employed as oxi-
dants for the elimination of sulfur-containing molecules
from liquid fuels. TBHP is an oil-soluble oxidant, which
minimizes mass transfer limitation and enhances the
overall oxidation rate of sulfur-containing molecules.
Various catalysts such as TiO2-SiO2 (Bazyari et  al.
2016a,b), Co/Mn/Al2O3 (Mokhtar et al. 2015), and MoO3/
Al2O3 (Wang et al. 2003) have been used in conjunction
with TBHP as oxidants. The operating conditions of a
few catalytic systems employed with TBHP are reported
in Table 6. Prasad et al. (2008) investigated the ODS of
DMDBT for the catalytic system composed of TBHP and
molybdenum oxide supported on the following sup-
­
ports: alumina, silica-alumina, and magnesia-alumina
and achieved the highest catalytic activity with MoO3/
Al2O3.
Some researchers also explored other organic hydrop-
eroxides, i.e. cumene hydroperoxide (CHP), cyclohex-
anone peroxide (CYHPO) for the oxidation of refractory
sulfur compounds in oil fractions. DBT oxidation was
carried out in a fixed bed reactor with CHP as an oxidiz-
ing agent and MoPxO/SiO2 as a catalyst. They found that
sulfur content in the diesel was decreased from 298 to
5 ppmw (Han et al. 2013). Safa and Ma (2016) also reported
the oxidation of DBT, 4-methyldibenzothiophene (MDBT),
and dimethyl DMDBT in a model fuel with CHP as an
oxidant over a MoO3/γ-Al2O3 catalyst. Details of the ODS
system comprising of CHP and different catalysts are
given in Table 6. CYHPO is also an oil-soluble oxidant and
possesses better oxidation capability, cheap, in compari-
son with other oil-soluble oxidants, and available in large
scale. ODS was investigated using various alkyl peroxides,
and it was found that the activity decreases in the fol-
lowing order: CYHPO > tert-amyl hydroperoxide > TBHP,
reversing the order of the peroxy oxygen electronic density
(Zhou et al. 2007).
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5.1.3 Other oxidants
A few studies have also been conducted on the ODS with
the following oxidants such as ozone (Otsuki et al. 1999,
Wang et  al. 2010a,b), oxygen (Lü et  al. 2007), potas-
sium ferrate (Liu et al. 2008), Fenton’s reagent (Dai et al.
2008), nitric acid (Tam et al. 1990a,b), nitrogen (Tam et al.
1990a), etc. Among these, nitrogen dioxide was used as
the oxidant in the first study of the ODS process. Ma et al.
(2007) investigated the ODS process for model and real
jet fuel (JP-8) in a batch system with the aid of molecular
oxygen as an oxidant followed by adsorption over acti-
vated carbon. Tang et al. (2014) also reported the oxidation
of DBT using molecular oxygen as an oxidant catalyzed by
tetradecavandaphosphate. A few ODS studies have also
employed ferrate (Fe(VI)) as an oxidant (Sharma et  al.
2011, Liu et al. 2013). It exhibits strong oxidizing proper-
ties in comparison with other oxidants such as O3, H2O2,
and KMnO4 and also possesses a reduction potential of
+2.20 V in an acidic medium (Sharma 2002). It is also an
environmental friendly oxidant since Fe(VI) is converted
to harmless Fe (III) (Liu et al. 2008). The ODS of diesel oil
was studied by employing Fe(VI)-acetic acid system with
manganese acetate as the catalyst, and different phases
transfer agents such as hexadecyl trimethyl ammonium
bromide, benzyl trimethyl ammonium chloride, and tetra-
methyl ammonium chloride (Liu et al. 2008).
5.2 Catalyst
In the ODS process, the catalyst plays a very important role
as it is responsible for the activation of oxidants. Both homo-
geneous and heterogeneous catalysts have been used in the
ODS process (Caero et  al. 2005, Green et  al. 2007, Huang
et al. 2008, Ali et al. 2009, Wang et al. 2009a,b, Xinrui et al.
2009). A particularly heterogeneous catalyst has attracted
more attention compared to the homogeneous catalyst,
and it is composed of the active phase and support mate-
rial. The active component present in the catalyst is able
to alter both structural and morphologic characteristics of
the supported catalyst and, thereby, increase in activity and
stability of the catalyst for the desulfurization process (Mei
et al. 2003, Prasad et al. 2008, Zhao et al. 2009, Bakar et al.
2012). The surface of the support material should be covered
with a thin layer of the active component. The active phase
of catalysts is primarily constituted of transition metals
viz, molybdenum, iridium, palladium, nickel, platinum,
tungsten, and rhodium (Qiu et al. 2016). Oxides of d-block
contain Lewis acidic sites; when these oxides disperse over
the support (high superficial area), it maximizes the contact
P. Sikarwar et al.: Desulfurization      19
area between the active sites and the reactants, and pro-
motes the conversion of sulfur compound into sulfoxides
and sulfones (Zhao et al. 2009, Bakar et al. 2012).
Transition metal oxides proved to be an efficient cata-
lyst for catalytic ODS because they can easily alter their
valence state and encourage the redox cycle (Franco et al.
2013). Among the transition metal oxides, molybdenum
oxide acts as a very effective catalyst for the ODS process.
The molybdenum-based catalyst has attracted consider-
able attention of many researchers in ODS of liquid fuels
due to its unique physical-chemical characteristic, and it
is also very reactive and highly potent for the desulfuri-
zation of DBT (Gonzalez-Garcia and Cedeno-Caero 2009).
However, the usage of transitional metal oxides alone
as a catalyst is limited because of its low pore diameter,
volume, and specific surface area (Samadi-Maybodi et al.
2011, Subhan and Liu 2011, Liu et al. 2012a,b). In addition,
generation of organic sulfides during the ODS process on
the surface would lead to blocking of active sites in the
pores and eventually decreases the capability to remove
sulfur compounds (Guo et  al. 2012). Furthermore, these
active components cannot be used as a homogenous reac-
tion due to the difficulty in separation from the organic
phase (Yang et  al. 2016a,b). Therefore, a support mate-
rial with a high specific surface area is needed in order
to remove the drawbacks associated with the catalytically
active component (transition metal oxides). The support
material is responsible for the number and nature of the
active sites present in the catalyst. As a result, the support
material affects the catalytic activity of the catalyst, and
it also promotes the separation of the catalyst from the
fuel (Qiu et al. 2016, Yang et al. 2016a,b). Selection of an
appropriate support is a very significant step in the desul-
furization process as it may affect both reaction selectiv-
ity and activity. Various supports have been used in ODS
studies such as alumina (Wang et al. 2003, Jia et al. 2011,
Safa et al. 2016), MCM-41 (Xie et al. 2015), molecular sieve
(Hulea et al. 2001), TiO2, SiO2 (Han et al. 2013), and SBA-15
(Chamack et al. 2014).
Wang et al. (2003) reported that the Mo catalyst sup-
ported on alumina showed the best sulfur removal capac-
ity compared with the Mo supported on titania and silica.
Modification of the molybdenum-based catalyst was also
carried out by many researchers to improve its catalytic
activity. The Mo-based catalyst was modified with bismuth
to increase the catalytic activity of desulfurization of light
cycle oil (Prasad et al. 2008). Chang et al. (2010) introduced
a series of alkaline earth metal dopant on Mo and reported
that CaMo/Al2O3 showed a high catalytic activity. In order
to improve the catalyst stability and ODS activity, differ-
ent synthesis methods for synthesis have been adopted by
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20      P. Sikarwar et al.: Desulfurization
researchers. For example, theMoO3-SiO2-mixed oxide was
synthesized by the sol-gel method. Because of the strong
interaction between MoO3 and SiO2, the loss of the active
metal was inhibited, which eventually enhanced the sta-
bility of MoO3-SiO2. The ODS activity of MoO3-SiO2 was
further promoted by the addition of a proper amount of
CeO2. The introduction of CeO2 enhanced the dispersion of
MoO3, and small amounts of Mo5+ may have been formed
owing to the electronic interactions between the Mo and
Ce species (Zhang et al. 2009).
Transition metals oxides supported on mesoporous
materials are a promising choice for the preparation of
catalysts to fulfill the demands imposed by industries.
Mesoporous silica materials such as MCM-41 and SBA-15
exhibit a high surface area, good thermal stability, narrow
and controllable pore size, and offers several other benefits
such as allowing the processing of various sizes of mole-
cules, allowing good diffusion of several compounds, and,
as a result, enhancing the effectiveness of the reaction at
the internal surface (Kwong et al. 2008, Popova et al. 2009,
Subbaramaiah et  al. 2013b). Abdalla and Li (2012) pre-
pared MCM-41 (Bu4N)4H3(PW11O39)-supported MCM-41 and
examined its capability for the ODS process. It was found
that synthesized catalysts showed a high catalytic activity
and can be reused for the ODS of organosulfur compounds.
Complete removal of DBT and Th was achieved under
mild operating conditions, and 97% of sulfur removal
was obtained for the ODS of the FCC cycle. Li et al. (2011)
synthesized mesoporous silicate with the incorporation
of phosphotungstic acid and achieved 98–99% DBT con-
version for model oil in the ODS process. The molecular
sieve as a support material has gained much attention in
the recent years owing to its inherent properties and envi-
ronmental friendliness (Li et al. 2009, Subhan et al. 2014).
Moreover, the 4A molecular sieve occupies a high surface
area (600–800 m2/g) for the dispersion of the active com-
ponent, and in addition, it is economic and non-toxic also
(Yang et al. 2016a,b). The performance of the catalytic ODS
using the Mo-supported 4A molecular sieve as a catalyst
and cyclohexanone peroxide (CYHPO) as an oil-soluble
oxidizing agent for the removal of BT and DBT was investi-
gated. Under optimum condition, 99% of DBT conversion
was achieved (Yang et al. 2016a,b).
Figure 6: Typical oxidation reaction scheme of DBTs in the presence of MoO3/Al2O3.
Reprinted from Safa et al. (2016), with permission from Elsevier.
Polyoxometalate (POM) catalysts have also been used
for the ODS process, and high sulfur removal efficiency
was observed due to their special unique properties (Wang
et  al. 2010a,b, Ribeiro et  al. 2013, Zhang et  al. 2013a,b,
Nogueira et  al. 2014). Moreover, transition metal-oxygen
cluster anions are present in POMs. The peroxocomplexes
are formed when the transitional metal derivatives react
with hydrogen peroxide. Peroxocomplexes are a stronger
oxidizing agent than the original peroxide (Arcoria et al.
1983). Ribeiro et al. (2016) investigated the desulfurization
efficiency of various hybrid zinc-substituted polyoxometa-
lates. POMs have been applied in various fields, among
them, catalysis is its most significant application (Wang
et al. 2010a,b). POMs composed of transition metals like
Ti, Mo, V, and W are potential catalysts for the ODS when
used with H2O2. Moreover, transition metal-oxygen clus-
ters anions are present in POMs. The peroxocomplexes
are formed when the transitional metal derivatives react
with hydrogen peroxide. Peroxocomplexes are a stronger
oxidizing agent than the original peroxide (Arcoria
et  al. 1983). Ribeiro et  al. (2016) investigated the desul-
furization efficiency of various hybrid zinc-substituted
polyoxometalates.
5.3 O
 xidative reaction mechanism
and ­reactivity trend
Typically, in the ODS process, the sulfur compound is oxi-
dized to the corresponding sulfone by the electrophilic
addition of oxygen atoms with the help of a catalyst and
an oxidant (Song and Ma 2003, Bhutto et al. 2016). Many
oxidative reaction mechanisms have been reported in the
literature. As an example, the reaction mechanism of DBT
over MoO3/Al2O3 was proposed in the presence of CHP
(Safa et al. 2016). It was proposed that an initial reaction
might occur due to the pseudo-cyclic structure, which
was generated owing to the coordination between per-
oxide and polar Mo-O band and the formation of nascent
oxygen. Further, this oxygen attack on the sulfur presents
in the DBTs to form sulfoxides, and finally, oxidation leads
to the corresponding sulfones. The schematic representa-
tion of the oxidation process is shown in Figure 6. It can
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be clearly seen in Figure 6 that DBT reacted with CHP in
the presence of MoO3/Al2O3 to produce DBT sulfoxide as an
intermediate product. The obtained intermediate product
further reacts with an oxidant in the presence of a cata-
lyst to form DBT sulfone and cumyl alcohol as the final
product of oxidation. Xie et  al. (2015) proposed the two-
step mechanism of catalytic oxidation using H2O2 as an
oxidant. In the first step, the sulfur atom of the DBT stages
a nucleophilic attack on the oxygen atom in the catalyst
due to which active oxygen is transferred to DBT and there
is transformation of DBT to DBTO or DBTO2. In the second
and last steps, H2O2 comes in contact with a catalyst, and
the peroxide bond regenerates. The catalytic ODS of DBT
in the presence oxidant (TBHP) is depicted in Figure 7
(Mokhtar et  al. 2015). Initially, the active metal species
(Co/Mn) react with TBHP to form a complex structure.
Because of the formation of complex species, electrophilic
characteristics of the oxygen were enhanced and became
more active. Subsequently, the active oxygen attacks on
the sulfur atom present in the DBT to form the DBT sul-
foxide and tert-butanol as the by-product. In the last step,
DBT sulfoxide further oxidized to form DBT sulfone.
Generally, two factors governed the reactivity trend of
aromatic sulfur compounds, namely, electron density and
steric hindrance. The higher electron density of the sulfur
atom present in sulfur-containing compounds that pro-
motes an electrophilic attack on the sulfur atom present in
the sulfur compound by the activated oxygen (Otsuki et al.
2000, Jeong et  al. 2013, Safa and Ma 2016) obtained the
following decreasing order of oxidation reactivity for the
DBTs: DMDBT > MDBT > DBT. This reactivity pattern was
obtained as the sulfur atom of DMDBT has a higher elec-
tron density than MDBT and DBT. On the other hand, Wang
et al. (2003) observed the following for oxidation r­ eactivity
Figure 7: Reaction mechanism for ODS of DBT in the presence of
TBHP and CoMn/Al2O3.
Adapted from Mokhtar et al. (2015), with permission from Springer
Nature.
P. Sikarwar et al.: Desulfurization      21
of sulfur compounds: DBT > MDBT > DMDBT > BT. They
considered that the steric hindrance of methyl substitu-
tion has lowered down the oxidation activity of methyl-
substituted DBT, and BT was very difficult to oxidize
because of its lower electron density.
5.4 U
 ltrasound-assistive oxidative
desulfurization
Ultrasound-assistive oxidative desulfurization (UAOD)
was introduced in order to enhance the desulfurization
efficiency of the ODS process. Ultrasonic power has a great
impact on the reaction rate in the ODS process, and the
oxidation rate can be significantly improved by employ-
ing ultrasound (Ukkirapandian et al. 2008). It was found
from the literature that when a liquid fuel is subjected
to ultrasound, formation and violent collapse of a vapor
bubble occurs (cavitation), and transient breakdown of
cavitation bubbles hastens the rate of reaction due to the
generation of active chemical intermediates (Suslick et al.
1999, Gopinath et  al. 2006, Kuppa and Moholkar 2010).
The application of ultrasound causes emulsion-like dis-
persion of two phases, which aids in increasing the oxi-
dation rate as the oxidation of organosulfur compounds
occur at the interface of the phases (Margeta et al. 2016).
The major benefit of the UAOD process in comparison to
the ODS process is the higher sulfur removal rate due to
smoother dispersion in the system (Wan and Yen 2007).
Margeta et  al. (2016) conducted a comparative study of
UAOD and ODS with the aid of a mechanical stirrer. It was
concluded that UAOD was more effective for the removal
of sulfur due to the remarkable decrease in reaction time
to get similar conversion values. The UAOD process was
studied with various oxidation systems such as the H2O2/
acetic acid (Dai et  al. 2008), H2O2/polyoxometalate cata-
lyst (Choi et  al. 2016), H2O2/photo catalysts (Matsuzawa
et  al. 2002), and H2O2/phosphotungstic acid (Wan and
Yen 2008). As shown in Table 7, more than 90% removal
was obtained when the oxidation system is comprised of
organic acid (acetic acid, formic acid) and H2O2. Wan and
Yen (2007) optimized a different phase-transfer agent in
combination with phosphotungstic acid and obtained a
remarkable sulfur removal efficiency for different diesel
fuels. The major disadvantage of using a homogeneous
catalyst (heteropoly acid) is the difficulty in its separa-
tion process from the reaction products, which eventu-
ally restricted their reusability. Impregnation of these
materials on support not only enhances the surface area
of the active phase but also makes the separation process
easier (Liu et  al. 2014a,b). Moreover, support particles
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 22      P. Sikarwar et al.: Desulfurization

help in the uniform distribution of the ultrasound field,

94 Deshpande et al. (2005)

100 Etemadi and Yen (2007)

96 Jalali and Sobati (2017)
which provides a large number of active nucleation sites

98 Margeta et al. (2016)

99, 75 Duarte et al. (2011)

100 Liu et al. (2014a,b)

95 Mello et al. (2009)
for cavitation bubbles and gives effective sonochemi-
cal results (Tuziuti et al. 2004, Chakinala et al. 2007, Liu
et  al. 2014a,b). Duarte et  al. (2011) conducted the UAOD
% Reference

for petroleum feedstocks containing BT, DBT, DMDBT,

and diesel oil without using a metal catalyst. Sulfur
removal was of 99% for petroleum feedstock, and more
(%) Removal

than 75% was obtained for diesel oil samples at the opti-
mized condition. Mello et  al. (2009) also achieved 95%
Temperature Frequency Time US amplitude

80

40

40

–
–
–
sulfur removal after 9 min of ultrasonic irradiation using
acetic acid and hydrogen peroxide at the optimized con-
dition. H2O2 is a preferable oxidant in the UAOD process
due to its low price and high oxidizing capability. Table 7
(kHz) (min)

30

20

120
9
10

depicts the performance of H2O2 in the UAOD process with

homogeneous and heterogeneous catalysts. The usage
20

20

20

20

23
40
20

of H2O2 offers certain disadvantages also such as longer

reaction time of the process, and its excessive decomposi-
tion restricts its industrial application (Collins et al. 1997,
(°C)

70

90

50

60
70
70

Zhang et al. 2008, Choi et al. 2014). In order to overcome

the problem arising from the usage of H2O2, Choi et  al.
(2014) investigated the UAOD of BT and DBT containing a
model oil using commercial ferrate (VI) as an oxidant with
Phosphotungstic acid/AC

the help of a phase-transfer catalyst. Under optimized

N,N-dimethylformamide
Extractant/adsorbent

conditions, 85.7% and 91% of the removal of BT and DBT

were achieved.
Acetonitrile
Methanol

Methanol

Alumina
MeCN

6 Extractive desulfurization (EDS)

Table 7: UAOD of organosulfur compounds under optimum reaction conditions.

hydrate/tetraoctylammonium
H2O2/phosphotungstic acid

EDS is a technique in which sour fuel is kept in contact

with a solvent to extract the organosulfur compounds by
liquid-liquid extraction. It has several benefits over the
Oxidation system

H2O2/formic acid
H2O2/acetic acid

H2O2/acetic acid

H2O2/acetic acid

other methods such as mild operating conditions and

H2O2-Na2CO3

low energy consumptions. However, the feasibility and

fluoride

economic efficiency of the selective extraction process

H2O2

strongly depends on the selection of solvent, i.e. it should

be cheap, highly miscible with sulfur compounds, readily
Alkylated BT, DBT
and its alkylated
BT, DBT, DMDBT

available, and must possess different boiling temperatures

S-compound

than that of sulfur compounds present in fuel (Babich and

derivatives

Moulijn 2003). Various solvents such as acetone, acetoni-

DMDBT
DBT

DBT

DBT

trile, 1-methyl-2-pyrrolidinon, ethanol, dimethylforma-

–

mide, dimethyl sulfoxide, and polyethylene glycol have

petroleum feedstock, diesel

been successfully utilized for the extraction of sulfur-con-

Sulfur-free hydrotreated

Hydrotreated petroleum

taining molecules from liquid fuels (Forte 1996, Funako-

Heptane + dodecane

shi and Aida 1998, Ban et al. 2013, Kianpour and Azizian
2014). The EDS performance of N,N dimethylformamide
Hexadecane

JP-8 jet fuel

and polyethylene glycol is listed in Table 8.

feedstock
Model oil

Octane

Bailes (1981) studied the extraction capability of

Gas oil

Diesel

acetonitrile, dimethyl sulfoxide, and tetramethylene

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 P. Sikarwar et al.: Desulfurization      23

sulfone for the extraction of organosulfur and aromatic

Kianpour and Azizian (2014)

compounds from light oil at room temperature. Petkov

Dharaskar et al. (2015)

et  al. (2004) achieved a sevenfold reduction (from 0.2%

Jian-long et al. (2007)

Mokhtar et al. (2014)

Le Bui et al. (2017)
Safa et al. (2016) to 0.029%) of sulfur content from hydrotreated middle

Gao et al. (2016)

Ban et al. (2013)

Yu et al. (2016)
distillate fuel, and the aromatic content was also reduced
three times when extraction was performed with the fol-
Reference

lowing solvents: methanol, furfural, and ethylene glycol.

Toteva et  al. (2007) conducted an EDS study for distil-
late gas oil cuts using dimethylformamide as a selective
solvent. It was reported that the sulfur content of fuel can
extractant
Oil/

1:1
1:1
1:1
1:1
1:1
5:1
5:1
3.5:1
20:1

1:1
1:1
be lowered from 2% to 0.33% by employing a two-stage
extraction. In addition, the aromatic content also reduced
by fivefold. However, these conventional solvents are not
able to produce ultra-low-sulfur fuels, and moreover, the
Removal
%

95
98
98
96
79
49
73
85, 91, 81
99, 99, 96

98
90, 97, 77
co-extraction of a lot of aromatic hydrocarbon compounds
leads to degradation of the quality of fuel (Stanislaus et al.
2010). Moreover, these solvents are volatile, poisonous,
flammable, and harmful to the environment.
Co (ppm)

500
498
500
498
500
385
180
500
200

500
50, 150, 300

6.1 Extraction through ionic liquids

Extraction
cycle

1
5
6
6
1
4
4
1
1

3
1

Ionic liquids (ILs) are salts of low melting point and com-
posed of an organic cation and an inorganic anion. ILs
are a promising alternative to traditional volatile organic
solvents as it can overcome the loss of solvent and hard-
Temperature
(°C)

25
25
25
25
30

30
25

25
29

to-recover problems, which are associated with the usage

of volatile solvents. These liquids have gained the atten-
tion of many researchers because of their special charac-
teristics such as thermal and chemical stability, low vapor
pressure, recyclability, and good solubility (Wu et al. 2011,
Table 8: EDS of organosulfur compounds under optimum reaction conditions.

Polyether-based ionic liquids

Dharaskar et  al. 2013, Aghabarari et  al. 2014, Du et  al.
N,N-dimethylformamide

2014, Kurnia et al. 2015). ILs possesses structural features

reminiscent of molten salts, ionic surfactants, ionic crys-
Polyethylene glycol
[Omim]Cl⋅2FeCl3
[OMIM][CH3COO]

tals, and molecular liquids, and it exhibits solvent proper-

[C1pyr]H2PO4
[Omim][NO3]

ties, which are similar to polar protic liquids, molten salts,

Extractant

[BMIM]Br

or bicontinuous microemulsions (Hayes et al. 2015). Infi-

[BPy]BF4

nite varieties of organic ions present in ionic liquids can

be arranged in numerous ways and combined together
to obtain different varieties of ionic liquids (Freeman-
Th, DBT, DMDBT
BT, DBT, DMDBT
BT, DBT, DMDBT

tle 2004). The extraction capability of the ionic liquid is

S-compound

Th, BT, DBT

influenced by various factors such as its size and structure

of both cations and anions. The main cations are imida-
DBT

DBT

DBT

DBT

zolium, ammonium, pyridinium, isoquinolonium, phos-

Th

phonium, and sulfonium (Bhutto et al. 2016). Ionic liquids

have been studied for the extraction of sulfur oxides, and
 n-Heptane and xylol

organic sulfur compounds from liquid fuel (Zhang and

Organic solvent

Zhang 2002), and combined oxidation and extraction (Lo

 n-Dodecane

 n-Dodecane
Ionic liquids

 n-Heptane
 n-Decane

 n-Octane

 n-Octane
 n-Octane

 n-Octane
 Gasoline

et al. 2003).
Model oil

 Diesel

ILs were first employed for the selective extraction of

sulfur-containing sulfur molecules from fuels in 2001 by

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24      P. Sikarwar et al.: Desulfurization
Wassercheid and co-workers (Bösmann et al. 2001). DBT
extraction was investigated using 1-3-dialkyl imidazolium
alkyl sulfate ionic liquids, and found that the ion size is a
significant parameter for EDS. The most common mecha-
nisms for extraction of sulfur-containing molecules are
the π-π interaction between rings of sulfur molecules and
aromatic ring of ILs (imidazolium, phosphonium) and for-
mation of liquid clathrates (Forsyth et al. 2004, Dharaskar
et  al. 2014a,b, Dharaskar et  al. 2016). The length of the
alkyl groups present in ILs also played a significant role in
determining its extraction ability. The alkyl chain length
of ILs is directly proportional to the induced polarity of
the ring’s π electron enhances. The long chain of the alkyl
group results into a strong π-π interaction between the
sulfur molecules and the imidazolium or pyridinium ring
of the ionic liquid (Jian-long et al. 2007). For example, four
nitrate-based ILs were investigated for the DBT removal
through extraction (Safa et al. 2016). It was reported that
ILs with cations of longer alkyl groups exhibited enhanced
desulfurization capability.
Wilfred et al. (2012) studied the extraction capability
of various types of ILs for the DBT extraction. The highest
extraction efficiencies of 66%, 66%, and 63% were exhib-
ited by imidazolium-based ILs with thiocyanate, dicyana-
mide, and octyl sulfate anions. Further, it was concluded
that π-π interaction between the ring of the sulfur mole-
cule and ionic liquids was not the main extraction mecha-
nism as tributylmethylammonium methyl carbonate ionic
liquid gave only 62% extraction efficiency. Phosphonium
and pyrrolidinium-based ionic liquids were studied
for EDS, and [B4P][MeSO4] showed the highest sulfur
removal, with the yields of 61%, 62%, and 69% for Th, BT,
DBT, respectively (Ahmed et  al. 2015). Non-halogen ILs
such as [BMIM][HSO4], [BMIM][CH3COO], [BMIM][DBP],
[OMIM][HSO4], and [OMIM][CH3COO] were also utilized for
extraction of sulfur compounds from liquid fuel. Among
these, [OMIM][CH3COO] showed the best extracting ability
toward DBT under identical operating conditions. Fur-
thermore, the structure of imidazolium cation resembles
with thiophene due to which it offered better selectivity
in comparison with the six-membered cation families of
pyridinium (Le Bui et al. 2017). Dharaskar et al. (2014a,b)
studied the removal of DBT in the model oil (octane + DBT)
with the aid of thiazolium ILs and reported around 81%
removal of DBT.
ILs along with an oxidant showed a substantial
reduction of sulfur-containing fuels. The reduction of
sulfur was insignificant (approx. 6%) with an ionic liquid
[HMIm]BF4 alone, whereas the desulfurization capacity
enhanced with an oxidant (H2O2), and significant removal
(~65% to 93%) was obtained (Lu et al. 2007). The intrinsic
acidic characteristic of ILs allows them to behave as both
catalyst and solvent. The acetic acid-based ILs function
as both phase transfer catalyst and solvent with better
oxidizing characteristics (Bhutto et al. 2016). The ODS of
fuels by employing acidic ILs provide very good results
without the aid of an external catalyst. Zhao et al. (2007)
achieved 99% DBT removal from the model oil by employ-
ing the ODS using bronsted acid ILs (N-methyl-pyrrolido-
nium tetrafluoroborate) as a catalytic solvent and H2O2 as
an oxidant under the optimum condition. The first study
for the combined oxidation and extraction of sulfur-bear-
ing fuel by employing ILs was reported by Lo et al. (2003).
They achieved 99% sulfur removal from model oil (tet-
radecane and DBT) using [C4MIM][PF6] as the extracting
agent, H2O2 and acetic acid as the oxidant and catalyst,
respectively. The research results conducted on EDS using
different types of ILs is shown in Table 8.
Commercialization of EDS through ILs is not feasible
due to certain drawbacks such as the unexplored effect
on the ecosystem, high cost, high mutual solubility of ILs
with oil, and a large amount of ILs is required for high
desulfurization efficiency (Kianpour and Azizian 2014, Yu
et al. 2016). However, the high cost of ILs can be compen-
sated by regeneration of an ionic liquid. For the hydropho-
bic ILs, regeneration is usually performed by distillation
followed by adsorption, while for hydrophilic ILs, it is per-
formed by first dilution with water and, then, followed by
the distillation process (Abro et al. 2014).
Deep eutectic solvents (DESs) have gained consider-
able attention in recent years as a low-cost alternative to
ILs. DESs can be synthesized from low-cost, non-toxic,
fully biodegradable, and biocompatible substances (Gano
et  al. 2015). DESs are generally a mixture of at least two
components (hydrogen bond donor and acceptor), and
the melting point of the new eutectic mixture is lower
than that of each individual component (Tomé et  al.
2018). Application of DESs in EDS showed a high extrac-
tion ability in comparison with most of the ILs (Campos-
Martin et  al. 2010). The performance of the EDS process
was mainly influenced by the type of hydrogen bond
donor associated with the salt in the structure of DESs (Li
et al. 2013). FeCl3 and ZnCl2-based DESs have been utilized
for EDS, and it was found that FeCl3-based DESs showed
higher solvation toward sulfur compounds compared to
ZnCl2-based DESs (Gano et  al. 2014). Tetra-butyl ammo-
nium bromide (TBAB) and polyethylene glycol-based DES
showed high extraction efficiencies for DBT (100%) and
thiophene (95%) (Rahma et al. 2017). EDS with DESs is a
potential method, but the single extraction efficiency is
low. Therefore, the few researchers used the DESs in com-
bination with the oxidant to obtain better desulfurization
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performance. Liu et  al. (2016) synthesized various DESs
(extractants) and employed them in combination with
HPW (catalyst) and H2O2 (oxidant) for the extractive cata-
lytic ODS of sulfur compounds.
7 Assessment of desulfurization
technologies
HDS is the main technique, which is industrially employed
for the desulfurization of liquid fuels. Alumina and silica-
supported cobalt or nickel molybdenum are the conven-
tional catalysts employed in the HDS process. In order to
achieve the desired level of sulfur in fuels, approximately
four times more active catalyst is required than conven-
tional along with severe operating conditions. Implemen-
tation of these conditions will lead to the dramatic rise in
capital and operational cost along with the loss of octane
number due to the undesired saturation of aromatic com-
pounds present in the fuel (Stanislaus et al. 2010, Bhutto
et al. 2016). In order to make the production of ultra-low-
sulfur fuel economic, HDS can be integrated with an avail-
able alternative technique. In the section below, merits,
demerits, and future perspective of alternative techniques
are presented.
The major challenge associated with the ADS process
is to synthesize a low-cost adsorbent with large surface
area and porosity, which can specifically adsorb sulfur
compounds from the fuel oil. The chosen adsorbent
should be easy to regenerate, and its adsorption capacity
should not be decreased very much after the regeneration
process. Nevertheless, ADS offers several advantages over
the HDS process such as mild operating conditions, and it
does not require expensive hydrogen. In the past, ADS was
commercially utilized as IRVAD (Irvine Robert Varraveto
Adsorption Desulfurization) for desulfurization of liquid
fuels (Irvine 1998). Further, IRVAD utilizes mild operating
conditions and employs an alumina-based adsorbent in
a multistage adsorber to remove sulfur compounds from
liquid fuel. It suffers from the drawback of frequent regen-
eration and recycling of adsorbents due to low adsorption
capacity. In addition, the Phillips Petroleum Company has
industrially employed the RADS technique to reduce the
sulfur content in diesel and gasoline, and it is named as
the S Zorb process (Kulkarni and Afonso 2010, Fihri et al.
2016). In this technique, the fuel is kept in contact with the
adsorbent (modified zinc oxide on a carrier) in the pres-
ence of hydrogen in a fluidized bed reactor. The adsorbent
is continuously regenerated and transferred again into
a fluidized bed reactor. However, the process conditions
P. Sikarwar et al.: Desulfurization      25
used are very similar to the conventional HDS process.
Further, this technique requires high temperature and
pressure to make the fluidized condition with the adsor-
bent. The adsorbent capacity may also reduce in the fre-
quent regeneration cycle. Most of the literature reported
on RADS is based on an adsorbent consisting of ZnO mod-
ified with transition metals such as copper or nickel (Fan
et al. 2010).
Desulfurization through ILs is also a promising alter-
native choice for deep desulfurization. ILs can be used
as catalysts and extractants for the removal of refractory
sulfur compounds present in the fuel oil. For the com-
mercial application of ILs for desulfurization, certain
factors require special attention such as miscibility of
the oil with ILs, regeneration ability, thermal and chemi-
cal stability. However, extensive research is needed in
the area of production of environmentally friendly ILs
for commercial-scale application. For example, chlorine-
containing ILs can bring down the sulfur content of liquid
fuel to the desired level but can pose a harmful effect
on the environment and mankind. Furthermore, ILs are
very expensive also; therefore, to make the deep desul-
furization economical, low-cost green ILs are required.
Although an enormous research has been conducted on
desulfurization using ILs, still, this process is not ready for
commercialization.
BDS is an attractive technique for deep desulfuriza-
tion of liquid fuels. It works at mild conditions, with the
operating and capital cost estimated to be lower than the
HDS process (Soleimani et al. 2007). However, the indus-
trial application of the BDS process is not possible in the
near future due to the low activity of the presently availa-
ble biocatalysts (Mohebali and Ball, 2016). Apart from the
commercialization of the BDS process, extensive research
is needed in the following areas such as design of effi-
cient biodesulfurizers, removal of inhibitors, separation
of oil from the biocatalyst, and efficient recovery of the
biocatalyst. Further, most of the researchers performed
with the model oil system. The real oil system should be
used in order to better understand the challenges associ-
ated with it.
The ODS is an effective process to remove heterocy-
clic sulfur compounds, which are difficult to remove by
the HDS process. However, the ODS suffers from some
limitations such as post-treatment of oxidized sulfur com-
pounds, oxidation of compounds present in fuel other
than sulfur, and efficient removal of oxidized sulfur from
fuel. Many researchers used hydrogen peroxide as an
oxidant in the process as it is cheap and readily avail-
able. However, hydrogen peroxide is immiscible in oil,
which forms a biphasic system and causes mass transfer
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26      P. Sikarwar et al.: Desulfurization
Table 9: Details of near-commercialized ODS industrial technology.
ODS technology Oxidation system
Sulphco process H2O2/tungsten phosphoric acid
Lyondell chemicals process TBHP
UOP/ENI Organic peroxide
Unipure ASR-2 H2O2-formic acid
PetroStar process Peroxy acid
limitation between the oil and oxidant. However, this
limitation can be overcome with the help of an oil-sol-
uble oxidant. The currently available soluble oxidants
are expensive, which can directly impact the cost of the
process. In order to make the process economic, a low-
cost active catalyst, and a cheap oil soluble oxidant are
required. A few processes adopted the ODS technology
and have reached the near-commercialized stage. The
processes are the Sulphco process, Lyondell chemicals
process, Enichem/UOP process, Unipure process, and
PetroStar process (Stanislaus et al. 2010, Ismagilov et al.
2011). The operating parameters of these processes are
given in Table 9.
The remarkable decrease in the cost of ultra-low-level-
sulfur fuel can be achieved when the existing HDS unit
integrate with the ODS/ADS unit. Extensive research is
needed in a few areas of the BDS and desulfurization with
an ionic liquid as discussed above. The ODS and ADS are
both the potential techniques to use in combination with
HDS. Nevertheless, the ADS can be preferred over the ODS
because the ADS is more economical compared to the ODS.
In the ADS, only the adsorbent is required to bring down
the sulfur level, while in the ODS, both the oxidant and cat-
alysts are required. In addition, efficient post-treatment of
oxidized compounds is also required. Hence, integration
of the HDS and ADS will be a more economical alternative
for the production of ultra-low-level-sulfur fuel.
8 Conclusion
Ultra-deep desulfurization of liquid fuels has recently
gained considerable attention owing to the strict envi-
ronmental rules and regulations. The demand for ultra-
low-level-sulfur fuels has increased globally in the past
years and will continue to increase consequently in the
upcoming years, and that might put immense pressure on
refineries. Currently, the HDS is industrially used for the
desulfurization of transportation fuel, but due to certain
restrictions, this process is not able to meet the minimum
Operating conditions Post sulfone treatment
Temperature (°C) Pressure (atm)
– – Solvent extraction
<93 <6.8 Solvent extraction
<93 <6.8 Adsorption
90 1 –
100 1 Solvent extraction
sulfur requirement of fuel imposed by environmental
agencies, and moreover, a huge amount of hydrogen and
severe operating conditions are required in order to meet
the increasing demand. For the ultra-deep desulfuriza-
tion, researchers are exploring other alternative tech-
niques, and most of the research is focused on mainly four
alternative techniques, namely, ADS, BDS, ODS, and EDS.
Commercialization of the BDS process is not feasible in
the near future as more research is needed in following
areas: production of highly active biocatalysts, develop-
ment of a large volume of bio-desulfurized reactor, effi-
cient separation of microbial cells from oil, storage, and
handling of living microbial cells in refineries. The ODS
has made a significant progress in recent years, and it is a
potential technique for the reduction of refractory sulfur
compounds. The ODS with ionic liquids and ultrasound
application gives a remarkable reduction in sulfur content
of oil. However, the ODS process is not very cost effec-
tive as it requires an additional step to remove the oxi-
dized sulfur molecules, and waste management of these
oxidized products is another challenging environmental
task. Further, the ADS is an effective method for producing
fuels with low sulfur content, i.e. below 10 ppm. Various
types of adsorbents, which can specifically adsorb sulfur
compounds, were investigated by researchers. The major
benefit of the ADS is that it normally operates at ambient
conditions without any use of a catalyst and hydrogen
gas. However, none of the above alternative processes can
solely replace the HDS process, and the HDS process is
also desirable as it also improves the quality of the fuel.
The most feasible and economic alternative, at present,
for the ultra-deep desulfurization of liquid fuels is to inte-
grate the existing HDS units with the ADS units.
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Bionotes
Prerana Sikarwar
Department of Chemical Engineering, MNIT
Jaipur, Jaipur-302017, India
Prerana Sikarwar is currently a PhD scholar under the supervision
of Dr. V. Subbaramaiah in the Chemical Engineering Department,
MNIT, Jaipur. She has completed her Master’s degree at the Indian
Institute of Technology Roorkee, Roorkee. Previously, she has
worked on CFD modeling of nucleate pool boiling. Currently, she
is doing research on desulfurization and denitrogenation of liquid
fuels using oxidative and adsorptive technologies.
P. Sikarwar et al.: Desulfurization      37
Vijayalakshmi Gosu
Department of Chemical Engineering, MNIT
Jaipur, Jaipur-302017, India
Vijayalakshmi Gosu is an assistant professor at the Department of
Chemical Engineering, MBM Engineering College, Jai Narain Vyas
University, Jodhpur. She earned her doctoral program at IIT Roorkee
in 2014 and did MTech from NIT Karnataka in 2009. For her research
contribution, she received the Young Engineer Award from the Insti-
tute of Engineers India (IEI) in 2014. Her current research interest
includes green process for water and wastewater treatment, devel-
opment of heterogeneous catalyst for waste to energy processing.
Verraboina Subbaramaiah
Department of Chemical Engineering, MNIT
Jaipur, Jaipur-302017, India,
vsr.chem@mnit.ac.in, vijaya.che@gmail.com
Verraboina Subbaramaiah works as an assistant professor in the
Department of Chemical Engineering, MNIT Jaipur. He obtained a
BTech. Chemical Engineering degree from JNTU Hyderabad in 2007,
his Master’s from IIT Roorkee in 2010, and his doctoral degree
in 2013. Among his research areas are the development of green
catalysts for water and wastewater treatment, desulfurization of
liquid fuels, and waste to value added production through catalytic
process.
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