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Efficient non-catalytic oxidative and extractive

desulfurization of liquid fuels using ionic liquids†
Cite this: RSC Adv., 2016, 6, 103606
Omar U. Ahmed,a Farouq S. Mjalli,*a Talal Al-Wahaibi,a Yahya Al-Wahaibia
and Inas M. AlNashefb

Received 2nd September 2016
Accepted 21st October 2016
DOI: 10.1039/c6ra22032k
www.rsc.org/advances
Oxidative desulfurization (ODS) is one of the promising alternative and heavily researched desulfurization
technologies. This is partly due to its ability to preferentially oxidize and ease the removal of refractory
sulfur compounds with the aid of a suitable solvent. Despite its long list of advantages, challenges in
different research areas within ODS technology still exist. In this work, an effort was made to bridge the
gap that exists in terms of the selection of suitable oxidant and strategy. A preliminary kinetic modeling
of the experimental data showed that the non-catalytic conversion of dibenzothiophene (DBT) and
benzothiophene (BT) to their corresponding sulfones using the electrophilic meta-chloroperoxybenzoic
acid (mCPBA) can be considered a bimolecular and a trimolecular reaction respectively. Using an ionic
liquid (IL) as an extraction solvent in a simultaneous oxidation and extraction setup (EODS), >78% BT was
removed at optimum experimental conditions. Using the post-oxidation extractive desulfurization setup
(OEDS), 99% removal of BT was achieved at milder optimum experimental conditions. Also using the
OEDS strategy, >99% of DBT removal was achieved after only 15 min at 60
C, with a mass fraction of
$0.5 and O/S of 3/1 for all the ILs tested. Finally, the sulfur content of a commercial diesel fuel was
reduced to 15.6 ppm using the OEDS strategy with tetrabutylphosphonium methanesulfonate as
a suitable extraction solvent, which can be readily regenerated.

crude oil products in 2010 and is expected to reach 33.3% by

1 Introduction
The presence of sulfur compounds in petroleum products is of
great concern to the processing industries and governments
around the world. In a petroleum renery, certain sulfur
compounds originating from crude oil react with metal surfaces
at temperatures exceeding 260
C to form metal suldes and
other products. This is known as suldic corrosion1 and it
occurs on process equipment. Furthermore, sulfur compounds
present in certain reactor feed streams in the renery may lead
to catalyst poisoning.2 Oxides of sulfur (SOx) generated during
combustion of sulfur-containing hydrocarbon fuels not only
lead to environmental and health hazards but also reduce the
efficiency of the advanced emission control devices installed in
modern cars. Increased particulate matter, CO2 and NOx emis-
sions are some of the consequences of the reduction in the
efficiency of these devices.3,4 As a result, stringent regulations
on the maximum level of sulfur allowable in transportation
fuels have been imposed to varying degrees by governments in
most parts of the world. Diesel fuel, which made up 29.0% of
a
Petroleum and Chemical Engineering Department, Sultan Qaboos University, 123,
Sultanate of Oman. E-mail: farouqsm@yahoo.com
b
Department of Chemical and Environmental Engineering, Masdar Institute for Science
and Technology, Masdar City, Abu Dhabi, United Arab Emirates
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c6ra22032k
2035,5 has been a subject of these international regulations. For
instance, the maximum allowable sulfur content in diesel fuel
was pegged at 10 ppm and 15 ppm in Europe and US respec-
tively.6 Hydrodesulfurization (HDS) is conventionally used for
efficient removal of sulfur compounds. However, owing to high
concentrations of a class of sulfur compounds (refractory sulfur
compounds) present in the heavier and sourer crude oils
produced in recent years, the efficiency of the once reliable HDS
has declined. This is especially true in the case of deep desul-
furization.4 For this reason, the potentials of other desulfur-
ization techniques have been under intense investigation.
Adsorptive,7–9 extractive,4,10,11 oxidative4,12,13 and bio-desul-
furization14,15 are among the promising desulfurization tech-
niques that have received a great deal of attention from the
scientic community. Extractive desulfurization (EDS) using
ionic liquids (ILs) has been considered promising in terms of
both environmental and technical efficiency. This is because it
can be carried out under mild operating conditions and without
any material consumption. Therefore, the major challenge that
may exist against the employment of EDS using ILs is nding
the most suitable solvent. The fact that ILs have been catego-
rized based on their constituent ions has simplied the
screening and application of ILs in EDS. The potential of the
oxidative desulfurization (ODS) technique lies in the fact that it
preferentially attacks refractory sulfur compounds owing to the

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Paper
presence of high electron density on the sulfur atom.16 It can,
therefore, serve as a complementary desulfurization technique
to be placed downstream of the conventional HDS unit in
reneries. Furthermore, the ease with which ODS can be inte-
grated with other techniques such as extractive and adsorptive
desulfurization makes it more attractive. In fact, ODS can serve
as an improvement to the performance of ionic liquid-based
EDS using techniques such as extractive oxidative desulfuriza-
tion (EODS) and extractive catalytic oxidative desulfurization
(ECODS).
Research activities in ODS can be categorized in terms of
catalytic/non-catalytic, type of oxidant and type of process,
among others. Using hydrogen peroxide (H2O2) as an oxidant,
various heterogenous17–19 and homogenous16,20,21 catalysts have
been used in ODS studies. H2O2 has been used extensively in
studies related to ODS partly because the by-product of the
oxidation reaction is water. However, this same advantage
negatively affects the performance of the oxidant as the pres-
ence of water results in formation of biphasic systems and
a consequent mass transfer problem. Furthermore, the pres-
ence of water during the IL-based EDS of oxidized fuel will result
in lower desulfurization efficiency. The potentials of other
oxidants have also been studied. These oxidants include
molecular oxygen,22 hydroperoxide generated in situ from air23
and alkyl hydroperoxides, among others.
Despite the elimination of the use of expensive catalysts, only
a few studies have been carried out on non-catalytic ODS.24,25
This can be attributed to the fact that results reported in the
literature for the non-catalytic ODS are not as impressive as
those reported for the catalytic systems. The apparently poor
performance of the non-catalytic ODS systems can be addressed
by using a systematically selected oxidant. In our previous
studies on the use of superoxide ion for oxidation of sulfur
compounds, it was observed that the superoxide ion, which acts
as a nucleophile, inefficiently oxidized thiophene while leaving
dibenzothiophene unreacted.26 This was understood to be as
a result of the relatively higher electron density of dibenzo-
thiophene as compared with thiophene, which is more
susceptible to the nucleophilic attack. This, therefore, implies
that either a very weak nucleophilic or a strong electrophilic
oxidant may react with dibenzothiophene to produce its corre-
sponding sulfone. meta-Chloroperoxybenzoic acid (mCPBA)
seems to be a plausible option. In a typical reaction, an oxygen
atom is transferred from the weak O–O bond of mCPBA to an
electron-rich substrate, thereby making it an electrophilic
oxidant. mCPBA may also serve as a nucleophilic oxidant in the
presence of certain aldehydes.27 Although ammable and
hygroscopic, mCPBA is easy to handle and the concentration of
its commercial grade can reach up to 77 wt%. At 77 wt%, it
possesses an active oxygen concentration of 7.14% and has
been used in organic syntheses such as Baeyer–Villiger oxida-
tion, Cope elimination and even oxidation of suldes.28 Despite
its application in the oxidation of suldes, work on oxidative
desulfurization of fuels using mCPBA as an oxidant is almost
non-existent.
The aim of this work is therefore to demonstrate the
importance of oxidant selection and particularly the efficiency
This journal is © The Royal Society of Chemistry 2016
RSC Advances
of an electrophilic oxidant in the non-catalytic oxidation of
sulfur compounds available in diesel fuel. The ionic liquids
(ILs) whose extractive desulfurization (EDS) efficiencies were
studied by our group29 were used as extraction solvents in
a simultaneous extraction and oxidation of the sulfur
compounds (EODS) and/or post-oxidation extraction of the
sulfur compounds (OEDS) from the diesel fuel. The EDS
performance of these ILs with and without an oxidation step
will be compared.
2 Materials and methods
2.1 Chemicals
The ionic liquids tetrabutylphosphonium methanesulfonate
[P4444][MeSO3] (98%) and triisobutyl(methyl)phosphonium p-
toluenesulfonate [Pi444,1][Tos] (98%) were supplied by Cytec and
Sigma-Aldrich respectively. Acetonitrile (99.9%, HPLC grade)
was supplied by Merck. Hexadecane (99%) was supplied by
BDH. Iso-dodecane (80%, mixture of isomers, tech.) and
toluene (ACS) were supplied by Alfa Aesar and Honeywell
respectively. 1-Benzothiophene for synthesis was supplied by
Merck. Dibenzothiophene (98%), dibenzothiophene sulfone
(97%) and meta-chloroperoxybenzoic (77%) acid were supplied
by Aldrich. Acetone (99.5%) was supplied by Sigma-Aldrich. All
chemicals were used as supplied without further purication.
Scheme 1 shows the structures of the cations and anions of
the ILs used in this work.
2.2 Experimental procedures
A mixture of iso-dodecane (51%), hexadecane (39%) and
toluene (10%) was prepared to represent the sulfur-free simu-
lated fuel. Appropriate amounts of benzothiophene (BT) and
dibenzothiophene (DBT) were dissolved in the aforementioned
mixture in order to obtain a mixture with 500 ppm each of
benzothiophene (BT) and dibenzothiophene (DBT). For the
kinetic studies, the BT- and DBT-doped simulated fuels were
prepared separately so that the kinetic studies carried out using
one particular sulfur compound are not affected by the presence
of the other.
2.2.1 Preliminary kinetic studies. To establish the
optimum oxidant-to-sulfur molar ratio (O/S) to be employed for
the preliminary kinetic studies, the effect of molar ratio on the
% sulfur conversion (SC) of BT- and DBT-doped simulated fuels
was studied at 30
C, 30 min and a mixing rate of 600 rpm. The
O/S molar ratios studied were in the range 2.5 to 20 mol mol1.
An appropriate amount of meta-chloroperbenzoic acid
(mCPBA) was added directly to about 2000 mg of BT- or DBT-
doped simulated fuel to make up a predetermined (optimum)
molar ratio with the sulfur compound (O/S) present in the
selected simulated fuel. The mixture of the oxidant and the
simulated fuel was agitated in a screw-capped vial using
a thermomixer. Aer a designated time, a sample of about
60 mg was withdrawn and diluted with acetone, and the
concentration of sulfur compound (DBT or BT) was analyzed by
HPLC. The mixing rate was xed at 600 rpm throughout the
studies while the temperature was varied in the range 30
C to
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RSC Advances
Scheme 1 Cation and anion used in this work.
45
C. The temperature was restricted to 45
C to allow
reasonable time of reaction. High temperatures resulted in
faster reaction. As a result, sampling and analysis of DBT in
particular becomes more complicated. To calculate the % SC (%
X), eqn (1) (see below) was used.
2.2.2 Extractive and oxidative desulfurization experiments.
Screw-capped Chromacol vials (20 mL) were used for both
simultaneous extractive oxidative desulfurization (EODS) and
post-oxidative extractive desulfurization (OEDS) studies. First,
preliminary runs using the EODS system were carried out.
During these runs, the oxidant-to-sulfur ratio (O/S) was kept at
3 : 1 and the fuel-to-solvent mass ratio (MR) of 1 : 1 was retained
while the temperature and time were varied between 30 and
80
C and 30 and 120 min respectively. At the end of each
experiment, the mixture was allowed to settle, aer which
a sample of fuel was withdrawn for analysis. HPLC was used for
determining the sulfur content of the simulated fuel before and
aer the experiment. The relationship shown as eqn (1) was
used to determine the percentage sulfur removal.
C0  Ct
% SR or % SC ¼  100 (1)
C0
where % SR is % sulfur removal, % SC is sulfur conversion in
the absence of an IL and the presence of mCPBA, C0 is initial
sulfur concentration (ppm), and Ct is sulfur concentration aer
t min of the experiment.
A response surface methodology was used for the optimiza-
tion of % SR of BT and DBT in the studied ILs. Design Expert 7.0
soware was used for the design, optimization and analysis of
the experiments. The four independent factors studied were
time (15–80 min), temperature (30–60
C), mass fraction (0.5–
0.83) and oxidant to sulfur ratio (3/1–9/1). All experiments were
carried out at a mixing speed of 600 rpm. A comparison between
the optimum EODS and OEDS was carried out.
2.2.3 Commercial diesel fuel desulfurization experiments.
To study the deep desulfurization of diesel fuel, an appropriate
amount of mCPBA was added into a 50 mL screw-capped bottle.
The amount of diesel required to make up a desired oxidant-to-
103608 | RSC Adv., 2016, 6, 103606–103617
Paper
sulfur (O/S) molar ratio was calculated and introduced into the
bottle. Finally, the amount of IL required to make up the desired
MR was added at the appropriate time. Agitation of the reaction
mixture was carried out using a magnetic stirrer. For the anal-
ysis of commercial diesel, energy dispersive X-ray uorescence
(EDXRF) was used to measure the concentration of elemental
sulfur before and aer each experiment.
2.2.4 Regeneration and recovery. Regeneration was carried
out by mixing distilled water with the spent IL at a ratio of 5 : 1
(water : IL). Cellulose nitrate lter paper (0.2 mm pore, Sartorius
Stedim) was used to lter out the precipitated sulfur
compounds. The mixture of water and IL was introduced into
the ask of a rotary evaporator (IKA RV 10), where water was
evaporated under vacuum (25 mbar) at 95
C for 2 h using tap
water at room temperature as the cooling uid. The regenerated
IL was then used for another extraction stage. The advance
regeneration method was carried out in a similar fashion. The
only difference was that n-hexane was mixed with the water–IL
mixture at a ratio of 1 : 1 for 30 min prior to water removal using
the rotary evaporator. The degree of IL recovery was calculated
aer each extraction–regeneration stage using eqn (2) below:
ðmIL ÞE  ðmIL ÞR
% recovery ¼  100 (2)
ðmIL ÞE
where (mIL)E is the mass of IL used in the extraction experiment,
and (mIL)R is the mass of IL recovered aer regeneration.
2.3 Optimized experimental data models
2.3.1 Response surface quadratic model. The following
quadratic equation (eqn (3)) was used for the tting and
subsequent optimization of the experimental data obtained
following the procedure outlined in Section 2.2.2.
P P P
Y ¼ b0 + biXi + biiXi2 + bijXiXj (3)
where Y is the response (% SR), Xi and Xj are the optimized
factors and b0, bi, bii and bij are coefficients of the intercept,
linear, square and interaction effects respectively.
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Paper RSC Advances

2.3.2 Kinetic reaction models. For the conversion of 3 min, then heated to 250
C at a heating rate of 6
C min, which
dibenzothiophene (DBT) and benzothiophene (BT) to their temperature was held for 10 min.
corresponding sulfones using meta-chloroperbenzoic acid Rigaku NexQC+ energy dispersive X-ray uorescence
(mCPBA) as an oxidant, the following stoichiometric reactions (EDXRF) was used for the elemental sulfur analysis of
were assumed: commercial diesel fuel. In a typical run, about 5 g of diesel fuel
was poured into the specialized sample cups (SC 3332), which
DBT + 2mCPBA / DBTO2 + 2mCBA (R1) were wrapped on one side with a thin lm (Prolene from
Chemplex) and inserted into the machine. Helium gas
BT + 2mCPBA / BTO2 + 2mCBA (R2) (99.9992%) was passed through the machine at 1 bar. Each
measurement took 300 seconds and was repeated three times.
The reactions with stoichiometry similar to (R1) and (R2) can
The minimum coefficient of determination (R2) for all calibra-
be assumed to be elementary irreversible bimolecular and tri-
tion curves for different sulfur ranges, 500–100 ppm, 100–
molecular reactions, respectively.30
20 ppm and 25–5 ppm, was 0.994867. The intensity extraction
The equation for the rate of an irreversible bimolecular
parameters were Ka (line), 2.24–2.37 (region) and low z (condi-
reaction is of the form:
tion). Acquisition conguration was set at low z, 6.5k, 100 mA
rDBT/BT ¼ kCDBT/BTCmCPBA (4) and open lter.

The reaction is rst order with respect to both DBT/BT and

mCPBA but second order overall.
3 Results and discussion
The linearized form is: 3.1 Preliminary kinetic studies
  3.1.1 Effect of O/S molar ratio. Fig. 1 shows the effect of O/S
M  2XA
ln ¼ CAO ðM  2Þkt; Ms2 (5) molar ratio on % SC. DBT, owing to its high electron density,
Mð1  XA Þ
reacts faster than BT. At a molar ratio of 5 : 1 (O/S), >85% SC was
where XA is the conversion and M is the initial molar ratio of achieved for DBT-containing simulated fuel while 11% SC was
reactants, which is 3 in this case. achieved in the case of BT. This is not very discouraging
The equation for the rate of an irreversible trimolecular considering the fact that typical hydrotreated diesel contains
reaction is of the form: 14% BTs (including their derivatives) and 86% DBT (and
derivatives) of total sulfur compounds31 with 4,6-dimethyldi-
rDBT/BT ¼ kCDBT/BTCmCPBA2 (6)
benzothiophene being the most refractory. However, dime-
thyldibenzothiophene possesses higher electron density. It is
The reaction is rst order with respect to DBT/BT and second
therefore safe to assume that its reaction rate will be faster than
order with respect to mCPBA but third order overall.
that of DBT if steric hindrance due to the alkyl group does not
The linearized form is:
  come into play.
ð2CAO  CBO ÞðCBO  CB Þ CAO CB
þ ln ¼ ð2CAO  CBO Þ2 kt; 3.1.2 Effect of mixing time and temperature. A molar ratio
CBO CB CA CBO of 3 : 1 (O/S) was used for studying the concentration–time
Ms2 (7) prole of DBT and BT. For DBT, the reaction time of 4200
seconds to 6600 seconds was used (Fig. 2). Because the reaction

2.4 Chemical analysis of samples

An Agilent high performance liquid chromatograph (HPLC)
1260 Innity equipped with a reversed-phase column and
variable wavelength detector was used. The column specica-
tion is 150  4.6 mm, 5 mm, 100A (Ecosil C18-extend). The
temperature of the column was set at 25
C. The mobile phase
consists of a mixture of 70 vol% acetonitrile and 30 vol% water.
Flow rate was kept at 1 mL min1 while the injection volume
was set to 1 mL. Detection of dibenzothiophene was made at
234 nm while that of benzothiophene was made at 290 nm.
Finally, the method R2 was determined as 0.99994 and 0.99972
for dibenzothiophene and benzothiophene respectively.
A Shimadzu GCMS-QP2010 Ultra equipped with HP-5MS
column was used for the determination of oxidation products.
The injection and oven temperatures were set to 250
C and
100
C respectively. Helium as the carrier gas was maintained at
a total ow rate of 14 mL min1 with column ow rate of 1 mL Fig. 1 Effect of oxidant/sulfur compound molar ratio on % sulfur
min1. The temperature program was as follows: 100
C held for conversion of DBT and BT at 30
C, 30 min and 600 rpm.

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RSC Advances
of BT with the oxidant is relatively slow, the reaction time of
28 800 seconds was used (Fig. 3). In both DBT and BT oxidation,
the concentration of the reactant decreases with time as
expected.
3.1.3 Kinetic model tting. Both the bimolecular and tri-
molecular reaction mechanisms were used in tting the data
obtained for DBT in an effort to determine the most suitable
rate equation. Fig. 4A and B show the result of these ts. By
visual observation, the bimolecular reaction seems to be
a better t to the data. This can be conrmed by observing the
regression coefficients (R2) in Table S1 (ESI†). For the bimolec-
ular reaction model, all the R2 values were greater than 0.9988
while the best R2 value obtained for the trimolecular reaction
model was 0.9916. The bimolecular reaction model was chosen
as the model that satises the reaction stoichiometry.
A plot of ln[k] against 1/T (Fig. S1†) was used to determine the
activation energy for the bimolecular reaction. The activation
energy was determined as 49.98 kJ mol1. The nal form of the
rate constant was determined as eqn (8)
rDBT ¼ kDBTCDBTCmCPBA, kDBT ¼ 2.82  1010 e49 978/RT (8)
Fig. 2 Concentration–time profile of DBT at O/S ¼ 3/1, 600 rpm.
Fig. 3 Concentration–time profile of BT at O/S ¼ 3/1, 600 rpm.
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Paper
Similar to the case of DBT, both bimolecular and trimo-
lecular rate orders were tted to the data obtained from the
experiment using BT-containing simulated fuel. From visual
observation of Fig. S2A and B,† the trimolecular reaction ts
more satisfactorily than the bimolecular. Although not as
pronounced as in the gures, the R2 values presented in Table
S2† also indicate this conclusion. Table S2† shows the rate
constant for both bimolecular and trimolecular reactions and
their corresponding R2 values. As expected, the kinetic rate
constants for both the bi- and trimolecular reactions were lower
than their corresponding values for DBT. If a bimolecular
reaction is assumed in both cases, the ratio of the rate constants
(kDBT/kBT)1 becomes 20 at 30
C. Similarly, if a trimolecular
reaction is assumed for both cases, the ratio of the rate
constants (kDBT/kBT)2 becomes 40 at 30
C. This is roughly
double as compared to the bimolecular reaction constant,
which was found to be the same for all temperatures measured.
In either case, this means that the reaction rate of DBT is far
greater than that of BT. The trimolecular reaction mechanism
was selected to describe the stoichiometry of the reaction of the
oxidant with BT. A plot of ln[k] against 1/T (Fig. S3†) was used to
determine activation energy for the trimolecular reaction. The
activation energy was determined as 41.90 kJ mol1. The nal
form of the rate constant was determined as presented in eqn
(S1).†
The implication of the results obtained from the kinetic
studies is that in the case of DBT the reaction only requires an
effective collision of a DBT molecule and an mCPBA molecule to
proceed. According to collision theory, an effective collision
takes place when the colliding molecules are in the proper
orientation and possess the right amount of energy. One would
think then that this reaction does not go directly to sulfone and
meta-chlorobenzoic acid (mCBA) as products. An intermediary,
possibly sulfoxide, can be assumed to be generated and then
subsequently converted to sulfone. In the case of BT, the reac-
tion requires a molecule of BT and two molecules of mCPBA to
collide effectively before it proceeds. The chance of a DBT
molecule and an mCPBA molecule colliding effectively is far
greater than that of a molecule of BT and two molecules mCPBA
colliding at the same time, considering that both of these
compounds are at the ppm level. Furthermore, the trimolecular
reaction is more sensitive to concentration change than the
bimolecular reaction. This, alongside the difference in the
electron density on the sulfur atom of these compounds, is
perhaps the reason why DBT is more reactive than BT.
Although sulfones of DBT and BT are the expected products
of the reaction, a GC-MS analysis was carried out to conrm
this. Fig. 5 shows the GC-MS result aer oxidation. Dibenzo-
thiophene sulfone (DBTO2) and benzothiophene sulfone peaks
could be clearly seen aer the oxidation reaction at 24.8 min
(mass ¼ 216) and 15.3 min (mass ¼ 137), respectively. meta-
Chlorobenzoic acid, which is the by-product of the oxidation
reaction can be seen at 10.0 min (mass ¼ 156). The oxidation of
DBT to DBTO2 can be assumed to follow the route presented
schematically in Fig. 6. It is therefore important to remove the
sulfones and mCBA as well as the unreacted mCPBA to ensure
effective oxidative and extractive desulfurization.
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Paper RSC Advances

Fig. 4 (A) Plot of ln[(M  2XA)/(M(1  XA)] versus time at different temperatures (bimolecular), M ¼ 3. (B) Plot of (2CAO  CBO)(CBO  CB)/(CBOCB) +
ln[CAOCB)/CACBO] against time at different temperatures (trimolecular) for DBT.

Fig. 5 Products of oxidation of DBT and BT in simulated fuel using mCPBA.

3.2 Oxidative and extractive desulfurization An IL that allows the oxidant to preferentially reside in the
fuel phase can be used in extractive oxidative desulfurization
Studies related to oxidative and extractive desulfurization can
(EODS) experiments, where extraction and oxidation occur
be kinetics-limiting or mass-transfer-limiting depending on
simultaneously. Because both oxidized and unoxidized sulfur
where the oxidant preferentially resides. If the oxidant resides
compounds simultaneously migrate to the IL phase, this
in the IL phase, then sulfur compounds have to migrate into the
process is expected to reduce the mixing time required for the
IL phase before they can be converted. When the reaction is fast
same IL. However, it must be ensured that unreacted mCPBA
relative to the rate of migration of the sulfur compounds, then
and mCBA either get extracted along with the sulfones or
the process is mass-transfer-limiting. Although a high reaction
subsequently removed. Thus, in this kinetics-limiting system,
rate, as in the case of DBT, will result in a concentration
ensuring high reaction rate is the main goal. There are two
gradient for DBT and a consequent faster migration into the IL
options for ILs that do not allow the oxidant to reside in the fuel
phase, the overall sulfur removal could still be low. On the other
phase. If the rate of the oxidation reaction in the IL phase
hand, if the oxidant preferentially resides in the fuel phase,
signicantly promotes the migration of the unoxidized sulfur
assuming the more polar sulfones produced from the oxidation
compounds, then an EODS process is suitable. Otherwise, post-
reaction migrate into the IL phase faster than the oxidation
oxidation extractive desulfurization (OEDS) is preferred despite
reaction occurs, the process becomes rate-limiting.
the advantages of EODS. In the OEDS process, the oxidant will

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Fig. 6 Non-catalytic oxidation route of DBT in the presence of mCPBA.

have maximum contact with the sulfur compounds, with of both EODS and OEDS strategies was carried out and
a consequent high reaction rate. The treated fuel can then be compared.
transferred into an EDS unit where the sulfones will be removed 3.2.1 Optimization of the EODS of simulated fuel using
by the IL. Generally, these ILs would also simultaneously [Pi444,1][Tos] IL. Response surface methodology using a central
remove the product of the oxidation reactions and the unreac- composite experimental design was employed for the analysis,
ted oxidant. It should be noted that the above discussion is tting and optimization of the factors affecting the EODS of the
applicable because the oxidant can dissolve in the fuel. simulated fuel. The details of this analysis can be found in the
Oxidants such as the 30 wt% H2O2 do not offer such exibility ESI† le. The coefficients of the reduced model (quadratic
except in the presence of a phase-transfer agent. model) terms are presented in Table S11 (ESI†). It was observed
A preliminary study carried out using the tri- that while DBT can be completely removed, only 78.7% of BT
isobutylphosphonium tosylate ([Pi444,1][Tos]) IL for the simul- can be removed (Tables 1 and 2). Although the % SR obtained is
taneous extractive and oxidative desulfurization (EODS) of the higher than that obtained prior to optimization, BT concen-
simulated fuel showed relative improvement as compared with tration is still beyond the acceptable limit of #15 ppm.
solely EDS of the same fuel. This was true at all temperatures It was also observed that mass fraction is the most signi-
and times considered (Fig. S4 and S5†). Although an improve- cant term in the ANOVA table (Table S4†) for the EODS of BT
ment was observed using the EODS strategy, the improvements using an IL. This is similar to the results obtained from the EDS
obtained were not as much as expected and this was attributed experiments, indicating mass transfer is an important factor in
to the preferential residence of the oxidant as discussed above. the % SR of BT using an IL.29 It also indirectly indicates that the
Therefore, the post-oxidative extractive desulfurization (OEDS) oxidant preferentially resides in the IL phase and the migration
might be a better strategy in this case. As a result, optimization of BT into the IL phase is responsible for the relatively low
improvements. Furthermore, going back to the preliminary
kinetic studies presented, DBT possesses high reaction rate,
Table 1 Validation of the predicted optimum of performance of the which resulted in 60% conversion even at 30
C, aer 30 min.
respective ILs in removing DBT But as seen in Fig. S5,† 90% SR (DBT) was achieved at 60
C aer
the same interval of time. It can be concluded that the sulfur
[Pi444,1][Tos] OEDS [P4444][MeSO3] OEDS
compounds in the presence of an IL do not have as much
Time (X1, min) 15 15 contact with oxidant as they have in its absence, which also
Temperature (X2,
C) 60 60 points toward mass transfer resistance. It is therefore safe to
Mass fraction (X3, w/w) 0.5(1 : 1) 0.67(2 : 1) assume that the process is mass-transfer-limiting and that the
O/S (X4, mol mol1) 3/1 3/1
rate of migration of the sulfur compounds even in the presence
Prediction (SR, %) 100 100
Validation (SR, %) >99 >99 of the oxidation step is not favorable. This calls for the adap-
tation of the OEDS strategy previously mentioned.

Table 2 Validation of the predicted optimum of performance of the respective ILs in removing BT

[Pi444,1][Tos] EODS [Pi444,1][Tos] OEDS [Pi444,1][Tos] OEDS [P4444][MeSO3] OEDS

Time (X1, min) 80 60 72 60

Temperature (X2,
C) 60 60 60 60
Mass fraction (X3, w/w) 0.5(1 : 1) 0.5(1 : 1) 0.5(1 : 1) 0.5(1 : 1)
O/S (X4, mol mol1) 7.5/1 6.5/1 8/1 6/1
Prediction (SR, %) 97 97 100 97
Validation (SR, %) 78.7 94.5 99 95

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Paper
3.2.2 Optimization of the OEDS of simulated fuel using
[Pi444,1][Tos] and [P4444][MeSO3] IL. In the OEDS, oxidation and
extraction take place in separate stages thereby allowing the
oxidant to come into maximum contact with the sulfur
compounds. The oxidized sulfur compounds, which become
more polar, can be removed easily in the extraction unit. The
variables used for the optimization of the EODS of BT using
[Pi444,1][Tos] can be assumed to be equally important and used
for the optimization of OEDS of BT. However, in OEDS, one
more variable has to be considered. This is the ratio of oxidation-
to-extraction times. This variable can be split into two variables,
namely oxidation time and extraction time, thereby removing
“time” as an independent variable. In both cases, there will be
a total of ve variables. This results in a large number of exper-
iments, thereby tending to produce more errors. Hence, an
experiment was carried out in order to retain the number of
variables at four while keeping the ratio of oxidation-to-extraction
(oxidation/extraction) times constant. This is shown in Fig. 7. It
should be noted that oxidation still takes place in the extraction
portion of the time and therefore an oxidation/extraction time of
zero corresponds to an EODS strategy.
It can be seen that as the oxidation/extraction time was
decreased from 20/10 to 0/30, DBT decreased from 96% to 61%.
Unexpectedly, BT increased from 42% to 50%. This implies
that, whereas the assumption made that the relatively poor DBT
removal was due to inefficient contact with the oxidant holds,
the same cannot be said for the removal of BT under these
conditions. This can be attributed to the low reaction rate of BT
with the oxidant. Therefore, a possibility exists that upon
increase in temperature, the increase in rate of oxidation of BT
in an OEDS setup will most likely be higher than that in an
EODS setup owing to higher collision rate, thereby resulting in
a better BT removal overall. The oxidation/extraction time of 20/
10 (two-thirds of total time) was selected for the purpose of the
optimization. This is due to the fact that it showed highest DBT
removal and a possibility that a change in one of the indepen-
dent variables or interaction between the variables might result
in higher BT removal than in an EODS setup.
Fig. 7 % SR as a function of ratio of oxidation-to-extraction time using
[Pi444,1][Tos], 30
C, 30 min, 600 rpm, 3/1 (O/S).
This journal is © The Royal Society of Chemistry 2016
RSC Advances
Since very high DBT removal (>99%) was achieved using the
OEDS strategy as compared with the EODS strategy, BT was the
limiting reactant and the design of the experiment and opti-
mization of the responses were carried out on BT in a similar
fashion to the foregoing section. The ranges in the variables are
the same, except for total time, which was made to be between
15 min and 81 min. This is to avoid fractions of either oxidation
or extraction time. Details of the experimental design and
optimization can be found in the ESI.†
Aer carrying out the optimization, it was evident that the
OEDS was superior to the EODS (Table 2). It can be seen that at
60
C, MR of 1 : 1, O/S of 6.5 and total time of 60 min, a % SR
(BT) of 97.4%, (which was validated as 94.5%), was achieved. In
comparison with the EODS strategy, this requires 20 min less
time and 1/1 lower O/S to achieve a better BT removal of 94.5%
as against 78.7%. Despite the improvement, the set target had
not yet been achieved. To achieve the target of #15 ppm, at least
97.0% of sulfur must be removed from a fuel containing
500 ppm sulfur. The conditions under which this was achieved
are presented in Table 2.
The OEDS strategy was employed to study the improvement
in the performance of the [P4444][MeSO3] IL upon the intro-
duction of an oxidation step. The OEDS was considered because
this IL is hydrophilic and is expected to have similar behavior to
[Pi444,1][Tos] in this context. Therefore an experiment was
designed and optimized using the same ranges of variables as
in the OEDS using [Pi444,1][Tos]. The only difference was that the
temperature was kept constant at 60
C and this brought down
the number of experimental runs to 17. The experimental
design matrix of the OEDS of BT using this IL is presented in
Table S9.†
3.2.3 Summary of the performances of the ILs. Having
carried out the preliminary investigation and optimization of
the factors affecting the EODS and OEDS processes, the coeffi-
cients of the tted quadratic model representing the response
surface in EODS/OEDS of the BT and DBT using the respective
ILs are presented in Table S11.† Values of terms with negative
coefficients need to be reduced while values of terms with
positive coefficients need to be increased to achieve high % SR.
The 3D response surface plot for the all the systems studied can
be found in the ESI.†
3.2.3.1 Dibenzothiophene removal. Table 1 presents the
validated result for the optimized OEDS of DBT using the
respective ILs. The fact that a better result was obtained using
[P4444][MeSO3] indicates that this IL is superior to the other IL.
Comparing the results obtained in this work with others avail-
able in the literature shows that the choice of mCPBA as an
oxidant is valid. This is because most of the reported studies
showed that >99% DBT removal can be achieved but either at
a higher time of up to 6 h, with a high O/S ratio or in the
presence of a catalyst.4 The results obtained in this work are
promising and clearly better than most of the results available
in the literature for DBT removal, to the best of the authors'
knowledge.
3.2.3.2 Benzothiophene removal. Table 2 presents the vali-
dation of EODS/OEDS optimum operating conditions for BT
using the respective ILs. The validations are in reasonable
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RSC Advances Paper

agreement with the predicted results, which indicates the

model, coefficients of which are presented in Table S11,†
reasonably describes the studied systems. It can be concluded
that the target of #15 ppm can be achieved by optimizing the
factors affecting the process. It can be seen (Table 2) that to
increase BT removal from 95% to 99%, time and O/S molar ratio
have to be increased from 60 to 72 min and from 6.5/1 to 8.0/1
respectively. This is because as more BT is removed its
concentration in the fuel phase becomes very low and conse-
quently the probability that it will engage in effective collisions
with oxidant becomes low. It should be recalled that the reac-
tions of BT and mCPBA were assumed to be trimolecular, and
therefore sensitive to changes in concentration. This means
that the rate of reaction becomes very low at low concentrations
Fig. 8 % SR for the OEDS of commercial diesel (iS ¼ 275 ppm) using
of BT in the fuel phase. the [Pi444,1][Tos] IL as a function of water-washing time, at 60
C, MR
The expected products of reaction are DBTO2, BTO2 and 1 : 1, O/S 6/1, for 60 min.
mCBA. At the optimum conditions, it was observed that neither
the aforementioned products of the reaction nor the unreacted
mCPBA were present in the fuel aer treating it with the It should be recalled that similar operating conditions when
hydrophilic phosphonium-based ILs. Furthermore, it should be applied on the simulated fuel resulted in SR of 95%. The rela-
noted that the OEDS process used was based on the oxidation tively low performance of the OEDS process using the same IL
time being kept at two-thirds of the total time. can be attributed to the possible presence of other similar
compounds such as aromatic nitrogen-based compounds that
may compete with the sulfur compounds in the oxidation or
3.3 Commercial diesel desulfurization
even extraction step. The washing time of 30 min at 1 : 1 diesel-
OEDS of commercial diesel fuel obtained from a local lling to-water ratio seemed to be the optimum option and therefore
station was carried out using the ILs selected in this work. XRF was used in studying the effect of O/S molar ratio, shown in
analysis on the diesel fuel samples indicated sulfur content of Fig. 9.
275 ppm. An SR of $94% is enough to ensure deep desulfur- The O/S molar ratio of zero indicates EDS of the diesel fuel
ization (#15 ppm) of this diesel fuel. To achieve this value using for 60 min. It can be seen that the O/S molar ratio has virtually
the [Pi444,1][Tos] IL in an OEDS strategy, it was shown that the no impact on the % SR at O/S $ 4/1. This implies that adding
temperature, mass ratio, O/S ratio and total time should be kept more oxidant will not result in any improvement in the process.
at 60
C, 1 : 1, 6.5/1 and 60 min (40 min oxidation and 20 min It also means that the possibility that the oxidation is the
extraction). Using the same parameters with the exception of O/ limiting step of the process is slim. Keeping the O/S molar ratio
S, which was kept at 6/1, the results presented in Fig. 8 were at 4/1 and increasing the total time to 90 min (60 min oxidation
obtained. The negative % SR actually indicates an increase in and 30 min extraction) did not improve the result (SR ¼ 74%)
the sulfur content in the diesel fuel. This is the result of the rst either.
experiment carried out and it was observed that the IL ([Pi444,1]
[Tos]), which contains sulfur in its anion, dissolved in the fuel.
It should be noted that the solubility of the IL in the diesel is
still relatively small considering the fact that a fuel-to-IL ratio of
1 : 1 is used while the sulfur content of diesel fuel only
increased from 275 ppm to 451 ppm. One of the advantages of
the hydrophilic phosphonium ILs is that they can easily be
removed from the fuel phase with water. While the IL can be
removed by water-washing the diesel fuel, the sulfur
compounds are not expected to dissolve in water. This implies
that any decrease in the sulfur content of the diesel fuel by
water-washing is as a result of the removal of the sulfur-
containing IL.
By adding water to the treated diesel fuel at a diesel-to-water
mass ratio of 1 : 1 and stirring for 30 min, an increase in the SR
to 74% (71 ppm) was observed. Increasing the washing time to
60 min did not affect the result, which indicates either complete
removal of the IL or a very low concentration of the IL in the Fig. 9 Effect of O/S molar ratio on % SR for the OEDS of commercial
diesel fuel phase. Increasing the diesel-to-water mass ratio to diesel using [Pi444,1][Tos], 60
C, MR 1 : 1, 60 min, washing time 30 min,
1 : 3 did not signicantly improve the result (SR ¼ 75%) either. diesel-to-water ratio 1 : 1.

103614 | RSC Adv., 2016, 6, 103606–103617 This journal is © The Royal Society of Chemistry 2016
Paper
If the extraction step is the limiting step, then using [P4444]
[MeSO3] will likely improve the result as it is a better extraction
solvent. Therefore, keeping the temperature at 60
C, MR at
1 : 1, O/S at 4 : 1, total OEDS time at 60 min, washing time at
30 min and diesel-to-water mass ratio at 1 : 1, the performance
of the two hydrophilic phosphonium-based ILs was compared
while introducing stage-wise water mixing. This result is pre-
sented in Fig. 10.
It can be seen that the decrease in the sulfur content of the
diesel from the second stage to the third stage is not very
signicant and therefore it can be assumed that adding another
stage is not worthwhile. Secondly, it can be seen that, at the
third stage, the sulfur content of the diesel treated using the
[P4444][MeSO3] IL (56 ppm) is less than that of the diesel treated
with the [Pi444,1][Tos] IL (61 ppm). Three-stage water washing
was adopted for all the subsequent experiments. An effort was
made to improve the performance of [P4444][MeSO3] by doubling
the O/S molar ratio to 8 : 1 using the current operating condi-
tions. However, the sulfur content obtained was 55 ppm, indi-
cating that the oxidation step may not be the limiting step,
similar to the case of the [Pi444,1][Tos] IL. Comparison between
the OEDS and EODS strategy using the two ILs is presented in
Table 3.
Fig. 10 Sulfur content in treated diesel fuel as a function of water-
washing stages, 60
C, MR 1 : 1, 60 min, washing time 30 min, diesel-
to-water ratio 1 : 1.
Table 3Performance of all selected ILs for the EODS/OEDS of
commercial diesela
Sulfur content aer EODS Sulfur content aer OEDS
IL treatment (ppm) treatment (ppm)
[Pi444,1][Tos] 145.39 60.99
[P4444][MeSO3] 144.69 55.63
a
Temperature 60
C, MR 1 : 1, O/S 4 : 1 (*6/1), total OEDS or EODS time
60 min, washing time 30 min, diesel-to-water mass ratio 1 : 1, three-
stage water washing.
This journal is © The Royal Society of Chemistry 2016
RSC Advances
Using [P4444][MeSO3] under the conditions shown in Table 3,
the sulfur content can be reduced from 56 ppm to 31 ppm by
addition of a new EDS stage and to 24 ppm by addition of yet
another EDS stage (Fig. 11). This therefore becomes a process
composed of a 40 min oxidation stage and three 20 min
extraction stages. Even with the three extraction stages the % SR
does not reach the target. It can be deduced that the sulfur
removal is becoming more difficult as the target is approached.
This is due to very low concentration of the sulfur compounds,
which affects their distribution. Maintaining the three extrac-
tion stages while doubling the extraction time from 20 min to
40 min resulted in a sulfur content of 15.6 ppm.
3.4 Regeneration and recovery
Having carried out the deep oxidative desulfurization of
commercial diesel using the [P4444][MeSO3] IL, the regeneration
of the same IL was carried out. Fig. 12 shows the result of this
study. The change in the % SR of the EDS of commercial diesel
using the regenerated IL as compared with the fresh IL is pre-
sented. The % SR dropped slightly aer the [P4444][MeSO3] IL
was used four times (third regeneration). The % SR obtained
aer the third regeneration stage was 95% that of the fresh IL.
However, using the advance regeneration method (Adv) the
original % SR of the IL was restored.
Fig. 13 shows the % recovery of the IL aer each regeneration
stage. The % recovery was 90% for the rst regeneration stage
and 86% for the advanced regeneration stage. It should be
noted that some of the ILs can be recovered from the water used
for the three-stage diesel water-washing process.
Therefore, a suitable system for the deep desulfurization of
the commercial diesel involves the use of [P4444][MeSO3] as
a solvent for the extraction of sulfur compounds from diesel fuel
treated with mCPBA at an O/S molar ratio of 4/1 at 60
C. The
extraction is carried out for 40 min in three stages at 60
C using
a fuel-to-solvent mass ratio (MR) of 1 : 1. Finally the treated
diesel is separated from dissolved IL by water-washing it in
Fig. 11 A plot of sulfur content of commercial diesel (initial concen-
tration of 275 ppm) as a function of number of post-oxidation
extraction stages.
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RSC Advances Paper

three stages using a diesel-to-water mass ratio of 1 : 1. This is

followed by a set of regeneration stages as presented in Fig. 14.

4 Conclusion
In this work, the feasibility of an electrophilic oxidant (meta-
chloroperoxybenzoic acid) as a suitable and efficient reagent for
the non-catalytic conversion of refractory sulfur compounds to
their corresponding sulfones has been presented. The oxidant
possesses a number of advantages over the commonly used
hydrogen peroxide by virtue of its electrophilicity, solubility in
the fuel phase and lower water content. A preliminary kinetic
study carried out employing benzothiophene (BT) and diben-
zothiophene (DBT) in a simulated fuel showed that the latter,
owing to the high electron density on its sulfur atom, is ex-
Fig. 12 Regeneration of [P4444][MeSO3]. pected to be more susceptible to electrophilic attack by the
oxidant. A bimolecular reaction kinetic model correlates well
with the experimental data obtained using DBT as the
compound of interest while a trimolecular reaction kinetic
model correlates well with that of BT. This partly explains the
reason why the DBT conversion is much faster.
Application of meta-chloroperoxybenzoic acid as oxidant in
an ionic liquid-based oxidative desulfurization of the simulated
fuel revealed noticeable improvements as compared with the
ionic liquid-based extractive desulfurization of the simulated
fuel using the same solvent and experimental conditions. It was
observed that the optimum performance of the ILs varies
depending on whether the extraction and oxidation stages were
carried out simultaneously as in extractive oxidative desulfur-
ization (EODS) or separately as in post-oxidation extractive
desulfurization (OEDS). This in turn was understood to be
dependent on the phase in which the oxidant preferentially
resides. It can then be concluded that while EODS may be
a suitable strategy when using a hydrophobic IL, which allows
the oxidant to preferentially reside in the fuel phase, the OEDS
Fig. 13 A plot of IL recovery against regeneration stage. strategy is suitable for the hydrophilic phosphonium-based ILs
used in this work. This is to allow maximum contact between
the oxidant and sulfur compounds.

Fig. 14 Schematic of the proposed post-oxidative extractive desulfurization of commercial diesel. ULSF, ultra-low-sulfur fuel; WS, waste solid
compounds; clean-up, 3-stage water-washing and drying.

103616 | RSC Adv., 2016, 6, 103606–103617 This journal is © The Royal Society of Chemistry 2016
Paper
Employing the OEDS strategy, deep desulfurization of
a commercial diesel fuel was achieved using the tetrabutyl-
phosphonium methanesulfonate IL at optimized experimental
conditions. The IL was successfully regenerated using a combi-
nation of water and n-hexane as primary and secondary regen-
eration solvents respectively.
Acknowledgements
The authors appreciate the nancial support of The Research
Council and Sultan Qaboos University, Muscat, Oman, under
the project RC/ENG/PCED/12/02.
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