catalysts

Review
A Comprehensive Review on Catalytic Oxidative
Desulfurization of Liquid Fuel Oil
Muhammad Nobi Hossain , Hoon Chae Park and Hang Seok Choi *
Department of Environmental Engineering, Yonsei University, Yonseidae-Gil, Wonju,
Gangwon-Do 26493, Korea; mnhossain.8911@gmail.com (M.N.H.); hcpark@yonsei.ac.kr (H.C.P.)
* Correspondence: hs.choi@yonsei.ac.kr




Received: 31 January 2019; Accepted: 26 February 2019; Published: 2 March 2019


Abstract: The production of green fuel oil is of the utmost importance for maintaining a
healthy life and environment in the current world. Effective and complete removal of sulfur
refractory compounds (such as 4,6-dimethyldibenzothiophene and other alkyl-substituted thiophene
derivatives) from fuel oil is essential to meet the new requirements of sulfur standards. Several
techniques have been proposed for desulfurization of fuel oil, such as hydrodesulfurization (HDS),
selective adsorption, extractive distillation, biodesulfurization, and oxidative desulfurization (ODS).
The removal of sulfur by the HDS process requires higher investment costs, high reaction temperature
(up to 400 ◦ C), and high pressure (up to 100 atm) reactors. On the other hand, studies have shown
that the ODS process is remarkably successful in the removal of sulfur under mild reaction conditions.
This review article presents a comparative analysis of various existing catalytic oxidation techniques:
acetic acid/formic acid catalytic oxidation, heteropolyacid (HPA) catalytic oxidation, ionic liquid
catalytic oxidation, molecular sieve catalytic oxidation, polyoxometalates catalytic oxidation, titanium
catalytic oxidation, and ultrasound-assisted oxidation systems, as well as discusses research gaps,
and proposes important recommendations for future challenges.

Keywords: hydrodesulfurization; oxidative desulfurization; refractory sulfur compounds; model

fuel oil

1. Introduction
The removal of sulfur from transportation fuel and petrochemicals is gaining more attention due
to the increased awareness of the adverse effects of burning sulfur containing oils on human health
and the environment [1]. Hence, desulfurization of petrol fuels or waste biomass derived fuel oils has
become a critical component of the oil refining industries [2].
Sulfur containing compounds (Figure 1) in fuel oil, such as mercaptans, thiophenes (T),
benzothiophenes (BT), and dibenzothiophenes (DBT), produce sulfur oxide (SOx) upon combustion,
which are the main sources of acid rain and air pollution. These compounds also cause corrosion and
deactivation of the catalyst during the desulfurization process of fuel oil in refining industries [3–5].
Therefore, removal of such sulfur-containing compounds is imperative for the production of green
fuel oils and to meet the new standards of sulfur content (10–15 ppm) as per the recommendations
of the United State Protection Agency (USEPA), given the environmental concerns surrounding
sulfur [1,2,6,7].

Catalysts 2019, 9, 229; doi:10.3390/catal9030229 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 229 2 of 12
Catalysts 2019, 9, x FOR PEER REVIEW 2 of 12

Catalysts 2019, 9, x FOR PEER REVIEW 2 of 12

Figure
Figure 1. Sulfurcompounds
1. Sulfur compounds present
present in crude
in crude oil. oil.

Several techniques,
Several techniques,such suchas hydrodesulfurization
Figure
as 1. Sulfur compounds(HDS),
hydrodesulfurization (HDS),
present in biodesulfurization
crude oil.
biodesulfurization (BDS), (BDS), adsorption,
adsorption,
andandoxidative
oxidative desulfurization (ODS), have been applied to remove sulfur‐containing compounds from
desulfurization (ODS), have been applied to remove sulfur-containing compounds
fuelfrom Several
oil [8].
fuel techniques,
Atoilpresent,
[8]. At the
present,suchtheas hydrodesulfurization
conventional HDS process
conventional HDS process (HDS),
is isbiodesulfurization
a well-established
a well‐established (BDS),
method atadsorption,
method theatindustrial
the
level. and oxidative
industrial
Hydrodesulfurizariondesulfurization
level. Hydrodesulfurizarion (ODS), have
reactions reactions been
are carried applied
are out
carried to remove
out presence
in the sulfur‐containing
in the presence of transition
of transition compounds
metallic
metallic (Ni, Co,
from fueland oil [8]. At present, thetemperature
conventional HDS
◦ C) processand is apressure
well‐established 100method at the
and(Ni,
Mo)Co,catalysts Mo) atcatalysts at high
high temperature (up to 400 (up to 400
and°C) pressure (up to(up 100toatm) atm) using
using hydrogen
industrial level. Hydrodesulfurizarion reactionsfor are carried of out in theand presence ofsulfur‐containing
transition metallic
gas hydrogen
[8–10]. It gas
is a[8–10]. It is a well‐known
well-known process for process
removal removal
of aliphatic aliphatic
and acyclic acyclic
sulfur-containing organic
organic compounds. HDS process is very effective to remove T, BT, and DBT, but the to
(Ni, Co, and Mo) catalysts at high temperature (up to 400 °C) and pressure (up 100refractory
more atm) using
compounds. HDS process is very effective to remove T, BT, and DBT, but the more refractory S
S hydrogen
compounds gasfound
[8–10]. inIt isheaviest
a well‐known process high
cuts require for removal
reaction of aliphatic
conditions and(high
acyclic sulfur‐containing
temperature and
compounds found
organic and
compounds. in heaviest cuts
HDS process require high reaction conditions (high temperature and pressure)
pressure) high operational costsis[11–13].
very effective to remove T, BT, and DBT, but the more refractory
and high operational
S compounds costs [11–13].
Research shows that there are severalrequire
found in heaviest cuts high reaction
other methods (Figureconditions (high ultra‐low
2) for obtaining temperaturesulfur and
fuel, which are alternatives to HDS, such as biodesulfurization [14–16], selective adsorption [17,18], sulfur
Research
pressure) shows
and high that there
operational are several
costs other
[11–13]. methods (Figure 2) for obtaining ultra-low
fuel,and
which Research shows desulfurization
are alternatives
catalytic oxidative thattothere
HDS, aresuchseveral other methodsthese
as biodesulfurization
[2,3,19,20]. However, (Figure 2) for obtaining
[14–16],
alternative methodsultra‐low
selective are still insulfur
adsorption the[17,18],
fuel,
anddevelopmentwhich are
catalytic oxidative alternatives
stage. At to
desulfurization HDS, such
the same time,[2,3,19,20]. as biodesulfurization
amongst allHowever, [14–16],
these alternative
the aforementioned selective
alternative adsorption
methods are[17,18],
desulfurizationstill in the
and catalytic oxidative
methods,
development the ODS
stage. At thedesulfurization
process has received
same [2,3,19,20].
allHowever,
a lot of attention
time, amongst as athese alternative
promising
the aforementioned methods
technique
alternativedueare
to still in the
its mild
desulfurization
development
reactionthe conditions stage. At the same
(low temperature time, amongst
and pressure) all the aforementioned
and higher alternative
selectivity in desulfurization
removingdue aromatic
methods, ODS process has received a lot of attention as a promising technique to its mild
methods,
sulfur the ODScompared
compounds process has to received
the HDS a lot of attention
process. as a promising
Additionally, it does technique
not requiredueexpensive
to its mild
reaction conditions
reaction [19–22].
(low temperature and pressure) and higher
conditions (low temperature and pressure) and higher selectivity in removing aromatic
selectivity in removing aromatic
hydrogen
sulfursulfur
compounds
compounds compared
compared to tothetheHDS HDSprocess. Additionally,it itdoes
process. Additionally, does notnot require
require expensive
expensive
hydrogen [19–22].
hydrogen [19–22].

.
Figure 2. Classification of desulfurization technologies to remove sulfur from liquid fuel oil [21].
Catalysts 2019, 9, x FOR PEER REVIEW 3 of 12
Catalysts 2019, 9, 229 3 of 12
Figure 2. Classification of desulfurization technologies to remove sulfur from liquid fuel oil [21].

The oxidative desulfurization

desulfurization reaction
reaction is
is a two-step
two‐step process
process (Figure
(Figure 3).
3). In the first step, the sulfur
containing compounds
containing compoundsininfuel
fuel
oil oil
are are oxidized
oxidized to their
to their respective
respective sulfones
sulfones or sulfoxides
or sulfoxides in the
in the presence
presence
of of oxidizing
oxidizing agents.
agents. In In the second
the second step, oxidized
step, these these oxidized
sulfursulfur compounds
compounds are removed
are removed fromfrom
the
the reaction
reaction mixtures
mixtures by adsorption
by adsorption or liquid/liquid
or liquid/liquid extraction
extraction method.
method.

Schematic representation of sulfur removal in the oxidative desulfurization process.

Figure 3. Schematic

The
The primary aim of
primary aim of this
this review
review article
article is
is to
to provide
provide aa comparative
comparative analysis
analysis of
of all
all the
the existing
existing
catalytic
catalytic oxidation systems applied in the oxidation desulfurization method, and evaluate the
oxidation systems applied in the oxidation desulfurization method, and evaluate the
difficulties arising in
difficulties arising inthe
theprocess.
process.One
Based on thetable
summary analyses, this review
for oxidative proposes
catalytic recommendations
desulfurization of liquid
for
fuelthe
oilsuccessful
has beenproduction
presented ofatgreen fuel oils.
the end (Table1). Based on the analyses, this review proposes
recommendations for the successful production of green fuel oils.
2. Catalytic Oxidation System
Table 1. Summary table for oxidative catalytic desulfurization of liquid fuel oil.
2.1. Acetic Acid/Formic Acid Catalytic Oxidation System
Sulfur removal
Catalyst desulfurization
The oxidative Sourcemethod
of sulfur has evolved
Oxidant as aReaction
viableconditions
alternative and a supplement Ref. to
efficiency (%)
the HDS method,
Liquid acidthereby creating newer avenues in the refinery industries. In the recent past, ODS
has beencatalytic
receivingsystemmore attention due to its higher removal rate of thiophene derivatives of sulfur
CH3COOH Heavy oil H2O2 T = 60 °C, t = 90 min 58.54 [27]
compounds compared to the HDS
CH3COOH
method.
Model gas oil H2O2 T = 90 °C, t = 30 min 90 [28]
Farsi et al. studied sulfur removal
HCOOH from heavy
Model fuel oil H2Ooil
2 using
T = an oxidation-extraction
65 °C, t = 56 min 100system, [29] with
aceticHeteropolyacid
acid (CH3 COOH) (HPA) as the catalyst and hydrogen peroxide (H2 O2 ) as the oxidant. The experiment
catalytic system
was conducted in a glass batch reactor. The results showed that the oxidation process was optimized
Heteropolyacid DBT O2 T = 60 °C, t = 120 min ~ 100 [35]
under the following reaction conditions:
PMo@HKUST‐1 DBT the oxidant H2Oand
2
catalyst
Notto sulfur content molar
specified 95 ratio in
[36]the
range of 5–10, reaction time of 90 min, ◦
HPW‐TUD‐1 Modelandoil optimized reaction
H2O 2 temperature
Not specified as 60 C at 98.0 a stirring rate[37] of
Ionic liquid catalytic system
750 rpm. This ODS method showed that the sulfur content in heavy oils can be lowered from 2.75 wt %
[ODBU]Cl/nZnCl2 Model oil
to 1.14(nwt % [23].
= 1, 2, 3, 4, and 5) (BT, DBT, and 4,6‐DBT)
H2O2 99.0 [40]
Similarly, Zannikos
1‐butyl‐3‐methylimidazolium et al. investigated
Model oil the desulfurization of model gas oil using H O
2 2 as oxidant
T = 30 °C, t = 30 min 73.02 [41]
and acetic acid as catalyst. The sulfur
tetrafluoroborate removal
(BT, T, and 3‐MT) efficiency improved to 90% under reaction conditions of
Molecular sieve catalytic
temperature 90 ◦ C and time 30 min [24].
system
Mamaghani et al. worked on oxidative desulfurization of model fuels containing93.23 benzothiophene,
=T
Copper phthalocyanine Model oil
dibenzothiophene,
molecular sieve/HZSM‐5
and DBT-derivatives, wherein
(BT, T, and DBT)
formic
O2 acid
T = (HCOOH) was
60 °C, t = 180 min used as
91.23 =a BT
catalyst[48]
and
87.32 = DBT
H2 O2 as an oxidizing agent. For extraction of the oxidized sulfur compounds, acetonitrile was used as
Molybdenum supported on
an extracting solvent. BT and DBT CYHPO T = 100 °C, t = 30 min 99.0 [49]
4A molecular sieve The sulfur removal efficiency was found to be 100% under the optimal reaction
conditions of formic
Vanadosilicate acid to sulfur molar ratio as 222:1, H2 O2 to sulfur as 2:1, temperature
catalyst
◦
= 65 C, and
Ultra‐low level
BT and DBT H2O2 T = 60 °C, t = 30 min [50]
(V‐HMS) (450 to 50 ppm)
Catalysts 2019, 9, 229 4 of 12

reaction time = 56 min [25]. In addition, there are studies that have reported oxidative desulfurization
of fuel oil through HCOOH-CH3 COOH/H2 O2 oxidation system [26,27].
The ODS process via H2 O2 -CH3 COOH/HCOOH organic acid system is a mild reaction condition
system, wherein the peroxide-organic acid mixture has strong oxidizing ability for achieving high
sulfur removal efficiency. Despite the evident benefits of this liquid acid-peroxide oxidation system,
the ODS process has certain disadvantages. The use of oil soluble organic acid as a catalyst in
the reaction mixture causes separation problems, which greatly affects the fuel properties of diesel
oil. Furthermore, oil soluble organic acid catalysts are not fully recoverable and are non-renewable.
Therefore, recoverable and recyclable catalysts are better alternatives for the fuel oil refining industries.

2.2. Heteropolyacid (HPA) Catalytic Oxidation System

Heteropolyacids are multifunctional heterogeneous acid catalysts, which have been used for
developing green technologies and as replacements for conventional liquid homogeneous acid
catalysts. They are a special type of polyoxometalate catalysts and are formed by the condensation
of various metallic oxyanions (Mo, W, V, and Nb). In recent times, heteropolyacids have been
recognized for their versatile function (acid-base characteristics and redox power). The most important
role of heteropolyacids has been their use for oxidizing organic substrates under mild reaction
conditions [28–30].
Li et al. studied the oxidative desulfurization of model fuel oil using macroporous supported
heteropolyacids. The model fuel was made by dissolving DBT in normal octane, and oxygen was used
as the oxidant. Under optimum conditions of temperature at 60 ◦ C, the conversion rate of fuel oil
reached nearly 100% in 120 min [31].
Rafiee et al. applied the Keggin type heteropolyacid catalysts for oxidative desulfurization
of model oils containing DBT under mild reaction conditions. Hydrogen peroxide was used as an
oxidizing agent in a biphasic system. The process removed more than 95% of the sulfur under optimum
conditions. Most importantly, the catalyst was found to be recyclable and reusable multiple times,
with negligible loss in activity [32].
Tang et al. also applied the HPA catalyst (HPW-TUD-1) for oxidative desulfurization of model fuel
oil, using H2 O2 as the oxidant. The catalyst was observed to be highly effective in the desulfurization
of benzothiophene derivatives of sulfur compounds. The achieved sulfur reduction rate was 98%
under optimum conditions, and the catalyst could be recycled three times [33].

2.3. Ionic Liquid Catalytic Oxidation System

The reactivity of sulfur refractory compounds in fuel oil during the oxidation process decreases
in the order of 4,6-dimethyldibenzothiophene (4,6-DMDBT) > 4-methylbenzothiophene (4-MDBT) >
DBT > T. In the ODS process, the sulfur compounds are oxidized to their respective sulfones, which
are then extracted by various organic solvents [34]. In recent years, ionic liquids as extractants have
gained attention in the refinery industry due to their remarkable characteristics. Ionic liquids could be
used in the ODS process as both catalyst and extractive agent and achieved ultra-low desulfurization
of the model fuel [35].
Wang et al. applied a Lewis acidic ionic liquid (ILs) [ODBU]Cl/nZnCl2 (n = 1, 2, 3, 4, and 5)
for oxidative desulfurization of model and diesel fuel oils, with H2 O2 as the oxidant. The model oil
was prepared by dissolving S-compounds (such as BT, DBT, and 4,6-DMDBT) in n-octane in desired
concentrations. The results revealed that the catalyst was highly reactive towards the reduction of
sulfur compounds in fuel oil, wherein the amount of sulfur reduced by 99% in a single step process,
under mild reaction conditions. The catalyst could also be successfully reused up to six times without
any change in its structure [36].
Dharaskar et al. studied the ODS process using 1-butyl-3-methylimidazolium tetrafluoroborate
ionic liquid as a catalyst for removing sulfur compounds from fuel oil. The model fuel oil was prepared
by dissolving sulfur compounds (BT, T, and 3-methylthiphene (3-MT) in dodecane. The conversion
Catalysts 2019, 9, 229 5 of 12

rate was obtained to be 73.02% at 30 ◦ C and 10 min under mild reaction conditions. The catalyst was
recyclable up to four times without regeneration [37]. Thus, to date, numerous research studies have
been conducted using ionic liquid in catalytic ODS of fuel oil [38–42].

2.4. Molecular Sieve Catalytic Oxidation System

The performance of the catalyst in a reaction depends on its number and the nature of active
sites. In addition, catalytic support material plays a crucial role in determining the active sites of
catalysts. A number of studies have shown that the use of molecular sieves significantly improves
the performance of catalysts in the removal of sulfur. Molecular sieve type of the catalyst has also
been drawing interest because of its large pore size and surface area, and for being environmentally
friendly [43].
Zhao et al. studied different phthalocyanine molecular sieve catalysts, such as
Cu2 (PcAN)2 –W-HZSM-5 and Cu2 (PcTN)2 /W-HZSM-5, for oxidative desulfurization of fuel oil.
The sample fuel oil was formed by dissolving different sulfur compounds, such as T, BT, and DBT,
while the molecular oxygen supplied to the reactor was used as an oxidant. The copper phthalocyanine
molecular sieve catalyst was successfully modified by HZSM-5 zeolite. The catalyst showed superior
activity under optimum reaction conditions of temperature 60 ◦ C, reaction time 3 h, and catalyst load
of 0.1 g. The sulfur removal efficiencies for T, BT, and DBT were obtained as 93.82%, 91.23%, and
87.32%, respectively [44].
Yang et al. investigated the catalytic ODS process using catalyst of molybdenum supported on 4A
molecular sieve. The sulfur refractory compounds selected for the model fuel oil were BT and DBT.
The solvent cyclohexanone peroxide (CYHPO) was chosen as the oxidant. To obtain optimum results,
the experiment was designed based on the Box–Behnken (BBD) method. The removal of DBT and
the residual sulfur content was achieved at 99% under optimum catalytic conditions of Mo loading
of 6 wt %, volume mass ratio of model gasoline to catalyst MoO3 /4A of 100, oxidant (CYHPO)/DBT
molar ratio of 2.5, and temperature of 100 ◦ C over 30 min [45].
Shiraishi et al. studied vanadosilicate molecular sieve as a catalyst for oxidative desulfurization
of light oil. The oil feedstock content of sulfur compounds (BT and DBT) was dissolved in acetonitrile,
with H2 O2 as the oxidant. The sulfur refractory compounds were catalyzed successfully by the
vanadosilicate molecular sieve and the amount of sulfur was reduced to ultra-low levels of less than
50 ppm from 450 ppm. In addition, the reduction in the sulfur content was accompanied by reduction
in the nitrogen content of the light oil. However, one of the disadvantages of this process is that the
recovered vanadosilicate cannot be used further because of the dissolution of the vanadium present on
the silica surface into the reaction media [46].
Shifu et al. examined the oxidative desulfurization of model light oil using Ti-MWW catalyst and
H2 O2 oxidant. The model oil was made with BT and DBT sulfur compounds, and their oxidized forms
were removed through extraction using acetonitrile. Consequently, the conversion of BT and DBT
were attained as 100% and 95%, respectively [47].

2.5. Polyoxometalates Catalytic Oxidation System

Polyoxometalates are a cluster of early transitional metal ions and polyoxoanions. They are
versatile catalysts due to their multifunctional active sites, such as protons, oxygen atoms, and metals.
Of late, polyoxometalate catalysts in the ODS process have attracted significant attention as green
catalysts in combination with H2 O2 oxidant [48].
Trakarnpruk et al. applied various polyoxometalate catalysts based on molybdenum and tungsten
transitional metals for desulfurization of model gas oil containing sulfur refractory compounds
(such as BT, DBT, and 4,6-DMBT) in a H2 O2 /acetic acid system. The results showed that the W-based
polyoxometalate catalysts were more active than the Mo-based catalysts in desulfurization of fuel
oil. In this study, the extraction stage was combined with the oxidation stage, and the sulfur removal
Catalysts 2019, 9, 229 6 of 12

efficiency was achieved as 98% under mild reaction conditions, along with 90% recovery of the gas
oil [49].
Julião et al. investigated the removal of sulfur from model diesel oil using zinc-substituted
polyoxotungstate anion, TBA4.2 H0.8 [PW11 Zn (H2 O) O39 ] (denoted PW11 Zn). The model diesel oil was
prepared by dissolving various sulfur compounds, such as BT, 1-DBT, and 4,6-DMBT in n-octane, while
H2 O2 was used as the oxidant. The oxidized oil was extracted in a biphasic system using ionic liquid
as a solvent, as well as another solvent, acetonitrile. Complete desulfurization of the diesel oil was
achieved within two hours of using ionic liquid as an extracting solvent compared to the acetonitrile.
However, it was found that when acetonitrile was used as the extraction solvent, the catalyst composite
was more stable, easily recoverable from the reaction mixture, and reusable several times [50].
Although these polyoxometalate catalysts have received notable attention for their high reactivity
in the ODS process, their low surface area that resulted in longer reaction time proved to be their
major limitation.

2.6. Titanium Catalytic Oxidation System

The examination of titanium silicate (TS) and modified titanium catalysts for oxidative
desulfurization of fuel oil revealed that these catalysts had remarkable oxidation ability and yielded
better results when used alongside eco-friendly peroxide solvent as an oxidant [51–53].
Bazyari et al. applied titania-silica nanocomposite catalysts for ultra-deep desulfurization of
model fuel oil. The catalysts were prepared by a sol-gel method with different TiO2 wt % loadings, and
the synthesized catalysts were further evaluated by several analytical techniques. The model fuel oil
was prepared by dissolving DBT in an isooctane solvent, while tert-butyl hydroperoxide (TBHP) was
added into the reactor as the oxidant. The various effects of titanium loading, reaction temperature,
and calcination temperature were investigated. It was found that the catalyst with 50 wt % TiO2
loading at high acidity showed high catalytic performance and was capable of reducing nearly 98% of
DBT within 20 min [54].
Yang et al. studied the catalytic oxidative desulfurization of mesoporous titanium silicalite-1
(TS-1) using a hybrid SiO2 –TiO2 xerogel for removal of sulfur refractory compounds from model oil,
which was dissolved in n-octane. The sulfur compounds (BT, DBT, and 4,6-DMDBT) were oxidized
in a H2 O2 /acetic acid oxidant system, and the reaction was run in a 100 mL glass batch reactor at
300 rpm. It was observed that the modified TS-1 hybrid, i.e., Mesoporous TS-1 (M-TS-1), was more
active than the conventional TS-1. The conversion rate for DBT using the former was 98%, whereas the
conversion was 5.6% upon usage of conventional TS-1 catalyst [55].
Zhao et al. examined desulfurization of diesel oil using Ti-containing zeolite photocatalysts.
The diesel oil was prepared by dissolving DBT sulfur compounds in n-octane solvent. The optimal
condition for the oxidative desulfurization process was obtained as 30 wt % H2 O2 oxidant system.
The achieved rate of sulfur reduction for DBT was 90% and the catalyst was found to be reusable
several times [56].

2.7. Ultrasound-Assisted Oxidation System

The ODS method has gained higher recognition in the desulfurization of fuel oil compared
to the hydrodesulfurization (HDS) process, because of its high selectivity under mild operating
conditions. Furthermore, in recent years, an effective and innovative ultrasound-assisted oxidative
desulfurization (UADO) method has been introduced in the desulfurization process, which has created
a new dimension in the petrochemical industry. The UADO method has several benefits over the
conventional mixing-assisted oxidative desulfurization process. The use of ultrasound probe in UADO
increases the rate of desulfurization because of its smoother dispersion capability. In the UADO
process, the reaction kinetics is better due to increased mass transfer in the heterogeneous reaction
system. The reaction rate and mass transfer are also enhanced because of the simultaneous physical
and mechanical effects [57–59].
Catalysts 2019, 9, 229 7 of 12

Gildo et al. studied ultrasound-assisted oxidative desulfurization of simulated fuel using activated
carbon-supported phosphotungstic acid catalyst. Simulated fuel oil containing sulfur refractory
compounds (T, BT, and DBT) was dissolved in toluene, and H2 O2 was added in the reaction mixture
as an oxidizing agent. The 24 factorial design and face centered method was applied for optimization
of the experiment. The oxidation of sulfur compounds was attained as 94.74% at reaction conditions
of 25.52 wt.% of H2 O2 concentration, catalyst loading of 983.9 mg, and sonication time of 76.36 min.
The study also found that 99% sulfur was removed from kerosene oil by applying optimized UADO
parameters in a 4-cycle extraction process, using acetonitrile as the extracting solvent [60].
Similarly, Jalali et al. applied ultrasound irradiation in the oxidative desulfurization process
of gas oil, with sulfur content at 0.221 wt %, H2 O2 as the oxidant, and formic acid as the catalyst.
The experiment was optimized using response surface methodology (RSM) and Box–Behnken design.
The various effects of reaction parameters, such as sonication time, temperature, peroxide to sulfur
molar ratio, formic acid to oxidant molar ratio, and sonication power per gas oil volume were
investigated in the desulfurization of gas oil. It was observed that maximum desulfurization was
achieved under the following optimum reaction conditions: temperature of 50 ◦ C, sonication time
of 19.81 min, oxidant to sulfur molar ratio of 46.36, formic acid to oxidant molar ratio of 3.22, and
sonication power of 7.78 W/mL. The sulfur removal efficiency obtained was 96.2% after the fourth
extraction cycle using acetonitrile solvent. The author also found that higher desulfurization efficiency
was obtained within a shorter reaction time as compared to the traditional mixing ODS process [61].
Some studies have also reported the successful result of ultrasound assisted oxidative desulfurization
of fuel oil performed under mild reaction conditions [62–67]. One summary table for oxidative catalytic
desulfurization of liquid fuel oil has been presented at the end (Table 1).

Table 1. Summary table for oxidative catalytic desulfurization of liquid fuel oil.

Sulfur Removal
Catalyst Source of Sulfur Oxidant Reaction Conditions Ref.
Efficiency (%)
Liquid acid
catalytic system
CH3 COOH Heavy oil H2 O2 T = 60 ◦ C, t = 90 min 58.54 [27]
CH3 COOH Model gas oil H2 O2 T = 90 ◦ C, t = 30 min 90 [28]
HCOOH Model fuel oil H 2 O2 T = 65 ◦ C, t = 56 min 100 [29]
Heteropolyacid (HPA) catalytic
system
Heteropolyacid DBT O2 T = 60 ◦ C, t = 120 min ~100 [35]
PMo@HKUST-1 DBT H 2 O2 Not specified 95 [36]
HPW-TUD-1 Model oil H2 O2 Not specified 98.0 [37]
Ionic liquid catalytic system
Model oil
[ODBU]Cl/nZnCl2 (n = 1, 2, 3, 4,
(BT, DBT, and H2 O2 99.0 [40]
and 5)
4,6-DBT)
1-butyl-3-methylimidazolium Model oil
T = 30 ◦ C, t = 30 min 73.02 [41]
tetrafluoroborate (BT, T, and 3-MT)
Molecular sieve catalytic system
93.23 = T
Copper phthalocyanine molecular Model oil
O2 T = 60 ◦ C, t = 180 min 91.23 = BT [48]
sieve/HZSM-5 (BT, T, and DBT)
87.32 = DBT
Molybdenum supported on 4A
BT and DBT CYHPO T = 100 ◦ C, t = 30 min 99.0 [49]
molecular sieve
Vanadosilicate catalyst Ultra-low level
BT and DBT H2 O2 T = 60 ◦ C, t = 30 min [50]
(V-HMS) (450 to 50 ppm)
Model light oil (BT 100.0 = BT
Ti-MWW H2 O2 T = 70 ◦ C, t = 180 min [51]
and DBT) 95.0 = DBT
Catalysts 2019, 9, 229 8 of 12

Table 1. Cont.

Sulfur Removal
Catalyst Source of Sulfur Oxidant Reaction Conditions Ref.
Efficiency (%)
Polyoxymetalate
catalytic system
MO-W based BT, DBT, and H2 O2 /
T = 60 ◦ C, t = 180 min 98.0 [53]
Polyoxymetalate 4,6-DBT Acetic acid
Model diesel
TBA4.2 H0.8 [PW11Zn (H2 O) O39 ] (BT, 1-DBT, and H2 O2 T = 50 ◦ C, t ~ 180 min 100.0 [54]
4,6-DBT)
Titanium catalytic
system
Model fuel
Titania-silica nanocomposite
BT, DBT, and 4,6- TBHP T = 60 ◦ C, t = 20 min 98.0 [58]
Ti-HMS/TS-1
DBT
Mesoporous TS-1 (M-TS-1) DBT H 2 O2 T = 80 ◦ C, t = 180 min 96.0 [59]
Ti-containing zeolite
DBT H 2 O2 Not specified 90.0 [60]
photocatalyst
Ultrasound-assisted
catalytic system
Activated carbon supported Simulated fuel oil T = not specified, t =
25.52% H2 O2 90.0 [64]
phosphotungstic acid catalyst (T, BT, and DBT) 76.36 min
HCOOH Gas oil H 2 O2 T = 50 ◦ C, t = 46.36 min 96.2 [65]

Despite having several advantages, the UADO process involves certain difficulties. It consumes
high energy and requires a sono-reactor, amplifier, and generator that increase the investment
costs. Therefore, for industrial applications, cost and energy-effective alternatives to UADO need to
be researched.

3. Conclusions, Future Challenges, and Recommendations

Hydrodesulfurization is a well-established and conventional technique used in oil refinery
industries. However, it involves certain constraints, such as higher investment costs. In order to
meet the new standards specified for sulfur, the HDS process needs to perform under high reaction
conditions, such as high temperature (~400 ◦ C), high pressure (~100 atm), and in a large reaction
vessel, which raises the amount of investment costs. Therefore, newer techniques, such as extractive
desulfurization, biodesulfurization, extraction with ionic liquids, selective adsorption, and oxidative
desulfurization have been proposed in addition, or as alternatives, to HDS. Amongst these alternative
methods, the oxidative desulfurization process has received more attention due to its mild operating
condition and high sulfur removal efficiency. However, there still exists many issues with the ODS
process, such as high loading of the oxidizing agent, deactivation of the catalyst, increasing investment
costs with increasing sulfur concentration in the feedstock, and waste management of the oxidized
sulfur compounds. Several initiatives have been proposed to address these drawbacks found in
the ODS method, which include developing a cost effective, high efficiency, and recyclable catalyst,
and developing an environment friendly and cheap oxidizing agent. Eventually, to meet the revised
sulfur standards recommended by USEPA and the public demand for safer fuels, effective catalytic
oxidative desulfurization of fuel oil is required by improvising the ODS process with technological
innovations. Until now, the hydrotreating activity of different oxidative catalysts is limited to model
sulfur compounds with short chains. On the contrary, the catalyst’s activity in the case of real feedstock
with heavy sulfur compounds would vary from the model feedstock, which has not yet been studied
in-depth. Therefore, another challenge that remains for researchers is to examine the application of the
catalyst in the oxidative desulfurization of real feedstock of heavy oil, such as waste tire pyrolysis oil.
Besides these challenges, the more critical challenge is the commercialization of the catalytic oxidative
desulfurization process due to some major obstacles, such as low selectivity for the sulfides present in
fuel feedstock, recovery, and separation of the used catalysts after the reaction.
Catalysts 2019, 9, 229 9 of 12

Author Contributions: Conceptualization, M.N.H. and H.S.C.; writing—original draft preparation, M.N.H.;
writing—review and editing, M.N.H.; H.C.P. and H.S.C.; visualization, H.C.P.; supervision, H.S.C.
Funding: This research received no external funding.
Acknowledgments: This work was supported by the National Research Foundation of Korea (NRF) grant funded
by the Ministry of Science, ICT, and Future Planning (MSIP) of Korea (NRF-2017R1A2B4009340). This work has
also been supported by the R&D Program of Forest Science Technology (Project No. 2017052C10-1819-BB02),
provided by the Korea Forest Service (Korea Forestry Promotion Institute).
Conflicts of Interest: The authors declare no conflict of interest.

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